WO2012128233A1 - Colored composition for color filters, and color filters - Google Patents

Abstract

Provided is a colored composition for color filters which comprises a colorant represented by general formula (1), a binder resin, and a solvent. In the formula, R¹ to R¹³ are each independently a hydrogen atom, a halogen atom, alkyl, alkoxy, aryl, an acid group or a salt thereof with either a metal or an alkylammonium, phthalimidomethyl, or sulfamoyl, and a pair of adjacent groups of R¹ to R⁴, or R¹⁰ to R¹³ is united to form an aromatic ring which may be substituted.

Description

Coloring composition for color filter and color filter

The present invention relates to a color liquid crystal display device, a color filter colorant used in the production of a color filter used for a color image pickup tube element, a color composition, and a color filter formed using the same. .

In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. The demand for higher brightness and higher color reproducibility is increasing.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in In general, it is often formed by three-color filter segments of red, green, and blue. Each segment is as fine as several microns to several hundreds of microns, and is arranged regularly in a predetermined arrangement for each hue. .

Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, it is required to use a colorant having excellent heat resistance and light resistance in the production of a color filter.

In the production of filter segments, yellow pigments are used as colorants for toning, and in particular, C.I. I. Pigment Yellow 138 is often used. However, C.I. I. Although pigment yellow 138 is relatively excellent in brightness, further improvement in brightness is desired. In recent years, there has been a strong demand for high contrast for color filters. I. Pigment Yellow 138 has a problem of low contrast.

C. I. A quinophthalone compound is known as a pigment dispersant for stabilizing the dispersion of Pigment Yellow 138. For example, Patent Document 1 discloses a quinophthalone compound containing a sulfonic acid, and Patent Document 2 discloses a quinophthalone compound to which a phthalimidomethyl group is added. By using these pigment dispersants, C.I. I. Although the dispersibility of Pigment Yellow 138 is improved, the contrast ratio has not yet achieved the desired characteristics.

Patent Document 3 discloses a quinophthalone compound starting from the following compound (1) as a pigment composition with improved dispersion stability over time.

Patent Document 4 describes that a pigment composition excellent in coloring power, sharpness, and the like can be obtained by using a compound in which a quinophthalone structure is dimerized.

However, the colorants containing these quinophthalone compounds have not been sufficiently improved in problems such as contrast ratio and insufficient coloring power when used for color filters.

Patent Document 5 discloses a quinophthalone compound having a naphthalene ring for coloring a polymer material. However, all of these quinophthalone compounds are for the purpose of coloring plastics, and their suitability for color filter applications is unknown.

It is also known to use an aluminum phthalocyanine pigment as a coloring composition for a green color filter segment (Patent Documents 6 to 12). When using an aluminum phthalocyanine pigment, it is necessary to use a yellow pigment in combination. However, since the conventional quinophthalone compound known as a yellow pigment has the above-mentioned problems, when these are used in combination, the contrast ratio and coloring power of the color filter are not sufficient.

Also, in order to realize high brightness and high contrast of the color filter, the pigment contained in the filter segment is subjected to a fine processing. However, even if the pigment is simply miniaturized, the pigment whose primary particles or secondary particles have been miniaturized generally tends to aggregate and it is very difficult to obtain a stable coloring composition even if it is intended to stabilize. there were. Further, it is known that a finely-treated pigment is difficult to stably disperse in a pigment carrier at a high concentration and causes various problems with respect to the production process and the product itself.

Therefore, in general, a pigment dispersant is used in order to maintain a good dispersion state. The pigment dispersant has both a structure that adsorbs to the pigment and a structure that has a high affinity for the solvent that is the dispersion medium, and the performance is determined by the balance between these two parts. Various pigment dispersants are used in accordance with the surface state of the pigment to be dispersed. However, pigments having an acid-biased surface have basic functional groups having electrostatic adsorption. Generally, a dispersant is used. In this case, the basic functional group serves as a pigment adsorption site. Examples of using a basic pigment dispersant having an amino group as a basic functional group in a coloring composition for a color filter are described in Patent Documents 13 to 17, for example.
However, although they have a certain degree of dispersion ability, it has not been possible to stabilize the dispersion of pigments that have been subjected to ultrafine processing, which is desired to be used for high contrast, as a color filter coloring composition. .

Therefore, by using a pigment dispersant formed by reacting an isocyanate group of a urethane prepolymer having an isocyanate group at both ends with an amine compound, coloring for a color filter having excellent dispersibility, fluidity, and storage stability. A composition has been proposed (Patent Document 18).

However, even when the dispersant described in Patent Document 18 was used, the ability to disperse into the quinophthalone pigment was insufficient, and it was not possible to achieve both high contrast and dispersion stability.

Moreover, a voltage holding ratio can be given as an index representing the display performance of the liquid crystal display device. Liquid crystal is an extremely high insulating material, and when the polar compound remaining in the color filter coloring composition elutes into the liquid crystal cell, the voltage between the electrodes decreases, leading to a decrease in voltage holding ratio, and display unevenness. Generation | occurrence | production, alignment failure, etc. arise and it becomes the cause of reducing the performance as a liquid crystal display device. Therefore, the color filter coloring composition is required to be insoluble in liquid crystals.

Patent Documents 19 to 21 propose green coloring compositions for color filters containing phthalocyanine dyes having various structures and quinophthalone dyes. However, these green coloring compositions for color filters have problems of insufficient lightness and poor heat resistance and light resistance.

Patent Document 22 proposes a green coloring composition for a color filter containing a zinc phthalocyanine pigment and a quinophthalone dye as a means for improving brightness. However, zinc phthalocyanine-based pigments have high acidity and are easily extracted into the liquid crystal phase laminated on the color filter layer, leading to a decrease in voltage holding ratio, resulting in display unevenness and poor alignment. There has been a problem that the performance as a liquid crystal display element is lowered.

Japanese Patent Laid-Open No. 2002-179979 JP 2008-95007 A JP 2008-81566 A JP 2008-74985 A Japanese Patent Laid-Open No. 51-147544 JP 2002-131521 A JP 2002-250812 A JP 2003-4930 A JP 2004-333817 A JP 2000-301833 A JP 2010-79247 A JP 57-90058 A Japanese Patent Laid-Open No. 09-176511 Japanese Patent Application Laid-Open No. 10-213898 JP 2001-240780 A JP 2002-31713 A JP 2004-54213 A JP 2010-39433 A JP-A-6-220339 JP-A-8-171201 JP 2009-51896 A JP 2010-168531 A

　ここで、一般式（１）中、Ｒ^１～Ｒ^１３は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有しても良いアルキル基、置換基を有しても良いアルコキシル基、置換基を有しても良いアリール基、－ＳＯ_３Ｈ；－ＣＯＯＨ；およびこれら酸性基の１価～３価の金属塩；アルキルアンモニウム塩、置換基を有しても良いフタルイミドメチル基、または置換基を有しても良いスルファモイル基を示す。Ｒ^１～Ｒ^４、および／または、Ｒ^１０～Ｒ^１３の隣接した基は、一体となって、置換基を有してもよい芳香環を形成する。つまり、Ｒ^１～Ｒ^４のうち少なくとも１つの隣接した一組の基、および／または、Ｒ^１０～Ｒ^１３のうち少なくとも１つの隣接した一組の基は、一体となって、置換基を有してもよい芳香環を形成する。 An embodiment of the present invention relates to a color composition for a color filter, comprising a colorant, a binder resin, and a solvent, wherein the colorant contains a colorant represented by the general formula (1). .

Here, in the general formula (1), R ¹ to R ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. An aryl group that may have a group, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts, an optionally substituted phthalimidomethyl group, or a substituent The sulfamoyl group which may have a group is shown. The adjacent groups of R ¹ to R ⁴ and / or R ¹⁰ to R ¹³ together form an aromatic ring which may have a substituent. That is, at least one adjacent set of groups out of R ¹ to R ⁴ and / or at least one adjacent set of groups out of R ¹⁰ to R ¹³ are combined to have a substituent. An aromatic ring that may be formed is formed.

　ここで、一般式（１Ａ）～（１Ｃ）中、Ｒ^１４～Ｒ^２８、Ｒ^２９～Ｒ^４３、Ｒ^４４～Ｒ^６０は、それぞれ独立に：水素原子；ハロゲン原子；置換基を有しても良いアルキル基；置換基を有しても良いアルコキシル基；置換基を有しても良いアリール基；－ＳＯ_３Ｈ、－ＣＯＯＨ、およびこれら酸性基の１価～３価の金属塩；アルキルアンモニウム塩；置換基を有しても良いフタルイミドメチル基；または置換基を有しても良いスルファモイル基を示す。 The colorant represented by the general formula (1) is preferably a colorant selected from the general formulas (1A) to (1C).

In the general formulas (1A) to (1C), R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , and R ⁴⁴ to R ⁶⁰ are each independently: a hydrogen atom; a halogen atom; A good alkyl group; an alkoxyl group that may have a substituent; an aryl group that may have a substituent; —SO ₃ H, —COOH, and monovalent to trivalent metal salts of these acidic groups; A salt; an optionally substituted phthalimidomethyl group; or an optionally substituted sulfamoyl group.

　ここで、一般式（８Ａ）中、Ｘ_１～Ｘ_４はそれぞれ独立して、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、または置換基を有してもよいアリールチオ基を表す。Ｙ_ｌ～Ｙ_４はそれぞれ独立して、ハロゲン原子、ニトロ基、置換基を有してもよいフタルイミドメチル基、または置換基を有してもよいスルファモイル基を表す。Ｚは、水酸基、塩素原子、－ＯＰ（＝Ｏ）Ｒ_１Ｒ_２、または－Ｏ－ＳｉＲ_３Ｒ_４Ｒ_５を表す。Ｒ_１～Ｒ_５はそれぞれ独立して、水素原子、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基、または置換基を有してもよいアリールオキシ基を表し、Ｒ同士が互いに結合して環を形成しても良い。ｍ_１～ｍ_４、ｎ_１～ｎ_４は、それぞれ独立して０～４の整数を表し、ｍ_１＋ｎ_１、ｍ_２＋ｎ_２、ｍ_３＋ｎ_３、ｍ_４＋ｎ_４は、各々、０～４で、同一でも異なっても良い。

　ここで、一般式（８Ｂ）中、Ｘ_５～Ｘ_１２はそれぞれ独立して、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、または置換基を有してもよいアリールチオ基を表す。Ｙ_５～Ｙ_１２はそれぞれ独立して、ハロゲン原子、ニトロ基、置換基を有してもよいフタルイミドメチル基、または置換基を有してもよいスルファモイル基を表す。Ｌは、－Ｏ－ＳｉＲ_６Ｒ_７－Ｏ－、－Ｏ－ＳｉＲ_６Ｒ_７－Ｏ－ＳｉＲ_８Ｒ_９－Ｏ－、または－Ｏ－Ｐ（＝Ｏ）Ｒ_１０－Ｏ－を表し、Ｒ_６～Ｒ_１０はそれぞれ独立して、水素原子、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基、または置換基を有してもよいアリールオキシ基を表す。ｍ_５～ｍ_１２、ｎ_５～ｎ_１２は、それぞれ独立して０～４の整数を表し、ｍ_５＋ｎ_５、ｍ_６＋ｎ_６、ｍ_７＋ｎ_７、ｍ_８＋ｎ_８、ｍ_９＋ｎ_９、ｍ_１０＋ｎ_１０、ｍ_１１＋ｎ_１１、ｍ_１２＋ｎ_１２は、各々、０～４で、同一でも異なっても良い。 The colorant may further contain a colorant selected from general formulas (8A) and (8B).

Here, in the general formula (8A), X ₁ to X ₄ may each independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. A good cycloalkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent Or an arylthio group which may have a substituent. Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group. Z represents a hydroxyl group, a chlorine atom, —OP (═O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ . R ₁ to R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or It represents an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring. m ₁ to m ₄ and n ₁ to n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , m ₄ + n ₄ are each 0 to 4 may be the same or different.

Here, in the general formula (8B), X ₅ to X ₁₂ may each independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. A good cycloalkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent Or an arylthio group which may have a substituent. Y ₅ to Y ₁₂ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group. L represents —O—SiR ₆ R ₇ —O—, —O—SiR ₆ R ₇ —O—SiR ₈ R ₉ —O—, or —O—P (═O) R ₁₀ —O—, R ₆ to R ₁₀ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. The aryloxy group which may have a group is represented. m ₅ to m ₁₂ and n ₅ to n ₁₂ each independently represent an integer of 0 to 4, and m ₅ + n ₅ , m ₆ + n ₆ , m ₇ + n ₇ , m ₈ + n ₈ , m ₉ + n ₉ , m ₁₀ + n ₁₀ , m ₁₁ + n ₁₁ , and m ₁₂ + n ₁₂ are each 0 to 4, and may be the same or different.

The colorant may further contain a dispersant. The dispersant is a urethane prepolymer having isocyanate groups at both ends, obtained by reacting the hydroxyl group of the vinyl polymer (A) having two hydroxyl groups in one terminal region with the isocyanate group of diisocyanate (B). A pigment dispersant obtained by reacting the isocyanate group of (E) with a primary and / or secondary amino group of an amine compound containing at least a polyamine (C), wherein the vinyl polymer (A) is ethylene oxide. An ethylenically unsaturated monomer (a1) having at least one of a chain or a propylene oxide chain may be included in the copolymer composition.

　ここで、一般式（６）中、Ｒ_１～Ｒ_６は、それぞれ独立に水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、置換もしくは無置換のアリール基、または、－Ｏ－Ｒ_７を表わす。また、Ｒ_７は置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、または、置換もしくは無置換のアリール基である。ただし、Ｒ_１～Ｒ_６が全て水素原子になる事はない。 The colorant may further contain a colorant represented by the general formula (6).

In the general formula (6), R ₁ to R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, Or, -O-R ₇ is represented. R ₇ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, R ₁ to R ₆ are not all hydrogen atoms.

　ここで、一般式（７）中、Ｒ_１～Ｒ_６は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、置換もしくは無置換のアリール基、または、－Ｏ－Ｒ_１１を表わす。また、Ｒ_１１は、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、または、置換もしくは無置換のアリール基を表わす。また、Ｒ_７～Ｒ_１０は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、置換もしくは無置換のアリール基、カルボキシル基、置換もしくは無置換のスルホアミド基、置換もしくは無置換の複素環状残基、－Ｓ－Ｒ_１２、－Ｏ－Ｒ_１２、または、－ＣＯＯ－Ｒ_１２を表わす。また、Ｒ_１２は、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、または、置換もしくは無置換のアリール基である。 Moreover, embodiment of this invention contains a coloring agent, binder resin, and a solvent, and the said coloring agent contains the coloring agent represented by General formula (6), The coloring composition for color filters characterized by the above-mentioned. Related to things. The colorant may further contain a colorant selected from general formulas (8A) and (8B). The colorant may further contain a colorant represented by the general formula (7).

In the general formula (7), R ₁ to R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group. Or represents —O—R ₁₁ . R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R ₇ to R ₁₀ are each independently a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, carboxyl group, substituted or unsubstituted And a sulfoamide group, a substituted or unsubstituted heterocyclic residue, —SR ₁₂ , —O—R ₁₂ , or —COO—R ₁₂ . R ₁₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

Furthermore, an embodiment of the present invention contains a colorant, a binder resin, and a solvent, and the colorant contains a colorant represented by the general formula (7A). Related to things.

　ここで、一般式（７Ａ）中、Ｒ_１～Ｒ_６は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、置換もしくは無置換のアリール基、または、－Ｏ－Ｒ_１１を表わす。また、Ｒ_１１は、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、または、置換もしくは無置換のアリール基を表わす。また、Ｒ_７～Ｒ_１０は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、置換もしくは無置換のアリール基、カルボキシル基、置換もしくは無置換のスルホアミド基、置換もしくは無置換の複素環状残基、－Ｓ－Ｒ_１２、または－Ｏ－Ｒ_１２または、－ＣＯＯ－Ｒ_１２を表わす。また、Ｒ_１２は、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、または、置換もしくは無置換のアリール基である。ただし、Ｒ_７～Ｒ_１０の少なくとも１つは－Ｏ－Ｒ_１２である。
　ここで、一般式（７Ｂ）中、Ｒ_１３は、置換もしくは無置換のアルキル基、または、置換もしくは無置換のアリール基である。Ｒ_１４～Ｒ_１７は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、または、－Ｏ－Ｒ_１８、または、－ＣＯＯ－Ｒ_１２を表わす。また、Ｒ_１８は置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、または、置換もしくは無置換のアリール基である。ただし、Ｒ_１４～Ｒ_１７の少なくとも１つは－Ｏ－Ｒ_１８である。 The colorant represented by the general formula (7A) may be a colorant represented by the general formula (7B).

In the general formula (7A), R ₁ to R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group. Or represents —O—R ₁₁ . R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R ₇ to R ₁₀ are each independently a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, carboxyl group, substituted or unsubstituted And a sulfoamide group, a substituted or unsubstituted heterocyclic residue, —S—R ₁₂ , —O—R ₁₂ or —COO—R ₁₂ . R ₁₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, at least one of R ₇ to R ₁₀ is —O—R ₁₂ .
Here, in the general formula (7B), R ₁₃ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ₁₄ to R ₁₇ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or —O—R ₁₈ or —COO—R ₁₂ . . R ₁₈ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, at least one of R ₁₄ to R ₁₇ is —O—R ₁₈ .

Furthermore, the above colorant may further contain a yellow colorant. The yellow colorant is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, and C.I. I. Preferably selected from the group consisting of CI Pigment Yellow 185. Further, the colorant may contain a colorant selected from the group consisting of a green colorant, a blue colorant and a red colorant. The color filter coloring composition may further contain a photopolymerizable monomer and / or a photopolymerization initiator.

Furthermore, an embodiment of the present invention relates to a color filter comprising a filter segment formed using the above-described color filter coloring composition.

Furthermore, the present invention relates to the following Embodiments I to VIII.

<Embodiment I>
The problem of the present embodiment is that it has excellent coloring power, and further, when used in a color filter, a colorant for color filter, a coloring composition, and a color filter using the same, which can obtain high brightness and high contrast ratio. Is to provide.

The present inventors have found that when used as a color filter colorant containing a quinophthalone compound having a specific structure, it is possible to produce a color filter that is excellent in dispersibility and coloring power and gives high brightness and contrast ratio. The present embodiment has been reached.

That is, this embodiment relates to a color filter colorant characterized by containing a quinophthalone compound represented by the general formula (1). The quinophthalone compound represented by the general formula (1) is preferably any one of the general formulas (1A) to (1C). In the general formulas (1A) to (1C), R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , and R ⁴⁴ to R ⁶⁰ may each independently be a hydrogen atom or a halogen atom. Furthermore, the colorant preferably contains a yellow colorant. Further, the yellow colorant is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, and C.I. I. It is preferably at least one selected from CI Pigment Yellow 185. Furthermore, it is good also as a coloring composition for color filters which consists at least said colorant, binder resin, and an organic solvent. Further, the color filter coloring composition may contain a green colorant and / or a blue colorant. Furthermore, the coloring composition for color filters may contain a photopolymerizable monomer and / or a photopolymerization initiator. Furthermore, in the color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, at least one green filter segment is a color formed by the above color filter coloring composition. It may be a filter.

According to the present embodiment, by using the quinophthalone compound represented by the general formula (1) as a color filter colorant, the color filter colorant has high brightness, high contrast ratio, and excellent coloring power. , A coloring composition, and a color filter using the same can be provided.

<Embodiment II>
The problem of the present embodiment is that it has excellent coloring power and dispersibility, and further, when used in a color filter, a color composition for a color filter capable of obtaining a high brightness and a high contrast ratio, and a color filter using the same Is to provide.

The present inventors have excellent dispersibility and coloring power, and give high brightness and contrast ratio when a pigment containing a quinophthalone compound having a specific structure and an aluminum phthalocyanine pigment are used as colorants for a color filter. The present inventors have found that a color filter can be produced and have reached this embodiment.

That is, this embodiment is a color filter coloring composition containing a colorant, a binder resin, and an organic solvent, and the colorant is represented by the general formula (1A), the general formula (1B), and the general formula (1C). The coloring composition for color filters characterized by containing the 1 or more types of pigment chosen from the quinophthalone compound represented by this, and an aluminum phthalocyanine pigment. Furthermore, it is preferable that the aluminum phthalocyanine pigment is any one of the general formula (8A) and the general formula (8B). Furthermore, it is preferable that the coloring composition for color filters contains a photopolymerizable monomer and / or a photopolymerization initiator. Furthermore, the color filter which comprises the filter segment formed from said coloring composition for color filters on a board | substrate may be sufficient.

According to this embodiment, when one or more pigments selected from the quinophthalone compounds represented by general formula (1A), general formula (1B) and general formula (1C) are used in combination with an aluminum phthalocyanine pigment, It is possible to provide a coloring composition for a color filter that has a high degree of contrast ratio, excellent coloring power, and low viscosity, and a color filter using the same.

<Embodiment III>
An object of the present embodiment is to provide a coloring composition for a color filter excellent in dispersibility, fluidity, and storage stability, and a color filter using the same.

In this embodiment, a pigment dispersant made of a vinyl polymer containing an ethylenically unsaturated monomer (a1) having at least one of an ethylene oxide chain or a propylene oxide chain in a copolymer composition is used for the quinophthalone pigment. .

That is, this embodiment is a color filter coloring composition comprising a colorant, a pigment dispersant, and an organic solvent, wherein the colorant is a quinophthalone pigment, and the pigment dispersant is The urethane prepolymer (E) having an isocyanate group at both ends, obtained by reacting the hydroxyl group of a vinyl polymer (A) having two hydroxyl groups at one end region with the isocyanate group of diisocyanate (B). A pigment dispersant obtained by reacting an isocyanate group with a primary and / or secondary amino group of an amine compound containing at least a polyamine (C), and the vinyl polymer (A) is an ethylene oxide chain or a propylene oxide chain. For color filters, wherein the copolymer composition contains an ethylenically unsaturated monomer (a1) having at least one of It related to the color composition.
The total number of repeating units of the ethylene oxide chain and the propylene oxide chain of the ethylenically unsaturated monomer (a1) is preferably 1 to 50. The content of the ethylenically unsaturated monomer (a1) is preferably in the range of 10 to 90% by weight out of the total 100% by weight of the copolymer composition of the vinyl polymer (A). The weight average molecular weight of the vinyl polymer (A) having two hydroxyl groups in one end region is preferably 500 to 20,000. The quinophthalone pigment is C.I. I. It is preferable to contain a pigment yellow 138 and / or a quinophthalone compound represented by the general formula (1). The quinophthalone compound is preferably represented by any one of the general formulas (1A) to (1C). Moreover, you may contain the photopolymerizable monomer and the photoinitiator. Moreover, the color filter which comprises the filter segment formed from said coloring composition for color filters on a board | substrate may be sufficient.

According to the present embodiment, the quinophthalone pigment is used in combination with a pigment dispersant composed of a vinyl polymer containing an ethylenically unsaturated monomer having at least one of an ethylene oxide chain or a propylene oxide chain in a copolymer composition. Thus, it is possible to provide a coloring composition for a color filter having both high contrast and dispersion stability, and a color filter using the same and having a high contrast ratio.
<Embodiment IV>
The problem to be solved by the present embodiment is a coloring composition for a color filter that is excellent in brightness, contrast ratio, and coloring power when used in a color filter, and has other characteristics (heat resistance, light resistance, sensitivity). And a color filter using the same.

The inventors of the present invention have the color composition containing the quinophthalone pigment [A] having a specific structure and the quinophthalone dye [B] having a specific structure, so that the coloring composition for a color filter can solve the above-described problems. As a result, the present embodiment has been reached.

That is, this embodiment is a color filter coloring composition containing a colorant, a binder resin, and an organic solvent, and the colorant is represented by general formula (1A), general formula (1B), and general formula ( 1 C) 1 or more types of quinophthalone pigment [A] and the quinophthalone dye [B] represented by General formula (6) are contained, It is related with the coloring composition for color filters characterized by the above-mentioned. In the general formulas (1A) to (1C), R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , and R ⁴⁴ to R ⁶⁰ are preferably each independently a hydrogen atom or a halogen atom. In addition, at least one of R ¹ to R ⁶ in the general formula (6) is preferably —OR ⁷ . Furthermore, you may contain a photopolymerizable monomer and / or a photoinitiator. Furthermore, the color filter which comprises the filter segment formed from the coloring composition for color filters on a board | substrate may be sufficient.

By using the coloring composition for a color filter of the present embodiment, it is possible to provide a color filter that is excellent in lightness, contrast ratio, and coloring power, and has good heat resistance and light resistance.
<Embodiment V>
The object of the present embodiment is a colorant that is excellent in color characteristics (lightness) and that satisfies other physical properties (heat resistance, light resistance, solvent resistance), a colored composition comprising the same, and a color using the same The object is to provide a color filter having excellent characteristics (brightness).

The present inventors have found a quinophthalone dye having excellent color characteristics (brightness), and have made this embodiment based on this finding.

That is, this embodiment relates to a quinophthalone dye represented by the general formula (6). Moreover, in the color composition for color filters comprising at least a colorant and a binder resin, the colorant may be a color filter color composition containing the quinophthalone dye. The colorant may contain a pigment. In addition, in a color filter including at least a red filter segment, a green filter segment, and a blue filter segment, at least one filter segment may be a color filter formed of the above-described color filter coloring composition.

In this embodiment, a quinophthalone dye having excellent color characteristics (brightness) and other physical properties (heat resistance, light resistance, solvent resistance) can be obtained. Furthermore, a color filter excellent in color characteristics (brightness) can be formed by preparing a color filter with a color filter coloring composition containing the quinophthalone dye. Moreover, the other physical properties (heat resistance, light resistance, solvent resistance) of the formed color filter are also good.

<Embodiment VI>
The problem to be solved by the present embodiment is to provide a green coloring composition for a color filter having excellent lightness and excellent heat resistance, light resistance, and voltage holding ratio, and a color filter using the same. .

　[一般式（８Ｃ）中、Ａ¹～Ａ¹⁶は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基を表す。Ｒ¹およびＲ²は、それぞれ独立して、水素原子、ヒドロキシ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、または－ＯＲ³を表し、Ｒ¹とＲ²とが互いに結合して環を形成しても良い。Ｒ³は、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基である。］
　 また、一般式（８Ｃ）におけるＲ¹およびＲ²のうちの少なくとも１つが、置換基を有してもよいアリール基、または－ＯＲ³であることが好ましい。さらに、カラーフィルタ用緑色着色組成物は、光重合性単量体および／または光重合開始剤を含有していてもよい。さらに、基板上に、上記カラーフィルタ用緑色着色組成物から形成されてなるフィルタセグメントを具備するカラーフィルタであってもよい。なお、一般式（８Ｃ）は、一般式（８Ａ）と置換基の表現方法は異なるが、同一構造である。 The present inventors have found that a green coloring composition for a color filter containing a phthalocyanine dye having a specific structure and a quinophthalone dye having a specific structure can solve the above-described problems, leading to the present embodiment.
That is, this embodiment is a green coloring composition for a color filter containing a colorant, a binder resin, and an organic solvent, in which the colorant is represented by the following general formula (8C) and a general formula It contains the quinophthalone pigment | dye represented by (6), It is related with the green coloring composition for color filters characterized by the above-mentioned.

[In General Formula (8C), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, or an aryl which may have a substituent. Represents a group. R ¹ and R ² are each independently hydrogen atom, hydroxy group, an optionally substituted alkyl group, an optionally substituted aryl group, or an -OR ^3, and R ¹ R ² may be bonded to each other to form a ring. R ³ is an alkyl group which may have a substituent or an aryl group which may have a substituent. ]
In addition, at least one of R ¹ and R ² in the general formula (8C) is preferably an aryl group which may have a substituent, or —OR ³ . Furthermore, the green coloring composition for color filters may contain a photopolymerizable monomer and / or a photopolymerization initiator. Furthermore, the color filter which comprises the filter segment formed from the said green coloring composition for color filters on a board | substrate may be sufficient. Note that general formula (8C) has the same structure as that of general formula (8A), although the method for expressing substituents is different.

By using the green coloring composition for a color filter of the present embodiment, it is possible to provide a color filter having excellent lightness and excellent heat resistance, light resistance, and voltage holding ratio.

<Embodiment VII>
The problem to be solved by the present embodiment is to provide a coloring composition for a color filter excellent in contrast ratio and coloring power, and a color filter using the same.

The present inventors have found that the coloring composition for color filters can solve the above-mentioned problems by containing the quinophthalone dye [A1] having a specific structure and the quinophthalone dye [A2] having a specific structure. This embodiment has been reached.

　ここで、一般式（７）中、Ｒ_１～Ｒ_６は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、置換もしくは無置換のアリール基、または、－Ｏ－Ｒ_１１を表わす。また、Ｒ_１１は、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、または、置換もしくは無置換のアリール基を表わす。また、Ｒ_７～Ｒ_１０は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、置換もしくは無置換のアリール基、カルボキシル基、置換もしくは無置換のスルホアミド基、置換もしくは無置換の複素環状残基、－Ｓ－Ｒ_１２、－Ｏ－Ｒ_１２、または、－ＣＯＯ－Ｒ_１２を表わす。また、Ｒ_１２は、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、または、置換もしくは無置換のアリール基である。 That is, in the present embodiment, in a color filter coloring composition containing a colorant, a binder resin, and an organic solvent, the colorant is a quinophthalone dye [A1] represented by the general formula (6) and the following general formula: The present invention relates to a coloring composition for a color filter comprising a quinophthalone dye [A2] represented by the formula (7).

In the general formula (7), R ₁ to R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group. Or represents —O—R ₁₁ . R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R ₇ to R ₁₀ are each independently a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, carboxyl group, substituted or unsubstituted And a sulfoamide group, a substituted or unsubstituted heterocyclic residue, —SR ₁₂ , —O—R ₁₂ , or —COO—R ₁₂ . R ₁₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

By using the coloring composition for color filter of this embodiment, a color filter excellent in contrast ratio and coloring power can be provided.
<Embodiment VIII>
An object of the present embodiment is to provide a pigment excellent in color characteristics (lightness), a coloring composition containing the same, and a color filter excellent in color characteristics (lightness) using the same.

The present inventors have found a quinophthalone dye having excellent color characteristics (brightness), and have made this embodiment based on this finding.

　ここで、一般式（７Ｂ）中、Ｒ_１３は、置換もしくは無置換のアルキル基、または、置換もしくは無置換のアリール基である。Ｒ_１４～Ｒ_１７は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、または、－Ｏ－Ｒ_１８を表わす。また、Ｒ_１８は置換もしくは無置換のアルキル基、または、置換もしくは無置換のアリール基である。ただし、Ｒ_１４～Ｒ_１７の少なくとも１つは－Ｏ－Ｒ_１８である。
　さらに、着色剤とバインダー樹脂とからなるカラーフィルタ用着色組成物において、該着色剤が、上記キノフタロン色素を含むことが好ましい。着色剤がさらに顔料を含有していてもよい。さらに、少なくとも赤色フィルタセグメント、緑色フィルタセグメント、および青色フィルタセグメントを備えるカラーフィルタにおいて、少なくとも１つのフィルタセグメントが、上記カラーフィルタ用着色組成物により形成されてなるカラーフィルタであってもよい。 That is, this embodiment is represented by the following general formula (7A), a quinophthalone dye for a color filter.
In the general formula (7A), R ₁ to R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group. Or represents —O—R ₁₁ . R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R ₇ to R ₁₀ are each independently a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, carboxyl group, substituted or unsubstituted And a sulfoamide group, a substituted or unsubstituted heterocyclic residue, —SR ₁₂ , —O—R ₁₂ , or —COO—R ₁₂ . R ₁₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, at least one of R ₇ to R ₁₀ is —O—R ₁₂ .
Further, the quinophthalone dye is preferably represented by the following general formula (7B).

Here, in the general formula (7B), R ₁₃ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ₁₄ to R ₁₇ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or —O—R ₁₈ . R ₁₈ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. However, at least one of R ₁₄ to R ₁₇ is —O—R ₁₈ .
Furthermore, in the color composition for color filters comprising a colorant and a binder resin, it is preferable that the colorant contains the quinophthalone dye. The colorant may further contain a pigment. Further, in a color filter including at least a red filter segment, a green filter segment, and a blue filter segment, at least one filter segment may be a color filter formed of the color filter coloring composition.

In this embodiment, a quinophthalone dye for a color filter having excellent color characteristics (brightness) can be obtained. Furthermore, a color filter excellent in color characteristics (brightness) can be formed by preparing a color filter with a color filter coloring composition containing the quinophthalone dye. Moreover, the other physical properties (heat resistance, light resistance, solvent resistance) of the formed color filter are also good.

The subject of the present invention is 2011-60734 filed on March 18, 2011, Japanese Patent Application No. 2011-093515 filed on April 19, 2011, and Japanese Patent Application No. 2011-93705 filed on April 20, 2011, May 2011. Japanese Patent Application No. 2011-118726 filed on the 27th, Japanese Patent Application No. 2011-143658 filed on June 29, 2011, Japanese Patent Application No. 2011-150514 filed on July 7, 2011, Japanese Patent Application No. 2011-150 filed on July 15, 2011 156970, Japanese Patent Application No. 2011-174656 filed on August 10, 2011, Japanese Patent Application No. 2011-181111 filed on August 23, 2011, and Japanese Patent Application No. 2011-286172 filed on December 27, 2011. And are hereby incorporated by reference in their entirety.

1 is a spectrum of a coating film in Example 5 of Embodiment V. FIG. FIG. 2 is a spectrum of the coating film in Reference Example 1 of Embodiment V. FIG. 3 is a spectrum of the coating film of Reference Example 3 of Embodiment V. FIG. 4 is a spectrum of the coating film in Example 1 of Embodiment VIII. FIG. 5 is a spectrum of the coating film in Reference Example 1 of Embodiment VIII. FIG. 6 is a spectrum of the coating film of Reference Example 4 of Embodiment VIII.

BEST MODE FOR CARRYING OUT THE INVENTION

<Colorant>
In the embodiment of the present invention, the coloring composition for a color filter includes a quinophthalone compound represented by the general formula (1), a quinophthalone dye represented by the general formula (6), and a quinophthalone represented by the general formula (7). A colorant selected from pigments is contained alone or in combination. Furthermore, the coloring composition for color filters may contain the phthalocyanine pigment represented by general formula (8A) or (8B), and may contain other colorants. Each colorant will be described below.

(Quinophthalone compound represented by the general formula (1))
Hereinafter, it is also referred to as a quinophthalone pigment represented by the general formula (1) or.
In R ¹ to R ¹³ , R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , and R ⁴⁴ to R ^{60 in the} general formulas (1) and (1A) to (1C), the halogen atom includes fluorine, chlorine, bromine, Iodine is mentioned.

Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a ptyl group, an isoptyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group. Group, stearyl group, linear or branched alkyl group such as 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, pendyl group, 4-methylpentyl group, 4-tert-butylbenzyl group, 4-methoxy Examples thereof include an alkyl group having a substituent such as a pendyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group.

Examples of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isoptyloxy group, a tert-butyloxy group, a neopentyloxy group, 2, In addition to linear or branched alkoxyl groups such as 3-dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro Examples include an alkoxyl group having a substituent such as a propoxy group and a benzyloxy group.

In addition, examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group, an anthranyl group, a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p- Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and the like aryl groups having a substituent.

Examples of acidic groups include —SO ₃ H and —COOH, and monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts. Etc. In addition, as the alkyl ammonium salt of acidic group, quaternary alkyl such as ammonium salt of long-chain monoalkylamine such as octylamine, laurylamine, stearylamine, palmityltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salt, etc. An ammonium salt is mentioned.

The “substituent” in the phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) which may have a substituent and the sulfamoyl group (H ₂ NSO ₂ —) which may have a substituent "Includes the above halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, and the like.

At least one adjacent set of groups out of R ¹ to R ^{4 in} the general formula (1) and / or at least one adjacent set of groups out of R ¹⁰ to R ¹³ are united, An aromatic ring which may have a substituent is formed. The aromatic ring herein includes a hydrocarbon aromatic ring and a heteroaromatic ring. The hydrocarbon aromatic ring includes a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the heteroaromatic ring includes pyridine. A ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring.

The quinophthalone compound used for the color filter colorant is preferably any one of the general formulas (1A) to (1C). Here, in R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ and R ⁴⁴ to R ⁶⁰ , a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, An aryl group which may have a substituent, —SO ₃ H; —COOH; and a monovalent to trivalent metal salt of these acidic groups; an alkylammonium salt, an optionally substituted phthalimidomethyl group, or The sulfamoyl group which may have a substituent is synonymous with the group demonstrated by General formula (1).

Further, in the quinophthalone compound used for the colorant for the color filter, R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , and R ⁴⁴ to R ^{60 in} the general formulas (1A) to (1C) are hydrogen atoms or halogen atoms. Is more preferable from the viewpoint of lowering the viscosity of the dispersion.

Specific examples of the quinophthalone compound used for the colorant for the color filter include the following quinophthalone compounds (a) to (r), but are not limited thereto.

(Method for producing quinophthalone compound represented by general formula (1))
The quinophthalone compound can be produced, for example, by the method described in Japanese Patent Publication No. 2930774. Hereinafter, a general method for producing the quinophthalone compound represented by the general formula (1) will be described. For 1 equivalent of 8-aminoquinaldine represented by the following general formula (2), 2 to 3 equivalents of phthalic anhydride represented by the following general formula (3) are added in 160 to A condensation reaction is carried out by heating at 200 ° C. When the reaction is carried out, the condensation of phthalic anhydride can proceed in a two-step process by maintaining the reaction mixture at 140 to 160 ° C. for 1 to 3 hours before reaching 160 to 200 ° C.

[Wherein, R ⁶¹ to R ⁶⁵ have the same meanings as R ⁵ to R ⁹ in formula (1). ]

[Wherein R ⁶⁶ to R ⁶⁹ have the same meanings as R ¹ to R ⁴ and R ¹⁰ to R ¹³ in formula (1). ]
During the reaction, 1 to 2 equivalents of phthalic anhydride represented by the general formula (3) is added to 1 equivalent of 8-aminoquinaldine represented by the general formula (2) and 1 to 140 to 160 ° C. After stirring for 3 hours, the phthalic anhydride represented by the general formula (3) having a different structure is added in an amount of 1 to 2 equivalents, and the mixture is heated and condensed at 160 to 200 ° C. It is possible to condense phthalic anhydrides having different structures on the amino group side and the methyl group side.

Also, two or more structurally different quinophthalone compounds can be synthesized simultaneously by reacting 8-aminoquinaldine with two or more structurally different phthalic anhydrides (hereinafter, “ Co-synthesis method). For example, by condensing 1.8 equivalent of tetrachlorophthalic anhydride and 1.2 equivalent of other phthalic anhydride to 1 equivalent of 8-aminoquinaldine, C.I. I. Pigment Yellow 138 and a specific quinophthalone compound can be produced simultaneously.

Further, according to the synthesis method described in Patent Document 3, the compound of the general formula (5) can be synthesized from the quinophthalone compound represented by the compound (1). Further, a quinophthalone compound represented by general formula (1) is synthesized by condensing phthalic anhydride represented by general formula (5) and general formula (3) in benzoic acid at 160 to 200 ° C. Is also possible. The manufacturing method of a quinophthalone compound is not limited to these methods.

[Wherein R ⁷⁰ to R ⁷⁸ have the same meanings as R ⁵ to R ¹³ in formula (1)]

The colorant of this embodiment may contain two or more quinophthalone compounds. At this time, quinophthalone compounds produced separately may be mixed together, or two or more quinophthalone compounds may be produced at the same time by a cosynthesis method and used as a colorant.

When using these separately prepared quinophthalone compounds, they may be simply mixed before dispersing the two kinds of pigments, or may be pulverized and mixed by a salt milling process described later.

Especially as a colorant C.I. I. When it contains CI Pigment Yellow 138, it is desirable to use it after being pulverized and mixed by a cosynthesis method or a salt milling process. C. having a quinophthalone skeleton I. Pigment Yellow 138 and the quinophthalone compound represented by the general formula (1) are pulverized and mixed together, so that fine particles are obtained and a high contrast ratio is obtained as compared with the case where each is subjected to salt milling alone. .

The colored composition containing the quinophthalone compound represented by the general formula (1) has a yellow hue itself, and when used in combination with other colorants, the same color yellow filter segment, and further green It can be set as the coloring composition for forming a filter segment and a red filter segment. Especially, the coloring composition of this embodiment can obtain the coloring composition used for the green filter segment which has high brightness and high contrast by using together a green coloring agent and / or a blue coloring agent.

(Quinophthalone dye represented by the general formula (6))
The quinophthalone dye represented by the general formula (6) is also referred to as a “quinophthalone dye” represented by the general formula (6) in the present specification.
The substituted or unsubstituted alkyl group in R ₁ to R ₇ in the general formula (6) is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms, or 2 carbon atoms. To 30 and includes one or more ester bonds (—COO—) and / or ether bonds (—O—), linear, branched, monocyclic or condensed polycyclic alkyl groups. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert- Examples include, but are not limited to, pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like. It is not something.

Specific examples of the linear or branched alkyl group having 2 to 30 carbon atoms and including one or more ester bonds include —CH ₂ —CH ₂ —CH ₂ —COO—CH ₂ —CH ₃ , —CH ₂ —CH (—CH ₃ ) —CH ₂ —COO—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —OCO—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —CH ₂ —COO—CH ₂ —CH (CH ₂ —CH ₃ ) —CH ₂ —CH ₂ —CH ₂ —CH ₃ , — (CH ₂ ) ₅ —COO— (CH ₂ ) ₁₁ —CH ₃ , —CH ₂ —CH Examples include ₂ -CH ₂ —CH— (COO—CH ₂ —CH ₃ ) _2, but are not limited thereto.

Specific examples of the linear or branched alkyl group having 2 to 30 carbon atoms and containing one or more ether bonds include —CH ₂ —O—CH ₃ , —CH ₂ —CH ₂ —O—. CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1 to 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —CH ₃ —, —CH Examples include _2- CH— (OCH ₃ ) _2, but are not limited thereto.

Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 30 carbon atoms and optionally including one or more ether bonds include the following, but are not limited thereto. Absent.

Further, specific examples of linear, branched, and alkyl groups having 3 to 30 carbon atoms and including one or more ester bonds (—COO—) and ether bonds (—O—) include —CH ₂ — CH ₂ —COO—CH ₂ —CH ₂ —O—CH ₂ —CH (CH ₂ —CH ₃ ) —CH ₂ —CH ₂ —CH ₂ —CH ₃ , —CH ₂ —CH ₂ —COO—CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —O—CH ₂ —CH (CH ₂ —CH ₃ ) —CH ₂ —CH ₂ —CH ₂ —CH ₃ may be mentioned, but is not limited thereto. .

Examples of the substituted or unsubstituted alkenyl group for R ₁ to R ₇ include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms. They may have a plurality of carbon-carbon double bonds in the structure. Specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4- Pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, cyclopentenyl, cyclohexenyl, 1,3-butadienyl, cyclohexadienyl, cyclopenta Although a dienyl group etc. can be mentioned, it is not limited to these.

The substituted or unsubstituted aryl group in R ₁ to R ₇ is a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms, such as a phenyl group, a 1-naphthyl group, 2-naphthyl group, p-biphenyl group, m-biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluorenyl group, 3-fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-methylbiphenyl group, terphenyl group, 4-methyl-1 -Naphtyl group, 4-tert-butyl-1-naphthyl group, 4-naphthyl-1-naphthyl group, 6-phenyl-2-naphthyl group, 10-phenyl-9-an Lil group, spirofluorenyl group, 4-maleimidyl phenyl group, such as 2-benzocyclobutenyl group.

In view of lightness, heat resistance, and light resistance, at least one of R ₁ to R ₆ in the general formula (6) is preferably —OR ₇ .

The quinophthalone dye represented by the general formula (6) can be obtained by reacting the corresponding 2-methylquinoline and naphthalenedicarboxylic anhydride in benzoic acid at a high temperature as shown in the following reaction formula.

The quinophthalone dye of the general formula (6) has tautomers having structures such as the following general formulas (6a) and (6b), and these tautomers are also within the scope of the present invention. It is.

Specific examples of the quinophthalone dye represented by the general formula (6) include the following dyes, but the dye of the present invention is not limited thereto.

The quinophthalone dye represented by the general formula (6) can be used as a coloring material for coloring printing ink, IJ ink, plastic, paint, fiber, stationery, writing instrument, cosmetics and the like.

(Quinophthalone dye represented by the general formula (7))

Examples of the halogen atom in R ₁ to R ₁₀ in the general formula (7) and the general formula (7A) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, but are not limited thereto. is not.

The substituted or unsubstituted alkyl group in R ₁ to R ₁₂ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms, or an ester bond having 2 to 30 carbon atoms A linear, branched, monocyclic or condensed polycyclic alkyl group containing at least one bond selected from (—COO—), ether bond (—O—) and sulfide bond (—S—) Is mentioned. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, 2-hexyldecyl group, sec-butyl group, tert-butyl group, sec -Pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group, etc. However, it is not limited to these.

Specific examples of the linear or branched chain having 2 to 30 carbon atoms include —CH ₂ —CH ₂ —CH ₂ —COO—CH ₂ —CH ₃ , —CH ₂ —CH (—CH ₃ ) — CH ₂ —COO—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —OCO—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —CH ₂ —COO—CH ₂ —CH (CH ₂ —CH ₃ ) —CH ₂ —CH ₂ —CH ₂ —CH ₃ , — (CH ₂ ) ₅ —COO— (CH ₂ ) ₁₁ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —CH— (COO —CH ₂ —CH ₃ ) ₂

—CH ₂ —O—CH ₃ , —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ — O) _n —CH ₃ (where n is 1 to 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —CH ₃ —, —CH ₂ —CH— (OCH ₃ ) ₂

—CH ₂ —S—CH ₃ , —CH ₂ —CH ₂ —S—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —S—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ — S) _n —CH ₃ (where n is 1 to 8), — (CH ₂ —CH ₂ —CH ₂ —S) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —S—CH ₂ —CH ₃ —, —CH ₂ —CH— (SCH ₃ ) ₂

—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —COO—CH ₂ —CH ₂ —O—CH ₂ —CH (CH ₂ —CH ₃ ) —CH ₂ —CH ₂ —CH ₂ —CH ₃ , —CH ₂ —CH ₃ , —CH ₂ —CH ₂ —COO—CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —O—CH ₂ —CH (CH ₂ —CH ₃ ) —CH ₂ —CH ₂ —CH ₂ -CH ₃ can be mentioned, but is not limited thereto.

Monocyclic or condensed having 2 to 30 carbon atoms and optionally containing at least one bond selected from an ester bond (—COO—), an ether bond (—O—), and a sulfide bond (—S—) Specific examples of the polycyclic alkyl group include the following, but are not limited thereto.

Examples of the substituted or unsubstituted alkenyl group for R ₁ to R ₁₂ include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms. They may have a plurality of carbon-carbon double bonds in the structure. Specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4- Pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, cyclopentenyl, cyclohexenyl, 1,3-butadienyl, cyclohexadienyl, cyclopenta Although a dienyl group etc. can be mentioned, it is not limited to these.

The substituted or unsubstituted aryl group in R ₁ to R ₁₂ is a monocyclic or condensed polycyclic aromatic group which may contain a substituted or unsubstituted heteroatom having 6 to 30 carbon atoms, such as a phenyl group 1-naphthyl group, 2-naphthyl group, p-biphenyl group, m-biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluorenyl group 3-fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perylenyl group, terphenyl group, thienyl group, benzothienyl group, naphthothienyl group, furyl group, pyranyl group, pyrrolyl group, imidazolyl Group, pyridyl group, indole group, thiazole group and the like.

In addition, the hydrogen atom of the substituted or unsubstituted alkyl group in R ₁ to R ₁₂ and the substituted or unsubstituted aryl group may be further substituted with another substituent.

Such substituents include halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, nitro groups, hydroxyl groups, substituted or unsubstituted alkoxyl groups, substituted or unsubstituted aryloxy groups. Can be mentioned.

Here, a halogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group include a halogen atom in R ₁ to R ₁₂ , a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group. Synonymous with group.

The substituted or unsubstituted alkoxyl group is a group in which an oxygen atom is bonded to a substituted or unsubstituted alkyl group in R ₁ to R ₁₂ .

The substituted or unsubstituted reeloxy group is a group in which an oxygen atom is bonded to a substituted or unsubstituted aryl group in R ₁ to R ₁₂ .

Among the quinophthalone dyes for color filters represented by the general formula (7A), the quinophthalone dye for color filters represented by the general formula (7B) is particularly preferable.

The halogen atom, the substituted or unsubstituted alkyl group, the substituted or unsubstituted alkyl group, and the substituted or unsubstituted aryl group in R ₁₃ to R ₁₈ in the general formula (7B) are a halogen atom in R ₁ to R ₁₂ . It is synonymous with an atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group.

The quinophthalone dye for a color filter represented by the general formula (7) can be obtained by reacting the corresponding 2-methylquinoline and the corresponding phthalic anhydride in benzoic acid at a high temperature as shown in the following reaction formula. I can do it.

The quinophthalone dye of the general formula (7) has tautomers having the structures of the following general formulas (7a) and (7b). These tautomers are also within the scope of the present invention. It is.

Specific examples of the quinophthalone dye represented by the general formula (7A) include the following dyes, but the dye of the present invention is not limited thereto.

(Phthalocyanine pigments represented by general formulas (8A) and (8B))
The aluminum phthalocyanine pigment used in the present embodiment is not particularly limited as long as it has a structure in which trivalent aluminum is coordinated at the center of the phthalocyanine ring. In an aluminum phthalocyanine pigment, aluminum is known to have a structure such as a dimer and a trimer in addition to a monomer, because it is trivalent and has a bond in addition to a bond with phthalocyanine. It is also known that the phthalocyanine ring can be chemically modified and can take various structures. The aluminum phthalocyanine pigment in the present embodiment may take any form such as not only a monomer but also a structure such as a dimer or a trimer, or a chemical modification of a phthalocyanine ring.

Among these, as the aluminum phthalocyanine pigment, those represented by the structure of the general formula (8A) or the general formula (8B) are preferable in terms of color characteristics and dispersibility.

In general formula (8A), X ₁ to X ₄ may be the same or different. Specific examples thereof include an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. A cycloalkyl group that may have a group, a heterocyclic group that may have a substituent, an alkoxyl group that may have a substituent, an aryloxy group that may have a substituent, and a substituent. An alkylthio group that may be substituted, and an arylthio group that may have a substituent. When X ₁ to X ₄ have a substituent, the substituents may be the same or different. Specific examples thereof include properties such as halogen groups such as fluorine, chlorine and bromine, amino groups, hydroxyl groups and nitro groups. In addition to the group, an alkyl group, an aryl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, and the like can be given. Moreover, there may be a plurality of these substituents.

As the “alkyl group” of the alkyl group which may have a substituent, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, Examples include a linear or branched alkyl group such as an n-octyl group, a stearyl group, and a 2-ethylhexyl group. Examples of the “alkyl group having a substituent” include a trichloromethyl group, a trifluoromethyl group, 2, 2, 2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4 -Methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group, etc. That.

Examples of the “aryl group” of the aryl group which may have a substituent include a phenyl group, a naphthyl group, and an anthryl group, and the “aryl group having a substituent” includes a p-methylphenyl group, p- Bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl Group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and the like.

Examples of the “cycloalkyl group” of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like, and examples of the “cycloalkyl group having a substituent” include 2,5 -Dimethylcyclopentyl group, 4-tert-butylcyclohexyl group and the like.

Examples of the “heterocyclic group” of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group, and the like. Examples of "" include 3-methylpyridyl group, N-methylpiperidyl group, N-methylpyrrolyl group and the like.

As the “alkoxyl group” of the alkoxyl group which may have a substituent, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, 2 , 3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and the like linear and branched alkoxyl groups such as “alkoxyl having a substituent” Examples of the group include trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoromethylpropoxy group, 2- Ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group And the like.

Examples of the “aryloxy group” of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, and an anthryloxy group, and the “aryloxy group having a substituent” includes p-methyl Examples include phenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group.

Examples of the “alkylthio group” of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group. Examples of the “alkylthio group having a substituent” include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group, and the like.

Examples of the “arylthio group” of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and the like, and “an arylthio group having a substituent” Chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group and the like.

Next, specific examples of Y ₁ to Y ₄ include a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —), a sulfamoyl group ( H ₂ NSO ₂ —). Moreover, the phthalimidomethyl group having a substituent represents a structure in which a hydrogen atom in the phthalimidomethyl group is substituted by a substituent, and the sulfamoyl group having a substituent is a hydrogen atom in the sulfamoyl group substituted by a substituent. Represents the resulting structure. Preferred Y is a halogen atom and a sulfamoyl group. A phthalocyanine compound in which m ₁ to m ₄ are 0 (that is, there is no Y ₁ to Y ₄ ) can also be suitably used. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The “substituent” of the phthalimidomethyl group which may have a substituent and the sulfamoyl group which may have a substituent has the same meaning as the substituents of X ₁ to X ₄ .

Z is represented by a hydroxyl group, a chlorine atom, —OP (═O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ , wherein R ₁ and R ₂ are a hydrogen atom, a hydroxyl group, respectively. Represents an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, R ₁ , R ₂ may be bonded to each other to form a ring.

Here, as the alkyl group in R ₁ and R ₂ , methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group A linear or branched alkyl group such as a stearyl group or 2-ethylhexyl group, and the substituent when the alkyl group is an alkyl group having a substituent includes a halogen atom such as chlorine, fluorine and bromine, Examples include alkoxyl groups such as methoxy groups, aromatic groups such as phenyl groups and tolyl groups, and nitro groups. Further, there may be a plurality of substituents. Examples of the alkyl group having a substituent include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, and a 2-butoxyethyl group. 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group, etc. Is mentioned.

As the aryl group in R ₁ and R ₂ , there are a phenyl group, a naphthyl group, an anthryl group, and the like. When the aryl group has a substituent, the substituent is a halogen atom such as chlorine, fluorine, bromine, an alkyl group, There are alkoxyl groups, amino groups, nitro groups and the like. Further, there may be a plurality of substituents. Examples of the aryl group having a substituent include p-tolyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-dimethylamino group. Examples include a phenyl group, 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group and the like.

Examples of the alkoxyl group in R ₁ and R ₂ include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3-dimethyl-3- Examples include a linear or branched alkoxyl group such as a pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, and the like. There are halogen atoms such as chlorine, fluorine and bromine, aryl groups such as alkoxyl groups, phenyl groups and tolyl groups, and nitro groups. Further, there may be a plurality of substituents. Examples of the alkoxyl group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2-ditrifluoro group. Examples include methylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

As the aryloxy group in R ₁ and R ₂ , there are a phenoxy group, a naphthaloxy group, an anthryloxy group, and the like. When the aryloxy group has a substituent, the substituent is a halogen atom such as chlorine, fluorine, bromine or the like. , Alkyl group, alkoxyl group, amino group, nitro group and the like. Further, there may be a plurality of substituents. Examples of the aryloxy group having a substituent include, for example, p-methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chloro There are phenoxy groups and the like.

As the aluminum phthalocyanine pigment represented by the general formula (8A), from the viewpoint of dispersibility and color characteristics, at least one of R ₁ and R ₂ is an aryl group or a substituent which may have a substituent. An aryloxy group which may have is preferable. More preferably, R ₁ and R ₂ are both aryl groups or aryloxy groups. Further preferably, R ₁ and R ₂ are both phenyl groups or phenoxy groups.

In general formula (8A), R ₃ , R ₄ and R ₅ are each independently an alkyl group having 1 to 18 carbon atoms or an aromatic group having 4 or less rings. If it is in said range, the extinction coefficient per unit weight is enough, and the pigment concentration in a coloring composition can be made into a suitable range.

The alkyl group in R ₃ , R ₄ and R ₅ may be linear, branched or cyclic, and has a functional group with a total number of heteroatoms of 3 or less. May be. For example, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl Group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and 3-nitrophenacyl group Etc.

As an aromatic group in R ₃ , R ₄ and R ₅ , the aromatic ring may contain a hetero atom, and each aromatic ring may have a functional group in the range of 2 or less hetero atoms. . For example, phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9 -Fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group , Quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracene Nyl group, anthraquinolyl group, phenanthri Group, triphenylenyl group, a pyrenyl group, naphthacenyl group, pleiadenyl group, picenyl group, a perylenyl group, tetraphenylenyl les group, and coronenyl group and the like.

Of the phthalocyanine compounds represented by the general formula (8A), Z is more preferably —OP (═O) R ₁ R ₂ from the viewpoint of heat resistance and light resistance.

In general formula (8B), X ₅ to X ₁₂ may be the same or different. Specific examples thereof include an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. A cycloalkyl group that may have a group, a heterocyclic group that may have a substituent, an alkoxyl group that may have a substituent, an aryloxy group that may have a substituent, and a substituent. An alkylthio group that may be substituted, and an arylthio group that may have a substituent. When X ₅ to X ₁₂ have a substituent, the substituents may be the same or different. Specific examples thereof include properties such as halogen groups such as fluorine, chlorine and bromine, amino groups, hydroxyl groups and nitro groups. In addition to the group, an alkyl group, an aryl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, and the like can be given. Moreover, there may be a plurality of these substituents.

As the “alkyl group” of the alkyl group which may have a substituent, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, Examples include a linear or branched alkyl group such as an n-octyl group, a stearyl group, and a 2-ethylhexyl group. Examples of the “alkyl group having a substituent” include a trichloromethyl group, a trifluoromethyl group, 2, 2, 2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4 -Methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group, etc. That.

Examples of the “aryl group” of the aryl group which may have a substituent include a phenyl group, a naphthyl group, and an anthryl group, and the “aryl group having a substituent” includes a p-methylphenyl group, p- Bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl Group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and the like.

Examples of the “cycloalkyl group” of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like, and examples of the “cycloalkyl group having a substituent” include 2,5 -Dimethylcyclopentyl group, 4-tert-butylcyclohexyl group and the like.

Examples of the “heterocyclic group” of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group, and the like. Examples of "" include 3-methylpyridyl group, N-methylpiperidyl group, N-methylpyrrolyl group and the like.

As the “alkoxyl group” of the alkoxyl group which may have a substituent, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, 2 , 3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and the like linear and branched alkoxyl groups such as “alkoxyl having a substituent” Examples of the group include trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoromethylpropoxy group, 2- Ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group And the like.

Examples of the “aryloxy group” of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, and an anthryloxy group, and the “aryloxy group having a substituent” includes p-methyl Examples include phenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group.

Examples of the “alkylthio group” of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group. Examples of the “alkylthio group having a substituent” include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group, and the like.

Examples of the “arylthio group” of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and the like, and “an arylthio group having a substituent” Chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group and the like.

Next, specific examples of Y ₅ to Y ₁₂ include a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —), a sulfamoyl group ( H ₂ NSO ₂ —). Moreover, the phthalimidomethyl group having a substituent represents a structure in which a hydrogen atom in the phthalimidomethyl group is substituted by a substituent, and the sulfamoyl group having a substituent is a hydrogen atom in the sulfamoyl group substituted by a substituent. Represents the resulting structure. Preferred Y is a halogen atom and a sulfamoyl group. A phthalocyanine compound in which m ₁ to m ₄ are 0 (that is, there is no Y ₅ to Y ₁₂ ) can also be suitably used. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The “substituent” of the phthalimidomethyl group which may have a substituent and the sulfamoyl group which may have a substituent has the same meaning as the substituent of X ₅ to X ₁₂ .

In the general formula (8B), L represents —O—SiR ₆ R ₇ —O—, —O—SiR ₆ R ₇ —O—SiR ₈ R ₉ —O—, or —O—P (═O) R ₁₀ —. O— represents that R ₆ to R ₁₀ each independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An alkoxyl group or an aryloxy group which may have a substituent is represented.

Here, the alkyl group in R ₆ to R ₁₀ includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group. A linear or branched alkyl group such as a stearyl group or 2-ethylhexyl group, and the substituent when the alkyl group is an alkyl group having a substituent includes a halogen atom such as chlorine, fluorine and bromine, Examples include alkoxyl groups such as methoxy groups, aromatic groups such as phenyl groups and tolyl groups, and nitro groups. Further, there may be a plurality of substituents. Examples of the alkyl group having a substituent include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, and a 2-butoxyethyl group. 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group, etc. Is mentioned.

As the aryl group in R ₆ to R ₁₀ , there are a phenyl group, a naphthyl group, an anthryl group, and the like. When the aryl group has a substituent, examples of the substituent include a halogen atom such as chlorine, fluorine, and bromine, an alkyl group, There are alkoxyl groups, amino groups, nitro groups and the like. Further, there may be a plurality of substituents. Examples of the aryl group having a substituent include p-tolyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-dimethylamino group. Examples include a phenyl group, 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group and the like.

Examples of the alkoxyl group in R ₆ to R ₁₀ include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3-dimethyl-3- Examples include a linear or branched alkoxyl group such as a pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group. Examples include halogen atoms such as chlorine, fluorine and bromine, aryl groups such as alkoxyl groups, phenyl groups and tolyl groups, and nitro groups. Further, there may be a plurality of substituents. Examples of the alkoxyl group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2-ditrifluoro group. Examples include methylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

As the aryloxy group in R ₆ to R ₁₀ , there are a phenoxy group, a naphthaloxy group, an anthryloxy group, and the like. When the aryloxy group has a substituent, the substituent is a halogen atom such as chlorine, fluorine, bromine or the like. , Alkyl group, alkoxyl group, amino group, nitro group and the like. Further, there may be a plurality of substituents. Examples of the aryloxy group having a substituent include, for example, p-methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chloro There are phenoxy groups and the like.

As the phthalocyanine compound represented by the general formula (8B), at least one of R ₆ to R ₇ and R ₆ to R ₉ and R ₁₀ have a substituent from the viewpoint of the viscosity and color characteristics of the dispersion. An aryl group which may have a substituent or an aryloxy group which may have a substituent is preferable. More preferably, R ₆ to R ₇ , R ₆ to R ₉ , and R ₁₀ are all aryl groups or aryloxy groups. More preferably, R ₆ to R ₇ , R ₆ to R ₉ , and R ₁₀ are all phenyl groups or phenoxy groups.

(Other colorants)
The coloring composition containing the colorant represented by the general formula (1), (6) or (7) has a yellow hue, and is used in combination with other pigments as necessary. Thus, a coloring composition that exhibits yellow, further green, and red can be obtained, and a colorant that is excellent in resistance, color development, and color reproducibility can be obtained. By using together with a green pigment and / or a blue pigment, a green colorant having a high brightness and used for a green filter segment can be obtained. Moreover, by using together with a red pigment (and using an orange pigment as needed), the red colorant used for the red filter segment which has high brightness can be obtained. Moreover, by using together with a yellow pigment, it is possible to obtain a yellow colorant for use in a yellow filter segment having excellent durability and high coloring power while maintaining high brightness. In addition, a dye can be used in combination with the above filter segment. Hereinafter, pigments and dyes are exemplified.

As the green pigment, it is preferable to use a polyhalogenated phthalocyanine pigment. The polyhalogenated phthalocyanine pigment represents a phthalocyanine pigment having at least two or more halogen atoms. Specifically, C.I. I. And CI Pigment Green 7, 10, 36, 37, 58 and the like. Of these, C.I. I. Pigment Green 36 and 58.

As the blue pigment, it is preferable to use an aluminum phthalocyanine pigment. Aluminum phthalocyanine pigments are preferred pigments because they have higher coloring power than halogenated phthalocyanine pigments. Thereby, the addition amount of a pigment can be reduced or the film thickness of a color filter can be reduced. Moreover, the point which does not contain a halogen atom is also preferable in consideration of environmental safety.

¡As yellow pigment, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or it can be mentioned yellow pigment 221, and the like. Among these, from the viewpoint of heat resistance, light resistance, and brightness, C.I. I. CI pigment yellow 138, 139, 150, and 185 are preferable.

As red pigment, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287 are used. Among them, C.I. I. It is preferable to use pigment red 177, 179, 254. Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338. Particularly preferred pigments here are C.I. I. Pigment Red 177,254.

Orange pigment includes C.I. I. And CI Pigment Blue Orange 38, 43, 71, or 73.

Yellow dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes , Naphthoquinone dyes and oxazine dyes.

Specific examples of yellow dyes include C.I. I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 19 Etc. The.

Also, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 etc. are also mentioned.

Also, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106 and the like.

Also, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195, etc. are also mentioned.

Also, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

The preferred colorant content in all the non-volatile components of the colored composition according to this embodiment is 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of sufficient color reproducibility and stability. And most preferably 20 to 80% by weight.

When a yellow pigment is used in combination, the weight ratio of yellow pigment / aluminum phthalocyanine pigment represented by the general formula (8A) and / or (8B) is preferably 80/20 to 10/90. By satisfying this range, it is possible to form a green filter segment having excellent brightness and a wide chromaticity range.

When the quinophthalone compound represented by the general formula (1) and the quinophthalone dye represented by the general formula (6) are used in combination, the general formula (1) is added to 100 parts by weight of the quinophthalone compound represented by the general formula (1). The range of 10 to 1500 parts by weight of the quinophthalone dye represented by 6) is preferred, and the range of 100 to 1200 parts by weight is more preferred. When the amount of the quinophthalone dye represented by the general formula (6) is more than 10 parts by weight, the effect of improving the brightness can be exhibited. Moreover, when it is less than 1500 parts by weight, the contrast ratio and sensitivity when used as a photosensitive coloring composition are preferable.

In the case of a colorant (or coloring composition) that forms a green filter segment, the usage ratio of the green pigment and / or blue pigment to the quinophthalone dye represented by the general formula (6) is generally based on 100 parts by weight of the pigment. The quinophthalone dye represented by the formula (6) is preferably 1 to 1200 parts by weight, more preferably 5 to 600 parts by weight. When the addition amount of the quinophthalone dye represented by the general formula (6) is 1 part by weight or more, the reproducible chromaticity region is wide, and when it is 1200 parts by weight or less, the hue does not change.

In addition, when a yellow pigment and a quinophthalone dye represented by the general formula (6) are used in combination as a colorant (or coloring composition) for forming a green filter segment, a green pigment and / or a blue pigment and yellow coloring are used. The use ratio of the colorant (yellow pigment and quinophthalone dye mixture represented by the general formula (6)) is preferably 1 to 1200 parts by weight, more preferably 5 to 600 parts by weight of the yellow colorant with respect to 100 parts by weight of the pigment. It is. The reproducible chromaticity region is wide when the amount of yellow colorant added is 1 part by weight or more, and the hue does not change when it is 1200 parts by weight or less.

As a colorant (or coloring composition) for forming a green filter segment, when a yellow pigment and a quinophthalone dye represented by the general formula (6) are used in combination, the yellow pigment and the general formula ( The blending ratio with the content of the quinophthalone dye represented by 6) is preferably 1 to 400 parts by weight of the quinophthalone dye represented by the general formula (6) with respect to 100 parts by weight of the yellow pigment. The amount is preferably 5 to 300 parts by weight.

In the case of a colorant (or coloring composition) that forms a red filter segment, the usage ratio of the red pigment and the quinophthalone dye represented by the general formula (6) is the general formula (6) with respect to 100 parts by weight of the red pigment. The quinophthalone dye represented by the formula is preferably 1 to 800 parts by weight, more preferably 5 to 400 parts by weight. When the addition amount of the quinophthalone dye represented by the general formula (6) is 1 part by weight or more, the reproducible chromaticity region is wide, and when it is 800 parts by weight or less, the hue does not change. In consideration of the color composition, the mixing ratio of the red pigment and the nophthalone dye represented by the general formula (6) is 1 for the quinophthalone dye represented by the general formula (6) with respect to 100 parts by weight of the red pigment. It is preferably ˜400 parts by weight, more preferably 5 to 300 parts by weight.

When the phthalocyanine dye represented by the general formula (8A) or (8B) and the quinophthalone dye represented by the general formula (6) are used in combination, 100 parts by weight of the phthalocyanine dye represented by the general formula (6) is used. On the other hand, the range of 3 to 1200 parts by weight of the quinophthalone dye represented by the general formula (6) is preferable, and the range of 5 to 800 parts by weight is more preferable. When the amount of the quinophthalone dye represented by the general formula (8A) or (8B) is more than 3 parts by weight, the effect of improving the brightness can be sufficiently exhibited. On the other hand, when the amount is less than 1200 parts by weight, the heat resistance and light resistance are improved, which is preferable.

When the quinophthalone dye represented by the general formula (6) and the quinophthalone dye represented by the general formula (7) are used in combination, the general formula is used with respect to 100 parts by weight of the quinophthalone dye represented by the general formula (6). The quinophthalone dye represented by (7) is preferably in the range of 11 to 900 parts by weight. A more preferred range is 27 to 650 parts by weight, and a further more preferred range is 43 to 400 parts by weight. When the amount of the quinophthalone dye represented by the general formula (7) is 11 parts by weight or more, the fluorescence of the quinophthalone dye represented by the general formula (6) is sufficiently quenched, the contrast ratio becomes high, and 900 parts by weight or less. The case is preferable because the coloring power is at a practical level.

The use ratio of the green pigment and / or blue pigment and the quinophthalone dye represented by the general formulas (6) and (7) is preferably 5 to 1000 parts by weight, more preferably 100 parts by weight of the pigment. 17 to 600 parts by weight. When the addition amount of the quinophthalone dye represented by the general formulas (6) and (7) is 5 parts by weight or more, the reproducible chromaticity region becomes narrow, and when it is 1000 parts by weight or less, the hue does not change.

When a yellow pigment and a quinophthalone dye represented by general formulas (6) and (7) are used in combination, a green pigment and / or a blue pigment and a yellow colorant (yellow pigment and general formulas (6) and (6)) 7) The mixture ratio of the quinophthalone dye represented by 7) is preferably 5 to 1000 parts by weight, more preferably 17 to 600 parts by weight of the yellow colorant with respect to 100 parts by weight of the green pigment and / or blue pigment. It is. When the added amount of the yellow colorant is 5 parts by weight or more, the reproducible chromaticity region is wide, and when it is 600 parts by weight or less, the hue does not change.

When the yellow pigment and the quinophthalone dye represented by the general formulas (6) and (7) are used in combination, the yellow pigment and the quinophthalone dye represented by the general formulas (6) and (7) are considered in consideration of the color composition. The content of the quinophthalone dye represented by the general formulas (6) and (7) is preferably 1 to 400 parts by weight, more preferably 5 to The range is 300 parts by weight.

When the colorant (or coloring composition) forming the red filter segment is used, the usage ratio of the red pigment and the quinophthalone dye represented by the general formulas (6) and (7) is 100 parts by weight of the red pigment. The quinophthalone dye represented by the general formulas (6) and (7) is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight. When the addition amount of the quinophthalone dye represented by the general formulas (6) and (7) is 1 part by weight or more, the reproducible chromaticity region is wide, and when it is 100 parts by weight or less, the hue does not change.

The use ratio of the green pigment and / or blue pigment to the quinophthalone dye represented by the general formula (7A) is preferably 1 to 1200 parts by weight of the quinophthalone dye represented by the general formula (7A) with respect to 100 parts by weight of the pigment. More preferably, it is 5 to 600 parts by weight. When the addition amount is 1 part by weight or more, the reproducible chromaticity region is wide, and when it is 1200 parts by weight or less, the hue does not change.

When a yellow pigment and a quinophthalone dye represented by the general formula (7A) are used in combination, a green pigment and / or a blue pigment and a yellow colorant (a yellow pigment, a color pigment, and a general formula (7A) The yellow colorant is preferably used in an amount of 1 to 1200 parts by weight, more preferably 5 to 600 parts by weight, based on 100 parts by weight of the pigment. When the addition amount is 1 part by weight, the reproducible chromaticity region is wide, and when it is 1200 parts by weight or less, the hue does not change.

When a yellow pigment and a quinophthalone dye represented by the general formula (7A) are used in combination to form a pigment for a green filter segment, considering the color composition, the yellow pigment and the quinophthalone dye represented by the general formula (7A) The blending ratio with the content is preferably 1 to 400 parts by weight of the quinophthalone dye represented by the general formula (7A) with respect to 100 parts by weight of the yellow pigment, and more preferably 100 parts by weight of the yellow pigment. On the other hand, the quinophthalone dye represented by the general formula (7A) is in the range of 5 to 300 parts by weight.

When the colorant (or coloring composition) for forming the yellow filter segment is used, the usage ratio of the yellow pigment and the quinophthalone dye represented by the general formula (7A) is represented by the general formula (100 parts by weight of the yellow pigment). The quinophthalone dye represented by 7A) is preferably 1 to 1200 parts by weight, more preferably 5 to 600 parts by weight. In consideration of the color composition, the mixing ratio of the yellow pigment and the quinophthalone dye represented by the general formula (7A) is 1 for the quinophthalone dye represented by the general formula (7A) with respect to 100 parts by weight of the yellow pigment. It is preferably ˜400 parts by weight, more preferably 5 to 300 parts by weight.

When the colorant (or coloring composition) for forming the red filter segment is used, the usage ratio of the red pigment and the quinophthalone dye represented by the general formula (7A) is the general formula (7A) with respect to 100 parts by weight of the red pigment. Is preferably 1 to 800 parts by weight, more preferably 5 to 400 parts by weight. When the addition amount of the quinophthalone dye represented by the general formula (7A) is 1 part by weight or more, the reproducible chromaticity region is wide, and when it is 800 parts by weight or less, the hue does not change. In consideration of the color composition, the mixing ratio of the red pigment and the quinophthalone dye represented by the general formula (7A) is 1 for the quinophthalone dye represented by the general formula (7A) with respect to 100 parts by weight of the red pigment. It is preferably from ˜400 parts by weight, more preferably from 5 to 300 parts by weight.
Any of the above blends can be appropriately adjusted and used in consideration of the heat resistance, light resistance, and brightness of the colorant.

<Miniaturization of pigment>
When the colorant is a pigment, it is preferable to use it after making it fine. There are no particular restrictions on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation methods can be used, and refinement is performed by performing a salt milling process using a kneader method, which is one type of wet grinding. Can do. The primary particle diameter of the pigment is preferably 5 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferred range is from 10 to 80 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles.

Salt milling is a batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the total weight of the pigment from the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, most preferably 50 to 500 parts by weight, based on 100 parts by weight of the total weight of the pigment.

When the salt is milled with a pigment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the total weight of the pigment.

<Binder resin>
The binder resin is one that disperses a colorant, or one that dyes or penetrates, and includes conventionally known thermoplastic resins, thermosetting resins, and the like. The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. In addition, the binder resin is preferable because it exerts a chemical interaction with the quinophthalone dye represented by the general formula (6), thereby improving the contrast ratio by quenching the fluorescence.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

Further, when used in the form of an alkali development type colored resist material, it is preferable to use an alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali development resist for color filters, no coating film foreign matter is generated after the colorant is applied. The stability of the colorant is preferably improved. When a linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the colorant is not easily trapped in the resin and the colorant mixture, and has a degree of freedom. The colorant component easily aggregates and precipitates, but by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, the colorant is converted into a resin in a mixture of resin and colorant. Because it is easily trapped, it is difficult for the dye to elute in the solvent resistance test, the colorant component does not easily aggregate and precipitate, and the resin is three-dimensionally crosslinked when exposed to active energy rays to form a film. It is estimated that the colorant component is less likely to aggregate and precipitate even if the colorant molecules are fixed and the solvent is removed in the subsequent development step.

Examples of the alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

Furthermore, the alkali-soluble resin preferably has a hydrophilic functional group separately from an acidic group such as acrylic acid from the viewpoint of dispersibility of the quinophthalone pigment. For the introduction of the hydrophilic functional group, an ethylenically unsaturated monomer having a hydroxyl group and / or a (poly) alkylene oxide structure and having no aromatic ring is preferably used. Specific examples of such ethylenically unsaturated monomers include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth). Hydroxyl group-containing (meth) acrylates such as acrylate, 4-hydroxyvinylbenzene, and 2-hydroxy-3-phenoxypropyl acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (Meth) acrylate, 3-methoxybutyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhex Ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol Monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate, and octoxypolyethylene glycol -Polypropylene glycol ( And (poly) alkylene glycol monoalkyl ether (meth) acrylates such as 2-acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate Diethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, and polypropylene glycol monomethyl ether (meth) acrylate are preferably used.

The content of the ethylenically unsaturated monomer having the hydroxyl group and / or (poly) alkylene oxide structure and having no aromatic ring can be appropriately selected within a range that does not impair the solubility in the synthesis solvent. When propylene glycol monomethyl ether acetate is used as the synthesis solvent, it can be suitably used in a range of preferably 5 to 50% by weight, more preferably 10 to 35% by weight.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 40,000. The number average molecular weight (Mn) is preferably in the range of 2,500 to 50,000, and the value of Mw / Mn is preferably 10 or less.

The glass transition temperature of the alkali-soluble resin (hereinafter sometimes referred to as Tg) is preferably −40 to 70 ° C., more preferably −30 to 30 ° C., and −20 to 10 from the viewpoint of dispersion stability. More preferably.

As the Tg of the alkali-soluble resin, a value calculated by the following Fox equation was used. 1 / Tg = W1 / Tg1 + W2 / Tg2 +... + Wn / Tgn W1 to Wn indicate the weight fraction of each monomer used, and Tg1 to Tgn are the respective homopolymers obtained from each monomer. Glass transition temperature (unit: absolute temperature “K”).

The following are examples of Tg of main homopolymers used for calculation. Methacrylic acid: 130 ° C (403K) Butyl acrylate: -54 ° C (219K) Benzyl methacrylate: 55 ° C (328K) Paracumylphenol ethylene oxide-modified acrylate (M-110, manufactured by Toagosei Co., Ltd.): 35 ° C (308K) 4-hydroxybutyl acrylate: −80 ° C. (193 K) 2-hydroxyethyl methacrylate: 55 ° C. (328 K) methoxypolyethylene glycol methacrylate (manufactured by NOF Corporation, PME-400): −60 ° C. (213 K) butyl methacrylate: 20 ° C (293K)

As a method for producing an active energy ray-curable resin having an ethylenically unsaturated active double bond, as a precursor of the above resin, for example, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, an amino group, etc. A molecule is prepared, and a (meth) acryl compound having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group or cinnamic acid is reacted to form a photocrosslinkable group such as a (meth) acryloyl group or a styryl group. A method of obtaining a resin introduced into a linear polymer, or a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer with a hydroxyalkyl (meth) acrylate A method of half-esterification with a (meth) acrylic compound having a hydroxyl group such as a hydroxyl group such as a hydroxyalkyl (meth) acrylate ( A) A method of adding a (meth) acrylic compound having an isocyanate group such as (meth) acryloyloxyethyl isocyanate to a linear polymer copolymerized with an acrylic compound, or a carboxyl group such as (meth) acrylic acid There is a method of adding a (meth) acryl compound having an epoxy group such as glycidyl (meth) acrylate to the linear polymer to be included.

A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferable as the color composition for color filters.

Examples of the monomer constituting the thermoplastic resin include the following. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypoly (Meth) acrylates such as tylene glycol (meth) acrylate, or (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, dye (Meth) acrylamides such as acetone (meth) acrylamide or acryloylmorpholine, styrenes such as styrene or α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether Examples thereof include vinyl ethers, vinyl acetate, and fatty acid vinyls such as vinyl propionate.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylenedimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-s Cinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000 in order to disperse the colorant preferably, and more preferably in the range of 5,000 to 80,000, 10,000. The range of ˜80,000, 7,000 to 50,000, 8,000 to 50,000 can be taken. . The number average molecular weight (Mn) is preferably in the range of 2,500 to 50,000, and more preferably in the range of 5,000 to 50,000 and 2,500 to 40,000. The value of Mw / Mn is preferably 10 or less. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are obtained by connecting four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene-equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by the company and using tetrahydrofuran as the mobile phase.

In addition, when using HLC-8220GPC (manufactured by Tosoh Corporation) as a device, TSK-GEL SUPER HZM-N connected in series as a column, and using polystyrene as a solvent, the molecular weight in terms of polystyrene was measured. The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

When the binder resin is used as a coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and an aromatic group The balance of groups is important for the dispersibility, penetrability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern does not remain by development.

The binder resin is preferably used in an amount of 20 to 500 parts by weight, more preferably 30 to 500 parts by weight with respect to 100 parts by weight of the colorant. When it is 20 parts by weight or more, the film formability and various resistances are good, and when it is 500 parts by weight or less, the color characteristics are well expressed. From the viewpoint of fluorescence quenching, it is preferably used in an amount of 20 to 400 parts by weight. If it is 20 parts by weight or more, the fluorescence is sufficiently quenched. On the other hand, when the amount is 400 parts by weight or less, self-quenching by the quinophthalone dyes represented by the general formula (6) is not inhibited. Moreover, it is preferable from a viewpoint of fluorescence quenching to contain an aromatic ring in the structure of binder resin. In particular, it is more preferable to contain more aromatic rings.

<Organic solvent>
In the coloring composition of the present embodiment, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easier to form, an organic solvent is included. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N -Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene , Tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether , Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Chill isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that alkyl lactates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate It is preferable to use glycol acetates such as ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

Organic solvents can be used singly or in combination of two or more at any ratio as necessary. In addition, the organic solvent is used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. It is preferably 800 to 4000 parts by weight.

<Dispersing aid>
One embodiment of the coloring composition may contain a dispersion aid. When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant can be appropriately used. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

In addition, when the quinophthalone dye emits fluorescence, the fluorescence of the quinophthalone dye is quenched by the chemical interaction between the quinophthalone dye and the dye derivative or the resin-type dispersant, resulting in a good contrast ratio. .

(Dye derivative)
Examples of the dye derivative include compounds obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more. When a dye derivative is used, those having a quinophthalone skeleton and an azo skeleton are preferable from the viewpoint of brightness.

When the quinophthalone dye emits fluorescence, those having an anthraquinone skeleton, an acridone skeleton, or a phthalocyanine skeleton are preferable from the viewpoint of fluorescence quenching. Furthermore, what has a sulfonamide as a substituent is preferable.

The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

(Resin type dispersant)
The resin-type dispersant has a colorant-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) and polyesters having free carboxyl groups, and their salts Oil-soluble dispersants such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.
When the quinophthalone compound represented by the general formula (1) is used, an ethylenically unsaturated monomer (a1) having at least one of an ethylene oxide chain or a propylene oxide chain is copolymerized as a resin-type dispersant. It is preferable to use a dispersant contained in the composition from the viewpoints of dispersibility, fluidity, and storage stability. The resin type dispersant will be described in the following item of pigment dispersant.

Among the above resin-type dispersants, a polymer dispersant having a basic functional group is preferred because the viscosity of the coloring composition is lowered and a high contrast is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer is preferred. In addition, a nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, or the like in the side chain are preferable.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324, 21407, 21715 or Lactimon, Lactimon-WS or Bykumen, etc., Japan Lou Brizo SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, manufactured by Ciba Japan 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 4 0, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajimoto PA 111, PB711 manufactured by Ajinomoto Fine Techno Co., Ltd. , PB821, PB822, PB824, and the like.

The content of the resin-type dispersant is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the content of the resin-type dispersant is 0.1 parts by weight or more, the added effect is sufficiently obtained, and when the content is 55 parts by weight or less, the dispersion is very good.

Alternatively, the resin-type dispersant is preferably used in an amount of about 5 to 200% by weight relative to the total amount of the pigment, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

<Pigment dispersant>
The pigment dispersant contains an ethylenically unsaturated monomer (a1) having at least one of an ethylene oxide chain or a propylene oxide chain in a copolymer composition, and a vinyl polymer having two hydroxyl groups in one terminal region (A ) And the isocyanate group of the urethane prepolymer (E) having an isocyanate group at both ends, obtained by reacting the hydroxyl group of the diisocyanate (B),
It is synthesized by reacting a primary and / or secondary amino group of an amine compound containing at least polyamine (C).

The vinyl polymer part derived from the vinyl polymer (A) having two hydroxyl groups in one end region is selected from a wide range of pigment carriers and dispersion media by selecting an ethylenically unsaturated monomer constituting the vinyl polymer part. It functions as a solvent affinity site. On the other hand, the amino group introduced via the hydroxyl group present in one end region of the vinyl polymer site and the urea binding site function as an acidic site adsorbing site on the pigment surface.

Hereinafter, each component of the pigment dispersant will be described.

(Vinyl polymer having two hydroxyl groups in one end region (A))
The vinyl polymer (A) having two hydroxyl groups in one terminal region constituting the pigment dispersant (hereinafter sometimes referred to as vinyl polymer (A)) is an ethylene oxide chain or a propylene oxide chain. An ethylenically unsaturated monomer (a1) having at least one, and an ethylenically unsaturated monomer (a2) copolymerizable with (a1), two hydroxyl groups and one thiol group in the molecule It is preferably obtained by radical polymerization in the presence of the compound (a3) having A method in which radical polymerization is carried out in the presence of a polymerization initiator and a polymerization solvent is preferably used.

(Ethylenically unsaturated monomer (a1) having at least one of ethylene oxide chain or propylene oxide chain)
The ethylenically unsaturated monomer (a1) is not particularly limited as long as it has at least one of an ethylene oxide chain or a propylene oxide chain, and a conventionally known monomer can be used. Specific examples include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate. , Diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether ( (Meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol Monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate, and octoxypolyethylene glycol-polypropylene glycol (meth) acrylate (Poly) alkylene glycol monoalkyl ether (meth) acrylates such as: phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxy Polyethylene glycol (meth) acrylate, paracumyl Enoxyethyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, and nonylphenoxypoly (ethylene) (Poly) alkylene glycol (meth) acrylates having an aromatic ring such as glycol-propylene glycol) (meth) acrylate; These ethylenically unsaturated monomers (a1) can be used alone or in combination of two or more. The ethylene oxide chain and / or propylene oxide chain of the ethylenically unsaturated monomer (a1) is used for the purpose of improving the dispersibility of the quinophthalone pigment. The ethylenically unsaturated monomer (a1) only needs to have at least one of an ethylene oxide chain or a propylene oxide chain, and more preferably has at least an ethylene oxide chain. The dispersibility with respect to the quinophthalone pigment is determined by the number of moles of ethylene oxide and / or propylene oxide added to the ethylenically unsaturated monomer (a1) forming the vinyl polymer (A) and the ethylenic property of the vinyl polymer (A). It is influenced by the blending ratio of the unsaturated monomer (a1). The preferred range varies depending on the quinophthalone pigment and the pigment dispersant, but is preferably 1 to 50 in terms of the number of moles of ethylene oxide and / or propylene oxide added in the ethylenically unsaturated monomer (a1). Is more preferable, and 4 to 13 is particularly preferable. When the added mole number is 50 or less, the compatibility with the solvent and the dispersibility are good, and the viscosity does not easily increase during dispersion. Further, the blending ratio of the ethylenically unsaturated monomer (a1) is preferably 10 to 90% by weight, preferably 20 to 80% by weight with respect to 100% by weight in total with the ethylenically unsaturated monomer (a2) described later. % Is more preferable, and 30 to 70 parts by weight is particularly preferable. When the content is 10% by weight or more, the dispersibility is good. When the content is 90% by weight or less, the compatibility with the solvent is excellent, the dispersibility is good, and the viscosity at the time of dispersion is good.

(Ethylenically unsaturated monomer (a2))
The ethylenically unsaturated monomer (a2) is a monomer other than the ethylenically unsaturated monomer (a1) and can be copolymerized with the ethylenically unsaturated monomer (a1). If it is, it will not specifically limit, According to a use, it can select suitably. For example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, iso Linear or branched alkyl (meth) acrylates such as myristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate;
Cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, tertiarybutylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate;
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
(Meth) acrylates having an aromatic ring of benzyl (meth) acrylate and phenoxyethyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate; (meth) acryloxy-modified polydimethyl Siloxanes (silicone macromers); N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meta) ) (Meth) acrylates having tertiary amino groups such as acrylate; (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) Acrylamide, diacetone (meth) acrylamide, and acryloyl N-substituted, such as morpholine (meth) acrylamide; and include (meth) nitriles such as acrylonitrile. And styrenes such as styrene and α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate can also be used.

Furthermore, a carboxyl group-containing ethylenically unsaturated monomer can be used in combination. Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, (meth) acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (meth) acryloyloxyethyl phthalate, 2 -(Meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth) acrylate, and ω-carboxypoly Examples include caprolactone (meth) acrylate.

One or two or more types can be selected from the ethylenically unsaturated monomers listed above, and at least methyl (meth) acrylate and ethyl (meth) from the viewpoint of solubility in solvents and resistance. An ethylenically unsaturated monomer selected from acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate; Part of it is preferably used.

(Compound having two hydroxyl groups and one thiol group in the molecule (a3))
The compound (a3) having two hydroxyl groups and one thiol group in the molecule (hereinafter sometimes referred to as compound (a3)) includes two hydroxyl groups and one thiol group in the molecule. Is not particularly limited as long as it is a compound having, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propane Diol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propane All, and the like. Of these, 3-mercapto-1,2-propanediol is preferred.

The compound (a3), the ethylenically unsaturated monomer (a1), the ethylenically unsaturated monomer (in accordance with the molecular weight of the vinyl polymer (A) having two hydroxyl groups in one end region of interest. A vinyl polymer (A) can be obtained by mixing and heating a2) and, optionally, a polymerization initiator. Compound (a3) is preferably obtained by bulk polymerization or solution polymerization using 0.5 to 30 parts by weight based on 100 parts by weight of the total of ethylenically unsaturated monomers (a1) and (a2), More preferred is 1 to 20 parts by weight, still more preferred is 2 to 15 parts by weight, and particularly preferred is 2 to 10 parts by weight.

The molecular weight of the vinyl polymer (A) can be adjusted to a suitable range by using the compound (a3) within the above preferred range. The weight average molecular weight (Mw) in terms of polystyrene in the gel permeation chromatography (GPC) of the vinyl polymer (A) is preferably 500 to 20,000, more preferably 1,000 to 10,000, and more preferably 2,000 to 7,500 is particularly preferred. When the molecular weight is 20,000 or less, the molecular weight of the vinyl polymer portion is in an appropriate range and the effect of dispersibility is good. As an affinity site, the effect of the steric repulsion is sufficient, and the aggregation of the pigment is sufficiently suppressed.

(Polymerization initiator)
In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the total of ethylenically unsaturated monomers (a1) and (a2). As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), and 2,2′-azobis [2- (2-imidazolin-2-yl) ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

(Polymerization solvent)
In the case of solution polymerization, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, hexane, acetone, hexane, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and Although diethylene glycol diethyl ether etc. are used, it is not specifically limited to these. These polymerization solvents may be used as a mixture of two or more, but are preferably used for final use.

(Diisocyanate (B))
As the diisocyanate (B) constituting the pigment dispersant, conventionally known diisocyanates (B) can be used. For example, aromatic diisocyanate (b1), aliphatic diisocyanate (b2), aromatic-aliphatic diisocyanate (b3) ), Alicyclic diisocyanate (b4) and the like.

Aromatic diisocyanates (b1) include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diene Examples include isocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, naphthylene diisocyanate, and 1,3-bis (isocyanatomethyl) benzene.

Examples of the aliphatic diisocyanate (b2) include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, Examples include dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

Examples of the aromatic-aliphatic diisocyanate (b3) include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4. -Diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

Examples of the alicyclic diisocyanate (b4) include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate. Methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

As mentioned above, the listed diisocyanates (B) are not necessarily limited to these, and two or more kinds can be used in combination.

The diisocyanate (B) is preferably an aliphatic diisocyanate (b2), an aromatic-aliphatic diisocyanate (b3), or an alicyclic diisocyanate (b4) from the viewpoint of hardly yellowing, and more preferably an alicyclic diisocyanate. (B4) is preferred, and most preferred is 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate, IPDI).

In addition to the above-mentioned diisocyanates, some polyisocyanates having three or more isocyanate groups in one molecule can be used as long as they do not gel when the pigment dispersant is produced. These include, for example, the isocyanurate bodies of the diisocyanate (B) listed above, trimethylolpropane adduct type, and biuret type.

(Urethane prepolymer (E))
The urethane prepolymer (E) refers to a product obtained by reacting the hydroxyl group of the vinyl polymer (A) having two hydroxyl groups in one terminal region with the isocyanate group of the diisocyanate (B).

For example, when the number of moles of the vinyl polymer (A) is α and the number of moles of the diisocyanate (B) is β, when α / β = α / (α + 1), a urethane having isocyanate groups at both ends theoretically. A prepolymer is obtained. When α is a positive integer, the molecular weight increases as α increases.

In synthesizing the urethane prepolymer (E), a known synthesis catalyst can be used, and examples thereof include tertiary amine compounds and organometallic compounds.

As the tertiary amine compound, for example,
Examples include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, and diazabicycloundecene (DBU).

Examples of organometallic compounds include tin compounds and non-tin compounds.

Examples of tin compounds include:
Dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyl Examples thereof include tin ethoxide, dioctyl tin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

As the non-tin compound, for example,
Titanium series such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, lead oleate;
Lead systems such as lead 2-ethylhexanoate, lead benzoate, and lead naphthenate;
Iron systems such as iron 2-ethylhexanoate and iron acetylacetonate;
Cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate;
Zinc series such as zinc naphthenate and zinc 2-ethylhexanoate; and
Zirconium-based compounds such as zirconium naphthenate can be mentioned.

Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

The catalysts such as the tertiary amine compounds and organometallic compounds can be used alone or in combination depending on the case.

The organometallic compound catalyst used in the synthesis of the urethane prepolymer (E) remarkably accelerates the reaction even in the further reaction with the amine described later.

A known solvent is preferably used for the synthesis of the urethane prepolymer (E). The use of a solvent serves to facilitate reaction control.

Examples of the solvent used for this purpose include:
Examples include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, hexane, acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether. Is not to be done.

Further, the concentration in the urethane prepolymer reaction system when a solvent is used is preferably 30 to 95% by weight in terms of reaction control in terms of the solid content concentration of the urethane prepolymer. More preferably, the content is 40 to 90% by weight. If it is 30% by weight or more, the reaction is fast and no unreacted material remains. If it is 95% by weight or less, the reaction does not proceed partly rapidly and the molecular weight and the like can be easily controlled.

Various methods are possible for the urethanization reaction in which the hydroxyl group of the vinyl polymer (A) and the isocyanate group of the diisocyanate (B) are reacted to form the urethane prepolymer (E). 1) A method of reacting by charging the whole amount, 2) A method of adding a vinyl polymer (A) and, if necessary, a solvent to a flask, dropping a diisocyanate (B) and adding a catalyst as required. Although it is different, 2) is preferable when the reaction is precisely controlled.

The reaction temperature for obtaining the urethane prepolymer (E) is preferably 120 ° C. or lower. More preferably, it is 50 to 110 ° C. When the temperature is higher than 110 ° C., it becomes difficult to control the reaction rate, and a urethane prepolymer having a predetermined molecular weight and structure cannot be obtained. The urethanization reaction is preferably carried out at 50 to 110 ° C. for 1 to 20 hours in the presence of a catalyst.

The molar ratio of the diisocyanate (B) to the vinyl polymer (A) is preferably 1.01 to 3.00 from the viewpoint of the productivity of the urethane prepolymer, and the design of the dispersant that is the final product (pigment adsorption site) 1.30 to 2.30 is more preferable from the viewpoint of the balance of the solvent-affinity part and 1.30 to 2.30 from the viewpoint of the dispersion stability of the pigment dispersion using the dispersant which is the final product. 00 is most preferred. When the blending molar ratio is too small, the dispersant as the final product has a high molecular weight, and the viscosity of the pigment dispersion using the dispersant, and further the paint or ink using the dispersant increases, which causes a practical problem. Further, as described above, when the blending molar ratio is larger than 3.00, the diisocyanate (B) having no vinyl polymer part derived from the vinyl polymer (A) and the urethane part derived therefrom increase, and the dispersant is the final product. May degrade performance.

(Polyamine (C))
The polyamine (C) constituting the pigment dispersant is a compound having at least two primary and / or secondary amino groups, and is used for reacting with an isocyanate group to form a urea bond. An example of such an amine is diamine (c1).

Examples of the diamine (c1) include diamine (c1-1) having two primary amino groups, diamine (c1-2) having two secondary amino groups, and diamine (c1-3) having primary and secondary amino groups. Can be mentioned.

As the diamine (c1-1) having two primary amino groups, known ones can be used. Specifically,
Ethylenediamine, propylenediamine [alias: 1,2-diaminopropane or 1,2-propanediamine], trimethylenediamine [alias: 1,3-diaminopropane or 1,3-propanediamine], tetramethylenediamine [alias: 1 , 4-diaminobutane], 2-methyl-1,3-propanediamine, pentamethylenediamine [alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane], 2,2- Aliphatic diamines such as dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, and tolylenediamine;
Alicyclic diamines such as isophorone diamine and dicyclohexylmethane-4,4′-diamine; and
Examples thereof include aromatic diamines such as phenylenediamine and xylylenediamine.

As the diamine (c1-2) having two secondary amino groups, known ones can be used. Specifically,
Examples thereof include N, N-dimethylethylenediamine, N, N-diethylethylenediamine, and N, N′-di-tert-butylethylenediamine.

As the diamine (c1-3) having primary and secondary amino groups, known ones can be used. Specifically,
N-methylethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias: ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or methylamino Propylamine], N, 2-methyl-1,3-propanediamine, N-isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1,3- Propanediamine or isopropylaminopropylamine], and N-lauryl-1,3-propanediamine [also known as N-lauryl-1,3-diaminopropane or laurylaminopropylamine].

The polyamine constituting the pigment dispersant is a compound having at least two primary and / or secondary amino groups, and the primary and / or secondary amine reacts with an isocyanate group to form a urea group. This urea group is a pigment. In the case where the polyamine (C) is a compound having two primary and / or secondary amino groups at both ends and further having a secondary and / or tertiary amino group at both ends other than the ends. Is particularly preferable because the adsorptivity to the quinophthalone pigment is improved.

Examples of such polyamine (C) include polyamines having two primary and / or secondary amino groups at both ends as shown below, and further having secondary and / or tertiary amino groups at both ends. c2).

Examples of the polyamine (c2) include a polyamine (c2-1) having a secondary amino group other than both ends and a polyamine (c2-2) having a tertiary amino group other than both ends.

Examples of the polyamine (c2-1) having a secondary amino group other than both ends include, for example, iminobispropylamine [also known as N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl- Examples thereof include 1,3-propylenediamine, N, N′-bisaminopropyl-1,4-butylenediamine, and the like.

Examples of the polyamine (c2-2) having a tertiary amino group other than both ends include, for example, methyliminobispropylamine [alias N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [alias] N, N-bis (3-aminopropyl) laurylamine] and the like.

As the polyamine (C) constituting the pigment dispersant, a polymer (c3) having two or more primary and / or secondary amino groups and having a molecular weight distribution can also be used.

Examples of the polymer (c3) having a primary and / or secondary amino group include an ethylenically unsaturated monomer having a primary amino group and an ethylenically unsaturated monomer having a secondary amino group, such as vinylamine and allylamine. Homopolymers (so-called polyvinylamine and polyallylamine), copolymers thereof with other ethylenically unsaturated monomers, ring-opening polymers of ethyleneimine, and polycondensates of ethylene chloride and ethylenediamine Or a ring-opening polymer of oxazolidone-2 (so-called polyethyleneimine).

Among (c1), (c2), and (c3) exemplified as the polyamine (C), (c1) and (c2) are preferable from the viewpoint of control of synthesis, and (c2) is preferable from the viewpoint of dispersion performance. Most preferred is a polyamine (c2-1) having a secondary amino group other than both ends.

As the amine compound constituting the pigment dispersant, in addition to the polyamine (C), a monoamine can also be used. The monoamine is a monoamine compound having one primary amino group or one secondary amino group in the molecule, and the monoamine suppresses excessively high molecular weight in the reaction of diisocyanate (B) and polyamine (C). Used as a reaction terminator. The monoamine may have a polar functional group other than the primary amino group or the secondary amino group in the molecule. Examples of such a polar functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.

As the monoamine, conventionally known ones can be used, specifically,
Aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3-aminopentane, isoamylamine, N-ethylisoamylamine, 1-amino Hexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-aminotridecane, 1-aminohexadecane, stearylamine, aminocyclopropane, aminocyclobutane Aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2-methylpropane, 3-amino-1-propene, 3-amino Methyl heptane, -Isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine, 3-lauryloxypropylamine, 3-myristoxypropylamine, 2 -Aminomethyltetrahydrofuran, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, di-sec-butylamine, N-ethyl- 1,2-Dimethylpropylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic Acid Isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidine ethanol, 4-piperidine ethanol, 4-piperidine butyric acid hydrochloride, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3- Pyrrolidinol, indoline, aniline, N-butylaniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonaphthalene, 1-aminoanthraquinone, 2-amino Anthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, β-aminoethylbenzene, 2-aminobenzophenone, 4-aminobenzophenone, o -Aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4-benzylpiperidine, α-phenylethylamine, phenacylamine, p- Examples include methoxyphenesylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine, and diphenylamine.

Among them, a monoamine compound having only a secondary amino group as an aliphatic amine having no rigidity is preferable because of good dispersibility.

As an aliphatic monoamine compound having only a secondary amino group,
Dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, di-sec-butylamine, N-ethyl-1,2-dimethyl Propylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, Examples include 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, and 3-pyrrolidinol.

In addition, since the tertiary amino group does not have an active hydrogen that reacts with the isocyanate group, the diamine having the primary or secondary amino group and the tertiary amino group is used as a monoamine constituting the pigment dispersant. In addition, a tertiary amino group having an effect of improving the pigment adsorption ability can be introduced into the polymer terminal of the dispersant.

Examples of the diamine having a primary or secondary amino group and a tertiary amino group include N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-propanediamine, and N, N A diamine having a primary amino group and a tertiary amino group, such as 1,2,2-tetramethyl-1,3-propanediamine; and
Examples thereof include a diamine having a secondary amino group and a tertiary amino group such as N, N, N′-trimethylethylenediamine.

These monoamines may be used alone or in combination of two or more. The urea-bonded active hydrogen after the reaction of the primary amine group and the isocyanate group has low reactivity, and under the polymerization conditions of the dispersant, it does not further react with the isocyanate group and the molecular weight does not increase.

(Method for producing pigment dispersant)
The pigment dispersant is
In the presence of a compound (a3) having two hydroxyl groups and one thiol group in the molecule, an ethylenically unsaturated monomer (a1) represented by the general formula (1) and an ethylenically unsaturated monomer A first step of producing a vinyl polymer (A) having two hydroxyl groups in one terminal region, which is obtained by radical polymerization of the body (a2);
A urethane prepolymer (E) having an isocyanate group at both ends is prepared by reacting the hydroxyl group of the vinyl polymer (A) having two hydroxyl groups in one terminal region with the isocyanate group of diisocyanate (B). The second step,
It is preferable to produce by the third step of reacting the isocyanate group of the urethane prepolymer (E) having an isocyanate group at both ends with the primary and / or secondary amino group of the polyamine (C).

Urethane reaction to obtain urethane urea resin or polyurethane urea having primary or secondary amino group at the terminal from urethane prepolymer (E) or polyamine (C): 1) Urethane prepolymer (E) solution into flask The method is roughly divided into a method of dropping polyamine (C) and 2) a method of adding a solution of polyamine (C) and a solvent as required to a flask and dropping a urethane prepolymer (E) solution. Either method may be used, but the method 2) is preferable from the viewpoint of the dispersion performance of the pigment dispersant to be synthesized.

The temperature of the urea reaction is preferably 100 ° C. or less. More preferably, it is 70 degrees C or less. Even at 70 ° C., the reaction rate is high, and when it cannot be controlled, 50 ° C. or less is more preferable. When the temperature is higher than 100 ° C., it is difficult to control the reaction rate, and it is difficult to obtain a urethane urea resin having a predetermined molecular weight and structure.

Moreover, the compounding ratio with the urethane prepolymer (E) and the polyamine (C) is not particularly limited, and can be arbitrarily selected depending on the pigment type.

The end point of the reaction can be judged from the disappearance of the isocyanate peak by the isocyanate% measurement or IR measurement due to titration.

The weight average molecular weight (Mw) in terms of polystyrene in gel permeation chromatography (GPC) of the pigment dispersant contained in the color filter coloring composition is preferably 1,000 to 100,000, more preferably 1, 500 to 50,000, particularly preferably 1,500 to 20,000.

When the weight average molecular weight is 1,000 or more, the stability of the pigment composition is good, and when it is 100,000 or less, the interaction between the resins is in a good range, and the pigment composition does not increase in viscosity. The amine value of the obtained dispersant is preferably 1 to 100 mgKOH / g, more preferably 2 to 80 mgKOH / g, and further preferably 3 to 60 mgKOH / g. When the amine value is 1 mgKOH / g or more, the functional group that adsorbs to the pigment is sufficient, so the dispersion of the pigment is good. When the amine value is 100 mgKOH / g or less, the pigments do not aggregate and the effect of reducing the viscosity is sufficient. The coating film appearance is good.

The pigment dispersant is preferably used in an amount of 5 to 70% by weight, more preferably 10 to 50% by weight, based on the quinophthalone pigment. If it is 5% by weight or more, a good pigment dispersion effect can be obtained, and if it is 70% by weight or less, it does not adversely affect, for example, heat resistance other than dispersibility.

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these may be used alone or in admixture of two or more, but are not necessarily limited thereto.

The content of the surfactant is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the content of the resin-type dispersant is 0.1 parts by weight or more, the added effect is sufficiently obtained, and when the content is 55 parts by weight or less, the dispersion is very good.

<Photopolymerizable monomer>
One embodiment of the coloring composition may contain a photopolymerizable monomer. The photopolymerizable monomer includes a monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in admixture of two or more. The content of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

Monomers and oligomers that are cured by ultraviolet rays or heat to produce transparent resins include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglyme Diether ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy Methyl (meth) acrylamide, N-vinylformamide, acrylonitrile, EO-modified bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate Polyester (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloylio Xylethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxypropyl succinic acid, 2-methacryloyloxypropyl succinic acid, methoxyethylene glycol acrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol Acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl Methacrylate and, as commercial products, 2-acryloyloxyethyl succinic acid (trade name M-5300) and others as mentioned, is not necessarily limited thereto.

<Photopolymerization initiator>
The colored composition of the present embodiment may contain a photopolymerization initiator. When the composition is cured by ultraviolet irradiation and a filter segment is formed by photolithography, it can be prepared in the form of a solvent developing type or alkali developing type photosensitive coloring composition by adding a photopolymerization initiator or the like. The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight, for example, from the viewpoint of photocurability and developability. 5 to 150 parts by weight, 5 to 200 parts by weight, 10 to 150 parts by weight can be taken.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-meth) Cyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxy) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 -Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used. These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

<Sensitizer>
One embodiment of the coloring composition may contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, biimidazole derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, Camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxyca Rubonyl) benzophenone, 4,4′-diethylaminobenzophenone and the like.

More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

Sensitizers can be used singly or in combination of two or more at any ratio as required. The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the coloring composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Multifunctional thiol>
One embodiment of the coloring composition may contain a polyfunctional thiol that acts as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene,
Examples include 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, and the like. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the weight (100% by weight) of the total solid content of the coloring composition. When the content of the polyfunctional thiol is 0.1% by weight or more, the effect of adding the polyfunctional thiol is sufficiently exhibited, and when it is 30% by weight or less, the sensitivity is in a good range and the resolution is increased.

<Antioxidant>
One embodiment of the coloring composition may contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the colored composition from oxidizing and yellowing due to the thermal process during thermal curing and ITO annealing. can do. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

The “antioxidant” may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type, a phosphorus type is used. , Sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers and antioxidants can be used.

Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

These antioxidants can be used singly or as a mixture of two or more at any ratio as required. Further, when the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the coloring composition (100% by weight), the brightness and sensitivity are more preferable.

<Amine compound>
One embodiment of the coloring composition may contain an amine-based compound that functions to reduce dissolved oxygen.

Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In one embodiment of the coloring composition, it is preferable to add a leveling agent in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule. Specifically, although it has a hydrophilic group, its solubility in water is small, and when added to a colored composition, its surface tension reducing ability is low, and even though it has low surface tension reducing ability, it can be applied to a glass plate. Those having good wettability and capable of sufficiently suppressing the chargeability at an addition amount that does not cause defects in the coating film due to foaming are preferable. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ -2207, but is not limited thereto.

¡Anionic, cationic, nonionic or amphoteric surfactants can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine laurylsulfate , Lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

Examples of chaotic surfactants include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc. And amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
One embodiment of the coloring composition may contain a curing agent, a curing accelerator, and the like as necessary in order to assist the curing of the thermosetting resin. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Of these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl- N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg, imidazole) 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl -4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyl Oxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin.

<Other additive components>
One embodiment of the coloring composition may contain other additive components as necessary. For example, a storage stabilizer can be included to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

Examples of the adhesion improver include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltri Toxisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing colored composition>
One embodiment of a colored composition (hereinafter also referred to as a pigment dispersion) comprises a colorant in a colorant carrier such as a binder resin and / or solvent, preferably together with a dispersion aid, kneader, It can be produced by finely dispersing using various dispersing means such as a roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. At this time, when two or more colorants are included, two or more colorants may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. In addition, if the colorant has high solubility, specifically, it is highly soluble in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is necessary to manufacture by finely dispersing as described above. There is no.

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent development type or alkali development type coloring composition. The solvent development type or alkali development type coloring composition includes the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other dispersion aids, and additives. Can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Removal of coarse particles>
One embodiment of the coloring composition is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more by means of centrifugation, filtration with a sintered filter or a membrane filter. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter will be described. A color filter comprises a filter segment formed using one embodiment of a colored composition. Examples of the color filter include those having a red filter segment, a green filter segment, and a blue filter segment. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

One embodiment of the colored composition is preferably used to form a red, green, or yellow filter segment, and particularly preferably used for a green filter segment. The color filter only needs to have at least one filter segment formed from the colored composition of one embodiment of the present invention, and filters of other colors that do not use the colored composition of one embodiment of the present invention. A conventionally well-known thing can be used for the coloring agent used for formation of a segment.

Examples of colorants used for the red filter segment include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 270, 272, 273, 274 Mention may be made of red pigments such as 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286 or 287. Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

Also, an orange colorant and / or a yellow colorant can be used in combination with the red filter segment. For example, C.I. I. Pigment orange 38, 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213,214,218,219,220, or include yellow pigments 221 or the like. Also, orange dyes and / or yellow dyes such as quinoline, azo, disazo, and methine dyes can be used.

Examples of colorants used for the green filter segment include C.I. I. And green pigments such as CI Pigment Green 7, 36, 37, 58. Blue pigments such as aluminum phthalocyanine pigments can also be used. A yellow colorant can be used in combination with the green filter segment, and specifically includes the yellow colorant described in the description of the red filter segment.

Examples of colorants used for the blue filter segment include C.I. I. And blue pigments such as CI Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and the like. A purple pigment can be used in combination. Examples of purple pigments that can be used in combination include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 27, 29, 30, 31, 32, Mention may be made of purple pigments such as 37, 39, 40, 42, 44, 47, 49 and 50. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When the dye is used, a triarylmethane dye or a xanthene dye is preferable in terms of lightness.

<Color filter manufacturing method>
One embodiment of the color filter can be manufactured by a printing method or a photolithography method.

The formation of the filter segment by the printing method allows patterning by simply repeating the printing and drying of the coloring composition prepared as a printing ink, and therefore, as a method for producing a color filter, it is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, it is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

The color filter can be manufactured by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method. The electrodeposition method is a method for producing a color filter by electrodepositing each color filter segment on a transparent conductive film by electrophoresis of colloidal particles using a transparent conductive film formed on a substrate. The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on one embodiment of the color filter as necessary.

The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

Hereinafter, Embodiments I to VIII will be described based on examples, but the present invention is not limited thereto. In Examples and Reference Examples, “parts” means “parts by mass” and “%” means “% by weight” unless otherwise specified. Moreover, the measurement of an average primary particle diameter and the identification of the compound were performed as follows.
<Average primary particle diameter of colorant>
The average primary particle diameter of the colorant was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the short axis diameter and the long axis diameter of the primary particles of each colorant were measured, and the average was used as the particle diameter of the colorant primary particles. Next, for 100 or more colorant particles, the volume (weight) of each particle was determined by approximating the determined particle size cube, and the volume average particle size was defined as the average primary particle size.
<Identification of compound>
The compound was identified by using a MALDI mass spectrometer autoflex III (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonics, Inc., with the coincidence between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. .

<< Embodiment I >>
First, prior to Examples, a method for producing the pigment derivative (1) and the blue colorant 1 (B-1) used in the colored composition will be described.

(Production of pigment derivative (1))
According to the synthesis method described in Japanese Patent No. 4585781, a pigment derivative (1) was obtained.

(Production of blue colorant 1 (B-1))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this was added 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), and the temperature was raised and refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine (AlPc—Cl). Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water, and dried to obtain 102 parts of hydroxyaluminum phthalocyanine (AlPc—OH).

Subsequently, 100 parts of hydroxyaluminum phthalocyanine (AlPc-OH), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of colorant (B-1) were obtained. The average primary particle size was 31.2 nm.

[Example 1]
(Production of yellow colorant 1 (Y-1))
Compound (1) was obtained according to the synthesis method described in JP-A-2008-81666.

To 300 parts of methyl benzoate, 100 parts of compound (1), 70 parts of 2,3-naphthalenedicarboxylic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. Formation of the quinophthalone compound (a) and disappearance of the starting compound (1) were confirmed by TOF-MS. Further, after cooling to room temperature, the reaction mixture was added to 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 120 parts of quinophthalone compound (a). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (a).

Next, 100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 1 (Y-1) were obtained. The average primary particle size was 31.3 nm.

[Example 2]
(Production of yellow colorant 2 (Y-2))
70 parts of quinophthalone compound (a), C.I. I. 30 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of yellow colorant 2 (Y-2) were obtained. The average primary particle size was 30.4 nm.

[Example 3]
(Production of yellow colorant 3 (Y-3))
70 parts of quinophthalone compound (a) and C.I. I. 30 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF) was added to 50 parts of quinophthalone compound (a) and C.I. I. Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF) was changed in the same manner as in the production of Yellow Colorant 2 (Y-2), except that Yellow Colorant 3 (Y-3) was used. Obtained. The average primary particle size was 29.6 nm.

[Example 4]
(Production of yellow colorant 4 (Y-4))
70 parts of quinophthalone compound (a) and C.I. I. 30 parts of Pigment Yellow 138 (“Pariotole Yellow K0960-HD” manufactured by BASF) was added to 20 parts of Cinophthalone Compound (a) and C.I. I. Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF) was changed to 80 parts except that Yellow Colorant 2 (Y-2) was produced. Obtained. The average primary particle size was 31.8 nm.

[Example 5]
(Production of yellow colorant 5 (Y-5))
Except for changing 70 parts of 2,3-naphthalenedicarboxylic anhydride to a mixture of 42 parts of 2,3-naphthalenedicarboxylic anhydride and 60 parts of tetrachlorophthalic anhydride, the yellow colorant (Y-1) In the same manner as in the production, yellow colorant 5 (Y-5) comprising a mixture of quinophthalone compound (a) and Pigment Yellow 138 was obtained. The average primary particle size was 28.0 nm. As a result of TOF-MS measurement, the composition ratio of the quinophthalone compound (a) and pigment yellow 138 in the yellow colorant 5 was 5: 5.

[Example 6]
(Production of yellow colorant 6 (Y-6))
To 200 parts of methyl benzoate, 35 parts of 8-aminoquinaldine, 33 parts of 2,3-naphthalenedicarboxylic anhydride, 47 parts of tetrachlorophthalic anhydride and 154 parts of benzoic acid are added, heated to 180 ° C., 2 Stir for hours. Subsequently, 95 parts of tetrachlorophthalic anhydride and 50 parts of benzoic acid were added and stirred at 180 ° C. for 3 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 6140 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 125 parts of a quinophthalone compound. As a result of TOF-MS measurement, it was confirmed that the yellow colorant 6 was composed mainly of a composition ratio of about 5: 5 between the quinophthalone compound (a) and Pigment Yellow 138. Further, a very small amount of molecular ion peak corresponding to the mass number of the quinophthalone compound (c) was observed, suggesting that a very small amount of the quinophthalone compound (c) was contained.

Subsequently, 100 parts of the obtained quinophthalone compound, 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product is put into warm water, stirred for 1 hour while being heated to 70 ° C. to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of Colorant 6 (Y-6) were obtained. The average primary particle size was 29.0 nm.

[Example 7]
(Production of yellow colorant 7 (Y-7))
To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid were added, heated to 180 ° C., and stirred for 4 hours. Further, after cooling to room temperature, the reaction mixture was added to 5440 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 116 parts of quinophthalone compound (c). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (c).

Subsequently, 100 parts of the obtained quinophthalone compound (c), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of yellow colorant 7 (Y-7) were obtained. The average primary particle size was 34.1 nm.

[Example 8]
(Production of yellow colorant 8 (Y-8))
Using the quinophthalone compound (c) as a raw material, the compound (2) was obtained by the same method as the synthesis of the compound (1) according to the synthesis method described in JP-A-2008-81666.

To 300 parts of methyl benzoate, 100 parts of compound (2), 108 parts of tetrachlorophthalic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. The formation of the quinophthalone compound (b) and the disappearance of the starting compound (2) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 120 parts of a quinophthalone compound (b). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (b).

Subsequently, 100 parts of the obtained quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 8 (Y-8) were obtained. The average primary particle size was 31.1 nm.

[Example 9]
(Production of yellow colorant 9 (Y-9))
Yellow colorant 9 (Y-9) was obtained in the same manner as in the production of yellow colorant 3 (Y-3), except that 50 parts of quinophthalone compound (a) was changed to 50 parts of quinophthalone compound (b). . The average primary particle size was 30.2 nm.

[Example 10]
(Production of yellow colorant 10 (Y-10))
Except that 70 parts of 2,3-naphthalenedicarboxylic anhydride was changed to 70 parts of 1,2-naphthalenedicarboxylic anhydride, the same procedure as in the production of yellow colorant 1 (Y-1) was carried out, and the quinophthalone compound (d Yellow colorant 10 (Y-10) was obtained. The average primary particle size was 31.6 nm.

[Example 11]
(Production of yellow colorant 11 (Y-11))
To 300 parts of methyl benzoate, 100 parts of compound (2), 176 parts of tetrabromophthalic anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 6 hours. The formation of the quinophthalone compound (h) and the disappearance of the starting compound (2) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was added to 7190 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 138 parts of quinophthalone compound (h). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (h).

Subsequently, 100 parts of the obtained quinophthalone compound (h), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of yellow colorant 11 (Y-11) were obtained. The average primary particle size was 28.3 nm.

[Example 12]
(Production of yellow colorant 12 (Y-12))
52 parts of the quinophthalone compound (a) was dissolved in 428 parts of 98% sulfuric acid and 472 parts of 25% fuming sulfuric acid and stirred at 85 ° C. for 2 hours to carry out sulfonation reaction. Next, this reaction solution was dropped into 6000 parts of ice water, and the precipitated quinophthalone compound was separated and washed with water to obtain a paste. The obtained paste was redispersed in 8000 parts of water and stirred at room temperature for 1 hour. After filtering off and washing with water, it was dried overnight at 80 ° C. to obtain 54 parts of a quinophthalone compound (k). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (k).

Subsequently, 50 parts of the obtained quinophthalone compound (k) and C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 95 parts of yellow colorant 12 (Y-12) were obtained. The average primary particle size was 36.8 nm.

[Example 13]
(Production of yellow colorant 13 (Y-13))
44 parts of the quinophthalone compound (b) were dissolved in 540 parts of 95% sulfuric acid, 38 parts of N-hydroxymethylphthalimide was added thereto, and the mixture was stirred at 85 ° C. for 7 hours. After cooling, the reaction solution was dropped into 3600 parts of ice water, and the precipitated quinophthalone compound was separated and washed with water to obtain a paste. The obtained paste was redispersed in 5000 parts of water and stirred at room temperature for 1 hour. After filtering off and washing with water, it was dried overnight at 80 ° C. to obtain 53 parts of a quinophthalone compound (r). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (r).

Subsequently, 50 parts of the obtained quinophthalone compound (r) and C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 13 (Y-13) were obtained. The average primary particle size was 35.4 nm.

[Example 14]
(Production of yellow colorant 14 (Y-14))
C. I. 50 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF Corporation) I. A yellow colorant 14 (Y-14) was obtained in the same manner as in the production of yellow colorant 3 (Y-3), except that it was changed to 50 parts of Pigment Yellow 150 (“E4GN” manufactured by LANXESS). The average primary particle size was 36.5 nm.

[Reference Example 1]
(Production of yellow colorant 15 (Y-15))
C. I. 100 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 15 (Y-15) were obtained. The average primary particle size was 35.8 nm.

[Reference Example 2]
(Production of yellow colorant 16 (Y-16))
C. I. 100 parts of CI Pigment Yellow 138 (“Paliotor Yellow K0960-HD” manufactured by BASF) I. A yellow colorant 16 (Y-16) was obtained in the same manner as in the production of the yellow colorant 15 (Y-15), except that it was changed to 100 parts of Pigment Yellow 150 (“E4GN” manufactured by LANXESS). The average primary particle size was 36.5 nm.

[Reference Example 3]
(Production of yellow colorant 17 (Y-17))
C. I. 100 parts of CI Pigment Yellow 138 (“Paliotor Yellow K0960-HD” manufactured by BASF) I. 50 parts of Pigment Yellow 138 (“Pariotor Yellow K0960-HD” manufactured by BASF) and C.I. I. Except for changing to a mixture with 50 parts of Pigment Yellow 150 (“E4GN” manufactured by LANXESS), yellow colorant 17 (Y-17) was obtained in the same manner as in the production of yellow colorant 15 (Y-15). . The average primary particle size was 37.2 nm.

The contents of the produced yellow colorants 1 to 17 (Y-1 to 17) are shown in Table 1. “PY138” and “PY150” described in Table 1 are C.I. I. Pigment yellow 138 and C.I. I. CI Pigment Yellow 150.

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and the mixture was stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

(Weight average molecular weight of binder resin)
The weight average molecular weight of the acrylic resin is a polystyrene equivalent weight average molecular weight measured by GPC (gel permeation chromatography).

<Preparation of yellow coloring composition>
[Example 15]
(Preparation of Yellow Coloring Composition 1 (YP-1)) After stirring and mixing a mixture of the following components uniformly, using a zirconia bead having a diameter of 0.5 mm, an Eiger Mill (manufactured by Eiger Japan, “Mini” Model M-250 MKII ”) was dispersed for 5 hours, and then filtered through a 5 μm filter to produce yellow colored composition 1 (YP-1).

Yellow colorant 1 (Y-1) 9.5 parts Dye derivative (1) 0.5 part Resin type dispersant (“PB821” manufactured by Ajinomoto Fine Techno Co.) 1.0 part Acrylic resin solution 1 45.0 parts Propylene glycol Monomethyl ether acetate 44.0 parts

[Examples 16 to 28, Reference Examples 4 to 6]
(Preparation of yellow colored compositions 2-14, 20-22 (YP-2-14, 20-22))
The yellow coloring compositions 2 to 14 and 20 to 22 were the same as the yellow coloring composition 1 (YP-1) except that the yellow coloring agent 1 (Y-1) was changed to the yellow coloring agent described in Table 2. (YP-2 to 14, 20 to 22) were prepared.

[Example 29]
(Preparation of yellow coloring composition 15 (YP-15))
After stirring and mixing the mixture consisting of the following components uniformly, using a zirconia bead having a diameter of 0.5 mm, the mixture was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan). A yellow colored composition 15 (YP-15) was produced by filtration through a 5 μm filter.

Yellow colorant 1 (Y-1) 10.0 parts Resin type dispersant (“PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.) 2.0 parts Acrylic resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate 40.0 parts

[Examples 30 to 33, Reference Examples 7 to 9]
(Preparation of yellow coloring compositions 16-19, 23-25 (YP-16-19, 23-25))
The yellow coloring compositions 16-19 and 23-25 were the same as the yellow coloring composition 15 (YP-15) except that the yellow coloring agent 1 (Y-1) was changed to the yellow coloring agent described in Table 2. (YP-16 to 19, 23 to 25) were produced.

<Evaluation of yellow coloring composition>
The yellow colored composition was evaluated by preparing a coating film using the yellow colored composition and measuring the brightness, film thickness, and contrast ratio. The evaluation method is shown below.

(Lightness evaluation)
The yellow coloring composition was applied onto a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and heated at 230 ° C. for 20 minutes to obtain a coating film. At this time, after the heat treatment at 230 ° C., the coating conditions (spin coater rotation speed and time) were appropriately changed so that the film thickness was x = 0.440 in the C light source. The lightness (Y) of the obtained coating film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) and judged according to the following criteria.

○: 89.0 or more Δ: 87.5 or more to less than 89.0 ×: less than 87.5

(Coloring power evaluation)
Using the same coating film as the one subjected to lightness evaluation, the film thickness when chromaticity of x (C) = 0.440 was measured was measured and judged according to the following criteria. It can be said that the smaller the film thickness that gives the chromaticity of x (C) = 0.440, the greater the coloring power, and the better.

○: Less than 2.0 [μm]
Δ: 2.0 to less than 3.0 [μm]
×: 3.0 or more [μm]

(Contrast ratio evaluation)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)
Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion. Using the same coating film as the one subjected to lightness evaluation, the determination was made according to the following criteria.

○: 3000 or more Δ: 2000 or more to less than 3000 ×: less than 2000 The evaluation results are shown together with the types of yellow coloring agents used in the yellow coloring compositions for the yellow coloring compositions prepared in Examples and Reference Examples. It is shown in 2.

From Table 2, it is clear that the yellow coloring compositions of Examples 15 to 33 using the quinophthalone compound represented by the general formula (1) as a colorant have excellent brightness and contrast ratio and high coloring power. It was. On the other hand, the yellow coloring compositions of Reference Examples 4 to 9 using a yellow coloring agent that has been conventionally used are inferior in lightness, contrast ratio, and coloring power, and all of the lightness, contrast ratio, and coloring power are obtained. It was clarified that a result satisfying the above was not obtained.

When the yellow coloring compositions of Examples 16 to 18 were compared, differences in brightness, contrast ratio, and coloring power were recognized by changing the ratio of the quinophthalone compound (a) and CI Pigment Yellow 138. As the ratio of the quinophthalone compound (a) is larger, the brightness and the coloring power tend to be higher. However, the contrast ratio is about the yellow colored composition of Example 17 (quinophthalone compound (a) /C.I. Pigment Yellow 138 = 5/5) showed the best results.

When the yellow coloring compositions of Examples 17, 19, and 20 were compared, the quinophthalone compound (a) and CI Pigment Yellow 138 were synthesized separately and then mixed with the colorant obtained during the salt milling process, It was revealed that almost the same results can be obtained with the yellow coloring composition using the coloring agent obtained by the method.

When Example 15 and Example 29, Example 16 and Example 30, Example 17 and Example 31, Example 18 and Example 32, Example 23 and Example 33 were compared, respectively, a yellow colored composition was obtained. It was revealed that when the pigment derivative (1) is contained, both the brightness and the contrast ratio are improved.

<Preparation of green and blue coloring composition>
(Preparation of green coloring composition 1 (GP-1))
After stirring and mixing the mixture consisting of the following components uniformly, using a zirconia bead having a diameter of 0.5 mm, the mixture was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan). A green colored composition 1 (GP-1) was produced by filtration through a 5 μm filter.

Green colorant 1 (CI Pigment Green 58) 10.0 parts Resin type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 45.0 parts Propylene glycol monomethyl ether acetate 44. 0 copies

(Preparation of blue coloring composition 1 (BP-1))
The following mixture was stirred and mixed to be uniform, then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then a 5 μm filter. To give a green colored composition 2 (GP-2).

Blue colorant 1 (B-1) 10.0 parts Resin type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 45.0 parts Propylene glycol monomethyl ether acetate 44.0 parts

<Preparation of photosensitive coloring composition>
[Example 34]
(Preparation of photosensitive coloring composition 1 (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare photosensitive coloring composition 1 (GR-1).

Yellow coloring composition 1 (YP-1) 18.4 parts Green coloring composition 1 (GP-1) 26.6 parts Acrylic resin solution 2 4.5 parts Photopolymerizable monomer (“Aronix M402 manufactured by Toagosei Co., Ltd.) ] 3.6 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan) 1.3 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts Ethylene glycol monomethyl ether Acetate 45.4 parts

[Examples 35 to 43, Reference Examples 10 to 15]
(Preparation of photosensitive coloring compositions 2 to 16 (GR-2 to 16))
Using the yellow coloring composition shown in Table 3, and the green coloring composition or the blue coloring composition, and at the time of coating film evaluation, the chromaticity of x = 0.290 and y = 0.600 with a C light source The photosensitive coloring composition 1 (GR) except that the ratio of the yellow coloring composition and the green coloring composition or the blue coloring composition is changed so as to match (the ratio is changed so that the total amount of the coloring composition is 45 parts). In the same manner as in -1), photosensitive coloring compositions 2 to 16 (GR-2 to 16) were prepared.

<Evaluation of coating film of photosensitive coloring composition>
The following methods were used to evaluate the brightness, film thickness, and contrast ratio of the coatings prepared using the photosensitive coloring compositions 1 to 16 (GR-1 to 16) obtained.

(Lightness evaluation)
The photosensitive coloring composition is applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate by spin coating, then dried at 70 ° C. for 20 minutes, and ultraviolet rays are used at 300 mJ / cm ² using an ultrahigh pressure mercury lamp. It exposed and developed with the alkaline developing solution of 23 degreeC. As an alkaline developer, sodium carbonate 1.5% by weight, sodium bicarbonate 0.5% by weight, an anionic surfactant (“Perilox NBL” manufactured by Kao Corporation) 8.0% by weight, and water 90% by weight The thing which consists of was used. Furthermore, the coating film was obtained by heating at 230 degreeC for 30 minutes. Using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), the brightness (Y) of the obtained coating film was measured and judged according to the following criteria. In addition, the produced coating film was made to become the chromaticity (C light source) shown in Table 3 after the heat treatment at 230 ° C.

○: 59.5 or more Δ: 58.0 or more to less than 59.5 ×: less than 58.0

(Coloring power evaluation)
Using the same coating film as the one subjected to lightness evaluation, the film thickness when the chromaticity of x (C) = 0.290 and y (C) = 0.600 was measured was measured and judged according to the following criteria. The smaller the film thickness that gives the chromaticity of x (C) = 0.290 and y (C) = 0.600, the greater the coloring power, and the better.

○: Less than 2.5 [μm]
Δ: 2.5 to less than 3.0 [μm]
×: 3.0 or more [μm]

(Contrast ratio evaluation)
The contrast ratio of the coating film was measured by the same method as the contrast ratio measurement of the yellow colored compositions of Examples 15 to 33 and Reference Examples 4 to 9. The contrast ratio was calculated using the same coating film that was evaluated for brightness, and judged according to the following criteria.

○: 3500 or more Δ: 3000 or more to less than 3500 ×: less than 3000

Table 3 shows the evaluation results of the photosensitive coloring compositions prepared in Examples and Reference Examples.

From the results in Table 3, in the color filter formation, the examples using the photosensitive coloring composition containing the quinophthalone compound represented by the general formula (1) are more lightness, contrast ratio, and coloring power than the reference examples. It became clear that a result satisfying all of the above was obtained, and it was found that the brightness was particularly excellent.

<Production of color filter>
The red photosensitive coloring composition 1 and the blue photosensitive coloring composition 1 used for preparation of the color filter were prepared. For green, photosensitive coloring composition 6 (GR-6) was used.

(Preparation of red coloring composition 1 (RP-1))
The mixture having the composition shown below was uniformly stirred and mixed, dispersed with picomil for 8 hours using zirconia beads having a diameter of 0.1 mm, filtered through a 5 μm filter, and red colored composition 1 (RP-1) Was made.

Red Colorant 1 (C.I. Pigment Red 254) 8.5 parts Red Colorant 2 (C.I. Pigment Red 177) 3.5 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 0 parts Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of red photosensitive coloring composition 1 (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a red photosensitive coloring composition 1 (RR-1).

Red coloring composition 1 (RP-1) 42.0 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907" manufactured by the company) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 39.6 parts ethylene glycol monomethyl ether acetate

(Preparation of blue coloring composition 2 (BP-2))
The mixture having the composition shown below was uniformly stirred and mixed, dispersed with picomil for 8 hours using zirconia beads having a diameter of 0.1 mm, filtered through a 5 μm filter, and blue colored composition 2 (BP-2) Was made.

Blue Colorant 2 (CI Pigment Blue 15: 6) 7.2 parts Purple Colorant 1 (CI Pigment Violet 23) 4.8 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of blue photosensitive coloring composition 1 (BR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare blue photosensitive coloring composition 1 (BR-1).

Blue coloring composition 2 (BP-2) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907" manufactured by KK 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

A black matrix is patterned on a glass substrate, and red photosensitive coloring composition 1 (RR-1) is applied onto the substrate with a film thickness such that x = 0.640 and y = 0.330 using a spin coater. A colored coating was formed. The coating was irradiated with 300 mJ / cm ² of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, the green photosensitive coloring composition 6 (GR-6) is formed to a film thickness such that x = 0.290 and y = 0.600, and the blue photosensitive coloring composition 1 (BR-1). Were used to form film thicknesses such that x = 0.150 and y = 0.060, and green filter segments and blue filter segments were formed to obtain color filters.

By using the photosensitive coloring composition 6 (GR-6), it was possible to produce a color filter having high brightness, high contrast, and excellent coloring power.

<< Embodiment II >>
“PGMAC” means propylene glycol monomethyl ether acetate.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, TSK-GEL SUPER HZM-N connected in series as a column, and THF as a solvent. The molecular weight in terms of polystyrene.

First, the manufacturing method of the binder resin solution, the pigment derivative, the colorant, the yellow coloring composition, and the blue coloring composition used in Examples and Reference Examples will be described.

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and the mixture was stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Production of pigment derivative (1)>
According to the synthesis method described in Japanese Patent No. 4585781, a pigment derivative (1) was obtained.

<Method for producing colorant>
(Production of yellow colorant 1 (PY-1))
Compound (1) was obtained according to the synthesis method described in JP-A-2008-81666.

To 300 parts of methyl benzoate, 100 parts of compound (1), 70 parts of 2,3-naphthalenedicarboxylic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. The formation of the quinophthalone compound (a) represented by the following formula (50) and the disappearance of the starting compound (1) were confirmed by TOF-MS. Further, after cooling to room temperature, the reaction mixture was added to 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 120 parts of quinophthalone compound (a). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (a).

Next, 100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 1 (PY-1) were obtained. The average primary particle size was 31.3 nm.

(Production of yellow colorant 2 (PY-2))
20 parts of a quinophthalone compound (a) obtained by production of yellow colorant 1 (PY-1), C.I. I. 80 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. And salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 2 (PY-2) were obtained. The average primary particle size was 31.3 nm.

(Production of yellow colorant 3 (PY-3))
Using the quinophthalone compound (c) as a raw material, the compound (2) was obtained by the same method as the synthesis of the compound (1) according to the synthesis method described in JP-A-2008-81666.

To 300 parts of methyl benzoate, 100 parts of compound (2), 108 parts of tetrachlorophthalic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. The formation of the quinophthalone compound (b) and the disappearance of the starting compound (2) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 120 parts of a quinophthalone compound (b) represented by the following formula (51). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (b).

Subsequently, 40 parts of the obtained quinophthalone compound (b), C.I. I. 60 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of yellow colorant 3 (PY-3) were obtained. The average primary particle size was 36.8 nm.

(Production of yellow colorant 4 (PY-4))
To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid were added, heated to 180 ° C., and stirred for 4 hours. Further, after cooling to room temperature, the reaction mixture was added to 5440 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 116 parts of a quinophthalone compound (c) represented by the following formula (52). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (c).

Subsequently, 20 parts of the obtained quinophthalone compound (c), C.I. I. 80 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of yellow colorant 4 (PY-4) were obtained. The average primary particle size was 34.1 nm.

(Production of yellow colorant (PY-5))
C. I. 100 parts of Pigment Yellow 138 (trade name Paliotor Yellow K0961HD, manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of a colorant (PY-5) were obtained. The average primary particle size was 35.5 nm.

(Production of blue colorant (PB-1))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this was added 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), and the temperature was raised and refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following formula (53).

Subsequently, 100 parts of the aluminum phthalocyanine pigment represented by the formula (53), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. . The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. A colorant (PB-1) was obtained. The average primary particle size was 30.4 nm.

(Production of blue colorant (PB-2))
In a reaction vessel, 100 parts of methanol and 100 parts of an aluminum phthalocyanine pigment represented by the formula (53) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain 114 parts of an aluminum phthalocyanine pigment represented by the following formula (54).

A blue colorant (PB-2) was obtained from the obtained aluminum phthalocyanine pigment represented by the formula (54) by the same salt milling method as that for the blue colorant (PB-1). The average primary particle size was 31.2 nm.

(Production of blue colorant (PB-3))
In a reaction vessel, 100 parts of methanol and 100 parts of an aluminum phthalocyanine pigment represented by the formula (53) and 43.2 parts of diphenylphosphinic acid were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain 112 parts of an aluminum phthalocyanine pigment represented by the following formula (55).
A blue colorant (PB-3) was obtained from the obtained aluminum phthalocyanine pigment represented by the formula (55) by the same salt milling method as that for the blue colorant (PB-1). The average primary particle size was 29.5 nm.

(Production of blue colorant (PB-4))
In accordance with the synthesis method described in JP 2010-79247 A, an aluminum phthalocyanine pigment represented by the following formula (56) was obtained.

A blue colorant (PB-4) was obtained from the obtained aluminum phthalocyanine pigment represented by formula (56) by the same salt milling method as that for the blue colorant (PB-1). The average primary particle size was 33.0 nm.

　続けて、青色着色剤（ＰＢ－１）と同様の方法でソルトミリング処理を行い、青色着色剤（ＰＢ－５）を製造した。得られた着色剤の体積平均一次粒子径は３７ｎｍであった。 (Production of blue colorant (PB-5))
To 100 parts of the aluminum phthalocyanine pigment represented by the formula (53), 200 parts of pyridine, 800 parts of xylene and 54.6 parts of phenylphosphonic acid were added, and heating and refluxing were continued for 8 hours. After filtration, washing with methanol, and drying, 110 parts of an aluminum phthalocyanine pigment represented by the following formula (57) was obtained.

Subsequently, a salt milling treatment was performed in the same manner as for the blue colorant (PB-1) to produce a blue colorant (PB-5). The obtained colorant had a volume average primary particle size of 37 nm.

<Method for producing colored composition>
(Preparation of yellow coloring composition (DY-1))
After stirring and mixing the mixture having the following composition to be uniform, using a zirconia bead having a diameter of 0.5 mm, using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser. After dispersing for 4 hours, the mixture was filtered through a 5 μm filter to produce a yellow colored composition (DY-1).
Yellow colorant (PY-1) 9.5 parts Dye derivative (1) 0.5 part Resin type dispersant (“PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.) 2.0 parts Acrylic resin solution 1 40.0 parts PGMAC 48. 0 copies

(Preparation of yellow coloring composition (DY-2))
A yellow colored composition (DY-2) was prepared in the same manner as in the preparation of the yellow colored composition (DY-1), except that the yellow colorant (PY-1) was changed to a yellow colorant (PY-2). Produced.

(Preparation of yellow coloring composition (DY-3))
A yellow colored composition (DY-3) was prepared in the same manner except that the yellow colorant (PY-1) was changed to a yellow colorant (PY-3) in the preparation of the yellow colored composition (DY-1). Produced.

(Preparation of yellow coloring composition (DY-4))
A yellow colored composition (DY-4) was prepared in the same manner except that the yellow colorant (PY-1) was changed to a yellow colorant (PY-4) in the production of the yellow colored composition (DY-1). Produced.

(Preparation of yellow coloring composition (DY-5))
A yellow colored composition (DY-5) was prepared in the same manner as in the preparation of the yellow colored composition (DY-1) except that the yellow colorant (PY-1) was changed to a yellow colorant (PY-5). Produced.

(Preparation of blue coloring composition (DB-1))
After stirring and mixing the mixture having the following composition to be uniform, using a zirconia bead having a diameter of 0.5 mm, using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser. After dispersing for 4 hours, the mixture was filtered with a 5 μm filter to prepare a blue colored composition (DB-1).
Blue colorant (PB-1) 10.0 parts Resin-type dispersant (“BYK-LPN6919” manufactured by Big Chemie) 8.3 parts Acrylic resin solution 1 25.0 parts PGMAC 56.7 parts

(Preparation of blue coloring composition (DB-2))
The blue colored composition (DB-2) was prepared in the same manner except that the blue colorant (PB-1) was changed to the blue colorant (PB-2) in the production of the blue colored composition (DB-1). Produced.

(Preparation of blue coloring composition (DB-3))
The blue colored composition (DB-3) was prepared in the same manner except that the blue colorant (PB-1) was changed to the blue colorant (PB-3) in the production of the blue colored composition (DB-1). Produced.

(Preparation of blue coloring composition (DB-4))
The blue colored composition (DB-4) was prepared in the same manner except that the blue colorant (PB-1) was changed to the blue colorant (PB-4) in the production of the blue colored composition (DB-1). Produced.

(Preparation of blue coloring composition (DB-5))
A blue colored composition (DB-5) was prepared in the same manner except that the blue colorant (PB-1) was changed to the blue colorant (PB-5) in the production of the blue colored composition (DB-1). Produced.

[Example 1]
(Green coloring composition (DG-1))
Using the yellow coloring composition (DY-1) and the blue coloring composition (DB-1), the green coloring composition (DG-1) was prepared by stirring and mixing with the following composition.
Yellow coloring composition (DY-1) 81.0 parts Blue coloring composition (DB-1) 19.0 parts

Next, the obtained green coloring composition (DG-1) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70 ° C. for 20 minutes, and then at 230 ° C. A coated substrate was prepared by heating and cooling for 1 hour. The chromaticity of the obtained coating film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), and the chromaticity of the substrate was x = 0.290 and y = 0.600 with a C light source. It was confirmed that

[Examples 2 to 17, Reference Examples 1 to 5]
(Green coloring composition (DG-2 to 22))
When changing to the yellow coloring composition and the blue coloring composition shown in Table 1 and forming a coated substrate in the same manner as the green coloring composition (DG-1), x = 0.290, y = Green colored compositions (DG-2 to 22) were prepared by stirring and mixing at a blending ratio of 0.600. The total content of the green coloring composition is 100.0 parts.

<Evaluation of green coloring composition>
The obtained green coloring composition (DG-1 to 22) was tested for the viscosity and coloring power of the dispersion by the following method. The results are shown in Table 2.

(Viscosity evaluation)
The viscosity of the coloring composition was measured at a rotation speed of 20 rpm using an E type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. on the adjustment day. The results were judged according to the following criteria.
○: Less than 10.0 [mPa · s]
Δ: 10.0 or more and less than 13.0 [mPa · s]
×: 13.0 or more [mPa · s]

(Coloring power evaluation)
The coloring power was evaluated by measuring the film thickness of the coating film. The film thickness of the obtained coating film was measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)”. The results were judged according to the following criteria. It can be said that the smaller the film thickness that gives the desired chromaticity, the greater the coloring power, and the better.
A: Less than 1.2 [μm]
○: 1.2 to 1.6 [μm]
Δ: 1.6 or more and less than 2.0 [μm]
×: 2.0 or more [μm]

From the results of Table 2, it is clear that the colored compositions of Examples containing a quinophthalone compound having a specific structure and an aluminum phthalocyanine pigment can obtain results with better viscosity and coloring power than the Reference Examples.

<Preparation of photosensitive coloring composition>
[Example 18]
(Green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1 μm filter to prepare a photosensitive green coloring composition (RG-1).
Green coloring composition (DG-1) 45.0 parts Acrylic resin solution 2 4.5 parts Photopolymerizable monomer 3.6 parts ("Aronix M402" manufactured by Toa Gosei Co., Ltd.)
Photoinitiator (“Irgacure 907” manufactured by Ciba Japan) 1.3 parts Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts Cyclohexanone 45.4 parts

[Examples 18 to 34, Reference Examples 6 to 10]
Preparation of (RG-2 to 20) Green photosensitive coloring compositions (RG-2 to 22) were prepared in the same manner as the green photosensitive coloring composition (RG-1) with the composition shown in Table 3.

<Evaluation of green photosensitive coloring composition>
The resulting green photosensitive coloring composition (RG-1 to 22) was tested for brightness, contrast ratio, and coloring power by the following method. The results are shown in Table 4.

(Lightness evaluation)
The green photosensitive coloring composition (RG-1 to 22) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, dried at 70 ° C. for 20 minutes, and an ultrahigh pressure mercury lamp was applied. Then, ultraviolet exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Subsequently, the coating-film board | substrate was produced by heating at 230 degreeC for 1 hour, and allowing to cool. The chromaticity of the obtained coating film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), and the chromaticity of the substrate was x = 0.290 and y = 0.600 with a C light source. The brightness: Y (c) was measured. In addition, as an alkaline developer, sodium carbonate 1.5% by weight, sodium hydrogen carbonate 0.5% by weight, an anionic surfactant ("PERI-LEX NBL" manufactured by Kao Corporation) and water 90% by weight. What was used. Judgment criteria are as follows.
○: 59.5 or more Δ: 58.0 or more and less than 58.5 ×: less than 58.0

(Contrast ratio evaluation)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)
Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion. Using the same coating film as the one subjected to lightness evaluation, the determination was made according to the following criteria.
○: 4000 or more Δ: 3500 or more and less than 4000 ×: less than 3500

(Coloring power evaluation)
The coloring power was evaluated by measuring the film thickness of the coating film using the same coating film as that for which the brightness was evaluated. The film thickness of the obtained coating film was measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)”. The results were judged according to the following criteria. It can be said that the smaller the film thickness that gives the desired chromaticity, the greater the coloring power, and the better.
A: Less than 2.0 [μm]
○: 2.0 or more and less than 2.5 [μm]
Δ: 2.5 or more and less than 3.0 [μm]
×: 3.0 or more [μm]

<Production of color filter>
First, the red photosensitive coloring composition and the blue photosensitive coloring composition used for preparation of a color filter were produced. Incidentally, (RG-6) was used as the green photosensitive coloring composition.

(Preparation of red photosensitive coloring composition (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A red colored composition (DR-1) was prepared by filtration through a 0.0 μm filter.
Red pigment (CI Pigment Red 254) 9.6 parts Red Pigment (CI Pigment Red 177) 2.4 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin Solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, a mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).
Red coloring composition (DR-1) 42.0 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907" manufactured) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

(Preparation of blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A blue colored composition (DB-6) was produced by filtration through a 0.0 μm filter.
Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple Pigment (CI Pigment Violet 23) 4.8 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).
Blue coloring composition (DB-6) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907", manufactured by 2.0) Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part 45.1 parts ethylene glycol monomethyl ether acetate

(Production of color filter)
A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (RR-1) was applied onto the substrate with a spin coater to form a colored coating. The film was irradiated with ultraviolet rays of 150 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water, and the substrate was heated at 220 ° C. for 20 minutes. A red filter segment was formed such that x = 0.640 and y = 0.330 (hereinafter also used for green and blue). By the same method, x is obtained using the blue photosensitive coloring composition (RB-1) so that x = 0.290 and y = 0.600 using the green photosensitive coloring composition (RG-6). = 0.150, y = 0.060. Green filter segments and blue filter segments were formed to obtain color filters.

By using the photosensitive coloring composition (RG-6), it was possible to produce a color filter having high brightness, high contrast, and excellent coloring power.

<< Embodiment III >>

Hereinafter, the weight average molecular weight (Mw) is a polystyrene-equivalent molecular weight when using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8320GPC) using DMF as a developing solvent. .

First, the yellow colorant and the pigment derivative used in the coloring composition of this embodiment will be described.

<Preparation of yellow colorant>
(Production of yellow colorant 1 (Y-1))
Quinophthalone yellow pigment C.I. I. 100 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, 98 parts of yellow colorant 1 (Y-1) was obtained. The average primary particle size was 30.1 nm.

(Production of yellow colorant 2 (Y-2))
Compound (1) was obtained according to the synthesis method described in JP-A-2008-81666.

To 300 parts of methyl benzoate, 100 parts of compound (1), 70 parts of 2,3-naphthalenedicarboxylic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. Formation of the quinophthalone compound (a) and disappearance of the starting compound (1) were confirmed by TOF-MS. Further, after cooling to room temperature, the reaction mixture was added to 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 120 parts of quinophthalone compound (a). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (a).

Next, 100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 2 (Y-2) were obtained. The average primary particle size was 31.3 nm.

(Production of yellow colorant 3 (Y-3))
70 parts of quinophthalone compound (a), C.I. I. 30 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of yellow colorant 3 (Y-3) were obtained. The average primary particle size was 30.4 nm.

(Production of yellow colorant 4 (Y-4))
70 parts of quinophthalone compound (a) and C.I. I. 30 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF) was added to 50 parts of quinophthalone compound (a) and C.I. I. Pigment Yellow 138 (BASF “Pariotol Yellow K0960-HD”) was changed in the same manner as Yellow Colorant 2 (Y-2) except that Yellow Colorant 4 (Y-4) was used. Obtained. The average primary particle size was 29.6 nm.

(Production of yellow colorant 5 (Y-5))
70 parts of quinophthalone compound (a) and C.I. I. 30 parts of Pigment Yellow 138 (“Pariotole Yellow K0960-HD” manufactured by BASF) was added to 20 parts of Cinophthalone Compound (a) and C.I. I. Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF) was changed to 80 parts except that Yellow Colorant 2 (Y-2) was produced. Obtained. The average primary particle size was 31.8 nm.

(Production of yellow colorant 6 (Y-6))
To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid were added, heated to 180 ° C., and stirred for 4 hours. Further, after cooling to room temperature, the reaction mixture was added to 5440 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 116 parts of quinophthalone compound (c). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (c).

Subsequently, 100 parts of the obtained quinophthalone compound (c), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of yellow colorant 6 (Y-6) were obtained. The average primary particle size was 34.1 nm.

(Production of yellow colorant 7 (Y-7))
Using the quinophthalone compound (c) as a raw material, the compound (2) was obtained by the same method as the synthesis of the compound (1) according to the synthesis method described in JP-A-2008-81666.

To 300 parts of methyl benzoate, 100 parts of compound (2), 108 parts of tetrachlorophthalic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. The formation of the quinophthalone compound (b) and the disappearance of the starting compound (2) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 120 parts of a quinophthalone compound (b). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (b).

Subsequently, 100 parts of the obtained quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 7 (Y-7) were obtained. The average primary particle size was 31.1 nm.

(Production of yellow colorant 8 (Y-8))
Except that 70 parts of 2,3-naphthalenedicarboxylic anhydride was changed to 70 parts of 1,2-naphthalenedicarboxylic anhydride, the same procedure as in the production of yellow colorant 1 (Y-1) was carried out, and the quinophthalone compound (d Yellow colorant 8 (Y-8) was obtained. The average primary particle size was 31.6 nm.

(Production of yellow colorant 9 (Y-9))
To 300 parts of methyl benzoate, 100 parts of compound (2), 176 parts of tetrabromophthalic anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 6 hours. The formation of the quinophthalone compound (g) and the disappearance of the starting compound (2) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was added to 7190 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 138 parts of quinophthalone compound (h). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (h).

Subsequently, 100 parts of the obtained quinophthalone compound (h), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of yellow colorant 9 (Y-9) were obtained. The average primary particle size was 28.3 nm.

(Production of yellow colorant 10 (Y-10))
52 parts of the quinophthalone compound (a) was dissolved in 428 parts of 98% sulfuric acid and 472 parts of 25% fuming sulfuric acid and stirred at 85 ° C. for 2 hours to carry out sulfonation reaction. Next, this reaction solution was dropped into 6000 parts of ice water, and the precipitated quinophthalone compound was separated and washed with water to obtain a paste. The obtained paste was redispersed in 8000 parts of water and stirred at room temperature for 1 hour. After filtering off and washing with water, it was dried overnight at 80 ° C. to obtain 54 parts of a quinophthalone compound (k). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (k).

Subsequently, 50 parts of the obtained quinophthalone compound (k) and C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 95 parts of yellow colorant 10 (Y-10) were obtained. The average primary particle size was 36.8 nm.

(Production of yellow colorant 11 (Y-11))
44 parts of the quinophthalone compound (b) were dissolved in 540 parts of 95% sulfuric acid, 38 parts of N-hydroxymethylphthalimide was added thereto, and the mixture was stirred at 85 ° C. for 7 hours. After cooling, the reaction solution was dropped into 3600 parts of ice water, and the precipitated quinophthalone compound was separated and washed with water to obtain a paste. The obtained paste was redispersed in 5000 parts of water and stirred at room temperature for 1 hour. After filtering off and washing with water, it was dried overnight at 80 ° C. to obtain 53 parts of a quinophthalone compound (r). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (r).

Subsequently, 50 parts of the obtained quinophthalone compound (r) and C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 11 (Y-11) were obtained. The average primary particle size was 35.4 nm.

(Production of yellow colorant 12 (Y-12))
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 (“Irgafore Yellow 2R-CF” manufactured by Ciba Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow colorant 12 (Y-12) were obtained. The average primary particle size was 34.2 nm.

(Production of yellow colorant 13 (Y-13))
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of yellow colorant 13 (Y-13) were obtained. The average primary particle size was 31.9 nm.

<Dye derivative (1), (2)>
According to the synthesis method described in Japanese Patent No. 4585781, etc., pigment derivatives (1) and (2) were obtained.

Next, the pigment dispersant agent of this embodiment will be described.
<Preparation of pigment dispersant>
(Production of vinyl polymer (A-1))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 100 parts of methyl methacrylate, 200 parts of butyl acrylate, 200 parts of diethylene glycol monomethyl ether methacrylate (Nippon Yushi Co., Ltd., Bremer PME-100), 1-thioglycerol 28 parts and 226 parts of propylene glycol monomethyl ether acetate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 90 ° C., and 0.5 part of AIBN was added, followed by reaction for 8 hours. After confirming that 95% had reacted by measuring the non-volatile content, it was cooled to room temperature, and the non-volatile content of the vinyl polymer (A-1) having a weight average molecular weight of about 3,500 and having two free hydroxyl groups in one end region A 70% min solution was obtained.

(Production of vinyl polymers (A-2) to (A-15) and comparative vinyl polymers (A′-1) to (A′-3))
Synthesis was carried out in the same manner as the above vinyl polymer (A-1) except that the raw materials and charge amounts shown in Table 1 were used, and the vinyl polymer (A-2) having two free hydroxyl groups in one end region. (A-15) and comparative vinyl polymers (A′-1) to (A′-3) having a nonvolatile content of 70% by weight were obtained.

The abbreviations in Table 1 are as shown below.

(Production of pigment dispersant (B-1))
In a reaction vessel 1 equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 100 parts of a 70% nonvolatile solution of vinyl polymer (A-1), 15.3 parts of isophorone diisocyanate, and 26 propylene glycol monomethyl ether acetate .8 parts and 0.027 part of dibutyltin dilaurate as a catalyst were charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C. and reacted for 4 hours, and then cooled to 40 ° C. to obtain a prepolymer solution having an isocyanate group. A reaction vessel 2 equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 6.08 parts of iminobispropylamine and 156.3 parts of propylene glycol monomethyl ether acetate and heated to 60 ° C. The said prepolymer solution was dripped there over 30 minutes, and also, after reacting for 30 minutes, it cooled to room temperature and complete | finished reaction. To this was added propylene glycol monomethyl ether acetate to obtain a 30% non-volatile solution of the pigment dispersant (B-1). The weight average molecular weight was about 10,000, and the theoretical amine value was 47 mg KOH / g.

(Production of pigment dispersants (B-2) to (B-18) and comparative pigment dispersants (B′-1) to (B′-3))
The synthesis was performed in the same manner as in the pigment dispersant (B-1) except that the raw materials and the charge amounts shown in Table 3 were used, and (B-2) to (B-18), (B′-1) to (B′-3) 30% non-volatile solutions of various pigment dispersants were obtained.

The abbreviations in Table 3 are as shown below. IPDI: isophorone diisocyanate HDI: hexamethylene diisocyanate DBTDL: dibutyltin dilaurate IBPA: iminobispropylamine [also known as N, N-bis (3-aminopropyl) amine] MIBPA: methyliminobispropylamine [also known as N, N-bis ( 3-aminopropyl) methylamine]

(Comparative pigment dispersant B'-4)
Ajinomoto Fine Techno Co., Ltd .: Addisper PB-711 (non-volatile content 40%)

(Comparative pigment dispersant B'-5)
A cationic comb-shaped graft polymer having a basic group equivalent of 48 mgKOH / g in which the backbone polymer part is dimethylaminomethylated glycidyl methacrylate-methacrylate esterified glycidyl methacrylate copolymer and the branched polymer part is polymethylmethacrylate. Non-volatile content 40% propylene glycol monomethyl ether acetate solution (Japanese Patent Laid-Open No. 9-176511: pigment dispersant described in Example 6)

<Preparation of binder resin>
(Manufacture of binder resin (C-1))
98.4 parts of propylene glycol monomethyl ether acetate is put in a reaction vessel, heated to 110 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 12.3 parts of methacrylic acid, 20 parts of butyl acrylate, 29.2 of benzyl methacrylate. 24.2 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M-110” manufactured by Toagosei Co., Ltd.) and 14.3 parts of 4-hydroxybutyl acrylate and 1.65 parts of AIBN were added dropwise over 2 hours. The polymerization reaction was carried out. After completion of dropping, the reaction was further continued at 110 ° C. for 3 hours, and then cooled to room temperature to complete the reaction. To this was added propylene glycol monomethyl ether acetate to obtain a 20% nonvolatile solution of binder resin (C-1). The binder resin had a weight average molecular weight of about 30,000 and a theoretical Tg of 2.1 ° C.

(Production of binder resins (C-2) to (C-4))
The synthesis was performed in the same manner as the binder resin (C-1) except that the raw materials and the charge amounts shown in Table 4 were used, and propylene glycol monomethyl ether acetate was added to add binder resins (C-2) to (C-4). A 20% nonvolatile solution.

Abbreviations in Table 4 are as shown below. MMA: methyl methacrylate nBA: butyl acrylate BzMA: benzyl methacrylate M-110: manufactured by Toagosei Co., Ltd. Paracumylphenol ethylene oxide modified acrylate 4HBA: 4-hydroxybutyl acrylate HEMA: 2-hydroxyethyl methacrylate PME-400: Nippon Oil & Fats ( Methoxypolyethylene glycol methacrylate AIBN: 2,2'-azobis (isobutyronitrile)

<Preparation of yellow coloring composition>
[Example 1]
(Preparation of yellow coloring composition 1 (YP-1))
After stirring and mixing the mixture consisting of the following components uniformly, using a zirconia bead having a diameter of 0.5 mm, the mixture was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan). The mixture was filtered through a 5 μm filter to produce yellow colored composition 1 (YP-1).
Yellow colorant 1 (Y-1) 9.5 parts Dye derivative (1) 0.5 part Pigment dispersant (B-1) 6.7 parts Binder resin (C-1) 40.0 parts Propylene glycol monomethyl ether acetate 43.3 parts

[Examples 2 to 33, Reference Examples 1 to 10]
(Preparation of yellow coloring compositions 2 to 43 (YP-2 to 43))
Yellow colored compositions 2 to 43 (YP-2 to 43) were prepared in the same manner as yellow colored composition 1 (YP-1) except that the materials were changed to those shown in Table 5.

The obtained yellow coloring composition (YP-1 to 43) was measured for viscosity characteristics, brightness and contrast ratio by the following methods. The evaluation results are shown in Table 5.

(Viscosity characteristics)
Using the E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.), the viscosity of the next day after preparing the yellow coloring composition (YP-1 to 43) (hereinafter referred to as initial viscosity) The measurement was performed at 25 ° C. under the condition of a rotation speed of 20 rpm. Moreover, the viscosity accelerated with time at 40 ° C. for 1 week (hereinafter referred to as viscosity with time) was measured, the rate of change in viscosity with time was calculated according to the following formula, and the stability with time was evaluated in the following four stages.

[Change in viscosity with time (%)] = [Viscosity with time] / [Initial viscosity] × 100
◎: Change rate with time is less than ~ 105% ○: Change rate with time is ~ 105% or more,
Less than 130% Δ: Change rate with time is ˜130% or more, less than 150% ×: Change rate with time is ˜150% or more

(brightness)
A yellow colored composition (YP-1 to 43) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater and heated at 230 ° C. for 20 minutes to obtain a coating film. At this time, after the heat treatment at 230 ° C., the coating conditions (spin coater rotation speed and time) were appropriately changed so that the film thickness was x = 0.440 in the C light source. The lightness (Y) of the obtained coating film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) and judged according to the following criteria.
○: 89.0 or more Δ: 87.5 or more to less than 89.0 ×: less than 87.5 (contrast ratio)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)

Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, using the same coating film as that for which the brightness was evaluated, measurement was performed through a black mask having a 1 cm square hole in the measurement portion, and the determination was made according to the following criteria.
○: 3500 or more
Δ: 3000 or more to less than 3500 ×: less than 3000

As is apparent from the evaluation results in Table 5, this embodiment is composed of a vinyl polymer containing a quinophthalone pigment and an ethylenically unsaturated monomer having at least one of an ethylene oxide chain or a propylene oxide chain in a copolymer composition. The colored compositions of Examples 1 to 33 using the pigment dispersant had a low initial viscosity and a low rate of change in viscosity with time, and exhibited good stability. In addition, both of them resulted in high brightness and high contrast, indicating that they are excellent as coloring compositions for color filters. In contrast, the colored compositions of Reference Examples 1 to 3 and 6 to 8 using a pigment dispersant made of a vinyl polymer having no ethylene oxide chain or propylene oxide chain have an initial viscosity of Reference Example 1. Although it was low, the rate of change in viscosity with time was high, and it was low brightness and low contrast. In Reference Examples 2, 3, and 6 to 8, both the initial viscosity and the rate of change with time were high, and the brightness was low and the contrast was low. The same was applied to Reference Examples 4 and 5 using pigment dispersants having different structures. Coloring compositions of Reference Examples 9 and 10 using a non-quinophthalone pigment and a pigment dispersant comprising a vinyl polymer containing an ethylenically unsaturated monomer having at least one of an ethylene oxide chain or a propylene oxide chain in a copolymer composition The product was satisfactory in contrast, but the brightness was inferior to the colored composition part of the example.

<Preparation of photosensitive coloring composition>
Next, the green coloring composition used for the photosensitive coloring composition of this embodiment is demonstrated. Will be described.

<Preparation of green coloring composition>
(Preparation of green coloring composition (GP-1))
After stirring and mixing the mixture consisting of the following components uniformly, using a zirconia bead having a diameter of 0.5 mm, the mixture was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan). A green colored composition (GP-1) was produced by filtration through a 5 μm filter.
Green colorant (CI Pigment Green 58) 10.0 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Binder resin (C-4) 45.0 parts Propylene glycol monomethyl ether acetate 44.0 parts

[Example 34]
(Preparation of photosensitive coloring composition 1 (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare photosensitive coloring composition 1 (GR-1). The ratio between the yellow coloring composition and the green coloring composition is a ratio that matches the chromaticity of x = 0.290 and y = 0.600 with the C light source.
Yellow coloring composition 1 (YP-1) 18.4 parts Green coloring composition (GP-1) 26.6 parts Binder resin (C-4) 4.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. Aronix M402 ") 3.6 parts Photopolymerization initiator (" Irgacure 907 "manufactured by Ciba Japan) 1.3 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts ethylene glycol 45.4 parts monomethyl ether acetate

[Examples 35 to 66, Reference Examples 11 to 20]
(Preparation of photosensitive coloring compositions 2 to 43 (GR-2 to 43))
In the same manner as photosensitive coloring composition 1 (GR-1) except that the combination of coloring compositions shown in Table 6 was changed and the ratio of the yellow coloring composition and the green coloring composition was changed. Coloring compositions 2 to 43 (GR-2 to 43) were produced. In addition, the ratio of the yellow coloring composition and the green coloring composition is selected so that when the coated substrate is produced, the ratio is adjusted so that the chromaticity of x = 0.290 and y = 0.600 is obtained with the C light source. did. The total content of the yellow coloring composition and the green coloring composition is 45.0 parts.

About each obtained photosensitive coloring composition, the brightness and contrast ratio were measured with the following method. (Lightness) The photosensitive coloring composition (GR1 to 43) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, dried at 70 ° C. for 20 minutes, and an ultrahigh pressure mercury lamp was applied. Then, ultraviolet exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Subsequently, it heated at 220 degreeC for 30 minute (s), and the coating-film board | substrate was produced by standing to cool. At this time, after the heat treatment at 230 ° C., the coating conditions (spin coater rotation speed, time) were appropriately changed so that y = 0.600 in the C light source. The lightness (Y) of the obtained coating film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) and judged according to the following criteria.
○: 59.5 or more Δ: 58.0 or more to less than 59.5 ×: less than 58.0

(Contrast ratio)
Regarding the method for measuring the contrast ratio of the coating film, using the same coating film as that for which the brightness evaluation was performed, the contrast ratio was measured by the same method as the contrast ratio measurement of the yellow coloring composition described above, and the following criteria were calculated. Judged according to.
○: 3500 or more
Δ: 3000 or more to less than 3500 ×: less than 3000

As is apparent from the evaluation results in Table 6, this embodiment is composed of a vinyl polymer containing a quinophthalone pigment and an ethylenically unsaturated monomer having at least one of an ethylene oxide chain or a propylene oxide chain in a copolymer composition. The photosensitive coloring compositions of Examples 34 to 66 to which a yellow coloring agent using a pigment dispersant was added gave good results in brightness and contrast, and were shown to be excellent as a coloring composition for a color filter. It was. On the other hand, the photosensitive coloring compositions of Reference Examples 11 to 20 using a pigment dispersant made of a vinyl polymer having no ethylene oxide chain or propylene oxide chain have both lightness and / or contrast. In result, it was inferior to the photosensitive coloring composition of Example. *

<Production of color filter>
Next, the red photosensitive coloring composition and the blue photosensitive coloring composition used for the color filter of this embodiment will be described. For the green photosensitive coloring composition, the photosensitive coloring composition 1 (GR-1) of this embodiment was used.

<Red photosensitive coloring composition>
(Preparation of red coloring composition (RP-1))
A mixture of the following composition is uniformly stirred and mixed, and dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then a 5 μm filter. And a red colored composition (RP-1) was produced.
Red coloring agent (CI Pigment Red 254) 8.5 parts Red coloring agent (CI Pigment Red 177) 3.5 parts Resin type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Binder resin (C-4) 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of red photosensitive coloring composition (RR-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to prepare a red photosensitive coloring composition (RR-1).
Red coloring composition (RP-1) 42.0 parts Binder resin (C-4) 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba・ "Irgacure 907" manufactured by Japan Co., Ltd.) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 39.6 parts ethylene glycol monomethyl ether acetate

(Preparation of blue coloring composition (BP-1))
A mixture having the composition shown below was stirred and mixed uniformly, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.1 mm for 5 hours. To prepare a blue colored composition (BP-1).
Blue colorant (CI Pigment Blue 15: 6) 7.2 parts Purple colorant (CI Pigment Violet 23) 4.8 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 0 part Binder resin (C-4) 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of blue photosensitive coloring composition (BR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive coloring composition (BR-1).
Blue coloring composition (BP-1) 34.0 parts Binder resin (C-4) 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba・ "Irgacure 907" manufactured by Japan Co., Ltd.) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

A black matrix is patterned on a glass substrate, and a red photosensitive coloring composition (RR-1) is applied on the substrate with a spin coater so that x = 0.640 and y = 0.330. A colored coating was formed. The coating was irradiated with 300 mJ / cm ² of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% aqueous sodium carbonate solution to remove the unexposed portion, and then the substrate was washed with ion-exchanged water. Formed. In the same manner, the green photosensitive coloring composition 1 (GR-1) was formed to a thickness such that x = 0.290 and y = 0.600, and the blue photosensitive coloring composition (BR-1) was added. The film was applied to a thickness of x = 0.150 and y = 0.060, respectively, to form a green filter segment and a blue filter segment to obtain a color filter.

By using the photosensitive coloring composition 1 (GR-1), it was possible to produce a color filter with high brightness and high contrast.

<< Embodiment IV >>
The measurement method of the weight average molecular weight (Mw) of the resin is as follows.

(Measurement method of weight average molecular weight (Mw) of resin)
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. It is a weight average molecular weight (Mw).

Then, the manufacturing method of the binder resin solution, the pigment derivative, the colorant, the green coloring composition, and the blue coloring composition used in Examples and Reference Examples will be described.

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and the mixture was stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Method for producing pigment derivative>
(Production of pigment derivative 1)
According to the synthesis method described in Japanese Patent No. 4585781, a pigment derivative (1) was obtained.

Dye derivative (1)

<Method for producing colorant>
(Production of quinophthalone compound (1))
The quinophthalone compound (1) was obtained according to the synthesis method described in JP-A-2008-81666. As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (1).

(Production of quinophthalone compound (2))
To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid were added, heated to 180 ° C., and stirred for 4 hours. Further, after cooling to room temperature, the reaction mixture was added to 5440 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 116 parts of a specific quinophthalone pigment represented by the formula (A-3). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone pigment of the formula (A-3).
Subsequently, using the quinophthalone pigment of formula (A-3) as a raw material, the quinophthalone compound (2) is obtained by the same method as the synthesis of the quinophthalone compound (1) according to the synthesis method described in JP-A-2008-81666. It was. As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (2).

(Production of quinophthalone compound (3))
20 parts of 8-hydroxy-2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 37 parts of quinophthalone compound (3). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (3).

(Production of yellow colorant (YA-1))
To 300 parts of methyl benzoate, 100 parts of quinophthalone compound (1), 70 parts of 2,3-naphthalenedicarboxylic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. The formation of the specific quinophthalone pigment represented by the formula (A-1) and the disappearance of the raw material quinophthalone compound (1) were confirmed by TOF-MS. Further, after cooling to room temperature, the reaction mixture was added to 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 120 parts of a specific quinophthalone pigment represented by the formula (A-1). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone pigment of the formula (A-1).

Subsequently, 100 parts of the quinophthalone pigment of formula (A-1), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of a yellow colorant (YA-1) were obtained. The average primary particle size was 31.3 nm.

(Production of yellow colorant (YA-2))
50 parts of a quinophthalone pigment of the formula (A-1), C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a yellow colorant (YA-2) were obtained. The average primary particle size was 30.2 nm.

(Production of yellow colorant (YA-3))
To 300 parts of methyl benzoate, 100 parts of quinophthalone compound (2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 118 parts of a specific quinophthalone pigment represented by the formula (A-2). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone pigment of the formula (A-2).

Subsequently, 100 parts of the quinophthalone pigment of the formula (A-2), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of a yellow colorant (YA-3) were obtained. The average primary particle size was 31.1 nm.

(Production of yellow colorant (YA-4))
50 parts of a quinophthalone pigment of the formula (A-2), C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a yellow colorant (YA-4) were obtained. The average primary particle size was 30.2 nm.

(Production of yellow colorant (YA-5))
20 parts of a quinophthalone pigment of the formula (A-2), C.I. I. 80 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 96 parts of a yellow colorant (YA-5) were obtained. The average primary particle size was 29.7 nm.

(Production of yellow colorant (YA-6))
100 parts of the quinophthalone pigment of formula (A-3), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a yellow colorant (YA-6) were obtained. The average primary particle size was 34.1 nm.

(Production of yellow colorant (YA-7))
To 300 parts of methyl benzoate, 100 parts of quinophthalone compound (2), 176 parts of tetrabromophthalic anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 6 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 7190 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 138 parts of a specific quinophthalone pigment represented by the formula (A-5). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone pigment of the formula (A-5).

Subsequently, 100 parts of the quinophthalone pigment of the formula (A-5), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a yellow colorant (YA-7) were obtained. The average primary particle size was 28.3 nm.

(Production of yellow colorant (YA-8))
50 parts of a quinophthalone pigment of the formula (A-5), C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of a yellow colorant (YA-8) were obtained. The average primary particle size was 28.1 nm.

(Production of yellow colorant (YB-1))
29 parts of 6-hexyl-2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 42 parts of a specific quinophthalone dye (yellow colorant (YB-1)) represented by the formula (B-1). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-1).

(Production of yellow colorant (YB-2))
34 parts of 8- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 50 parts of a specific quinophthalone dye (yellow colorant (YB-2)) represented by the formula (B-5). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-5).

(Production of yellow colorant (YB-3))
44 parts of 8- (2-ethylhexyloxy) -5-phenyl-2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 57 parts of a specific quinophthalone dye (yellow colorant (YB-3)) represented by the formula (B-6). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-6).

(Production of yellow colorant (YB-4))
46 parts of 8-dodecoxy-5-bromo-2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 46 parts of a specific quinophthalone dye (yellow colorant (YB-4)) represented by the formula (B-8). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-8).

(Production of yellow colorant (YB-5))
34 parts of 6- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 43 parts of a specific quinophthalone dye (yellow colorant (YB-5)) represented by the formula (B-10). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-10).

(Production of yellow colorant (YB-6))
29 parts of 6- (2-ethoxyethoxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 39 parts of a specific quinophthalone dye (yellow colorant (YB-6)) represented by the formula (B-11). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-11).

(Production of yellow colorant (YB-7))
34 parts of 6- (2- (1,3-dioxane-2-yl) ethoxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 33 parts of a specific quinophthalone dye (yellow colorant (YB-7)) represented by the formula (B-12). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-12).

(Production of yellow colorant (YB-8))
34 parts of 4- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 42 parts of a specific quinophthalone dye (yellow colorant (YB-8)) represented by the formula (B-13). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-13).

(Production of yellow colorant (YB-9))
20 parts of quinophthalone compound (3) was mixed with 200 parts of N, N-dimethylacetamide, 3 parts of sodium hydroxide and 18 parts of 2-ethylhexyl-4-bromobutyric acid were further mixed, and the mixture was stirred at 90 ° C. for 1 hour. After allowing to cool, 1000 parts of methanol and 1000 parts of water were added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 1000 parts of methanol and stirred for 1 hour, and then the solid was collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 16 parts of a specific quinophthalone dye (yellow colorant (YB-9)) represented by the formula (B-27). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-27).

(Production of yellow colorant (YB-10))
20 parts of quinophthalone compound (3) was mixed with 200 parts of N, N-dimethylacetamide, 3 parts of sodium hydroxide and 19 parts of 2-ethylhexyl-5-bromovaleric acid were further mixed, and the mixture was stirred at 90 ° C. for 1 hour. . After allowing to cool, 1000 parts of methanol and 1000 parts of water were added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 1000 parts of methanol and stirred for 1 hour, and then the solid was collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 20 parts of a specific quinophthalone dye (yellow colorant (YB-10)) represented by the formula (B-28). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-28).

(Production of yellow colorant (YB-11))
To 200 parts of N, N-dimethylacetamide, commercially available C.I. I. Disperse Yellow 160 (20 parts) was mixed, sodium hydroxide (3 parts) and 2-ethylhexyl-4-bromobutyric acid (18 parts) were further mixed and stirred at 90 ° C. for 1 hour. After allowing to cool, 1000 parts of methanol and 1000 parts of water were added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 1000 parts of methanol and stirred for 1 hour, and then the solid was collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 20 parts of a specific quinophthalone dye (yellow colorant (YB-11)) represented by the formula (B-30). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-30).

(Production of yellow colorant (YC-1))
C. I. 100 parts of Pigment Yellow 138 (trade name Paliotor Yellow K0961HD, manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is poured into warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night. YC-1) 98 parts were obtained. The average primary particle size was 35.5 nm.

(Production of green colorant (GC-1))
C. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is poured into warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night. GC-1) 97 parts were obtained. The average primary particle size was 28.2 nm.

(Production of blue colorant (BC-1))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this was added 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), and the temperature was raised and refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of aluminum phthalocyanine (1).

Subsequently, 100 parts of methanol, 100 parts of aluminum phthalocyanine (1) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol in a reaction vessel, heated to 40 ° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of aluminum phthalocyanine (2).

Furthermore, a salt milling process was performed. 100 parts of aluminum phthalocyanine (2), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is put into warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture is dried at 80 ° C. for a whole day and night. BC-1) 98 parts were obtained. The average primary particle size was 31.2 nm.

<Method for producing green and blue coloring composition>
(Preparation of green coloring composition (DG-1))
After stirring and mixing the mixture having the following composition to be uniform, using a zirconia bead having a diameter of 0.5 mm, using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser. After dispersing for 5 hours, the mixture was filtered with a 5 μm filter to prepare a green coloring composition (DG-1).
Green colorant (GC-1) 10.0 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 2.0 parts Acrylic resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate 48.0 parts

(Preparation of blue coloring composition (DB-1))
After stirring and mixing the mixture having the following composition to be uniform, using a zirconia bead having a diameter of 0.5 mm, using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser. After dispersing for 5 hours, the mixture was filtered through a 5 μm filter to produce a blue colored composition (DB-1).
Blue colorant (BC-1) 10.0 parts Resin-type dispersant ("BYK-LPN6919" manufactured by Big Chemie) 5.0 parts Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 50.0 parts

<The manufacturing method of a yellow coloring composition>
[Example 1]
(Preparation of yellow coloring composition (DY-1))
After stirring and mixing the mixture having the following composition to be uniform, using a zirconia bead having a diameter of 0.5 mm, using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser. After dispersing for 5 hours, the mixture was filtered through a 5 μm filter to produce a yellow colored composition (DY-1).
Yellow colorant (YA-1) 4.8 parts Yellow colorant (YB-1) 4.8 parts Dye derivative (1) 0.4 part Resin-type dispersant ("PB821" manufactured by Ajinomoto Fine Techno Co., Ltd.) 2.0 Acrylic resin solution 1 40.0 parts Cyclohexanone 24.0 parts Propylene glycol monomethyl ether acetate 24.0 parts

[Examples 2 to 33, Reference Examples 1 to 5]
(Yellow coloring composition (DY-2 to 38))
A yellow colored composition (DY-2 to 38) was obtained in the same manner as the yellow colored composition (DY-1) of Example 1, except that the type and blending amount of the yellow colorant were changed as shown in Table 1. It was. Further, the total content of the yellow colorant is 9.6 parts.

Yellow colorant (YC-2); I. Disperse Yellow 54
Yellow colorant (YC-3); I. Disperse Yellow 64

<Evaluation of yellow coloring composition>
Evaluation of spectral transmittance, contrast ratio, coloring power, heat resistance, and light resistance of the yellow coating film produced using the obtained yellow coloring composition (DY-1 to 38) was performed by the following methods. Table 2 shows the evaluation results.

(Spectral transmittance evaluation)
The yellow coloring composition (DY-1 to 38) was applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 20 minutes. A coated substrate was prepared by heating and cooling for a minute. The prepared coated substrate was subjected to heat treatment at 220 ° C. so that the transmittance at 450 nm became 5%, and a spectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) was used for spectroscopic analysis at 500 nm and 550 nm. The transmittance was measured. The higher the transmittance at 500 nm and 550 nm, the better the brightness. The spectral transmittances at 500 nm and 550 nm were determined according to the following criteria.
○: 99% or more Δ: 97 or more, less than 99% ×: less than 97%

(Contrast ratio evaluation)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)

Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low. A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion.

In addition, as a coating film substrate used for contrast ratio evaluation, a yellow coloring composition (DY-1 to 38) is applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then 70 It was prepared by drying at 20 ° C. for 20 minutes, then heating at 220 ° C. for 20 minutes and allowing to cool. The prepared coated substrate was adjusted to a chromaticity of x = 0.440 with a C light source after heat treatment at 220 ° C. The contrast ratio was determined according to the following criteria.
○: 3000 or more Δ: 2000 or more and less than 3000 ×: less than 2000

(Coloring power evaluation)
Using the same coating film as that used for the contrast ratio evaluation, the film thickness when x (C) = 0.440 chromaticity was measured was measured and judged according to the following criteria. It can be said that the smaller the film thickness that gives the chromaticity of x (C) = 0.440, the greater the coloring power, and the better.
○: Less than 2.0 [μm]
Δ: 2.0 to less than 3.0 [μm]
×: 3.0 or more [μm]

(Heat resistance evaluation)
The yellow coloring composition (DY-1 to 38) was applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 20 minutes. A coated substrate was prepared by heating and cooling for a minute. The prepared coated substrate was adjusted to a chromaticity of x = 0.440 with a C light source after heat treatment at 220 ° C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following three stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
○: ΔEab * is less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

(Light resistance evaluation)
A coated substrate is prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) is attached on the substrate, and irradiated with ultraviolet rays using a 470 W / m ² xenon lamp for 100 hours, and then the chromaticity ([ L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the above formula and evaluated according to the same criteria as for heat resistance.

As shown in Table 2, the yellow color of the examples containing the quinophthalone pigment represented by the general formula (1) and the quinophthalone dye represented by the general formula (6) as the colorant that is a feature of the present embodiment. The coloring composition was excellent in spectral transmittance, contrast ratio, and coloring power, and the heat resistance and light resistance of the coating film were satisfactory.

On the other hand, the yellow coloring compositions (DY-34 to 36) of Reference Examples 1 to 3 had low brightness. Specific quinophthalone dye used alone, and C.I. The yellow coloring compositions (DY-37, 38) of Reference Examples 4 and 5 used in combination with I. Pigment Yellow 138 had good brightness but a low contrast ratio. In addition, the existing pigment C.I. The yellow coloring composition (DY-34) of Reference Example 1 using I. Pigment Yellow 138 alone had a problem of low coloring power in addition to low brightness. C. not quinophthalone dye [B] I. Disperse Yellow 54, and C.I. I. The yellow coloring compositions (DY-35, 36) of Reference Examples 2 and 3 using Disperse Yellow 64 had poor contrast ratio, heat resistance and light resistance.

<Method for producing green photosensitive coloring composition>
[Example 34]
(Green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a green photosensitive coloring composition (RG-1).
Green coloring composition (DG-1) 23.5 parts Yellow coloring composition (DY-1) 21.5 parts Acrylic resin solution 2 2.0 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd.) 4.4 parts Photopolymerization initiator ("Irgacure OXE02" manufactured by Ciba Japan) 1.2 parts Cyclohexanone 20.0 parts Propylene glycol monomethyl ether acetate 27.4 parts

[Examples 35 to 70, Reference Examples 6 to 15]
(Preparation of green photosensitive coloring composition (RG-2 to 47))
Using the yellow coloring composition shown in Table 3, and the green coloring composition or the blue coloring composition, and at the time of coating film evaluation, the chromaticity of x = 0.290 and y = 0.600 with a C light source Except for changing the ratio of the yellow coloring composition and the green coloring composition or the blue coloring composition so as to match (change the ratio so that the total amount of the coloring composition is 45 parts), the photosensitive coloring composition (RG- In the same manner as in 1), photosensitive coloring compositions (RG-2 to 47) were prepared.

<Evaluation of green photosensitive coloring composition>
Evaluation of the brightness, contrast ratio, coloring power, heat resistance, light resistance and sensitivity of the green coating film produced using the obtained green photosensitive coloring composition (RG-1 to 47) was carried out by the following methods. Table 4 shows the evaluation results.

(Lightness evaluation)
The green photosensitive coloring composition (RG-1 to 47) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain ultrahigh pressure mercury. Using a lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating at 220 ° C. for 20 minutes and allowing to cool, the brightness Y (C) of the obtained coated substrate was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The prepared coated substrate was adjusted to a chromaticity of x = 0.290 and y = 0.600 with a C light source after heat treatment at 220 ° C. As an alkali developer, sodium carbonate 1.5% by weight, sodium hydrogen carbonate 0.5% by weight, an anionic surface active agent (“Perex NBL” manufactured by Kao Corporation) 8.0% by weight and water 90% by weight Was used. Furthermore, the brightness value was determined according to the following criteria.
○: 60.5 or more Δ: 58.5 or more, less than 60.5 ×: less than 58.5

(Contrast ratio evaluation)
About the measuring method of the contrast ratio of a coating film, it measured by the method similar to the contrast ratio measurement of a yellow coloring composition. The contrast ratio was calculated using the same coating film that was evaluated for brightness, and judged according to the following criteria.
○: 3500 or more Δ: 3000 or more and less than 3500 ×: less than 3000

(Coloring power evaluation)
Using the same coating film as the one subjected to lightness evaluation, the film thickness when the chromaticity of x (C) = 0.290 and y (C) = 0.600 was measured was measured and judged according to the following criteria. The smaller the film thickness that gives the chromaticity of x (C) = 0.290 and y (C) = 0.600, the greater the coloring power, and the better.
○: Less than 2.5 [μm]
Δ: 2.5 or more and less than 3.0 [μm]
×: 3.0 or more [μm]

(Heat resistance evaluation)
The green photosensitive coloring composition (RG-1 to 47) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain ultrahigh pressure mercury. Using a lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. Subsequently, it was heated at 220 ° C. for 20 minutes and allowed to cool to obtain a coated substrate. The prepared coated substrate was adjusted to a chromaticity of x = 0.290 and y = 0.600 with a C light source after heat treatment at 220 ° C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following three stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
○: ΔEab * is less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

(Light resistance evaluation)
A coated substrate is prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) is attached on the substrate, and irradiated with ultraviolet rays using a 470 W / m ² xenon lamp for 100 hours, and then the chromaticity ([ L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the above formula and evaluated according to the same criteria as for heat resistance.

(Sensitivity evaluation)
After coating the green photosensitive coloring composition (RG-1 to 47) on a 10 cm × 10 cm glass substrate by a spin coating method, the solvent was removed by heating at 70 ° C. for 15 minutes in a clean oven, and about 2 μm A coating film was obtained. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 220 ° C. for 20 minutes in a clean oven. The pattern film thickness in the 100 μm photomask portion of the filter segment formed by the above method was measured, and the minimum exposure amount that was 90% or more with respect to the film thickness after coating was determined according to the following criteria. It can be said that the smaller the minimum exposure, the higher the sensitivity and the better the photosensitive coloring composition.
○: Less than 50 mJ / cm ² Δ: 50 mJ / cm ² or more, less than 100 mJ / cm ² ×: 100 mJ / cm ² or more

As shown in Table 4, the green color of the example containing the quinophthalone pigment represented by the general formula (1) and the quinophthalone dye represented by the general formula (6) as the colorant that is a feature of the present embodiment. The photosensitive coloring composition was excellent in lightness, contrast ratio, and coloring power, and the heat resistance and light resistance of the coating film were satisfactory. Furthermore, despite the fact that it contains a dye, the sensitivity was also good.

On the other hand, the existing pigment C.I. The green photosensitive coloring compositions (RG-38 and 43) of Reference Examples 6 and 11 using I. Pigment Yellow 138 alone had low coloring power. A specific quinophthalone dye alone as a yellow colorant, and C.I. The green photosensitive coloring compositions (RG-41, 42, 46, and 47) of Reference Examples 9, 10, 14, and 15 used in combination with I. Pigment Yellow 138 have good brightness but low contrast ratios. The result was poor sensitivity. As a yellow colorant, C.I. which is not a quinophthalone dye [B]. I. Disperse Yellow 54, and C.I. I. The green photosensitive coloring compositions of Reference Examples 7, 8, 12, and 13 (RG-39, 40, 44, and 45) using Disperse Yellow 64 had bad results in all properties.

<Production of color filter>
First, the red photosensitive coloring composition and the blue photosensitive coloring composition used for preparation of a color filter were produced.

(Preparation of red photosensitive coloring composition (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A red colored composition (DR-1) was prepared by filtration through a 0.0 μm filter.
Red pigment (CI Pigment Red 254) 9.6 parts Red Pigment (CI Pigment Red 177) 2.4 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin Solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, a mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).
Red coloring composition (DR-1) 42.0 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907" manufactured) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

(Preparation of blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A blue colored composition (DB-1) was produced by filtration through a 0.0 μm filter.
Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple Pigment (CI Pigment Violet 23) 4.8 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).
Blue coloring composition (DB-1) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907", manufactured by 2.0) Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part 45.1 parts ethylene glycol monomethyl ether acetate

(Production of color filter)
A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (RR-1) was applied onto the substrate with a spin coater to form a colored coating. The film was irradiated with ultraviolet rays of 150 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 220 ° C. for 20 minutes to obtain a red filter segment. Formed. Here, the red filter segment was adjusted to a chromaticity of x = 0.640 and y = 0.330 in a C light source (hereinafter also used for green and blue) after heat treatment at 220 ° C. Further, by the same method, the green filter segment is adjusted to chromaticity of x = 0.290, y = 0.600 using the green photosensitive coloring composition (RG-19), and the blue filter segment is Each filter segment was formed using a blue photosensitive coloring composition (RB-1) so that the chromaticity of x = 0.150 and y = 0.060 was obtained, thereby obtaining a color filter.

By using the green photosensitive coloring composition (RG-19), it was possible to increase the brightness and contrast of the color filter, and it could be suitably used without any other physical properties.

<< Embodiment V >>

<Method for producing quinophthalone dye>

2.9 parts of 6-hexyl-2-methylquinoline, 2.5 parts of naphthalenedicarboxylic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 4.2 parts of product. The yield was 82%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 408 (molecular weight 407.5).

2.3 parts of 6-i-propyl-2-methylquinoline, 2.5 parts of naphthalenedicarboxylic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.1 parts of product. The yield was 67%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 366 (molecular weight 365.4).

2.7 parts of 7-trifluoromethyl-2-methylquinoline, 2.5 parts of naphthalenedicarboxylic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 2.9 parts of product. The yield was 58%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 392 (molecular weight 391.3), which confirmed the intended product.

2.7 parts of 8-n-butyloxy-2-methylquinoline, 2.5 parts of naphthalenedicarboxylic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.1 parts of product. The yield was 62%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 396 (molecular weight 395.5), which confirmed the intended product.

8- (2-ethylhexyloxy) -2-methylquinoline (3.4 parts), naphthalenedicarboxylic anhydride (2.5 parts) and benzoic acid (30 parts) were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 5.0 parts of product. The yield was 88%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 452 (molecular weight 451.5).

8- (2-ethylhexyloxy) -5-phenyl-2-methylquinoline 4.4 parts, 2.5 parts of naphthalenedicarboxylic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 5.7 parts of product. The yield was 85%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 528 (molecular weight 527.7).

8. 4.1 parts of 8-dodecoxy-2-methylquinoline, 2.5 parts of naphthalenedicarboxylic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.6 parts of product. The yield was 57%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 508 (molecular weight 507.6).

8- (2-ethylhexyloxy) -5-bromo-2-methylquinoline (4.4 parts), naphthalenedicarboxylic anhydride (2.5 parts) and benzoic acid (30 parts) were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 4.1 parts of product. The yield was 61%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 531 (molecular weight 530.5) was confirmed to be the desired product.

2.9 parts of 6-trifluoromethyloxy-2-methylquinoline, 2.5 parts of naphthalenedicarboxylic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 4.3 parts of product. The yield was 83%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 408 (molecular weight 407.3).

6. 3.4 parts of 6- (2-ethylhexyloxy) -2-methylquinoline, 2.5 parts of naphthalenedicarboxylic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.9 parts of product. The yield was 68%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 452 (molecular weight 451.5).

2.9 parts of 6- (2-ethoxyethoxy) -2-methylquinoline, 2.5 parts of naphthalenedicarboxylic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.3 parts of product. The yield was 64%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 412 (molecular weight 411.5).

6- (2- (1,3-dioxan-2-yl) ethoxy) -2-methylquinoline (3.4 parts), naphthalenedicarboxylic anhydride (2.5 parts) and benzoic acid (30 parts) were mixed and mixed at 200 ° C. for 7 parts. Stir for hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.0 parts of product. The yield was 53%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 454 (molecular weight 453.5).

4- (2-Ethylhexyloxy) -2-methylquinoline (3.4 parts), naphthalenedicarboxylic anhydride (2.5 parts) and benzoic acid (30 parts) were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 4.2 parts of product. The yield was 74%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 452 (molecular weight 451.5).

Ethyl 5- (2-methylquinolin-8-yloxy) pentanoate 3.8 parts, 2.5 parts of naphthalene dicarboxylic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 4.5 parts of product. The yield was 74%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 482 (molecular weight 481.5).

8-hydroxy-2-methylquinoline (2.0 parts), naphthalenedicarboxylic anhydride (2.5 parts) and benzoic acid (30 parts) were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.7 parts of product. The yield was 86%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 339 (molecular weight 339.3).

2.0 parts of quinophthalone dye 15 parts are mixed with 20 parts of N, N-dimethylacetamide, 0.3 parts of sodium hydroxide and 1.8 parts of 2-ethylhexyl 4-bromobutyric acid are further mixed and stirred at 90 ° C. for 1 hour did. After allowing to cool, 100 parts of methanol and 100 parts of water were added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 100 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 1.6 parts of product. The yield was 51%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 538 (molecular weight 537.7).

2.0 parts of quinophthalone dye 15 parts are mixed with 20 parts of N, N-dimethylacetamide, 0.3 parts of sodium hydroxide and 1.9 parts of 2-ethylhexyl ヘ 5-bromovaleric acid are further mixed, and the mixture is heated at 90 ° C. for 1 hour. Stir. After allowing to cool, 100 parts of methanol and 100 parts of water were added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 100 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 2.0 parts of product. The yield was 62%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 552 (molecular weight 551.7).

2.0 parts of 15 parts of quinophthalone dye are mixed with 20 parts of N, N-dimethylacetamide, 0.3 parts of sodium hydroxide, 2- (2- (2-ethylhexyloxy) ethoxy) ethyl-2-bromobutanoate 2 4 parts were further mixed and stirred at 100 ° C. for 2 hours. After allowing to cool, the reaction solution was added to 50 parts of water, and further 100 parts of chloroform was added to extract the organic layer. Magnesium sulfate was added to the organic layer, dried, filtered and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 2.8 parts of product. The yield was 76%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 626 (molecular weight 625.8).

2.0 parts of quinophthalone dye 15 parts are mixed with 20 parts of N, N-dimethylacetamide, 0.3 parts of sodium hydroxide, 2- (2- (2-ethylhexyloxy) ethoxy) ethyl-5-bromopentanoate 2 .5 parts were further mixed and stirred at 100 ° C. for 2 hours. After allowing to cool, the reaction solution was added to 50 parts of water, and further 100 parts of chloroform was added to extract the organic layer. Magnesium sulfate was added to the organic layer, dried, filtered and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 2.7 parts of product. The yield was 72%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 640 (molecular weight 639.8).

2.0 parts of quinophthalone dye 15 ロ ン is mixed with 20 parts of N, N-dimethylacetamide, 0.3 parts of sodium hydroxide, bis (2-ethylhexyl) 7-oxabicyclo [4,1,0] heptane-3,4 -9.7 parts of diloxylate were further mixed and stirred at 150 ° C for 10 hours. After allowing to cool, the reaction solution was added to 50 parts of water, and further 100 parts of chloroform was added to extract the organic layer. Magnesium sulfate was added to the organic layer, dried, filtered and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 1.3 parts of the product. The yield was 30%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 750 (molecular weight 749.9), which confirmed the intended product.

Disperse Yellow 160 2.0 parts is mixed with N, N-dimethylacetamide 20 parts, sodium hydroxide 0.3 parts and 2-ethylhexyl 4-bromobutyric acid 1.8 parts are further mixed and stirred at 90 ° C for 1 hour. did. After allowing to cool, 100 parts of methanol and 100 parts of water were added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 100 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 2.0 parts of product. The yield was 60%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 538 (molecular weight 537.7).

The synthesis was carried out based on the synthesis method of dye (IV) described in JP-A-6-009891.

Disperse Yellow 54 was used.

Disperse Yellow 64 was used.

<Preparation of acrylic resin solution>
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Addition to prepare an acrylic resin solution.

Here, the polymerization average molecular weight (Mw) of the acrylic resin was measured using a TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. The weight average molecular weight (Mw) in terms of polystyrene.

<Pigment production method>
(Preparation of blue pigment 1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Ink Manufacturing Co., Ltd.) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. did. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of blue pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 79 nm.

(Preparation of purple pigment 1)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of violet pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 28 nm.

(Preparation of blue pigment 2)
A glass 4-necked flask was charged with 60.0 parts of phthalonitrile, 300 parts of 1-chloronaphthalene, and 15.6 parts of aluminum chloride, and stirred under reflux for 6 hours. Thereafter, heating was stopped, the mixture was allowed to cool to about 200 ° C., filtered while hot, and washed by sprinkling with 600 parts of hot toluene and 300 parts of acetone. The obtained wet cake was dispersed in 250 parts of toluene and stirred and refluxed for 3 hours. It was again filtered while hot, washed by sprinkling with 600 parts of hot toluene and 300 parts of acetone, dispersed in 1500 parts of ion-exchanged water, and heated and stirred at 60 to 70 ° C. for 60 minutes. Filtration, washing with water and vacuum drying at 50 ° C. gave a blue solid aluminum phthalocyanine pigment (AlPc—Cl) having the desired structure. 30 parts of the obtained pigment were gradually dissolved in 1200 parts of concentrated sulfuric acid while keeping the temperature at about 5 ° C., and stirred at this temperature for 1 hour. This was added to 6000 parts of ice water with stirring so that the temperature did not exceed 5 ° C., and further stirred for 1 hour after the end of the addition. After filtration and washing with water, it was redispersed in 6500 parts of ion exchange water and filtered again. After washing with water, the wet cake was redispersed in 2500 parts of 4% aqueous ammonia and stirred under reflux for 6 hours. After filtration, the cake was washed with ion-exchanged water and then vacuum dried at 50 ° C. to obtain a blue solid aluminum phthalocyanine pigment (AlPc—OH) having the desired structure.

50 parts of this (AlPc-OH) pigment, 150 parts of sodium chloride, and 25 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 6 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A blue pigment 2 was obtained. The average primary particle diameter of the obtained pigment was 28 nm.

(Preparation of green pigment 1)
Phthalocyanine green pigment C.I. I. Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC Corporation) was used as it was on the market. The average primary particle diameter of the green pigment 1 was 22 nm.

(Preparation of yellow pigment 1)
Quinophthalone yellow pigment C.I. I. 270 parts of Pigment Yellow 138 (trade name Paliotor Yellow K0961HD, manufactured by BASF), 1350 parts of sodium chloride, and 500 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 250 parts of yellow pigment 3 were obtained. The average primary particle diameter of the obtained pigment was 36 nm.

(Preparation of yellow pigment 2)
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of yellow pigment 2 were obtained. The obtained pigment had a volume average primary particle size of 67 nm.

(Preparation of yellow pigment 3)
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 (“Irgafore Yellow 2R-CF” manufactured by Ciba Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. did. Next, this kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 490 parts of Yellow Pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 92 nm.

(Preparation of red pigment 1)
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“Chromophthalred A2B” manufactured by Ciba Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 54 nm.

(Preparation of colored composition Q-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition Q-1 was produced by filtration using a filter.
Quinophthalone dye 1: 11.0 parts Acrylic resin solution prepared previously: 40.0 parts Cyclohexanone: 48.0 parts

(Preparation of colored compositions Q-2 to 24)
Hereinafter, colored compositions Q-2 to 24 were prepared in the same manner as colored composition Q-1, except that quinophthalone dye 1 was replaced with the quinophthalone dye shown in Table 2.

(Preparation of colored composition DP-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition (DP-1) was produced by filtration using a filter.
Blue Pigment 1 (CI Pigment Blue 15: 6): 11.0 parts previously prepared acrylic resin solution: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin-type dispersant (Ciba・ "EFKA4300" manufactured by Japan Co., Ltd.): 1.0 part

(Preparation of colored compositions DP-2 to 8)
Hereinafter, colored compositions DP-2 to 8 were produced in the same manner as the colored composition DP-1, except that the blue pigment 1 was replaced with the pigment shown in Table 3.

[Examples 1 to 20, Reference Examples 1 to 7]
<Coating foreign matter test of colored compositions Q-1 to 24 and DP-5 to 7>
The evaluation was performed by preparing a test substrate and counting the number of particles. The coloring composition was applied onto the transparent substrate so that the dried coating film was about 2.0 μm, and heated in an oven at 230 ° C. for 20 minutes to obtain a test substrate. The evaluation was carried out using a Olympus system metal microscope “BX60”). The magnification is 500 times, and the number of particles that can be observed in any five fields of view through transmission is counted. In the following evaluation results, ◎ and ○ are good, Δ is a level that does not cause a problem in use although there are many foreign matters, and × indicates coating unevenness (spots) due to foreign matters.
未 満: Less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or less, Table 4 shows the results.

<Spectroscopic evaluation of colored compositions Q-1 to 24 and DP-5 to 7>
A coating film was prepared on a transparent substrate so that the transmittance at a wavelength of 450 nm was 5%, and the transmittance values at 500 nm and 550 nm at that time were measured. The higher the transmittance at 500 nm and 550 nm, the better the brightness. In the following evaluation results, the transmittance of 500 nm and 550 nm when the quinophthalone dye and the yellow pigment are standardized is ◯ is 99% or more, Δ is 97 or more and less than 99%, and × is less than 97%. It is preferable that it is 99% or more because the brightness becomes high. The results are shown in Table 4 below. Also, the spectra of the coating films of Example 5 and Reference Examples 1 and 3 are shown in FIGS.

Examples 1 to 20 gave good results with few coating film foreign matters. In addition, Examples 1 to 20 were the results of excellent spectral characteristics, and showed spectral shapes with high brightness. Reference Examples 2 to 6 showed spectral shapes in which the transmittance at 550 nm was relatively good, but the transmittance at 500 nm was low and no improvement in brightness was expected.

Reference Examples 1 to 4 using a dye having a hydroxyl group in the quinoline ring are compared with the spectral shapes of Examples 1 to 20 using a dye having no hydroxyl group (for example, Example 5 in FIG. 1, Reference Examples 1 and 3). The dye having a low transmittance at 500 nm and having a hydroxyl group in the quinoline ring is a dye that cannot be expected to improve brightness.

<Method for producing blue resist material>
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a blue resist material B-1.
Colored composition (DP-1): 48.0 parts Colored composition (DP-2): 12.0 parts Previously prepared acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (new Nakamura Chemical Co., Ltd. “NK ESTER ATMPT”)
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan): 1.2 parts sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts propylene glycol monomethyl ether acetate (PGMAC): 23 .2 parts

[Example 21]
<Adjustment of resist material G-1>
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a green resist material (G-1).
Colored composition (DP-3): 18.0 parts Colored composition (Q-1): 42.0 parts previously prepared acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (new Nakamura Chemical Co., Ltd. “NK ESTER ATMPT”)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts propylene glycol monomethyl ether acetate (PGMAC): 23 .2 parts

[Examples 22 to 66, Reference Examples 8 to 15]
<Adjustment of resist materials G-2 to 46, R-1 to 4, Y-1 to 4>
Hereinafter, the resist materials G-2 to 46, R-1 to 4, Y-1 to the same as the resist material G-1, except that the type and blending amount of the coloring composition are changed as shown in Tables 5 and 6 4 was obtained.

<Evaluation of resist material>
The following tests were conducted for the color characteristics (Y: brightness), coating foreign matter, heat resistance, and light resistance of the obtained resist materials G-1 to 46, R-1 to 4, and Y-1 to 4, respectively. I went there. The test results are shown in Table 7.

<Color characteristics (Y: brightness)>
A resist material was applied on a glass substrate in a C light source so that the resist materials G-1 to 46 had a thickness of x = 0.264 and y = 0.600, and this substrate was heated at 230 ° C. for 20 minutes. . The resist materials R-1 to R-4 were coated with a resist material so that x = 0.340 and y = 0.640, and this substrate was heated at 230 ° C. for 20 minutes. The resist materials Y-1 to Y-4 were coated with a resist material so that x = 0.440 and y = 0.506, and this substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).
The results are shown in Table 7 below.

<Coating foreign matter test>
A resist material was applied on the transparent substrate so that the dried coating film became about 2.5 μm, and the whole surface was exposed to ultraviolet light, and then heated in an oven at 230 ° C. for 20 minutes and allowed to cool to obtain an evaluation substrate. The evaluation was performed by observing the surface using a metal microscope “BX60” manufactured by Olympus System. The magnification is 500 times, and the number of particles that can be confirmed in any five visual fields through transmission is counted. In the following evaluation results, ◎ and ○ are good, Δ is a level that does not cause a problem in use although there are many foreign matters, and × indicates coating unevenness due to the foreign matters.
未 満: Less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or less, Table 7 shows the results.

<Film heat resistance test>
A resist material is applied on a transparent substrate so that the dry coating thickness is about 2.5 μm, and after UV exposure through a mask having a predetermined pattern, an alkali developer is sprayed to remove uncured parts. Thus, a desired pattern was formed. Then, after heating in an oven at 230 ° C. for 20 minutes and allowing to cool, the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source is microspectrophotometric. Measurement was performed using a meter (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Further, as a heat resistance test, the sample was heated in an oven at 230 ° C. for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured. Using the measured color difference value, the color difference ΔEab * was calculated by the following formula, and the heat resistance of the coating film was evaluated in the following four stages. Moreover, if evaluation is more than (triangle | delta), it is a level which is satisfactory practically.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
：: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0 Δ: ΔEab * is 3.0 or more and less than 5.0 ×: ΔEab * is 5.0 or more, Table 7 The results are shown in.

<Coating light resistance test>
A test substrate was prepared in the same procedure as the coating heat resistance test, and the chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source was measured with a microspectrophotometer (Olympus Optics). Measurement was performed using “OSP-SP200” manufactured by the company. Thereafter, the substrate was placed in a light resistance tester (“SUNTSTCPS +” manufactured by TOYOSEIKI) and left for 500 hours. After removing the substrate, measure chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source, and calculate the color difference ΔEab * in the same manner as the coating film heat resistance test. Then, the solvent resistance of the coating film was evaluated according to the same criteria as the coating film heat resistance test. Moreover, if evaluation is more than (triangle | delta), it is a level which is satisfactory practically.
The results are shown in Table 7 below.

<Film resistance test>
A test substrate was prepared in the same procedure as the coating heat resistance test, and the chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source was measured with a microspectrophotometer (Olympus Optics). Measurement was performed using “OSP-SP200” manufactured by the company. Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After removing the substrate, measure chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source, and calculate the color difference ΔEab * in the same manner as the coating film heat resistance test. Then, the solvent resistance of the coating film was evaluated according to the same criteria as the coating film heat resistance test. Moreover, if evaluation is more than (triangle | delta), it is a level which is satisfactory practically.
The results are shown in Table 7 below.

The resist materials (G-1 to 20, G-22 to 41, R-1 to 3, Y-1 to 3) of Examples 21 to 66 have brightness (Y), coating film foreign matter, heat resistance, light resistance, Good results in solvent resistance were shown.

On the other hand, the resist materials (G-44 and G-45) of Reference Examples 11 and 12 are difficult to actually use because of their poor heat resistance and light resistance. The resist materials (G-21, G-43 to 46, R-4, Y-4) of Reference Examples 8 to 15 had lower brightness (Y) than the examples.

[Example 58]
<Color filter (CF-1)>
A black matrix is patterned on a glass substrate, and a red resist material (R-1) is applied on the substrate with a spin coater to a film thickness such that x = 0.640, y = 0.340. A colored coating was formed. The coating was irradiated with 300 mJ / cm ² of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, the green resist material (G-36) is formed to a thickness of x = 0.264 and y = 0.600, and x = 0.150 using the blue resist material (B-1). The film was applied to a thickness such that y = 0.060, and a green filter segment and a blue filter segment were formed to obtain a color filter (CF-1).

<Production of liquid crystal display device>
A transparent ITO electrode layer was formed on the obtained RGB color filter, and a polyimide alignment layer was formed thereon. A color display device was produced on the other surface of this glass substrate in combination with a three-wavelength CCFL light source of a polarizing plate. Formed. On the other hand, a TFT array and a pixel electrode were formed on one surface of another (second) glass substrate, and a polarizing plate was formed on the other surface. The two glass substrates prepared in this way are arranged facing each other so that the electrode layers face each other, and are aligned using spacer beads while keeping the distance between the two substrates constant, and an opening for injecting a liquid crystal composition The periphery was sealed with a sealant so as to leave After injecting the liquid crystal composition from the opening, the opening was sealed. A liquid crystal display device thus produced was combined with a three-wavelength CCFL light source of a backlight unit to produce a color display device.

[Examples 68 to 71, Reference Examples 16 and 17]
(Color filter (CF-2 to 7))
Thereafter, the color filters (CF-2 to 65) of Examples 68 to 71 and Reference Examples 16 and 17 were combined in the same manner as in the production of the color filter (CF-1) by combining the resist material shown in Table 8 with a three-wavelength CCFL light source. 7) and a color display device were produced.

Thereafter, in the obtained color display device, a light source was emitted to display a color image, and the brightness (Y) of each color filter segment portion was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 8.

Comparing Examples 68 and 69 with Reference Example 16, the color filter formed using the quinophthalone dye of this embodiment has at least one filter segment (green or red) as compared with the filter segment using the conventional pigment. In the color filter (CF-2, 3) using the quinophthalone dye of this embodiment, the brightness was improved. As a result, the brightness of the white display increased, and the improvement of the performance as a color filter was confirmed.

Furthermore, it was confirmed that the brightness of the color filter (CF-1) formed using the quinophthalone dye of this embodiment for both green and red in Example 67 was further improved, and as a result, the brightness of white display was increased. It was.

In addition, when Example 71 and Reference Example 17 are compared, the color filter formed using the quinophthalone dye of this embodiment has at least one filter segment (yellow) as compared with a filter segment containing a conventionally used pigment. However, the brightness of the color filter (CF-6) containing the quinophthalone dye of this embodiment also improved, and as a result, the brightness of white display increased, and the improvement of the performance as a color filter was confirmed.

Furthermore, when all of the green, red, and yellow colors of Example 70 contain the color filter dye of this embodiment (CF-5), it was confirmed that the brightness was further improved, and as a result, the brightness of white display was increased. .

From the above results, by using the quinophthalone dye of this embodiment and a coloring composition containing the same, it is possible to increase the brightness of the color filter, and it can be suitably used without any other physical properties.

<< Embodiment VI >>
The weight average molecular weight (Mw) of the resin is as follows.

(Resin polymerization average molecular weight (Mw))
The polymerization average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. It is a weight average molecular weight (Mw).

Then, the manufacturing method of the binder resin solution, the colorant, the fine pigment, and the acrylic resin solution used in Examples and Reference Examples is described.

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and the mixture was stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Method for producing colorant>
(Production of hydroxyaluminum phthalocyanine 1)
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this was added 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), and the temperature was raised and refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water, and dried to obtain 102 parts of hydroxyaluminum phthalocyanine 1 represented by the following formula (3).

(Production of hydroxyaluminum phthalocyanine 2)
In the production of hydroxyaluminum phthalocyanine 1, hydroxyaluminum phthalocyanine 2 represented by the following formula (4) was obtained by the same production method except that 250 parts of 4-methylphthalodinitrile was used instead of phthalodinitrile. .

(Production of hydroxyaluminum phthalocyanine 3)
In the production of hydroxyaluminum phthalocyanine 1, hydroxyaluminum phthalocyanine 3 represented by the following formula (5) was obtained by the same production method except that the amount was changed to 285 parts of 4-chlorophthalodinitrile instead of phthalodinitrile. .

(Production of blue colorant (BC-1))
100 parts of hydroxyaluminum phthalocyanine 1, 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. A colorant (BC-1) was obtained. The average primary particle size was 30.4 nm.

(Production of blue colorant (B-1))
In a reaction vessel, 100 parts of methanol, 100 parts of hydroxyaluminum phthalocyanine 1 and 49.5 parts of diphenyl phosphate were added, heated to 40 ° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of a specific phthalocyanine dye represented by formula (1-1). Subsequently, a salt milling process was performed. 100 parts of a specific phthalocyanine dye represented by the formula (1-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of colorant (B-1) were obtained. The average primary particle size was 31.2 nm.

(Production of blue colorant (B-2))
In a reaction vessel, 1000 parts of methanol, 100 parts of hydroxyaluminum phthalocyanine 1 and 43.2 parts of diphenylphosphinic acid were added, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 112 parts of a specific phthalocyanine dye represented by formula (1-2). A blue colorant (B-2) was obtained by subjecting the obtained specific phthalocyanine dye represented by the formula (1-2) to a salt milling method similar to that for the blue colorant (B-1). The average primary particle size was 29.5 nm.

(Production of blue colorant (B-3))
In a reaction vessel, 100 parts of methanol, 100 parts of hydroxyaluminum phthalocyanine 2 and 28.0 parts of phenylphosphinic acid were added, heated to 40 ° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 102 parts of a specific phthalocyanine dye represented by formula (1-3). A blue colorant (B-3) was produced from the obtained specific phthalocyanine dye represented by formula (1-3) by the same salt milling method as that for the blue colorant (B-1). The average primary particle size was 33.1 nm.

(Production of blue colorant (B-4))
In a reaction vessel, 100 parts of methanol, 100 parts of hydroxyaluminum phthalocyanine 3 and 41.5 parts of dibutyl phosphate were added, heated to 40 ° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 109 parts of a specific phthalocyanine dye represented by formula (1-4). A blue colorant (B-4) was produced from the obtained specific phthalocyanine dye represented by formula (1-4) by the same salt milling method as that for the blue colorant (B-1). The average primary particle size was 28.9 nm.

(Production of green colorant (G-1))
C. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night. 97 parts of colorant (G-1) were obtained. The average primary particle size was 28.2 nm.

(Manufacture of kinophthalone 1)
20 parts of 8-hydroxy-2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 h. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 37 parts of quinophthalone 1 represented by following formula (6). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 339 (molecular weight 339.3).

(Production of yellow colorant (Y-1))
29 parts of 6-hexyl-2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 42 parts of a specific quinophthalone dye (yellow colorant (Y-1)) represented by the formula (2-1). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 408 (molecular weight 407.5).

(Production of yellow colorant (Y-2))
34 parts of 8- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 50 parts of a specific quinophthalone dye (yellow colorant (Y-2)) represented by the formula (2-5). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 452 (molecular weight 451.5).

(Production of yellow colorant (Y-3))
44 parts of 8- (2-ethylhexyloxy) -5-phenyl-2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 57 parts of a specific quinophthalone dye (yellow colorant (Y-3)) represented by the formula (2-6). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 528 (molecular weight 527.7).

(Production of yellow colorant (Y-4))
46 parts of 8-dodecoxy-5-bromo-2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 46 parts of a specific quinophthalone dye (yellow colorant (Y-4)) represented by the formula (2-8). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 531 (molecular weight 530.5) was confirmed to be the desired product.

(Production of yellow colorant (Y-5))
34 parts of 6- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 43 parts of a specific quinophthalone dye (yellow colorant (Y-5)) represented by the formula (2-10). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 452 (molecular weight 451.5).

(Production of yellow colorant (Y-6))
29 parts of 6- (2-ethoxyethoxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 39 parts of a specific quinophthalone dye (yellow colorant (Y-6)) represented by the formula (2-11). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 412 (molecular weight 411.5).

(Production of yellow colorant (Y-7))
34 parts of 6- (2- (1,3-dioxane-2-yl) ethoxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 33 parts of a specific quinophthalone dye (yellow colorant (Y-7)) represented by the formula (2-12). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 454 (molecular weight 453.5).

(Production of yellow colorant (Y-8))
34 parts of 4- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 42 parts of a specific quinophthalone dye (yellow colorant (Y-8)) represented by the formula (2-13). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 452 (molecular weight 451.5).

(Production of yellow colorant (Y-9))
20 parts of quinophthalone 1 represented by the formula (6) is mixed with 200 parts of N, N-dimethylacetamide, and 3 parts of sodium hydroxide and 18 parts of 2-ethylhexyl-4-bromobutyric acid are further mixed at 90 ° C. Stir for 1 hour. After allowing to cool, 1000 parts of methanol and 1000 parts of water were added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 1000 parts of methanol and stirred for 1 hour, and then the solid was collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 16 parts of a specific quinophthalone dye (yellow colorant (Y-9)) represented by the formula (2-27). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 538 (molecular weight 537.7).

(Production of yellow colorant (Y-10))
20 parts of quinophthalone 1 represented by the formula (6) is mixed with 200 parts of N, N-dimethylacetamide, 3 parts of sodium hydroxide and 19 parts of 2-ethylhexyl-5-bromovaleric acid are further mixed, and 90 ° C. For 1 hour. After allowing to cool, 1000 parts of methanol and 1000 parts of water were added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 1000 parts of methanol and stirred for 1 hour, and then the solid was collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 20 parts of a specific quinophthalone dye (yellow colorant (Y-10)) represented by the formula (2-28). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 552 (molecular weight 551.7).

(Production of yellow colorant (Y-11))
To 200 parts of N, N-dimethylacetamide, commercially available C.I. I. Disperse Yellow 160 (20 parts) was mixed, sodium hydroxide (3 parts) and 2-ethylhexyl-4-bromobutyric acid (18 parts) were further mixed and stirred at 90 ° C. for 1 hour. After allowing to cool, 1000 parts of methanol and 1000 parts of water were added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 1000 parts of methanol and stirred for 1 hour, and then the solid was collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 20 parts of a specific quinophthalone dye (yellow colorant (Y-11)) represented by the formula (2-30). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 538 (molecular weight 537.7).

(Production of yellow colorant (YC-3))
C. I. 100 parts of Pigment Yellow 138 (trade name Paliotor Yellow K0961HD, manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of a colorant (YC-3) were obtained. The average primary particle size was 35.5 nm.

[Example 1]
(Green coloring composition (DG-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A green colored composition (GP-1) was produced by filtration through a 0.0 μm filter. At this time, when the coated substrate is produced, the blue colorant (B-1) and the yellow colorant (Y-1) are matched with the chromaticity of x = 0.290 and y = 0.600 with the C light source. The ratio was selected.
Blue colorant (B-1) 5.2 parts Yellow colorant (Y-1) 5.8 parts Resin-type dispersant (“BYK-LPN6919” manufactured by Big Chemie) 5.5 parts Acrylic resin solution 1 28.5 parts Propylene glycol monomethyl ether acetate 39.0 parts Cyclohexanone 16.0 parts

[Examples 2 to 24, Reference Examples 1 to 10]
(Green coloring composition (DG-2-34))
The green coloring composition of Example 1 except that the blue coloring agent (B-1) and the yellow coloring agent (Y-1) were changed to the combination of coloring agents shown in Table 1 and the blending ratio of the coloring agents was changed. Green colored compositions (DG-2 to 34) were obtained in the same manner as (DG-1). The mixing ratio of the blue colorant and the yellow colorant was selected so that when the coated substrate was prepared, the ratio was adjusted to chromaticity of x = 0.290 and y = 0.600 with the C light source. . Further, the total content of the colorants is 11.0 parts.

<Coating preparation and evaluation>
The lightness (color characteristics), heat resistance, and light resistance of the green coating film produced using the obtained green coloring composition (DG-1 to 34) were evaluated by the following methods. Table 1 shows the evaluation results.

(Brightness evaluation of coating film)
The green coloring composition (DG-1-34) was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 30 minutes. A coated substrate was prepared by heating and cooling for a minute. The brightness Y (C) of the obtained coating film was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The prepared coated substrate was adjusted to a chromaticity of x = 0.290 and y = 0.600 with a C light source after heat treatment at 220 ° C. Regarding brightness Y (C), it can be said that there is a clear difference if it is 0.2 points or more.

(Evaluation of heat resistance of coating film)
The green coloring composition (DG-1-34) was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 30 minutes. A coated substrate was prepared by heating and cooling for a minute. The prepared coated substrate was adjusted to a chromaticity of x = 0.290 and y = 0.600 with a C light source after heat treatment at 220 ° C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following three stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
○: ΔEab * is less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

(Light resistance evaluation of coating film)
A coated substrate is prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) is attached on the substrate, and irradiated with ultraviolet rays using a 470 W / m ² xenon lamp for 100 hours, and then the chromaticity ([ L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the above formula and evaluated according to the same criteria as for heat resistance.

Yellow colorant (YC-1); I. Disperse Yellow 54
Yellow colorant (YC-2); I. Disperse Yellow 64

As shown in Table 1, the colorant which is a feature of the embodiment includes a phthalocyanine dye represented by the general formula (8A) and a quinophthalone dye represented by the general formula (6). It was excellent in lightness, and the heat resistance and light resistance of the coating film were satisfactory.

On the other hand, the green coloring compositions (DG-25 to 30, 33, and 34) of Reference Examples 1 to 6, 9, and 10 had low brightness and had problems with heat resistance and light resistance. In addition, the green coloring compositions (DG-31 and 32) of Reference Examples 7 and 8 had no problem in heat resistance and light resistance, but the brightness was lower than that in Examples.

<Method for producing green photosensitive coloring composition>
[Example 25]
(Green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a green photosensitive coloring composition (RG-1).
Green coloring composition (DG-1) 55.0 parts Acrylic resin solution 2 9.8 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd.) 4.6 parts Photopolymerization initiator (Ciba Japan Co., Ltd.) "Irgacure OXE02") 0.8 parts Propylene glycol monomethyl ether acetate 19.8 parts Cyclohexanone 10.0 parts

[Examples 26 to 48, Reference Examples 11 to 20]
(Green photosensitive coloring composition (RG-2-34))
Green photosensitive coloring compositions (RG-2 to RG34) were obtained in the same manner as in Example 25 except that the green coloring composition (DG-1) was changed to the green coloring composition shown in Table 2.

<Coating preparation and evaluation>
Evaluation of the lightness (color characteristics), heat resistance, light resistance, and voltage holding ratio of the green coating film produced using the obtained green photosensitive coloring composition (RG-1 to 34) was performed by the following methods. Table 2 shows the evaluation results.

(Brightness evaluation of coating film)
The green photosensitive coloring composition (RG-1 to 34) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain ultrahigh pressure mercury. Using a lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating at 220 ° C. for 30 minutes and allowing to cool, the brightness Y (C) of the obtained coated substrate was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The prepared coated substrate was adjusted to a chromaticity of x = 0.290 and y = 0.600 with a C light source after heat treatment at 220 ° C. As an alkali developer, sodium carbonate 1.5% by weight, sodium hydrogen carbonate 0.5% by weight, an anionic surface active agent (“Perex NBL” manufactured by Kao Corporation) 8.0% by weight and water 90% by weight Was used. Regarding brightness Y (C), it can be said that there is a clear difference if it is 0.2 points or more.

(Evaluation of heat resistance of coating film)
The green photosensitive coloring composition (RG-1 to 34) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain ultrahigh pressure mercury. Using a lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. Subsequently, it heated at 220 degreeC for 30 minute (s), and after standing to cool, the coating-film board | substrate was obtained. The prepared coated substrate was adjusted to a chromaticity of x = 0.290 and y = 0.600 with a C light source after heat treatment at 220 ° C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following three stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
○: ΔEab * is less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

(Light resistance evaluation of coating film)
A coated substrate is prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) is attached on the substrate, and irradiated with ultraviolet rays using a 470 W / m ² xenon lamp for 100 hours, and then the chromaticity ([ L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the above formula and evaluated according to the same criteria as for heat resistance.

(Voltage holding ratio evaluation)
The green photosensitive coloring composition (RG-1 to 34) was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the dry film thickness was 2.0 μm. The film was exposed to ultraviolet light with an integrated light quantity of 50 mJ / cm ² and developed with an alkaline developer at 23 ° C. to obtain a coated substrate. Next, after heating and cooling at 220 ° C. for 30 minutes, 0.05 parts of the coating film was scraped off from the obtained coated substrate, and then immersed in 1.5 parts of liquid crystal (MLC-2041 manufactured by Merck Co., Ltd.) After aging at 120 ° C. for 1 hour and centrifugation at 4000 rpm for 15 minutes, the supernatant liquid was collected to prepare a coating film extraction liquid crystal sample liquid.

On the other hand, two glass substrates having an ITO transparent electrode with an effective electrode size of 10 mm × 10 mm are arranged facing each other so that the ITO transparent electrode surfaces face each other, and a small cell is produced using a sealing agent so that the cell gap is 9 μm. did. A resist extraction liquid crystal sample solution is injected into the small cell between the cell gaps, a voltage of 5 V is applied at 60 ° C. for 60 μsec, and the cell voltage [V1] after the passage of 16.67 msec after the voltage is released Measured with a VHR-1S manufactured by Technica. The measurement was repeated 5 times, and the measured cell voltages were averaged. And using the obtained cell voltage, voltage retention (%) was calculated | required from the following formula, and it evaluated in the following three steps.
Voltage holding ratio (%) = ([V1] / 5) × 100
○: 95% or more △: 90% or more and less than 95% ×: less than 90%

As shown in Table 2, the colorant which is a feature of the present embodiment includes a green photosensitive coloring containing a phthalocyanine dye represented by the general formula (8A) and a quinophthalone dye represented by the general formula (6). The composition had excellent brightness and showed good results in heat resistance, light resistance, and voltage holding ratio.

On the other hand, the green photosensitive coloring compositions (RG-25 to 30, 33, and 34) of Reference Examples 11 to 16, 19, and 20 had low lightness and poor heat resistance and light resistance. Further, in Reference Examples 15 to 18 using CI Pigment Green 58, the voltage holding ratio was lower than that in Examples.

<Production of color filter>
First, the red photosensitive coloring composition and the blue photosensitive coloring composition used for preparation of a color filter were produced.

(Preparation of red photosensitive coloring composition (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A red colored composition (DR-1) was prepared by filtration through a 0.0 μm filter.
Red pigment (CI Pigment Red 254) 9.6 parts Red Pigment (CI Pigment Red 177) 2.4 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin Solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, a mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).
Red coloring composition (DR-1) 42.0 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907" manufactured) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

(Preparation of blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A blue colored composition (DB-1) was produced by filtration through a 0.0 μm filter.
Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple Pigment (CI Pigment Violet 23) 4.8 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).
Blue coloring composition (DB-1) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907", manufactured by 2.0) Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part 45.1 parts ethylene glycol monomethyl ether acetate

(Production of color filter)
A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (RR-1) was applied onto the substrate with a spin coater to form a colored coating. The film was irradiated with ultraviolet rays of 150 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 220 ° C. for 20 minutes to obtain a red filter segment. Formed. Here, the red filter segment was adjusted to a chromaticity of x = 0.640 and y = 0.330 in a C light source (hereinafter also used for green and blue) after heat treatment at 220 ° C. Further, by the same method, the green filter segment is adjusted to chromaticity of x = 0.290, y = 0.600 using the green photosensitive coloring composition (RG-6), and the blue filter segment is Each filter segment was formed using a blue photosensitive coloring composition (RB-1) so that the chromaticity of x = 0.150 and y = 0.060 was obtained, thereby obtaining a color filter.

By using the green photosensitive coloring composition (RG-6), it was possible to increase the brightness of the color filter, and it could be suitably used without any other physical properties.

<< Embodiment VII >>
Hereinafter, “PGMAC” means propylene glycol monomethyl ether acetate. The weight average molecular weight (Mw) of the resin and the method for measuring the contrast ratio are as follows.

<Weight average molecular weight (Mw) of resin>
The weight average molecular weight (Mw) of the resin was measured using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, TSK-GEL SUPER HZM-N connected in series as a column, and THF as a solvent. The molecular weight in terms of polystyrene.

<Contrast ratio>
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)
Therefore, when scattering occurs due to the colorant in the coating film, the luminance when orthogonal is increased, and the contrast ratio is lowered.
A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion.

First, a method for producing quinophthalone dye [A1] and quinophthalone dye [A2], binder resin solution, resin-type dispersant solution, quinophthalone pigment [B], and aluminum phthalocyanine pigment used in Examples and Reference Examples, and fine pigments The method for producing, the method for producing the green coloring composition and the red coloring composition, and the method for producing the green photosensitive coloring composition and the red photosensitive coloring composition will be described.

<Method for producing quinophthalone dye [A1]>
[Quinophthalone dye (A1-1)]

6. 2.3 parts of 6-iso-propyl-2-methylquinoline, 2.5 parts of naphthalene dicarboxylic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.1 parts of product. The yield was 67%. The product was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 366 (molecular weight 365.4).

[Quinophthalone dye (A1-2)]

Bromination of a dye obtained by reacting 8- (1,3-dioxane-2-yl) methyl-2-methylquinoline and naphthalenedicarboxylic acid with N-bromosuccinimide in the same manner as quinophthalone dye (A1-1) To obtain a quinophthalone dye (A1-2). The product was identified as a target product by identifying the compound with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics).

[Quinophthalone dye (A1-3-14)
The corresponding 2-methylquinolines and naphthalenecarboxylic anhydride were reacted in the same manner as for quinophthalone dye (A1-1) to obtain quinophthalone dyes (A1-3 to 14). The product was identified as a target product by identifying the compound with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics).

<Method for producing quinophthalone dye [A2]>
[Quinophthalone dye (A2-1)]

10.8 parts of 6-iso-propyl-2-methylquinoline, 12.1 parts of trimellitic anhydride, and 60 parts of benzoic acid were mixed and reacted at 200 ° C. for 7 hours. The purified yellow solid was washed with dimethylformamide to obtain 14 g of a yellow product. To 5 g of the yellow product, 0.2 g of pyridine and o-dichlorobenzene were added, and then 3.8 parts of thionyl chloride were allowed to act. After distilling off under reduced pressure, 1.76 g of 3-amino-2-propanol was added, The mixture was allowed to react for a period of time, cooled, washed with hexane, dried, and column purified with silica gel to obtain a yellow powder. As for the structure, the compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics) and confirmed to be the target product.

[Quinophthalone dye (A2-2)]

5-Bromo-8- (1,3-dioxane-2-yl) methyl-2-methylquinoline and phthalic anhydride were reacted in the same manner as in the quinophthalone dye (A2-1) to obtain a yellow powder. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics) and confirmed to be the target product.

[Quinophthalone dye (A2-3 to 16)]
The corresponding 2-methylquinolines and phthalic anhydrides were reacted in the same manner as for the quinophthalone dye (A2-1) to obtain quinophthalone dyes (A2-3 to 16). The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics) and confirmed to be the target product.

The structures of the produced quinophthalone dye [A1] and quinophthalone dye [A2] are shown in Table 1.

<Method for producing binder resin solution>
(Acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of benzyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add PGMAC to the previously synthesized resin solution so that the nonvolatile content is 20% by mass Thus, an acrylic resin solution 1 (resin solution 1) was obtained. The weight average molecular weight (Mw) was 26000.

(Acrylic resin solution 2)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. A mixture of 18.2 parts of methacrylate, 53 parts of methyl methacrylate, and 2.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (equivalent of glycidyl group), and 6 parts at 120 ° C. The reaction was continued for a period of time, and the reaction was terminated when the acid value of the solid content reached 0.5 to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (equivalent of generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMAC was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. Thus, an acrylic resin solution 2 (resin solution 2) was obtained. The weight average molecular weight (Mw) was 19000.

<Production of resin-type dispersant solution>
(Resin Dispersant Solution 1)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 80 parts of n-butyl methacrylate and 120 parts of benzyl methacrylate and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 30 parts of pyromellitic anhydride, 242 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was completed to obtain a resin-type dispersant 1. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, a resin-type dispersant solution 1 (dispersant 1) was prepared. The weight average molecular weight (Mw) was 9,500.

(Resin Dispersant Solution 2)
A resin-type dispersant (“BYK-LPN6919” manufactured by Big Chemie) was diluted with PGMAC to prepare a resin-type dispersant solution 2 (dispersant 2) having a nonvolatile content of 20% by weight.

<Method for producing quinophthalone pigment [B]>
(Production of quinophthalone pigment (B-1))
First, according to the synthesis method described in JP-A-2008-81666, compound (1) was obtained.

Subsequently, 100 parts of compound (1), 70 parts of 2,3-naphthalenedicarboxylic anhydride and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was heated to 180 ° C. and reacted for 4 hours. The formation of the quinophthalone pigment (B-1) represented by the following formula (50) and the disappearance of the starting compound (1) were confirmed by TOF-MS. Further, after cooling to room temperature, the reaction mixture was added to 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 120 parts of quinophthalone pigment (B-1). Mass spectrometry by TOF-MS confirmed that it was a quinophthalone pigment (B-1).

(Production of quinophthalone pigment (B-2))
First, compound (2) was obtained by the same method as the synthesis of compound (1) according to the synthesis method described in JP-A-2008-81666 using quinophthalone pigment (B-1) as a raw material.

Subsequently, 100 parts of compound (2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, heated to 180 ° C., and reacted for 4 hours. The formation of quinophthalone pigment (B-2) and the disappearance of the starting compound (2) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 120 parts of quinophthalone pigment (B-2) represented by the following formula (51). Mass spectrometry by TOF-MS confirmed that it was a quinophthalone pigment (B-2).

<Method for producing aluminum phthalocyanine pigment>
(Aluminum phthalocyanine pigment (C-1))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this was added 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), and the temperature was raised and refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of an aluminum phthalocyanine pigment (C-1) represented by the following formula (53).

(Aluminum phthalocyanine pigment (C-2))
In a reaction vessel, add 100 parts of aluminum phthalocyanine pigment (C-1) represented by formula (53) and 49.5 parts of diphenyl phosphate to 1000 parts of methanol, heat to 40 ° C., and react for 8 hours. I let you. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of an aluminum phthalocyanine pigment (C-2) represented by the following formula (54).

(Aluminum phthalocyanine pigment (C-3))
In a reaction vessel, add 1000 parts of methanol, 100 parts of aluminum phthalocyanine pigment (C-1) represented by formula (53) and 43.2 parts of diphenylphosphinic acid, and heat to 40 ° C. for 8 hours. Reacted. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 112 parts of an aluminum phthalocyanine pigment (C-3) represented by the following formula (55).

<Pigment refinement method>
(Yellow colorant (PY-1))
100 parts of quinophthalone pigment (B-1), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of a yellow colorant (PY-1) were obtained. The average primary particle size was 31.3 nm.

(Yellow colorant (PY-2))
40 parts of quinophthalone pigment (B-2), C.I. I. 60 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a yellow colorant (PY-2) were obtained. The average primary particle size was 36.8 nm.

(Yellow colorant (PY-3))
C. I. 100 parts of Pigment Yellow 138 (trade name Paliotor Yellow K0961HD, manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of a colorant (PY-3) were obtained. The average primary particle size was 35.5 nm.

(Yellow colorant (PY-4))
Metal complex yellow pigment C.I. I. 500 parts of Pigment Yellow 150 (LANXESS "E4GN"), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C for 6 hours. Next, this kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a yellow colorant (PY-4) was obtained. The obtained pigment had a volume average primary particle size of 28.3 nm.

(Yellow colorant (PY-5))
Isoindoline yellow pigment C.I. I. 500 parts of Pigment Yellow 139 (“Pariotol Yellow D1819” manufactured by BASF), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C. for 6 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a yellow colorant (PY-5) was obtained. The obtained pigment had a volume average primary particle size of 29.3 nm.

(Green colorant (PG-1))
Green pigment C.I. I. Pigment Green 58 (zinc phthalocyanine, DIC Corporation “First Gain Green A110”) 500 parts, sodium chloride 1500 parts, and diethylene glycol 250 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) at 120 ° C. for 8 hours. Kneaded. Next, this kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green colorant (PG-1) was obtained. The obtained pigment had a volume average primary particle size of 25.2 nm.

(Green colorant (PG-2))
Green pigment C.I. I. 500 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 100 ° C. for 2 hours. . Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of a green colorant (PG-2) was obtained. The obtained pigment had a volume average primary particle size of 26.6 nm.

(Green colorant (PG-3))
500 parts of green pigment (CI Pigment Green 7, “Lionol Green Y-101” manufactured by Toyo Ink Mfg. Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol are added to a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). Charged and kneaded at 120 ° C. for 8 hours. Next, this kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green colorant (PG-3) was obtained. The obtained pigment had a volume average primary particle size of 33.1 nm.

(Red colorant (PR-1))
500 parts of red pigment (CI Pigment Red 177, “Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals), 1500 parts of sodium chloride, and 250 parts of diethylene glycol, 1 gallon kneader (manufactured by Inoue Seisakusho) And kneaded at 120 ° C. for 8 hours. Next, this kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a red colorant (PR-1) was obtained. The obtained pigment had a volume average primary particle size of 28.3 nm.

(Blue colorant (PB-1))
100 parts of an aluminum phthalocyanine pigment (C-1), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. A colorant (PB-1) was obtained. The average primary particle size was 30.4 nm.

(Blue colorant (PB-2))
A blue colorant (PB-2) is obtained by the same salt milling method as the blue colorant (PB-1) except that the aluminum phthalocyanine pigment (C-1) is changed to the aluminum phthalocyanine pigment (C-2). It was. The average primary particle size was 31.2 nm.

(Blue colorant (PB-3))
The blue colorant (PB-3) was obtained by the same salt milling method as the blue colorant (PB-1) except that the aluminum phthalocyanine pigment (C-1) was changed to the aluminum phthalocyanine pigment (C-3). It was. The average primary particle size was 29.5 nm.

(Blue colorant (PB-4))
500 parts of blue pigment (CI Pigment Blue 15: 6, “Heliogen Blue L-6700F” manufactured by BASF), 2500 parts of sodium chloride, and 250 parts of diethylene glycol are charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel. And kneading at 100 ° C. for 2 hours. Next, this kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of a blue colorant (PB-4) was obtained. The obtained pigment had a volume average primary particle size of 26.6 nm.

(Blue colorant (PB-5))
500 parts of α-type copper phthalocyanine-based cyan pigment (CI Pigment Blue 15: 1, “Lionol Blue 7120-V” manufactured by Toyo Ink Co., Ltd.), sodium chloride: 2500 parts, and diethylene glycol: 250 parts made of stainless steel A 1 gallon kneader (manufactured by Inoue Seisakusho) was charged and kneaded at 100 ° C. for 2 hours. Next, this kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of a blue colorant (PB-5) was obtained. The obtained pigment had a volume average primary particle size of 35.2 nm.

Table 2 shows the obtained colorants.

<Method for Producing Green Coloring Composition (DG-1)>
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. Filtration through a 0.0 μm filter gave a green colored composition (DG-1).
Green colorant (PG-1) 10.0 parts Resin-type dispersant solution 2 10.0 parts Acrylic resin solution 1 40.0 parts PGMAC 40.0 parts

<Method for producing red coloring composition (DR-1)>
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0.0 μm filter to obtain a red coloring composition (DR-1).
Red colorant (PR-1) 3.3 parts Red colorant (Pigment Red 254) 6.7 parts “IRGAPHOR RED B-CF” manufactured by Ciba Specialty Chemicals
Resin-type dispersant solution 2 10.0 parts Acrylic resin solution 1 40.0 parts PGMAC 40.0 parts

<Method for producing green photosensitive coloring composition (RG-1)>
A mixture having the following composition was uniformly stirred and mixed, and then filtered through a 1 μm filter to prepare a photosensitive colored composition (RG-1).
Coloring composition (DG-1) 60.0 parts Acrylic resin solution 1 15.0 parts (resin solution 1)
Photopolymerizable monomer A 3.0 parts (“Aronix M402” manufactured by Toagosei Co., Ltd.)
1.6 parts of photopolymerization initiator ("Irgacure 379" manufactured by Ciba Japan)
Cyclohexanone 20.4 parts

<Method for producing red photosensitive coloring composition (RR-1)>
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1 μm filter to prepare a photosensitive colored composition (RR-1).
Coloring composition (DR-1) 60.0 parts Acrylic resin solution 1 15.0 parts (resin solution 1)
Photopolymerizable monomer A 3.0 parts (“Aronix M402” manufactured by Toagosei Co., Ltd.)
1.6 parts of photopolymerization initiator ("Irgacure 379" manufactured by Ciba Japan)
Cyclohexanone 20.4 parts

[Example 1]
(Coloring composition (P-1))
The mixture consisting of the following components was stirred for 0.5 hours so as to be uniform while being heated at 50 ° C. Thereafter, using 0.5 mm diameter zirconia beads, the mixture was dispersed for 0.5 hours in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), filtered through a 5 μm filter, and colored composition (P- 1) was produced.
Quinophthalone dye (A1-1) 5.0 parts Quinophthalone dye (A2-1) 5.0 parts Acrylic resin solution 1 50.0 parts (Resin solution 1)
Cyclohexanone 40.0 parts

[Examples 2 to 24, Reference Examples 1 and 2]
(Coloring composition (P-2 to 24 and P-46, 47))
A colored composition (P-1) was prepared in the same manner as in the colored composition (P-1) except that the quinophthalone dye, the resin-type dispersant solution, the acrylic resin solution, the type of solvent, and the amount (parts by weight) were changed as shown in Table 3. P-2 to 24) and a colored composition (P-46, 47) were prepared. In addition, when using a coloring agent together, the total amount of a coloring agent is 10 parts in all the coloring compositions.

Abbreviations in Table 3 are shown below.
Organic solvent / anone: cyclohexanone

[Example 25]
(Coloring composition (P-25))
The mixture consisting of the following components was stirred and mixed at 50 ° C. so as to be uniform, and then Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. After dispersion for 5 hours, the mixture was filtered through a 5 μm filter to prepare Colored Composition 22 (P-22).
Quinophthalone dye (A1-1) 2.5 parts Quinophthalone dye (A2-1) 2.5 parts Yellow colorant (PY-1) 5.0 parts Resin-type dispersant solution 1 10.0 parts (Dispersant 1)
Acrylic resin solution 1 40.0 parts (resin solution 1)
Cyclohexanone 40.0 parts

[Examples 26 to 45, Reference Examples 3 to 8]
(Coloring compositions (P-26 to 45 and P-48 to 53))
Colored composition in the same manner as the colored composition (P-25) except that the quinophthalone dye, pigment, resin-type dispersant solution, acrylic resin solution, solvent type and blending amount (parts by weight) were changed as shown in Table 4. (P-26 to 45) and a colored composition (P-48 to 53) were prepared. In addition, when using a coloring agent together, the total amount of a coloring agent is 10.0 parts in all the coloring compositions.

Abbreviations in Table 4 are shown below.
Organic solvent / anone: cyclohexanone

[Evaluation of coloring composition]
The contrast ratio and coloring power of the colored compositions (P-1 to 53) were evaluated by the following methods. The results are shown in Tables 5 and 6.

(Contrast ratio evaluation)
The obtained colored composition (P-1 to 53) is applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes and allowed to cool. Thus, a coated substrate was produced. The initial contrast ratio (initial CR) of the obtained coated substrate was measured. Under the present circumstances, the coating condition of a spin coater was adjusted so that the film thickness measured using surface shape measuring apparatus "Dektak8 (made by Veeco)" might suit 1 micrometer, and the coating film was produced.

(Coloring power evaluation)
The obtained colored composition (P-1 to 32 and P-34 to 53) and the green colored composition (DG-1) were mixed to prepare a green colored composition. Note that the mixing ratio of the coloring composition (P-1 to 32 and P-34 to 53) and the green coloring composition (DG-1) is x = 0 with the C light source when the coated substrate is prepared. The ratio was selected to match the chromaticity of .290, y = 0.600. Next, the obtained mixed colored composition was applied using a spin coater so that y = 0.600 with a C light source, and then dried at 70 ° C. for 20 minutes to obtain a coated substrate. The coloring power was evaluated based on the measurement result of the film thickness of the obtained coated substrate. The film thickness of the obtained coating film was measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)”. The results were judged according to the following criteria. It can be said that the smaller the film thickness that gives the desired chromaticity, the greater the coloring power, and the better.
A: Less than 2.40 [μm]
○: 2.40 or more and less than 2.56 [μm]
×: 2.56 or more [μm]

Further, the obtained colored composition (P-33) and the red colored composition (DR-1) were mixed to prepare a red colored composition. The blending ratio of the coloring composition (P-33) and the red coloring composition (DR-1) is such that x = 0.640 and y = 0.334 with a C light source when a coated substrate is prepared. The ratio was selected so as to match the chromaticity. Next, the obtained mixed colored composition was applied using a spin coater so that x = 0.640 using a C light source, and then dried at 70 ° C. for 20 minutes to obtain a coated substrate. The coloring power was evaluated based on the measurement result of the film thickness of the obtained coated substrate. The film thickness of the obtained coating film was measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)”. The results were judged according to the following criteria. It can be said that the smaller the film thickness that gives the desired chromaticity, the greater the coloring power, and the better.
A: Less than 1.52 [μm]
○: 1.52 or more and less than 1.60 [μm]
×: 1.60 or more [μm]

As shown in Table 5 and Table 6, the coloring composition that is a feature of the present embodiment contains a quinophthalone dye [A1] having a specific structure and a quinophthalone dye [A2] having a specific structure. The ratio was very high and the coloring power was excellent.

In particular, when the colorant further contained a pigment as in Examples 25 to 45 (coloring composition (P-25 to 45)), the contrast ratio was even better.
Further, when Example 3 (Coloring Composition (P-3)) and Examples 6 and 7 (Coloring Composition (P-6, 7)) were compared, Coloring Composition (P- 6 and 7) were even better in terms of contrast ratio.

On the other hand, when the quinophthalone dye [A2] was not included as in the colored composition of the reference example, the contrast ratio was low due to the influence of fluorescence. When the quinophthalone dye [A1] was not included, the fluorescence was not emitted and the contrast ratio was good, but the coloring power was very bad.

[Example 46]
(Photosensitive coloring composition (R-1))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1 μm filter to prepare a photosensitive colored composition (R-1).
Coloring composition (P-1) 60.0 parts Acrylic resin solution 1 15.0 parts (resin solution 1)
Photopolymerizable monomer A 3.0 parts (“Aronix M402” manufactured by Toagosei Co., Ltd.)
1.6 parts of photopolymerization initiator ("Irgacure 379" manufactured by Ciba Japan)
Cyclohexanone 20.4 parts

[Examples 47 to 90, Reference Examples 9 to 16]
(Photosensitive coloring composition (R-2 to 53))
Other than changing the color composition, acrylic resin solution, photopolymerizable monomer, photopolymerization initiator, sensitizer, organic solvent, type of antioxidant, and amount (parts by weight) as shown in Tables 7-9 Prepared photosensitive colored compositions (R-2 to 53) in the same manner as the photosensitive colored composition (R-1).

The abbreviations in Tables 7-9 are shown below. Photopolymerizable monomer / photopolymerizable monomer A: Dipentaerythritol hexaacrylate / pentaacrylate mixture (“Aronix M402” manufactured by Toagosei Co., Ltd.) Photopolymerization initiator / initiator A: 2- (dimethylamino) -2-[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (“Irgacure 379” manufactured by Ciba Japan) ・ Initiator B: Ethanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (“Irgacure OXE02” manufactured by Ciba Japan) Sensitizer / sensitization Agent A: 4,4′-diethylaminobenzophenone (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) Antioxidant / antioxidant A: Hindered phenol antioxidant Pentae Lithritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate / antioxidant B: sulfur-based antioxidant 3,3′-thiodipropanoic acid dioctadecyl / antioxidant C: phosphorus Antioxidant tris [2,4-di- (tert) -butylphenyl] phosphine / antioxidant D: hindered amine antioxidant bis (2,2,6,6-tetramethyl-4-piperidyl) Sebacate / antioxidant E: salicylate-based antioxidant p-octylphenyl salicylate organic solvent / anone: cyclohexanone

[Evaluation of photosensitive coloring composition]
The photosensitive coloring compositions (R-1 to 53) were evaluated for contrast ratio, coloring power, and brightness by the following methods. The results are shown in Tables 10-12.

(Contrast ratio evaluation)
The obtained photosensitive coloring composition (R-1 to 53) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and then released. The coated substrate was produced by cooling. The initial contrast ratio (initial CR) of the obtained coated substrate was measured. Under the present circumstances, the coating condition of a spin coater was adjusted so that the film thickness measured using surface shape measuring apparatus "Dektak8 (made by Veeco)" might suit 1 micrometer, and the coating film was produced.

(Coloring power evaluation)
The resulting photosensitive coloring composition (R-1 to 32 and R-34 to 53) and the green photosensitive coloring composition (RG-1) were mixed to prepare a green photosensitive coloring composition. . The mixing ratio of the green photosensitive coloring composition (R-1 to 53) and the green photosensitive coloring composition (RG-1) is such that x = 0.290 with a C light source when a coated substrate is prepared. The ratio was selected so as to match the chromaticity of y = 0.600. Next, the obtained mixed colored composition was applied using a spin coater so that y = 0.600 with a C light source, and then dried at 70 ° C. for 20 minutes to obtain a coated substrate. The coloring power was evaluated based on the measurement result of the film thickness of the obtained coated substrate. The film thickness of the obtained coating film was measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)”. The results were judged according to the following criteria. It can be said that the smaller the film thickness that gives the desired chromaticity, the greater the coloring power, and the better.
A: Less than 3.91 [μm]
○: 3.91 or more and less than 4.17 [μm]
×: 4.17 or more [μm]

The resulting photosensitive coloring composition (R-33) and the red photosensitive coloring composition (RR-1) were mixed to prepare a red coloring composition. The blending ratio of the photosensitive coloring composition (R-33) and the red photosensitive coloring composition (RR-1) is such that x = 0.640, y with a C light source when a coated substrate is produced. The ratio was selected to match the chromaticity = 0.334. Next, the obtained mixed colored composition was applied using a spin coater so that x = 0.640 using a C light source, and then dried at 70 ° C. for 20 minutes to obtain a coated substrate. The coloring power was evaluated based on the measurement result of the film thickness of the obtained coated substrate. The film thickness of the obtained coating film was measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)”. The results were judged according to the following criteria. It can be said that the smaller the film thickness that gives the desired chromaticity, the greater the coloring power, and the better.
A: Less than 2.47 [μm]
○: 2.47 or more and less than 2.61 [μm]
×: 2.61 or more [μm]

(Brightness evaluation of coating film)
The photosensitive coloring composition (R-1 to 32, R-34 to 53) is applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes. Then, the coated substrate was prepared by heating at 220 ° C. for 30 minutes and allowing to cool. The brightness Y (C) of the obtained coating film was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The prepared coated substrate was adjusted to a chromaticity of x = 0.290 and y = 0.600 with a C light source after heat treatment at 220 ° C.
The lightness of the photosensitive coloring composition (R-33) was evaluated by the above-described method except that the chromaticity was adjusted to chromaticity of x = 0.640 and y = 0.334.

As shown in Tables 10 to 12, the photosensitive coloring composition containing the quinophthalone dye [A1] having a specific structure and the quinophthalone dye [A2] having a specific structure as a colorant that is a feature of the present embodiment is The contrast ratio was very high and the coloring power was excellent.

In particular, as in Examples 70 to 90 (photosensitive coloring composition (R-25 to 45)), when a pigment was further contained, the contrast ratio was even better.
Further, when Example 48 (photosensitive coloring composition (R-3)) and Examples 51 and 52 (photosensitive coloring composition (R-6, 7)) were compared, the photosensitivity containing the resin-type dispersant was compared. The colored composition (R-6, 7) was better from the viewpoint of contrast ratio.

On the other hand, when the quinophthalone dye [A2] was not included as in the photosensitive coloring composition of the reference example, the result was that the contrast ratio was low due to the influence of fluorescence. When the quinophthalone dye [A1] was not included, the fluorescence was not emitted and the contrast ratio was good, but the coloring power was very bad.

Further, regarding the lightness, all of the photosensitive coloring compositions of the present embodiment had higher lightness than the photosensitive coloring composition of the reference example, and were good results. Furthermore, the lightness of the photosensitive coloring composition (R-30, 31 to 33, 36 to 45) containing zinc phthalocyanine pigment or aluminum phthalocyanine pigment as the pigment was very high and excellent.

[Production of color filter]
First, the blue photosensitive coloring composition used for preparation of a color filter was produced. The photosensitive coloring composition (R-33) was used for red, and the photosensitive coloring composition (R-41) was used for green.

(Preparation of blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A blue colored composition (DB-6) was produced by filtration through a 0.0 μm filter.
Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple Pigment (CI Pigment Violet 23) 4.8 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 35.0 parts PGMAC 52.0 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).
Blue coloring composition (DB-6) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907", manufactured by 2.0) Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part 45.1 parts ethylene glycol monomethyl ether acetate

(Production of color filter)
A black matrix is patterned on a glass substrate, and a red photosensitive coloring composition (R-33) is applied on the substrate with a spin coater at a C light source (hereinafter also used for green and blue) x = 0.640, The coating was applied to a thickness such that y = 0.334 to form a colored coating. The film was irradiated with ultraviolet rays of 300 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, x = 0.150, y = 0 using the blue photosensitive coloring composition (RB-1) so that the green photosensitive coloring composition (R-41) becomes y = 0.600. The green color filter segment and the blue color filter segment were formed to obtain 0.060, respectively, and a color filter was obtained.

By using the red photosensitive coloring composition (R-33) and the green photosensitive coloring composition (R-41), it was possible to produce a color filter having a high contrast ratio and high brightness.

<< Embodiment VIII >>
<Method for producing quinophthalone dye>
Kinophthalone dye 1

6.8 parts of 8-hydroxyquinaldine, 9 parts of 4-ethoxyphthalic anhydride and 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 5 hours. After allowing to cool, 50 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 400 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 6.1 parts of product. The yield was 42%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 333.23 (molecular weight 333.10), which confirmed the intended product.

Kinophthalone dye 2

9.7 parts of 8-hydroxyquinaldine, 10 parts of 4-hydroxyphthalic anhydride, 30 parts of benzoic acid and 40 parts of methyl benzoate were mixed and stirred at 200 ° C. for 5 hours. After allowing to cool, 50 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 400 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.4 parts of product. The yield was 18%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 305.15 (molecular weight 305.07), confirming the target product.

Example 1
Kinophthalone dye 3

3.0 parts of quinophthalone dye 1 is mixed with 30 parts of N, N-dimethylacetamide, 0.4 parts of sodium hydroxide and 2.1 parts of 1-bromo-2-ethylhexane are further mixed, and at 105 ° C. for 1 hour. Stir. After allowing to cool, 20 parts of chloroform and 100 parts of water were added to extract the organic layer. The organic layer was added with 5 parts of magnesium sulfate, dried, filtered and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 5/1 (volume ratio)) to obtain 3.2 parts of the product. The yield was 81%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 445.33 (molecular weight: 445.23), which confirmed the intended product.

Example 2
Kinophthalone dye 4

8- (2-ethylhexyloxy) -5-phenyl-2-methylquinoline (3.0 parts), 4-ethoxyphthalic anhydride (1.7 parts) and benzoic acid (30 parts) were mixed and stirred at 200 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.4 parts of product. The yield was 75%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 521.35 (molecular weight 521.26), which was confirmed to be the target product.

Example 3
Kinophthalone dye 5

3.0 parts of quinophthalone dye 1 was mixed with 30 parts of N, N-dimethylacetamide, 0.4 parts of sodium hydroxide and 1.7 parts of 1-bromodiethyl ether were further mixed, and the mixture was stirred at 105 ° C. for 1 hour. After allowing to cool, 20 parts of chloroform and 100 parts of water were added to extract the organic layer. The organic layer was added with 5 parts of magnesium sulfate, dried, filtered and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 5/1 (volume ratio)) to obtain 3.0 parts of product. The yield was 83%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 405.32 (molecular weight 405.16).

Example 4
Kinophthalone dye 6

3.0 parts of quinophthalone dye 2 is mixed with 30 parts of N, N-dimethylacetamide, 0.9 parts of sodium hydroxide and 4.2 parts of 1-bromo-2-ethylhexane are further mixed, and at 105 ° C. for 1 hour. Stir. After allowing to cool, 20 parts of chloroform and 100 parts of water were added to extract the organic layer. The organic layer was added with 5 parts of magnesium sulfate, dried, filtered and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 7/1 (volume ratio)) to obtain 4.1 parts of the product. The yield was 78%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 529.45 (molecular weight 529.32), which confirmed the intended product.

Example 5
Kinophthalone dye 7

8- (2-ethylhexyloxy) -2-methylquinoline (3.0 parts), 4-cyclohexyloxyphthalic anhydride (2.7 parts) and benzoic acid (30 parts) were mixed and stirred at 200 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 4.6 parts of product. The yield was 83%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 499.29 (molecular weight 499.27), which confirmed the intended product.

Example 6
Kinophthalone dye 8

8- (2-ethylhexyloxy) -2-methylquinoline (3.0 parts), 4-phenoxyphthalic anhydride (2.7 parts) and benzoic acid (30 parts) were mixed and stirred at 200 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 4.4 parts of product. The yield was 81%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 493.41 (molecular weight 493.23).

Example 7
Quinophthalone dye 9

3.0 parts of quinophthalone dye 2 is mixed with 30 parts of N, N-dimethylacetamide, 0.9 part of sodium hydroxide and 5.3 parts of 1-bromo-4-trifluoromethylbenzene are further mixed at 105 ° C. Stir for 1 hour. After allowing to cool, 20 parts of chloroform and 100 parts of water were added to extract the organic layer. The organic layer was added with 5 parts of magnesium sulfate, dried, filtered and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 5/1 (volume ratio)) to obtain 4.5 parts of product. The yield was 78%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 593.58 (molecular weight 593.11), confirming the target product.

Example 8
Quinophthalone dye 10

8- (2-ethylhexyloxy) -2-methylquinoline (3.0 parts), 4- (2-ethoxyethoxy) phthalic anhydride (2.6 parts) and benzoic acid (30 parts) were mixed and stirred at 200 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 4.3 parts of product. The yield was 79%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 489.46 (molecular weight 489.25), which confirmed the intended product.

Example 9
Quinophthalone dye 11

Mixing 3.0 parts of 8- (2-ethylhexyloxy) -2-methylquinoline, 3.1 parts of 4- (2- (1,3-dioxan-2-yl) ethoxy) phthalic anhydride and 30 parts of benzoic acid And stirred at 200 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 4.3 parts of product. The yield was 74%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 531.56 (molecular weight 531.26), which confirmed the intended product.

Example 10
Quinophthalone dye 12

3.0 parts 2-ethylhexyl 5- (2-methylquinolin-8-yloxy) butanoate and 2.2 parts methyl 4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-yloxy) butanoate, benzoic acid 30 parts of the acid was mixed and stirred at 200 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.6 parts of product. The yield was 72%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 603.62 (molecular weight: 603.28), which confirmed the intended product.

Example 11
Quinophthalone dye 13

3.0 parts of quinophthalone dye 2 is mixed with 30 parts of N, N-dimethylacetamide, 0.9 part of sodium hydroxide and 6.6 parts of 2-ethylhexyl 4-bromobutyric acid are further mixed and stirred at 105 ° C. for 1 hour. did. After allowing to cool, 20 parts of chloroform and 100 parts of water were added to extract the organic layer. The organic layer was added with 5 parts of magnesium sulfate, dried, filtered and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 4.9 parts of product. The yield was 71%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 701.67 (molecular weight 701.39), which confirmed the intended product.

Example 12
Kinophthalone dye 14

3.0 parts of quinophthalone dye 2 is mixed with 30 parts of N, N-dimethylacetamide, 0.9 part of sodium hydroxide and 6.9 parts of 2-ethylhexyl 5-bromovaleric acid are further mixed, and at 105 ° C. for 1 hour. Stir. After allowing to cool, 20 parts of chloroform and 100 parts of water were added to extract the organic layer. The organic layer was added with 5 parts of magnesium sulfate, dried, filtered and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 5.0 parts of the product. The yield was 70%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 729.83 (molecular weight 729.42), which confirmed the intended product.

Example 13
Quinophthalone dye 15

3.0 parts of 2-ethylhexyl 5- (2-methylquinolin-8-yloxy) pentanoate and 3.0 parts of 2-ethylhexyl 4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-yloxy) butanoate 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.5 parts of product. The yield was 65%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 715.90 (molecular weight: 715.41).

Example 14
Quinophthalone dye 16

3.0 parts of quinophthalone dye 2 is mixed with 30 parts of N, N-dimethylacetamide, 0.9 parts of sodium hydroxide and 8.0 parts of 2- (2-ethylhexyloxy) ethyl 5-bromovaleric acid are further mixed. , And stirred at 105 ° C. for 1 hour. After allowing to cool, 20 parts of chloroform and 100 parts of water were added to extract the organic layer. The organic layer was added with 5 parts of magnesium sulfate, dried, filtered and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 5.9 parts of product. The yield was 73%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 817.88 (molecular weight 817.48), confirming the target product.

Example 15
Kinophthalone dye 17

3.0 parts of quinophthalone dye 2 is mixed with 30 parts of N, N-dimethylacetamide, 0.9 parts of sodium hydroxide, 2- (3- (2-ethylhexyloxy) propoxy) ethyl 5-bromovaleric acid 9.3 The parts were further mixed and stirred at 105 ° C. for 1 hour. After allowing to cool, 20 parts of chloroform and 100 parts of water were added to extract the organic layer. The organic layer was added with 5 parts of magnesium sulfate, dried, filtered and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 6.4 parts of product. The yield was 71%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 919.91 (molecular weight 919.54), which confirmed the intended product.

Example 16
Quinophthalone dye 18

3. 3.0 parts of quinophthalone dye 1 is mixed with 30 parts of N, N-dimethylacetamide, 0.5 parts of sodium hydroxide, 2-ethylhexyl 7-oxabicyclo [4.1.0] heptane-3-carboxylate 5 parts were further mixed and stirred at 105 ° C. for 1 hour. After allowing to cool, 20 parts of chloroform and 100 parts of water were added to extract the organic layer. The organic layer was added with 5 parts of magnesium sulfate, dried, filtered and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)) to obtain 3.9 parts of product. The yield was 75%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 587.51 (molecular weight 587 · 29), which was confirmed to be the target product.

Example 17
Quinophthalone dye 19

4-hydroxy-3- (2-methylquinolin-8-yloxy) cyclohexanecarboxylate-2-ethylhexyl (3.0 parts), 5- (2-phenoxyethoxy) phthalic anhydride (2.1 parts) and benzoic acid (30 parts) were mixed. And stirred at 200 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.6 parts of product. The yield was 73%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 679.76 (molecular weight 679.31), which confirmed the intended product.

Example 18
Quinophthalone dye 20

Bis (2-ethylhexyl) 4-hydroxy-5- (2-methylquinolin-8-yloxy) cyclohexane-1,2-dicarboxylic acid 3.0 parts and 5- (2-phenoxyethoxy) phthalic anhydride 1.5 parts 30 parts of benzoic acid were mixed and stirred at 200 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.4 parts of product. The yield was 78%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 835.88 (molecular weight 834.43), which confirmed the intended product.

Example 19
Quinophthalone dye 21

Bis (2-ethylhexyl) 4-hydroxy-5- (2-methylquinolin-8-yloxy) cyclohexane-1,2-dicarboxylic acid 3.0 parts, 1.4-phenoethoxyphthalic anhydride 1.4 parts, benzoic acid 30 parts The parts were mixed and stirred at 200 ° C. for 5 hours. After allowing to cool, 100 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 200 parts of methanol, stirred for 1 hour, and then collected by suction filtration. Drying overnight in a vacuum dryer (40 ° C.) gave 3.2 parts of product. The yield was 75%. The compounds were identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 819.72 (molecular weight 819.43), which was confirmed to be the target product.

Reference example 1
Kinophthalone dye 22

The synthesis was carried out based on the synthesis method of dye (IV) described in JP-A-6-009891.

Reference example 2
Kinophthalone dye 23

Disperse Yellow 54 was used.

<Preparation of acrylic resin solution>
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Addition to prepare an acrylic resin solution.

Here, the polymerization average molecular weight (Mw) of the acrylic resin was measured using a TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. The weight average molecular weight (Mw) in terms of polystyrene.

<Pigment production method>
(Preparation of blue pigment 1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Ink Manufacturing Co., Ltd.) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. did. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of blue pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 79 nm.

(Preparation of purple pigment 1)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of violet pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 28 nm.

(Preparation of green pigment 1)
Phthalocyanine green pigment C.I. I. Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC Corporation) was used as it was on the market. The average primary particle diameter of the green pigment 1 was 22 nm.

(Preparation of blue pigment 2)
In a reaction vessel, 1250 parts of n-amyl alcohol and 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were mixed and stirred. To this was added 266 parts of DBU (1,8-Diazabicclo [5.4.0] undec-7-ene), the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine (AlPc—Cl). Next, 100 parts of chloroaluminum phthalocyanine was added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. After stirring at 40 ° C. for 3 hours, this sulfuric acid solution was poured into 24,000 parts of cold water at 3 ° C. The resulting blue precipitate was filtered, washed with water and dried to obtain 92 parts of hydroxyaluminum phthalocyanine (AlPc—OH).

In a reaction vessel, 2000 parts of N, N-dimethylformamide, 100 parts of AlPc-OH, and 53.9 parts of diphenyl phosphate were added. After reacting at 85 ° C. for 3 hours, this solution was poured into 12000 parts of water. The reaction product was filtered, washed with 24,000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 123 parts of aluminum phthalocyanine (AlPc-DPP). 50 parts of this AlPc-DPP pigment, 150 parts of sodium chloride, and 25 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 6 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A blue pigment 2 was obtained. The average primary particle diameter of the obtained pigment was 29 nm.

(Preparation of yellow pigment 1)
Quinophthalone yellow pigment C.I. I. 270 parts of Pigment Yellow 138 (trade name Paliotor Yellow K0961HD, manufactured by BASF), 1350 parts of sodium chloride, and 500 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 250 parts of yellow pigment 3 were obtained. The average primary particle diameter of the obtained pigment was 36 nm.

(Preparation of yellow pigment 2)
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of yellow pigment 2 were obtained. The average primary particle diameter of the obtained pigment was 67 nm.

(Preparation of yellow pigment 3)
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 (“Irgafore Yellow 2R-CF” manufactured by Ciba Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. did. Next, this kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 490 parts of Yellow Pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 92 nm.

(Preparation of red pigment 1)
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“Chromophthalred A2B” manufactured by Ciba Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 54 nm.

(Preparation of colored composition Q-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition Q-1 was produced by filtration using a filter.
Quinophthalone dye 1: 11.0 parts Acrylic resin solution prepared previously: 40.0 parts Cyclohexanone: 48.0 parts

(Preparation of colored compositions Q-2 to 23)
Hereinafter, colored compositions Q-2 to 23 were produced in the same manner as colored composition Q-1, except that quinophthalone dye 1 was replaced with the quinophthalone dye shown in Table 1.

(Preparation of colored composition DP-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition (DP-1) was produced by filtration using a filter. Blue Pigment 1 (CI Pigment Blue 15: 6): 11.0 parts previously prepared acrylic resin solution: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin-type dispersant (Ciba・ "EFKA4300" manufactured by Japan Co., Ltd.): 1.0 part

(Preparation of colored compositions DP-2 to 8)
Hereinafter, colored compositions DP-2 to 8 were produced in the same manner as colored composition DP-1, except that blue pigment 1 was replaced with the pigment shown in Table 2.

[Examples 20 to 38, Reference Examples 3 to 9]
<Coating foreign matter test of coloring compositions Q-1 to 23 and DP-5 to 7>
The evaluation was performed by preparing a test substrate and counting the number of particles. The coloring composition was applied onto the transparent substrate so that the dried coating film was about 2.0 μm, and heated in an oven at 230 ° C. for 20 minutes to obtain a test substrate. The evaluation was performed by observing the surface using a metal microscope “BX60” manufactured by Olympus System. The magnification is 500 times, and the number of particles that can be observed in any five fields of view through transmission is counted. In the following evaluation results, ◎ and ○ are good, Δ is a level that does not cause a problem in use although there are many foreign matters, and × indicates coating unevenness (spots) due to foreign matters.
A: Less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or less, Table 3 shows the results.

<Spectroscopic evaluation of colored compositions Q-1 to 23 and DP-5 to 7>
A coating film was prepared on a transparent substrate so that the transmittance at a wavelength of 450 nm was 5%, and the transmittance values at 500 nm and 550 nm at that time were measured. The higher the transmittance at 500 nm and 550 nm, the better the brightness. In the following evaluation results, the transmittance of 500 nm and 550 nm when the quinophthalone dye and the yellow pigment are standardized is ◯ is 99% or more, Δ is 97 or more and less than 99%, and × is less than 97%. It is preferable that it is 99% or more because the brightness becomes high. The results are shown in Table 3 below. Also, the spectra of the coating films of Example 1 and Reference Examples 1 and 4 are shown in FIGS.

Examples 20 to 38 had good results with few coating film foreign matters. In addition, Examples 20 to 38 were the results of excellent spectral characteristics, and showed spectral shapes with high brightness. Reference Examples 5 to 8 showed spectral shapes in which the transmittance at 550 nm was relatively good, but the transmittance at 500 nm was low and no improvement in brightness was expected.

Reference Examples 3 to 7 using a dye having a hydroxyl group in the quinoline ring are compared with the spectral shapes of Examples 20 to 38 using a dye having no hydroxyl group (for example, Example 20 in FIGS. 1 to 3 and Reference Example). (Spectrum of coating films 3 and 6) A dye having a low transmittance at 500 nm and having a hydroxyl group in the quinoline ring cannot be expected to improve the brightness.

<Method for producing blue resist material>
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a blue resist material B-1.
Colored composition (DP-1): 48.0 parts Colored composition (DP-2): 12.0 parts Previously prepared acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (new “NK ester ATMPT” manufactured by Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts propylene glycol monomethyl ether acetate (PGMAC): 23 .2 parts

[Example 39]
<Adjustment of resist material G-1>
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a green resist material (G-1).
Colored composition (DP-3): 18.0 parts Colored composition (Q-1): 42.0 parts Previously prepared acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (new “NK ester ATMPT” manufactured by Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts propylene glycol monomethyl ether acetate (PGMAC): 23 .2 parts

[Examples 40 to 82, Reference Examples 10 to 18]
<Adjustment of resist materials G-2 to 45, R-1 to 4, Y-1 to 4>
Hereinafter, the resist materials G-2 to 45, R-1 to 4, Y-1 to Y are the same as the resist material G-1, except that the types and blending amounts of the coloring compositions are changed as shown in Tables 5 and 6. 4 was obtained.

<Evaluation of resist material>
The following tests were conducted for the color characteristics (Y: brightness), coating foreign matter, heat resistance, and light resistance of the obtained resist materials G-1 to 45, R-1 to 4, and Y-1 to 4, respectively. I went there. The results of the test are shown in Table 6.

<Color characteristics (Y: brightness)>
On a glass substrate, with a C light source, resist materials G-1 to 45 were coated with a resist material having a thickness such that x = 0.264 and y = 0.600, and this substrate was heated at 230 ° C. for 20 minutes. . The resist materials R-1 to R-4 were coated with a resist material so that x = 0.340 and y = 0.640, and this substrate was heated at 230 ° C. for 20 minutes. The resist materials Y-1 to Y-4 were coated with a resist material so that x = 0.440 and y = 0.506, and this substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).
The results are shown in Table 6 below.

<Coating foreign matter test>
A resist material was applied on the transparent substrate so that the dried coating film became about 2.5 μm, and the whole surface was exposed to ultraviolet light, and then heated in an oven at 230 ° C. for 20 minutes and allowed to cool to obtain an evaluation substrate. The evaluation was performed by observing the surface using a metal microscope “BX60” manufactured by Olympus System. The magnification is 500 times, and the number of particles that can be confirmed in any five visual fields through transmission is counted. In the following evaluation results, ◎ and ○ are good, Δ is a level that does not cause a problem in use although there are many foreign matters, and × indicates coating unevenness due to the foreign matters.
A: Less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or less, Table 6 shows the results.

<Film heat resistance test>
A resist material is applied on a transparent substrate so that the dry coating thickness is about 2.5 μm, and after UV exposure through a mask having a predetermined pattern, an alkali developer is sprayed to remove uncured parts. Thus, a desired pattern was formed. Then, after heating in an oven at 230 ° C. for 20 minutes and allowing to cool, the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source is microspectrophotometric. Measurement was performed using a meter (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Further, as a heat resistance test, the sample was heated in an oven at 230 ° C. for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured. Using the measured color difference value, the color difference ΔEab * was calculated by the following formula, and the heat resistance of the coating film was evaluated in the following four stages. Moreover, if evaluation is more than (triangle | delta), it is a level which is satisfactory practically. ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
：: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0 Δ: ΔEab * is 3.0 or more and less than 5.0 X: ΔEab * is 5.0 or more, Table 6 The results are shown in.

<Coating light resistance test>
A test substrate was prepared in the same procedure as the coating heat resistance test, and the chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source was measured with a microspectrophotometer (Olympus Optics). Measurement was performed using “OSP-SP200” manufactured by the company. Thereafter, the substrate was placed in a light resistance tester (“SUNTSTCPS +” manufactured by TOYOSEIKI) and left for 500 hours. After removing the substrate, measure chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source, and calculate the color difference ΔEab * in the same manner as the coating film heat resistance test. Then, the solvent resistance of the coating film was evaluated according to the same criteria as the coating film heat resistance test. Moreover, if evaluation is more than (triangle | delta), it is a level which is satisfactory practically.
The results are shown in Table 6 below.

<Film resistance test>
A test substrate was prepared in the same procedure as the coating heat resistance test, and the chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source was measured with a microspectrophotometer (Olympus Optics). Measurement was performed using “OSP-SP200” manufactured by the company. Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After removing the substrate, measure chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source, and calculate the color difference ΔEab * in the same manner as the coating film heat resistance test. Then, the solvent resistance of the coating film was evaluated according to the same criteria as the coating film heat resistance test. Moreover, if evaluation is more than (triangle | delta), it is a level which is satisfactory practically.
The results are shown in Table 6 below.

The resist materials (G-1 to 19, G-25 to 43, R-1 to 3, and Y-1 to 3) of Examples 39 to 82 have brightness (Y), coating film foreign matter, heat resistance, light resistance, Good results in solvent resistance were shown.

On the other hand, the resist materials (G-20 to G-24, G-44, 45, R-4, Y-4) of Reference Examples 10 to 16 were used in Examples 39 to 82 (G-1 to 19, G). The brightness (Y) was lower than that of −25 to 43, R−1 to 3, and Y−1 to 3).

[Example 83]
<Color filter (CF-1)>
A black matrix is patterned on a glass substrate, and a red resist material (R-1) is applied on the substrate with a spin coater to a film thickness such that x = 0.640, y = 0.340. A colored coating was formed. The coating was irradiated with 300 mJ / cm ² of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, the green resist material (G-15) is formed to a thickness such that x = 0.264 and y = 0.600, and x = 0.150 using the blue resist material (B-1). The film was applied to a thickness such that y = 0.060, and a green filter segment and a blue filter segment were formed to obtain a color filter (CF-1).

<Production of liquid crystal display device>
A transparent ITO electrode layer was formed on the obtained RGB color filter, and a polyimide alignment layer was formed thereon. A color display device was produced on the other surface of this glass substrate in combination with a three-wavelength CCFL light source of a polarizing plate. Formed. On the other hand, a TFT array and a pixel electrode were formed on one surface of another (second) glass substrate, and a polarizing plate was formed on the other surface. The two glass substrates prepared in this way are arranged facing each other so that the electrode layers face each other, and are aligned using spacer beads while keeping the distance between the two substrates constant, and an opening for injecting a liquid crystal composition The periphery was sealed with a sealant so as to leave After injecting the liquid crystal composition from the opening, the opening was sealed. A liquid crystal display device thus produced was combined with a three-wavelength CCFL light source of a backlight unit to produce a color display device.

[Examples 83 to 87, Reference Examples 19 and 20]
(Color filter (CF-2 to 7))
Hereinafter, the color filters (CF-2˜) of Examples 83 to 87 and Reference Examples 19 and 20 were combined with the resist material shown in Table 8 and a three-wavelength CCFL light source in the same manner as the production of the color filter (CF-1). 7) and a color display device were produced.

Thereafter, in the obtained color display device, a light source was emitted to display a color image, and the brightness (Y) of each color filter segment portion was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 8.

Comparing Examples 84 and 85 with Reference Example 19, the color filter formed using the quinophthalone dye of this embodiment has at least one filter segment (green or red) as compared with the filter segment using the conventional pigment. In the color filter (CF-2, 3) using the quinophthalone dye of this embodiment, the brightness was improved. As a result, the brightness of the white display increased, and the improvement of the performance as a color filter was confirmed.

Furthermore, it was confirmed that the brightness of the color filter (CF-1) formed using the quinophthalone dye of this embodiment for both green and red in Example 83 was further improved, and as a result, the brightness of white display was increased. It was.

In addition, when Example 87 and Reference Example 20 are compared, the color filter formed using the quinophthalone dye of the present embodiment has at least one filter segment (yellow) as compared with a filter segment containing a conventionally used pigment. However, the brightness of the color filter (CF-6) containing the quinophthalone dye of this embodiment also improved, and as a result, the brightness of white display increased, and the improvement of the performance as a color filter was confirmed.

Furthermore, when all of green, red, and yellow of Example 86 contained the color filter dye of this embodiment (CF-5), it was confirmed that the brightness was further improved, and as a result, the brightness of white display was increased. .

From the above results, by using the quinophthalone dye of this embodiment and a coloring composition containing the same, it is possible to increase the brightness of the color filter, and it can be suitably used without any other physical properties.

Claims (16)

Contains a colorant, a binder resin, and a solvent,
The said coloring agent contains the coloring agent represented by General formula (1), The coloring composition for color filters characterized by the above-mentioned.

Here, in the general formula (1), R ¹ to R ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. An aryl group that may have a group, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts, an optionally substituted phthalimidomethyl group, or a substituent The sulfamoyl group which may have a group is shown. The adjacent groups of R ¹ to R ⁴ and / or R ¹⁰ to R ¹³ together form an aromatic ring which may have a substituent. 2. The color filter coloring composition according to claim 1, wherein the colorant represented by the general formula (1) is a colorant selected from the general formulas (1A) to (1C).

In the general formulas (1A) to (1C), R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , and R ⁴⁴ to R ⁶⁰ are each independently: a hydrogen atom; a halogen atom; A good alkyl group; an alkoxyl group that may have a substituent; an aryl group that may have a substituent; —SO ₃ H, —COOH, and monovalent to trivalent metal salts of these acidic groups; A salt; an optionally substituted phthalimidomethyl group; or an optionally substituted sulfamoyl group. The coloring composition for a color filter according to claim 2, wherein the coloring agent further contains a coloring agent selected from the general formulas (8A) and (8B).

Here, in the general formula (8A), X ₁ to X ₄ may each independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. A good cycloalkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent Or an arylthio group which may have a substituent. Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group. Z represents a hydroxyl group, a chlorine atom, —OP (═O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ . R ₁ to R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or It represents an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring. m ₁ to m ₄ and n ₁ to n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , m ₄ + n ₄ are each 0 to 4 may be the same or different.

Here, in the general formula (8B), X ₅ to X ₁₂ may each independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. A good cycloalkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent Or an arylthio group which may have a substituent. Y ₅ to Y ₁₂ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group. L represents —O—SiR ₆ R ₇ —O—, —O—SiR ₆ R ₇ —O—SiR ₈ R ₉ —O—, or —O—P (═O) R ₁₀ —O—, R ₆ to R ₁₀ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. The aryloxy group which may have a group is represented. m ₅ to m ₁₂ and n ₅ to n ₁₂ each independently represent an integer of 0 to 4, and m ₅ + n ₅ , m ₆ + n ₆ , m ₇ + n ₇ , m ₈ + n ₈ , m ₉ + n ₉ , m ₁₀ + n ₁₀ , m ₁₁ + n ₁₁ , and m ₁₂ + n ₁₂ are each 0 to 4, and may be the same or different. The color composition for a color filter according to claim 2, wherein the colorant further contains a dispersant. The dispersant is a urethane prepolymer having isocyanate groups at both ends, which is obtained by reacting a hydroxyl group of a vinyl polymer (A) having two hydroxyl groups at one end region with an isocyanate group of diisocyanate (B). A pigment dispersant obtained by reacting an isocyanate group of a polymer (E) with a primary and / or secondary amino group of an amine compound containing at least a polyamine (C), wherein the vinyl polymer (A) is ethylene The colored composition for a color filter according to claim 4, wherein the copolymer composition contains an ethylenically unsaturated monomer (a1) having at least one of an oxide chain or a propylene oxide chain. The said coloring agent contains the coloring agent represented by General formula (6) further, The coloring composition for color filters of Claim 2 characterized by the above-mentioned.

In the general formula (6), R ₁ to R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, Or, -O-R ₇ is represented. R ₇ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, R ₁ to R ₆ are not all hydrogen atoms. Contains a colorant, a binder resin, and a solvent,
The said coloring agent contains the coloring agent represented by General formula (6), The coloring composition for color filters characterized by the above-mentioned.

In the general formula (6), R ₁ to R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, Or, -O-R ₇ is represented. R ₇ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, R ₁ to R ₆ are not all hydrogen atoms. The color composition for a color filter according to claim 7, wherein the colorant further contains a colorant selected from the general formulas (8A) and (8B).

Here, in the general formula (8A), X ₁ to X ₄ may each independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. A good cycloalkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent Or an arylthio group which may have a substituent. Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group. Z represents a hydroxyl group, a chlorine atom, —OP (═O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ . R ₁ to R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or It represents an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring. m ₁ to m ₄ and n ₁ to n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , m ₄ + n ₄ are each 0 to 4 may be the same or different.

Here, in the general formula (8B), X ₅ to X ₁₂ may each independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. A good cycloalkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent Or an arylthio group which may have a substituent. Y ₅ to Y ₁₂ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group. L represents —O—SiR ₆ R ₇ —O—, —O—SiR ₆ R ₇ —O—SiR ₈ R ₉ —O—, or —O—P (═O) R ₁₀ —O—, R ₆ to R ₁₀ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. The aryloxy group which may have a group is represented. m ₅ to m ₁₂ and n ₅ to n ₁₂ each independently represent an integer of 0 to 4, and m ₅ + n ₅ , m ₆ + n ₆ , m ₇ + n ₇ , m ₈ + n ₈ , m ₉ + n ₉ , m ₁₀ + n ₁₀ , m ₁₁ + n ₁₁ , and m ₁₂ + n ₁₂ are each 0 to 4, and may be the same or different. The color composition for color filters according to claim 7 or 8, wherein the colorant further contains a colorant represented by the general formula (7).

In the general formula (7), R ₁ to R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group. Or represents —O—R ₁₁ . R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R ₇ to R ₁₀ are each independently a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, carboxyl group, substituted or unsubstituted And a sulfoamide group, a substituted or unsubstituted heterocyclic residue, —SR ₁₂ , —O—R ₁₂ , or —COO—R ₁₂ . R ₁₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. Contains a colorant, a binder resin, and a solvent,
The said coloring agent contains the coloring agent represented by general formula (7A), The coloring composition for color filters characterized by the above-mentioned.

In the general formula (7A), R ₁ to R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group. Or represents —O—R ₁₁ . R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R ₇ to R ₁₀ are each independently a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, carboxyl group, substituted or unsubstituted And a sulfoamide group, a substituted or unsubstituted heterocyclic residue, —SR ₁₂ , —O—R ₁₂ , or —COO—R ₁₂ . R ₁₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. However, at least one of R ₇ to R ₁₀ is —O—R ₁₂ . The coloring composition for a color filter according to claim 10, wherein the coloring agent represented by the general formula (7A) is a coloring agent represented by the general formula (7B).

Here, in the general formula (7B), R ₁₃ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ₁₄ to R ₁₇ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or —O—R ₁₈ . R ₁₈ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. However, at least one of R ₁₄ to R ₁₇ is —O—R ₁₈ . Furthermore, the said colorant contains a yellow colorant further, The colorant for color filters of Claim 1, 7, 10 or 11 characterized by the above-mentioned. The yellow colorant is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, and C.I. I. The colorant for a color filter according to claim 12, wherein the colorant is selected from the group consisting of CI Pigment Yellow 185. The color composition for a color filter according to any one of claims 1 to 11, further comprising a colorant selected from the group consisting of a green colorant, a blue colorant and a red colorant. The coloring composition for a color filter according to any one of claims 1 to 11, further comprising a photopolymerizable monomer and / or a photopolymerization initiator. A color filter comprising a filter segment formed using the color filter coloring composition according to any one of claims 1 to 15.

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