JP2019113676A - Color filter coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for a color filter excellent in brightness, coloring power, contrast, heat resistance and electrical characteristics. A coloring composition for a color filter containing a coloring agent, a resin, and a solvent, wherein the coloring agent is a quinophthalone compound (A1) represented by the general formula (1). It is solved by a coloring composition for a color filter, which comprises a quinophthalone compound (A2) represented by one or more selected from the group consisting of the general formulas (2), (3) and (4). [Selection diagram] None

Description

The present invention relates to a coloring composition for color filters used in the production of color filters used in color liquid crystal display devices, color imaging devices, organic EL display devices and the like, and color filters.

  On a color filter used in a color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. It is formed. In order to sufficiently obtain the performance of the transparent electrode and the alignment film, the formation process needs to be generally performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher, and the color filter is required to have heat resistance.

  The important quality items required for color filters include contrast ratio and lightness. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state) when light leaks or light must be transmitted (ON) In the state, the transmitted light is attenuated, resulting in a blurred screen. Therefore, in order to realize a high quality liquid crystal display device, it is essential to increase the contrast ratio.

  In addition, when a color filter with low lightness is used, the light transmittance is low and the screen is dark. In order to obtain a bright screen, it is necessary to increase the number of backlights serving as light sources. However, from the viewpoint of suppressing power consumption, increasing the brightness of color filters has become a trend. Furthermore, from the viewpoint of improving the image quality of color liquid crystal display devices and organic EL display devices, there is also a growing demand for color filters to have high color gamut such as Adobe RGB standard, DCI standard, and BT 2020 standard.

  Moreover, a voltage holding ratio is mentioned as a parameter | index showing the display performance of a liquid crystal display device. The liquid crystal is an extremely high insulating material, and when the polar compound remaining in the coloring composition for color filter dissolves into the liquid crystal cell, the voltage between the electrodes decreases, leading to a decrease in the voltage holding ratio, causing display unevenness. It causes generation, poor alignment, and the like, which causes the performance of the liquid crystal display device to deteriorate. Therefore, the color composition for color filters is required to have non-solubility in liquid crystals.

Also, a color imaging device represented by C-MOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device: Charge Coupled Device), etc. has a red filter layer (R) on its light receiving element, In general, it is common to dispose color filters having filter segments of the primary colors of the additive mixture of the green filter layer (G) and the blue filter layer (B) for color separation. In addition, since high sensitivity can be obtained compared to primary color filters, color filters having cyan, magenta and yellow (CMY) filter segments corresponding to complementary colors of red, green and blue are also often used. Complementary color filters are often employed in video cameras and the like in which auxiliary light sources such as flash are difficult to use.
In recent years, also in color filters used in color imaging devices, demands for high transmittance, that is, lightness, thinning, and high reliability are increasing.

  In the production of a green filter segment, a yellow pigment is used as a coloring agent for toning, and in particular, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment Yellow 185 is mainly used. Among them, a quinophthalone compound C.I. I. Pigment Yellow 138 is often used. However, C.I. I. Although pigment yellow 138 is relatively excellent in lightness, further improvement in lightness is desired. Also, in recent years, there has been a strong demand for higher contrast for color filters. I. Pigment Yellow 138 has a problem that the contrast is low. Furthermore, C.I. I. In pigment yellow 138, when heat is applied at 230 ° C. or more, crystal precipitation occurs, and there is also a problem of poor heat resistance. Therefore, conventional C.I. I. There is a need for a yellow colorant that is more excellent in brightness, contrast, and heat resistance than Pigment Yellow 138.

  In order to solve such problems, various developments have been made with respect to quinophthalone compounds. For example, Patent Document 1 discloses a structure having excellent coloring power as a novel quinophthalone compound and providing high brightness and contrast ratio. Further, Patent Document 2 describes a quinophthalone compound containing a fluorine atom. However, the colorants containing these quinophthalone compounds are not satisfactory in heat resistance and coloring power.

  Also, in order to achieve higher brightness and a wider color reproduction area in the production of red filter segments, red pigments and C.I. I. It has been generally accepted that yellow pigments such as C.I. Pigment Yellow 138, 139, and 185 are used in combination as colorants (Patent Documents 3 to 5). However, for example, C.I. I. Although pigment yellow 138 is relatively excellent in lightness, it has a problem that it has no coloring power and the color filter becomes thick. Conversely, C.I. I. In pigment yellow 139, there is a problem that the coloring power is high but the lightness and contrast ratio are low, and at present it is not possible to sufficiently achieve all the items required for the color filter.

JP 2012-226110 A Unexamined-Japanese-Patent No. 2016-145282 JP 2007-133131 A JP, 2011-095491, A JP 2008-81566 A

An object of the present invention is to achieve the following objects.
That is, an object of the present invention is to provide a coloring composition for a color filter which is excellent in lightness, coloring power, contrast, heat resistance and electrical properties.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have been able to solve the problems described above by using a colorant for a color filter in which two or more types of quinophthalone compounds having a specific structure are used in combination. The present invention has been achieved. In the quinophthalone compound, it was confirmed that the maximum absorption wavelength is longer than that of the conventional PY 138 by using naphthalene in which both the 2-position phthalic acid modification site and the 8-position phthalimide site are introduced with a halogen. The quinophthalone compound has two maximum absorption wavelengths between 400 and 500 nm in the absorption spectrum, but of the two maximum absorption wavelengths of a certain quinophthalone compound, the maximum absorption wavelength on the longer wavelength side is another quinophthalone compound. It has been found that coloring power and lightness can be increased by using the two quinophthalone compounds in combination when located between two maximum absorption wavelengths. Furthermore, it was also found that the heat resistance and the electrical properties are improved by introducing a halogen, so that the solubility of the dye is lowered and the particle growth by heat becomes difficult.

  That is, the present invention is a coloring composition for a color filter containing a colorant, a resin, and a solvent, wherein the colorant is a quinophthalone compound (A1) represented by the following general formula (1): The present invention relates to a coloring composition for a color filter comprising a quinophthalone compound (A2) represented by one or more selected from the group consisting of the general formulas (2), (3) and (4).

General formula (1)
[In general formula (1), X, Y and Z each independently represent a halogen atom. n and m show the number of 0-6, and the sum total of (n + m) is three or more. p shows the number of 0-5. ]

General formula (2)
General formula (3)
General formula (4)
[In the general formula (2) ~ (4), R 18 ~R 30, R 31 ~R 45, R 46 ~R 60 are each independently a hydrogen atom, a halogen atom, an alkyl which may have a substituent A group, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent is shown. ]

  Moreover, this invention relates to the coloring composition for color filters whose content of a quinophthalone compound (A1) is 3 mass%-90 mass% with respect to the sum total of a quinophthalone compound (A1) and a quinophthalone compound (A2).

  In addition, the present invention is further directed to a color filter characterized in that it further comprises a dye derivative, and the dye derivative is a quinophthalone compound (B) having a sulfo group, or a metal salt or alkyl ammonium salt of a sulfo group. It relates to a coloring composition.

  In addition, the present invention further includes any one or more selected from the group consisting of phthalocyanine pigments, isoindoline pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, and azo pigments. The present invention relates to a coloring composition for a filter.

  The present invention also relates to a coloring composition for color filter, which further comprises a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention also relates to a color filter comprising a filter segment formed from the coloring composition for color filter on a substrate.

  According to the present invention, the quinophthalone compound (A1) represented by the general formula (1) and the quinophthalone compound represented by one or more selected from the group consisting of the general formulas (2), (3) and (4) By containing (A2), it is possible to provide a coloring composition for color filters which is excellent in lightness, coloring power, contrast, heat resistance and electrical properties, and a color filter using the same.

  Hereinafter, the present invention will be described in detail. In the present specification, "CI" means a color index.

<Colorant>
The present invention relates to a quinophthalone compound (A1) represented by the general formula (1) and a quinophthalone compound represented by one or more selected from the group consisting of the general formulas (2), (3) and (4) as a coloring agent It is characterized by using (A2) in combination.

<Quinophthalone Compound (A1)>
The quinophthalone compound (A1) represented by the general formula (1) will be described.

General formula (1)
[In general formula (1), X, Y and Z each independently represent a halogen atom. n and m show the number of 0-6, and the sum total of (n + m) is three or more. p shows the number of 0-5. ]

  Here, as the halogen atom, fluorine, chlorine, bromine and iodine can be mentioned. As a halogen atom, chlorine or bromine is preferable, and chlorine is particularly preferable.

  X and Y each represent a naphthalene ring substituent. Also, Z represents a quinaldine substituent.

  The quinophthalone compound (A1) of general formula (1) used for the coloring agent of this invention shows the substituent number n of a halogen atom, and m shows 0-6, and the sum total of (n + m) is three or more. It may be a mixture of compounds having different numbers of substituents, for example, a mixture of a compound in which n is 3 and a compound in which n is 4. Moreover, p shows 0-5.

  The number of substituents (n + m) of the halogen atom is 3-12. When (n + m) is large, the contrast and heat resistance are improved. From the viewpoint of coloring power and lightness, 5 to 10 are preferable.

  The halogen distribution width is preferably 6 or less from the viewpoint of lightness and contrast. Here, the "halogen distribution width" is a distribution of the number of halogens substituted in the quinophthalone compound represented by the general formula (1). The halogen distribution width is obtained by integrating the signal intensity (each peak value) of a molecular ion peak (each peak value) corresponding to the molecular weight of the quinophthalone compound of each component according to the number of halogen substitution in the mass spectrum obtained by mass analysis The value (total peak value) was calculated, and the number of peaks in which the ratio of each peak value to the total peak value was 1% or more was counted as a halogen distribution width.

  The quinophthalone compound (A1) is represented by general formula (5), 8-aminoquinaldine, 2,3-naphthalenedicarboxylic acid anhydride represented by general formula (6), or 2, 2, It can be obtained by reacting 3-naphthalenedicarboxylic acid.

General formula (5)

General formula (6)
General formula (7)
[In the general formula (5) ~ (7), R 61 ~R 65, R 66 ~R 71, R 72 ~R 77 each independently represent a hydrogen atom, a halogen atom. ]

  The quinophthalone compound (A1) can also be obtained by halogenating the following compound (8). Further, after halogenating the compound (9), the 2,3-naphthalenedicarboxylic acid anhydride represented by the general formula (6) or the 2,3-naphthalenedicarboxylic acid represented by the general formula (7) is reacted Thus, naphthalenedicarboxylic acid anhydrides having different structures on the amino group side and the methyl group side of 8-aminoquinaldine can be condensed.

Compound (8)

Compound (9)

  In addition, the quinophthalone compound (A1) can be obtained by using a compound represented by the general formula (6) after obtaining a compound represented by the general formula (10) according to the synthesis method described in JP-A-2012-226110. It is also possible to react naphthalene dicarboxylic acid anhydride or 2,3-naphthalene dicarboxylic acid represented by the general formula (7).

General formula (10)
[In general formula (10), R _{78 to} R ₈₈ each independently represent a hydrogen atom or a halogen atom. ]

A halogenating agent is used in the synthesis of the quinophthalone compound (A1) and its intermediate. By halogenating agents are meant fluorinating agents, chlorinating agents, brominating agents and iodifying agents. For example, as the fluorinating agent, fluoroxy trifluoromethane, cesium fluoride sulfate, acetyl hypofluorite, N-fluorosulfonamide, diethylaminosulfur trifluoride, N-fluoropyridinium salt and the like can be mentioned. As a chlorinating agent, chlorine (Cl2), N-chlorosuccinimide, sulfuryl chloride, trichloroisocyanuric acid, sodium dichloroisocyanurate, 2,3,4,5,6,6-hexachloro-2,4-cyclohexadienone, 2,3,4,4,5,6-hexachloro-2,5-cyclohexadienone, N-chlorotriethyl ammonium chloride, benzeneselenenyl chloride and the like. As a brominating agent, bromine (Br ₂ ), N-bromosuccinimide, silver sulfate-bromine, tetramethylammonium tribromide, trifluoroacetyl hypobromide, dibromoisocyanuric acid, 2,4,4,6-tetrabromocyclohexene Thio-2,5-dienion, hydrogen bromide-dimethyl sulfoxide, N-bromosuccinimide-dimethylformamide, 2,4-diamino-1,3-thiazole hydrotribromide, 1,3-dibromo-5,5-dimethyl hydantoin, etc. Can be mentioned. Examples of the iodinating agent include iodine (I2), 1,3-diiodo-5,5-dimethylhydantoin, trifluoroacetyl hypoiodite, iodine-periodic acid, ethylene iodochloride, N-iodosuccinimide and the like.

  Specific examples of the quinophthalone compound (A1) used in the coloring composition of the present invention include those shown below, but the present invention is not limited thereto.

<Quinophthalone Compound (A2)>
The quinophthalone compound (A2) represented by the general formulas (2) to (4) will be described.

General formula (2)
General formula (3)
General formula (4)
[In the general formula (2) ~ (4), R 18 ~R 30, R 31 ~R 45, R 46 ~R 60 are each independently a hydrogen atom, a halogen atom, an alkyl which may have a substituent A group, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent is shown. ]

  Here, as a halogen atom, it is synonymous with what was demonstrated about the substituent of General formula (1).

  As the alkyl group which may have a substituent in the general formulas (2) to (4), a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isopropyl group, an tert-butyl group, a neopentyl group, n Trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, in addition to linear or branched alkyl groups such as hexyl group, n-octyl group, stearyl group, 2-ethylhexyl group, etc. 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, diethylaminoethyl group, benzyl group, 4-methylbenzyl Having a substituent such as 4-, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl and 2,4-dichlorobenzyl. Include the Kill group.

  Moreover, as an alkoxyl group which may have a substituent, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group, 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, etc., 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 The alkoxyl group which has substituents, such as a propoxy group and a benzyloxy group, is mentioned.

  In addition, as the aryl group which may have a substituent, in addition to aryl groups such as phenyl group, naphthyl group and anthranyl group, 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 And aryl groups having a substituent such as 5,8-trichloro-2-naphthyl, anthraquinonyl and 2-aminoanthraquinonyl.

As 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 And the above-mentioned 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.

Moreover, quinophthalone compound used in the color filter for coloring composition of the invention, R ₁₈ to R ₃₀ in the general formula (2) ~ (4), R 31 ~R 45, R 46 ~R 60 is a hydrogen atom or More preferably, it is a halogen atom.

  Specific examples of the quinophthalone compound (A2) used in the coloring composition of the present invention include those shown below, but the present invention is not limited thereto.

  In the coloring composition for color filters of the present invention, the content of the quinophthalone compound (A1) is 3 to 3 based on the total of the quinophthalone compound (A1) and the quinophthalone compound (A2) from the viewpoint of lightness, coloring power and contrast ratio. It is preferable that it is 90 mass%, More preferably, it is 10-70 mass%. As the proportion of the quinophthalone compound (A1) is larger, the heat resistance and the electrical properties are improved.

The quinophthalone compound (A2) used in combination with the quinophthalone compound (A1) has a maximum absorption wavelength on the long wavelength side of two maximum absorption wavelengths between the two maximum absorption wavelengths of the absorption spectrum of the quinophthalone compound (A1) It is preferable to select one having a high coloring power and lightness.
<Method for producing quinophthalone compound>
Although the quinophthalone compound used by this invention can be manufactured by the method of Unexamined-Japanese-Patent No. 4-226163 and 2012-226110, for example, it is not limited to these methods.

  Each of the quinophthalone compounds (A1) and (A2) used in the present invention exhibits a yellow hue, and by using other colorants in combination, yellow filter segments of the same color, and further, green filter segments, It can be a coloring composition for forming a red filter segment.

  In addition to the quinophthalone compound (A1) and the quinophthalone compound (A2), the coloring composition of the present invention can optionally contain various pigments and dyes conventionally known as coloring materials. The following are representative pigments and dyes that can be used in the present invention.

  Examples of red pigments that can be used in the present invention include C.I. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221, 224, 242, 246, 254, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 2 2, 283, 284, 285, 286, 287, or the diketopyrrolopyrrole pigment described in JP-A-2011-523433, the azo dye described in JP-A-2011-173971, and the like, but not particularly limited thereto. . In addition, red dyes such as xanthene dyes, azo dyes, disazo dyes, and anthraquinone dyes can also be used. Specifically, C.I. I. Salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289, 338 and the like can be mentioned.

  Orange pigments that can be used in the present invention are, for example, C.I. I. Pigment orange 38, 43, 71, or 73, but not limited thereto.

  Examples of yellow pigments that can be used in the present invention include C.I. I. Pigment yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 119, 120, 123, 125, 126, 127, 128, 129, 137, 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, 221, or the quinophthalone-based pigments described in Japanese Patent No. 4993026, etc. There may be mentioned, but not particularly limited thereto. In addition, yellow dyes such as quinoline, azo, disazo and methine dyes can also be used.

  Green pigments that can be used in the present invention are, for example, C.I. I. Pigment greens 7, 10, 36, 37, 58, JP 2008-19383 A, JP 2007-320986 A, JP 2004 70342 A, etc., and the like, and zinc phthalocyanine pigments and the like can be mentioned. It is not limited to.

  Blue pigments that can be used in the present invention are, for example, C.I. I. Pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP-A-2004-333817, Although the aluminum phthalocyanine pigment etc. which are described in the patent 4893859 grade | etc., Are mentioned, it is not limited in particular in these.

  Among the colorants, any of the yellow pigments can be used singly or in combination of two or more in view of the color characteristics of the quinophthalone compounds (A1) and (A2). The yellow pigment is more preferably a quinophthalone pigment, an isoindoline pigment, and an azo pigment.

  As the above-mentioned isoindoline based pigments, C.I. I. Pigment yellow 139 and 185, and as the above-mentioned azo pigments, C.I. I. Pigment yellow 150 is preferred.

  Among the colorants, one or more phthalocyanine pigments may be used alone as a green coloring composition in view of the color characteristics of the quinophthalone compounds (A1) and (A2). Is preferred.

  As said phthalocyanine type pigment, a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, or an aluminum phthalocyanine pigment is preferable. More preferably, C.I. I. Pigment Green 7, 36, 58, Patent No. 4893859, JP-A-2016-153481, JP-A-2017-197685, etc. are aluminum phthalocyanine pigments.

  Moreover, it can also be used as a red coloring composition in combination with a red pigment. As the red pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment and an azo pigment are preferable.

  As the above diketopyrrolopyrrole pigment, C.I. I. Pigment red 254, brominated diketopyrrolopyrrole pigments described in JP-A-2011-523433, and examples of the above anthraquinone pigments include C.I. I. Pigment red 177, and as the above-mentioned azo pigments, C.I. I. Pigment orange 38, C.I. I. Pigment red 176, C.I. I. Pigment red 242, C.I. I. Pigment Red 269, and the azo compounds described in JP-A-2011-173971 and JP-A-2012-229344.

<Finening of pigment>
The quinophthalone compounds (A1) and (A2) used in the coloring agent of the present invention are preferably used after being finely divided. The method of refining is not particularly limited, and any of wet grinding, dry grinding and solution precipitation methods can be used, for example, and as exemplified in the present invention, salt milling treatment by kneader method which is one of wet grinding Etc. to be miniaturized. The average primary particle size of the pigment determined by TEM (transmission electron microscopy) is preferably in the range of 5 to 90 nm. From the viewpoint of dispersion in an organic solvent and contrast ratio, a more preferable average primary particle size is in the range of 10 to 70 nm.

  In the salt milling process, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is heated while using a kneader such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill etc. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and at the time of salt milling, the pigment is crushed using the hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

  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 in terms of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, most preferably 300 to 1000% by mass, based on the total mass of the pigment (100% by mass), from both the processing efficiency and the 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 used. However, since the temperature rises during salt milling and the solvent is easily evaporated, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. 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% by mass, and most preferably 50 to 500% by mass, based on the total mass of the pigment (100% by mass).

  When the pigment is subjected to salt milling, a resin may be added as necessary. The type of resin to be 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 preferably solid at room temperature, preferably water insoluble, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 2 to 200% by mass based on the total mass of the pigment (100% by mass).

  In the colorant used in the present invention, the quinophthalone compound (A1) and the quinophthalone compound (A2) may be simply mixed at the time of dispersion, or may be ground and mixed by salt milling. By grinding and mixing the quinophthalone compound (A1) and the quinophthalone compound (A2) together, finer particles can be obtained and a high contrast ratio can be obtained as compared to when each of them is separately subjected to salt milling treatment and simple mixing. .

<Dye derivative>
The coloring composition for a color filter of the present invention preferably further comprises a dye derivative, and the dye derivative is a quinophthalone compound (B) having a sulfo group, or a metal salt or alkyl ammonium salt of a sulfo group.

  The quinophthalone compound (B) having a sulfo group is described.

  The quinophthalone compound is a compound skeleton having a skeleton represented by the chemical formula (11) in its molecular structure. As specific examples of quinophthalone compounds having a sulfo group, C.I. I. Commercially available dyes such as Acid Yellow 3, 5 and the like, and C.I. I. Pigment yellow 138, C.I. I. Solvent yellow 33, 114, 157, C.I. I. Besides the compounds obtained by sulfonation of commercially available pigments and dyes such as disperse yellow 54, 64, 67 etc. using known methods, the following may be mentioned, but the present invention is not limited thereto Absent.

Chemical formula (11)

Specific examples of the quinophthalone compound (B) used in the coloring composition for a color filter of the present invention include those shown below, but the present invention is not limited thereto. Further, the following exemplified compounds are a -SO ₃ H, it can be counter replaced easily metal salt or alkyl ammonium salt in a known manner.

The mass ratio to the dye derivative is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, based on the total amount of the colorant (100% by mass).
That is, when the ratio of the dye derivative is too small, the contrast tends to be low with high viscosity, and when the ratio of the dye derivative is too large, the lightness tends to be low at low lightness.

  In addition to the quinophthalone compound (B) as a pigment derivative, the coloring composition of the present invention can optionally contain various pigment derivatives conventionally known. Examples of dye derivatives include organic pigments, anthraquinones, acridones or triazines, compounds having a basic substituent, an acid substituent, or a phthalimidomethyl group which may have a substituent, for example, 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 2003-167112, JP-A 2004-091497, JP-A 2004-307854, JP-A 2007-156395, JP-A 2008-094873, JP-A 2008-094986 Publication No. 2008-095007 Publication No. 2008-19591 JP, it may be used those described in Japanese Patent No. 4585781 Patent Publication.

<Binder resin>
The coloring composition of the present invention can contain a binder resin. The binder resin used for the coloring composition of the present invention disperses, dyes, or penetrates a coloring agent, and includes thermoplastic resins and the like. In the case of using in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an acidic group-containing ethylenic unsaturated monomer. Furthermore, 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, when an active energy ray-curable resin having an ethylenically unsaturated double bond in a side chain is used as the alkali-developable colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the coloring agent is fixed, the heat resistance is improved, and the color fading (the deterioration of the spectral characteristics) due to the heat of the coloring agent can be suppressed. In addition, it also has the effect of suppressing aggregation and precipitation of the colorant component in the development step.

  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 range of 400 to 700 nm in the visible light range.

  The mass average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000, and more preferably in the range of 7,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for color filters, a colorant-adsorbing group, a carboxyl group acting as an alkali-soluble group during development, an aliphatic group acting as an affinity group for a colorant carrier and a solvent, The balance of the aromatic group is important for the dispersibility, permeability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mg KOH / g. If the acid value is less than 20 mg KOH / g, the solubility in a developer may be poor, and it may be difficult to form a fine pattern. If it exceeds 300 mg KOH / g, fine patterns may not be left.

  The binder resin is preferably used in an amount of 20 parts by mass or more based on 100 parts by mass of the coloring agent because the film forming property and the various resistances are good, the coloring agent concentration is high, and good color characteristics are expressed. It is preferable to use in an amount of 1000 parts by mass or less because it can be carried out.

  As a thermoplastic resin used for binder resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

As a vinyl type alkali soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer, resin which has acidic groups, such as a carboxyl group and a sulfone group, is mentioned, for example.
Specifically as an alkali-soluble resin, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or An isobutylene / (anhydride) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, in particular an acrylic resin having an acidic group, is preferably used because it is high in heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins in which an unsaturated ethylenic double bond is introduced by the method (i) or (ii) shown below.

[Method (i)]
As the method (i), for example, to a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers. And the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is added, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an unsaturated ethylenic double bond and a carboxyl group There is a way to introduce it.

  Examples of unsaturated ethylenic monomers having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxy butyl (meth) acrylate, And 3,4 epoxycyclohexyl (meth) acrylates, which may be used alone or in combination of two or more. Glycidyl (meth) acrylate is preferred from the viewpoint of the reactivity with the unsaturated monobasic acid in the next step.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted, etc. Monocarboxylic acids and the like can be mentioned, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, which may be used alone or in combination of two or more. I do not mind. The remaining anhydride is obtained by using tricarboxylic acid anhydride such as trimellitic acid anhydride or using tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride, if necessary, such as increasing the number of carboxyl groups. It is also possible to hydrolyze the group. In addition, unsaturated ethylenic double bonds can be further increased by using, as the polybasic acid anhydride, ethahydrophthalic anhydride having maleic unsaturated double bonds, or maleic anhydride.

  As a similar method of method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of the carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]
As method (ii), the unsaturated ethylenic monomer having a hydroxyl group is used, and the monomer of another unsaturated monobasic acid having a carboxyl group or the other monomer is copolymerized. There is a method of reacting the isocyanate group of the unsaturated ethylenic monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  As the unsaturated ethylenic monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol (Meth) acrylates or hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate may be mentioned, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and / or butylene oxide etc. to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylates to which (poly) 12-hydroxystearic acid or the like is added can also be used. From the viewpoint of coating foreign matter suppression, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferred.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethylisocyanate or 1,1-bis [(meth) acryloyloxy] ethylisocyanate, but are not limited thereto. Alternatively, two or more types can be used in combination.

(Thermosetting compound)
In the present invention, a thermosetting compound may be further included in combination with the thermoplastic resin which is a binder resin.

  As the thermosetting compound, for example, an epoxy compound and / or a resin, an oxetane compound and / or a resin, a benzoguanamine compound and / or a resin, a rosin modified maleic acid compound and / or a resin, a rosin modified fumaric acid compound and / or a resin Examples include melamine compounds and / or resins, urea compounds and / or resins, phenolic compounds and / or resins, but the present invention is not limited thereto.

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and infiltrated into the coloring agent carrier, and the coloring film is coated by applying a dry film thickness of 0.2 to 5 μm on a substrate such as a glass substrate. It is preferred to include an organic solvent to facilitate formation. The organic solvent is selected in consideration of the solubility of each component of the coloring composition as well as the safety, as well as the application property of the coloring composition is good.

As an organic solvent, for example, ethyl lactate, benzyl alcohol, 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, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, n-propyl acetate, o-xylene, o-diethylbenzene, 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, 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 Chill 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, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, Acetic acid Propyl, and dibasic acid esters.
These solvents may be used alone or in combination of two or more at an arbitrary ratio as needed.

  Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl from the viewpoint of good dispersibility of colorant, permeability and coatability of coloring composition. It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent is used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the coloring agent because it can adjust the coloring composition to an appropriate viscosity and form a colored film having an intended uniform film thickness. Is preferred.

<Photopolymerizable monomer>
The photopolymerizable monomer which may be added to the coloring composition of the present invention includes a monomer or an oligomer which is cured by ultraviolet light, heat or the like to form a transparent resin.

Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin 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 ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglyci 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 Various acrylic and methacrylic esters such as (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy ester Examples include, but not limited to, chill (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The compounding amount of the photopolymerizable monomer is preferably 5 to 400 parts by mass based on the total mass of the colorant (100 parts by mass), and 10 to 300 parts by mass from the viewpoint of photocurability and developability. It is more preferable that

<Photoinitiator>
A photopolymerization initiator is added to the coloring composition of the present invention to cure the composition by ultraviolet irradiation and to form a filter segment by photolithography, and a solvent development type or alkali development type photosensitive coloring composition It can be prepared in the form of

As the photopolymerization initiator, 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 dil dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Thioxanthone compounds of the formula: 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphen) Nyl) -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-benzoyloxime)] Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenyl phosphine oxide or 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphor quinone, ethyl anthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound etc. are used.
These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 3 to 150 parts by mass from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
As sensitizers, unsaturated ketones represented by chalcone derivatives, dibenzalacetone etc., 1,2-diketone derivatives represented by benzyl and camphorquinone etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyrin derivative, anurene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, biimidazole derivative, α-acyloxy ester, acyl phosphine oxide, methyl phenyl glyoxylate, benzyl, 9, 10-phenanthrene quinone, Camphor quinone, ethyl anthraquinone, 4,4'-diethyl isophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxyca) Rubonyl) benzophenone, 4,4'-diethylamino benzophenone and the like.
These sensitizers can be used alone or in combination of two or more at an arbitrary ratio as required.

  More specifically, edited by Ogawara Shin et al., "Dye Handbook" (1986, Kodansha), edited by Ogawara Shin et al., "Chemicals of functional dyes" (1981, CMC), edited by Ikemori Tadajiro et al. Specific examples thereof include, but are not limited to, the sensitizers described in “Specially functional materials” (1986, CMC). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator contained in the coloring composition, and 5 to 50 parts by mass from the viewpoint of photocurability and developability. It is more preferable that

<Multifunctional thiol>
The coloring composition of the present invention can contain a multifunctional thiol which acts as a chain transfer agent.
The polyfunctional thiol may be any compound having two or more thiol groups, and examples thereof include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bis thioglycolate, ethylene glycol bis thiopropionate, trimethylol propane tris thio glycolate, trimethylol propane tris thio propionate, trimethylol propane tris (3-mercaptobutyrate), pentaerythritol tetrakis thio glycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapic acid -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used alone or in combination of two or more at any ratio as required.

  The content of the multifunctional thiol is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass based on the mass (100% by mass) of the total solid content of the coloring composition for a color filter. . When the content of the polyfunctional thiol is less than 0.1% by mass, the effect of adding the multifunctional thiol is insufficient, and when it exceeds 30% by mass, the sensitivity is too high and the resolution is lowered.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant increases the transmittance of the coating film in order to prevent the photopolymerization initiator and the thermosetting compound contained in the coloring composition from being oxidized and yellowed due to the heat step during heat curing or ITO annealing. be able to. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation in the heating step and to obtain a high transmittance of the coating film.

  The "antioxidant" in the present invention may be a compound having an ultraviolet light absorbing function, a radical trapping function, or a peroxide decomposing function, and specifically, a hindered phenol type or hindered amine type as an antioxidant. Examples thereof include phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylate and triazine compounds, and known ultraviolet light absorbers, antioxidants and the like can be used.

  Among these antioxidants, preferred are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants from the viewpoint of achieving both the transmittance and sensitivity of the coating film. Agents. Also, more preferably, hindered phenol antioxidants, hindered amine antioxidants, or phosphorus antioxidants are used.

  These antioxidants can be used alone or in combination of two or more at an arbitrary ratio as required.

  The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on the solid content mass of the coloring composition for a color filter (100% by mass) because the lightness and sensitivity are good.

<Amine compounds>
In addition, the coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen.

  As such an amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethyl paratoluidine etc. are mentioned.

<Leveling agent>
It is preferable to add a leveling agent to the colored composition of the present invention in order to improve the leveling properties of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. 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, and the like. As a specific example of dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by BYK-Chemie company, BYK-370, etc. are mentioned. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by mass based on the total mass of the coloring composition (100% by mass).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when it is added to a coloring composition, It is characterized by low surface tension reduction ability, and in addition to low surface tension reduction ability, it is useful that the wettability to the glass plate is good, and the addition amount at which defects of the coating film due to foaming do not appear. Those which can sufficiently suppress the chargeability can be preferably used. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. 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-2203. -2-207, but not limited thereto.

The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.
Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And polyethylene glycol monolaurate. Moreover, as an amphoteric surfactant to be added to the leveling agent in an auxiliary manner, there may be mentioned an amphoteric surfactant such as an alkylbetaine such as alkyldimethylaminoacetic acid betaine and an alkyl imidazoline.

<Hardening agent, hardening accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening agent, the hardening accelerator, etc. as needed. As a curing agent, a phenolic resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound and the like are effective, but not particularly limited thereto, a thermosetting resin Any curing agent may be used as long as it can react with it. Among these, a compound having two or more phenolic hydroxyl groups in one molecule, and an amine curing agent are preferably mentioned. 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- Tyl-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- Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct etc. can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

<Other additive components>
The coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity over time. Further, in order to enhance the adhesion to the transparent substrate, an adhesion improver such as a silane coupling agent may be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl phosphine, etc. Organic phosphine, phosphite and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

  Adhesion improvers include vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,3, 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-aminopropyl trie Xysilane, 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 mass, preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the colorant in the coloring composition.

<Method of producing coloring composition>
The coloring composition of the present invention comprises a colorant, a colorant carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid, a kneader, a 2-roll mill, a 3-roll mill, a ball mill, a horizontal sand mill, It can be finely dispersed and manufactured using various dispersing means such as a vertical sand mill, an annular type bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants and the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. The dye derivative may be simultaneously dispersed in the colorant carrier, or may be separately dispersed in the colorant carrier. When the solubility of coloring agents such as dyes is high, specifically, the solubility in the solvent used is high, and if it is in a state where it is not dissolved by stirring and no foreign matter is observed, it is finely dispersed and manufactured as described above. There is no need.

  Moreover, when using as a photosensitive coloring composition for color filters (resist material), it can prepare as a solvent development type or an alkali development type coloring composition. A solvent-developable or alkali-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, another pigment dispersant, and an additive. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersion aid>
When the coloring agent is dispersed in the coloring agent carrier, it may contain a dispersing aid such as a dye derivative, a resin type dispersing agent and a surfactant as appropriate. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the coloring composition formed by dispersing the colorant in the colorant carrier using the dispersion aid has brightness and viscosity stability. It becomes good. The dye derivative is as described above.

(Resin type dispersant)
The resin type dispersant has a colorant affinity site having a property of adsorbing to the additive colorant, and a site compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed in the colorant carrier Work to stabilize the Specific examples of the resin type dispersant include polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt , Polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) with polyester having free carboxyl group, and salts thereof Etc., (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resin, water soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

Among the above-mentioned dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion becomes low and a high contrast is exhibited by a small amount of addition, and a nitrogen atom-containing graft copolymer or a side chain is preferable. A nitrogen atom-containing acrylic block copolymer, a urethane polymer dispersant and the like having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring and the like are preferable.
The resin-type dispersant is preferably used at about 5 to 200% by mass with respect to the total amount of the colorant, and more preferably about 10 to 100% by mass from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2070, 2095, 2150, 2155, 2155, 2163, 2164 or Anti -Terra-U, 203, 204 or BYK-P104, P104S, 220S, 6919 or Lactimon, Lactimon-WS or Bykumen et al., SOLSPERSE-3000, 9000, 1 manufactured by Japan Lubrisole, Inc. 000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 20000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 41090, 41090 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 452, 4008, 4009, 4010, 4015, 4020, 4050, 4050, 4060, 4080, 4804, 4401, 4402, 4402 by BASF Japan Ltd. 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 456 , 4800,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

<Surfactant>
As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene 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 stearic acid, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl dimethylamino There may be mentioned amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines, which may be used alone or in combination of two or more, but it is not necessarily limited thereto.

  When a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. When the blending amount of the surfactant is less than 0.1 parts by mass, the added effect is difficult to be obtained, and when the content is more than 55 parts by mass, the dispersing agent may affect the dispersion by an excessive dispersing agent. .

<Removal of coarse particles>
The coloring composition of the present invention may be coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, filtration with a sintered filter or membrane filter, and the like. It is preferable to carry out the removal of the mixed dust. Thus, the coloring composition preferably contains substantially no particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Furthermore, in addition to the three color filter segments, a yellow filter segment can be provided.
At least one of the red filter segment, the green filter segment, and the yellow filter segment is formed using the coloring composition of the present invention.

  The blue filter segment can be formed using a conventional blue coloring composition comprising a blue colorant and a colorant carrier. As a blue coloring agent, for example, C.I. I. Pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP-A-2004-333817, Blue pigments such as the aluminum phthalocyanine pigment described in Japanese Patent No. 4893859 and the like are used. In addition, a purple coloring agent can be used in combination with the blue coloring composition. As purple colorants which can be used in combination, 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, 32, Purple pigments such as 37, 39, 40, 42, 44, 47, 49, 50 and the like can be mentioned. In addition, it is also possible to use a salt forming compound of a basic dye or an acid dye exhibiting a blue or purple color. When a dye is used, triarylmethane dyes or xanthene dyes are preferred in terms of lightness.

<Method of manufacturing color filter>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  Since formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition containing the coloring composition for color filters of the present invention prepared as printing ink, as a manufacturing method of a color filter, Low cost and excellent mass productivity. Furthermore, with the development of printing technology, printing of fine patterns having high dimensional accuracy and smoothness can be performed. In order to perform printing, it is preferable to have a composition such that the ink does not dry and solidify on a printing plate or on a blanket. In addition, control of the flowability of the ink on the printing machine is also important, and adjustment of the ink viscosity can be performed by a dispersant or an extender pigment.

  When a filter segment is formed by photolithography, a photosensitive coloring composition containing the blue coloring composition of the present invention prepared as the above-mentioned solvent-developing type or alkali-developing type coloring resist is spray-coated or spin-coated on a transparent substrate. The dry film is coated to a dry film thickness of 0.2 to 5 μm by a coating method such as coating, slit coating, or roll coating. The film dried if necessary is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact or non-contact with the film. Thereafter, the uncured area is removed by immersion in a solvent or an alkaline developer or by spraying the developer to remove a non-cured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate | stimulate superposition | polymerization of a coloring resist material, heating can also be given as needed. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above-mentioned printing method.

  In the development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, 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 ultraviolet exposure sensitivity, after applying and drying the colored resist material, 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. After that, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by the electrodeposition method, transfer method, etc. in addition to the above method, but the blue coloring composition for color filter of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. . In the transfer method, filter segments are formed in advance on the surface of a peelable transfer base sheet, and the filter segments are transferred to a desired substrate.

  Before forming the color filter segments on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, although a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, it is not limited thereto. Alternatively, thin film transistors (TFTs) may be formed in advance on the transparent substrate or the reflective substrate and then the color filter segments may be formed. Moreover, an overcoat film, a transparent conductive film, etc. are formed on the color filter of this invention as needed.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereby. In the examples, “parts” and “%” represent “parts by mass” and “mass%”, respectively.

(Mass average molecular weight of resin (Mw))
The mass average molecular weight (Mw) of the resin was measured using a TSK gel column (manufactured by Tosoh Corporation) and a GPC equipped with a RI detector (HLC-8120GPC manufactured by Tosoh Corporation) using polystyrene as the developing solvent and polystyrene conversion It is a mass mean molecular weight (Mw).

  Then, the manufacturing method of the binder resin solution used by the Example and the comparative example, the resin type dispersing agent solution, a pigment derivative, and a coloring agent is demonstrated.

<Method of producing binder resin solution>
(Preparation of Acrylic Resin Solution 1)
196 parts of cyclohexanone is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer are attached to a separable four-necked flask, the temperature is raised to 80 ° C., and the inside of the reaction vessel is purged with nitrogen and then dropped. From tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumyl phenol ethylene oxide modified acrylate ("Alonix M110" manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1 part and 1.1 parts 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 a solution of acrylic resin. After cooling to room temperature, approximately 2 parts of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and methoxypropyl acetate is made so that non-volatile content is 20% by mass in the resin solution synthesized above. Was added to prepare an acrylic resin solution 1. The mass average molecular weight (Mw) was 26000.

(Preparation of Acrylic Resin Solution 2)
Charge 207 parts of cyclohexanone into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer are attached to a separable four-necked flask, raise the temperature to 80 ° C, replace the inside of the reaction vessel with nitrogen, and drop it. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Alonix 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 the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, after stopping nitrogen gas and stirring while injecting dry air for 1 hour, after cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Karen manufactured by Showa Denko KK) A mixture of 6.5 parts of MOI, 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was dropped at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, approximately 2 parts of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and cyclohexanone is added to the resin solution synthesized above so that the non-volatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The mass average molecular weight (Mw) was 18,000.

<Production Method of Resin-type Dispersant Solution>
(Preparation of resin type dispersant solution 1)
In a flask equipped with a condenser and a stirrer, 1.0 part by mass of AIBN (2,2'-azobisisobutyronitrile) and 186 parts by mass of propylene glycol monomethyl ether acetate are charged, and subsequently 27 parts by mass of methyl methacrylate, butyl methacrylate 27 parts by mass, 21 parts by mass of 2-ethylhexyl methacrylate, 18 parts by mass of benzyl methacrylate and 3.6 parts by mass of cumyl dithiobenzoate were charged, and nitrogen substitution was performed for 30 minutes. After that, while stirring gently, the temperature of the reaction solution was raised to 60 ° C., and this temperature was maintained for 24 hours to carry out living radical polymerization. Then, to this reaction solution is added a solution of 1.0 part by mass of AIBN and 35 parts by mass of dimethylaminoethyl methacrylate dissolved in 70 parts by mass of propylene glycol monomethyl ether acetate and nitrogen substitution for 30 minutes, and living radical polymerization at 60 ° C. for 24 hours By doing this, a solution of the block copolymer was obtained. To the obtained block copolymer solution, 25 parts by mass of benzyl chloride and 50 parts by mass of propylene glycol monomethyl ether are added, and the reaction is performed at 80 ° C. for 2 hours to adjust the solid content concentration to 40%. Dispersant solution 1 was obtained. Resin type dispersant 1 is an A block having repeating units derived from methacryloyloxyethyl benzyldimethyl ammonium chloride and dimethylaminoethyl methacrylate, and a B block having repeating units derived from methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and benzyl methacrylate. It is a block copolymer consisting of As a result of proton NMR measurement, the copolymerization ratio of each repeating unit was methacryloyloxyethyl benzyldimethyl ammonium chloride / dimethylaminoethyl methacrylate / methyl methacrylate / butyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate = 34/4/18/18 / It was 14/12 (mass ratio).

<Method of producing coloring agent>
(Production of Colorant (P-1))
The coloring agent (P-1) which is an aluminum phthalocyanine pigment was obtained by the manufacturing method similar to the phthalocyanine pigment (P-10) as described in the Example of Unexamined-Japanese-Patent No. 2017-197685.

(Production of Colorant (P-2))
A 300 mL flask was charged with 109 parts of sulfuryl chloride, 131 parts of aluminum chloride, 18 parts of sodium chloride, 30 parts of zinc phthalocyanine and 52 parts of bromine. The temperature was raised to 130 ° C. over 40 hours, taken out into water, and filtered to obtain a green crude pigment. Twenty parts of the obtained green crude pigment, 140 parts of ground sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-arm type kneader and kneaded at 100 ° C. for 6 hours. After kneading, the mixture was taken out to 2 kg of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a colorant (P-2). The obtained colorant (P-2) has an average of 12.69 halogen atoms in one molecule according to fluorescent X-ray analysis, and of these, an average of 8.54 bromine atoms and an average of chlorine atoms are included. It was a halogenated zinc phthalocyanine pigment of 4.16.

(Production of Colorant (P-3))
The coloring agent (P-3) which is an aluminum phthalocyanine pigment was obtained by the manufacturing method similar to the blue coloring agent (PB-1) as described in the Example of patent 4893859.

(Production of Colorant (P-4))
The coloring agent (P-4) which is an aluminum phthalocyanine pigment was obtained by the manufacturing method similar to the phthalocyanine pigment (PCY-9) as described in the Example of Unexamined-Japanese-Patent No. 2016-153481.

(Production of Colorant (P-5))
A coloring agent (P-5) was obtained by the same production method as that of the azo dye 1 described in the examples of Japanese Patent No. 5187326.
<Method of producing dye derivative>

  The quinophthalone compound (B-1) was obtained by the manufacturing method similar to the quinophthalone compound (QL-c-1) as described in the Example of Unexamined-Japanese-Patent No. 2015-172732.

  The Al salt of the quinophthalone compound (B-2) was obtained according to the synthesis method described in Japanese Patent No. 4585781.

  The lauryl trimethyl ammonium salt of a quinophthalone compound (B-3) was obtained by the manufacturing method similar to the quinophthalone compound (B-3) as described in the Example of the patent 6160061 gazette.

  The quinophthalone compound (B-4) was obtained by the manufacturing method similar to the quinophthalone compound (QL-f-1) as described in the Example of Unexamined-Japanese-Patent No. 2015-172732.

(Method for identifying quinophthalone compounds)
MALDI TOF-MS spectrum was used for identification of the quinophthalone compound used for this invention. For MALDI TOF-MS spectrum, identification of the obtained compound was carried out using a MALDI mass spectrometer autoflex III manufactured by Bruker Daltonics Inc., and matching the molecular ion peak of the obtained mass spectrum with the mass number obtained by calculation. The
The average value of the number of substituted halogen atoms is analyzed by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX), a liquid obtained by burning a pigment by an oxygen combustion flask method and absorbing the combusted substance in water. Then, the amount of halogen was determined and converted to the average value of the number of substitution of halogen atoms.

(Halogen distribution width of quinophthalone compound (A1))
The halogen distribution width is the value obtained by integrating the signal intensity (each peak value) of the molecular ion peak corresponding to each component and each peak value (all peak values) in the obtained mass spectrum using the MALDI TOF-MS spectrum The ratio of each peak value to the total peak value was counted, and the number of peaks having a percentage of 1% or more was counted as a halogen distribution width.

<Method of producing quinophthalone compound (A1)>
(Synthesis of Quinophthalone Compound (A1-1))
150 parts of 2,3-naphthalenedicarboxylic acid anhydride and 350 parts of trichloroisocyanuric acid were added to 1200 parts of 98% sulfuric acid and reacted at 80 ° C. for 4 hours. The reaction solution is poured into 9,000 parts of stirred ice water, and the formed precipitate is treated in the order of filtration, water washing, 1% aqueous solution of sodium hydroxide, and water washing, and dried to give intermediate (a1-1) 220 parts were obtained. The number of chlorine substituents of intermediate (a1-1) was calculated to be 3.5 on average. 190 parts of the obtained intermediate (a1-1), 45 parts of 8-aminoquinaldine, and 60 parts of benzoic acid were added to 280 parts of methyl benzoate, and the mixture was heated and stirred at 180 ° C. for 6 hours. After cooling to room temperature, the reaction mixture was poured into 3000 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 152 parts of a quinophthalone compound (A1-1). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (A1-1). The halogen distribution width was four.

(Synthesis of Quinophthalone Compound (A1-2))
Synthesis of intermediate (a1-1) was carried out in the same manner, except that 350 parts of trichloroisocyanuric acid was changed to 500 parts, to obtain intermediate (a1-2). The number of chlorine substituents in the intermediate (a1-2) was calculated to be 5 on average. 230 parts of the obtained intermediate (a1-2), 45 parts of 8-aminoquinaldine, and 60 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was heated and stirred at 180 ° C. for 6 hours. After cooling to room temperature, the reaction mixture was poured into 3000 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 170 parts of a quinophthalone compound (A1-2). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (A1-2). The halogen distribution width was five.

(Synthesis of Quinophthalone Compound (A1-3))
150 parts of 2,3-naphthalenedicarboxylic acid anhydride and 220 parts of N-chlorosuccinimide were added to 1200 parts of 98% sulfuric acid, and reacted at 80 ° C. for 4 hours. The reaction solution was poured into 9,000 parts of stirred ice water, the precipitate was separated by filtration, washed with water, and washed with water until the specific conductivity of the filtrate became 50 μS / cm or less, to obtain a water paste. The obtained water paste was dried at 80 ° C. for 24 hours to obtain 220 parts of an intermediate (a1-3). When the number of chlorine substituents was calculated about intermediate (a1-3), it was an average of two. The obtained intermediate (a1-3) 220 parts, 45 parts of 8-aminoquinaldine, and 60 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was heated and stirred at 180 ° C. for 6 hours. After cooling to room temperature, the reaction mixture was poured into 3000 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 170 parts of a quinophthalone compound (A1-3). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (A1-3). In addition, the halogen distribution width was 3.

(Synthesis of Quinophthalone Compound (A1-4))
Synthesis of intermediate (a1-1) was carried out in the same manner as in synthesis of intermediate (a1-4) except that 350 parts of trichloroisocyanuric acid was changed to 244 parts of N-bromosuccinimide. It was 1.5 on average when the number of bromine substituents was computed about intermediate (a1-4). The obtained intermediate (a1-4) 225 parts, 45 parts of 8-aminoquinaldine, and 60 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was heated and stirred at 180 ° C. for 6 hours. After cooling to room temperature, the reaction mixture was poured into 3000 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 204 parts of a quinophthalone compound (A1-4). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (A1-4). In addition, the halogen distribution width was 3.

(Synthesis of Quinophthalone Compound (A1-5))
Intermediates (a1-5) were synthesized in the same manner except that 350 parts of trichloroisocyanuric acid was changed to 100 parts of 1,3-dibromo-5,5-dimethylhydantoin in the synthesis of the intermediate (a1-1) I got The number of bromine substituents in the intermediate (a1-5) was calculated to be 3.8 on average. 225 parts of the obtained intermediate (a1-5), 45 parts of 8-aminoquinaldine, and 60 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was heated and stirred at 180 ° C. for 6 hours. After cooling to room temperature, the reaction mixture was poured into 3000 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 204 parts of a quinophthalone compound (A1-5). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (A1-5). In addition, the halogen distribution width was 6.

(Synthesis of Quinophthalone Compound (A1-6))
To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic acid anhydride, and 154 parts of benzoic acid were added, and the mixture was heated to 180 ° C. and stirred for 4 hours. Further, after cooling to room temperature, the reaction mixture is poured into 5440 parts of acetone, and 1
Stir for hours. The product was filtered off, washed with methanol and dried to give 116 parts of compound (8). Eighty parts of the resulting quinophthalone intermediate compound (8) and 123 parts of N-chlorosuccinimide were added to 900 parts of 98% sulfuric acid, and the mixture was heated and stirred at 30 ° C. for 2 hours. The reaction solution is poured into 9,000 parts of stirred ice water, and the formed precipitate is treated in the order of filtration, water washing, 1% aqueous sodium hydroxide solution washing, and water washing, and dried to give a quinophthalone compound (A1-6) 105 parts were obtained. As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (A1-6). The average number of chlorine substituents was 5, and the halogen distribution width was 4.

(Synthesis of Quinophthalone Compound (A1-7))
Compound (9) was obtained according to the synthesis method described in JP 2012-226110 A. To 500 parts of methyl benzoate, 105 parts of Compound (9), 150 parts of Intermediate (a1-1) and 100 parts of benzoic acid were added, and the mixture was heated to 180 ° C. and stirred for 4 hours. Furthermore, after cooling to room temperature, the reaction mixture was poured into 5000 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to give 183 parts of a quinophthalone compound (A1-7). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (A1-7). In addition, the halogen distribution width was 3.

(Synthesis of Quinophthalone Compound (A1-8))
To 700 parts of methanesulfonic acid, 100 parts of 8-aminoquinaldine and 115 parts of N-bromosuccinimide were added and reacted at 80 ° C. for 4 hours. The reaction solution is poured into 6000 parts of stirred ice water, and the formed precipitate is treated in the order of filtration, water washing, 1% aqueous solution of sodium hydroxide, and water washing, and dried to give intermediate (a1-8) 142 parts were obtained. 130 parts of obtained intermediate (a1-8), 400 parts of intermediate (a1-3) and 100 parts of benzoic acid were added to 400 parts of methyl benzoate, and the mixture was heated and stirred at 180 ° C. for 6 hours. After cooling to room temperature, the reaction mixture was poured into 4000 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 445 parts of a quinophthalone compound (A1-8). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (A1-8). In addition, the halogen distribution width was 6.

(Synthesis of Quinophthalone Compound (A1-9))
To 200 parts of methyl benzoate, 50 parts of 8-aminoquinaldine, 115 parts of intermediate (a1-1) and 140 parts of benzoic acid were added, and the mixture was stirred at 120 ° C. for 4 hours. Subsequently, 143 parts of intermediates (a1-4) were further added to the reaction mixture, the mixture was heated to 180 ° C., and stirring was performed for 4 hours while distilling off water. After cooling to room temperature, the reaction mixture was poured into 2000 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 167 parts of a quinophthalone compound (A1-9). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (A1-9). The halogen distribution width was four.
<Method of producing quinophthalone compound (A2)>

  As the quinophthalone compound (A2-1), C.I. I. Pigment Yellow 138 ("Palitol Yellow K0960-HD" manufactured by BASF Corp.) was used.

  The quinophthalone compound (A2-4) was obtained by the manufacturing method similar to the quinophthalone compound (r) as described in the Example of Unexamined-Japanese-Patent No. 2012-47306.

(Synthesis of Quinophthalone Compound (A2-7))
190 parts of intermediate (a1-1), 48 parts of 6-methyl-8-aminoquinaldine, and 60 parts of benzoic acid were added to 280 parts of methyl benzoate, and the mixture was heated and stirred at 180 ° C. for 6 hours. After cooling to room temperature, the reaction mixture was poured into 3000 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to give 148 parts of an intermediate (a2-7). Next, 82 parts of a compound (12) were obtained according to the synthesis method described in JP-A-2008-81566. 80 parts of the compound (12), 55 parts of tetterachlorophthalic anhydride and 50 parts of benzoic acid were added to 400 parts of methyl benzoate, and the mixture was heated and stirred at 160 ° C. for 5 hours. After cooling to room temperature, the reaction mixture was poured into 4000 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 445 parts of a quinophthalone compound (A2-7) 101 parts. As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (A2-7).

Compound (12)

  According to the synthesis method described in JP 2012-226110 A, a quinophthalone compound (A2-3) was obtained.

(Synthesis of Quinophthalone Compound (A2-13))
40 parts of compound (9) and 22 parts of N-bromosuccinimide were added to 300 parts of N, N-dimethylformamide, and the mixture was stirred at 80 ° C. for an hour. The reaction solution was poured into a stirred mixed solvent of 300 parts of methanol / 700 parts of water, and stirred at room temperature for 1 hour. The formed precipitate was treated in the order of filtration, water washing, methanol washing and water washing, and dried to obtain 48 parts of an intermediate (a2-13).
The obtained intermediate (a2-13) 45 parts, tetrachlorophthalic anhydride 37 parts and benzoic acid 35 parts were added to 100 parts of methyl benzoate, and the mixture was heated and stirred at 160 ° C. for 4 hours. After cooling to room temperature, the reaction mixture was poured into 1000 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 65 parts of a quinophthalone compound (A2-13). As a result of mass analysis by TOF-MS, it was identified as a quinophthalone compound (A2-13).

Compound (9)

(Production of yellow colorant (Y-1))
One hundred parts of the quinophthalone compound (A1-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is poured into warm water and stirred for 1 hour while heating to about 70 ° C. to form a slurry, filtration and washing with water are repeated to remove sodium chloride and diethylene glycol, and then dried overnight at 80 ° C. 97 parts of a yellow colorant (Y-1) were obtained.

(Production of yellow colorant (Y-2 to 21))
Hereinafter, as shown in Table 1, yellow colorants (Y-2 to 21) were obtained in the same manner as the yellow colorant (Y-1) except that the composition and the blending amount were changed.

(Production of yellow colorant (Y-22))
100 parts of compound (8), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is poured into warm water and stirred for 1 hour while heating to about 70 ° C. to form a slurry, filtration and washing with water are repeated to remove sodium chloride and diethylene glycol, and then dried overnight at 80 ° C. 95 parts of a yellow colorant (Y-22) are obtained.

Compound (8)

<Method of Producing Colored Composition for Color Filter>
Example 1-1
(Production of Colored Composition (YP-1))
A mixture of the following composition is stirred and mixed so as to be uniform, and then 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 the pore diameter It filtered with a 5.0 micrometer filter, and produced coloring composition (YP-1).
Yellow coloring agent (Y-1) 5.2 parts Yellow coloring agent (Y-17) 5.2 parts Dye derivative quinophthalone compound (B-1) 0.6 parts Resin type dispersant solution 1 6.9 parts Acrylic resin solution 1 31.2 parts Propylene glycol monomethyl ether acetate 50.9 parts

[Examples 1-2 to 33, Comparative Examples 1-1 to 4]
(Production of Colored Composition (YP-2 to 37))
The total content of the coloring agent and the dye derivative is fixed to 11.0 parts, and the kind and the mass ratio of the coloring agent and the dye derivative are changed as described in Table 2 in the same manner as Example 1-1. Thus, a colored composition (YP-2 to 37) was obtained.

<Evaluation of yellow coloring composition>
The evaluation of the yellow coloring composition was performed by producing a coating film using the yellow coloring composition, and measuring the lightness, film thickness, and contrast ratio. In addition, the heat resistance was also evaluated. The evaluation method is shown below.

(Brightness evaluation)
The yellow coloring composition was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and a coating film was obtained by heating at 230 ° C. for 20 minutes. At this time, after the heat treatment at 230 ° C., the film thickness of the coating film was coated by appropriately changing the coating conditions (the number of rotations of the spin coater, time) so that x = 0.440 in the C light source. The lightness (Y) of the resulting coated film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), and judged according to the following criteria.
:: 90.0 or more (very good)
○: 89.0 or more and less than 90.0 (good)
Δ: 87.5 or more and less than 89.0 (possible)
X: less than 87.5 (defective)

(Coloring evaluation)
The film thickness at the time of showing the chromaticity of x = 0.440 was measured using the same coating film as the thing which did the lightness evaluation, and it determined in accordance with the following reference | standard. The smaller the film thickness giving the chromaticity of x = 0.440, the larger the coloring power, which is excellent.
○: less than 1.0 [μm] (good)
:: 1.0 or more and less than 1.5 [μm] (possible)
X: 1.5 or more [μm] (defective)

(Contrast ratio evaluation)
The light emitted from the liquid crystal display backlight unit is polarized through the polarizing plate, passes through the coating of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, light passes through the polarizing plate if the polarizing planes of the polarizing plate and the polarizing plate are parallel, but light is blocked by the polarizing plate if the polarization planes are orthogonal to each other. However, when light polarized by the polarizing plate passes through the coating film of the coloring composition, the colorant particles cause scattering or the like, and when a part of the polarization plane is deviated, transmission occurs when the polarizing plates are parallel. The amount of light to be reduced decreases, and when the polarizing plates are orthogonal, some light is transmitted. The transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness when the polarizing plate was parallel to the brightness when orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (brightness in parallel) / (brightness in orthogonal)
Therefore, when scattering occurs due to the coloring agent in the coating film, the brightness in parallel decreases and the brightness in orthogonal increases, so the contrast ratio decreases.

A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as a luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as a polarizing plate. In the measurement, it measured through the black mask which opened the 1-cm square hole in the measurement part. It judged according to the following standard using the same coating film as what carried out lightness evaluation.
:: 3000 or more (very good)
○: 2500 or more and less than 3000 (good)
Δ: 2000 or more and less than 2500 (possible)
X: less than 2000 (defective)

(Evaluation of heat resistance)
The coloring composition (YP-1 to 37) is applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater under the condition that x = 0.440 with a C light source, and then The coated substrate was manufactured by drying at 70 ° C. for 20 minutes and then heating at 230 ° C. for 60 minutes and allowed to cool. As a heat resistance test, it was heated at 250 ° C. for 60 minutes. Thereafter, the coated substrate was observed with an optical microscope to confirm the presence or absence of crystal precipitation. The heat resistance was evaluated in the following three stages.
○ · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · heat treatment after 250 ° C for 60 minutes without crystallization precipitation · · · · · after heat treatment for 30 minutes without heat treatment at 230 ° C 60 minutes In the crystal precipitation × · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

From Table 3, the yellow coloring compositions of Examples 1-1 to 33, in which the quinophthalone compound (A1) and the quinophthalone compound (A2) were used in combination as a coloring agent, exhibited excellent lightness and contrast ratio and exhibited high coloring power. It became clear. On the other hand, the yellow coloring composition of Comparative Example 1-1 using a single yellow coloring agent with the quinophthalone compound (A1) is inferior in the lightness, color and power contrast ratio when mixed with the quinophthalone compound (A2). It became.
In addition, the yellow coloring compositions of Comparative Examples 1-2 to 4 using the yellow colorant alone with the quinophthalone compound (A2) are inferior in lightness, contrast ratio, coloring power, and heat resistance also results in poor results. It turned out that the result which can not satisfy simultaneously all of coloring strength, contrast ratio, and heat resistance was not obtained.

<Preparation of a green coloring composition>
(Green coloring composition (GP-1): coloring agent (P-1))
11.0 parts of coloring agent (P-1), 31.2 parts of acrylic resin solution 1, 6.9 parts of resin type dispersant solution 1, and 50.9 parts of propylene glycol monomethyl ether acetate were uniformly stirred and mixed. Then, after dispersing for 3 hours with Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, filter with a filter having a pore size of 5 μm, and colorant (P-1) Green colored composition (GP-1) was produced.

(Green coloring composition (GP-2): coloring agent (P-2))
A green coloring composition of the coloring agent (P-2) (the coloring method (P-1) was changed to the coloring agent (P-2) in the same manner as the green coloring composition (GP-1) except that the coloring agent (P-1) was changed to the coloring agent (P-2) GP-2) was produced.

(Green coloring composition (GP-3): coloring agent (P-3))
A green coloring composition of the coloring agent (P-3) (the coloring method (P-1) was changed to a coloring agent (P-3) in the same manner as the green coloring composition (GP-1) except that the coloring agent (P-1) was changed to the coloring agent (P-3) GP-3) was produced.

(Green coloring composition (GP-4): coloring agent (P-4))
A green coloring composition (coloring agent (P-4)) (coloring agent (P-1)) except that coloring agent (P-4) is changed to coloring agent (P-4) in the same preparation method as green coloring composition (GP-1) GP-4) was produced.

(Green coloring composition (GP-5): PG 58)
As the colorant (P-1), C.I. I. Pigment Green 58 ("FASTGEN GREEN A110" manufactured by DIC Corporation), except that a green coloring composition (GP-5) of PG58 was produced in the same manner as the green coloring composition (GP-1).

<Preparation of Red-Colored Composition>
(Red colored composition (RP-1): PR254)
As the colorant (P-1), C.I. I. Pigment Red 254 ("IRGAPHOR RED B-CF" manufactured by BASF Corp.), except that the red coloring composition (RP-1) of PR254 is prepared by the same preparation method as the green coloring composition (GP-1). did.

(Red colored composition (RP-2): PR177)
As the colorant (P-1), C.I. I. Pigment red 177 ("A2B" manufactured by BASF Corporation) was manufactured in the same manner as the green coloring composition (GP-1) to prepare a red coloring composition (RP-2) of PR177.

(Red coloring composition (RP-3): coloring agent (P-5))
Red coloring composition (P-5) of coloring agent (P-5) by the same preparation method as green coloring composition (GP-1) except that coloring agent (P-1) is changed to coloring agent (P-5) RP-3) was produced.

(Red colored composition (RP-4): PR 269)
The colorant (P-1) was commercially available as C.I. I. Pigment Red 269, except that the red colored composition (RP-4) of PR269 was prepared by the same preparation method as the green colored composition (GP-1).

<Preparation of a yellow coloring composition>
(Yellow coloring composition (YP-38): PY 185)
As the colorant (P-1), C.I. I. Pigment Yellow 185 ("Pariogen Yellow D 1155" manufactured by BASF Corp.), except that a yellow coloring composition (YP-38) of PY 185 was prepared by the same preparation method as the green coloring composition (GP-1). .

(Yellow coloring composition (YP-39): PY 139)
As the colorant (P-1), C.I. I. Pigment Yellow 139 ("IRGAFOR Yellow 2R-CF" manufactured by BASF Corporation), except that the yellow coloring composition (YP-39) of PY139 is prepared in the same manner as the green coloring composition (GP-1). Made.

<Production of Photosensitive Colored Composition>
Example 2-1
(Preparation of photosensitive coloring composition (GR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore diameter of 1 μm to prepare a photosensitive coloring composition (GR-1).
Yellow coloring composition (YP-1) 18.4 parts Green coloring composition (GP-1) 26.6 parts Acrylic resin solution 2 4.5 parts Photopolymerizable monomer ("ALONIX M402" manufactured by Toagosei Co., Ltd.) 2.6 parts Photopolymerizable monomer ("Alonics M350" manufactured by Toagosei Co., Ltd.) 2.0 parts Photopolymerization initiator ("IRGACURE OXE 02" manufactured by BASF Corp.) 1.2 parts Photosensitizer (Hodoya Chemical Industry Co., Ltd.) Company "EAB-F") 0.2 parts propylene glycol monomethyl ether acetate 45.4 parts

[Examples 2-2 to 47, Comparative Examples 2-1 to 7]
(Preparation of Photosensitive Colored Composition (GR-2 to 54))
The yellow coloring composition and the green coloring composition shown in Table 4 are used, and the yellow coloring composition is matched so that the chromaticity of x = 0.240 and y = 0.660 with a C light source in the film evaluation. The photosensitive coloring composition is the same as the photosensitive coloring composition 1 (GR-1) except that the ratio of the product to the green coloring composition is changed (the ratio is changed so that the total amount of the coloring composition is 45 parts). Objects (GR-2 to 54) were produced.

<Evaluation of coating film of photosensitive coloring composition>
The evaluation of the lightness, coloring power, contrast ratio (CR), heat resistance and electrical property of the coating film produced using the obtained photosensitive coloring composition (GR-1-54) was performed by the following method.

(Brightness evaluation)
The photosensitive coloring composition is spin-coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate, then dried at 70 ° C. for 20 minutes, and ultraviolet light is applied at 300 mJ / cm ² using an ultra-high pressure mercury lamp. Exposure was performed, and development was performed with an alkaline developer at 23 ° C. As the alkaline developer, 1.5% by mass of sodium carbonate, 0.5% by mass of sodium hydrogencarbonate, 8.0% by mass of anionic surfactant ("Perilex NBL" manufactured by Kao Corporation), and 90% by mass of water The one consisting of Furthermore, the coating film was obtained by heating at 230 degreeC for 30 minutes. The lightness (Y) of the obtained coating film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), and it was judged according to the following criteria. In addition, the produced coating film was made to be x (C) = 0.240 and y (C) = 0.660 after the heat processing at 230 degreeC.
:: 44.0 or more (very good)
○: 43.0 or more, less than 44.0 (good)
:: 42.0 or more, less than 43.0 (possible)
X: less than 42.0 (defective)

(Evaluation of coloring ability)
The film thickness at the time of showing the chromaticity of y (C) = 0.660 was measured using the same coating film as the one subjected to the lightness evaluation, and the judgment was made according to the following four steps. The smaller the film thickness giving the chromaticity of x (C) = 0.240 and y (C) = 0.660, the larger the coloring power, which is excellent.
◎: less than 2.7 μm (very good)
○: film thickness 2.7 μm or more and less than 3.0 μm (good)
Δ: Film thickness of 3.0 μm or more and less than 3.3 μm (possible)
X: Film thickness of 3.3 μm or more (defect)

(Evaluation of contrast)
Contrast measurements were performed using the substrate used in the brightness evaluation. Evaluation of the contrast was evaluated in the following four steps.
:: 6000 or more (very good)
○: 5000 or more and less than 6000 (good)
Δ: 4000 or more and less than 5000 (possible)
X: less than 4000 (defective)

(Evaluation of heat resistance)
The coating used in the lightness evaluation was additionally heated at 250 ° C. for 60 minutes as a heat resistance test. Thereafter, the coated substrate was observed with an optical microscope to confirm the presence or absence of crystal precipitation. The heat resistance was evaluated in the following three stages.
○ · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · heat treatment after 250 ° C for 60 minutes without crystallization precipitation · · · · · · 230 ° C for 30 minutes after heat treatment without crystallization. In the crystal precipitation × · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Heat treatment at 250 ° C for 60 minutes

(Evaluation of electrical characteristics)
A photosensitive coloring composition (GR-1 to 54) is coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater to a film thickness of 2.5 μm, and then at 70 ° C. The film was dried for 20 minutes, exposed to ultraviolet light with an integrated light quantity of 200 mJ / cm ² using an ultrahigh pressure mercury lamp, and developed with an alkaline developer at 23 ° C. to obtain a coated substrate. 0.05 g of the coating film is scraped from the obtained coated substrate, immersed in 2.0 g of liquid crystal (MJ 971189 manufactured by Merck Ltd.), aged for 60 minutes in a 90 ° C. clean oven, and centrifuged at 5000 rpm for 20 minutes After separation, the supernatant was collected to prepare a boiled liquid for contamination source to liquid crystals. After completion of boiling of the contamination source, the liquid crystal is taken out and sealed in a glass cell with an ITO electrode, and using a liquid crystal physical property evaluation machine (6254 manufactured by Toyo Corporation), the holding ratio after 16.7 milliseconds at an applied voltage of 5 V ) (%) Was measured and evaluated according to the following criteria. X is a difficult level to use.
○: 95% or more (good)
:: 90% or more and less than 95% (available)
X: less than 90% (difficult to use)

  Table 4 shows the evaluation results of the photosensitive coloring compositions prepared in Examples and Comparative Examples.

  As shown in Table 4, Examples 2-1 to 47 in which the quinophthalone-based pigment (A1) and the quinophthalone-based pigment (A2), which are features of the present invention, were used as a yellow coloring composition, the lightness, coloring power, contrast, There was no x evaluation in any item of heat resistance and electrical property, and it was a very good result.

  On the other hand, in Comparative Examples 2-1, 6 and 7 in which the quinophthalone pigment (A1) was used alone as a yellow coloring composition, the lightness and coloring power were inferior to those of the examples of the present invention. In Comparative Examples 2-2 to 4 in which the quinophthalone-based pigment (A2) was used alone as a yellow coloring composition, the lightness, the heat resistance and the electrical properties were poor. Moreover, in PY185 of Comparative Example 2-5, the result was that the contrast was significantly inferior to the example of the present invention.

Red photosensitive coloring composition
[Examples 3-1 to 20, Comparative Examples 3-1 to 5]
(Preparation of photosensitive coloring composition (RR-1 to 25))
The yellow coloring composition shown in Table 5 and the red coloring composition are used, and the yellow coloring is performed so as to match the chromaticity of x = 0.640, y = 0.330 with a C light source in the film evaluation. The photosensitive coloring is the same as the photosensitive coloring composition 1 (GR-1) except that the ratio of the composition to the red coloring composition is changed (the ratio is changed so that the total amount of the coloring composition is 45 parts). Compositions (RR-1 to 25) were produced.

<Evaluation of coating film of photosensitive coloring composition>
The lightness, coloring power, contrast ratio (CR), heat resistance, and electrical property of the coating film produced using the obtained photosensitive coloring composition (RR-1-25) were evaluated. Evaluation of lightness and coloring power was performed by the following method. The heat resistance, the contrast ratio and the evaluation of the electrical properties were carried out in the same manner as the photosensitive coloring compositions (GR-1 to 54).

(Brightness evaluation)
The coating film board | substrate was produced on the glass substrate of 100 mm x 100 mm and 1.1 mm thickness similarly to photosensitive coloring composition (GR-1-54) from photosensitive coloring composition (RR-1-25).
The lightness (Y) of the obtained coating film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), and it was judged according to the following criteria. In addition, the produced coating film was made to be x = 0.640 and y = 0.330 after the heat processing at 230 degreeC.

:: 21.0 or more (very good)
○: 20.5 or more and less than 21.0 (good)
:: 20.0 or more and less than 20.5 (possible)
×: less than 20.0 (defective)

(Evaluation of coloring ability)
The film thickness at the time of showing chromaticity of x = 0.640 was measured using the same coating film as what carried out lightness evaluation, and it determined in accordance with the following four-step standard. The smaller the film thickness giving the chromaticity of x = 0.640 and y = 0.330, the larger the coloring power, which is excellent.
:: less than 2.2 μm film thickness ○: less than 2.2 μm film thickness, less than 2.5 μm Δ: less than 2.5 μm film thickness, less than 2.8 μm, ×: 2.8 μm film thickness or more

  As shown in Table 5, Examples 3-1 to 20 in which the quinophthalone based pigment (A1) and the quinophthalone based pigment (A2), which are features of the present invention, were used as a yellow coloring composition, the lightness, coloring power, contrast, There was no x evaluation in any item of heat resistance and electrical property, and it was a very good result.

  On the other hand, in Comparative Examples 3-1 and 4 in which the quinophthalone-based pigment (A1) was used alone as a yellow coloring composition, the contrast was inferior to the example of the present invention, and the lightness and coloring power were not satisfactory. Moreover, in the case of PY 139 of Comparative Examples 3-3 and 5, the result was that the contrast was significantly inferior to the example of the present invention.

<Preparation of color filter>
First, a blue photosensitive coloring composition used for producing a color filter was produced.

(Preparation of blue photosensitive coloring composition (BR-1))
The following mixture is stirred and mixed so as to be uniform, and after being 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, a pore diameter of 5. The mixture was filtered through a 0 μm filter to produce a blue colored composition (BP-1).
Blue pigment (CI pigment blue 15: 6) 7.2 parts Purple pigment (CI pigment violet 23) 4.8 parts Resin type dispersant ("EFKA 4300" manufactured by BASF Japan Ltd.) 1.0 part acrylic Resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Next, the mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore diameter of 1 μm to prepare a blue photosensitive colored composition (BR-1).
Blue colored composition (BP-1) 34.0 parts Acrylic resin solution 15.2 parts Photopolymerizable monomer ("Alonix M400" manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (manufactured by BASF Japan Ltd.) “IRGACURE 907”) 2.0 parts Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Propylene glycol monomethyl ether acetate 45.1 parts

(Preparation of color filter)
A black matrix is patterned on a glass substrate, and a film is formed on the substrate with a spin-coater so that the red photosensitive coloring composition (RR-13) of the present invention becomes x = 0.640, y = 0.330. It was applied thickly to form a colored film. The film was irradiated with ultraviolet light of 200 mJ / cm ² through a photomask using an extra-high pressure mercury lamp. Next, after spray development with an alkaline developer consisting of a 0.2% by mass aqueous solution of sodium carbonate to remove an unexposed part, the substrate is washed with ion exchanged water and heated at 230 ° C. for 30 minutes to obtain a red filter segment. Formed. Also, in the same manner, the green filter segment is made to match the chromaticity of x = 0.240, y = 0.660 using the green-sensitive coloring composition (GR-2) of the present invention, and a blue filter The segments are each coated with a blue photosensitive coloring composition (BR-1) to a film thickness of x = 0.150 and y = 0.060 to form each filter segment to form a color filter. Obtained.

  By using the red photosensitive coloring composition (RR-13) and the green photosensitive coloring composition (GR-2) of the present invention, the coloring power, the lightness and the contrast can be achieved at high levels, and further, other physical properties can be obtained. It could be used favorably without problems.

Claims (6)

It is a coloring composition for color filters containing a coloring agent, a resin, and a solvent,
A quinophthalone compound (A1) represented by the following general formula (1), and a quinophthalone compound represented by one or more selected from the group consisting of the following general formulas (2), (3) and (4) A2) and the coloring composition for color filters characterized by the above-mentioned.

General formula (1)

[In general formula (1), X, Y and Z each independently represent a halogen atom. n and m show the number of 0-6, and the sum total of (n + m) is three or more. p shows the number of 0-5. ]

General formula (2)
General formula (3)
General formula (4)

[In the general formula (2) ~ (4), R 18 ~R 30, R 31 ~R 45, R 46 ~R 60 are each independently a hydrogen atom, a halogen atom, an alkyl which may have a substituent A group, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent is shown. ]   The coloring composition for color filters according to claim 1, wherein the content of the quinophthalone compound (A1) is 3 to 90% by mass with respect to the total of the quinophthalone compound (A1) and the quinophthalone compound (A2).   The color filter according to claim 1 or 2, further comprising a pigment derivative, wherein the pigment derivative is a quinophthalone compound (B) having a sulfo group or a metal salt or alkyl ammonium salt of a sulfo group. Composition.   Furthermore, any one or more selected from the group consisting of phthalocyanine pigments, isoindoline pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, and azo pigments are included. The coloring composition for color filters of any one of-.   Furthermore, the photopolymerizable monomer and / or the photoinitiator is contained, The coloring composition for color filters of any one of the Claims 1-4 characterized by the above-mentioned.   The color filter formed with the coloring composition for color filters of any one of Claims 1-5.