JP2013181104A - Pigment derivative, coloring composition and color filter - Google Patents

Abstract

（式（ａ）〜（ｃ）中、Ｘ¹、Ｘ²、Ｘ³は−ＳＯ₂−等、Ｙ¹、Ｙ²、Ｙ³は−ＮＨ−等、Ｚ¹は−ＣＯＮＨ−等、ｎは０〜１０の整数、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶は、−（ＣＨ₂）_mＮＲ⁷Ｒ⁸で表される基であり、Ｒ⁷、Ｒ⁸は、アルキル基等であり、Ｒ⁷とＲ⁸は一体となって環を形成しても良い。ｍは、０〜１０の整数である。）］
【選択図】なしProvided are a color filter giving high brightness and contrast, and a pigment derivative and a coloring composition for use therein.
A formula: pigment derivative represented by P-L _m. [Wherein, P is a phthalocyanine pigment residue, m is an integer of 1 to 4, and L is a group represented by the following formula (a), (b) or (c).

(In the formulas (a) to (c), X ¹ , X ² , X ³ are —SO ₂ — etc., Y ¹ , Y ² , Y ³ are —NH— etc., Z ¹ is —CONH— etc., n is An integer of 0 to 10, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ is a group represented by — (CH ₂ ) _m NR ⁷ R ⁸ , and R ⁷ , R ⁸ are An alkyl group or the like, and R ⁷ and R ⁸ may be combined to form a ring, and m is an integer of 0 to 10.)]
[Selection figure] None

Description

  The present invention relates to a pigment derivative, a coloring composition, and a color filter formed using the same.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. By providing a color filter between the two polarizing plates, color display is possible, and it has come to be used for televisions, personal computer monitors and the like. In recent years, demands for higher brightness, higher contrast, and higher color reproducibility are increasing for color filters from the viewpoint of energy saving.

  The reason why the polarization plane of the light transmitted through the first polarizing plate is disturbed by the color filter is that the light polarized by the first polarizing plate is reflected on the pigment surface when passing through the color filter, and polarized. It is thought that the plane is rotated and the polarized light is broken (depolarization).

  Therefore, in order to increase the contrast ratio of the color liquid crystal display, the primary particles of the pigment contained in the color filter are made finer to have a size smaller than the wavelength of light, and the refractive index difference between the pigment and the medium is reduced. It is important to. In general, the primary particles of the pigment are miniaturized by subjecting the pigment to mechanical pulverization (see Patent Documents 1 and 2).

  In addition, in order to increase the brightness of a color liquid crystal display, it is necessary to design a pigment composition having an optimal spectral shape. In the case of blue, in the transmission spectrum of the color filter, the rise from around 500 nm to the short wavelength side The transmittance from around 400 nm to 450 nm is important.

  In order to obtain a pigment composition having the above optimal spectral shape, selection of a material having an appropriate spectral region, improvement of transmission by miniaturization of primary particles, pigment derivatives and dispersion methods for reliably dispersing these primary particles, and There is a need for pigment derivatives with controlled hue.

  As the phthalocyanine pigment derivative, pigment derivatives described in Patent Documents 3 to 9 are known. However, the terminal portion of the pigment derivatives described in these documents is “a structure in which a heterocycle is formed with a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an oxygen atom and a nitrogen atom”, and is disclosed in these documents. In the derivative, the fineness and dispersion of the pigment are insufficient, and thus higher brightness and contrast cannot be obtained than conventionally known color filters.

  Further, in recent years, a color filter using a dye has been proposed (see Patent Document 10), but it has been pointed out that fluorescence derived from the dye has an adverse effect on the color filter (see Patent Document 11). Therefore, how to suppress the generation of fluorescence derived from such a dye is an important problem.

JP 2001-220520 A JP 2005-189672 A JP-A-49-59136 JP-A-51-18736 Japanese Patent Laid-Open No. 52-133201 JP 54-62227 A JP 2000-258602 A JP 2005-181383 A JP 2007-226161 A JP 2010-26334 A JP 2011-227491 A

  In the production of the blue filter segment, a coloring composition containing a blue pigment is used. In addition to CI pigment blue 15: 6 and CI pigment violet 23, which are conventionally blue pigments, and dyes, Pigment derivatives have been used to obtain dispersion, refinement and crystal type stability.

  However, conventionally, a large amount of a phthalocyanine pigment derivative has been required for pigment miniaturization. In addition, since it is difficult to disperse even if it can be miniaturized, the lightness and heat resistance due to an increase in the amount of pigment derivative added are sacrificed as a result.

  The problem to be solved by the present invention is to provide a color filter that provides high brightness and contrast, and a pigment derivative and a coloring composition for use therein. In addition, it is to provide a color filter in which fluorescence derived from a dye is suppressed, and a pigment derivative and a coloring composition for use therein.

  As a result of intensive research, the present inventors have found that a phthalocyanine pigment derivative having a specific triamine structure is superior in pigment refining ability and dispersibility as compared with conventionally known pigment derivatives, and a coloring composition. As a result, the present inventors have found that a color filter giving high brightness and contrast ratio can be obtained by suppressing the fluorescence derived from the dye used in combination as needed.

［式（ａ）〜（ｃ）中、
Ｘ¹、Ｘ²、Ｘ³は、−ＳＯ₂−、−ＣＯ−、−ＣＨ₂−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−ＣＨ₂ＮＨＳＯ₂ＣＨ₂−、または直接結合であり、
Ｙ¹、Ｙ²、Ｙ³は、−ＮＨ−、−Ｏ−、−Ｓ−、−ＮＨ−（ＣＨ₂）_n−または直接結合であり、
Ｚ¹は、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＳＯ₂ＮＨ−、または−ＮＨＳＯ₂−であり、
ｎは、０〜１０の整数であり、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶は、下記一般式（２）で表される基である。］
一般式（２）

−（ＣＨ₂）_mＮＲ⁷Ｒ⁸

［一般式（２）中、Ｒ⁷、Ｒ⁸は、それぞれ独立に、水素原子、置換基を有しても良い炭素数１〜３０のアルキル基、または置換基を有しても良い炭素数２〜３０のアルケニル基であり、Ｒ⁷とＲ⁸は一体となって窒素、酸素、および硫黄原子を含む複素環を形成しても良い。ｍは、０〜１０の整数である。］ That is, the present invention relates to a pigment derivative represented by the following general formula (1).
General formula (1)

P-L _m

[In general formula (1),
P is a phthalocyanine pigment residue;
m is an integer of 1 to 4,
L is a group represented by the following formula (a), (b) or (c). ]

[In the formulas (a) to (c),
X ^1, X ^2, X ³ _{are, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y ¹ , Y ² and Y ³ are —NH—, —O—, —S—, —NH— (CH ₂ ) _n — or a direct bond,
Z ¹ is —CONH—, —NHCO—, —SO ₂ NH—, or —NHSO ₂ —,
n is an integer of 0 to 10,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are groups represented by the following general formula (2). ]
General formula (2)

^{_{- (CH 2) m NR 7}} R 8

[In General Formula (2), R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms that may have a substituent, or a carbon number that may have a substituent. 2 to 30 alkenyl groups, R ⁷ and R ⁸ may together form a heterocycle containing nitrogen, oxygen and sulfur atoms. m is an integer of 0-10. ]

  The present invention also relates to the pigment derivative, wherein the phthalocyanine pigment residue is one or more metal phthalocyanine pigment residues selected from the group consisting of cobalt, nickel and copper as a central metal.

  The present invention also relates to a colored composition comprising the phthalocyanine pigment, a binder resin, and an organic solvent in the pigment derivative.

  The present invention also relates to a color filter comprising a filter segment formed from the colored composition according to claim 3 on a substrate.

  INDUSTRIAL APPLICABILITY Since the present invention can provide a color filter that provides high brightness and contrast ratio, it can be used in display fields such as liquid crystal display panels, plasma display panels, and organic EL display panels that require high brightness and contrast. can do.

  Hereinafter, the present invention will be described in detail. Note that “CI” described below means a color index (CI).

(Pigment)
In the present invention, the production method of phthalocyanine used as a pigment is not particularly limited. However, the production method of copper phthalocyanine described in PIGMENT HANDBOOK, Volume 1 page 667 (1988), “Phthalocyanine-chemistry and Function- ”It can be produced by a known production method described in pages 55 to 62 (1997). Moreover, it can also atomize by well-known methods, such as the process of a pigment derivative, a sulfuric acid method, and an alkaline reduction dissolution method, as needed.

  The phthalocyanine pigment is obtained by adding a photoinitiator or a binder resin to a pigment composition obtained by mixing with a pigment derivative represented by the general formula (1) and, if necessary, another pigment, a three-roll mill, The pigment composition can be produced using various dispersion and refinement means such as a two-roll mill, a sand mill, and a kneader. In the present specification, unless otherwise specified, the “pigment composition” means a composition comprising a phthalocyanine pigment and a pigment derivative represented by the general formula (1). Further, when simply referred to as “pigment”, it means a phthalocyanine pigment.

(Pigment derivative)
The pigment derivative of the present invention is a pigment derivative represented by the general formula (1). The pigment derivative can be synthesized by a known production method in which chlorosulfonation is carried out using chlorosulfonic acid and thionyl chloride and then further sulfonamidation is carried out by reacting with an amine component.

When a phthalocyanine pigment and a dye are used as colorants, a color filter with high brightness can be obtained from the high transparency derived from the high solubility of the dye, compared to the case where only the pigment is used. Fluorescence is generated from the light, and the contrast ratio is lowered. This is mainly due to the presence of fluorescence in the leakage light at the time of contrast measurement, and the luminance on the cross side increases.

As a result of studies conducted by the present inventors to solve the problem of reduction in contrast due to fluorescence emission, the use of the pigment derivative represented by the general formula (1) eliminates the generation of fluorescence from the dye, and the cross side. It was possible to realize high contrast by lowering the brightness of.

The reason why the fluorescence quenching effect becomes remarkable when these substances are used is not clear, but when the pigment derivative represented by the general formula (1) is used, it is easy to form a charge transfer complex with the dye. It is considered that the fluorescence emission itself is remarkably suppressed and the fluorescence is remarkably quenched. Below, the amine used for this invention is demonstrated concretely.

  Examples of the amine (triamine) component used for forming the substituent represented by the above formula (a), formula (b), and formula (c) include N, N, N ″, N ″ — Tetramethyldiethylenetriamine, N, N, N ", N" -tetraethyldiethylenetriamine, N, N-dimethylN ", N" -diethyldiethylenetriamine, N, N-diethylN ", N" -diisopropyldiethylenetriamine, N, N-diethyl N ", N" -dipropyldiethylenetriamine, N, N-dimethylN ", N" -dibutyldiethylenetriamine, N, N-dimethylN ", N" -diisobutyldiethylenetriamine, N, N-dibutylN ", N" -diethyl Diethylenetriamine, N, N-ditert-butyl N ", N" -diethyldiethylenetriamine, N, N, N ", N" -tetraisopro Rudiethylenetriamine, N, N, N ", N" -tetrapropyldiethylenetriamine, N, N, N ", N" -tetrasec-butylpropyldiethylenetriamine, N, N, N ", N" -tetrabutyldiethylenetriamine, N, N, N ", N" -tetra-sec-butyldiethylenetriamine, N, N, N ", N" -tetraisobutyldiethylenetriamine, N, N-diisobutyl-N ", N" -disec-butyldiethylenetriamine, N, N , N ", N" -tetradiamildiethylenetriamine, N, N, N ", N" -tetraisoamyldiethylenetriamine, N, N, N ", N" -tetrahexyldiethylenetriamine, N, N, N ", N"- Tetracyclohexyldiethylenetriamine, N, N, N ", N" -tetra (2-ethylhexyl) diethylenetria N, N, N ", N" -tetraoctyldiethylenetriamine, N, N-dimethylN ", N" -dioctadecyldiethylenetriamine, N, N, N ", N" -tetradecyldiethylenetriamine, N, N, N ", N" -tetraallyldiethylenetriamine, N, N-diethyl-N ", N" -di (1,2-dimethylpropyl) diethylenetriamine, N, N-dimethyl-N ", N" -dihexyldiethylenetriamine, N, N , N ", N" -tetraoleyldiethylenetriamine, N, N, N ", N" -tetrastearyldiethylenetriamine, N, N, N ", N" -tetramethyldimethylenetriamine, N, N, N ", N" -Tetramethyldimethylenetriamine, N, N, N ", N" -tetramethyldiamylenetriamine, N, N, N ", N" -tetramethyldibutylenetri Amine, N, N, N ", N" -tetraethyldimethylenetriamine, N, N, N ", N" -tetraethyldipropylenetriamine, N, N, N ", N" -tetraethyldihexylenetriamine, N, N , N ", N" -tetraethyldibutylenetriamine, N, N, N ", N" -tetraethyldipentylenetriamine, N, N, N ", N" -tetrapropyldibutylenetriamine, N, N, N " , N "-tetrabutyldipropylenetriamine, N, N, N", N "-tetrabutyldimethylenetriamine, N, N, N", N "-tetrabutyldibutylenetriamine, N, N, N", N "-Tetraisobutyldipentylenetriamine, N, N-dimethyl-N", N "-dilauryldipropylenetriamine, N, N-diethyl-N", N "-dihexyldimethylenetriamine, N, N, ", N" -tetrastearyldimethylenetriamine, N, N, N ", N" -tetraoleyldimethylenetriamine, N, N, N ", N" -tetrastearyldibutylenetriamine, di-N-piperidylmethylamine Di-N-piperazylmethylamine, di-N-morpholylmethylamine, di-4-piperidylmethylamine, di-N-piperidylethylamine, di-N-piperazylethylamine, di-N-morpholyl Ethylamine, di-4-piperidylethylamine, di-N-piperidylpropylamine, di-N-piperidylpropylamine, di-N-morpholylpropylamine, di-4-piperidylbutylamine, di-N-piperidylbutylamine, Di-N-piperidylbutylamine, di-N-morpholylbutylamine, di-4-piperidylbutyl 1,1,7,7-tetramethyl-1,4,7-triazaheptane, 1,1,7,7-tetraethyl-1,4,7-triazaheptane, 1,1,7,7 -Tetrapropyl-1,4,7-triazaheptane, 1,1,7,7-tetraisopropyl-1,4,7-triazaheptane, 1,1,7,7-tetrabutyl-1,4,7 -Although triazaheptane etc. are mentioned, this invention is not limited to these.

  In addition to the method of mixing the pigment derivative when dispersing the pigment, a method of mixing in water or an organic solvent at the time of manufacturing the pigment composition or a method of adding at the time of salt milling can be mentioned. The method of mixing the pigment derivative in water or an organic solvent during the production of the pigment composition or the method of adding the pigment derivative during the salt milling treatment has the effect of suppressing the crystal growth of the pigment composition. The pigment derivative is required to be efficiently adsorbed on the pigment surface and not easily desorbed. For this reason, the structure of the pigment derivative is often suitable to have a partial structure similar to the pigment used. For these reasons, when the pigment is a phthalocyanine pigment, a phthalocyanine pigment derivative is preferred.

  In addition, the pigment derivative can be used as long as the color tone of the coloring composition is not impaired as much as possible. From the viewpoint of hue, a pigment exhibiting a blue color can be preferably used as the pigment derivative.

  It is preferable that the compounding quantity of a pigment derivative is the range of 0.5-40 mass parts with respect to 100 mass parts of pigment compositions. More preferably, it is the range of 13-35 mass parts.

  Hereinafter, although the specific example of the pigment derivative used for this invention is described, this invention is not limited to these.

(Specific examples of pigment derivatives)
As the pigment derivative, specifically, a compound represented by the following formula can be used, but is not limited thereto. Note that i-C ₃ H ₇ represents an isopropyl group, and C ₃ H ₆ represents a propylene group.

  In order to refine the pigment composition, a salt milling process which is wet pulverization and mixing is preferable. Salt milling is a process in which a mixture of a pigment composition, a water-soluble inorganic salt, and a water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt works as a crushing aid, and it is considered that the pigment composition is crushed using the high hardness of the inorganic salt during salt milling, resulting in an active surface and crystal growth. It has been. Therefore, the crushing and crystal growth of the pigment composition occur simultaneously during kneading, and the primary particle size of the pigment composition obtained varies depending on the kneading conditions.

  In order to promote crystal growth of the pigment composition by heating, the heating temperature is preferably 35 to 150 ° C. When the heating temperature is less than 35 ° C., crystal growth does not occur sufficiently, and the shape of the pigment composition particles becomes nearly amorphous, which is not preferable. On the other hand, a heating temperature exceeding 150 ° C. is not preferable because crystal growth proceeds excessively and the primary particle diameter of the pigment composition becomes large. The kneading time for the salt milling treatment is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the pigment composition subjected to the salt milling treatment and the cost required for the salt milling treatment.

  By optimizing the conditions at the time of subjecting the pigment composition to salt milling, a pigment composition having a very fine primary particle diameter and a narrow particle size distribution range can be obtained.

  As the water-soluble inorganic salt used for the salt milling treatment, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, more preferably 300 to 1500 parts by mass with respect to 100 parts by mass of the pigment composition, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment composition and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during the salt milling process and these solvents are easily evaporated.

  Examples of the water-soluble organic solvent include 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, etc. Is used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, more preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment composition.

  In the salt milling treatment, the above pigment derivative may be used in combination to improve kneading efficiency, which is very effective for making the pigment composition finer and sized. In the refinement of the pigment composition used in the present invention, it is preferable to use the pigment derivative, but the invention is not limited thereto. The amount of the pigment derivative used is preferably in the range of 0.5 to 40 parts by mass with respect to the amount that does not affect the color tone, that is, 100 parts by mass of the pigment composition.

  Moreover, when performing a salt milling process, you may add resin as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. It is preferable that the usage-amount of resin is the range of 5-200 mass parts with respect to 100 mass parts of pigment compositions.

  The pigment composition can be used as a colored composition by forming a composition together with a binder resin and an organic solvent. At that time, other colorants other than the pigment composition may be used in combination.

(Other colorants)
In order to adjust the chromaticity, the pigment composition may be used in combination with a pigment or a dye as a colorant in addition to the pigment composition as long as the effects of the present invention are not impaired.

  Other pigments that can be used in the colorant include, for example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, Mention may be made of red pigments such as 279, 280, 281, 282, 283, 284, 285, 286 or 287. Other red dyes that can be used in the colorant include xanthene series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, anthraquinone series, and the like. Specifically, C.I. I. And salt forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  In addition, C.I. I. Pigment Orange 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or a yellow pigment 221 and the like can be used in combination. Examples of the orange dye and / or yellow dye include quinoline series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and methine series.

  Other preferred colorants that can be used in combination are C.I. I. And CI Pigment Violet 23.

  The colorant for adjusting the chromaticity is preferably in the range of 0 to 75 parts by mass with respect to 100 parts by mass of the pigment composition, although it depends on the backlight and the target hue.

(Binder resin)
Examples of the binder resin contained in the colored composition of the present invention include conventionally known thermoplastic resins and thermosetting resins.

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

  When used as a coloring composition for a color filter, the spectral transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

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

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, formyl groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. In addition, polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer are half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

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

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

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

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

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by connecting four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene-equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by Corporation and using tetrahydrofuran as the mobile phase.

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

  The binder resin is preferably used in an amount of 20 to 500 parts by mass with respect to 100 parts by mass of the pigment composition.

(Organic solvent)
In the colored composition of the present invention, it is easy to form a filter segment by sufficiently dispersing the pigment composition and applying it onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to do so, an organic solvent is included. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

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

  Among them, since the solubility of each component in the coloring composition and the coating property of the coloring composition are good, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol It is preferable to use glycol acetates such as monoethyl ether acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. The organic solvent is used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the colored composition in order to adjust the colored composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness. Is preferred.

(Dispersion of coloring composition)
In the coloring composition of the present invention, the pigment composition is a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular type in a colored composition carrier composed of the binder resin and an organic solvent. It can be produced by finely dispersing using various dispersing means such as a bead mill or an attritor. In the colored composition of the present invention, the pigment composition and other colorants may be simultaneously dispersed in the colored composition carrier, or those separately dispersed in the colored composition carrier may be mixed. The carrier means a composition comprising a binder resin and an organic solvent.

  Further, when the pigment composition is dispersed in the colored composition carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the coloring composition using the dispersion aid can be expected to improve contrast and viscosity stability.

(Resin type dispersant and surfactant)
The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colored composition and a part compatible with the colored composition carrier, and adsorbs to the pigment composition to disperse in the colored composition. It works to stabilize. Specific examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkyls. Amine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) and polyesters having free carboxyl groups, Oil-based dispersants such as salts thereof, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester, modified Li acrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. -EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfone. Anionic surface activity such as sodium lauryl sulfate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Agents: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxye Nonionic surfactants such as lenalkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethyl Examples include amphoteric surfactants such as alkylbetaines such as aminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When adding a resin-type dispersant and a surfactant, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, with respect to 100 parts by weight of the pigment composition.

  The colored composition of the present invention can be used as a photosensitive colored composition by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

(Photopolymerizable monomer)
The photopolymerizable monomer used in the coloring composition of the present invention includes a monomer or an oligomer that is cured by ultraviolet rays or heat to form a transparent resin. These may be used alone or in combination of two or more. Can be used. It is preferable that the compounding quantity of a monomer is 5-400 mass parts with respect to 100 mass parts of coloring compositions, and it is more preferable that it is 10-300 mass parts from a photocurable and developable viewpoint.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

(Photopolymerization initiator)
When the colored composition of the present invention is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator is added to form a photosensitive colored composition. Or it can adjust with the form of an alkali image development type colored resist material.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Phenyl) -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- Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole A imidazole compound; a titanocene compound, or the like.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment composition in the coloring composition, and 3 to 150 parts by mass from the viewpoint of photocurability and developability. It is more preferable.

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

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

  Two or more kinds of sensitizers may be used in any ratio as required. It is preferable that the compounding quantity at the time of using a sensitizer is 3-60 mass parts with respect to 100 mass parts of photoinitiators contained in a coloring composition, and from a viewpoint of photocurability and developability. It is more preferable that it is 5-50 mass parts.

(Amine compounds)
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

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

(Leveling agent)
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5 parts by mass with respect to 100 parts by mass of the colored composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

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

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used. Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene 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 stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

(Curing agent, curing accelerator)
In order to assist the curing of the thermosetting resin, the coloring composition of the present invention may contain a curing agent, a curing accelerator, and the like as necessary. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. 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- Til-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, it is preferable to use 0.01-15 mass parts with respect to 100 mass parts of thermosetting resins.

(Other additive components)
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

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

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include 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% by mass, preferably 0.05 to 5% by mass, based on the total amount of the colorant in the coloring composition (100% by mass).

(Removal of coarse particles)
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

(Color filter)
Next, the color filter of the present invention will be described. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, and the red filter segment therein is formed from a coloring composition containing the disazo coloring composition of the present invention. The

  The green filter segment can be formed using a normal green coloring composition containing a green pigment and a coloring composition carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used.

  A yellow pigment can be used in combination with the green coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition including a blue pigment and a coloring composition carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. A purple pigment can be used in combination with the blue coloring composition. Examples of purple pigments that can be used in combination include C.I. I. And violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When using a dye, a xanthene dye is preferable in terms of heat resistance and lightness.

(Color filter manufacturing method)
The color filter of the present invention can be produced by a printing method or a photolithography method.

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

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

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

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, etc. in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

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

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “part” means “part by mass” and “%” means “% by mass” unless otherwise specified.

(Identification method of pigment derivative)
The pigment derivative of the present invention was identified by a MALDI TOF-MS spectrum. The MALDI TOF-MS spectrum was determined by measuring the mass spectrum using a MALDI mass spectrometer autoflex III manufactured by Bruker Daltonics, and the molecular ion peak of the obtained mass spectrum was identified as coincident with the calculated value.

<Synthesis of pigment derivative>
Example 1
In a reaction vessel, 300 parts of chlorosulfonic acid and 30 parts of copper phthalocyanine were added and completely dissolved. Then, 24 parts of thionyl chloride was added, and the temperature was gradually raised and reacted at 101 ° C. for 3 hours. The reaction solution was poured into 9000 parts of ice water, stirred, filtered and washed with water. The obtained press cake was made into a slurry with 300 parts of water, 17 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane was added, and the mixture was stirred at 65 ° C. for 4 hours, followed by filtration. The pigment derivative 1 was obtained by washing with water and drying. As a result of mass spectrometry by TOF-MS, 797.39 was observed as a molecular ion peak, and thus the structure of Formula 1 was identified.

(Example 2)
17 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 1 was converted to 24 parts of 1,1,7,7-tetraethyl-1,4,7-triazaheptane. A pigment derivative 2 was obtained in the same manner as in Example 1 except that the pigment derivative was changed. As a result of mass spectrometry by TOF-MS, 853.5 was observed as a molecular ion peak, and thus the structure of Formula 2 was identified.

(Example 3)
17 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 1 is replaced with 30 parts of 1,1,7,7-tetrapropyl-1,4,7-triazaheptane. A pigment derivative 3 was obtained in the same manner as in Example 1 except that the pigment derivative 3 was changed. As a result of mass spectrometry by TOF-MS, 909.6 was observed as a molecular ion peak, and thus the structure of Formula 3 was identified.

Example 4
17 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 1 is replaced with 30 parts of 1,1,7,7-tetraisopropyl-1,4,7-triazaheptane. A pigment derivative 4 was obtained in the same manner as in Example 1 except that the pigment derivative 4 was changed. As a result of mass spectrometry by TOF-MS, 909.6 was observed as a molecular ion peak, and thus the structure of Formula 4 was identified.

(Example 5)
17 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 1 was replaced with 36 parts of 1,1,7,7-tetrabutyl-1,4,7-triazaheptane. A pigment derivative 5 was obtained in the same manner as in Example 1 except that the pigment derivative was changed. As a result of mass spectrometry by TOF-MS, 965.71 was observed as a molecular ion peak, and thus the structure of Formula 5 was identified.

(Example 6)
In a reaction vessel, 300 parts of chlorosulfonic acid and 30 parts of copper phthalocyanine were added and completely dissolved. Then, 24 parts of thionyl chloride was added, and the temperature was gradually raised and reacted at 101 ° C. for 3 hours. The reaction solution was poured into 9000 parts of ice water, stirred, filtered and washed with water. After making the obtained press cake into a slurry with 300 parts of water, 11 parts of 1,4-phenylenediamine was added and stirred at 5 ° C. for 3 hours and then at 50 ° C. for 1 hour. After completion of stirring, filtration, washing with water and drying were performed to obtain an intermediate. Next, 400 parts of acetone was cooled to 5 ° C., and 10 parts of cyanuric chloride was added. Next, 35 parts of the intermediate was gradually added while maintaining 5 ° C. Thereafter, 90 parts of a 10% -sodium carbonate aqueous solution was added, stirred at 5 ° C. for 3 hours, filtered and washed with water. The obtained paste was gradually added to a mixed solution of 320 parts of 1,4-dioxane and 60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane at a temperature of 60 ° C. or lower. . Then, it stirred at 50-60 degreeC for 1.5 hours, and 90 degreeC for 3.5 hours. 200 parts of water was added to the reaction mixture and heated to reflux temperature to distill off 1,4-dioxane. Cool to room temperature and adjust the pH to 4.0 with acetic acid to dissolve the product. The reaction mixture was poured into 1 L of water and the pH was adjusted to 11 with sodium hydroxide. The supernatant was removed by decantation and washed until neutral. By vacuum drying at 50 ° C., pigment derivative 6 was obtained. As a result of mass spectrometry by TOF-MS, 1139.83 was observed as a molecular ion peak, and thus the structure of Formula 6 was identified.

(Example 7)
60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 6 was changed to 84 parts of 1,1,7,7-tetraethyl-1,4,7-triazaheptane. A pigment derivative 7 was obtained in the same manner as in Example 1 except that the pigment derivative was changed. As a result of mass spectrometry by TOF-MS, 1252.04 was observed as a molecular ion peak, and thus the structure of Formula 7 was identified.

(Example 8)
60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 6 was replaced with 105 parts of 1,1,7,7-tetrapropyl-1,4,7-triazaheptane. A pigment derivative 8 was obtained in the same manner as in Example 1 except that the pigment derivative 8 was changed. As a result of mass spectrometry by TOF-MS, 1364.26 was observed as a molecular ion peak, and thus the structure of Formula 8 was identified.

Example 9
60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 6 was replaced with 105 parts of 1,1,7,7-tetraisopropyl-1,4,7-triazaheptane. A pigment derivative 9 was obtained in the same manner as in Example 1 except that the pigment derivative 9 was changed. As a result of mass spectrometry by TOF-MS, 1364.26 was observed as a molecular ion peak, and thus the structure of Formula 9 was identified.

(Example 10)
60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 6 was changed to 126 parts of 1,1,7,7-tetrabutyl-1,4,7-triazaheptane. Except having changed, it synthesize | combined like Example 1 and the pigment derivative 10 was obtained. As a result of mass spectrometry by TOF-MS, 1476.47 was observed as a molecular ion peak, and thus the structure of Formula 10 was identified.

(Example 11)
A pigment derivative 11 was obtained in the same manner as in Example 6 except that 11 parts of 1,4-phenylenediamine in Example 6 were changed to 10 parts of 1,4-diaminobutane. As a result of mass spectrometry by TOF-MS, 1119.84 was observed as a molecular ion peak, and thus the structure of Formula 11 was identified.

(Example 12)
60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 11 was changed to 84 parts of 1,1,7,7-tetraethyl-1,4,7-triazaheptane. Except having changed, it synthesize | combined similarly to Example 11, and the pigment derivative 12 was obtained. As a result of mass spectrometry by TOF-MS, 1218.03 was observed as a molecular ion peak, and thus the structure of Formula 12 was identified.

(Example 13)
60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 11 was replaced with 105 parts of 1,1,7,7-tetrapropyl-1,4,7-triazaheptane. A pigment derivative 13 was obtained in the same manner as in Example 11 except that the pigment derivative 13 was changed. As a result of mass spectrometry by TOF-MS, 1344.27 was observed as a molecular ion peak, and thus the structure of Formula 13 was identified.

(Example 14)
60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 11 was replaced with 105 parts of 1,1,7,7-tetraisopropyl-1,4,7-triazaheptane. A pigment derivative 14 was obtained in the same manner as in Example 11 except that the pigment derivative 14 was changed. As a result of mass spectrometry by TOF-MS, 1117.87 was observed as a molecular ion peak, and thus the structure of Formula 14 was identified.

(Example 15)
60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 11 was changed to 126 parts of 1,1,7,7-tetrabutyl-1,4,7-triazaheptane. The pigment derivative 15 was obtained by synthesizing in the same manner as in Example 11 except for the change. As a result of mass spectrometry by TOF-MS, 1470.51 was observed as a molecular ion peak, and thus the structure of Formula 15 was identified.

(Comparative Example 1)
Example 1 except that 17 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 1 were changed to 10 parts of 1,1-dimethyl-1,4-diazabutane. And pigment derivative 16 was obtained. As a result of mass spectrometry by TOF-MS, 740.3 was observed as a molecular ion peak, and thus the structure of Formula 16 was identified.

(Comparative Example 2)
Example 1 except that 17 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 1 were changed to 13 parts of 1,1-diethyl-1,4-diazabutane. And pigment derivative 2 was obtained. As a result of mass spectrometry by TOF-MS, 768.35 was observed as a molecular ion peak, and thus the structure of Formula 17 was identified.

(Comparative Example 3)
Example 1 except that 17 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 1 were changed to 16 parts of 1,1-dipropyl-1,4-diazabutane. And pigment derivative 18 was obtained. As a result of mass spectrometry by TOF-MS, 796.4 was observed as a molecular ion peak, and thus the structure of Formula 18 was identified.

(Comparative Example 4)
Example 1 except that 17 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 1 were changed to 16 parts of 1,1-diisopropyl-1,4-diazabutane. And pigment derivative 19 was obtained. As a result of mass spectrometry by TOF-MS, 796.4 was observed as a molecular ion peak, and thus the structure of Formula 19 was identified.

(Comparative Example 5)
Example 1 except that 17 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 1 were changed to 19 parts of 1,1-dibutyl-1,4-diazabutane. And pigment derivative 20 was obtained. As a result of mass spectrometry by TOF-MS, 824.15 was observed as a molecular ion peak, and thus the structure of Formula 20 was identified.

(Comparative Example 6)
Example 6 except that 60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 6 was changed to 34 parts of 1,1-dimethyl-1,4-diazabutane. And pigment derivative 21 was obtained. As a result of mass spectrometry by TOF-MS, 10225.64 was observed as a molecular ion peak, and thus the structure of Formula 21 was identified.

(Comparative Example 7)
Example 6 is the same as Example 6 except that 60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 6 is changed to 45 parts of 1,1-diethyl-1,4-diazabutane. In the same manner, pigment derivative 22 was obtained. As a result of mass spectrometry by TOF-MS, 1081.75 was observed as a molecular ion peak, and thus the structure of Formula 22 was identified.

(Comparative Example 8)
Example 6 is the same as Example 6 except that 60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 6 is changed to 56 parts of 1,1-dipropyl-1,4-diazabutane. In the same manner, pigment derivative 23 was obtained. As a result of mass spectrometry by TOF-MS, 1137.86 was observed as a molecular ion peak, and thus the structure of Formula 23 was identified.

(Comparative Example 9)
Example 6 is the same as Example 6 except that 60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 6 is changed to 56 parts of 1,1-diisopropyl-1,4-diazabutane. In the same manner, pigment derivative 24 was obtained. As a result of mass spectrometry by TOF-MS, 1137.86 was observed as a molecular ion peak, and thus the structure of Formula 24 was identified.

(Comparative Example 10)
Example 6 is the same as Example 6 except that 60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 6 is changed to 67 parts of 1,1-dibutyl-1,4-diazabutane. In the same manner, pigment derivative 25 was obtained. As a result of mass spectrometry by TOF-MS, 1193.96 was observed as a molecular ion peak, and thus the structure of Formula 25 was identified.

(Comparative Example 11)
Example 11 is the same as Example 11 except that 60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 11 is changed to 34 parts of 1,1-dimethyl-1,4-diazabutane. In the same manner, pigment derivative 26 was obtained. As a result of mass spectrometry by TOF-MS, 1005.65 was observed as a molecular ion peak, and thus the structure of Formula 26 was identified.

(Comparative Example 12)
Example 11 is the same as Example 11 except that 60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 11 is changed to 45 parts of 1,1-diethyl-1,4-diazabutane. In the same manner, pigment derivative 27 was obtained. As a result of mass spectrometry by TOF-MS, 1061.76 was observed as a molecular ion peak, and thus the structure of Formula 27 was identified.

(Comparative Example 13)
Example 11 is the same as Example 11 except that 60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 11 is changed to 56 parts of 1,1-dipropyl-1,4-diazabutane. In the same manner, pigment derivative 28 was obtained. As a result of mass spectrometry by TOF-MS, 1117.87 was observed as a molecular ion peak, and thus the structure of Formula 28 was identified.

(Comparative Example 14)
Example 11 is the same as Example 11 except that 60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 11 is changed to 56 parts of 1,1-diisopropyl-1,4-diazabutane. In the same manner, pigment derivative 29 was obtained. As a result of mass spectrometry by TOF-MS, 1117.87 was observed as a molecular ion peak, and thus the structure of Formula 29 was identified.

(Comparative Example 15)
Example 11 is the same as Example 11 except that 60 parts of 1,1,7,7-tetramethyl-1,4,7-triazaheptane in Example 11 is changed to 67 parts of 1,1-dibutyl-1,4-diazabutane. In the same manner, pigment derivative 30 was obtained. As a result of mass spectrometry by TOF-MS, 1173.97 was observed as a molecular ion peak, and thus the structure of Formula 30 was identified.

<Preparation of finer pigments>
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Ink Mfg. Co., Ltd., specific surface area 60 m ² / part) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts in a 1 gallon kneader (manufactured by Inoue Seisakusho) The mixture was kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a refined pigment were obtained.

<Preparation of acrylic resin solution>
700 parts of cyclohexanone was added to a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirring device, and heated to 80 ° C. After replacing the inside of the reaction vessel with nitrogen, 133 parts of n-butyl methacrylate, 46 parts of 2-hydroxyethyl methacrylate, 43 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 74 A mixture of 4.0 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 an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 parts of the resin solution was heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added so that the nonvolatile content of the resin solution was 20% to obtain an acrylic resin solution.

<Preparation of salt-forming compound (A)>
In the following procedure, C.I. I. A salt-forming compound (A-1) composed of Acid Red 289 and distearyldimethylammonium chloride (Cotamine D86P) (the molecular weight of the cation moiety was 550) was produced. In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 289 was dissolved, thoroughly mixed and stirred, heated to 70 to 90 ° C., and then Cotamine D86P (manufactured by Kao Corporation) was added dropwise little by little. Next, the reaction was sufficiently carried out by stirring at 70 to 90 ° C. for 60 minutes. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of Acid Red 289 and distearyldimethylammonium chloride, a salt-forming compound (A-1) was obtained.

<Preparation of dye solution>
The following mixture was stirred and mixed to be uniform and then filtered through a 5.0 μm filter to prepare a dye solution.
Salt-forming compound (A-1): 11.0 parts Acrylic resin solution: 40.0 parts Dye dilution solvent (cyclohexanol acetate): 49.0 parts

<Preparation of Colored Composition> (Examples 31 to 75 and Comparative Examples 16 to 60)
In the composition shown in Table 1, each of a pigment derivative, a refined pigment, an acrylic resin solution, and cyclohexanone as a solvent were uniformly stirred and mixed, and then a zirconia bead having a diameter of 1 mm was used to make an Eiger mill ("Mini Model M" manufactured by Eiger Japan). -250 MKII ") for 3 hours to prepare a colored composition. After filtering this colored composition through a 5 μm filter, 12 parts of a dye solution, 14 parts of an acrylic resin solution, 4.2 parts of trimethylolpropane triacrylate as a monomer, a photoinitiator (“Irgacure 907 manufactured by Ciba Japan Co., Ltd.) "] 1.2 parts, 0.4 parts of sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.) and 23.2 parts of cyclohexanone as a solvent were stirred and mixed uniformly, and then 1.0 .mu.m. A colored composition was prepared by filtering with a filter.

(Creation of color filter and evaluation of coloring composition)
A coating film (color filter) was prepared using the obtained colored composition, and each evaluation result of brightness and contrast was performed by the following methods.

(Create color filter)
The colored compositions obtained in Examples 31 to 75 and Comparative Examples 16 to 60 were placed on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and y = 0 in a C light source on the glass substrate. The film was applied to a thickness of 0.060, then dried at 70 ° C. for 20 minutes, exposed to ultraviolet light with an integrated light amount of 150 mJ using an ultrahigh pressure mercury lamp, and an alkaline developer (sodium carbonate 1. Develop with 5% by weight, 0.5% by weight of sodium bicarbonate, an anionic surfactant (“Periox NBL” manufactured by Kao Corporation), 8.0% by weight, and 90% by weight of water) A membrane substrate was obtained. Then, after heating and cooling at 230 ° C. for 1 hour, a coating film substrate (color filter) was prepared.

<Evaluation of brightness>
The brightness (Y) of the color filter obtained above was measured using a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The prepared substrate was made to have the chromaticity with the C light source shown in Table 5 after heat treatment at 230 ° C. The lightness was evaluated based on the relative value in the following five levels, based on the lightness of the color filter obtained using the colored composition of Comparative Example 18.
A: + 5% or more (very good)
○: Less than + 5% to + 2% or more (good)
Δ: Less than + 2% to -5% or more (equivalent to conventional)
X: Less than -5% (inferior to conventional)

<Evaluation of contrast>
Using a color luminance meter BM-5A manufactured by Topcon Corporation and a polarizing film LLC2-92-18 manufactured by Sanritsu Co., Ltd. as a polarizing plate, the luminance of the color filter prepared above was measured. When the color filter is sandwiched between two polarizing plates, the luminance at y = 0.060 is measured when the polarizing plates are parallel and perpendicular to each other, and the luminance at the orthogonality with the parallel luminance is measured. The ratio was contrast.

Contrast = (Brightness when polarizing plates are parallel) / (Brightness when polarizing plates are perpendicular)

In the measurement, in order to block scattered light, the measurement was performed by applying a black mask having a 1 cm square hole in the measurement portion. Based on the contrast of the color filter obtained by using the colored composition of Comparative Example 18, the evaluation was made based on the relative values in the following five stages.
A: + 10% or more (very good)
○: Less than + 10% to + 5% or more (good)
Δ: Less than + 5% to -10% or more (equivalent to conventional)
×: Less than −10% to −30% or more (inferior to conventional)
XX: -30% or less (not practical)

Based on the above results, the phthalocyanine pigment derivative having a specific triamine structure, which is the product of the present invention, is superior in pigment refining ability and dispersibility compared to conventional pigment derivatives, and is necessary for obtaining a colored composition. It was proved that a color filter giving a high brightness and contrast ratio can be obtained by suppressing the fluorescence derived from the dye used in combination. In particular, even if the conventional product is not dispersible or needs to be improved, it can be dispersed even at a low additive amount when the product of the present invention is used. This level is more effective than the conventional standard additive product. It became clear to show.

<Production of color filter>
In addition to the blue colored composition, a red colored composition and a green colored composition used for the production of a color filter were produced.

(Preparation of red dispersion 1)
A mixture having the composition shown below was stirred and mixed uniformly, and dispersed with Picomill (manufactured by Asada Tekko Co., Ltd.) for 8 hours using zirconia beads having a diameter of 0.1 mm. Was made.
Diketopyrrolopyrrole pigment (PR254) 12.0 parts Acrylic resin solution 40.0 parts Propylene glycol monomethyl ether acetate 48.0 parts

(Preparation of red coloring composition 1)
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a red colored composition 1 (RR-1).
Red dispersion 1 38.2 parts Acrylic resin solution 13.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan) ) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

(Preparation of green dispersion 1 (GP-1))
The mixture having the composition shown below was stirred and mixed uniformly, dispersed with picomil for 8 hours using zirconia beads having a diameter of 0.1 mm, filtered through a 5 μm filter, and Green Dispersion 1 (GP-1) was obtained. Produced.
Green pigment (CI Pigment Green 36) 6.8 parts Yellow pigment (CI Pigment Yellow 150) 5.2 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin Solution 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of green coloring composition 1 (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to produce a green colored composition 1 (GR-1).
Green dispersion 1 (GP-1) 42.0 parts Acrylic resin solution 13.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan Co., Ltd.) "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

  A black matrix is patterned on a glass substrate, and the red colored composition 1 (RR-1) of the present invention is formed on the substrate with a spin coater so that x = 0.640 and y = 0.328. It was applied to form a colored film. The coating was irradiated with 300 mJ / cm 2 of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, the green colored composition 1 (GR-1) is formed to a thickness such that x = 0.300 and y = 0.600, and the blue colored composition 1 (BR-1) is used. The film was applied to a film thickness such that 0.150 and y = 0.060, and a green filter segment and a blue filter segment were formed to obtain a color filter.

Claims (4)

A pigment derivative represented by the following general formula (1).
General formula (1)

P-L _m

[In general formula (1),
P is a phthalocyanine pigment residue;
m is an integer of 1 to 4,
L is a group represented by the following formula (a), (b) or (c). ]

[In the formulas (a) to (c),
X ^1, X ^2, X ³ _{are, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y ¹ , Y ² and Y ³ are —NH—, —O—, —S—, —NH— (CH ₂ ) _n — or a direct bond,
Z ¹ is —CONH—, —NHCO—, —SO ₂ NH—, or —NHSO ₂ —,
n is an integer of 0 to 10,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are groups represented by the following general formula (2). ]
General formula (2)

^{_{- (CH 2) m NR 7}} R 8

[In General Formula (2), R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms that may have a substituent, or a carbon number that may have a substituent. 2 to 30 alkenyl groups, R ⁷ and R ⁸ may together form a heterocycle containing nitrogen, oxygen and sulfur atoms. m is an integer of 0-10. ]   The pigment derivative according to claim 1, wherein the phthalocyanine pigment residue is one or more metal phthalocyanine pigment residues selected from the group consisting of cobalt, nickel and copper as a central metal.   A coloring composition comprising a phthalocyanine pigment, a binder resin, and an organic solvent in the pigment derivative according to claim 1.   A color filter comprising a filter segment formed from the colored composition according to claim 3 on a substrate.