JP7210913B2 - Photosensitive coloring composition and color filter - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive coloring composition that can be used for forming color filters used in color liquid crystal display devices, color organic EL display devices, color imaging tube elements, and the like.

Color filters used in liquid crystal display devices, solid-state imaging devices, and the like are widely known by a method of forming a photosensitive coloring composition in which a pigment is dispersed by a photolithography method.
The color filter is obtained by applying a photosensitive coloring composition to a transparent substrate such as glass, removing the solvent by drying, and then performing pattern exposure of one (one color) filter segment, followed by developing the unexposed area. After removing to form one filter segment and applying treatment such as heating as necessary, the same operation is sequentially repeated for filter segments of all colors.

Color filters are basically composed of three primary color filter segments (red, green, and blue), and in addition to green pigments, yellow pigments are generally used together to adjust the color tone of the green filter segment. was targeted.
Patent Documents 1 and 2 disclose photosensitive coloring compositions using a phthalocyanine pigment as a green pigment and an isoindoline pigment or an azo pigment as a yellow pigment.

Japanese Patent Application Laid-Open No. 2004-333817 JP 2016-075837 A

However, conventional photosensitive coloring compositions have low lightness of coatings. Therefore, when a quinophthalone pigment was used as a yellow pigment, the brightness was improved, but on the other hand, there was a problem that foreign matter was generated in the film after heating and the contrast was lowered.

An object of the present invention is to provide a photosensitive coloring composition capable of forming a color filter in which foreign matters are less likely to form on the film after heating, and to provide a color filter.

The photosensitive coloring composition of the present invention contains a coloring agent (A), a thiol compound (B), a binder resin (C), a photopolymerizable compound, and a photopolymerization initiator (D),
The coloring agent (A) contains a quinophthalone pigment and a phthalocyanine green pigment, and the thiol compound (B) contains two or more thiol groups.

ADVANTAGE OF THE INVENTION According to said invention, the photosensitive coloring composition which can form a color filter which a coating film is hard to produce a foreign substance after a heating, and a color filter can be provided.

FIG. 1 is a schematic cross-sectional view of a liquid crystal display device.

The terms used in this specification are defined below. "(Meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" unless otherwise specified , “acryloyl and/or methacryloyl”, “acrylic and/or methacrylic”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, or “acrylamide and/or methacrylamide”.
As used herein, "C.I." means Color Index (C.I.). A monomer is an ethylenically unsaturated group-containing monomer.

The photosensitive coloring composition of the present specification contains a coloring agent (A), a thiol compound (B), a binder resin (C), a photopolymerizable compound, and a photopolymerization initiator (D),
The coloring agent (A) contains a quinophthalone pigment and a phthalocyanine green pigment, and the thiol compound (B) contains two or more thiol groups. The photosensitive coloring composition of the present specification is preferably used for coating the green filter segment of the color filter.

<Colorant (A)>
Colorant (A) contains a quinophthalone pigment and a phthalocyanine green pigment. By containing the quinophthalone pigment and the phthalocyanine green pigment, a high-brightness and high-contrast color filter can be obtained. The coloring agent (A) can be used in combination with a dye. This allows the hue to be adjusted.

The quinophthalone pigment is Pigment Yellow 138 and one or more selected from the group consisting of the following quinophthalone compounds (a), (b), (c) and (d). In addition, quinophthalone-based pigments described in JP-A-2012-226110 can also be used in combination.

Quinophthalone pigments can be used alone or in combination of two or more.

Phthalocyanine green pigments include, for example, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 36, Pigment Green 58, and compounds represented by the following general formula (1) are preferred.

(wherein X represents a halogen atom, n represents an integer of 0 to 16, Y represents -OP(=O)R ₁ R ₂ , -OC(=O)R ₃ , -OS(= O) Represents ₂ R _4. R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituent or an optionally substituted aryloxy group, R ₃ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cyclo represents an alkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, wherein R ₄ represents a hydroxyl group, an optionally substituted alkyl group, or a substituent; represents an aryl group which may have or a heterocyclic group which may have a substituent.)

Examples of the compound represented by the general formula (1) in this specification include the following phthalocyanine compounds (a) to (r).

Phthalocyanine-based green pigments can be used alone or in combination of two or more.

The coloring agent (A) can be used in combination with the following other pigments. This makes it possible to easily adjust the hue of the coating.

Red pigments include, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, diketopyrrolopyrrole pigments described in JP-A-2011-523433, azo pigments described in JP-A-2014-112527, JP-A-2013-161026 and the azo pigments described in . Among these, C.I. I. Pigment Red 48:1, 122, 177, 224, 242, 254 are preferred, C.I. I. Pigment Red 254 is more preferred.

Orange pigments include, for example, C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 and the like.

Blue pigments include, for example, C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of heat resistance, light resistance and transmittance of the filter segment, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6, more preferably C.I. I. Pigment Blue 15:6.

Purple pigments include, for example, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among these, C.I. I. Pigment Violet 19, 23 are preferred, C.I. I. Pigment Violet 23 is more preferred.

Green pigments include, for example, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 37, 45, 48, 50, 51, 54, 55, JP-A-2008-19383, Zinc phthalocyanine pigments described in JP-A-2007-320986, JP-A-2004-70342, etc., and aluminum phthalocyanine pigments described in JP-A-4893859, etc. can be mentioned, but are not particularly limited thereto.

Yellow pigments include, for example, 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, 192, 193, 194, 196, 198, 199, 213, 214, 231 and the like.

<Dye>
Other coloring agents include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, and the like. Also, as the dye, derivatives thereof or lake pigments obtained by converting dyes into lakes can be used.

Also, the acid dye preferably has an acidic group such as sulfonic acid or carboxylic acid. The direct dye can form a salt-forming compound of an inorganic salt of an acid dye, or an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound. preferable. A salt-forming compound that forms a salt from a resin component having these functional groups and an acid dye is also preferred. Further, the salt-forming compound is sulfonamidated to be modified into a sulfonic acid amide compound, thereby easily obtaining a colored composition having excellent fastness.
A salt-forming compound of an acid dye and a compound having an onium base is also preferable because of its excellent fastness. The compound having an onium base is preferably a resin having a cationic group.

Basic dyes can be used as they are, but salt-forming compounds that form salts with organic acids, perchloric acid, or metal salts thereof are preferred. Salt-forming compounds of basic dyes are preferable because they have excellent resistance (light resistance, solvent resistance) and affinity with pigments. In salt-forming compounds of basic dyes, cation components that act as counterions, for example, include organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, A salt-forming compound obtained by salt-forming an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group and an acid dye is preferred. It should be noted that the resistance of the salt-forming compound is further improved when it contains a polymerizable unsaturated group in the molecule.

Dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthra pyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes Dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo thioindigo-based dyes, quinoline-based dyes, nitro-based dyes, nitroso-based dyes, rhodamine-based dyes, and metal complex-based dyes thereof. Among these, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium Xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes and phthalocyanine dyes are more preferable. Specific compounds of dyes are described in "New Edition Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and Colorists), "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986) and others.

Colorant (A) can be used alone or in combination of two or more.

The content of the coloring agent (A) is preferably 31 to 50% by weight, more preferably 31 to 40% by weight, based on 100% by weight of the non-volatile content of the coloring composition. When contained in an appropriate amount, color reproducibility is further improved.

<Refinement of pigment>
In this specification, the colorant (A) is preferably blended with other materials after being pulverized. Refining methods include, for example, wet grinding, dry grinding, dissolution precipitation, and the like. Salt milling treatment by a kneader method, which is one type of wet grinding, is preferred herein.
The average primary particle size of the pigment is preferably 20 nm or more because of good dispersibility. Moreover, since a color filter having a high contrast ratio can be formed, the thickness is preferably 100 nm or less. In addition, an average primary particle size of 25 to 85 nm is more preferable. The average primary particle size is obtained by directly measuring the size of the primary particles from an enlarged image of the pigment obtained by a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of about 20 pigment primary particles were measured, and the average was taken as the average primary particle diameter of the pigment particles.

The salt milling process involves milling a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent while heating using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, and sand mill. This is a treatment in which water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water after kneading to a certain extent. The water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Water-soluble inorganic salts, for example. Examples include sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like. Among these, inexpensive sodium chloride (salt) is preferable. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000% by weight, more preferably 300 to 1,000% by weight, based on 100% by weight of the pigment, in terms of both processing efficiency and production efficiency.

A water-soluble organic solvent can wet the pigment and the water-soluble inorganic salt. Any water-soluble organic solvent may be used as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. In this specification, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety. Water-soluble organic solvents include, 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, etc. mentioned. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, more preferably 50 to 500% by weight, based on 100% by weight of the pigment.

When salt milling the pigment, a resin can be added as necessary. Types of resins include, for example, natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Preferably, the resin is solid at room temperature (25° C.) and water-insoluble. It is also preferred that the resin is partially soluble in organic solvents. The amount of resin used is preferably 5 to 200% by weight with respect to 100% by weight of the pigment.

The photosensitive coloring composition preferably contains a dispersant. Dispersants include resin-type dispersants and other dispersants.

<Resin Dispersant>
The resin type dispersant has a pigment adsorption site and adsorbs to the pigment to form a dispersion. Portions other than the pigment adsorption site (x) act as steric hindrance sites, thereby improving pigment dispersibility.
Resin-type dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, Long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, salts thereof, etc. Water-soluble resins such as oil-based dispersants, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble polymer compounds, polyesters, modified polyacrylates, allene oxide/propylene oxide addition compounds, phosphoric acid esters and the like can be mentioned. Among these, polymer dispersants having a basic functional group are preferable because the addition of a small amount thereof reduces the viscosity of the composition and facilitates obtaining a high contrast. More preferred are nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups containing groups, quaternary ammonium bases, nitrogen-containing heterocycles, and the like.

Commercially available resin type dispersants are Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by BYK-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- P104, P104S, 220S, LPN6919, LPN21116, LPN21324 or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000000, 20000000, 16000, 17000000, 10800000, manufactured by Nippon Lubrizol , 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., E6 manufactured by BASF Japan Co., Ltd. 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajinomoto Fine-Techno Co., Inc. Ajisper PA111, PB411, PB821 , PB822, PB824, and the like.

The amount of the resin-type dispersant is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the colorant (A). This makes it easier to form a coating.

<Other Dispersants>
When other dispersing agents are used, reaggregation of the colorant (A) after dispersion is easily suppressed. Other dispersants include, for example, pigment derivatives and surfactants.

(dye derivative)
The dye derivative is a compound having a structure selected from the group consisting of organic pigments, anthraquinone, acridone, and triazine into which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced. mentioned. Further, dye derivatives are disclosed, for example, in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. The listed compounds are mentioned.

From the viewpoint of improving the dispersibility of the colorant, the amount of the pigment derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and 3 parts by mass or more with respect to 100 parts by mass of the colorant (A). More preferred. Moreover, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, relative to 100 parts by mass of the colorant (A).

(Surfactant)
Surfactants include, for example, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, alkyldiphenyl ether disulfonic acid. Anionic surfactants such as sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkylbetaines such as alkyldimethylaminoacetic acid betaine; and amphoteric surfactants such as alkylimidazoline.

The content of the surfactant is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, per 100 parts by mass of the colorant (A). A good dispersing effect can be easily obtained by adding an appropriate amount of surfactant.

A dispersing agent can be used individually or in combination of 2 or more types.

<Thiol compound (B)>
Thiol compound (B) contains two or more thiol groups. When the thiol compound (B) is used together with a photopolymerization initiator, it functions as a chain transfer agent in radical polymerization after light irradiation. As a result, thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated, so that photosensitivity is improved. In addition, the number of thiol groups is more preferably 4 or more. As a result, good photocuring can be easily obtained from the surface to the deep part of the film, so that, for example, it is possible to further suppress the generation of foreign matters due to precipitation of the coloring agent (A) in the heat-curing process during the production of a color filter.

The thiol compound (B) is, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. Pionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionate acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s -triazine, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

A thiol compound (B) can be used individually or in combination of 2 or more types.

The content of the thiol compound (B) is 0.1 to 10% by mass, preferably 1 to 10% by mass, based on 100% by mass of the non-volatile content of the coloring composition for color filters. When an appropriate amount of the thiol compound (B) is blended, the ability to suppress generation of foreign matters due to precipitation of the coloring agent (A) in the thermosetting step is further improved.

<Binder resin>
The binder resin (B) is a so-called transparent resin, and preferably has a transmittance of 80% or more, preferably 95% or more, in the entire wavelength range of 400 to 700 nm. Examples of the binder resin (B) include thermoplastic resins, thermosetting resins, and active energy ray-curable resins having ethylenically unsaturated double bonds (hereinafter referred to as active energy ray-curable resins). In addition, the active energy ray-curable resin may have thermosetting properties. Furthermore, the active energy ray-curable resin may be an alkali-soluble resin from the viewpoint of developability. Also, the thermoplastic resin preferably has alkali solubility.

(Thermoplastic resin)
Thermoplastic resins include, for example, acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, Examples include polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

The thermoplastic resin preferably has alkali solubility. Alkali-soluble thermoplastic resins include, for example, resins having acidic groups such as carboxyl groups and sulfone groups. The thermoplastic resin is an acrylic resin having an acidic group, an α-olefin/(anhydrous) maleic acid copolymer, a styrene/styrenesulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/(anhydrous ) maleic acid copolymers and the like. Among these, acrylic resins having acidic groups and styrene/styrenesulfonic acid copolymers are preferred in terms of developability, heat resistance and transparency.

(Active energy ray-curable resin)
The active energy ray-curable resin preferably has alkali solubility. The active energy ray-curable resin having alkali solubility can obtain alkali solubility by having a carboxyl group.

The acid value of the active energy ray-curable resin having alkali solubility is preferably 20 to 300 mgKOH/g. If it has an appropriate acid value, the developability is further improved, and a fine pattern can be easily formed by development.

The active energy ray-curable resin having alkali solubility is not limited as long as it has a carboxyl group and an ethylenically unsaturated group, and is synthesized by the method (i), method (ii), and method (iii) shown below. resin is preferred. A film formed by using an active energy ray-curable resin having alkali solubility is crosslinked by three-dimensional crosslinking to further improve chemical resistance.

[Method (i)]
In method (i), for example, 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, The carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce

Unsaturated ethylenic monomers with epoxy groups are, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4 epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylates may be mentioned, and these may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

Unsaturated monobasic acids include, for example, (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid. and the like, 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, etc. These may be used alone or in combination of two or more. I don't mind. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic anhydride such as trimellitic anhydride, or use a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group and the like. Further, when etrahydrophthalic anhydride or maleic anhydride having unsaturated ethylenic double bonds is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

As a method analogous to 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)]
Method (ii) uses, for example, an unsaturated ethylenic monomer having a hydroxyl group, and another unsaturated monobasic acid monomer having a carboxyl group, or copolymerizes with another monomer. There is a method of reacting the side chain hydroxyl group of the copolymer obtained by the above reaction with the isocyanate group of the unsaturated ethylenic monomer having an isocyanate group.

Unsaturated ethylenic monomers with hydroxyl groups are, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth) Examples include hydroxyalkyl (meth)acrylates such as acrylate, glycerol (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate, and these may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylate obtained by addition polymerization of 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 added with (poly)12-hydroxystearic acid and the like can also be used. 2-Hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred from the viewpoint of suppressing coating film foreign substances.

The unsaturated ethylenic monomer having an isocyanate group includes, for example, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but is limited to these. It is also possible to use two or more types in combination.

(Thermosetting compound)
Thermosetting compounds may be included herein in place of or in conjunction with thermoplastic resins. Thermosetting compounds include thermosetting resins and thermosetting compounds.

Thermosetting compounds include, for example, epoxy compounds, epoxy resins, benzoguanamine compounds, benzoguanamine resins, rosin-modified maleic acid compounds, rosin-modified maleic acid resins, melamine compounds, melamine resins, urea compounds, urea resins, phenolic compounds, phenolic resins, etc. is mentioned.

The weight average molecular weight (Mw) of the binder resin is preferably 4,000 to 100,000, more preferably 6,000 to 80,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 50,000. The molecular weight distribution (Mw/Mn) is preferably 10 or less.

The blending amount of the binder resin is preferably 20 to 1000 parts by weight per 100 parts by weight of the colorant (A). Good color characteristics can be easily obtained by using an appropriate amount.

<Photopolymerizable compound>
Photopolymerizable compounds include photopolymerizable monomers and photopolymerizable oligomers.

Photopolymerizable monomers include various (meth)acrylic acid esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (Meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

Commercially available photopolymerizable monomers are KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYARAD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD manufactured by Nippon Kayaku Co., Ltd. R712, KAYARAD R-604, KAYARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPHA-2C, KAYARAD D-310, KAYARAD D-330, KAYARAD DPCA-20, KAYARAD -30, KAYARAD DPCA-60, KAYARAD DPCA-120, and Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M- manufactured by Toagosei Co., Ltd. 350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, Viscoat #335HP, Viscoat #700, Viscoat #295, Viscoat #330, Viscoat #360, Viscoat #GPT, Viscoat #400, Viscoat #405, Shin A-9300 manufactured by Nakamura Chemical Co., Ltd. and the like can be mentioned.

(Photopolymerizable compound having an acidic group)
The photopolymerizable compound also includes a photopolymerizable compound having an acidic group. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups.

Photopolymerizable compounds having an acidic group, for example, polyhydric alcohol and (meth) acrylic acid and free hydroxyl group-containing poly (meth) acrylate, esters with dicarboxylic acid; Examples thereof include esterified products with alkyl (meth)acrylates. Specific compounds include, for example, monohydroxy oligoacrylates or monohydroxy Free carboxyl group-containing monoesters of oligomethacrylates and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2 ,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid and other tricarboxylic acids, 2-hydroxyethyl acrylate, Examples include monohydroxy monoacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and free carboxyl group-containing oligoesters with monohydroxy monomethacrylates.

Commercially available photopolymerizable compounds having an acidic group include, for example, Viscoat #2500P manufactured by Osaka Organic Co., Ltd., and M-5300, M-5400, M-5700, M-510 and M-520 manufactured by Toagosei Co., Ltd. mentioned.

(Photopolymerizable oligomer)
Photopolymerizable oligomers include photopolymerizable oligomers having one or more urethane bonds (hereinafter referred to as urethane acrylate oligomers). The urethane acrylate oligomer preferably has about 2 to 10 (meth)acryloyl groups.
Methods for synthesizing urethane acrylate oligomers include, for example, a method of reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate to synthesize it, a method of reacting a polyfunctional isocyanate with an alcohol, and then a (meth)acrylate having a hydroxyl group. A method of synthesizing by reacting is mentioned.

(Meth)acrylates having a hydroxyl group are, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylol Propane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate , glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy (meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

Polyhydric alcohols increase the degree of cross-linking of the film and improve various tolerances. Examples of polyhydric alcohols include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

These commercial products are, for example, Kyoeisha Chemical Co., Ltd. AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167, Shin-Nakamura Chemical Co., Ltd. and UV-4108F and UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like.

A photopolymerizable compound can be used individually or in combination of 2 or more types.

The amount of the photopolymerizable compound is preferably 5 to 400 parts by mass, more preferably 10 to 300 parts by mass, per 100 parts by mass of the colorant (A). When blended in an appropriate amount, the photocurability and developability are further improved.

<Photoinitiator (D)>
The photopolymerization initiator (D) is a compound that generates active species capable of initiating polymerization of the photopolymerizable compound (D) upon exposure to radiation such as ultraviolet rays, visible rays, deep ultraviolet rays, electron beams, and X-rays.

The photopolymerization initiator (D) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1- one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) Acetophenone compounds such as methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4- Benzophenone compounds such as benzoyl-4′-methyldiphenyl sulfide or 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone , 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl- 4,6-bis(trichloromethyl)-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 Triazine compounds such as 2,4-trichloromethyl-(4′-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], or oxime ester compounds such as O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; bis(2,4,6 -trimethylbenzoyl)phenylphosphine oxide or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole-based compounds; imidazole-based compounds; or titanocene-based compounds. Among these, oxime ester compounds are preferred because they can suppress crystal precipitation in the coating after photocuring.

A photoinitiator (D) can be used individually or in combination of 2 or more types.

The blending amount of the photopolymerization initiator (D) is preferably 1 to 200 parts by mass, more preferably 2 to 150 parts by mass, per 100 parts by mass of the colorant (A). When blended in an appropriate amount, the photocurability and developability are further improved.

(sensitizer)
The photosensitive coloring composition can contain a sensitizer together with the photopolymerization initiator (D).
Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and 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, tetrapyrazinoporphyrazine 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, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3', or 4,4 '-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone and the like. Also, edited by Shin Kawahara, "Dye Handbook" (1986, Kodansha), edited by Shin Okawara, "Chemistry of Functional Dyes" (1981, CMC), edited by Chuzaburo Ikemori, "Special Functional Materials" ( 1986, CMC).

A sensitizer can be used alone or in combination of two or more.

The blending amount of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator (D). When blended in an appropriate amount, the photocurability and developability are further improved.

<Organic solvent>
The photosensitive coloring composition can contain an organic solvent. This facilitates viscosity adjustment.

Organic solvents include, 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-dimethylacetamide , N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, 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 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 monopropyl ether Propylene 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, methoxypropyl acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate , dibasic acid esters, and the like. Among them, glycol acetates such as ethyl lactate, methoxypropyl acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone. preferable.

An organic solvent can be used individually or in combination of 2 or more types.

The blending amount of the organic solvent is preferably 500 to 4000 parts by mass with respect to 100 parts by mass of the colorant (A). When mixed in an appropriate amount, the viscosity can be easily adjusted, and a uniform film can be easily formed.

(leveling agent)
The photosensitive coloring composition can contain a leveling agent. As a result, coatability is further improved, and the surface smoothness of the coating is further improved. Examples of leveling agents include silicone surfactants, fluorosurfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.
Commercially available silicone surfactants include, for example, BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, and BYK-330 manufactured by BYK Chemie. , BYK-331, BYK-333, BYK-342, BYK-345/346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510 , BYK-3570, Dow Corning Toray Co., Ltd., FZ-7001, FZ-7002, FZ-2110, FZ-2122, FZ-2123], FZ-2191, FZ-5609, Shin-Etsu Chemical Co., Ltd. X-22- 4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22- 4515, KF-6004 and the like.

Examples of fluorosurfactants include compounds having a fluorocarbon chain.
Commercial products of fluorine-based surfactants include, for example, Surflon S-242, S-243, S-420, S-611, S-651, S-386 manufactured by AGC Seimi Chemical Co., Ltd., and Megafac F-253 manufactured by DIC Corporation. , F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72 -K, DS-21, Sumitomo 3M FC-4430, FC-4432, Mitsubishi Materials Electronic Chemicals EF-PP31N09, EF-PP33G1, EF-PP32C1, Neos Ftergent 602A, and the like.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyl Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monolaurate, sorbitan esquioleate, Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene orbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, Polyoxyethylene sorbitol tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol mooleate, polyoxyethylene hydrogenated castor oil, poly oxyethylene alkylamines, alkylalkanolamides, alkylbetaines such as alkylimidazolines and alkyldimethylaminoacetic acid betaine;

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, and monoethanol lauryl sulfate. amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

Surfactants can be used alone or in combination of two or more.

The content of the surfactant is preferably 0.001 to 2% by mass, more preferably 0.005 to 1.0% by mass, based on 100% by mass of non-volatile matter in the photosensitive coloring composition. When contained in an appropriate amount, the coatability, the adhesion of the coating to the substrate, and the permeability of the coating are further improved.

(Curing agent, curing accelerator)
The photosensitive coloring composition can contain a curing agent and a curing accelerator. This further improves the curability when the thermosetting resin is contained.
Curing agents include, for example, phenol-based resins, amine-based compounds, acid anhydrides, active esters, carboxylic acid-based compounds, and sulfonic acid-based compounds. Among these, compounds having two or more phenolic hydroxyl groups and amine curing agents are preferred.
Curing accelerators include, for example, amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N , N-dimethylbenzylamine, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4 -methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine etc.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (e.g., 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.). be done.

Curing agents and curing accelerators can be used alone or in combination of two or more.

Moreover, the amount of the curing agent and the curing accelerator to be blended is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting resin.

(Other additives)
The photosensitive coloring composition can contain other additives. Other additives include, for example, storage stabilizers and adhesion improvers. Containing a storage stabilizer further improves the viscosity stability of the photosensitive coloring composition over time. If an adhesion improver is contained, the adhesion between the substrate and the coating is further improved.

(storage stabilizer)
Storage stabilizers include, for example, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The content of the storage stabilizer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant (A).

(Adhesion improver)
The adhesion improver is preferably a silane coupling agent, and examples thereof include vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, and (meth)acrylics such as γ-methacryloxypropyltrimethoxysilane. Silanes, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β- Epoxysilanes such as (3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, etc. Methoxysilane, N-β (aminoethyl)γ-aminopropyltriethoxysilane, N-β (aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane , aminosilanes such as N-phenyl-γ-aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane; thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; A silane coupling agent is mentioned. The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant (A).

(Method for producing photosensitive coloring composition)
As an example of the method for producing a photosensitive coloring composition, it is preferable to finely disperse the quinophthalone pigment and the phthalocyanine green pigment of the coloring agent (A) simultaneously or separately as described above. Next, together with a dispersant, a dispersing aid, etc., the colorant is dispersed by using various dispersing means such as a kneader, two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor. Create a body. Next, a photopolymerizable compound, a photopolymerization initiator, a binder resin, and an organic solvent are added to the colorant dispersion, and the mixture is stirred and mixed to prepare a photosensitive coloring composition. In addition, a compounding component can be added at arbitrary timings, respectively.

(Removal of coarse particles)
Coarse particles are preferably removed from the photosensitive coloring composition in order to form fine filter segments. The photosensitive coloring composition is separated into 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, membrane filter, or the like. And it is preferable to remove the mixed dust.

(color filter)
The color filter of this specification comprises a base material (also referred to as a substrate) and a filter segment formed from a photosensitive coloring composition. The color filters also comprise a black matrix. A typical color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and at least one magenta filter segment, at least one cyan filter segment, and at least one There may be one yellow color filter segment. Green filter segments can be formed from the photosensitive coloring compositions herein.

(Manufacturing method of color filter)
A color filter can be produced by a printing method, a photolithography method, or the like, and a photolithography method is preferable.

A photolithographic method is preferable for forming the filter segments. In the photolithography method, for example, a photosensitive colored composition prepared as a solvent-developable or alkali-developable colored resist is applied onto a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating. Then, the dry film thickness is 0.2 to 10 μm. The film is exposed to ultraviolet rays through a mask having a predetermined pattern.

After that, it is immersed in a solvent or alkaline developer, or the developer is sprayed by spraying or the like to remove the uncured portion, and a desired pattern is formed to form a filter segment and a black matrix. In addition, it can be heated as necessary to promote polymerization of the filter segments and black matrix formed by development. The photolithographic method can form filter segments with higher precision than the printing method.

For development, for example, aqueous solutions such as sodium carbonate and sodium hydroxide as alkaline developers; and organic alkalis such as dimethylbenzylamine, triethanolamine and tetramethylammonium hydroxide can be used. Moreover, the developer can use an antifoaming agent or a surfactant. The development processing method includes, for example, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid puddle) development method, and the like.

In order to increase the exposure sensitivity to ultraviolet rays, a water-soluble or alkali-soluble resin (for example, polyvinyl alcohol, water-soluble acrylic resin, etc.) can be formed as a film on the resist film formed from the photosensitive coloring composition. Oxygen that inhibits ultraviolet curing of the resist film can thereby be prevented.

Examples of the substrate include glass plates such as soda lime glass, low-alkali borosilicate glass, and alkali-free aluminoborosilicate glass; and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. Moreover, it is preferable to provide a transparent electrode made of indium oxide, tin oxide, or the like on the surface of the substrate for driving the liquid crystal after panelization. Moreover, when the color filter is used for a solid-state imaging device, the substrate is preferably a silicon wafer. The substrate includes a transmissive substrate and a reflective substrate depending on the application.

The thickness of the substrate is approximately 0.01 to 3 mm.

The film thickness of the filter segment is preferably 0.2-10 μm, more preferably 0.2-5 μm. A drying process can be performed during coating. Examples of the drying apparatus include vacuum dryers, convection ovens, IR ovens, hot plates, and the like.

The contrast of the display panel can be further enhanced by forming the black matrix in advance before forming the filter segments on the substrate. Examples of the black matrix include, but are not limited to, 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. Alternatively, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then the filter segments may be formed. By forming the filter segments on the TFT substrate, the aperture ratio of the panel can be increased and the luminance can be improved.
An overcoat film and a transparent conductive film can be formed on the color filter as needed.

(Liquid crystal display device)
The liquid crystal display device of this specification includes a color filter. Preferably, the liquid crystal display device further comprises a light source. Light sources include cold cathode fluorescent tubes (CCFL) and white LEDs. Among these, in the present specification, white LEDs are preferable in terms of widening the reproduction range of red. An embodiment of the liquid crystal display device will be described with reference to FIG. In addition, 1 upper side of FIG. 1 is called up, and the lower side is called down. The liquid crystal display device 10 includes a pair of transparent substrates 11 and 21 that are spaced apart and opposed to each other. A liquid crystal LC is sealed between them.

The liquid crystal LC is aligned according to a drive mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence). A TFT (thin film transistor) array 12 is formed on the upper side of the transparent substrate 11 . A transparent electrode layer 13 is formed thereon. An alignment layer 14 is provided on the upper side of the transparent electrode layer 13 . A polarizing plate 15 is formed below the transparent substrate 11 . The transparent electrode layer 13 can be formed by vapor-depositing ITO (indium tin oxide), for example.

A color filter 22 is formed under the transparent substrate 21 . The red, green and blue filter segments that make up color filter 22 are separated by a black matrix (not shown).

A transparent substrate 21 is installed above the color filter 22 . In addition, a transparent electrode layer 23 is formed under the color filter 22, and an alignment layer 24 is further formed thereunder.

A polarizing plate 25 is installed on the upper side of the transparent substrate 21 . A backlight unit 30 is provided below the polarizing plate 15 .
The backlight unit 30 preferably uses a white LED light source 31 .

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED, and those in which a phosphor is contained in a resin package of a blue LED. For example, the emitted light has a wavelength (λ3) at which the emission intensity is maximized within the wavelength range of 430 nm to 485 nm, has a wavelength (λ4) at which the emission intensity is maximized within the range of 530 nm to 580 nm, and has a wavelength (λ4) of 600 nm to 650 nm. and the ratio (I4/I3) of the emission intensity I3 at the wavelength λ3 to the emission intensity I4 at the wavelength λ4 is 0.2 or more and 0.4 or less A white LED light source (LED1) having spectral characteristics in which the ratio (I5/I3) of the emission intensity I3 at the wavelength λ3 to the emission intensity I5 at the wavelength λ5 is 0.1 or more and 1.3 or less is preferable. In addition, the emitted light has a wavelength (λ1) at which the emission intensity is maximum within the wavelength range of 430 nm to 485 nm, has a second emission intensity peak wavelength (λ2) within the range of 530 nm to 580 nm, and has a wavelength λ1 A white LED light source (LED2) having a spectral characteristic in which the ratio (I2/I1) of the emission intensity I1 at the wavelength λ2 to the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less.

Commercially available LEDs 1 include, for example, NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

Commercially available LEDs 2 include, for example, NSSW440 (manufactured by Nichia Corporation) and NSSW304D (manufactured by Nichia Corporation).

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited by these. In the examples, "part" means "mass part" and "%" means "mass%". The compounding amounts in the table are parts by mass unless otherwise specified.

Each measurement method is described below.

(Average primary particle size of pigment)
A solvent (methoxypropyl acetate) is added to the pigment powder, a small amount of dispersant (DIsperbyk-161: BYK-Chemie dispersant) is added, and the mixture is treated with ultrasonic waves for 1 minute to prepare a sample for measurement. Then, with a transmission type (TEM) electron microscope, create 3 photographs (for 3 fields of view) in which 100 or more primary particles of the pigment can be confirmed, and measure the size of 100 primary particles in order from the upper left. . Specifically, the short axis diameter and long axis diameter of each primary particle of the pigment are measured in nm units, and the average is used as the primary particle diameter of the pigment particles, and a total of 300 distributions are created in increments of 5 nm, The median value in increments of 5 nm (for example, 8 nm for 6 nm or more and 10 nm or less) is approximated as the particle diameter of those particles, and the number average particle diameter is calculated based on the respective particle diameters and the number thereof.

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

<Method for producing finely divided colorant>
(Refining treatment coloring agent (A-1))
phthalocyanine green pigment C.I. I. Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyocolor Co., Ltd.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. bottom. Next, this kneaded product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. to obtain a finely divided colorant (A-1).

(Refining Colorant (A-2))
phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 ("FASTOGEN GREEN A110" manufactured by DIC), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80°C for 6 hours. Next, this kneaded product is put into 8000 parts of hot water and stirred for 2 hours while heating to 80°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and night. , to obtain a finely divided coloring agent (A-2).

(Refining treatment coloring agent (A-3))
500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (2), 500 parts of N-methylpyrrolidone, and 13.9 parts of diphenyl phosphate were added to a three-necked flask and heated to 90° C. for 8 hours. reacted. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a finely divided colorant (A-3) which was a phthalocyanine green pigment.

(Refining treatment coloring agent (A-4))
500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (2), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added to a three-necked flask and stirred at 20°C. , was allowed to react for 6 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3°C, and the precipitated solid was collected by filtration and washed with water. 500 parts of a 2.5% aqueous sodium hydroxide solution and the filtered residue were added to a beaker and stirred at 80° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water and dried to obtain a pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of the resulting pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-necked flask. ℃ and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a finely divided colorant (A-4) which was a phthalocyanine green pigment.

formula (2)

(Refining treatment coloring agent (A-5))
yellow pigment C.I. I. Pigment Yellow 138 (BASF "Paliotol Yellow L 0962 HD") 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product was put into 8 liters of hot 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 for a day and night. , to obtain a finely divided coloring agent (A-5).

(Refining treatment coloring agent (A-6))
100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. 97 parts of a finely divided colorant (A-6) were obtained.

(Refining Colorant (A-7))
100 parts of the quinophthalone compound (b), 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. 97 parts of a finely divided colorant (A-7) were obtained.

(Refining treatment coloring agent (A-8))
100 parts of the quinophthalone compound (c), 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. 97 parts of a finely divided colorant (A-8) were obtained.

(Refining treatment coloring agent (A-9))
100 parts of the quinophthalone compound (d), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. 97 parts of a finely divided colorant (A-9) were obtained.

<Production of resin type dispersant solution>
LPN21116 manufactured by BYK, which is a commercially available resin-type dispersant, was mixed with methoxypropyl acetate to prepare a solution having a non-volatile content of 20% by mass, thereby obtaining a resin-type dispersant solution.

<Method for producing binder resin (C)>
(Production of binder resin (C-1))
196 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and after replacing the inside of the reaction vessel with nitrogen, the mixture was added dropwise. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) , 2,2'-azobisisobutyronitrile 1.1 parts was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. was added to prepare a binder resin (C-1) solution. The weight average molecular weight (Mw) of the resin was 26,000.

(Production of binder resin (C-2))
Put 100 parts of methoxypropyl acetate in a reaction vessel equipped with a separable four-necked flask, a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and heat to 120 ° C. while injecting nitrogen gas into the vessel. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was dropped from the dropping pipe over 2.5 hours to initiate the polymerization reaction. went. Next, the inside of the flask is replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone are added to 17.0 parts of acrylic acid, the reaction is continued at 120° C. for 5 hours, and tetrahydrophthalic anhydride is added. 30.4 parts and 0.5 parts of triethylamine were added and reacted at 120° C. for 4 hours to obtain an acrylic resin solution having a weight average molecular weight of 8000 and an acid value of 71 mgKOH/g. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. was added to prepare a binder resin (C-2) solution.

<Method for Producing Colorant Dispersion>
(Colorant dispersion (P1))
After stirring and mixing the following mixture uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 5 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), 5.0 μm to prepare a colorant dispersion (P1).

Micronized colorant (A-1): 15.0 parts Resin type dispersant solution: 5.0 parts Binder resin (C-1) solution: 25.0 parts Solvent/PGMAC (methoxypropyl acetate): 50.0 parts Department

(Colorant Dispersion (P2-9))
In the same manner as for the pigment dispersion (P1), except that the colorant, the resin-type dispersant solution, the binder resin solution, and the solvent were changed to the compositions and blending amounts (parts by mass) shown in Table 1, the colorant Dispersions (P2-9) were made respectively.

<Thiol compound (B)>
· Bifunctional thiol compound (B-1)
("1,4-bis(3-mercaptobutyryloxy)butane" manufactured by Showa Denko)
· Trifunctional thiol compound (B-2)
("Trimethylolpropane tris (3-mercaptobutyrate)" manufactured by Showa Denko)
· Tetrafunctional thiol compound (B-3)
(“Pentaerythritol tetrakis (3-mercaptopropionate)” manufactured by SC Organic Chemical Co., Ltd.)
· Monofunctional thiol compound (B-4)
2-ethylhexyl-mercaptoacetate

<Photopolymerization initiator>
・Oxime ester initiator (D-1)
(Compound represented by the following formula (3))

・ Acetophenone-based initiator (D-2)
("Omnirad 369" manufactured by IGM Resins B.V.)

[Example 1]
(Photosensitive coloring composition (G-1))
A mixture having the following composition was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (G-1).
Colorant dispersion 1 (P4): 26.1 parts Colorant dispersion 2 (P5): 20.2 parts Thiol compound (B-1): 0.2 parts Binder resin (C-2): 6.5 parts Photopolymerizable compound ["Aronix M-402" manufactured by Toagosei Co., Ltd.]: 3.4 parts Photopolymerization initiator (D-1): 0.2 parts Solvent / methoxypropyl acetate (PGMAC): 43.5 parts

[Examples 2 to 23, Comparative Examples 1 to 2]
(Photosensitive coloring composition (G-2 to 22))
The composition shown in Table 2, and except for changing the amount (parts by weight) of the photosensitive coloring composition (G-1) of Example 1, were performed in the same manner as in Examples 2 to 23 and Comparative Examples 1 to 2. A natural coloring composition (G-2 to 25) was obtained, respectively.
However, Examples 1 to 12 are reference examples.

<Evaluation of photosensitive coloring composition>
Coating films of the obtained photosensitive coloring compositions (G-1 to 25) were tested by the following method. Table 3 shows the results of the test. In the following evaluation results, ⊚, ◯, and Δ indicate practical use, and × indicate non-practical use.

<Evaluation of gas generation rate>
For the obtained photosensitive coloring composition (G-1 to 25), the photosensitive coloring composition was heated on a glass substrate having a length of 100 mm × width of 100 mm × thickness of 0.7 mm so that the film thickness was 2.2 μm. , and exposed to ultraviolet rays under the condition of 40 mJ/cm ² . After that, the coating film sprayed with the alkaline developer by spraying was subjected to heat treatment (post-baking) in an oven at 230° C. for 20 minutes. 10 mg of the resulting coating film was scraped off and heated at 230 ° C. for 3 hours by TG-DTA measurement (“Thermo plus evo2” manufactured by RIGAKU) to confirm the amount of gas generated from the weight reduction of the coating film. evaluated with In addition, the film thickness of the coating film was measured using Dektak 8 (manufactured by Japan Vacuum Engineering Co., Ltd.).
◎: Gas generation amount is 0% or more and less than 2% ○: Gas generation amount is 2% or more and less than 5% △: Gas generation amount is 5% or more and less than 10% ×: Gas generation amount is 10% or more

<Crystal precipitation evaluation>
For the obtained photosensitive coloring composition (G-1 to 25), the photosensitive coloring composition was heated on a glass substrate having a length of 100 mm × width of 100 mm × thickness of 0.7 mm so that the film thickness was 2.2 μm. and exposed to ultraviolet rays under the condition of 40 mJ/cm ² through a mask having a predetermined pattern. After that, an alkaline developer was sprayed to remove the uncured portion to form a desired pattern. The resulting coating film was subjected to heat treatment (post-baking) in an oven at 230° C. for 3 hours, and the presence or absence of crystals was confirmed with a microscope (“BX-51” manufactured by Olympus Optical Co., Ltd.). For evaluation, an area of 100 μm long×300 μm wide on a glass surface with a distance between pixel patterns of 100 μm was observed with a microscope and evaluated according to the following criteria. Dektak 8 (manufactured by Japan Vacuum Engineering Co., Ltd.) was used to determine the film thickness of the coating film.
◎: Crystals did not occur in the observation area ○: Crystals occurred in the range of less than 5% of the observation area △: Crystals occurred in the range of 5% to less than 10% of the observation area ×: Crystals were observed Occurred in a range of 10% or more of the area

<Pattern linearity evaluation>
The obtained photosensitive coloring composition (G-1 to 25) was coated on a glass substrate having a length of 100 mm, a width of 100 mm and a thickness of 0.7 mm so that the film thickness after heat treatment was 2.2 μm, and a predetermined pattern was obtained. UV exposure was performed under the condition of 40 mJ/cm ² through a mask having After that, an alkaline developer was sprayed to remove the uncured portion to form a desired pattern. The obtained coating film was subjected to heat treatment (post-baking) in an oven at 230° C. for 20 minutes, and the pattern linearity was confirmed with a microscope (“BX-51” manufactured by Olympus Optical Co., Ltd.). For evaluation, a pattern formed with a mask opening width of 50 μm was observed and evaluated as follows. Dektak 8 (manufactured by Japan Vacuum Engineering Co., Ltd.) was used to determine the film thickness of the coating film.
○: The difference between the maximum value and the minimum value within the same pattern line width is 0 μm or more and less than 1 μm △: The difference between the maximum value and the minimum value within the same pattern line width is 1 μm or more and less than 2 μm ×: The maximum value within the same pattern line width and the minimum value difference is 2 μm or more

From the results in Table 3, it can be seen that Examples 1 to 23 can form color filters in which foreign matters are less likely to form on the film after heating. In addition, since the generation of gas can be suppressed, in the case of manufacturing a liquid crystal display device by forming another layer on the color filter, it is easy to suppress deterioration in the visibility of the displayed image caused by the gas.
On the other hand, in Comparative Examples 1 and 2, many crystals are precipitated, and it is difficult to solve the problem of foreign substance suppression.

10 liquid crystal display device 11 transparent substrate 12 TFT array 13 transparent electrode layer 14 alignment layer 15 polarizing plate 21 transparent substrate 22 color filter 23 transparent electrode layer 24 alignment layer 25 polarizing plate 30 backlight unit 31 white LED light source LC liquid crystal

Claims (6)

Colorant (A), thiol compound (B), binder resin (C), photopolymerizable compound, and photopolymerization initiator (D),
The coloring agent (A) contains a quinophthalone pigment and a phthalocyanine green pigment, and the thiol compound (B) contains 4 or more thiol groups,
A photosensitive coloring composition in which the photopolymerization initiator (D) contains a compound represented by the following formula (3) .
Formula (3)

The photosensitive coloring composition according to claim 1, comprising 0.1 to 10% by weight of the thiol compound in 100% by weight of the nonvolatile matter of the photosensitive coloring composition. The photosensitive coloring according to claim 1 or 2, wherein the quinophthalone pigment is Pigment Yellow 138 and one or more selected from the group consisting of the following quinophthalone compounds (a), (b), (c), and (d). Composition.

The phthalocyanine green pigment is one or more selected from the group consisting of Pigment Green 36, Pigment Green 58, and compounds represented by the following general formula (1), according to any one of claims 1 to 3. Photosensitive coloring composition.

(wherein X represents a halogen atom, n represents an integer of 0 to 16, Y represents -OP(=O)R ₁ R ₂ , -OC(=O)R ₃ , -OS(= O) Represents ₂ R _4. R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituted represents an optionally substituted alkoxyl group or an optionally substituted aryloxy group, wherein R ₃ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group , represents an optionally substituted aryl group or an optionally substituted heterocyclic group, R ₄ represents a hydroxyl group, an optionally substituted alkyl group, an optionally substituted represents a heterocyclic group which may have a good aryl group or a substituent.) A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition according to any one of claims 1 to 4. A liquid crystal display device comprising the color filter according to claim 5 .

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