JP2020064099A - Coloring composition for color filter, color filter and liquid crystal display - Google Patents

Abstract

To provide a coloring composition for a color filter capable of forming a color filter in which foreign matter is hard to occur in a coat after heating, and a color filter.SOLUTION: A coloring composition for a color filter contains a colorant (A), a binder resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D), wherein the colorant (A) contains a quinophthalone pigment, and a phthalocyanine green pigment, and the acid value of the binder resin (B) is 90 to 140 mgKOH/g.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a color filter coloring composition, a color filter, and a liquid crystal display device that can be used for forming a color filter used in a color liquid crystal display device, a color organic EL display device, a color image pickup tube element, and the like.

As a color filter used in a liquid crystal display device, a solid-state imaging device, or the like, a method of forming a coloring composition for a color filter in which a pigment is dispersed by a photolithography method is widely known.
For the color filter, a coloring composition for a color filter is applied to a transparent substrate such as glass, the solvent is removed by drying, pattern exposure of one (one color) filter segment is performed, and then an unexposed portion is developed. Are removed to form one filter segment, and if necessary, treatment such as heating is performed, and then the same operation is sequentially repeated for all color filter segments.

A color filter basically has three primary color (red, green, and blue) filter segments. The pigment used for the green filter segment generally uses a yellow pigment in addition to the green pigment to adjust the color tone. It was target.
Patent Document 1 and Patent Document 2 disclose a coloring composition for a color filter using a phthalocyanine pigment as a green pigment, an isoindoline pigment as a yellow pigment, and an azo pigment.

JP 2004-333817 A JP, 2016-075837, A

  However, the conventional coloring composition for a green color filter has a low lightness of the film. Therefore, when a quinophthalone pigment was used as the yellow pigment, the brightness was improved, but on the other hand, there was a problem that foreign matter was generated in the coating film after heating and the contrast was lowered.

  An object of the present invention is to provide a coloring composition for a color filter, a color filter, and a liquid crystal display device capable of forming a color filter in which foreign matter is unlikely to be generated in a coating film after heating.

  The present invention contains a colorant (A), a binder resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D), and the colorant (A) is a quinophthalone pigment and a phthalocyanine-based green color. The present invention relates to a coloring composition for a color filter, which contains a pigment, and the binder resin (B) has an acid value of 90 to 140 mgKOH / g.

  The present invention also relates to the above coloring composition for a color filter, wherein the binder resin (B) has a weight average molecular weight of 10,000 to 30,000.

  The present invention also relates to the above coloring composition for color filters, wherein the binder resin (B) has a double bond equivalent of 300 to 400 g / mol.

  The present invention also relates to the above coloring composition for a color filter, which further contains a thiol compound.

  Further, the present invention provides the color filter, wherein the quinophthalone pigment is at least one selected from the group consisting of Pigment Yellow 138 and the following quinophthalone compounds (a), (b), (c), and (d). A coloring composition for use.

  Further, the present invention provides the coloring composition for a color filter, wherein the phthalocyanine-based green pigment is one or more selected from the group consisting of Pigment Green 36, Pigment Green 58, and a compound represented by the following general formula (1). Regarding things.

(In formula, X represents a halogen atom, n represents the integer of 0-16. Y represents -OP (= O) R < ₁ > R < ₂ >, -OC (= O) R < ₃ >, or -OS. (= O) ₂ R _4. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an alkoxyl group which may have or an aryloxy group which may have a substituent, R ₃ represents a hydrogen atom, an alkyl group which may have a substituent, or a cyclo group which may have a substituent. Represents an alkyl group, an aryl group which may have a substituent or a heterocyclic group which may have a substituent, R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, or a substituent Represents an optionally substituted aryl group or a heterocyclic group which may have a substituent.)

  The present invention also relates to a color filter including a base material and a filter segment formed from the coloring composition for a color filter.

    The present invention also relates to a liquid crystal display device including the color filter.

  According to the present invention described above, it is possible to provide a coloring composition for a color filter, a color filter, and a liquid crystal display device capable of forming a color filter in which a foreign substance is less likely to be generated in a coating film after heating.

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

The terms used in this specification are defined below. Unless otherwise specified, when described as “(meth) acryloyl”, “(meth) acrylic”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide”, respectively. , "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.). The monomer means an ethylenically unsaturated group-containing monomer.

  The coloring composition for a color filter of the present invention contains a colorant (A), a binder resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D), and the colorant (A) is quinophthalone. The binder resin (B) contains a pigment and a phthalocyanine green pigment and has an acid value of 90 to 140 mgKOH / g. The coloring composition for a color filter of the present invention is preferably used for forming a film on a green filter segment of a color filter.

<Colorant (A)>
The colorant (A) contains a quinophthalone pigment and a phthalocyanine-based green pigment. By containing the quinophthalone pigment and the phthalocyanine-based green pigment, a color filter having high brightness and high contrast can be obtained. The colorant (A) may be used in combination with a dye. This makes it possible to adjust the hue.

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

  The quinophthalone pigment can be used alone or in combination of two or more kinds.

  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, 63 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 preferable.

(In formula, X represents a halogen atom, n represents the integer of 0-16. Y represents -OP (= O) R < ₁ > R < ₂ >, -OC (= O) R < ₃ >, or -OS. (= O) ₂ R _4. R ₁ and R ₂ are each independently a hydrogen atom, a water acidic group, an alkyl group which may have a substituent, an aryl group which may have a substituent, Represents an alkoxyl group which may have a substituent or an aryloxy group which may have a substituent, R ₃ represents a hydrogen atom, an alkyl group which may have a substituent, or a substituent which may have a substituent. Represents a good cycloalkyl group, an aryl group which may have a substituent or a heterocyclic group which may have a substituent, R ₄ represents a water acidic group, an alkyl group which may have a substituent, a substituent Represents an aryl group which may have a group or a heterocyclic group which may have a substituent.)

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

  The phthalocyanine green pigment can be used alone or in combination of two or more kinds.

  As the colorant (A), the following other pigments can be used in combination. This allows the hue of the coating to be easily adjusted.

  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, 17 , 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, 291 and Japanese Patent Publication No. 2011-523433. Diketopyrrolopyrrole pigment described in JP-A-2014-112527 Azo pigments and the like described in the azo pigment, JP 2013-161026 described. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 254, 291 are preferred, and C.I. I. Pigment Red 254 is more preferable.

  Orange pigments include, for example, C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, 73 or 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, and 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, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Violet 19, 23 are preferable, and C.I. I. Pigment Violet 23 is more preferable.

  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 2008-19383 A, Examples thereof include zinc phthalocyanine pigments described in JP-A 2007-320986 and 2004-70342, aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, etc., 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, 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, 85,187,188,192,193,194,196,198,199,213,214, and the like.

<Dye>
Among other colorants, examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Further, as the dye, a derivative thereof or a lake pigment obtained by lakeizing the dye can also be used.

The acidic dye preferably has an acidic group such as sulfonic acid or carboxylic acid. The direct dye may form an inorganic salt of an acid dye, or a salt-forming compound of 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. Further, a salt-forming compound for salt-forming a resin component having these functional groups and an acid dye is also preferable. In addition, the salt-forming compound is easily converted into a sulfonamide and modified into a sulfonic acid amide compound to easily obtain 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 it has excellent fastness. The compound having an onium base is preferably a resin having a cationic group.

  The basic dye can be used as it is, but a salt-forming compound which forms a salt with an organic acid, perchloric acid or a metal salt thereof is preferable. Salt forming compounds of basic dyes are preferable because of their excellent resistance (light resistance, solvent resistance) and affinity with pigments. Further, in a salt-forming compound of a basic dye, the counter ion, for example, the cation component that acts, organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus anion compound, fluorine group-containing boron anion compound, cyano group-containing nitrogen anion compound, An anion compound having a conjugated base of an organic acid having a halogenated hydrocarbon group and a salt-forming compound obtained by salt-forming with an acid dye are preferable. The salt-forming compound has a further improved resistance when it contains a polymerizable unsaturated group in the molecule.

  Examples of dyes include azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthraquinone dyes, anthraquinone dyes 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 dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes, and the like of these metal complex dyes. Among these, from the viewpoint of color characteristics such as hue, color separation difficulty, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium. Dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferable. Specific compounds of the dyes are "New Edition Dye Handbook" (Organic Synthetic Chemistry Association, edited by Maruzen, 1970), "Color Index" (The Society of Dyers and colors), "Dye Handbook" (Ogawara et al., Kodansha, Kodansha, 1986).

  The colorant (A) can be used alone or in combination of two or more kinds.

The content of the colorant (A) is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass in 100% by mass of the nonvolatile content of the coloring composition. Color reproducibility is further improved by containing an appropriate amount.

<Refinement of pigment>
Of the colorants (A) used in the present invention, the pigment is preferably blended with other materials after being made fine. Examples of the refining method include wet grinding, dry grinding, and dissolution precipitation method. In the present invention, a salt-milling treatment by a dissolution-precipitation method using an acid or a kneader method which is one type of wet grinding is preferable.
The average primary particle diameter of the pigment is preferably 20 nm or more because the dispersibility is good. Further, it is preferably 100 nm or less because a color filter having a high contrast ratio can be formed. The average primary particle diameter of 25 to 85 nm is more preferable. For the average primary particle diameter, the size of the primary particles can be directly measured from an enlarged image of the pigment by a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of about 20 primary particles of the pigment were measured, and the average was taken as the average primary particle diameter of the pigment particles.

  Salt milling treatment is a method of heating a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or the like while heating. After the kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt functions as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt 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.

  The water-soluble inorganic salt is, for example. Examples thereof include sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like. Of these, inexpensive sodium chloride (salt) is preferable. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, more preferably 300 to 1000% by mass, based on 100% by mass of the pigment.

  The 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 (mixes) in water and does not substantially dissolve the inorganic salt used. In the present invention, a solvent having a high boiling point of 120 ° C. or higher is preferable from the viewpoint of safety, because the temperature rises during salt milling and the solvent is easily evaporated. The water-soluble organic solvent is, 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. Can be mentioned. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, more preferably 50 to 500% by mass, based on 100% by mass of the pigment.

  When the salt is subjected to the salt milling treatment, a resin can be added if necessary. Examples of the type of resin include natural resin, modified natural resin, synthetic resin, and synthetic resin modified with natural resin. The resin is preferably solid at room temperature (25 ° C.) and water-insoluble. It is also preferable that the resin is partially soluble in the organic solvent. The amount of the resin used is preferably 5 to 200 mass% with respect to 100 mass% of the pigment.

  The coloring composition for a color filter preferably contains a dispersant. Examples of the dispersant include resin type dispersants and other dispersants.

<Resin type dispersant>
The resin type dispersant has a pigment adsorption site and is adsorbed on the pigment to form a dispersion. The part other than the pigment adsorption site (x) acts as a steric hindrance site to improve the pigment dispersibility.
The resin type dispersant includes polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, Long-chain polyaminoamide phosphates, hydrocarboxylic group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, and salts thereof. Oil-based dispersants, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, and other water-soluble resins Water-soluble polymer, polyester, modified polyacrylate , Ellen oxide / propylene oxide adduct, phosphoric acid ester, and the like. Among these, a polymer dispersant having a basic functional group is preferable in that the viscosity of the composition becomes low with the addition of a small amount and a high contrast is easily obtained. More preferred are nitrogen atom-containing acrylic block copolymers and urethane-based polymer dispersants having a functional group containing a group, a quaternary ammonium salt group, a nitrogen-containing heterocycle, and the like.

  Commercial products of resin type dispersants are Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 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-. P104, P104S, 220S, LPN6919, LPN21116, LPN21324 or Lactimon, Lactimon-WS or Bykumen, etc., SOLPPERSE-3000, 9000, 13000, 13240 manufactured by Lubrizol Japan. 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408 manufactured by BASF Japan. 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 506. , 5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB411, PB821, PB822, PB824, and the like.

  The resin type dispersant is preferably 1 to 200 parts by mass, and more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the colorant (A). This facilitates the formation of a coating.

<Other dispersants>
When another dispersant is used, it is easy to suppress reaggregation of the colorant (A) after dispersion. Other dispersants include, for example, dye derivatives and surfactants.

(Dye derivative)
The dye derivative is a compound in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into a structure selected from the group consisting of an organic pigment, anthraquinone, acridone, and triazine. Can be mentioned. Dye derivatives are described in, for example, JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. Mention may be made of the compounds mentioned.

  From the viewpoint of improving the dispersibility of the colorant, the amount of the dye derivative is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more, relative to 100 parts by mass of the colorant (A). More preferable. Further, from the viewpoint of heat resistance and light resistance, 40 parts by mass or less is preferable, and 35 parts by mass or less is more preferable, relative to 100 parts by mass of the colorant (A).

(Surfactant)
Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, and alkyldiphenyletherdisulfonic 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 ester. ; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples thereof include alkyl betaines such as betaine acetate and amphoteric surfactants such as alkyl imidazoline.

  The content of the surfactant is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, relative to 100 parts by mass of the colorant (A). If a surfactant is added in an appropriate amount, it is easy to obtain a good dispersion effect.

  The dispersants can be used alone or in combination of two or more.

<Thiol compound>
When a thiol compound is used together with a photopolymerization initiator, the thiol compound functions as a chain transfer agent in radical polymerization after irradiation with light. As a result, thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated, and photosensitivity is improved. The thiol group is more preferably 4 or more. As a result, good photocuring is easily obtained from the surface to the deep part of the coating film, and therefore, for example, it is possible to further suppress the generation of foreign matter due to the precipitation of the colorant (A) in the thermosetting process during the production of the color filter.

  The thiol compound is, for example, mercaptoimidazole, mercaptooxazole, mercaptothiazole, mercaptotriazole, mercaptothiadiazole, mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 2-mercapto-5-methylthio-1,3,4-thiadiazole, 2- Mercapto-5-methoxyethylthio-1,3,4-thiadiazole, 5-hexanoxyethoxy-2-mercapto-6-methyl-1,3-benzoxazole mercaptobenzoxazole, mercaptobenzothiazolehexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol Bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, Tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6- Examples thereof include dimercapto-s-triazine, and preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate. It is below.

The thiol compounds can be used alone or in combination of two or more.

  The compounding amount of the thiol compound is preferably 1 to 10 parts by mass in 100% by mass of the nonvolatile content of the coloring composition for color filters. When an appropriate amount of the thiol compound is blended, the ability to suppress the generation of foreign matter due to the precipitation of the colorant (A) in the thermosetting step is further improved.

<Binder resin (B)>
The binder resin (B) is a so-called transparent resin and preferably has a transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm. Examples of the binder resin (B) include a thermoplastic resin, a thermosetting resin, and an active energy ray-curable resin having an ethylenically unsaturated double bond (hereinafter referred to as an active energy ray-curable resin). The active energy ray curable resin may have thermosetting property. Furthermore, the binder resin (B) has an acid value of 90 to 140 mgKOH / g.

(Thermoplastic resin)
The thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, Examples thereof 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. Examples of the alkali-soluble thermoplastic resin include resins having an acidic group such as a carboxyl group and a sulfone group. The thermoplastic resin is an acrylic resin having an acid group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or an isobutylene / (anhydrous ) Maleic acid copolymers and the like can be mentioned. Among these, acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers are preferable 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 be alkali soluble because it has a carboxyl group.

  The alkali-soluble active energy ray-curable resin is not particularly limited as long as it has a carboxyl group and an ethylenically unsaturated group, but resins synthesized by the methods (i) and (ii) shown below are preferable. The coating film formed by using the alkali-soluble active energy ray-curable resin has further improved chemical resistance due to three-dimensional crosslinking.

[Method (i)]
Method (i) includes, 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, A carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the produced water-acidic group is reacted with a polybasic acid anhydride to form an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce.

  The unsaturated ethylenic monomer having an epoxy group is, for example, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more kinds. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.

  Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano substituents. And the like. These may be used alone or in combination of two or more kinds.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. These may be used alone or in combination of two or more kinds. I don't care. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic acid anhydride such as trimellitic anhydride, or use a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to leave the remaining anhydride. It is also possible to hydrolyze the group. Further, when polyethylenic acid anhydride, such as etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond, is used, the unsaturated ethylenic double bond can be further increased.

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

[Method (ii)]
In the method (ii), for example, an unsaturated ethylenic monomer having a water acidic group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain water acidic group of the copolymer obtained by the above.

  The unsaturated ethylenic monomer having a water acid group is, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth). Examples thereof 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 kinds. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to the hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone. And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added can also be used. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

Examples of the unsaturated ethylenic monomer having an isocyanate group include, but are not limited to, 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate. It is also possible to use two or more types in combination.

(Thermosetting compound)
Instead of the thermoplastic resin used in the present invention, or together with the thermoplastic resin, a thermosetting compound can be contained. Thermosetting compounds include thermosetting resins and thermosetting compounds.

  The thermosetting compound is, for example, an epoxy compound, an epoxy resin, a benzoguanamine compound, a benzoguanamine resin, a rosin-modified maleic acid compound, a rosin-modified maleic acid resin, a melamine compound, a melamine resin, a urea compound, a urea resin, a phenol compound, a phenol resin, or the like. Is mentioned.

  In the present invention, the acid value of the binder resin (B) is 90 to 140 mgKOH / g, more preferably 100 to 130 mgKOH / g. When the binder resin (B) is blended in an appropriate amount, the curability of the coating film in the heat curing step is improved, and the ability to suppress the generation of foreign matter due to the precipitation of the colorant (A) is further improved.

  The weight average molecular weight of the binder resin (B) is preferably 10,000 to 30,000, more preferably 15,000 to 30,000. By blending the binder resin (B), it becomes an obstacle to the precipitation of the colorant (A) in the thermosetting process, and the ability to suppress the generation of foreign matter is further improved.

  Furthermore, the double bond equivalent of the binder resin (B) is preferably 300 to 400 g / mol, and more preferably 330 to 380 g / mol. By blending the binder resin (B) with an appropriate double bond equivalent, the curability of the coating film in the photocuring step is improved, and it becomes an obstacle to the precipitation of the colorant (A) in the thermosetting step, which prevents foreign matter from occurring. The suppression ability is further improved.

  The content of the binder resin is preferably 20 to 1000 parts by mass with respect to 100 parts by mass of the colorant (A). When used in an appropriate amount, good color characteristics are easily obtained.

<Photopolymerizable compound (C)>
The photopolymerizable compound includes a photopolymerizable monomer and a photopolymerizable oligomer.

  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 can be mentioned.

  Commercially available products of the photopolymerizable monomer are KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYARD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, and 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, KAYAPARADA, ADA-AD, 330-KAAYADAD-330. -30, KAYARAD DPCA-60, KAYARAD DPCA-120, and East Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M manufactured by Gosei Co., Ltd. -400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Osaka Organic Viscourt #. 310HP, viscoat # 335HP, viscoat # 700, viscoat # 295, viscoat # 330, viscoat # 360, viscoat #GPT, viscoat # 400, viscoat # 405, A-9300 manufactured by Shin Nakamura Chemical Co., Ltd., and the like.

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

  The photopolymerizable compound having an acidic group is, for example, an esterification product of a polycarboxylic acid containing a free water acidic group of a polyhydric alcohol and (meth) acrylic acid, and a dicarboxylic acid; a polyvalent carboxylic acid and a monohydroxy group. Examples thereof include esterified products with alkyl (meth) acrylate. Specific compounds include, for example, monohydroxy oligoacrylate or monohydroxy oligoacrylate such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate. Free carboxyl group-containing monoesters of oligomethacrylate 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, etc. A free carboxyl group-containing oligoesterification product of an acid and monohydroxy monoacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, or monohydroxy monomethacrylate. To be

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

(Photopolymerizable oligomer)
The photopolymerizable oligomer includes a photopolymerizable oligomer having one or more urethane bonds (hereinafter referred to as urethane acrylate oligomer). The urethane acrylate oligomer preferably has about 2 to 10 (meth) acryloyl groups.
The urethane acrylate oligomer can be synthesized by, for example, a method of synthesizing a (meth) acrylate having a water-acidic group with a polyfunctional isocyanate, a method of reacting an alcohol with a polyfunctional isocyanate, and then a (meth) acrylate having a water-acidic group. And a method of synthesizing by reacting.

  Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and 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, epoxy group Containing compound and the carboxy (meth) reaction product of acrylate, water acidic group-containing polyol polyacrylate, and the like.

  Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate and the like.

  As the alcohol, when a polyhydric alcohol is used, the degree of cross-linking of the coating is increased and various resistances are improved. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

  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. UA-160TM manufactured by Osaka, UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like.

  The photopolymerizable compound can be used alone or in combination of two or more kinds.

  The blending amount of the photopolymerizable compound is preferably 5 to 400 parts by mass, and more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the colorant (A). Addition of an appropriate amount further improves photocurability and developability.

<Photopolymerization initiator (D)>
The photopolymerization initiator (D) is a compound that generates active species capable of initiating the polymerization of the photopolymerizable compound (D) upon exposure to radiation such as ultraviolet rays, visible rays, far 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-. On, 1-hydroxycyclohexyl phenyl 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, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin compounds such as tellurium or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- ( -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 2,4-trichloro. Triazine compounds such as methyl- (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 a phosphine compound such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; a quinone compound such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; a borate compound; Examples thereof include a carbazole compound; an imidazole compound; or a titanocene compound. Among these, oxime ester compounds are preferable because they can suppress crystal precipitation in the coating film after photocuring.

  The photopolymerization initiator (D) can be used alone or in combination of two or more kinds.

  The blending amount of the photopolymerization initiator (D) is preferably 0.1 to 200 parts by mass, and more preferably 0.5 to 150 parts by mass with respect to 100 parts by mass of the colorant (A). Addition of an appropriate amount further improves photocurability and developability.

(Sensitizer)
The coloring composition for a color filter can contain a sensitizer together with the photopolymerization initiator (D).
Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, etc., 1,2-diketone derivatives represented by 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, oxonole derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives , Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative Tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, anulene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzophene Non, 4,4'-diethylamino benzophenone etc. are mentioned. Also, Shin Kawara et al., "Dye Handbook" (1986, Kodansha), Okawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Tadamasarou et al., "Special Functional Materials" ( The sensitizer described in 1986, CMC) may also be mentioned.

  The sensitizers can be used alone or in combination of two or more.

  The compounding amount of the sensitizer is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (D). Addition of an appropriate amount further improves photocurability and developability.

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

  The organic solvent is, 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-butylbenze Amine, 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 Ether, ethylene glycol Methyl 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 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 ester, etc. And the like. Among these, ethyl lactate, methoxypropyl acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol acetate such as ethylene glycol monoethyl ether acetate, benzyl alcohol, alcohols such as diacetone alcohol and ketones such as cyclohexanone. preferable.

  The organic solvent may be used alone or in combination of two or more kinds.

  The blending amount of the organic solvent is preferably 200 to 4000 parts by mass with respect to 100 parts by mass of the colorant (A). When it is mixed in an appropriate amount, the viscosity can be easily adjusted and a uniform film can be easily formed.

(Leveling agent)
The coloring composition for color filters may contain a leveling agent. This further improves the coatability and the surface smoothness of the coating. Examples of the leveling agent include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and the like.

Examples of the silicone-based surfactant include a linear polymer having a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.
Commercial products of silicone-based surfactants are, for example, BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, 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, Toray Dow Corning, FZ-7001, FZ-7002, FZ-2110, FZ-2122, FZ-2123], FZ-2191, FZ-5609, Shin-Etsu Chemical X-22-. 4952, X-22-4272, X-22-6266, KF-351A, K3 4L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, etc. KF-6004 and the like.

Examples of the fluorine-based surfactant include compounds having a fluorocarbon chain.
Commercial products of the fluorinated surfactant are, for example, Surflon S-242, S-243, S-420, S-611, S-651, S-386 manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253 manufactured by DIC. , 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 Kasei EF-PP31N09, EF-PP33G1, EF-PP32C1, Neos Futgent 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 myristyl ether, polyoxyethylene octyl. Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sodium Bitan 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, tetraoleic acid polyoxyethylene sorbit, glycerol monostearate, glycerol monooleate Ate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol Stearate, polyethylene glycol monomethyl oleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl amines, alkyl alkanol amides, alkyl betaine such as alkyl imidazoline and alkyl dimethyl amino acetic acid betaine.

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

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

  The surfactants can be used alone or in combination of two or more kinds.

  The content of the surfactant is preferably 0.001 to 2% by mass and more preferably 0.005 to 1.0% by mass in 100% by mass of the nonvolatile content of the coloring composition for a color filter. When contained in an appropriate amount, coatability, adhesion of the coating film to the base material, and permeability of the coating film are further improved.

(Curing agent, curing accelerator)
The coloring composition for a color filter may contain a curing agent and a curing accelerator. This further improves the curability when a thermosetting resin is included.
Examples of the curing agent include phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, and the like. Among these, compounds having two or more phenolic water acidic groups and amine-based curing agents are preferable.
The curing accelerator is, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N). , N-dimethylbenzylamine etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4). -Methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compound (for example, triphenylphosphine) Etc.), Gua Min 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.) and the like.

  The curing agent and the curing accelerator can be used alone or in combination of two or more kinds.

  Moreover, the compounding quantity of a hardening | curing agent and a hardening accelerator is respectively 0.01-15 mass parts with respect to 100 mass parts of thermosetting resins.

(Other additives)
The coloring composition for color filters may contain other additives. Other additives include, for example, storage stabilizers and adhesion improvers. When the storage stabilizer is contained, the temporal stability of the viscosity of the coloring composition for color filters is further improved. When the adhesion improver is contained, the adhesion between the base material and the film is further improved.

(Storage stabilizer)
Examples of the storage stabilizer include organic acids such as lactic acid and oxalic acid and methyl ethers thereof, t-butylpyrocatechol, organic phosphines such as 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, for example, vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane, and (meth) acryl 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 Methoxysilane, N-β (ami Noethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples of the silane coupling agent include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The content of the adhesion improver is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant (A).

(Method for producing colored composition for color filter)
As an example of the method for producing a coloring composition for a color filter, it is preferable that the quinophthalone pigment of the colorant (A) and the phthalocyanine-based green pigment are micronized simultaneously or separately as described above. Then, the colorant is dispersed by using a dispersing machine such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor together with a dispersant and a dispersion aid. Make 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 produce a colored composition for a color filter. The components can be added at any timing.

(Removal of coarse particles)
The coloring composition for a color filter preferably removes coarse particles in order to form fine filter segments. The colored composition for a color filter can be obtained by using a means such as centrifugation, filtration with a sintered filter or a membrane filter, and coarse particles of 5 μm or more, preferably 1 μm or more, and more preferably 0.5 μm or more. It is preferable to remove particles and entrained dust.

(Color filter)
The color filter of the present invention includes a base material (also referred to as a substrate) and a filter segment formed from the color filter coloring composition. The color filter also includes 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 further comprises at least one magenta color filter segment, at least one cyan color filter segment, and at least one It may include one yellow color filter segment. A green filter segment can be formed from the coloring composition for a color filter of the present invention.

(Color filter manufacturing method)
The color filter can be produced by a printing method, a photolithography method or the like, and the photolithography method is preferable.

  The photolithography method uses, for example, a coating method such as spray coating, spin coating, slit coating, or roll coating of a coloring composition for a color filter prepared as a solvent developing type or alkali developing type colored resist on a transparent substrate. Then, the coating is applied so that the dry film thickness is 0.2 to 10 μm. The film is exposed to ultraviolet light through a mask having a predetermined pattern.

  After that, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developing solution, or spraying the developing solution with a spray or the like to remove the uncured portion to form a desired pattern. Further, in order to accelerate the polymerization of the filter segment and the black matrix formed by the development, heating can be carried out if necessary. The photolithography method can form a filter segment with higher accuracy than the printing method.

  For the development, for example, an aqueous solution of sodium carbonate, sodium hydroxide or the like as an alkaline developer; an organic alkali such as dimethylbenzylamine, triethanolamine or tetramethylammonium hydroxide can be used. Further, a defoaming agent or a surfactant can be used in the developing solution. Examples of the development processing method include a shower development method, a spray development method, a dip (immersion) development method, and a paddle (fluid) development method.

  In addition, in order to enhance the exposure sensitivity to ultraviolet rays, a water-soluble or alkali-soluble resin (for example, polyvinyl alcohol or water-soluble acrylic resin) can be formed on the resist film formed from the color filter coloring composition. This makes it possible to prevent oxygen that impedes the ultraviolet curing of the resist film.

  Examples of the substrate include glass plates such as soda lime glass, low-alkali borosilicate glass, and non-alkali aluminoborosilicate glass; resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate. In addition, it is preferable that a transparent electrode formed of indium oxide, tin oxide, or the like is provided on the surface of the substrate for driving the liquid crystal after paneling. Further, when the color filter is used for a solid-state image sensor, 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 about 0.01 to 3 mm.

  The thickness of the filter segment is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. A drying step can be performed during coating. Examples of the drying device include a vacuum dryer, a convection oven, an IR oven, and a hot plate.

If the black matrix is formed in advance before forming the filter segment on the substrate, the contrast of the display panel can be further enhanced. For the black matrix, for example, chromium, a 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 the black matrix 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 the filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the panel can be increased and the brightness can be improved.
If necessary, an overcoat film or a transparent conductive film can be formed on the color filter.

(Liquid crystal display)
The liquid crystal display device of the present invention includes a color filter. It is preferable that the liquid crystal display device further includes a light source. Examples of the light source include a cold cathode tube (CCFL) and a white LED. Among them, in the present invention, the white LED is preferable in that the red reproduction area is widened. An example of an embodiment of the liquid crystal display device will be described with reference to FIG. The upper side of FIG. 1 is called the upper side, and the lower side is called the lower side. The liquid crystal display device 10 includes a pair of a transparent substrate 11 and a transparent substrate 21 that are arranged to face each other with a space therebetween. 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 on it. 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 depositing ITO (indium tin oxide), for example.

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

  The transparent substrate 21 is installed above the color filter 22. Further, the transparent electrode layer 23 is formed below the color filter 22, and the alignment layer 24 is further provided below the transparent electrode layer 23.

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.

  The white LED light source includes a blue LED having a fluorescent filter formed on the surface thereof, and a blue LED resin package containing a fluorescent substance. For example, the emission has a wavelength (λ3) that maximizes the emission intensity within the wavelength range of 430 nm to 485 nm, a wavelength (λ4) that maximizes the emission intensity within the range of 530 nm to 580 nm, and 600 nm to 650 nm. Has a wavelength (λ5) that maximizes the emission intensity within the range of, and the ratio (I4 / I3) of the emission intensity I3 at the wavelength λ3 and 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 a spectral characteristic that the ratio (I5 / I3) of the emission intensity I3 at the wavelength λ3 and the emission intensity I5 at the wavelength λ5 is 0.1 or more and 1.3 or less is preferable. Further, the emission has a wavelength (λ1) that maximizes the emission intensity 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 of λ1. A white LED light source (LED2) having a spectral characteristic that the ratio (I2 / I1) of the emission intensity I1 at 1 to the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less is also preferable.

  When LED1 is a commercial product, for example, NSSW306D-HG-V1 (manufactured by Nichia), NSSW304D-HG-V1 (manufactured by Nichia), etc. may be mentioned.

  When the LED2 is a commercial product, for example, NSSW440 (manufactured by Nichia Corporation), NSSW304D (manufactured by Nichia Corporation) and the like can be mentioned.

  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". The blending amounts in the table are parts by mass unless otherwise specified.

  Each measuring method will be described below.

(Average primary particle size of pigment)
A solvent (methoxypropyl acetate) is added to the pigment powder, a small amount of a dispersant (Disperbyk-161: a dispersant from Big Chemie) is added, and the mixture is treated with ultrasonic waves for 1 minute to prepare a measurement sample. Then, using a transmission (TEM) electron microscope, three photographs (for three fields of view) in which 100 or more primary particles of the pigment can be confirmed are prepared, and the sizes of 100 primary particles are measured in order from the upper left. . Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment are measured in nm units, and the average is taken as the primary particle diameter of the pigment particles, and a total of 300 distributions are created in 5 nm increments. The number average particle diameter is calculated by approximating the median value in 5 nm increments (for example, 8 nm in the case of 6 nm or more and 10 nm or less) as the particle diameters of these particles, and calculating based on each particle diameter and the number thereof.

(Acid value of resin)
To 0.5 to 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added and stirred to be uniformly dissolved, and a 0.1 mol / L KOH aqueous solution was used as a titration liquid to prepare an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo Co., Ltd.). ) Was used to measure the acid value (mgKOH / g) of the resin solution. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

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

(Double bond equivalent of resin)
The double bond equivalent was calculated as the mass of the resin per 1 mol of the double bond.

<Method for producing finely treated colorant>
(Refining treatment colorant (A-1))
Phthalocyanine green pigment C.I. I. Pigment Green 36 (“Ryonor Green 6YK” manufactured by Toyo Color 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. did. Next, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. Then, the refined colorant (A-1) was obtained.

(Refining treatment colorant (A-2))
Phthalocyanine green pigment C.I. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC) (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 poured into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Then, a refined colorant (A-2) was obtained.

(Refining treatment colorant (A-3))
To a three-necked flask, 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 are added, and heated to 90 ° C. for 8 hours. It was made to react. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain a micronized colorant (A-3) which was a phthalocyanine green pigment.

(Fine treatment colorant (A-4))
To a three-necked flask, 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 and stirred, and the mixture was stirred at 20 ° C. The reaction was carried out for 6 hours. Then, the above 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. To a beaker, 500 parts of a 2.5% sodium hydroxide aqueous solution and the residue collected by filtration were added, and the mixture was stirred at 80 ° C for 1 hour. Then, 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 a pigment having an average of 10.1 bromine atoms substituted on the obtained phthalocyanine ring and 13.9 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to ° C and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain a finely treated colorant (A-4) which was a phthalocyanine green pigment.

Formula (2)

(Fine treatment colorant (A-5))
Yellow pigment C.I. I. Pigment Yellow 138 (“Paliotol Yellow L 0962 HD” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Then, this kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Then, a refined colorant (A-5) was obtained.

(Fine treatment colorant (A-6))
100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was poured into warm water and stirred for 1 hour while heating to about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night, 97 parts of a finely-processed colorant (A-6) was obtained.

(Fine treatment colorant (A-7))
100 parts of the quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was poured into warm water and stirred for 1 hour while heating to about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night, 97 parts of the finely-processed colorant (A-7) was obtained.

(Fine processing colorant (A-8))
100 parts of the quinophthalone compound (c), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was poured into warm water and stirred for 1 hour while heating to about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night, 97 parts of a finely-processed colorant (A-8) was obtained.

(Fine treatment colorant (A-9))
100 parts of the quinophthalone compound (d), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was poured into warm water and stirred for 1 hour while heating to about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night, 97 parts of a finely-processed colorant (A-9) was obtained.

<Production of resin type dispersant solution>
Resin type dispersant "LPN21116" manufactured by BYK was mixed with methoxypropyl acetate to prepare a solution having a nonvolatile content of 20% by mass to obtain a resin type dispersant solution.

<Method for producing binder resin (B)>
(Production of binder resin (B-1))
196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device in a separable 4-necked flask, heated to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen, and then dropped. 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.) A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 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 non-volatile content. Methoxypropyl acetate was added to the resin solution synthesized above so that the non-volatile content was 40% by mass. Was added to prepare a binder resin (B-1) solution. The weight average molecular weight (Mw) of the resin was 26000.

(Production of binder resin (B-2))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 0.8 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 47.3 parts of glycidyl methacrylate and 8.0 parts of azobisisobutyronitrile was added dropwise from a dropping tube over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 24.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 24.4 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 10313, an acid value of 90 mgKOH / g, and a double bond equivalent of 300 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-2) solution was prepared by adding.

(Production of binder resin (B-3))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel, A mixture of 0.8 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 47.3 parts of glycidyl methacrylate and 3.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out the polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 24.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 24.4 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 2,090, an acid value of 91 mgKOH / g, and a double bond equivalent of 300 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate was added to the resin solution synthesized above so that the non-volatile content was 40% by mass. A binder resin (B-3) solution was prepared by adding.

(Production of binder resin (B-4))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 0.8 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 47.3 parts of glycidyl methacrylate and 1.0 part of azobisisobutyronitrile was added dropwise from a dropping tube over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 24.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 24.4 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 29566, an acid value of 91 mgKOH / g, and a double bond equivalent of 300 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-4) solution was prepared by adding.

(Production of binder resin (B-5))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 11.0 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 40.6 parts of glycidyl methacrylate and 8.0 parts of azobisisobutyronitrile was added dropwise from a dropping tube over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.6 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 24.4 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 10198, an acid value of 90 mgKOH / g and a double bond equivalent of 350 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-5) solution was prepared by adding.

(Production of binder resin (B-6))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 11.0 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 40.6 parts of glycidyl methacrylate and 3.0 parts of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.6 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 24.4 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 20394, an acid value of 92 mgKOH / g, and a double bond equivalent of 350 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-6) solution was prepared by adding.

(Production of binder resin (B-7))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 11.0 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 40.6 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.6 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 24.4 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 29801, an acid value of 91 mgKOH / g, and a double bond equivalent of 350 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-7) solution was prepared by adding.

(Production of binder resin (B-8))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel, A mixture of 18.6 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 35.5 parts of glycidyl methacrylate and 8.0 parts of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 18.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 24.4 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 10065, an acid value of 90 mgKOH / g, and a double bond equivalent of 400 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate was added to the resin solution synthesized above so that the non-volatile content was 40% by mass. A binder resin (B-8) solution was prepared by adding.

(Production of binder resin (B-9))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 18.6 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 35.5 parts of glycidyl methacrylate, and 3.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to conduct a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 18.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 24.4 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 20248, an acid value of 91 mgKOH / g, and a double bond equivalent of 400 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate was added to the resin solution synthesized above so that the non-volatile content was 40% by mass. A binder resin (B-9) solution was prepared by adding.

(Production of binder resin (B-10))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 18.6 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 35.5 parts of glycidyl methacrylate and 1.0 part of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 18.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 24.4 parts and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 29636, an acid value of 90 mgKOH / g, and a double bond equivalent of 400 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-10) solution was prepared by adding.

(Production of Binder Resin (B-11))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 2.0 parts of dicyclopentanyl methacrylate, 44.4 parts of glycidyl methacrylate and 8.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Then, the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 22.5 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 31.2 parts and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 10227, an acid value of 114 mgKOH / g, and a double bond equivalent of 320 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-11) solution was prepared by adding.

(Production of binder resin (B-12))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 2.0 parts of dicyclopentanyl methacrylate, 44.4 parts of glycidyl methacrylate and 3.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Then, the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 22.5 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 31.2 parts and triethylamine 0.5 parts were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 20523, an acid value of 115 mgKOH / g, and a double bond equivalent of 320 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-12) solution was prepared by adding.

(Production of Binder Resin (B-13))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 2.0 parts of dicyclopentanyl methacrylate, 44.4 parts of glycidyl methacrylate and 1.0 part of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Next, the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 22.5 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 31.2 parts and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 29357, an acid value of 115 mgKOH / g, and a double bond equivalent of 320 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-13) solution was prepared by adding.

(Production of Binder Resin (B-14))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 4.2 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 40.6 parts of glycidyl methacrylate, and 8.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to conduct a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.6 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 31.2 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 10119, an acid value of 114 mg KOH / g, and a double bond equivalent of 350 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-14) solution was prepared by adding.

(Production of Binder Resin (B-15))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 4.2 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 40.6 parts of glycidyl methacrylate, and 3.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out the polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.6 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 31.2 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 20111, an acid value of 116 mgKOH / g, and a double bond equivalent of 350 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-15) solution was prepared by adding.

(Production of binder resin (B-16))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 4.2 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 40.6 parts of glycidyl methacrylate and 1.0 part of azobisisobutyronitrile was added dropwise from a dropping tube over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.6 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 31.2 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 29885, an acid value of 115 mgKOH / g, and a double bond equivalent of 350 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-16) solution was prepared by adding.

(Production of Binder Resin (B-17))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 11.8 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 35.5 parts of glycidyl methacrylate and 8.0 parts of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 18.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 31.2 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 10006, an acid value of 117 mgKOH / g, and a double bond equivalent of 400 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-17) solution was prepared by adding.

(Production of binder resin (B-18))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 11.8 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 35.5 parts of glycidyl methacrylate and 3.0 parts of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 18.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 31.2 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 20343, an acid value of 116 mgKOH / g, and a double bond equivalent of 400 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-18) solution was prepared by adding.

(Production of Binder Resin (B-19))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 11.8 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 35.5 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 18.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 31.2 parts and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 29702, an acid value of 115 mgKOH / g, and a double bond equivalent of 400 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-19) solution was prepared by adding.

(Production of binder resin (B-20))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 2.6 parts of dicyclopentanyl methacrylate, 39.4 parts of glycidyl methacrylate and 8.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 37.9 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 10329, an acid value of 140 mgKOH / g, and a double bond equivalent of 360 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-20) solution was prepared by adding.

(Production of binder resin (B-21))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 2.6 parts of dicyclopentanyl methacrylate, 39.4 parts of glycidyl methacrylate and 3.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 37.9 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 20146, an acid value of 140 mgKOH / g, and a double bond equivalent of 360 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-21) solution was prepared by adding.

(Production of Binder Resin (B-22))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 2.6 parts of dicyclopentanyl methacrylate, 39.4 parts of glycidyl methacrylate and 1.0 part of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 37.9 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 29811, an acid value of 139 mgKOH / g, and a double bond equivalent of 360 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate was added to the resin solution synthesized above so that the non-volatile content was 40% by mass. A binder resin (B-22) solution was prepared by adding.

(Production of Binder Resin (B-23))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 2.3 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 37.4 parts of glycidyl methacrylate, and 8.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to conduct a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 18.9 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 37.9 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 10234, an acid value of 140 mgKOH / g, and a double bond equivalent of 380 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-23) solution was prepared by adding.

(Production of binder resin (B-24))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 2.3 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 37.4 parts of glycidyl methacrylate and 3.0 parts of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 18.9 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 37.9 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 20468, an acid value of 139 mgKOH / g, and a double bond equivalent of 380 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-24) solution was prepared by adding.

(Production of binder resin (B-25))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 2.3 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 37.4 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out the polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 18.9 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 37.9 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 29599, an acid value of 139 mgKOH / g, and a double bond equivalent of 380 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-25) solution was prepared by adding.

(Production of Binder Resin (B-26))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 5.1 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 35.5 parts of glycidyl methacrylate and 8.0 parts of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 18.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 37.9 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 10315, an acid value of 139 mgKOH / g, and a double bond equivalent of 400 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-26) solution was prepared by adding.

(Production of Binder Resin (B-27))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel, A mixture of 5.1 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 35.5 parts of glycidyl methacrylate and 3.0 parts of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 18.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 37.9 parts and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 20538, an acid value of 140 mgKOH / g, and a double bond equivalent of 400 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate was added to the resin solution synthesized above so that the non-volatile content was 40% by mass. A binder resin (B-27) solution was prepared by adding.

(Production of Binder Resin (B-28))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 5.1 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 35.5 parts of glycidyl methacrylate and 1.0 part of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 18.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 37.9 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 29724, an acid value of 138 mgKOH / g, and a double bond equivalent of 400 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-28) solution was prepared by adding.

(Production of Binder Resin (B-29))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 2.8 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 40.6 parts of glycidyl methacrylate and 8.7 parts of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.6 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 32.5 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 8018, an acid value of 120 mgKOH / g and a double bond equivalent of 350 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-29) solution was prepared by adding.

(Production of Binder Resin (B-30))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 2.8 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 40.6 parts of glycidyl methacrylate and 0.7 part of azobisisobutyronitrile was added dropwise from a dropping tube over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.6 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 32.5 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 34899, an acid value of 121 mgKOH / g, and a double bond equivalent of 350 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-30) solution was prepared by adding.

(Production of binder resin (B-31))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel, A mixture of 0.5 parts of dicyclopentanyl methacrylate, 49.8 parts of glycidyl methacrylate and 3.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 25.3 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 24.4 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 20212, an acid value of 91 mg KOH / g, and a double bond equivalent of 280 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate was added to the resin solution synthesized above so that the non-volatile content was 40% by mass. A binder resin (B-31) solution was prepared by adding.

(Production of Binder Resin (B-32))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 16.4 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 31.6 parts of glycidyl methacrylate and 3.0 parts of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 16.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 32.5 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 20256, an acid value of 120 mgKOH / g, and a double bond equivalent of 450 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate was added to the resin solution synthesized above so that the non-volatile content was 40% by mass. A binder resin (B-32) solution was prepared by adding.

(Production of Binder Resin (B-33))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 5.6 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 40.6 parts of glycidyl methacrylate and 3.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to conduct a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.6 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 29.8 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 20334, an acid value of 109 mg KOH / g, and a double bond equivalent of 350 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-33) solution was prepared by adding.

(Production of Binder Resin (B-34))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 21.8 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 40.6 parts of glycidyl methacrylate and 8.0 parts of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.6 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 13.5 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 10531, an acid value of 50 mgKOH / g, and a double bond equivalent of 350 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-34) solution was prepared by adding.

(Production of Binder Resin (B-35))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 40.6 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 20.6 parts of glycidyl methacrylate and 3.0 parts of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 16.0 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 13.5 parts and triethylamine 0.5 parts were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 19901, an acid value of 50 mgKOH / g and a double bond equivalent of 350 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate was added to the resin solution synthesized above so that the non-volatile content was 40% by mass. A binder resin (B-35) solution was prepared by adding.

(Production of Binder Resin (B-36))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 21.8 parts of dicyclopentanyl methacrylate, 3.5 parts of styrene, 40.6 parts of glycidyl methacrylate and 1.0 part of azobisisobutyronitrile was added dropwise from a dropping pipe over 2.5 hours to carry out a polymerization reaction. went. Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 20.6 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 13.5 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 29990, an acid value of 50 mgKOH / g and a double bond equivalent of 350 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-36) solution was prepared by adding.

(Production of Binder Resin (B-37))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 1.5 parts of dicyclopentanyl methacrylate, 38.4 parts of glycidyl methacrylate and 8.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 19.5 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 40.6 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 10022, an acid value of 150 mgKOH / g and a double bond equivalent of 370 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-37) solution was prepared by adding.

(Production of Binder Resin (B-38))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 1.5 parts of dicyclopentanyl methacrylate, 38.4 parts of glycidyl methacrylate, and 3.0 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 19.5 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 40.6 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 20145, an acid value of 150 mgKOH / g, and a double bond equivalent of 370 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-38) solution was prepared by adding.

(Production of Binder Resin (B-39))
100 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, and a stirrer in a separable four-necked flask, and heated to 120 ° C while injecting nitrogen gas into the vessel at the same temperature. A mixture of 1.5 parts of dicyclopentanyl methacrylate, 38.4 parts of glycidyl methacrylate and 1.0 part of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 19.5 parts of acrylic acid, the reaction was continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride was further added. 40.6 parts and triethylamine 0.5 part were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 29811, an acid value of 150 mgKOH / g, and a double bond equivalent of 370 g / mol. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (B-39) solution was prepared by adding.

<Method for producing colorant dispersion>
(Colorant dispersion (P1))
After the following mixture was stirred and mixed so as to be uniform, the mixture was dispersed for 5 hours with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. To obtain a colorant dispersion (P1).

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

(Colorant dispersion (P2-9))
The colorant, the resin-type dispersant solution, the binder resin solution, and the solvent were changed in the same manner as the pigment dispersion (P1) except that the composition and the blending amount (parts by mass) shown in Table 1 were changed. Dispersions (P2-9) were prepared respectively.

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

Chemical formula (3)

[Example 1]
(Coloring composition for color filter (G-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a 1.0 μm filter to prepare a colored composition (G-1) for a color filter.
Colorant dispersion 1 (P4): 22.4 parts Colorant dispersion 2 (P5): 17.3 parts Binder resin (B-2): 9.7 parts Photopolymerizable compound (C-1) [Toagosei "Aronix M-402"]: 3.4 parts Photopolymerizable initiator (D-1): 0.2 parts Solvent / methoxypropyl acetate (PGMAC): 47.0 parts

[Examples 2-37, Comparative Examples 1-6]
(Coloring composition for color filter (G-2 to 43))
Except for changing the composition and the blending amount (parts by mass) shown in Tables 2-1 to 3, the same procedure as in the coloring composition for a color filter (G-1) in Example 1 was carried out, and Examples 2 to 37 and Comparative Example Coloring compositions for color filters 1 to 6 (G-2 to 43) were obtained.

<Evaluation of colored composition for color filter>
The coating film of the obtained colored composition for color filters (G-1 to 43) was tested by the following method. The test results are shown in Table 3. In the following evaluation results, ⊚, ○, and Δ are practical, and x is impractical.

<Evaluation of gas generation rate>
About the obtained colored composition for color filters (G-1 to 43), the colored composition for color filter was heat-treated on a glass substrate having a length of 100 mm × a width of 100 mm × a thickness of 0.7 mm to have a film thickness of 2.2 μm. Each of these was coated and exposed to ultraviolet light under the condition of 40 mJ / cm ² . Thereafter, the coating film sprayed with an alkali developing solution and washed with water was subjected to heat treatment (post-baking) for 20 minutes in an oven at 230 ° C. 10 mg of the obtained coating film was scraped off, and the amount of gas generated was confirmed from the weight loss of the coating film when heated at 230 ° C. for 3 hours by TG-DTA measurement (“Thermo plus evo2” manufactured by RIGAKU). It was evaluated by. The thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).
◎: Gas generation amount is 0% or more and less than 2% ○: Gas generation amount is 2% or more and less than 5% Δ: Gas generation amount is 5% or more and less than 10% ×: Gas generation amount is 10% or more

<Evaluation of crystal precipitation>
About the obtained colored composition for color filters (G-1 to 43), the colored composition for color filter was heat-treated on a glass substrate having a length of 100 mm × a width of 100 mm × a thickness of 0.7 mm to have a film thickness of 2.2 μm. It was applied so that it was exposed to ultraviolet light under the condition of 40 mJ / cm ² through a mask having a predetermined pattern. After that, an alkaline developing solution was sprayed to remove the uncured portion and washed with water to form a desired pattern. The obtained 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.). The evaluation was performed by observing an area of 100 μm in length × 300 μm in width on a glass surface having a distance between pixel patterns of 100 μm with a microscope, and evaluated according to the following criteria. The thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).
⊚: Crystals did not occur in the observation area ○: Crystals occurred in less than 5% of the observation area Δ: Crystals occurred in 5% to less than 10% of the observation area ×: Crystals were observed Occurred in the range of 10% or more of the area

<Pattern linearity evaluation>
The obtained coloring composition for color filters (G-1 to 43) was applied on a glass substrate having a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so as to have a film thickness of 2.2 μm after heat treatment, and a predetermined thickness was obtained. UV exposure was carried out under the condition of 40 mJ / cm ² through a mask having a pattern. After that, an alkaline developing solution was sprayed to remove the uncured portion and washed with water to form a desired pattern. The obtained coating film was heat-treated (post-baked) 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 the evaluation, the pattern formed with the mask opening width of 50 μm was observed and evaluated as follows. The thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).
◎: The difference between the maximum value and the minimum value within the same pattern line width is 0 μm or more and less than 0.5 μm ○: The difference between the maximum value and the minimum value within the same pattern line width is 0.5 μm or more and less than 1 μm Δ: The same pattern line width The difference between the maximum value and the minimum value is 1 μm or more and less than 2 μm ×: The difference between the maximum value and the minimum value within the same pattern line width is 2 μm or more

From the results in Table 3, Examples 1 to 37 were all practical in terms of the gas generation amount, crystal precipitation, and pattern linearity.
On the other hand, Comparative Examples 1 to 6 were difficult to put into practical use.

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 (8)

  A colorant (A), a binder resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D) are included, and the colorant (A) includes a quinophthalone pigment and a phthalocyanine-based green pigment, The coloring composition for a color filter, wherein the binder resin (B) has an acid value of 90 to 140 mgKOH / g.   The coloring composition for a color filter according to claim 1, wherein the binder resin (B) has a weight average molecular weight of 10,000 to 30,000.   The colored composition for a color filter according to claim 1, wherein the double bond equivalent of the binder resin (B) is 300 to 400 g / mol.   The coloring composition for a color filter according to claim 1, further comprising a thiol compound. 5. The quinophthalone pigment is one or more selected from the group consisting of Pigment Yellow 138 and the following quinophthalone compounds (a), (b), (c), and (d). The colored composition for a color filter according to item 1.
6. The phthalocyanine-based green pigment is one or more selected from the group consisting of Pigment Green 36, Pigment Green 58, and a compound represented by the following general formula (1). Coloring composition for color filter.
(In formula, X represents a halogen atom, n represents the integer of 0-16. Y represents -OP (= O) R < ₁ > R < ₂ >, -OC (= O) R < ₃ >, or -OS. (= O) ₂ R _4. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an alkoxyl group which may have or an aryloxy group which may have a substituent, R ₃ represents a hydrogen atom, an alkyl group which may have a substituent, or a cyclo group which may have a substituent. Represents an alkyl group, an aryl group which may have a substituent or a heterocyclic group which may have a substituent, R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, or a substituent Represents an optionally substituted aryl group or a heterocyclic group which may have a substituent.)   A color filter comprising a substrate and a filter segment formed from the coloring composition for a color filter according to claim 1.   A liquid crystal display device comprising the color filter according to claim 7.