JP7255172B2 - Photosensitive coloring composition, color filter and liquid crystal display device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive coloring composition, a color filter, and a liquid crystal display device.

A liquid crystal display device is equipped with a member in which a substrate, a color filter, a transparent electrode, and an alignment film are sequentially laminated. Since a specific organic solvent such as N-methylpyrrolidone with high dissolving power is often used for the alignment film, a part of the color filter is eluted due to contact with the organic solvent, resulting in poor light distribution and color deterioration. In some cases, unevenness occurs, resulting in display defects in the liquid crystal display device. Therefore, there has been a demand for improved solvent resistance to specific organic solvents.

Liquid crystal display devices are widely used in liquid crystal color televisions, car navigation systems, personal computers, smartphones, and the like, and are required to be even thinner. Therefore, a photosensitive coloring composition used for forming a pixel pattern (hereinafter simply referred to as a pattern) of a color filter needs to contain a coloring agent at a high concentration so that a desired color tone can be obtained even if the color filter is a thin film. was there. However, since the high concentration of the pigment inhibits the photocurability, there is a problem that it is difficult to form a good pattern.

Patent Document 1 contains a coloring agent, a photopolymerizable compound dipentaerythritol hexaacrylate, a photopolymerization initiator 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone-1, etc. A photosensitive coloring composition is disclosed. Patent Document 2 discloses that the colorant and the photopolymerizable compound are at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate, and the photopolymerization initiator is an acetophenone compound and biimidazole. at least one selected from the group of acetophenone-based compounds and triazine-based compounds, or at least one photopolymerization initiator selected from the group of acetophenone-based compounds and triazine-based compounds in addition to biimidazole-based compounds. A composition is disclosed.

JP 2009-098594 A Japanese Patent Application Laid-Open No. 2001-154013

However, since the conventional photosensitive coloring composition uses a highly curable photopolymerizable compound and a specific photopolymerization initiator, the solvent resistance is improved, but it is difficult to form a pattern with a good shape. I had a problem.

The present invention aims to provide a photosensitive coloring composition, a color filter, and a liquid crystal display device that can achieve both solvent resistance and good pattern shape (linearity, cross-sectional shape) even when the pigment is contained at a high concentration. do.

The photosensitive coloring composition of the present invention contains a pigment (A), a dispersant (B), a binder resin (C), a photopolymerizable compound (D), a photopolymerization initiator (E),
Pigment (A) contains a pigment represented by the following chemical formula (1),
The photopolymerizable compound (D) contains at least one of an isocyanurate ring-containing photopolymerizable compound [D1] and an alkylene chain-containing photopolymerizable compound [D2].

chemical formula (1)

According to the present invention, it is possible to provide a photosensitive coloring composition, a color filter, and a liquid crystal display device that can achieve both solvent resistance and good pattern shape (linearity, cross-sectional shape) even when the pigment is contained at a high concentration. .

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

First, the terms used in this specification are defined. "(Meth)acryloyl" is "acryloyl and methacryloyl". "(Meth)acrylic" is "acrylic and methacrylic". , "(meth)acrylic acid" is "acrylic acid and methacrylic acid". "(Meth)acrylates" are "acrylates and methacrylates." A monomer is an ethylenically unsaturated group-containing monomer. "C.I." means a color index (C.I.).

The photosensitive coloring composition of the present invention contains a pigment (A), a dispersant (B), a binder resin (C), a photopolymerizable compound (D), a photopolymerization initiator (E),
Pigment (A) contains a pigment represented by the following chemical formula (1),
The photopolymerizable compound (D) contains at least one of an isocyanurate ring-containing photopolymerizable compound [D1] and an alkylene chain-containing photopolymerizable compound [D2]. In this specification, the synergistic effect of the pigment represented by the chemical formula (1) and the photopolymerizable compound (D) allows solvent resistance and good pattern shape (linearity, cross-sectional shape) even when the pigment is contained at a high concentration. can be obtained.

chemical formula (1)

<Pigment (A)>
In this specification, the pigment (A) includes pigments represented by the above chemical formula (1).

(Pigment (Ab) represented by general formula (2))
In this specification, the pigment (A) preferably further contains a pigment represented by general formula (2). As a result, when used for color filters, brightness and contrast are improved, and crystal precipitation is easily suppressed after post-baking.

general formula (2)

In the general formula (2), X represents a chlorine atom or a bromine atom, and A and B each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbon number of 1 to 12 alkyl groups, optionally substituted phenyl groups, -CF ₃ , -OR ¹ , -SR ² , -N(R ³ )R ⁴ , -COOR ⁵ , -CONH ₂ , -CONHR ⁶ , - CON(R ⁷ )R ⁸ , —SO ₂ NH ₂ , —SO ₂ NHR ⁹ , or —SO ₂ N(R ¹⁰ )R ¹¹ , wherein each of R ¹ to R ¹¹ independently has 1 carbon atom; 1 to 12 alkyl groups, optionally substituted phenyl groups, or optionally substituted aralkyl groups. However, A and B cannot be hydrogen atoms at the same time. Also, A is not X and B is a hydrogen atom, nor is B both X and A a hydrogen atom.

The alkyl group having 1 to 12 carbon atoms may be linear or branched, and examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group and pentyl group. , hexyl group, heptyl group, octyl group, decyl group, dodecyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group and the like.

The phenyl group which may have a substituent is an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, and an alkoxyl group having 1 to 4 carbon atoms. A phenyl group having a substituent such as is mentioned. More specifically, phenyl group, p-methylphenyl group, 4-tert-butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, p-chlorophenyl group, 2,4-dichlorophenyl group, 3-carbamoyl A phenyl group and the like can be mentioned.

Examples of the aralkyl group optionally having a substituent include benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichloro A benzyl group and the like can be mentioned.

In this specification, the pigment represented by the general formula (2) is the following general formula (4-1), the following general formula (4-2), the following general formula (4-3), and the following general formula (4-4 ) is preferably one or more pigments selected from the group consisting of: As a result, brightness and contrast are further improved, and crystals are less likely to precipitate. In addition, R ¹² to R ¹⁴ in general formula (4-3) and general formula (4-4) are alkyl groups having 4 or more carbon atoms or phenyl groups which may have substituents. This is preferable in terms of suppression. The effect of improving contrast and suppressing crystal precipitation is believed to be due to the steric hindrance effect of bulky substituents such as carboxamide groups, phenyl groups, and t-butyl groups having alkyl groups of 4 or more carbon atoms, which suppresses aggregation of pigments. I'm guessing. In addition, the pigments represented by the general formula (4-3) and the following general formula (4-4) have carboamide groups, phenyl groups, and t-butyl groups, so that they have excellent color characteristics, so they are represented by the chemical formula (1). Does not impair the excellent brightness of pigments.

[In general formula (4-1), general formula (4-2), general formula (4-3), and general formula (4-4), X represents a chlorine atom or a bromine atom. In general formulas (4-3) and (4-4), R ¹² to R ¹⁴ each independently represent an alkyl group having 1 to 12 carbon atoms, or a phenyl group which may have a substituent. is the base. R ¹³ and R ¹⁴ may form a ring]

(Other diketopyrrolopyrrole pigments)
In this specification, the pigment (A) can be used in combination with a diketopyrrolopyrrole pigment in addition to the pigment represented by the chemical formula (1) and the pigment represented by the general formula (2). Other diketopyrrolopyrrole pigments include, for example, C.I. I. Pigment Red 254, 255, 264, 270, 272, 283, C.I. I. Pigment Orange 71, 73, or 81, and the like. Among these, C.I. I. Pigment Red 254 is preferred.

(Manufacturing method of pigment represented by chemical formula (1))
The pigment represented by the chemical formula (1) can be synthesized, for example, by a so-called succinic acid diester synthesis method. That is, 2 mol of 4-bromobenzonitrile is added to 1 mol of succinic acid diester in an inert organic solvent such as tert-amyl alcohol in the presence of an alkali metal or alkali metal alkoxide at a high temperature of 80 to 110 ° C. A condensation reaction is performed to produce an alkali metal salt of the diketopyrrolopyrrole compound. Then, the alkali metal salt of the diketopyrrolopyrrole compound is protonated using water, alcohol, acid, or the like, thereby synthesizing the pigment represented by the chemical formula (1). At this time, the primary particle size obtained can be controlled by the temperature in protonation, the type, ratio and amount of water, alcohol or acid. The method for producing the pigment represented by the chemical formula (1) is not limited to the above synthetic method.

The pigment represented by the general formula (2) is described in, for example, Synth. Commun. , 1988, 18, 1213 and Tetrahedron, 58 (2002) 5547-5565.

Further, the pigment represented by formula (2) is C.I. I. Pigment Red 254 or C.I. I. Pigment Red 291 can be synthesized at the same time. This synthesis can be performed by a method using at least two structurally different benzonitrile compounds in the succinic acid diester synthesis method (hereinafter referred to as "succinic acid diester co-synthesis method"). For example, in the method described in WO2009/081930, by selecting a plurality of benzonitrile compounds from 4-chlorobenzonitrile or 4-bromobenzonitrile and benzonitrile compounds represented by the following general formula (6), a pigment represented by formula (2); I. Pigment Red 254 or C.I. I. Pigment Red 291 can be synthesized at the same time.

general formula (6)

[In the general formula (6), A and B each independently have a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, a substituent, -CF ₃ , -OR ¹ , -SR ² , -N(R ³ )R ⁴ , -COOR ⁵ , -CONH ₂ , -CONHR ⁶ , -CON(R ⁷ )R ⁸ , -SO ₂ NH ₂ , —SO ₂ NHR ⁹ , or —SO ₂ N(R ¹⁰ )R ¹¹ , and R ¹ to R ¹¹ each independently have an alkyl group having 1 to 12 carbon atoms or a substituent; a phenyl group which may be substituted, or an aralkyl group which may have a substituent. However, A and B cannot be hydrogen atoms at the same time. ]

In the present specification, the pigment (A) can be used by mixing each synthesized pigment represented by the chemical formula (1) and the pigment represented by the general formula (2).

In the photosensitive coloring composition of the present specification, in addition to the pigment represented by the chemical formula (1), the pigment (A) further contains C.I. I. Pigment Red 254, C.I. I. Pigment Red 242, C.I. I. Pigment Red 177, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185 and one or more selected from the group consisting of yellow pigments represented by the following general formula (3) are preferably included. This expands the range of color expression.

General formula (3)

[In general formula (3), Z ₁ to Z ₁₃ each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, or a substituent an aryl group that may have, —SO ₃ H, —COOH, and monovalent to trivalent metal salts, alkylammonium salts, phthalimidomethyl groups that may have substituents, or substituents of these acidic groups; represents a sulfamoyl group which may have,
Adjacent groups of Z ₁ to Z ₄ and/or Z ₁₀ to Z ₁₃ may combine to form an aromatic ring which may have a substituent. ]

A yellow pigment represented by the general formula (3) is particularly effective in improving brightness and is therefore preferred.

(Other red pigments (AR))
The photosensitive coloring composition of the present specification can be used in combination with a red pigment (AR) and a pigment other than red (AY) other than the pigments described so far.

Other red pigments (AR) include, for example, C.I. I. Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 122, 146, 168, 169, 176, 178, 179, 184, 185, 187, 200, 202, 208, 210, 246, 269, 273, 274, 276, 277, 278, 279, 280, 281, 282, 284, 285, 286, 287 and the like. Also included are the azo pigments described in JP-A-2014-112527 and the azo pigments described in JP-A-2013-161026.

(Pigments other than red (AY))
Pigments other than red (AY) 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, 147, 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, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 and other yellow pigments. Furthermore, C.I. I. Orange pigments such as Pigment Orange 43 can also be used.

<Dye (AS)>
The photosensitive coloring composition herein can contain a dye (AS).
Dyes (AS) include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, and the like. Also, as the dye (AS), derivatives thereof or lake pigments obtained by converting dyes into lakes can be used.

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

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

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

<Refinement of pigment>
In this specification, the pigment (A) is preferably blended with other materials after being pulverized. Refining methods include, for example, wet grinding, dry grinding, dissolution precipitation, and the like. Salt milling treatment by a kneader method, which is one type of wet grinding, is preferred herein.
The average primary particle size of the pigment is preferably 5-90 nm, more preferably 10-70 nm. If the average primary particle size is appropriate, the dispersibility is further improved, and the contrast ratio is also further improved. The average primary particle size is obtained by averaging about 20 particles from an enlarged image of a TEM (transmission electron microscope).

The salt milling treatment is a batch process such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or a planetary mixer, for example. Alternatively, the mixture is mechanically kneaded while being heated using a continuous kneader, and then washed with water to remove the water-soluble inorganic salt and the water-soluble organic solvent. The water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, sodium sulfate and the like. Among these, inexpensive sodium chloride (salt) is preferable. The amount of the water-soluble inorganic salt to be used is preferably 50 to 2000% by mass, more preferably 300 to 1000% by mass, based on 100% by mass of the pigment (A), in terms of both processing efficiency and production efficiency.

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 (miscible in) water and does not substantially dissolve the inorganic salt used. In this specification, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety. Water-soluble organic solvents include, for example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. mentioned. The amount of the water-soluble organic solvent used is preferably 5 to 1000% by mass, more preferably 50 to 500% by mass, based on 100% by mass of the pigment (A).

When salt milling the pigment, a resin can be added as necessary. Types of resins include, for example, natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Preferably, the resin is solid at room temperature (25° C.) and water-insoluble. In addition, it is also preferable that the resin is partially soluble in an organic solvent depending on the embodiment. The amount of the resin used is preferably 5 to 200% by mass based on 100% by mass of the pigment (A).

<Dispersant (B)>
The photosensitive coloring composition can use a resin-type dispersant or a pigment derivative as the dispersant (B). The resin-type dispersant has a pigment adsorption site that adsorbs to the pigment (A) and a relaxation site that has a high affinity with components other than the pigment and causes steric repulsion between dispersed particles.
The dispersant (B) is, for example, a urethane-based dispersant such as polyurethane, a polycarboxylic acid ester such as polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, a polycarboxylic acid ammonium salt, a poly Carboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; amides and salts thereof; (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc.; Examples include polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphoric acid esters.
Further, the polymer dispersant having a basic functional group is a nitrogen atom-containing graft copolymer, a nitrogen atom-containing Examples include acrylic block copolymers and urethane polymer dispersants.

Commercially available resin-type dispersants include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK-Chemie Japan, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, LPN21116, LPN21324 or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240 manufactured by Nippon Lubrizol, 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、 EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408 manufactured by BASF, such as 56000, 76500 , 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine-Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824 and the like.

The resin-type dispersant is preferably a resin-type dispersant having a carboxyl group. The resin-type dispersant having a carboxyl group includes, for example, a comb-shaped resin-type dispersant and a linear resin-type dispersant.

[Comb-shaped resin-type dispersant having carboxyl group]
A comb-shaped resin-type dispersant having a carboxyl group is produced by known methods such as WO2008/007776, JP-A-2008-029901, JP-A-2009-155406, and JP-A-2011-157416. be able to.
For example, a resin-type dispersant that is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride, or a hydroxyl group of a compound having a hydroxyl group and a tetracarboxylic dianhydride A resin-type dispersant that is a polymer obtained by polymerizing a monomer in the presence of a reaction product with an acid anhydride group of a compound, or a hydroxyl group of a compound having a hydroxyl group and an acid anhydride of a tetracarboxylic dianhydride A resin type dispersant having a side chain polymerized with a monomer having a thermal cross-linking group such as a hydroxyl group, a t-butyl group, an oxetane skeleton, or a blocked isocyanate, and other monomers in the presence of a reaction product with a molecular group; It is a resin-type dispersant obtained by reacting a ethylenically unsaturated monomer having an isocyanate group with the hydroxyl group of its side chain.

[Linear resin-type dispersant having carboxyl group]
A linear resin-type dispersant having a carboxyl group can be produced by known methods such as those disclosed in JP-A-2009-251481, JP-A-2007-23195 and JP-A-1996-143651. As an example of a method for producing a linear dispersant, a dispersant having a carboxyl group can be produced by adding a tricarboxylic acid anhydride to the hydroxyl group of a vinyl polymer having one hydroxyl group at one end. can be done.

The dispersing agent (B) has a carboxyl group obtained by reacting an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in the hydroxyl group-containing compound. a polyester portion (X1);
a monomer (b1) having at least one thermally crosslinkable functional group selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group and a blocked isocyanate group, and a monomer (b2) having a carboxyl group; A dispersant (B1) having a radically polymerized vinyl polymer portion (X2) and having such a crosslinkable functional group is preferable because it has excellent solvent resistance.
Furthermore, the dispersant (B) preferably contains a vinyl-based resin-type dispersant (B2) having a piperidyl skeleton.

Preferred embodiments of the dispersant (B) are described below.
(Dispersant (B1))
In the dispersant (B1), the polyester part (X1) acts as a pigment adsorption site and the vinyl polymer part (X2) acts as a relaxation site, so that the aggregation of the pigment (A) is suppressed, and the dispersion has excellent dispersion stability. is obtained. Further, when the vinyl polymer portion (X2) of the dispersant (B1) has a thermally crosslinkable group, the combined use of an epoxy compound further improves the solvent resistance of the film after curing.

The content of the dispersant (B1) is preferably 0.01 to 100 parts by mass, more preferably 0.01 to 60 parts by mass, and still more preferably 5 to 40 parts by mass, relative to 100 parts by mass of the pigment (A). be. When the dispersant (B1) is contained in an appropriate amount, the dispersibility and solvent resistance are further improved.

The weight average molecular weight of the dispersant (B1) is preferably 2,000 to 100,000. Having an appropriate weight average molecular weight further improves dispersion stability.

The acid value of the dispersant (B1) is preferably from 5 to 200 mgKOH/g, more preferably from 5 to 150 mgKOH/g, even more preferably from 5 to 100 mgKOH/g. If it has an appropriate acid value, the dispersibility is further improved, and the viscosity of the photosensitive coloring composition can be easily adjusted.

Each component of the dispersant (B1) will be described.
[Hydroxyl group-containing compound constituting polyester portion (X1) in dispersant (B1)]
The hydroxyl group-containing compound constituting the polyester portion (X1) includes, for example, a compound having two hydroxyl groups and one thiol group in the molecule, a hydroxyl group-containing vinyl polymer at one end, and other polyols. Among these, it is preferable to use at least one hydroxyl group-containing compound selected from the group of compounds having two hydroxyl groups and one thiol group in the molecule and vinyl polymers containing hydroxyl groups at one end.

[Compound having two hydroxyl groups and one thiol group in the molecule]
Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, and 3-mercapto-1,2-propane. Diol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto -2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

[Vinyl polymer containing one terminal hydroxyl group]
The method for synthesizing the dispersant (B1) includes (1) first synthesizing the polyester portion (X1) and then synthesizing the vinyl polymer portion (X2), and (2) first synthesizing the vinyl polymer portion ( A method of synthesizing X2) and then synthesizing the polyester portion (X1) can be mentioned. When synthesizing the polyester portion (X1) first, the hydroxyl group-containing compound containing at least the compound having two hydroxyl groups and one thiol group in the molecule is reacted with an acid anhydride. Further, when synthesizing the vinyl polymer portion (X2) first, the monomer is polymerized in the presence of the compound having two hydroxyl groups and one thiol group in the molecule to form two A vinyl polymer portion (X2) having a terminal hydroxyl group derived from a compound having a hydroxyl group and one thiol group is obtained. Therefore, the terminal hydroxyl group of the vinyl polymer portion (X2) is reacted with the acid anhydride when synthesizing the next polyester portion (X1). That is, when synthesizing the vinyl polymer portion (X2) first, the hydroxyl group-containing compound that constitutes the polyester portion (X1) has a hydroxyl group derived from a compound having two hydroxyl groups and one thiol group in the molecule. It also includes the introduced vinyl polymer portion (X2) (one-end hydroxyl group-containing vinyl polymer).

[Other polyols]
Other polyols include, for example, compounds belonging to the following groups (1) to (7). The combined use of these polyol compounds facilitates adjustment of the physical properties of the dispersant (B1).

(1) ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, 4-bis(hydroxymethyl)cyclohexane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, or Polyhydric alcohols such as hexanetriol;

(2) Various polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol kind;

(3) Ring-opening of the polyhydric alcohol with a (cyclic) ether bond-containing compound such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether modified polyether polyols obtained by polymerization;

(4) Polyester polyols obtained by co-condensation of the above polyhydric alcohols and polyhydric carboxylic acids. Polycarboxylic acids include, for example, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2 ,5-hexanetricarboxylic acid, 1,4-cyclohexanecarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid, or 2, 5,7-naphthalenetricarboxylic acid and the like.

(5) Lactone-based polyester polyols obtained by the polycondensation reaction of the above polyhydric alcohols and lactones; lactone-modified obtained by the polycondensation reaction of the above polyhydric alcohols, polyhydric carboxylic acids and lactones Polyester polyols. Examples of lactones include ε-caprolactone, δ-valerolactone, 3-methyl-δ-valerolactone and the like.

(6) Epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and/or polyhydric alcohols, or glycidyl esters of monobasic and/or polybasic acids, Epoxy-modified polyester polyols obtained by using one or more in combination during the synthesis of the polyester polyol;

(7) Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine compound, or hydroxyl group-containing silicone resin etc.

Other polyols can be used alone or in combination of two or more.

The weight average molecular weight of other polyols is preferably 40 to 10,000, more preferably 100 to 2,000, even more preferably 100 to 1,000. Moderate weight average molecular weight further improves dispersion stability.

As for the number of hydroxyl groups of other polyols, diols are preferable from the viewpoint of adjusting the molecular weight of the dispersant (B1) and adjusting the viscosity of the photosensitive coloring composition.

[Acid anhydride constituting the polyester portion (X1) in the dispersant (B1)]
The acid anhydride constituting the polyester portion (X1) of the dispersant (B1) contains one or more selected from tetracarboxylic anhydrides and tricarboxylic anhydrides.
The two anhydride groups of the tetracarboxylic dianhydride react with the hydroxyl groups of the hydroxyl group-containing compound described above, thereby regularly arranging the carboxyl groups that serve as colorant adsorption groups on the main chain of the dispersant (B1). and improve dispersibility.
Also, when a tricarboxylic anhydride is used, it reacts with a hydroxyl group to form an ester bond, leaving a carboxyl group.

Further, dicarboxylic anhydrides, which are polycarboxylic anhydrides other than tetracarboxylic anhydrides and tricarboxylic anhydrides, and anhydrides of compounds having 5 or more carboxylic acids can also be used in combination.

[Tetracarboxylic anhydride]
Tetracarboxylic dianhydrides are, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6 -tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1 ,2-dicarboxylic dianhydride, aliphatic tetracarboxylic dianhydride such as bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyro Melitic dianhydride, ethylene glycol dianhydride trimellitic ester, propylene glycol dianhydride trimellitic ester, butylene glycol dianhydride trimellitic ester, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride , 3,3′,4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 3,3′,4,4′-Biphenylethertetracarboxylic dianhydride, 3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3′,4,4′ -tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'- Perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4 '-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1- Aromatic tetracarboxylic acid dianhydrides such as naphthalenesuccinic acid dianhydride can be mentioned. Among these, aromatic tetracarboxylic dianhydrides are preferable, and tetracarboxylic dianhydrides having two or more aromatic rings are more preferable in view of excellent adsorption to the colorant.

[Tricarboxylic anhydride]
Examples of tricarboxylic acid anhydrides include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

Aliphatic tricarboxylic anhydrides include, for example, 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid-1 , 2-anhydride, 1,3,4-cyclopentanetricarboxylic anhydride and the like.

Aromatic tricarboxylic acids include, for example, benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic acid Anhydrides (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride etc.), 3,4,4′-benzophenonetricarboxylic anhydride, 3,4,4′-biphenyl ethertricarboxylic anhydride, 3,4,4′-biphenyltricarboxylic anhydride, 2,3,2′- biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, 3,4,4'-biphenylsulfonetricarboxylic anhydride, and the like. Among these, aromatic tricarboxylic acid anhydrides are preferred because of their excellent adsorption to colorants.

[Monomer Constituting Vinyl Polymer Portion (X2) in Dispersant (B1)]
The vinyl polymer moiety (X2) comprises a monomer (b1) having at least one thermally crosslinkable functional group selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group and a blocked isocyanate group, and a carboxyl group. It is a radical polymer with the monomer (b2) having.

(Hydroxyl group-containing monomer)
The hydroxyl group-containing monomer is a (meth)acrylate monomer having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4 )-hydroxyalkyl (meth)acrylates such as hydroxybutyl (meth)acrylate and cyclohexanedimethanol mono(meth)acrylate, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate;
Examples of (meth)acrylamide-based monomers having a hydroxyl group include N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl) ( N-(hydroxyalkyl)(meth)acrylamides such as meth)acrylamide;
Vinyl ether monomers having a hydroxyl group, such as hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-(or 3-) hydroxypropyl vinyl ether, 2-(or 3- or 4-) hydroxybutyl vinyl ether;
As allyl ether monomers having a hydroxyl group, hydroxyalkyls such as 2-hydroxyethyl allyl ether, 2-(or 3-) hydroxypropyl allyl ether, 2-(or 3- or 4-) hydroxybutyl allyl ether Allyl ethers are mentioned.

In addition, the hydroxyalkyl (meth)acrylate, alkyl-α-hydroxyalkyl acrylate, N-(hydroxyalkyl) (meth)acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether are obtained by adding alkylene oxide and/or lactone. The monomers used are also hydroxyl group-containing monomers. Alkylene oxides include, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide. When two or more kinds of alkylene oxides are used in combination, the form of bonding may be random and/or block. Lactones include, for example, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and the like. Alkylene oxide and lactone can be used in combination.

(Monomer having an oxetane group)
Examples of monomers having an oxetane group include (vinyloxyalkyl)alkyloxetane, (meth)acryloyloxyalkyloxetane, [(meth)acryloyloxyalkyl]alkyloxetane and the like. Among these, (3-ethyloxetan-3-yl)methyl methacrylate is preferred. Commercially available products include, for example, ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate) (manufactured by Ube Industries, Ltd.).

(monomer having a t-butyl group)
Examples of monomers having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.

(monomer having a blocked isocyanate group)
Monomers having a blocked isocyanate group include, for example, 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, and the like. is mentioned. Commercially available products include, for example, Karenz MOI-BM (2-(0-[1′-methylpropylideneamino]carboxyamino)ethyl methacrylate) (manufactured by Showa Denko), Karenz MOI-BP (2-[(3, 5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate) (manufactured by Showa Denko KK) and the like.

The content of the monomer having an oxetane group, the monomer having a t-butyl group, and the monomer having a blocked isocyanate group is preferably 5 to 90% by mass, preferably 20 to 60% by mass, in all monomers. % is more preferred. If it is 5% by mass or more, it is possible to obtain a photosensitive coloring composition having excellent resistance due to the effect of crosslinking, and if it is 90% by mass or less, the stability of the photosensitive coloring composition is further improved.

(Carboxyl group-containing monomer (b2))
Examples of the monomer (b2) having a carboxyl group include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid and the like. Among these, (meth)acrylic acid is preferred.

[Other monomers]
In the vinyl polymer portion (X2) in the dispersant (B1), other monomers other than the monomer (b1) having a thermally crosslinkable functional group and the monomer (b2) having a carboxyl group are radically polymerized. can.
Other monomers include, for example, (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth) (meth)acrylic acid alkyl esters such as acrylates, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, and lauryl (meth)acrylate;
Aliphatic ring (meth)acrylates such as cyclohexyl (meth)acrylate, tertiarybutylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate;
aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate;
Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate;
Alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate;

Nitrogen-containing group monomers include, for example, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, N-substituted (meth)acrylamides such as acryloylmorpholine;
N,N-dimethylaminoethyl (meth)acrylate, amino group-containing (meth)acrylates such as N,N-diethylaminoethyl (meth)acrylate;
and nitriles such as (meth)acrylonitrile.

Vinyl monomers include, for example, styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; Examples include fatty acid vinyls.

[Method for synthesizing dispersant (B1)]
Methods for synthesizing the dispersant (B1) include, for example, the following synthesis methods (1) and (2).

[Synthesis method (1)]
In the presence of a compound having two hydroxyl groups and one thiol group in the molecule (hereinafter referred to as a thiol compound), a monomer having an oxetane group, a monomer having a t-butyl group, and a blocked isocyanate group. Hydroxyl groups in a vinyl polymer having two hydroxyl groups at one terminal region obtained by radically polymerizing a monomer containing at least one selected from the group consisting of monomers, and tetracarboxylic anhydride and tricarboxylic anhydride A dispersant having an oxetane group, a t-butyl group, or a blocked isocyanate group as a crosslinkable group is obtained by reacting with an acid anhydride group in one or more acid anhydrides selected from.

[Synthesis method (2)]
The hydroxyl group in the hydroxyl group-containing compound (but not including the one-end hydroxyl group-containing vinyl polymer) constituting the polyester portion (X1), and one or more acid anhydrides selected from tetracarboxylic anhydrides and tricarboxylic anhydrides In the presence of a compound formed by reacting with an acid anhydride group, a hydroxyl group-containing monomer, a monomer having an oxetane group, a monomer having a t-butyl group, and a monomer having a blocked isocyanate group A dispersant having a hydroxyl group, an oxetane group, a t-butyl group, or a blocked isocyanate group as a crosslinkable group can be obtained by radically polymerizing a monomer containing at least one selected from the group consisting of monomers. The radical polymerization is preferably solution polymerization or bulk polymerization.

When radical polymerization is performed using a hydroxyl group-containing monomer, it is preferable to synthesize the dispersant (B1) using synthesis method (1).

The content of the hydroxyl group-containing monomer, the oxetane group-containing monomer, the t-butyl group-containing monomer, and the blocked isocyanate group-containing monomer is 5 to 90 mass% of the total monomer. Preferably, 20 to 60% by mass is more preferable. If it is 5% by mass or more, the solvent resistance is further improved. Moreover, if it is 90 mass % or less, dispersion stability will improve more.

[Synthesis of polyester moiety (X1)]
Synthesis of the polyester portion (X1) is a step of reacting an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in the hydroxyl group-containing compound. A catalyst can be used in combination for the reaction. Also, an organic solvent can be used for the reaction.

(catalyst)
Catalysts are, for example, triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene or 1,5-diazabicyclo-[4 and tertiary amine compounds such as 3.0]-5-nonene; and mono-n-butyltin (IV) oxide.

(Organic solvent)
Organic solvents include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, acetonitrile, hexane, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol. monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

(reaction temperature)
The reaction temperature for synthesizing the polyester portion (X1) is preferably 50°C to 180°C, more preferably 80°C to 140°C. If the reaction is carried out at an appropriate temperature, the reaction can be completed in an appropriate time. At the end of the reaction, it is preferable to carry out the reaction until the absorption of the acid anhydride by infrared absorption disappears. performance is obtained.

[Synthesis of vinyl polymer portion (X2)]
The vinyl polymer portion (X2) in the dispersant (B1) is formed by radically polymerizing a monomer and contains at least one selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group and a blocked isocyanate group. It has a thermally crosslinkable functional group. Since the vinyl polymer portion (X2) functions as a relaxation site, good dispersion stability is easily obtained even when fine pigments or dyes are used. In addition, by having a thermally crosslinkable group, it is easy to obtain solvent resistance due to reaction with an epoxy compound.

The weight average molecular weight of the vinyl polymer portion (X2) is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000 to 12,000, and particularly preferably 3,000 to 8,000. The vinyl polymer portion (X2) functions as a relaxation site. An appropriate weight-average molecular weight further improves the dispersion stability and facilitates adjustment of the viscosity of the photosensitive coloring composition.

The content of the monomer is preferably 3 to 100 parts by mass, more preferably 8 to 25 parts by mass, and even more preferably 10 to 20 parts by mass with respect to 1 part by mass of the thiol compound. When a proper amount of the monomer is used, it is easy to form moderately sterically repulsive relaxation sites, so that the dispersibility of the pigment is further improved.

Polymerization initiators include azo compounds and organic peroxides. Azo compounds include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane 1-carbonitrile), 2, 2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane ] and the like. Organic peroxides include, for example, benzoyl peroxide, t-butylperbenzoate, cumene hydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, carbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionylperoxide, diacetylperoxide and the like.

A polymerization initiator can be used individually or in combination of 2 or more types.

The content of the polymerization initiator is usually about 0.001 to 5 parts by mass relative to the photopolymerizable compound (D).

In the case of solution polymerization, it is preferable to use the organic solvents already exemplified.

As the dispersant (B1), a dispersant described in JP-A-2009-155406 can also be used.

<Vinyl resin type dispersant having a piperidyl skeleton (B2)>
The vinyl resin type dispersant (B2) having a piperidyl skeleton (hereinafter referred to as dispersant (B2)) is a dispersant synthesized using a monomer having a piperidine skeleton represented by general formula (8).

general formula (8)

In general formula (8), R ¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR ⁴ , R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group ^having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group; Each R ³ independently represents a methyl group, an ethyl group, or a phenyl group. "*" indicates a bond.

Examples of alkyl groups having 1 to 18 carbon atoms for R ¹ and R ⁴ in general formula (8) include linear, branched and cyclic alkyl groups. Specific examples include methyl group, ethyl group, normal propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group and hexadecyl group.

Examples of the aryl group having 6 to 20 carbon atoms for R ¹ and R ⁴ in formula (8) include phenyl group, 1-naphthyl group and 2-naphthyl group.

Examples of the aralkyl group having 7 to 12 carbon atoms for R ¹ and R ⁴ in general formula (8) include groups in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms. Specific examples include benzyl group, phenethyl group, α-methylbenzyl group, 2-phenylpropan-2-yl group and the like.

Examples of acyl groups for R ¹ and R ⁴ in formula (8) include alkanoyl groups having 2 to 8 carbon atoms and aroyl groups. Specific examples include an acetyl group and a benzoyl group. R ¹ is, for example, preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an oxy radical group, more preferably a hydrogen atom or a methyl group, particularly preferably a methyl group.

The dispersant (B2) has an antioxidant function by having a piperidine skeleton represented by general formula (8).

The content of the monomer having a piperidyl skeleton is preferably 1 to 100% by mass, more preferably 25 to 100% by mass, and even more preferably 40 to 100% by mass, based on 100% by mass of the monomer used for synthesis. By containing an appropriate amount, in addition to obtaining the desired anti-oxidation property, it is easy to suppress a decrease in the brightness of the film (pixel).

Further, the dispersant (B2) preferably has an amine value of 50 to 350 mgKOH/g. Having an appropriate amine value facilitates adjustment of the viscosity of the photosensitive coloring composition, and further improves the brightness.

The dispersant (B2) preferably has a number average molecular weight of 500 to 30,000. This facilitates adjustment of the viscosity of the photosensitive coloring composition and improves viscosity stability.

Specific examples of monomers having a piperidyl skeleton include compounds represented by the following general formula (8-1) and compounds represented by the following general formula (8-2).

In general formulas (8-1) and (8-2), R ⁵ and R ⁷ each independently represent a hydrogen atom or a methyl group, R ⁶ is a methylene group, a C 2-5 represents an alkylene group, and X represents the group represented by the general formula (8). Y represents -CONH-*, -SO ₂ -, or -SO ₂ NH-* (where the bond marked with "*" bonds to X), and n represents an integer of 0-9. ^R6 is preferably an ethylene group or a propylene group, more preferably an ethylene group. n is an integer of 0-8, preferably an integer of 0-6.

Examples of the monomer represented by the general formula (8-1) include compounds represented by the following general formulas (9-1) to (9-7).

In general formulas (9-1) to (9-7), R ⁵ has the same definition as R ⁵ in general formula (8-1) above.

Examples of the monomer represented by the general formula (8-2) include compounds represented by the following general formulas (10-1) to (10-4).

In general formulas (10-1) to (10-4), R ⁷ has the same definition as R ⁷ in general formula (8-2) above.

Among these, 2,2,6,6-tetramethylpiperidyl methacrylate (compound in which R ⁵ is a methyl group in the above general formula (10-1)), 1,2,2,6,6-pentamethyl Piperidyl methacrylate (the compound in which R ⁵ is a methyl group in the above general formula 10-2) is preferred, and 1,2,2,6,6-pentamethylpiperidyl methacrylate (the above general formula (10-2)) is more preferred. .

Other monomers are not particularly limited as long as they are copolymerizable with the monomer having a piperidyl skeleton, and can be appropriately selected depending on the application.
Other monomers include (meth)acrylic acid alkyl esters, amino group-containing (meth)acrylates, nitriles, vinyl monomers, (hydroxyl group-containing monomers) and (poly)alkylene glycol monomers already exemplified. , alkoxysilyl group-containing (meth)acrylates, fluoroalkyl (meth)acrylates, silicone macromers, carboxyl group-containing monomers, and amino group-containing monomers.

(Poly) alkylene glycol monomers, for example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl Ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, tri Propylene glycol monomethyl ether (meth)acrylate, Tetraethylene glycol monomethyl ether (meth)acrylate, Polyethylene glycol monomethyl ether (meth)acrylate, Polypropylene glycol monomethyl ether (meth)acrylate, Polyethylene glycol monolauryl ether (meth)acrylate, Polyethylene glycol mono (poly)alkylene glycol monoalkyl ether (meth)acrylates such as stearyl ether (meth)acrylate and octoxy polyethylene glycol-polypropylene glycol (meth)acrylate;
Phenoxyethyl (meth)acrylate, Phenoxydiethyleneglycol (meth)acrylate, Phenoxytetraethyleneglycol (meth)acrylate, Phenoxyhexaethyleneglycol (meth)acrylate, Phenoxypolyethyleneglycol (meth)acrylate, Paracumylphenoxyethyl (meth)acrylate, Parac Milphenoxyethylene glycol (meth)acrylate, paracumylphenoxypolyethyleneglycol (meth)acrylate, nonylphenoxypolyethyleneglycol (meth)acrylate, nonylphenoxypolypropyleneglycol (meth)acrylate, and nonylphenoxypoly(ethylene glycol-propylene glycol) (meth)acrylate. ) (poly)alkylene glycol (meth)acrylates having an aromatic ring such as acrylate;
(Meth)acrylates having an alkoxysilyl group include, for example, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane and the like.
Fluoroalkyl (meth)acrylates include, for example, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate and the like.
Examples of silicone macromers include (meth)acryloxy-modified polydimethylsiloxane.

Carboxyl group-containing monomers include (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acrylic acid Loyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth)acrylate, ω carboxypolycaprolactone (meth)acrylate, etc. mentioned.

Amino group-containing monomers include, for example, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylamino (Meth)acrylates having a tertiary amino group such as propyl (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl ( meth)acrylamide, and (meth)acrylamides having a tertiary amino group such as N,N-diethylaminopropyl(meth)acrylamide; dimethylaminostyrene, diethylaminostyrene and the like.

Examples of polymerization initiators include azo compounds and peroxides. The amount of the polymerization initiator used is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the monomer.

Synthesis of the vinyl-based resin type dispersant (B2) having a piperidyl skeleton can use a solventless or an organic solvent.

Moreover, it is desirable to use the resin-type dispersant (B1) having a carboxyl group and the vinyl-based resin-type dispersant (B2) having a piperidyl skeleton when dispersing the pigment.
By using it when dispersing the pigment, the vinyl-based resin dispersant (B2) having a piperidyl skeleton becomes more likely to adsorb to the surface of the pigment, and the interaction with the pigment becomes stronger, thereby improving the dispersibility.

<Dye derivative>
When the pigment derivative is adsorbed on the surface of the pigment, the surface of the pigment has polarity, and the affinity with the binder resin (C) increases, thereby further improving the dispersibility of the pigment. A dye derivative is a known dye derivative having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. For example, compounds having an acidic substituent such as a sulfo group, a carboxyl group, and a phosphoric acid group, amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group, a phenyl group, and phthalimide Examples thereof include compounds having a neutral substituent such as an alkyl group. Since the resin-type dispersant used in combination has an acidic group, a dye derivative having a basic group is preferred.
Organic dyes include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, benzoiso Indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo.

Specifically, as diketopyrrolopyrrole dye derivatives, JP 2001-220520, WO2009/081930, WO2011/052617, WO2012/102399, JP 2017-156397, phthalocyanine As the dye derivative, JP-A-2007-226161, WO2016/163351 pamphlet, JP-A-2017-165820, Japanese Patent No. 5753266, as the anthraquinone dye derivative, JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325 pamphlet, quinacridone dye derivatives, JP-A-48- 54128, JP 03-9961, JP 2000-273383, JP 2011-162662 as a dioxazine dye derivative, JP 2007-314785 as a thiazine indigo dye derivative Publications, as triazine dye derivatives, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole-based dye derivative, JP-A-2003-167112 as a quinophthalone-based dye derivative, JP-A-2006-291194, JP-A-2006-291194 2008-31281, JP 2012-226110, as a naphthol dye derivative, JP 2012-208329, JP 2014-5439, as an azo dye derivative, JP 2001-172520 Publication, JP 2012-172092, JP 2004-307854 as an acidic substituent, JP 2002-201377 as a basic substituent, JP 2003-171594, JP 2005 -181383, Japanese Patent Laid-Open No. 2005-213404, and other known dye derivatives. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound. A compound having a substituent such as a sexual group is synonymous with a dye derivative.

A dye derivative can be used individually or in mixture of 2 or more types.

The content of the dye derivative is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, based on 100 parts by mass of the pigment (A).

By adding a pigment derivative to the pigment and performing pigmentation treatments such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the pigment derivative is adsorbed on the surface of the pigment. In comparison, the primary particles of the pigment can be made finer.

The dispersant (B) can be used alone or in combination of two or more.

<Binder resin (C)>
The photosensitive coloring composition of the present invention contains a binder resin (C). The binder resin (C) preferably has a transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm. The binder resin (C) includes thermoplastic resins and thermosetting resins. Among these, thermoplastic resins are preferred. Further, the binder resin (C) is preferably an alkali-soluble resin that can be patterned by photolithography.

<Thermoplastic resin>
Thermoplastic resins include, for example, acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, Examples include polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.
The alkali-soluble resin is preferably a thermoplastic resin having an acidic group. Examples of acidic groups include carboxyl groups and sulfone groups. The alkali-soluble resin is, for example, an acrylic resin having an acidic group, an α-olefin/(anhydride) maleic acid copolymer, a styrene/styrenesulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/ (anhydrous) maleic acid copolymer and the like. Among these, acrylic resins and styrene/styrenesulfonic acid copolymers having acidic groups are preferred in terms of developability, heat resistance and transparency, and acrylic resins having acidic groups are more preferred.

<Alkali-soluble resin>
When the color filter is produced by photolithography, the alkali-soluble resin dissolves in the film formed from the photosensitive coloring composition, and developability is obtained.

The mass average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, even more preferably 4,000 to 20,000. Moreover, the value of Mw/Mn is preferably 10 or less. An appropriate Mw further improves the solubility in alkali development.
The acid value of the alkali-soluble resin is preferably from 50 to 200 (KOHmg/g), more preferably from 70 to 180, even more preferably from 90 to 170. If it has a moderate acid value, the alkali developability is further improved.

The alkali-soluble resin includes an alkali-soluble resin (C1) having no ethylenically unsaturated double bond (hereinafter referred to as an alkali-soluble resin (C1)) and an alkali-soluble resin (C2) having an ethylenically unsaturated double bond (C2) ( hereinafter referred to as an alkali-soluble resin (C2)).

<Alkali-soluble resin (C1)>
The alkali-soluble resin (C1) is a resin that polymerizes a carboxyl group-containing monomer and a monomer other than the carboxyl group-containing monomer.

<Alkali-soluble resin (C2)>
The alkali-soluble resin (C2) is preferably, for example, a resin synthesized by the method (i) or (ii) below. Thereby, the cross-linking density of the film formed from the photosensitive coloring composition by light irradiation is further improved.

[Method (i)]
In method (i), for example, first, an epoxy group-containing monomer and a polymer of the monomer are synthesized. Next, there is a method of adding a carboxyl group-containing monomer to the epoxy group of the polymer, and reacting the generated hydroxyl group with a polybasic acid anhydride to obtain an alkali-soluble resin (C2).

Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4- Epoxycyclohexyl (meth)acrylates can be mentioned. Among these, glycidyl (meth)acrylate is preferable from the viewpoint of reactivity.

Carboxyl group-containing monomers include, for example, (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid. monocarboxylic acids such as

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

A monomer and a polybasic acid anhydride can be used individually or in combination of 2 or more types, respectively.

As a method similar to method (i), for example, a carboxyl group-containing monomer and other monomers are synthesized to produce a polymer. Next, there is a method of adding an epoxy group-containing monomer to a part of the carboxyl groups of the polymer to obtain an alkali-soluble resin (C2).

[Method (ii)]
In method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to produce a polymer. Next, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer can be mentioned.

As the hydroxyl group-containing monomer, the monomers already exemplified can be used. Among them, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferable because foreign substances are less likely to form in the coating. In terms of photosensitivity, glycerol mono(meth)acrylate is preferred.

Monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate and the like.

Binder resin (C) can be used individually or in combination of 2 or more types.

The content of the binder resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the pigment (A). 20 parts by mass or more is preferable because the film formability and various resistances are good, and 400 parts by mass or less is preferable because the concentration of the coloring agent is high and good color characteristics can be exhibited.

<Thermosetting compound>
The photosensitive coloring composition can contain a thermosetting compound. Thereby, when a color filter is produced, the crosslink density is improved in a heating step after forming a pattern on the film by a photolithography method, so that the heat resistance is improved. In addition, since the pigment (A) is less likely to agglomerate in the heating step, the contrast ratio is further improved.

A thermosetting compound is a low-molecular-weight compound or polymer (thermosetting resin) and is not limited by molecular weight.
Thermosetting compounds include, for example, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds. Among these, epoxy compounds and oxetane compounds are preferred.

(epoxy compound)
Epoxy compounds include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted polycondensates of various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), phenol polymers with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones Polycondensates with (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol , α,α,α',α'-biphenyldimethanol, etc.), polycondensation products of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.) , polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based An epoxy resin etc. are mentioned.

Commercially available products include, for example, Epicoat 807, Epicote 815, Epicote 825, Epicote 827, Epicote 828, Epicote 190P, Epicote 191P (trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicote 1004, and Epicote 1256 (trade names). Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (trade name; Mitsui Chemicals Co., Ltd.), EPPN-501H, 502H (trade name; Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EOCN-102S, EOCN- 103S, EOCN-104S, EOCN-1020 (trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (trade names; manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211, 212, 252, 313 , 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, (the above are trade names; manufactured by Nagase ChemteX Corporation), TEPIC-L, TEPIC-H, TEPIC- S (manufactured by Nissan Chemical Industries, Ltd.) and the like.

The content of the epoxy compound is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, per 100 parts by mass of the pigment (A). When blended in an appropriate amount, the heat resistance and pattern shape of the film are further improved.

(oxetane compound)
An oxetane compound is a compound having an oxetane group. Oxetane compounds include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

Monofunctional oxetane compounds include, for example, (3-ethyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxy silyl)propoxy]methyl}oxetane and the like.
Commercially available products include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd., and the like.

Bifunctional oxetane compounds include, for example, 4,4′-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis {[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether- 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl) -5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3 -ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3- ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanyl) methyl) ether and the like.
Commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei.

Trifunctional or higher oxetane compounds include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3 -oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (e.g. , oxetane-modified phenolic novolak resins described in Japanese Patent No. 3783462) and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

The content of the oxetane compound is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, based on 100 parts by mass of the pigment (A). If it is contained in an appropriate amount, the solvent resistance of the film will be further improved.

(melamine compound)
A melamine compound is a compound having a melamine ring. Melamine compounds include low-molecular-weight compounds and high-molecular-weight compounds. The melamine compound used herein is preferably a compound in which a methylol group or an ether group is bonded to a melamine ring. The average number of bonds of methylol groups and/or ether groups per melamine ring is preferably 5.0 or more. If it has an appropriate number of bonds, the solvent resistance of the film is further improved, and the contrast ratio is less likely to decrease.

Commercially available products include, for example, Nicarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS- 001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 ( Sanwa Chemical Co., Ltd.), Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 (Nihon Cytec Industries Co., Ltd.).

Among these, dicarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, and MW-30 having an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more , MW-22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nippon Cytec Industries Co., Ltd.) is preferable in terms of further improving the crosslink density of the coating.

The content of the melamine compound is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, per 100 parts by mass of the pigment (A). If it is contained in an appropriate amount, the solvent resistance of the film will be further improved.

(curing agent)
A curing agent may be included herein to aid in curing the thermosetting compound. Curing agents include, for example, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like.
Amine compounds include (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethyl benzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole , 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine , 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.).

The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound.

<Photopolymerizable compound (D)>
The photopolymerizable compound (D) is a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin. As used herein, the photopolymerizable compound (D) includes at least one of an isocyanurate ring-containing photopolymerizable compound [D1] and an alkylene chain-containing photopolymerizable compound [D2]. The photopolymerizable compound (D) is, for example, a monomer or oligomer that forms a transparent resin by curing with ultraviolet light, heat, or the like, as exemplified below.

(Isocyanurate ring-containing photopolymerizable compound [D1])
The isocyanurate ring-containing photopolymerizable compound [D1] includes, for example, a photopolymerizable compound [D1] represented by the following general formula (11) (hereinafter referred to as photopolymerizable compound [D1]).

general formula (11)

[In the general formula (11), R ₁ , R ₂ and R ₃ are each independently a group represented by the following general formulas (12-1) to (12-5), but at least one Any of the groups represented by general formulas (12-1) to (12-4)]

[In general formulas (12-1) to (12-5), R ₄ , R ₅ and R ₆ are each independently H or CH ₃ ; and l is an integer from 1 to 5. * is a bond that binds to R ₁ , R ₂ or R ₃ of general formula (11). ]

Commercial products of the photopolymerizable compound [D1] include ethoxylated isocyanuric acid triacrylate (A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)), tris(2-acryloyloxyethyl) isocyanurate (Fancryl FA-731A (Hitachi Kasei Kogyo Co., Ltd.)), ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate (A-9300-1CL (manufactured by Shin-Nakamura Chemical Co., Ltd.)), A9300-3CL (manufactured by Shin-Nakamura Chemical Co., Ltd.), CIC acid acrylate (manufactured by Shikoku Kasei Co., Ltd.) and the like.

The content of the photopolymerizable compound [D1] is preferably 5 to 400 parts by mass, more preferably 10 to 300 parts by mass, per 100 parts by mass of the pigment (A). When contained in an appropriate amount, the photosensitivity is further improved.

(Alkylene chain-containing photopolymerizable compound [D2])
The alkylene chain-containing photopolymerizable compound [D2] (hereinafter referred to as photopolymerizable compound [D2]) is a monomer having an alkylene chain in its molecule. When the photosensitive coloring composition contains the photopolymerizable compound [D2], the mobility of the ethylenically unsaturated group indirectly bonded to the alkylene chain is improved, and the curability of the coating is further improved. Examples of alkylene chains include ethylene chains, propylene chains, pentylene chains and the like. Among these, pentylene is preferable because the photopolymerizable compound [D2] has high photoreactivity. Multiple alkylene chains may be present in the molecule. The photopolymerizable compound [D2] does not include the photopolymerizable compound [D1] containing an alkylene chain.

Examples of the photopolymerizable compound [D2] include compounds synthesized by reacting a polyhydric alcohol, (meth)acrylic acid and a cyclic ester.
Examples of the cyclic esters include α-acetolactone, β-propionlactone, γ-butyrolactone, σ-valerolactone, ε-caprolactone and the like. Among these, ε-caprolactone is preferred. The photopolymerizable compound [D2] having a pentylene chain synthesized by reacting ε-caprolactone is also referred to as a caprolactone-modified photopolymerizable compound.
Examples of the polyhydric alcohol include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine.

Examples of the photopolymerizable compound [D2] include compounds represented by the following general formula (12).

general formula (12)

In the general formula (12), all of the 6 R are groups represented by the following general formula (13), or 1 to 5 of the 6 R are groups represented by the following general formula (13) , and the residue is a group represented by the following general formula (14).

general formula (13)

In general formula (13), R ¹ represents a hydrogen atom or a methyl group, m represents the number of 1 or 2, and "*" is a bond.

general formula (14)

In general formula (14), R ¹ represents a hydrogen atom or a methyl group, and "*" is a bond.

Commercial products of the photopolymerizable compound [D2] are, for example, KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd. DPCA-20 (m = 1 in the above formulas (12) to (14), represented by general formula (13) number of groups = 2, all R ¹ are hydrogen atoms), DPCA-30 (same formula, m = 1, number of groups represented by general formula (13) = 3, all R ¹ are hydrogen atoms) ), DPCA-60 (same formula, m = 1, number of groups represented by general formula (13) = 6, R ¹ are all hydrogen atoms), DPCA-120 (m = 2 in the same formula, general formula (13), wherein the number of groups is 6, and all R ¹ are hydrogen atoms), and the like.

In the present specification, it is preferable to use the photopolymerizable compound [D1] and the photopolymerizable compound [D2] in combination. By using the above combination, both solvent resistance and good pattern shape can be achieved at a higher level.

The content of the photopolymerizable compound [D2] is preferably 5 to 400 parts by mass, more preferably 10 to 300 parts by mass, per 100 parts by mass of the pigment (A). Although the reason for the appropriate content is not clear, this further improves the pattern linearity.

The photopolymerizable compound (D) includes a photopolymerizable compound having an acid group, a photopolymerizable compound having a urethane bond, and other monomers in addition to the photopolymerizable compound [D1] and the photopolymerizable compound [D2]. can be contained.

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

Photopolymerizable compounds having an acid group, for example, poly(meth)acrylates containing free hydroxyl groups of polyhydric alcohol and (meth)acrylic acid, and esters of dicarboxylic acids; Examples thereof include esterified products with (meth)acrylates.
The photopolymerizable compound having an acid group is, for example, a monohydroxy oligo such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate. free carboxyl group-containing monoesters of acrylates or monohydroxy oligomethacrylates with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), tricarboxylic acids such as butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid and benzene-1,3,5-tricarboxylic acid; monohydroxy monoacrylates such as -hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates.

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

(Photopolymerizable compound having urethane bond)
The photopolymerizable compound can contain a photopolymerizable compound containing at least one ethylenically unsaturated bond and at least one urethane bond (hereinafter referred to as a polymerizable compound having a urethane bond). The polymerizable compound having a urethane bond is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional isocyanate obtained by reacting an alcohol with a polyfunctional isocyanate and further having a hydroxyl group (meth) Examples include polyfunctional urethane acrylates obtained by reacting acrylates.

(Meth)acrylates having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane 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 Examples include acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

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

Although the structure of the alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of cross-linking of the cured coating increases and the solvent resistance increases. Polyhydric alcohols include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

Commercially available polymerizable compounds having a urethane bond include, for example, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G and DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd. , UA-160TM manufactured by Shin-Nakamura Chemical Industry Co., Ltd., UV-4108F and UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like.
Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) ) acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxy Tetraethylene glycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanurate Acid EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester Acrylate, methylolated melamine (meth)acrylic acid ester, epoxy (meth)acrylate, various acrylic acid esters and methacrylic acid esters such as urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol di vinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

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

The content of the photopolymerizable compound (D) is preferably 5 to 400 parts by mass, more preferably 10 to 300 parts by mass, based on 100 parts by mass of the pigment (A). This further improves the photosensitivity.

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

<Photoinitiator (E)>
The photopolymerization initiator (E) includes a photopolymerization initiator [E1] (hereinafter referred to as a photopolymerization initiator [E1]) represented by the following general formula (15), and a photopolymerization initiator represented by the following general formula (16). At least one of [E2] (hereinafter referred to as photopolymerization initiator [E2]) is preferably included. Due to the inclusion, the photosensitive coloring composition has high sensitivity and can form a film with a good pattern shape.

(Photoinitiator (E1))
general formula (15)

In general formula (15), X ¹ , X ³ and X ⁶ each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and X ² has a substituent an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, and an optionally substituted carbon number of 7 represents an arylalkyl group of up to 30 or an optionally substituted heterocyclic group of 2 to 20 carbon atoms, wherein X ⁴ and X ⁵ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , COSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , CN, halogen atom or hydroxyl group; R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom having represents an aryl group of 6 to 30, an optionally substituted arylalkyl group of 7 to 30 carbon atoms, or a heterocyclic group of optionally substituted carbon atoms of 2 to 20; . a and b are each independently an integer of 0 to 3;

X ¹ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. Alkyl groups with 10 or less carbon atoms such as isobutyl, t-butyl, n-amyl, isoamyl, t-amyl, n-hexyl and 2-ethylhexyl groups; 10 carbon atoms such as cyclopentyl and cyclohexyl groups Cyclic alkyl groups which may have the following side chains; is preferably an alkyl group having one ether bond in the methylene chain.

X ³ is hydrogen, or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- Alkyl groups with 6 or less carbon atoms such as butyl, isobutyl, t-butyl, n-amyl, isoamyl, t-amyl and n-hexyl groups; cyclopentyl and cyclohexyl groups with 6 or less carbon atoms Cyclic alkyl group; methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2-(1-methoxypropyl) group, 2-(1-ethoxypropyl) group, etc., having a carbon number of 6 or less and an ether bond in the methylene chain An alkyl group having one is preferred.

X ⁶ is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, from the viewpoint of ease of synthesis, sensitivity, solubility, storage stability when contained in a photosensitive coloring composition, C6 or less alkyl groups such as isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group and n-hexyl group; C6 or less cyclic alkyl groups such as cyclopentyl group and cyclohexyl group ; methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2-(1-methoxypropyl) group, 2-(1-ethoxypropyl) group, etc., having 6 or less carbon atoms and having one ether bond in the methylene chain Alkyl groups are preferred.

X ² is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. Alkyl groups with 6 or less carbon atoms such as isobutyl, t-butyl, n-amyl, isoamyl, t-amyl and n-hexyl groups, cyclic alkyl groups with 6 or less carbon atoms such as cyclopentyl and cyclohexyl groups , methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2-(1-methoxypropyl) group, 2-(1-ethoxypropyl) group, etc. having 6 or less carbon atoms and having one ether bond in the methylene chain Alkyl groups are preferred.

X ⁴ and X ⁵ are hydrogen, or a methyl group, an ethyl group, an n-propyl group, or an isopropyl group from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. , n-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group and other alkyl groups having 6 or less carbon atoms are preferable.

Examples of heterocyclic groups having 2 to 20 carbon atoms include 3 to 7 membered heterocyclic rings, preferably pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, 5- to 7-membered heterocycles such as tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl and morpholinyl.

Examples of the photopolymerization initiator (E1) include the following compounds.

Examples of the method for synthesizing the photopolymerization initiator (E1) include the following methods.
<Step 1> Synthesis of acyl derivative: Nitrocarbazole compound 1 and acid chloride 2 are reacted in the presence of aluminum chloride to obtain the desired acyl derivative 3.
<Step 2> Synthesis of Formula (1): Acyl derivative 3, hydroxylamine hydrochloride, and dimethylformamide are charged and heated with stirring to obtain oxime compound 4. The oxime compound 4 and the acid anhydride 5 are heated and stirred, and neutralized with an alkali after the reaction is completed to obtain a photopolymerization initiator (E1).

When the photosensitive coloring composition contains the photopolymerization initiator (E1), it is possible to achieve both solvent resistance and good pattern shape (linearity, cross-sectional shape), and it is easy to obtain a color filter with excellent production stability.
When the photopolymerization initiator (E1) absorbs ultraviolet rays, the N—O bond of the oxime in the compound is cleaved to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. Furthermore, since it has an absorption wavelength of 330 nm to 430 nm due to the nitrocarbazole group in the compound, it has high reaction efficiency with various ultraviolet-visible light sources. In addition, it is believed that the —C ₆ H ₃ (X ³ )OX ² site in general formula (15) enhances the development resistance.

The content of the photopolymerization initiator (E1) is preferably 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, based on 100 parts by mass of the pigment (A).

(Photoinitiator (E2))
general formula (16)

R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted Alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclicoxy group, substituted or unsubstituted alkylsulfanyl group, It represents a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. The hydrogen atoms of the substituents in R1 to R4 may be further substituted with other substituents.

The other substituents include, for example, halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl Acyl groups such as methylsulfanyl groups, alkylsulfanyl groups such as tert-butylsulfanyl groups, phenylsulfanyl groups, arylsulfanyl groups such as p-tolylsulfanyl groups, methylamino groups, alkylamino groups such as cyclohexylamino groups, dimethyl Amino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, phenylamino group, arylamino group such as p-tolylamino group, methyl group, ethyl group, tert-butyl group, alkyl group such as dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, aryl group such as benzofuranyl group, furyl group, heterocyclic group such as thienyl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethyl A sulfoniumyl group, a triphenylphenacylphosphoniumyl group, and the like can be mentioned.

The most preferred structures of the photopolymerization initiator (E2) include compounds represented by the following chemical formulas (E2-1) and (E2-2).

化学式（Ｅ２－２）

Chemical formula (E2-1)

Chemical formula (E2-2)

The photopolymerization initiator (E1) is an oxime ester photopolymerization initiator. In the oxime ester-based photopolymerization initiator, the oxime ester moiety is decomposed by absorbing ultraviolet rays to generate iminyl radicals and alkyloxy radicals, and the radicals of the active species generated by further decomposition cause a reaction. Since the photosensitive coloring composition of the present specification contains the photopolymerization initiator [E1], the decomposition efficiency by light irradiation is very high, and a pattern can be formed with a small amount of exposure (high sensitivity).
The reason why the photopolymerization initiator (E1) is more sensitive than other photopolymerization initiators is that (1) having a structure represented by general formula (15) efficiently absorbs light energy. be able to. Furthermore, it is presumed that the obtained light energy is efficiently used to decompose the oxime ester moiety, so that the decomposition by light irradiation is rapid and a large amount of radicals are generated instantaneously. Alternatively, (2) the photopolymerization initiator (E1) decomposes the iminyl radical generated by light irradiation into the radical of the active species, deriving from the structure represented by the general formula (15), presumed to be very fast. are doing. If the iminyl radical to be generated is metastable, the decomposition will be slow and the amount of active radicals generated will be small. We speculate that the resulting iminyl radical decomposes very quickly and produces a large amount of radicals. In addition, the photopolymerization initiator (E1) decomposes iminyl radicals very quickly, so it is considered that recombination of radicals is suppressed. When the recombination of radicals is large, the active species generated by decomposition are reduced, so that the function as a radical polymerization initiator is lowered.

The photopolymerization initiator (E) can contain other photopolymerization initiators in addition to the photopolymerization initiators (E1) and (E2).
Other photopolymerization initiators include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl] -1-[4-(4-morpholinyl)phenyl]-1-butanone, or acetophenone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin , benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide or 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone compounds such as ,4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2 -(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4, 6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)- s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2, Triazine compounds such as 4-trichloromethyl-(4′-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), JP 2011-209710, JP 2012- 145721, JP 2012-177826, etc. oxime ester compounds; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; Among these, acetophenone-based initiators are preferred.

Other commercially available photopolymerization initiators are "IRGACURE 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) and "IRGACURE 369" manufactured by BASF Japan. (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), “IRGACURE 379” 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)-butan-1-one and the like.

<Sensitizer (F)>
The photosensitive coloring composition can further contain a sensitizer.
Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone. derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives , azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4' -tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone and the like. In addition, Shin Okawara et al., "Dyes Handbook" (1986, Kodansha), Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al., and "Special Functional Materials" (1986) CMC, 2003). Among these, thioxanthone derivatives, Michler's ketone derivatives and carbazole derivatives are preferred, and 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone and 1-chloro-4-propoxy Thioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethyl Carbazole, 3,6-dibenzoyl-N-ethylcarbazole and the like are more preferred.

Commercially available sensitizers include "KAYACURE DETX-S" (2,4-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.), "CHEMARK DEABP" (4,4'-bis(diethylamino)benzophenone, manufactured by Chemmark Chemical), and the like. mentioned.

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

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

<Thiol chain transfer agent>
The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol chain transfer agent. A thiol-based chain transfer agent, when used in combination with a photopolymerization initiator, generates thiyl radicals that are less likely to be inhibited by oxygen during radical polymerization after photoirradiation, improving the sensitivity of the photosensitive coloring composition.

The thiol-based chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). The thiol-based chain transfer agent more preferably has 4 or more SH groups. As the number of functional groups increases, photocuring from the surface to the deepest part of the film becomes easier.

Polyfunctional thiols include, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate , trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris trimercaptopropionate (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, and the like.

A thiol-based chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 1 to 10% by mass, more preferably 2.0 to 8.0% by mass, based on the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, the photosensitivity and pattern shape are further improved.

<Polymerization inhibitor>
The photosensitive coloring composition can contain a polymerization inhibitor. This prevents sensitization due to diffracted light from the mask during exposure, making it easier to obtain a good pattern shape.

Polymerization inhibitors include, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propyl catechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert Alkylcatechol compounds such as -butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol , 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, alkylresorcinol compounds such as 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2 ,5-di-tert-butylhydroquinone and other alkylhydroquinone compounds; tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine and other phosphine compounds; Phosphine oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, phloroglucine and the like.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass in the non-volatile content of the photosensitive coloring composition. If it is contained in an appropriate amount, it becomes easy to obtain a good pattern shape.

<Ultraviolet absorber>
The photosensitive coloring composition can contain an ultraviolet absorber. Examples of ultraviolet absorbers include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylate-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds.

Benzotriazole compounds include, for example, 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3 ,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2′- Hydroxy-5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1 -dimethylethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) Phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3 -(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol-2-yl)-4-(1 , 1,3,3-tetramethylbutyl)phenol, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] , 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3 ,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3- tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5- Chloro-2H-benzotriazol-2-yl)phenyl]propionate.

Commercial products of benzotriazole compounds include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF, Adekastab LA-29, LA-31RG, LA manufactured by ADEKA. -32, LA-36, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., and the like.

Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxy Reaction product of phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate, 2,4-bis'2-hydroxy-4 -butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-( hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6- and tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Commercial products of triazine compounds include KEMISORB 102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF, Adekastab LA-46, LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical. etc.

Benzophenone compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- Octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octade siloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

Commercial products of benzophenone compounds include KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., SEESORB 101, 107 manufactured by Shipro Kasei Co., Ltd., Adekastab 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like.

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total 100% by weight of the photopolymerization initiator and the ultraviolet absorber. A good pattern shape can be easily obtained when it is contained in an appropriate amount. In addition, suppose that content of a sensitizer is included in content of a photoinitiator when a photosensitive coloring composition contains a sensitizer.

Moreover, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile matter of the photosensitive coloring composition. When contained in an appropriate amount, the adhesion of the film to the substrate is further improved, making it easier to obtain good sensitivity.

<Antioxidant>
The photosensitive coloring composition can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the photosensitive coloring composition from yellowing due to oxidation during the thermal process during thermal curing and ITO annealing, and can suppress the decrease in the transmittance of the coating. . Especially when the concentration of the coloring agent in the photosensitive coloring composition is high, the content of the photopolymerizable compound (D) is relatively reduced. is prone to yellowing. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process, and to suppress a decrease in the transmittance of the coating.

Antioxidants are compounds with radical-scavenging or peroxide-decomposing functions. Antioxidants include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, hydroxylamine compounds, and the like. The antioxidant is preferably a compound containing no halogen atoms.

Hindered phenol compounds include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H ,5H)-trione, 1,1,3-tris-(2′-methyl-4′-hydroxy-5′-t-butylphenyl)-butane, 4,4′-butylidene-bis-(2-t- butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearylpropionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxy phenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10 -tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5 -tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2′-methylenebis (6-t-butyl-4-ethylphenol), 2,2′ thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3, 5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,6-bis(dodecylthiomethyl )-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3 -methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate , 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2′-thio-bis-(6 -t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2′-isobutylidene-bis-(4,6 -dimethyl-phenol), 2,2′-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc. mentioned.

Commercially available products are Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA, KEMINOX101, 179, 76, 9425 manufactured by Chemipro, manufactured by BASF. IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Cyanox CY-1790, CY-2777 manufactured by Sun Chemical Co., and the like.

Hindered amine compounds include, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl -4-piperidyl) 1,2,3,4-butane tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl) -4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2, 2,6,6-tetramethyl-4-piperidyl methacrylate, a polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[ [6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5 -ester of trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}- 1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-decanedioate piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyliperidyl)[[3,5-bis(1,1 dimethylethyl )-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl] -[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6 ,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine , 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide and the like.

Commercially available products are ADEKA Co. Adekastab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA- 402F, LA-502XP, KAMISTAB29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin249 manufactured by BASF, TINUVIN111FDL, 123, 144, 292, 5100, Cyasorb UV-3346 manufactured by Sun Chemical Co., UV-3529, UV-3853, etc. mentioned.

Phosphorus compounds include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, 2,2′-methylenebis(4,6-di -t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15alkyl)-4,4'-isopropyl redene diphenyl diphosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4, 4-biphenyldiphosphonate, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4' isopropyl Redenediphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl)phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl) ) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite Phyto, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4 -di-tert-butyl-6-methylphenyl) and the like.

Commercially available products include Adekastab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA, IRGAFOS168 manufactured by BASF, and HostanoxP-EPQ manufactured by Clariant Chemicals. .

Sulfur compounds include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3′-thiobis ditridecyl propionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol and the like.

Commercially available products include Adekastab AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemipro Kasei.

An antioxidant can be used individually or in mixture of 2 or more types.

The content of the antioxidant is preferably 0.5 to 5% by mass based on 100% by mass of non-volatile matter in the photosensitive coloring composition. This further improves transmittance, spectral characteristics, and sensitivity.

<Leveling agent (K)>
The photosensitive coloring composition can contain a leveling agent. This further improves the wettability with respect to the transparent substrate and the drying property of the coating when the coating is formed. Examples of leveling agents include silicone surfactants, fluorosurfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

Examples of silicone-based surfactants include chain polymers having siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.

Commercially available silicone surfactants are BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345/346, 347, 348, 349, 370 manufactured by BYK Chemie. , 377, 378, 3455, UV3510, 3570, Dow Corning Toray FZ-7002, 2110, 2122, 2123, 2191, 5609, Shin-Etsu Chemical Co., Ltd. X-22-4952, X-22-4272, X- 22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 and the like.

A fluorosurfactant is a compound having a fluorocarbon chain.

Commercially available fluorosurfactants include Surflon S-242, S-243, S-420, S-611, S-651, S-386 manufactured by AGC Seimi Chemical Co., Ltd., and Megafac F-253, F manufactured by DIC Corporation. -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, FC-4430, FC-4432 manufactured by Sumitomo 3M, EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals, Futergent 602A manufactured by Neos, and the like.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyl Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan mono Laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene tetraoleate Sorbit, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamides, alkylimidazolines, and the like.

Commercially available nonionic surfactants include Kao Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, Rhodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP- O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V , TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40 , CH-60 (K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Adeka Pluronic L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical Co., Ltd. (meth)acrylic acid copolymer POLYFLOW No. 75, No. 90, No. 95 and the like.

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

Examples of commercially available cationic surfactants include Acetamine 24, Kotamine 24P, 60W and 86P Conch manufactured by Kao Corporation.

Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenylether disulfonates, and monoethanol lauryl sulfate. amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

Commercially available anionic surfactants include Futergent 100 and 150 manufactured by Neos, Adekahope YES-25 manufactured by ADEKA, Adekacol TS-230E, PS-440E and EC-8600.

Amphoteric surfactants include, for example, lauramidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkylbetaines such as alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

Commercially available amphoteric surfactants include Amphithol 20AB, 20BS, 24B, 55AB, 86B, 20YB, 20N, etc. manufactured by Kao Corporation.

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

The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the non-volatile content of the photosensitive coloring composition. Within this range, the applicability of the photosensitive coloring composition, the pattern adhesion, and the transmittance balance are further improved.

<Storage stabilizer>
The photosensitive coloring composition can contain storage stabilizers to stabilize the viscosity of the composition over time. Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine; organic acids such as lactic acid and oxalic acid and their methyl ethers; phosphine, phosphite and the like.

The content of the storage stabilizer is preferably 0.1 to 10% by mass with respect to 100 parts by mass of the pigment (A).

<Adhesion improver>
The photosensitive coloring composition can contain an adhesion improver. This further improves the adhesion between the coating and the substrate. In addition, it becomes easier to form a narrow pattern by photolithography. Adhesion improvers include, for example, silane coupling agents.

Examples of silane coupling agents include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth)acrylsilanes such as 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3- dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilanes such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyl mercaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; Examples include sulfides and isocyanates such as 3-isocyanatopropyltriethoxysilane.

The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the pigment (A). When contained in an appropriate amount, the photosensitivity of the photosensitive coloring composition is improved, the adhesion of the coating is further improved, and the resolution of the pattern is also further improved.

<Solvent>
The photosensitive coloring composition can contain a solvent. This facilitates the adjustment of the viscosity of the photosensitive coloring composition, making it easier to form a film with a smooth surface. The solvent may be appropriately selected according to the purpose of use and contained in an appropriate amount.

Solvents include, for example, ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- in the molecule but not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not -COO-), alcohol solvents (containing OH in the molecule, -O -, -CO- and -COO--free solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

Ester solvents include, for example, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid. Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

Ether solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl. Ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl Ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenetol, methylanisole and the like.

Ether ester solvents are, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- ethyl ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate , ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol diacetate and the like.

Ketone solvents are, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin and the like.

Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

Amide solvents include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and the like.

Among these, a solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm is preferable in terms of coating properties and drying properties. For example, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N,N-dimethylformamide, N-methylpyrrolidone and the like are more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are even more preferred.

A solvent can be used individually or in mixture of 2 or more types.

<Method for producing a photosensitive coloring composition>
The photosensitive coloring composition is subjected to dispersion treatment using, for example, the pigment (A) and the dispersant (B) to prepare a pigment (A) dispersion. Then, the pigment (A) dispersion, the binder resin (C), the photopolymerizable compound (D), and the photopolymerization initiator (E) can be mixed to prepare.

For the dispersion treatment, for example, 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 can be used.

<Removal of coarse particles>
In the present specification, it is preferable to remove contained coarse particles after preparing the pigment (A) dispersion stage or the photosensitive coloring composition. As a result, foreign matter can be removed from the film, making it easier to form a fine pattern.
The removal is preferably carried out by a method such as centrifugal separation, sintered filter, membrane filter, or the like. As a result, foreign substances such as coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more can be removed. Thus, the photosensitive coloring composition preferably does not substantially contain particles of 0.5 μm or more, and preferably does not contain particles of 0.3 μm or less.

<Color filter>
A color filter herein includes a base material (also referred to as a transparent substrate) and filter segments formed from a photosensitive coloring composition. The color filter segment (hereinafter also referred to as filter segment) preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of pigment (A) used. Moreover, the color filter can further have a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment as color filter segments. A reflective substrate can be used instead of the transparent substrate. Examples of transparent substrates include glass substrates. Examples of the reflective substrate include those using an aluminum electrode or a metal thin film as a reflective surface.

<Manufacturing method of color filter>
A color filter is preferably formed by first forming a black matrix on a substrate and then forming filter segments. In addition, the black matrix can be formed after thin film transistors (TFTs) are formed on the substrate in advance.
The black matrix includes, for example, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed.

Filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like.
In the printing method, a pattern can be formed only by repeating printing and drying of a photosensitive coloring composition prepared as a printing ink, and therefore, as a method for producing a color filter, it is low cost and excellent in mass productivity. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to have a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, it is also important to control the fluidity of the ink on the printing press, and it is also possible to adjust the viscosity of the ink using a dispersant or an extender.

In the electrodeposition method, a transparent conductive film formed on a transparent substrate is used to fabricate a color filter by electrodepositing filter segments of each color on the transparent conductive film by electrophoresis of colloidal particles. In the transfer method, filter segments are formed on the release-treated surface of the release sheet. Next, this filter segment is transferred to a transparent substrate to produce.

In the photolithography method, for example, a photosensitive coloring composition containing a coloring agent of a certain tone is applied onto a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a film. The obtained coating (hereinafter referred to as the first coating) is exposed (light irradiation) through a mask having a predetermined pattern. Next, the film is developed by immersing it in a solvent or an alkaline developer or by spraying the developer to remove uncured portions to obtain a desired pattern. A color filter having filter segments of each color can be produced by performing this step in the same manner using a photosensitive coloring composition having a colorant of another color tone. Also, a second coating (oxygen blocking film) can be formed on the first coating before exposure using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first film does not come into contact with oxygen, thereby further improving the exposure sensitivity. Also, the color filters can be heated to cure uncured photopolymerizable compounds in the filter segments. In addition, the photolithographic method is preferable because a color filter with higher accuracy can be manufactured than the printing method.

Coating devices include, for example, spray coating, spin coating, slit coating, and roll coating. A drying process can be performed in the case of coating. Examples of the drying device include hot air ovens, infrared heaters, and the like.

Examples of the developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; and organic alkalis such as dimethylbenzylamine and triethanolamine. Also, the developer can contain an antifoaming agent and a surfactant.

In this specification, the color filter is formed by forming a filter segment, then bonding it to a counter substrate using a sealing agent, injecting liquid crystal from an injection port provided in the sealing portion, sealing the injection port, and optionally using a polarizing film. A liquid crystal display device can be produced by laminating a retardation film or a retardation film on the outside of a substrate. This liquid crystal display device includes, for example, twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optically convened bend ( OCB) and the like.

In this specification, the color filter can be used for solid-state imaging devices, organic EL display devices, quantum dot display devices, electronic paper, and the like, in addition to liquid crystal display devices.

<Liquid crystal display device>
The liquid crystal display device of this specification includes a color filter.
A liquid crystal display device comprises the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED. In the present invention, it is preferable to use a white LED in terms of widening the reproduction range of red. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 having a color filter of the present invention. The device 10 shown in FIG. 1 comprises a pair of transparent substrates 11 and 21 spaced and opposed to each other, with a liquid crystal LC 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 inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of ITO, for example, is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13 . A polarizing plate 15 is formed on the outer surface of the transparent substrate 11 .

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21 . The red, green and blue filter segments that make up color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filters 22, and a transparent electrode layer 23 made of, for example, ITO is formed thereon. is provided.

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21 . A backlight unit 30 is provided below the polarizing plate 15 .

The white LED light source includes, for example, a blue LED with a fluorescent filter formed on its surface, and a blue LED resin package containing a phosphor. (λ3), a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, and a wavelength (λ5) at which the emission intensity is maximum within the range of 600 nm to 650 nm, and The ratio (I4/I3) of the emission intensity I3 at the wavelength λ3 to the emission intensity I4 at the wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio (I5/ A white LED light source (LED1) having a spectral characteristic in which I3) is 0.1 or more and 1.3 or less, or a wavelength (λ1) at which the emission intensity is maximized in the range of 430 nm to 485 nm, and 530 nm to 580 nm. A spectrum having a second emission intensity peak wavelength (λ2) within the range, and having a ratio (I2/I1) between the emission intensity I1 at the wavelength λ1 and the emission intensity I2 at the wavelength λ2 of 0.2 or more and 0.7 or less A white LED light source (LED2) with properties is preferred.

Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Corporation) and NSSW304D (manufactured by Nichia Corporation).

The following examples illustrate the invention. "Parts" and "%" in the examples represent "parts by mass" and "% by mass", respectively.

Weight-average molecular weight (Mw), number-average molecular weight (Mn), acid value (mgKOH/g), amine value (mgKOH/g), ammonium salt for resins such as binder resins, resin-type dispersants, and salt-forming resins for dyes Values (mgKOH/g) are as follows.

<Weight average molecular weight (Mw), number average molecular weight (Mn),>
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resins were determined by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as an apparatus, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used as both packing materials, and the oven temperature was 40. °C, a THF solution was used as an eluent, and the flow rate was 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent and injected in 20 microliters. All molecular weights are polystyrene equivalent values.

<Acid value (mgKOH/g)>
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution and stir to dissolve uniformly. ) 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.

<Amine value (mgKOH/g)>
The amine value is a value obtained by converting the total amine value (mgKOH/g) measured according to ASTM D 2074 into solid content.

<Ammonium salt value (mgKOH/g)>
The ammonium salt value is determined by titration with a 0.1N aqueous solution of silver nitrate using a 5% aqueous solution of potassium chromate as an indicator, and then converted into the equivalent weight of potassium hydroxide.

<Synthesis of Pigment (A)>
<Synthesis of diketopyrrolopyrrole pigment (Aa)>
200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide are added to a stainless steel reaction vessel equipped with a reflux tube under a nitrogen atmosphere, and heated to 100° C. with stirring to form an alcoholate solution. prepared. Separately, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating to 90° C. with stirring to prepare a mixture. The heated solution of this mixture was slowly added dropwise at a constant rate over 2 hours into the above alcoholate solution heated to 100° C. with vigorous stirring. After the dropwise addition was completed, heating and stirring were continued at 90° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a jacketed glass reaction vessel and cooled to -10°C. This cooled mixture was cooled to 75° C. while rotating a shear disk with a diameter of 8 cm at 4000 rpm using a high-speed stirring disperser. The solution was added in small portions. At this time, the rate of adding the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always kept at -5 ° C. or less. was added in portions over approximately 120 minutes, adjusting the . After addition of the alkali metal salt, red crystals precipitated to form a red suspension. Subsequently, the resulting red suspension was washed with an ultrafiltration device at 5° C. and filtered to obtain a red paste. This paste was re-dispersed in 3500 parts of methanol cooled to 0° C. to form a suspension having a methanol concentration of about 90%, stirred at 5° C. for 3 hours, and subjected to particle sizing and washing accompanied by crystal transition. Subsequently, the water paste of the diketopyrrolopyrrole compound obtained by filtration with an ultrafilter is dried at 80° C. for 24 hours and pulverized to give a diketopyrrolopyrrole pigment (Aa) 150. .8 parts were obtained.

<Synthesis of diketopyrrolopyrrole pigment (Ab)>
(Diketopyrrolopyrrole pigment (A-b_1))
220 parts of tert-amyl alcohol was placed in reaction vessel 1, and while cooling in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90°C. Then, 100 parts of tert-amyl alcohol, 85.0 parts of the compound of the following chemical formula (17) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl are heated in reaction vessel 2. It was dissolved and added dropwise to reaction vessel 1 over 2 hours. After reacting at 120° C. for 10 hours, the mixture was cooled to 60° C., 400 parts of methanol and 50 parts of acetic acid were added, filtered and washed with methanol to give diketopyrrolopyrrole pigment (A-b_1)88. Got 1 copy.

chemical formula (17)

(Diketopyrrolopyrrole pigment (A-b_2))
Except for changing 60.9 parts of 4-cyanobiphenyl to 54.1 parts of 4-tert-butylbenzonitrile, the diketopyrrolopyrrole pigment (A-b_1) was produced in the same manner as the diketopyrrolopyrrole pigment. (A-b_2) 83.9 parts were obtained.

(Diketopyrrolopyrrole pigment (A-b_3))
Except for changing 60.9 parts of 4-cyanobiphenyl to 68.7 parts of N-butyl-4-cyanobenzamide, the diketopyrrolopyrrole pigment (A-b_1) was produced in the same manner as the diketopyrrolopyrrole pigment. 87.0 parts of Pigment (A-b_3) were obtained.

(Diketopyrrolopyrrole pigment (A-b_4))
Except for changing 60.9 parts of 4-cyanobiphenyl to 75.5 parts of N-phenyl-4-cyanobenzamide, the diketopyrrolopyrrole pigment (A-b_1) was produced in the same manner as the diketopyrrolopyrrole pigment. 86.9 parts of pigment (A-b_4) were obtained.

(Diketopyrrolopyrrole pigment (A-b_5))
Except for changing 60.9 parts of 4-cyanobiphenyl to 87.8 parts of N,N-dibutyl-4-cyanobenzamide, the same procedure as in the production of the diketopyrrolopyrrole pigment (A-b_1) was carried out to obtain the diketopyrrolo 87.1 parts of pyrrole pigment (A-b_5) was obtained.

(Diketopyrrolopyrrole pigment (A-b_6))
220 parts of tert-amyl alcohol was placed in reaction vessel 1, and while cooling in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90°C. Then, 100 parts of tert-amyl alcohol, 99.2 parts of the compound of the following chemical formula (18) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl are heated in reaction vessel 2. It was dissolved and added dropwise to reaction vessel 1 over 2 hours. After reacting at 120° C. for 10 hours, cooling to 60° C., adding 400 parts of methanol and 50 parts of acetic acid, filtering and washing with methanol, diketopyrrolopyrrole pigment (A-b_6)87. 8 copies were obtained.

chemical formula (18)

(Diketopyrrolopyrrole pigment (A-b_7))
Except for changing 60.9 parts of 4-cyanobiphenyl to 87.8 parts of N,N-dibutyl-4-cyanobenzamide, the diketopyrrolopyrrole pigment (A-b_6) was produced in the same manner as the diketopyrrolopyrrole pigment. 87.1 parts of pyrrole pigment (A-b_7) was obtained.

<Diketopyrrolopyrrole Pigment>
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by BASF) was used as pigment (Ac).

Table 1 shows the structures of Ab_1 to Ab_7 thus obtained.

Table 2 shows each symbol of finely divided pigments and dyes and their contents.

<Refinement of Diketopyrrolopyrrole Pigment>
The diketopyrrolopyrrole pigments produced as described above were pulverized as follows to obtain P-1 to P-9.

(Micronized diketopyrrolopyrrole pigment (P-1))
100 parts of the diketopyrrolopyrrole pigment (Aa), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 10 hours. Next, the kneaded mixture is put into hot water, stirred for 1 hour while heating to about 80°C to form a slurry, filtered and washed with water to remove salt and diethylene glycol, dried at 80°C for a day and night, and pulverized. As a result, 96.9 parts of fine diketopyrrolopyrrole pigment (P-1) was obtained.

(Micronized diketopyrrolopyrrole pigments (P-2 to 9))
The finely divided diketopyrrolopyrrole pigment (P-1) was changed to the pigment shown in Table 2 in the same manner as the finely divided diketopyrrolopyrrole pigment (P-1). Pyrrolopyrrole pigments (P-2 to P-9) were obtained.

<Method for refining other red pigments (AR)>
(Refined pigment (P-10))
C. I. Pigment Red 177 (“Chromophthal Red A2B” manufactured by BAS-F) (AR-1): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), The mixture was kneaded at 120°C for 8 hours. Next, this kneaded product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. to obtain a finely divided pigment (P-10).

(Refined pigment (P-11))
C. I. Pigment Red 269 (“Toner Magenta F8B” manufactured by Clariant) (AR-2) 100 parts, sodium chloride 800 parts, and diethylene glycol 180 parts were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. bottom. This mixture is poured into 4000 parts of hot water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, then heated at 80°C for 24 hours. After drying, a finely divided pigment (P-11) was obtained.

(Refined pigment (P-12))
A finely divided pigment (P-12) of a coloring agent (AR-3) represented by the following chemical formula (19) was obtained by the same manufacturing method as the red coloring agent 1 described in the example of Japanese Patent No. 6350885. .

chemical formula (19)

<Method for refining pigment (AY) other than red>
(Refined pigment (P-13))
C. I. Pigment Yellow 138 (“Pariotol Yellow K0961HD” manufactured by BAS-F) (AY-1) 100 parts, 800 parts of crushed salt, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and heated to 70°C. and kneaded for 4 hours. This mixture is poured into 3000 parts of hot water, heated to about 80°C and stirred with a high speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, and then heated at 80°C for 24 hours. After drying, a finely divided pigment (P-13) was obtained.

(Refined pigment (P-14))
A finely divided pigment (P-14) of a coloring agent (AY-2) represented by the following chemical formula (20) was obtained by the same manufacturing method as the yellow coloring agent 8 described in the examples of Japanese Patent No. 4993026. rice field.

chemical formula (20)

(Refined pigment (P-15))
A compound represented by the following chemical formula (21) was obtained according to the synthesis method described in JP-A-2012-226110. 40 parts of chemical formula (21) and 22 parts of N-bromosuccinimide were added to 300 parts of N,N-dimethylformamide and stirred at 80° C. for hours. The reaction solution was poured into a stirred mixed solvent of 300 parts of methanol/700 parts of water, and stirred at room temperature for 1 hour. The resulting precipitate was filtered, washed with water, washed with methanol, washed with water in that order, and dried to obtain 48 parts of intermediate (a-1). 45 parts of the obtained intermediate (a-1), 37 parts of tetrachlorophthalic anhydride and 35 parts of benzoic acid were added to 100 parts of methyl benzoate, and the mixture was heated and stirred at 160° C. for 4 hours. After cooling to room temperature, the reaction mixture was poured into 1000 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 65 parts of a quinophthalone compound. 100 parts of a quinophthalone compound, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. A finely divided pigment (P-15) of a coloring agent (AY-3) represented by the following chemical formula (22) was obtained.

(Refined pigment (P-16))
150 parts of 2,3-naphthalenedicarboxylic anhydride and 230 parts of trichloroisocyanuric acid were added to 1200 parts of 98% sulfuric acid and reacted at 80° C. for 4 hours. The reaction solution is poured into 9,000 parts of stirred ice water, and the precipitate formed is filtered, washed with water, washed with a 1% aqueous sodium hydroxide solution, and washed with water in that order, and dried to give intermediate (a-2). 220 copies were obtained. 105 parts of the compound represented by the chemical formula (21), 150 parts of the intermediate (a-2) and 100 parts of benzoic acid were added, heated to 180° C., and stirred for 4 hours. After cooling to room temperature, the reaction mixture was poured into 5000 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 183 parts of a quinophthalone compound. 100 parts of a quinophthalone compound, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. A finely divided pigment (P-16) of a coloring agent (AY-4) represented by the following chemical formula (23) was obtained.

chemical formula (23)

(Refined pigment (P-17))
Intermediate (a-2) was synthesized in the same manner except that 350 parts of trichloroisocyanuric acid in the synthesis of intermediate (a-2) was changed to 244 parts of N-bromosuccinimide to obtain intermediate (a-3). The average number of bromine substituents in the intermediate (a-3) was 1.5.
50 parts of 8-aminoquinaldine, 115 parts of the intermediate (a-2) and 140 parts of benzoic acid were added to 200 parts of methyl benzoate, and the mixture was stirred at 120° C. for 4 hours. Next, 143 parts of intermediate (a-3) was further added to the reaction mixture, heated to 180° C., and stirred for 4 hours while distilling off water. After cooling to room temperature, the reaction mixture was poured into 2000 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain a quinophthalone compound. 100 parts of a quinophthalone compound, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. A finely divided pigment (P-17) of a coloring agent (AY-5) represented by the following chemical formula (24) was obtained.

chemical formula (24)

(Refined pigment (P-18))
C. I. Pigment Yellow 150 ("Yellow Pigment E4GN" manufactured by Lanxess) (AY-6) 100 parts, sodium chloride 1600 parts, and diethylene glycol 190 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and heated at 60 ° C. for 10 hours. Kneaded. Next, this mixture is poured into 3 liters of hot water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is filtered and washed repeatedly to remove sodium chloride and the solvent. C. for one day to obtain a finely divided pigment (P-18).

(Refined pigment (P-19))
C. I. Pigment Yellow 139 (“Irgafor Yellow 2R-CF” manufactured by BAS-F) (AY-7) 100 parts, sodium chloride 1600 parts, and diethylene glycol 190 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), The mixture was kneaded at 60°C for 10 hours. Next, this mixture is poured into 3 liters of hot water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is filtered and washed repeatedly to remove sodium chloride and the solvent. C. for one day to obtain a finely divided pigment (P-19).

(Refined pigment (P-20))
C. I. Pigment Yellow 185 (“Pariotol Yellow D1155” manufactured by BAS-F) (AY-8) 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 120 C. for 8 hours. Next, this kneaded product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. , to obtain a finely divided pigment (P-20).

<Method for producing resin salts of dyes (AS-1 to 3)>
Resin salts of dyes (AS-1 to 3) were produced using the following resin 1 having a cationic group in the side chain and each of the dyes.
(Resin 1 having a cationic group in the side chain)
A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis(2,4-dimethylvaleronitrile ) and 25.1 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and added dropwise over 2 hours. After 2 hours from the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the non-volatile matter and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50°C. 3.2 parts of methyl chloride and 22.0 parts of ethanol were added thereto, and the mixture was reacted at 50° C. for 2 hours, then heated to 80° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a cationic group in a side chain containing 47% by mass of ammonium group as a resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH/g.

(Dye (AS-1))
To 2000 parts of water was added 30 parts of Resin 1 having a cationic group on its side chain in terms of non-volatile content, and the mixture was sufficiently stirred and mixed, and then heated to 60°C. On the other hand, 10 parts of C.I. I. An aqueous solution was prepared by dissolving Acid Red 52, and was added dropwise to the previous resin solution. After dropping, the mixture was stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was added dropwise to a filter paper, and the point at which no bleeding occurred was regarded as the end point, and it was determined that a salt-forming compound was obtained. After allowing to cool to room temperature while stirring, suction filtration is performed, and after washing with water, salt-forming compounds remaining on the filter paper are dried by removing moisture with a drier. I. A dye (AS-1) was obtained as a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in the side chain. At this time, C.I. I. The content of the active coloring component derived from Acid Red 52 was 25% by mass.

(Dye (AS-2))
C. I. Add Acid Red 52 to C.I. I. The procedure was carried out in the same manner as the coloring agent (AS-1) except that C.I. Acid Red 289 was used. I. A dye (AS-2) was obtained as a salt-forming compound of Acid Red 289 and Resin 1 having a cationic group in the side chain. At this time, C.I. I. The content of the active pigment component derived from Acid Red 289 was 27% by mass.

(Dye (AS-3))
In a 1 L stainless steel reaction vessel equipped with a reflux tube, C.I. I. 5.0 parts of Basic Violet 10 (BV10: manufactured by Taoka Chemical Co., Ltd.: Rodamine B) and 1.6 parts of hydroxyethyl methacrylate (HEMA) are dissolved in 40 ml of dichloromethane, and 1-(3-dimethylaminopropyl)-3-ethyl 2.2 parts of carbodiimide hydrochloride and 0.25 parts of dimethylaminopyridine were added and stirred at room temperature for 24 hours. The resulting dichloromethane solution was washed with water, dried under reduced pressure, and purified with a silica gel column to obtain a dye (AS-3).

<Acidic resin type dispersant: B1>
(Synthesis of acidic resin-type dispersant: B1-1)
10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of propylene glycol monomethyl ether acetate are charged into a reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer, and nitrogen gas is introduced. replaced with
The inside of the reaction vessel was heated to 50° C. with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution obtained by adding 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. It was confirmed by measuring the non-volatile content that 95% had reacted.
19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and heated at 100°C. The reaction was allowed to proceed for 7 hours. After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value, the reaction is terminated. An acidic resin-type dispersant (B1-1) having a molecular weight of 70 mgKOH/g and a mass average molecular weight of 8,500 was obtained.

(Synthesis of acidic resin type dispersant: B1-2)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, 80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of methacrylic acid, 20 parts of Karenz MOI-BM (manufactured by Showa Denko), ETERNACOLL OXMA ( manufactured by Ube Industries, Ltd.) and 100 parts of propylene glycol monomethyl ether acetate were charged, and the mixture was purged with nitrogen gas. The inside of the reaction vessel is heated to 80° C., and a solution of 0.1 part of 2,2′-azobisisobutyronitrile dissolved in 14 parts of 2-mercapto-2-methyl-1,3-propanediol is added. and reacted for 10 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. Next, BPAF: 39 parts of 9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride (manufactured by JFE Chemical Co., Ltd.), C-1015N (bifunctional polycarbonate polyol, trade name Kuraray Polyol C-1015N ( Hydroxyl value 112 mgKOH/g, manufactured by Kuraray Co., Ltd.)) 106 parts, trimellitic anhydride 33 parts, cyclohexanone 392 parts, 1,8-diazabicyclo-[5.4.0]-7-undecene 0.40 parts as a catalyst was added and reacted at 100° C. for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. The nonvolatile content was adjusted to 30% with propylene glycol monomethyl ether acetate to obtain an acidic resin-type dispersant (B1-2) liquid having an acid value of 94 mgKOH/g and a weight average molecular weight of 25,000.

(Synthesis of acidic resin-type dispersant: B1-3)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic dianhydride, 23.5 parts of cyclohexanone, 0.01 part of mono-n-butyltin (IV) oxide was charged to each, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 100° C. and reacted for 7 hours. After confirming that 97% or more of the acid anhydride is half-esterified by measuring the acid value, the temperature in the system is cooled to 70°C, and 80 parts of methyl methacrylate and 20 parts of hydroxyethyl methacrylate are charged. A solution prepared by dissolving 0.1 part of 2′-azobisisobutyronitrile in 26.2 parts of cyclohexanone was added and reacted for 10 hours. After confirming that the polymerization had progressed by 95% by measuring the solid content, the reaction was terminated. After completion of the reaction, the nonvolatile matter was adjusted to 30% with propylene glycol monomethyl ether acetate to obtain an acidic resin-type dispersant (B1-3) liquid having a weight average molecular weight of 9,500.

(Synthesis of acidic resin-type dispersant: B1-4)
108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc (methoxypropyl acetate), and 0.2 parts of monobutyltin oxide as a catalyst in a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer. was charged and purged with nitrogen gas, followed by reaction at 120° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate Parts, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the inside of the reaction vessel was heated to 80° C., 1.2 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours. (Second step). It was confirmed by measuring the non-volatile content that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate, and 0.1 part of hydroquinone were charged, and the concentration of 2270 cm-1 based on the isocyanate group was measured by IR. The reaction was continued until disappearance of the peak was confirmed (third step). After confirming disappearance of the peak, the reaction solution was cooled and the non-volatile content was adjusted with propylene glycol monomethyl ether acetate to obtain a dispersant (B1-3) solution with a non-volatile content of 30%. The resulting acidic resin-type dispersant had an acid value of 68, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

[Production of Vinyl Resin Dispersant (B2) Having Piperidyl Skeleton]
(Production of Vinyl Resin Dispersant (B2-1) Having Piperidyl Skeleton)
133 parts of propylene glycol monomethyl ether acetate was charged into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110°C while replacing with nitrogen. 120 parts of tetramethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Fancryl FA-712HM), 70 parts of methyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 61 parts of propylene glycol monomethyl ether acetate, and 2,2'- After 6 parts of azobis(2,4-dimethylvaleronitrile) was charged and stirred until uniform, it was added dropwise to the reactor over 2 hours, and then the reaction was continued at the same temperature for 3 hours. A vinyl resin type dispersant (B2-1) having a piperidyl skeleton adjusted to a nonvolatile content of 30% with propylene glycol monomethyl ether acetate, having an amine value per nonvolatile content of 145 mgKOH/g and a number average molecular weight of 3,500 (Mn) I got the liquid.

(Production of vinyl-based resin dispersant (B2-2) having a piperidyl skeleton)
133 parts of propylene glycol monomethyl ether acetate was charged into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110°C while replacing with nitrogen. 80 parts of pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Funcryl FA-711MM), 100 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of propylene glycol monomethyl ether acetate, and 2,2'- After 6 parts of azobis(2,4-dimethylvaleronitrile) was charged and stirred until uniform, it was added dropwise to the reactor over 2 hours, and then the reaction was continued at the same temperature for 3 hours. A vinyl resin type dispersant (B2-2) having a piperidyl skeleton adjusted to a nonvolatile content of 30% with propylene glycol monomethyl ether acetate, having an amine value per nonvolatile content of 91 mgKOH/g and a number average molecular weight of 3,800 (Mn). I got the liquid.

(Production of Vinyl Resin Dispersant (B2-3) Having Piperidyl Skeleton)
30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet tube, condenser, stirring blade, and thermometer, and nitrogen was flowed. While stirring at 50° C. for 1 hour, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of methoxypropyl acetate were charged, and the temperature was raised to 110°C under a nitrogen stream to polymerize the first block (B block). started. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of methoxypropyl acetate and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate as a second block (A block) monomer (manufactured by Hitachi Chemical Co., Ltd., Funcryl FA-711MM) was added, and the reaction was continued by stirring while maintaining the temperature at 110° C. under nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the nonvolatile content was measured. % or more, the reaction solution was cooled to room temperature to terminate the polymerization.
Thus, a vinyl resin type dispersant having a piperidyl skeleton with an amine value per non-volatile content of 57 mgKOH/g and a number average molecular weight of 4,500 (Mn) was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. A vinyl resin type dispersant (B2-3) liquid having a piperidyl skeleton was prepared by adding glycol monomethyl ether acetate.

(Production of vinyl resin type dispersant (B3-1))
133 parts of propylene glycol monomethyl ether acetate was introduced into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 100°C while replacing with nitrogen. After charging 200 parts of N,N-dimethylaminoethyl methacrylate, 61 parts of propylene glycol monomethyl ether acetate, and 6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) into a dropping vessel and stirring until uniform, was added dropwise to the reactor over 2 hours, and the reaction was continued at the same temperature for 3 hours. Thereafter, the nonvolatile content was adjusted to 30% with propylene glycol monomethyl ether acetate, and the amine value per nonvolatile content was 345 mgKOH/g and the number average molecular weight was 2,500 (Mn). ) to obtain a liquid.

<Dye derivative>
The following dye derivatives were used.

<Production example of binder resin (C) liquid>
<Production of binder resin (C1: non-photosensitive resin)>
(Preparation of binder resin (C1-1) liquid)
196 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and the inside of the reaction vessel was replaced with nitrogen. After that, from the dropping tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) A mixture of 20.7 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin (C1-1) liquid was prepared by adding acetate. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (C1-2) liquid)
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was filled with a nitrogen atmosphere, 210 parts of propylene glycol monomethyl ether acetate was added, and the temperature was raised to 100°C while stirring. Then, 106 parts of benzyl methacrylate, 22 parts of acrylic acid and 22 parts of dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) are dissolved in 215 parts of propylene glycol monomethyl ether acetate, and further 2,2'-azobisisobutyl A solution prepared by dissolving 3.6 parts of lonitrile was dropped into the flask, and the mixture was stirred at 100° C. for 5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin was prepared by adding acetate to obtain a resin (C1-2) solution having a mass average molecular weight (Mw) of 10,000.

(Preparation of binder resin (C1-M) liquid)
Equal amounts of binder resin (C1-1) liquid and binder resin (C1-2) liquid were mixed and stirred to prepare binder resin (C1-M) liquid.

<Production example of binder resin (C2: photosensitive resin)>
(Preparation of binder resin (C2-1) liquid)
207 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and the inside of the reaction vessel was replaced with nitrogen. After that, from a dropping tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2 A mixture of 1.33 parts of '-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the total amount of the copolymer solution obtained was stirred while injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin (C2-1) was prepared by adding acetate. The weight average molecular weight (Mw) was 18,000.

(Preparation of binder resin (C2-2) liquid)
333 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere inside the flask was changed from air to nitrogen, and then heated to 100°C. 70.5 g (0.40 mol) of benzyl methacrylate, 71.1 g (0.50 mol) of glycidyl methacrylate, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and , 164 g of propylene glycol monomethyl ether acetate and 3.6 g of azobisisobutyronitrile was added dropwise from the dropping funnel to the flask over 2 hours, and the mixture was further stirred at 100°C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 g [0.5 mol, (100 mol % relative to the glycidyl group of the glycidyl methacrylate used in this reaction)] of methacrylic acid and 0.5 mol of trisdimethylaminomethylphenol were added. 9 g of hydroquinone and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110° C. for 6 hours until the acid value of the non-volatile matter reached 1 mgKOH/g. Next, 60.9 g (0.40 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain a photosensitive transparent resin solution with an acid value of 80 mgKOH/g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. A binder resin (C2-2) solution was prepared by adding propylene glycol monomethyl ether acetate as in the above. The weight average molecular weight (Mw) was 12,000.

(Adjustment of binder resin (C2-3) liquid)
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and after the atmosphere inside the flask was changed from air to nitrogen, the temperature was raised to 100°C, 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and A solution of 3.6 g of azobisisobutyronitrile added to a mixture of 136 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over 2 hours, and the mixture was further stirred at 100° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g [0.25 mol of glycidyl methacrylate (50 mol % based on the carboxyl group of methacrylic acid used in this reaction)] and 0.5 g of trisdimethylaminomethylphenol were added. 9 g of hydroquinone and 0.145 g of hydroquinone were put into the flask and the reaction was continued at 110° C. for 6 hours to obtain a photosensitive transparent resin solution with an acid value of 79 mgKOH/g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. A binder resin (C2-3) solution was prepared by adding propylene glycol monomethyl ether acetate as in the above. The weight average molecular weight (Mw) was 13,000.

(Preparation of binder resin (C2-4) liquid)
A separable flask equipped with a cooling tube is prepared as a reaction tank, and on the other hand, as a monomer dropping tank, 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, Prepare a mixture of 120 parts of methyl methacrylate, 4 parts of t-butyl peroxy-2-ethylhexanoate (NOF "PERBUTYL O"), and 40 parts of propylene glycol monomethyl ether acetate, and add a chain transfer agent. A dropping tank was prepared by thoroughly stirring and mixing 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate.
A reaction vessel was charged with 395 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the temperature of the reaction vessel was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. Each dropping was performed over 135 minutes while maintaining the temperature at 90°C. After 60 minutes from the completion of dropping, the temperature of the reactor was raised to 110°C. After maintaining the temperature at 110° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen=5/95 (volume ratio) was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2′-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were charged into the reaction vessel and allowed to react at 110° C. for 12 hours. rice field. Then, 150 parts of propylene glycol monomethyl ether acetate is added and cooled to room temperature, and about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was added to 20% by mass to obtain a binder resin (C2-4) liquid. The resin had a mass average molecular weight (Mw) of 18,000 and an acid value of 2 mgKOH/g per nonvolatile matter.

(Preparation of binder resin (C2-M) liquid)
Binder resin (C2-M) liquid was prepared by mixing and stirring equal amounts of four types of binder resin (C2-1) to (C2-4) liquids.

<Preparation of colored composition>
(Production of colored composition (single color: R-1))
[Production Example 1]
After stirring and mixing the following mixture uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.), the pore size is 5.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (R-1) having a nonvolatile content of 20% by mass.
Colorant (P-1) 14.0 parts Dispersant (B1-1: 30% non-volatile liquid) 4.0 parts Binder resin (C1-M: 20.0% non-volatile liquid) 24.0 parts Solvent (N ) 58.0 copies

[Production Examples 2 to 35]
(Production of colored composition (R-2 to 36))
Coloring compositions (R-2 to 36) were prepared in the same manner as the coloring composition (R-1) except that the compositions shown in Table 3 were changed.

(Production of colored composition (mixed color resin liquid addition or resin liquid addition: S-1))
[Production Example 101]
(Preparation of colored composition (S-1))
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a colored composition (S-1).
Coloring composition 1 (R-1: non-volatile content 20.0% liquid) 95.0 parts binder resin (C1-M: non-volatile content 20.0% liquid) 5.0 parts

[Production Examples 102 to 142]
(Preparation of colored composition (S-2 to 42))
Colored compositions (S-2 to 42) were prepared in the same manner as in Production Example 101, except that the material species and masses were changed as described in Table 4.

[Synthesis of photopolymerization initiators E1-1 to E1-4]
The above photopolymerization initiators E1-1 to E1-4 were synthesized by the following method.

<Synthesis of photopolymerization initiator (E1-1)>
(Step 1)
In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, and 53 mmol of N-ethyl-3-nitro-carbazole were introduced into an ice-cooled reactor. 64 millimoles of 4-(2-methoxy-1-methyl-ethoxy)-2-methyl-benzoyl chloride was slowly added dropwise to this mixture while maintaining the reaction temperature below 5°C. After completion of dropping, the mixture was stirred at 20° C. for 4 hours. Thereafter, the reaction liquid was poured into ice water to separate into an oily phase and an aqueous phase, and the liquid constituting the oily phase was dried using magnesium sulfate. The drying agent was then removed from this liquid by filtration, and the solvent was further removed by distillation. An acyl derivative was obtained as described above.

(Step 2)
In a nitrogen stream, 20 millimoles of the above acyl derivative, 2.1 g (30 millimoles) of hydroxylamine hydrochloride, and 16.9 g of dimethylformamide were charged into a reactor. After the mixture was stirred at 80° C. for 1 hour, it was cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent was removed by distillation from the liquid constituting the oily phase, and then 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added to the distillation residue. After the mixture was stirred at 90° C. for 1 hour, it was cooled to room temperature and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil-water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and recrystallization was performed using ethyl acetate as a solvent. Photopolymerization initiator (E1-1) was obtained as described above.

<Synthesis of photopolymerization initiator (E1-2)>
(Step 1)
In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, and 53 mmol of N-(2-ethyl-hexyl)-3-nitrocarbazole compound were charged into an ice-cooled reaction vessel. bottom. 64 millimoles of 4-(2-methoxy-1-methyl-ethoxy)-2-methyl-benzoyl chloride was slowly added dropwise to this mixture while maintaining the reaction temperature below 5°C. After completion of dropping, the mixture was stirred at 20° C. for 4 hours. Thereafter, the reaction liquid was poured into ice water to separate into an oily phase and an aqueous phase, and the liquid constituting the oily phase was dried using magnesium sulfate. The drying agent was removed from this liquid by filtration, and the solvent was further removed by distillation. An acyl derivative was obtained as described above.

(Step 2)
In a nitrogen stream, 20 millimoles of the above acyl derivative, 2.1 g (30 millimoles) of hydroxylamine hydrochloride, and 16.9 g of dimethylformamide were charged into a reactor. After the mixture was stirred at 80° C. for 1 hour, it was cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent was removed by distillation from the liquid constituting the oily phase, and then 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added to the distillation residue. After the mixture was stirred at 90° C. for 1 hour, it was cooled to room temperature and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil-water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and recrystallization was performed using ethyl acetate as a solvent. As described above, a photopolymerization initiator (E1-2) was obtained.

<Synthesis of photopolymerization initiator (E1-3)>
(Step 1)
In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, and 53 mmol of N-ethyl-3-nitrocarbazole compound were charged into an ice-cooled reactor. 64 millimoles of 4-(ethoxymethyl)-2-methyl-benzoyl chloride was slowly added dropwise to this mixture while maintaining the reaction temperature below 5°C. After completion of dropping, the mixture was stirred at 20° C. for 4 hours. Thereafter, the reaction liquid was poured into ice water to separate into an oily phase and an aqueous phase, and the liquid constituting the oily phase was dried using magnesium sulfate. The drying agent was removed from this liquid by filtration, and the solvent was further removed by distillation. An acyl derivative was obtained as described above.

(Step 2)
In a nitrogen stream, 20 millimoles of the above acyl derivative, 2.1 g (30 millimoles) of hydroxylamine hydrochloride, and 16.9 g of dimethylformamide were charged into a reactor. After the mixture was stirred at 80° C. for 1 hour, it was cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent was removed by distillation from the liquid constituting the oily phase, and then 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added to the distillation residue. After the mixture was stirred at 90° C. for 1 hour, it was cooled to room temperature and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil-water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and recrystallization was performed using ethyl acetate as a solvent. As described above, a photopolymerization initiator (E1-3) was obtained.

<Synthesis of photopolymerization initiator (E1-4)>
(Step 1)
In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, and 53 mmol of N-(2-ethyl-hexyl)-3-nitrocarbazole compound were charged into an ice-cooled reaction vessel. bottom. 64 millimoles of 4-(2-methoxy-1-methyl-ethoxy)-2-methyl-benzoyl chloride was slowly added dropwise to this mixture while maintaining the reaction temperature below 5°C. After completion of dropping, the mixture was stirred at 20° C. for 4 hours. Thereafter, the reaction liquid was poured into ice water to separate into an oily phase and an aqueous phase, and the liquid constituting the oily phase was dried using magnesium sulfate. The drying agent was removed from this liquid by filtration, and the solvent was further removed by distillation. An acyl derivative was obtained as described above.
(Step 2)
In a nitrogen stream, 20 millimoles of the above acyl derivative, 2.1 g (30 millimoles) of hydroxylamine hydrochloride, and 16.9 g of dimethylformamide were charged into a reactor. After the mixture was stirred at 80° C. for 1 hour, it was cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent was removed by distillation from the liquid constituting the oily phase, and then 25.4 g of butyl acetate and 3.12 g (24 mmol) of propionic anhydride were added to the distillation residue. After the mixture was stirred at 90° C. for 1 hour, it was cooled to room temperature and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil-water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and recrystallization was performed using ethyl acetate as a solvent. As described above, a photopolymerization initiator (E1-4) was obtained.

<Method for producing a photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition (X-1))
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y-1).
Coloring composition (S-1: non-volatile content 20.0%): 50.0 parts binder resin (C2-M: non-volatile content 20.0%): 15.0 parts thermosetting compound (CE-1): 1 .0 parts thermosetting compound (CE-2): 1.0 parts polymerizable compound (D1-1/D2-2): 3.0 parts photopolymerization initiator (E11-1): 1.8 parts sensitization Agent (F): 0.2 parts Thiol chain transfer agent (G): 0.4 parts Polymerization inhibitor (H): 0.1 parts Ultraviolet absorber (I): 0.1 parts Antioxidant (J) : 0.1 part Leveling agent (K: 3% non-volatile content): 1.0 part Storage stabilizer: 0.1 part Silane coupling agent (M): 0.2 part Solvent (N): 26.0 parts

[Examples 2 to 59, Comparative Examples 1 and 2]
(Preparation of photosensitive coloring composition (X-2 to 61))
Photosensitive coloring compositions (X-2 to 61) were prepared in the same manner as in Example 1 except that the types of the coloring composition and binder resin solution of Example 1 were changed as shown in Table 5. Examples 1-44 and 46-59 herein are reference examples.
In addition, about each raw material, it is as follows.

<Thermosetting compound (CE)>
・ Epoxy compound (CE-1)
(CE-1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel Corporation)],
(CE-1-2) Glycidyl-etherified epoxy compound of sorbitol [Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
(CE-1-3) Equal amounts of triglycidyl isocyanurate (CE-1-1) to (CE-1-3) were mixed to obtain an epoxy compound (CE-1).
- Oxetane compound (CE-2):
3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane [aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

<Polymerizable compound (D)>
(D1-1) Ethoxylated isocyanuric acid triacrylate [A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(D1-2) Pentylene chain-containing tris-(2-acryloxyethyl) isocyanurate [A-9300-1CL (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(D2-1) KAYARAD DPCA30 [manufactured by Nippon Kayaku] pentylene chain-containing polyfunctional (meth) acrylate (D2-2) KAYARAD DPCA60 [manufactured by Nippon Kayaku] pentylene chain-containing polyfunctional (meth) acrylate (D1-1 /D2-2): The above (D1-1) and (D2-2) were mixed at a ratio of 80:20.
(D3-M): The same amounts of the following (D3-1) to (D3-5) were mixed to obtain a polymerizable compound (D3-M).
(D3-1) trimethylolpropane triacrylate [Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(D3-2) Dipentaerythritol penta and hexaacrylate (E-2) [Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(D3-3) Polybasic acidic acrylic oligomer [Aronix M520 (manufactured by Toagosei Co., Ltd.)]

(D3-4) Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged into a 1-liter, five-necked reaction vessel synthesized by the following method, reacted at 60 ° C. for 8 hours, (meth ) A product containing polyfunctional urethane acrylate (D3-4) having an acryloyl group was obtained.In the product, the proportion of polyfunctional urethane acrylate (D3-4) is 70% by mass, and the rest is other It was confirmed by IR analysis that no isocyanate group was present in the reaction product.

(D3-5) Bifunctional bisphenol A type (meth)acrylate [ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]

<Photoinitiator (E)>
(E1-1 to E1-4) As described above.
(E11-1) 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one Irgacure 369 (manufactured by BASF Japan) and (E1-1 to E1-4) A mixture of equal amounts of five photopolymerization initiators.
(E2-1) the compound represented by the chemical formula (E2-1) (E2-2) the compound represented by the chemical formula (E2-2) (E21-1) 2-benzyl-2-dimethylamino-1-(4 -Morpholinophenyl)-butan-1-one Irgacure 369 (manufactured by BASF Japan) and three photopolymerization initiators (E2-1 and E2-2) were mixed in equal amounts.
(E1-1/E2-1) Two photopolymerization initiators (E1-1) and (E2-1) are mixed in equal amounts.
(E3-1) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Irgacure 907 (manufactured by BASF Japan)]
(E3-2) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Irgacure 379 (manufactured by BASF Japan)]
(E3-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [Lucirin TPO (manufactured by BASF Japan)]
(E3-4) 2,2′-bis(o-chlorophenyl)-4,5,4′,5′-tetraphenyl-1,2′-biimidazole [Biimidazole (manufactured by Kurogane Kasei Co., Ltd.)]
(E3-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(E3-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime) [Irgacure OXE02 (BASF Japan company)]]
(E3-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one [Irgacure 2959 (manufactured by BASF Japan)]
(E3-8) bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Irgacure 819 (manufactured by BASF Japan)]
The above (E3-1) to (E3-8) were mixed in equal amounts to obtain a photopolymerization initiator (E3-M).

<Sensitizer (F)>
(F-1) 2,4-diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(F-2) 4,4′-bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemmark Chemical)]
The above (F-1) and (F-2) were mixed in equal amounts to obtain a sensitizer (F).

<Thiol-based chain transfer agent (G)>
(G-1) Trimethylolethane tris (3-mercaptobutyrate) [TEMB (manufactured by Showa Denko)]
(G-2) Trimethylolpropane tris(3-mercaptobutyrate) [TPMB (manufactured by Showa Denko)]
(G-3) Pentaerythritol tetrakis (3-mercaptopropionate) [PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(G-4) Trimethylolpropane tris(3-mercaptopropionate) [TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(G-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
The above (G-1) to (G-5) were mixed in equal amounts to obtain a thiol-based chain transfer agent (G).

<Polymerization inhibitor (H)>
(H-1) 3-methylcatechol (H-2) methylhydroquinone (H-3) tert-butylhydroquinone and above, (H-1) to (H-3) are mixed in equal amounts, and a polymerization inhibitor is added. (H).

<Ultraviolet absorber (I)>
(I-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 , 3,5-triazine [TINUVIN400 (manufactured by BASF Japan)]
(I-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (manufactured by BASF Japan)]
The above (I-1) and (I-2) were mixed in the same amount to prepare the UV absorber (I).

<Antioxidant (J)>
(J-1) pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (J-2) dioctadecyl 3,3′-thiodipropanoate (J-3) tris[2 ,4-di-(tert)-butylphenyl]phosphine (J-4) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (J-5) p-octylphenyl salicylate or more, (J -1) to (J-5) were mixed in equal amounts to obtain an antioxidant (J).

<Leveling agent (K)>
1 part of "BYK-330: polyether-modified polydimethylsiloxane" manufactured by BYK Chemie,
1 part of "Megafac F-551: fluorine-containing group/lipophilic group-containing oligomer" manufactured by DIC,
A mixed solution prepared by dissolving 1 part of "Emulgen 103: polyoxyethylene lauryl ether" manufactured by Kao Corporation in 97 parts of propylene glycol monomethyl ether acetate.

<Storage stabilizer>
(L-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol ("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)
(L-2) Triphenylphosphine (“TPP” manufactured by Hokko Chemical Industry Co., Ltd.)
Equal amounts of (L-1) and (L-2) were mixed to obtain a storage stabilizer.

<Adhesion improver>
(M-1) 3-glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-2) 3-methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-4) 3-mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
The above (M-1) to (M-4) were mixed in equal amounts to prepare an adhesion improver.

<Solvent (N)>
(N-1) 20 parts of cyclohexanone (N-2) 20 parts of ethyl 3-ethoxypropionate (N-3) 20 parts of propylene glycol monomethyl ether (N-4) 20 parts of cyclohexanol acetate (N-5) dipropylene glycol 20 parts of methyl ether acetate (N-1) to (N-5) were mixed in the above parts by mass to obtain a solvent (N).

<Evaluation of photosensitive coloring composition>
Evaluation of the photosensitive coloring composition was performed as follows. Table 6 shows the results.

[Filter segment formation]
After applying the obtained photosensitive coloring composition to a glass substrate of 10 cm long×10 cm wide by spin coating, the solvent was removed by heating in a clean oven at 70° C. for 15 minutes to obtain a film of about 2 μm. rice field. Then, after cooling the glass substrate to room temperature, it was exposed to ultraviolet light through a photomask having a stripe pattern of 100 μm width (pitch: 200 μm) and 25 μm width (pitch: 50 μm) using an extra-high pressure mercury lamp. Thereafter, the substrate was developed by spraying with an aqueous solution of sodium carbonate at 23° C., washed with deionized water, air-dried, and heated in a clean oven at 230° C. for 30 minutes to produce a filter segment. The spray development was carried out for the shortest time possible to form a pattern with no development residue, and this was taken as the appropriate development time. In addition, the film thickness of the coating film was measured using Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.).

[Sensitivity evaluation]
The thickness of the pattern in the 100 μm photomask portion of the obtained filter segment was measured, and the minimum exposure amount at which 90% or more of the thickness immediately after coating was obtained was evaluated. The smaller the minimum exposure amount, the higher the sensitivity and the better the photosensitive coloring composition is evaluated. Evaluation criteria are as follows.
○: less than 50 mJ/cm ² (good)
△: 50 mJ/cm ² or more and less than 100 mJ/cm ² (practical range)
×: 100 mJ/cm ² or more (not practical)

<Pattern shape evaluation>
[Linearity evaluation]
The linearity of the pattern at the 100 μm photomask portion of the obtained filter segment was observed and evaluated using an optical microscope. Evaluation criteria are as follows.
○: good linearity (good)
△: Partially poor linearity (slight chipping) (practical range)
×: Poor linearity (not practical)

[Cross-sectional shape evaluation]
The cross section of the pattern at the 100 μm photomask portion of the obtained filter segment was observed and evaluated using an electron microscope. Evaluation criteria are as follows. It should be noted that the forward taper of the cross section of the turn is good.
〇: Forward tapered shape with gentle cross section (good)
△: Cross section is forward tapered shape (practical range)
×: Reverse tapered cross section (impossible to use)

<Regarding coating resistance>
[Solvent resistance evaluation]
The resulting filter segment was immersed in an N-methylpyrrolidone solution for 30 minutes, washed with deionized water, air-dried, and the pattern on the 100 μm photomask portion was observed and evaluated using an optical microscope. Evaluation criteria are as follows.
○: Good with no change in appearance or color (good)
△: Some wrinkles, etc. occur, but the color does not change and is good (practical range)
×: Color fading occurs (not practical)

From the results of Table 6, Examples 1 to 59 contain a diketopyrrolopyrrole pigment, and the photopolymerizable compound (D) is an isocyanurate ring-containing photopolymerizable compound [D1], and an alkylene chain-containing photopolymerizable compound. At least one of [D2] is contained, and good sensitivity, pattern linearity, cross-sectional shape, and solvent resistance can be obtained.

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

Claims (6)

Contains a pigment (A), a dispersant (B), a binder resin (C), a photopolymerizable compound (D), and a photopolymerization initiator (E),
The pigment (A) includes pigments represented by the following chemical formula (1) and C.I. I. Pigment Red 254, C.I. I. Pigment Red 242, C.I. I. Pigment Red 177, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185, and one or more selected from the group consisting of yellow pigments represented by the following general formula (3),
Photopolymerizable compound (D) is a photosensitive coloring composition containing ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate .
chemical formula (1)

General formula (3)

[In general formula (3), Z ₁ to Z ₁₃ each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, or a substituent an aryl group that may have, —SO ₃ H, —COOH, and monovalent to trivalent metal salts, alkylammonium salts, phthalimidomethyl groups that may have substituents, or substituents of these acidic groups; represents a sulfamoyl group which may have,
Adjacent groups of Z ₁ to Z ₄ and/or Z ₁₀ to Z ₁₃ may combine together to form an aromatic ring which may have a substituent. ] 2. The photosensitive coloring composition according to claim 1, wherein the pigment (A) contains a pigment represented by the following general formula (2).
general formula (2)

[In the general formula (2), X represents a chlorine atom or a bromine atom, and A and B each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a -12 alkyl groups, optionally substituted phenyl groups, -CF ₃ , -OR ¹ , -SR ² , -N(R ³ )R ⁴ , -COOR ⁵ , -CONH ₂ , -CONHR ⁶ , —CON(R ⁷ )R ⁸ , —SO ₂ NH ₂ , —SO ₂ NHR ⁹ , or —SO ₂ N(R ¹⁰ )R ¹¹ , and R ¹ to R ¹¹ each independently represent the number of carbon atoms; 1 to 12 alkyl groups, optionally substituted phenyl groups, or optionally substituted aralkyl groups. However, A and B cannot be hydrogen atoms at the same time. Also, A is not X and B is a hydrogen atom, nor is B both X and A a hydrogen atom. ] 3. The photosensitive coloring composition according to claim 1, further comprising an antioxidant. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the content of the pigment (A) is 30 to 70% by weight in the non-volatile content of the photosensitive coloring composition. A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition according to any one of claims 1-4. A liquid crystal display device comprising the color filter according to claim 5 .

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