JP2021060539A - Photosensitive coloring composition, color filter and display device - Google Patents

Abstract

To provide a photosensitive coloring composition that can form a pixel with excellent adhesion to a base material and little decrease in brightness by heating.SOLUTION: A photosensitive coloring composition contains an organic pigment (A), a resin type dispersant (B), a photopolymerizable compound (C), a photopolymerizable initiator (D), a compound (E1) having an alicyclic epoxy group, and an alkali-soluble resin (F). The organic pigment (A) contains a diketopyrrolopyrrole-based organic pigment (A1) and/or at least one organic pigment (A2) selected from the group consisting of represented by an organic pigment the following formula and a specific azo-based organic pigment.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive coloring composition used for producing a color filter used in a color liquid crystal display device, a color solid-state image sensor, an organic EL display device, a quantum dot display device, and a display device such as electronic paper.

The black matrix and color filter segments (hereinafter, may be referred to as pixels and coatings) constituting the color filter are often produced by a photolithography method, and solvent resistance is emphasized.

Patent Document 1 discloses a photosensitive coloring composition containing a polymer having an oxylanyl group or an oxetanyl group.

Japanese Unexamined Patent Publication No. 2015-194735

However, the conventional photosensitive coloring composition has problems of how to improve the adhesion to the substrate and how to suppress the change in chromaticity due to heating of the formed film.

An object of the present invention is to provide a photosensitive coloring composition having good adhesion to a substrate and capable of forming pixels having a small change in chromaticity even after heating.

The present invention relates to an organic pigment (A), a resin-type dispersant (B), a photopolymerizable compound (C), a photopolymerizable initiator (D), a compound having an alicyclic epoxy group (E1), and an alkali-soluble substance. A photosensitive coating composition containing a resin (F).
The organic pigment (A) is one selected from the group consisting of the diketopyrrolopyrrole organic pigment (A1) and / or the organic pigment represented by the following general formula (1) and the organic pigment represented by the following general formula (2). Including the above organic pigment (A2)
The thermosetting compound (E) relates to a photosensitive coloring composition containing a compound (E1) having an alicyclic epoxy group.

General formula (1)

[In the general formula (1), R ₁ is a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. Represents. R ₂ and R ₃ independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
Each of X _{1 to} X ₄ is independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group, a carboxyl group, or a sulfo group. , Or represents a halogen atom. ]

General formula (2)

[In the general formula (2), R ₄ is a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. Represents. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X _{5 to} X ₁₂ each independently contain a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group, or a halogen atom. Represent. A is a direct bond, an optionally substituted alkylene group, -O -, - S -, - CO -, - SO 2 -, - COO -, - CONH-, or a _-SO 2 NH- Represent. ]

The present invention also relates to the above-mentioned photosensitive coloring composition containing 0.01 to 10% by mass of the compound (E1) having an alicyclic epoxy group in 100% by mass of the non-volatile content of the photosensitive coloring composition.

The present invention also relates to the above-mentioned photosensitive coloring composition in which the epoxy equivalent of the compound (E1) having an alicyclic epoxy group is 160 g / eq or less.

Further, in the present invention, the alkali-soluble resin (F) is selected from the group consisting of the following resins (I) and resin (II), and the alkali-soluble resin (F1) having a carboxyl group and a polymerizable unsaturated bond in the side chain. ), The above-mentioned photosensitive coloring composition.
Resin (I) A resin resin obtained by further reacting a polybasic acid anhydride with a reaction product of an epoxy group in an epoxy group-containing monomer and a copolymer of other monomers and a carboxyl group of a carboxyl group-containing monomer ( II) A resin that is a reaction product of a carboxyl group in a carboxyl group-containing monomer and a copolymer of other monomers and an epoxy group of an epoxy group-containing monomer.

The present invention also relates to a color filter including a base material and a color filter segment formed of the above-mentioned photosensitive coloring composition.

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

According to the present invention, it is possible to provide a photosensitive coloring composition, a color filter, and a display device which have good adhesion to a substrate and can form pixels having a small change in chromaticity even after heating.

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

The terminology of the present specification is defined. "(Meta) acryloyl,""(meth)acrylic,""(meth) acrylic acid,""(meth)acrylate," or "(meth) acrylamide" are "acryloyl and / or methacrylic," respectively. And / or methacrylic "," acrylic acid and / or methacrylic acid "," acrylate and / or methacrylate ", or" acrylamide and / or methacrylic acid ".
"CI" is a color index (CI). Colorants include pigments and dyes. The monomer is a polymerizable unsaturated group-containing monomer. The polymerizable unsaturated group is a (meth) acryloyl group, a vinyl group, or an allyl group.

The photosensitive coloring composition of the present invention comprises an organic pigment (A), a resin-type dispersant (B), a photopolymerizable compound (C), a photopolymerizable initiator (D), and a compound having an alicyclic epoxy group (a compound having an alicyclic epoxy group. E1) and the alkali-soluble resin (F) are included, and the organic pigment (A) is a diketopyrrolopyrrole organic pigment (A1) and / or an organic pigment represented by the following general formula (1) and the following general formula (2). Includes one or more organic pigments (A2) selected from the group consisting of organic pigments shown in.

General formula (1)

[In the general formula (1), R ₁ is a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. Represents. R ₂ and R ₃ independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
Each of X _{1 to} X ₄ is independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group, a carboxyl group, or a sulfo group. , Or represents a halogen atom. ]

General formula (2)

[In the general formula (2), R ₄ is a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. Represents. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X _{5 to} X ₁₂ each independently contain a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group, or a halogen atom. Represent. A is a direct bond, an optionally substituted alkylene group, -O -, - S -, - CO -, - SO 2 -, - COO -, - CONH-, or a _-SO 2 NH- Represent. ]

<Organic pigment (A)>
The organic pigment (A) is a colorant. The colorant may contain a dye or an inorganic pigment, if necessary.
The organic pigment (A) contains a diketopyrrolopyrrole red pigment (A1). The diketopyrrolopyrrole red pigment (A1) is, for example, C.I. I. Pigment Red 254, 255, 264, 270, 272, 283, 291 and pigments represented by the following general formula (4) can be mentioned. Among these, C.I. I. Pigment Red 254,291 and the pigment represented by the following general formula (4) are preferable.

General formula (4)

In the general formula (4), X represents a chlorine atom or a bromine atom, and A and B independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, and 1 carbon atom. Alkyl group of ~ 12, phenyl group which may have 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 have independent carbon atoms. It is an alkyl group of 1 to 12, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. However, A and B do not become hydrogen atoms at the same time. Further, X is A and B is not a hydrogen atom, X is B and A is not a hydrogen atom.

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

The phenyl group which may have a substituent is, for example, 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, an alkoxyl having 1 to 4 carbon atoms. Examples thereof include a phenyl group having a substituent such as a group. 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. Examples include a phenyl group.

Aralkyl groups that may have a substituent include, for example, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group. And so on.

The pigments represented by the general formula (4) in the present specification are 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). It is preferable that it is one or more selected from the group consisting of. As a result, the brightness and contrast are further improved, and crystals are less likely to precipitate.

In the general formula (4-1), the general formula (4-2), the general formula (4-3), and the general formula (4-4), X independently represents a chlorine atom or a bromine atom, respectively. Further, in the general formula (4-3) and the general formula (4-4), R ^{12 to} R ¹⁴ are phenyl groups which may independently have an alkyl group having 1 to 12 carbon atoms or a substituent. is there. R ¹³ and R ¹⁴ may form a ring.
^{The contrast and crystal that R 12 to} R ¹⁴ of the general formula (4-3) and the general formula (4-4) are an alkyl group having 4 or more carbon atoms or a phenyl group which may have a substituent. It is preferable in terms of suppressing precipitation.
The effect of improving contrast and suppressing crystal precipitation is that the phenyl group directly linked to the diketopyrrolopyrrole skeleton has a bulky substituent such as a carboamide group, a phenyl group, or a t-butyl group having an alkyl group having 4 or more carbon atoms. It is speculated that the aggregation of the pigment is suppressed by the steric hindrance effect.

<Organic pigment (A2)>
The organic pigment (A) further preferably contains one or more pigments (A2) selected from the group consisting of the pigment represented by the following general formula (2) and the pigment represented by the following general formula (3).

一般式（２）

General formula (2)

In the general formula (2), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aryloxy group which may have a substituent. R ₂ and R ₃ independently represent a hydrogen atom, an alkyl group which may have a substituent, and a phenyl group which may have a substituent.
X _{1 to} X ₄ are independently hydrogen atoms, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group, a carboxyl group, and a sulfo group. , Represents a halogen atom.

一般式（３）

General formula (3)

In the general formula (3), R ₄ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aryloxy group which may have a substituent. R ₅ and R ₆ independently represent a hydrogen atom, an alkyl group which may have a substituent, and a phenyl group which may have a substituent.
X _{5 to} X ₁₂ independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group, and a halogen atom. A represents a direct bond or a divalent linking group. As the divalent linking group, an alkylene group which may have a substituent, -O-, -S-, -CO-, -SO _2- , -COO-, -CONH-, and -SO ₂ NH- are used. Represent.

<Other pigments>
The pigments and dyes that can be contained in the photosensitive coloring composition of the present specification are exemplified below.

The red pigment is, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 256, 257, 258, 259, 260, 262, 263, 265, 266, 267, 268, 269, 271, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 284, 285, 286, 287, 295 and the like can be mentioned. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of pixels, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 269, 295, preferably C.I. I. Pigment Red 177, 295 is more preferred.

In addition, C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, 73 and other orange pigments and yellow pigments can be used in combination.

The yellow pigment is, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231,233 and the like can be mentioned. Among these, C.I. I. Pigment Yellow 138,231,233, and the pigments described in JP-A-2012-226110 are preferable.

Inorganic pigments include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, etc. Synthetic iron black and the like can be mentioned.

<Pigment miniaturization>
When an organic pigment is used, it is preferable to perform a miniaturization treatment and then mix it with another material. Examples of the miniaturization treatment method include wet grinding, dry grinding, dissolution and precipitation, and the like. Among these, salt milling treatment by the kneader method, which is a kind of wet grinding, is preferable. The average primary particle size of the organic pigment after the miniaturization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. The appropriate particle size further improves the dispersibility and the contrast ratio of the coating film. The average primary particle size is an average value of about 20 particles arbitrarily selected from a magnified image of a TEM (transmission electron microscope). If there is a vertical axis length and a horizontal axis length of the particles, the vertical axis length is used.

The salt milling treatment is a batch of a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent, for example, a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, a sand mill, a planetary type mixer, or the like. This is a process of mechanically kneading while heating using a formula or continuous kneader, and then removing the water-soluble inorganic salt and the water-soluble organic solvent by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate and the like. Among these, sodium chloride (salt) is preferable from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, based on 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. A water-soluble organic solvent is a compound that dissolves (mixes) in water and does not substantially dissolve a water-soluble inorganic salt. The water-soluble organic solvent is preferably a high boiling point solvent having a boiling point of 120 ° C. or higher in terms of being less likely to volatilize due to a temperature rise during salt milling. 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, and the like. Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Can be mentioned. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

Resin can be added as needed during the salt milling process. Examples of the resin include a natural resin, a modified natural resin, a synthetic resin, and a synthetic resin modified with a natural resin. The resin is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in a water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

<Dye>
Examples of the dye include acidic dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, medium dyes, construction dyes, sulfide dyes and the like. In addition, a derivative of a dye and a rake pigment obtained by leaking a dye can also be mentioned.

The dye is an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, or in the case of a direct dye, an inorganic salt of the acidic dye; an acidic dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, a salt-forming compound with a primary amine compound; a resin component having these amino groups and a salt-forming compound such as an acidic dye can be mentioned. A salt-forming compound of an acid dye and a compound having an onium base is also preferable because it has excellent fastness. The compound having an onium base is preferably a resin having a cationic group in the side chain.

Examples of the basic dye include organic acids, perchloric acids, and salt-forming compounds with these metal salts. Among the salt-forming compounds, salt-forming compounds of basic dyes are preferable because they are excellent in various resistances and compatibility with pigments.

The chemical structure of the dyes is, for example, azo dyes, disazo dyes, azomethine dyes (Indoaniline dyes, Indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes). Dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acrydin dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes , Polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, Examples thereof include perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rodamine dyes. Among these, from the viewpoint of color characteristics such as hue, color separability, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, Kinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferable. The specific structure of dyes is "New Edition Dye Handbook" (edited by Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colorists), "Dye Handbook" (edited by Okawara et al. It is described in.

<Dye derivative>
The photosensitive coloring composition may contain a dye derivative, if necessary. The dye derivative is a dispersion aid and is a compound having an acidic group, a basic group, a neutral group or the like in the organic dye residue. The dye derivative has, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphorus acidic group, and a basic substituent such as an amine salt, a sulfonamide group, or a tertiary amino group at the terminal thereof. Examples thereof include compounds and compounds having a neutral substituent such as a phenyl group and a phthalimidealkyl group.
Organic pigments include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzoiso. Indol pigments such as indole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo, disazo, polyazo and other azo pigments, etc. Can be mentioned.

The dye derivative may be used alone or in combination of two or more.

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 with respect to 100 parts by mass of the pigment.

When a pigment derivative is added to a pigment and pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, solvent salt milling, etc. is performed so that the pigment derivative is adsorbed on the pigment surface and the pigment derivative is not added. The primary particles of the pigment can be made finer as compared with the above.

By adding a dye derivative to the pigment and performing dispersion treatment such as wet dispersion using two rolls, three rolls, and beads, the dye derivative is adsorbed on the pigment surface and the pigment surface is polar, and the resin type dispersant is adsorbed. Is promoted, compatibility with pigments, pigment derivatives, resin-type dispersants, solvents, and other additives is improved, and dispersion stability and temporal viscosity stability when made into a coloring composition or a coloring curable composition are improved. To do. Further, by improving the compatibility, the photosensitive coloring composition is excellent in stability over time when the photosensitive coloring composition is applied to a glass substrate or the like, and the waiting time from application to exposure of the coloring curable composition (PCD: Post Coating). Stability and characteristic dependence such as pattern shape with respect to Delay) and waiting time from exposure to heat treatment (PED: Post Exposure Delay), and line width sensitivity stability are improved. Further, by adsorbing and coating the pigment surface with the pigment derivative and the resin type dispersant, it is possible to suppress crystal precipitation due to aggregation and sublimation of the pigment when the coating film is heated and fired. Furthermore, variations in development time and development residues are suppressed.

<Resin type dispersant (B)>
The resin-type dispersant (B) has a colorant-affinity site that adsorbs to the organic pigment (A) and a relaxation site that has a high affinity for components other than the colorant and causes steric repulsion between the dispersed particles. The resin-type dispersant (B) is, for example, a urethane-based dispersant such as polyurethane, a polycarbonic acid ester such as polyacrylate, an unsaturated polyamide, a polycarbonic acid, a polycarbonic acid (partial) amine salt, an ammonium polycarbonate salt, and an alkyl polycarbonate. Amine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarbonic acid esters and their modifications; amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups and their amides. Salts; (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc .; polyester, modified polyacrylate, Examples thereof include ethylene oxide / propylene oxide addition compounds and phosphoric acid ester-based compounds.

Examples of the acidic resin type dispersant include resins having a phosphoric acid group, a carboxyl group, or a sulfo group as acidic groups. Among these, a resin having a carboxyl group is preferable, and an aromatic carboxylic acid is more preferable. The acidic resin type dispersant is preferably a resin having a heat-crosslinking group. Examples of the thermally crosslinkable functional group include a hydroxyl group, an oxetane group, a t-butyl group, and a blocked isocyanate group. Of these, the oxetane group is preferable.

The basic resin type dispersant has a nitrogen atom-containing graft copolymer and a nitrogen atom-containing acrylic block copolymer having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc. in the side chain. Examples thereof include coalescing and urethane-based polymer dispersants.
Further, the basic resin type dispersant can also be used by neutralizing the basic group with phosphoric acid or sulfonic acid.

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

The content of the resin type dispersant (B) is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, based on the total amount of the colorant. When an appropriate amount is contained, a film is easily formed.

<Photopolymerizable compound (C)>
The photopolymerizable compound (C) is a compound having a polymerizable unsaturated group, and is a monomer or oligomer that is cured by ultraviolet rays, heat, or the like to produce a transparent resin.

The photopolymerizable compound (C) is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxy. Ethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethyl propantri (meth) Acrylate, Phenoxytetraethylene glycol (meth) acrylate, Phenoxyhexaethylene glycol (meth) acrylate, Trimethylolpropane PO-modified tri (meth) acrylate, Trimethylolpropane EO-modified tri (meth) acrylate, Isocyanuric acid EO-modified di (meth) Acrylate, EO-modified tri (meth) acrylate of isocyanuric acid, ditrimethylolpropanetetra (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) Various acrylic acid esters and methacrylate esters such as acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol di Examples thereof include vinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

Further, as the photopolymerizable compound (C), a compound having an acidic group is also preferable. Examples of the acidic group include a sulfone acidic group, a carboxyl group, and a phosphorus acidic group.

Compounds having an acidic group include, for example, esters of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid and dicarboxylic acids; polyhydric carboxylic acid and monohydroxyalkyl (meth). Examples thereof include esterified products with acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropane diacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. , Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxy Examples thereof include monohydroxymonoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates.

As the photopolymerizable compound (C), a urethane bond-containing compound is also preferable. Urethane bond-containing compounds include, for example, a polyfunctional urethane acrylate obtained by reacting a hydroxyl group-containing monomer with a polyfunctional isocyanate, a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate, and further reacting the hydroxyl group-containing monomer. Can be mentioned.

The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylol propanetri (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate methacrylate, glycerol Examples thereof include dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth) acrylate, and a hydroxyl group-containing polyol polyacrylate.

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

The photopolymerizable compound (C) can be used alone or in combination of two or more.

The content of the photopolymerizable compound (C) is preferably 1 to 50% by mass, more preferably 2 to 40 parts by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, curability and developability are further improved.

<Photopolymerizable initiator (D)>
The photopolymerizable initiator (D) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1. -On, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1- [4- (4- (4- (4-) Morphorino) phenyl] -2- (phenylmethyl) -1-butanone, or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1 -Acetophenone compounds such as butanone; benzophenones such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, Benzophenone compounds such as hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3', 4,4'-tetra (t-butylpaoxycarbonyl) benzophenone; thioxanthone, 2-chlor. Thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6- Bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- Triazine compounds such as (piperonyl) -6-triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) pheni Lu-, 2- (O-benzoyloxime)], or etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole 3-yl]-, 1- (O-acetyloxime), etc. Oxime ester compounds; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrene quinone, camphor -Kinone-based compounds such as quinone and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanosen-based compounds and the like can be mentioned. Among these, oxime ester compounds are preferable.

(Oxime ester compound)
When an oxime ester compound absorbs ultraviolet rays, the NO bond of the oxime is cleaved to generate an iminyl radical and an alkyroxy radical. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the curing degree of the coating film may be low, but the oxime ester compound has high quantum efficiency and can be suitably used. ..

Oxime ester compounds are described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-0372223, JP-A-2010-215575, JP-A-2011-02998, and the like. Oxime ester-based photopolymerization initiators can be mentioned.

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

The content of the photopolymerizable initiator (D) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the colorant. When an appropriate amount is blended, the photocurability and developability are further improved.

<Sensitizer>
The photosensitive coloring composition may further contain a sensitizer.
The sensitizer includes, for example, chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, etc. Polymethine dyes such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonor derivatives, aclysine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azulenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triallylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospyropyrane derivative, Metal allene complex, Organic ruthenium complex, or Mihira-ketone derivative, α -Acyloxyester, acylphosphine oxide, methylphenylglycolate, benzyl, 9,10-phenanthrene quinone, campha-quinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or Examples thereof include 4,4'-tetra (t-butylpaoxycarbonyl) benzophenone and 4,4'-bis (diethylamino) benzophenone.

Among these, thioxanthone derivatives, Mihira-ketone derivatives, and carbazole derivatives are preferable. For example, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis (dimethylamino). Benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole Etc. are more preferable.

The 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, based on 100 parts by mass of the photopolymerizable compound (C). When an appropriate amount is contained, curability and developability are further improved.

<Compound having an alicyclic epoxy group (E1)>
By containing the compound (E1) having an alicyclic epoxy group in the photosensitive coloring composition, for example, when producing a color filter, in addition to improving solvent resistance and adhesion to a substrate, heating is performed. It is possible to form pixels with less decrease in brightness due to the above. The epoxy equivalent of the compound (E1) having an alicyclic epoxy group is preferably 160 g / eq or less. As a result, the reaction during heating is efficiently generated, so that the solvent resistance is improved, and the decrease in brightness due to heating can be further suppressed. The compound having an alicyclic epoxy group is preferably a compound having no resin skeleton such as a vinyl resin.

Examples of the compound having an alicyclic epoxy group of a low molecular weight compound include a monofunctional or bifunctional alicyclic epoxy compound.

Monofunctional alicyclic epoxy compounds include, for example, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethylmethacrylate, cyclohexeneoxide, 3-methacryloyloxymethylcyclohexeneoxide, 3-acryloyloxymethyl. Cyclohexene oxide, 3-vinylcyclohexene oxide and the like can be mentioned.

Bifunctional alicyclic epoxy compounds include, for example, limonendiepoxide, 1-methyl-4- (2-methyloxylanyl) -7-oxabicyclo [4.1.0] heptane, 3', 4'-. Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, ε-caprolactone-modified 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and the like can be mentioned.

The compound having a cyclic epoxy group of the polymer compound is composed of the compound represented by the following general formula (e-1), the compound represented by the following general formula (e-2), and the compound represented by the following general formula (e-3). One or more monomers selected, as well as polymers of other monomers are preferred.

General formula (e-1)

In the general formula (e-1),
R ¹ represents a hydrogen atom or a methyl group.
X ¹ represents an alkanediyl group having 1 to 6 carbon atoms which may contain a single bond or a heteroatom.

General formula (e-2)

General formula (e-3)

In the general formula (e-2) and the general formula (e-3),
R ² represents a hydrogen atom or a methyl group independently of each other.
X ² represents an alkanediyl group having 1 to 6 carbon atoms, which may contain a single bond or a heteroatom independently of each other. ]

The alkanediyl groups having 1 to 6 carbon atoms in ^{X 1} and X ^{2 may be linear or branched.} For example, methylene group, ethylene group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2- Diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples thereof include a 1,5-diyl group and a hexane-1,6-diyl group. Among these, an alkanediyl group having 1 to 4 carbon atoms is preferable, and an alkanediyl group having 1 or 2 carbon atoms is more preferable.
The alkanediyl group having 1 to 6 carbon atoms may contain a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like. The alkanediyl group containing the heteroatom is, for example, (*)-CH ₂ CH _2- O-, (*) -CH _2- O-CH _{2- , (*) -CH 2} CH _2- S-, (*)-CH 2 CH 2-S-, *) -CH _2- S-CH _2- , (*) -CH ₂ CH _2- NH-, (*) -CH _2- NH-CH _2-, and the like can be mentioned. However, (*) means a bond with −COO−.

Examples of the compound represented by the general formula (e-1) include 3,4-epoxycyclohexylmethylmethacrylate and 3,4-epoxycyclohexylmethylacrylate.

The content of the compound having an alicyclic epoxy group is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the adhesion and the decrease in brightness can be further suppressed.

In addition to the compound (E1) having an alicyclic epoxy group, other thermosetting compounds can be used in combination.

The content of the compound (E1) having an alicyclic epoxy group and other thermosetting compounds is preferably 0.02 to 15% by mass, preferably 0.05 to 15% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. 5% by mass is more preferable.

<Other thermosetting compounds>
Examples of the thermosetting compound include low molecular weight compounds and high molecular weight compounds. Low-molecular-weight compounds are preferable because they have a high degree of freedom of molecular motion in the curing process and therefore have high reactivity.
The thermosetting compounds include, for example, an epoxy compound having no alicyclic epoxy group, a compound having an oxetanyl group, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound. Can be mentioned.

<Compound having an oxetanyl group>
The compound having an oxetanyl group is a compound having an oxetanyl group, and examples thereof include a low molecular weight compound and a high molecular weight compound. Among these, a polymer compound (resin) is preferable.
Examples of the resin having an oxetanyl group include an oxetanyl group-containing monomer and a polymer of other monomers.

(Oxetanyl group-containing monomer)
Examples of the oxetanyl group-containing monomer include (vinyloxyalkyl) alkyloxetane, (meth) acryloyloxyalkyl oxetane, and [(meth) acryloyloxyalkyl] alkyl oxetane. Of these, methyl methacrylate (3-ethyloxetane-3-yl) methyl is preferable.

[Other monomers]
Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl ( Alkyl (meth) acrylates such as meta) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, and isobolyl (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;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) N-substituted (meth) acrylamides such as acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholin;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
Examples thereof include nitriles such as (meth) acrylonitrile.

Further, 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, and fatty acid vinyls such as vinyl acetate and vinyl propionate can also be mentioned. ..

Examples of the compound having a low molecular weight oxetanyl group include a monofunctional oxetanyl group-containing compound and a bifunctional oxetanyl group-containing compound.

The monofunctional oxetane group-containing compound is, 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- ( Triethoxysilyl) propoxy] methyl} oxetane and the like.

Bifunctional oxetanyl group-containing compounds include, for example, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl) and 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl]. Ethylene, 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 -Subis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (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) -Oxetanylmethyl) ether and the like can be mentioned.

The content of the compound having an oxetanyl group is preferably 0.5 to 8% by mass, more preferably 1 to 5% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the chemical resistance of the coating film is further improved.

<Alkali-soluble resin (F)>
The alkali-soluble resin (F) is a resin that has an acidic group and can be dissolved in a developing solution. The alkali-soluble resin (F) is a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm.
As the alkali-soluble resin (F), the alkali-soluble resin is preferably a thermoplastic resin having an acidic group. Examples of the acidic group include a carboxyl group and a sulfone group. The alkali-soluble resin is, for example, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or an isobutylene /. (Anhydrous) maleic anhydride copolymer and the like can be mentioned. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferable in terms of developability, heat resistance, and transparency, and an acrylic resin having an acidic group is more preferable.

Further, in the present specification, the alkali-soluble resin (F) is a photosensitive alkali-soluble resin (F1) having a polymerizable unsaturated bond (hereinafter, an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated bond in a side chain (hereinafter, an alkali-soluble resin). It is preferable to appropriately select and use from F1)), a non-photosensitive alkali-soluble resin having no polymerizable unsaturated bond. The transmittance is preferably 95% or more.

<Alkali-soluble resin (F1) having a carboxyl group and a polymerizable unsaturated bond in the side chain>
As the alkali-soluble resin (F1) having a carboxyl group and a polymerizable unsaturated bond in the side chain, a resin selected from the following resins (I) and resin (II) can be preferably used.
Resin (I) A resin obtained by reacting a polybasic acid anhydride with a product of an epoxy group-containing monomer and an epoxy group in a copolymer of other monomers and a carboxyl group-containing monomer.
Resin (II) A resin which is a reaction product of a carboxyl group in a carboxyl group-containing monomer and a copolymer of other monomers and an epoxy group-containing monomer.

In the resin (I), a hydroxyl group is generated when the carboxyl group of the carboxyl group-containing monomer is reacted with the epoxy group in the copolymer of the epoxy group-containing monomer and other monomers, and then the hydroxyl group of the reaction product and the polybasic acid. It is obtained by reacting an anhydride group of an anhydride. The resin (I) has a polymerizable unsaturated group derived from a carboxyl group-containing monomer and a carboxyl group derived from the polybasic acid anhydride in the side chain.
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 (. Meta) acrylate and the like can be mentioned. Among these, glycidyl (meth) acrylate, which has high reactivity with a carboxyl group-containing monomer, is preferable.

The carboxyl group-containing monomer is monocarboxylic acid such as (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted products. Examples include acid.

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl ( Meta) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isoborenyl (meth) acrylate, phenyl (meth) (Meta) acrylates such as acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene glycol (meth) acrylate,
Alternatively, (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholin. Acrylamides styrenes, styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ethers, n-propyl vinyl ethers, isopropyl vinyl ethers, n-butyl vinyl ethers, or isobutyl vinyl ethers, vinyl acetates, and fatty acid vinyls such as vinyl propionate. etc;

Cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidecoumarin, 4,4'-Bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimoleimide, N, N'-1,4-phenylenedi Maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl maleimide, N-Bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl -6-Maleimide hexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, N-substituted maleimides such as 9-maleimideacrinedin, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl Acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO) -modified (meth) acrylate of phenol, EO or propylene oxide (PO) -modified (meth) acrylate of paracumylphenol, EO-modified (meth) acrylate of nonylphenol, PO-modified of nonylphenol Examples include (meth) acrylate.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like. If necessary, such as by increasing the number of carboxyl groups, a method using a tricarboxylic dianhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride remained. Anhydrous groups can also be hydrolyzed before use.

The resin (II) is obtained by reacting a part of the carboxyl groups in the copolymer of the carboxyl group-containing monomer and other monomers with the epoxy group of the epoxy group-containing monomer. The resin (II) has a carboxyl group derived from the carboxyl group-containing monomer and a polymerizable unsaturated group derived from the epoxy group-containing monomer in the side chain.

As the epoxy group-containing monomer, the carboxyl group-containing monomer, and other monomers, the monomers exemplified in the resin (I) can be used.

As the photosensitive alkali-soluble resin having a polymerizable unsaturated bond, other photosensitive alkali-soluble resin can be used in addition to the photosensitive alkali-soluble resin (F1) having a carboxyl group and a polymerizable unsaturated bond in the side chain. ..

<Other photosensitive alkali-soluble resins>
As the other photosensitive alkali-soluble resin, a resin synthesized by the following method is preferable. For example, a resin obtained by reacting an isocyanate group of an isocyanate group-containing monomer with a hydroxyl group of a side chain of a copolymer obtained by copolymerizing a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and another monomer. Is. As the carboxyl group-containing monomer and other monomers, the monomers exemplified in (I) above can be used.

The hydroxyl group-containing monomer includes, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and the like. Alternatively, hydroxyalkyl methacrylates such as cyclohexanedimethanol mono (meth) acrylate can be mentioned. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth) acrylate, poly γ-valerolactone, poly ε-caprolactone, and / or poly. Examples thereof include polyester mono (meth) acrylates to which 12-hydroxystearic acid and the like are added. Among these, 2-hydroxyethyl methacrylate and glycerol mono (meth) acrylate are preferable in terms of suppressing foreign substances in the pixels. Further, in terms of sensitivity, a monomer having 2 to 6 hydroxyl groups is preferable, and glycerol mono (meth) acrylate is more preferable.

Examples of the isocyanate group-containing monomer include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 1,1-bis [methacryloyloxy] ethyl isocyanate.

Examples of other monomers that can form the alkali-soluble resin include N-substituted maleimides, alkyleneoxy group-containing monomers, phosphoric acid ester group-containing monomers, and carboxyl group-containing monomers, in addition to the other monomers already described.
N-substituted maleimides include, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-. 4-Methyl-3-maleimidecoumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimoleimide, N, N'-1,4-phenylenedi maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitro) Phenyl) Maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4- Maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, 9-maleimide acrydin and the like can be mentioned. The alkyleneoxy group-containing monomer includes, for example, EO-modified cresol acrylate, n-nonylphenoloxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO) -modified (meth) acrylate of phenol, EO of paracumylphenol, or Examples thereof include propylene oxide (PO) modified (meth) acrylate, EO-modified (meth) acrylate of nonylphenol, and PO-modified (meth) acrylate of nonylphenol.

As the carboxyl group-containing monomer body, the monomers already described can be used.

The phosphoric acid ester group-containing monomer is, for example, a compound obtained by reacting the hydroxyl group of the hydroxyl group-containing monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

<Non-photosensitive alkali-soluble resin>
The photosensitive coloring composition may contain a non-photosensitive alkali-soluble resin in order to adjust the degree of curing of the film.

The weight average molecular weight (Mw) of the alkali-soluble resin (F) is preferably 2,000 to 40,000, more preferably 3,000 to 3,000, and even more preferably 4,000 to 20,000. Adhesion to the base material is further improved by an appropriate Mw, and residues due to alkaline development are less likely to be generated. The value of Mw / Mn (number average molecular weight) is preferably 10 or less.

The acid value of the alkali-soluble resin (F) is preferably 50 to 200 (mgKOH / g), more preferably 70 to 180, and even more preferably 90 to 170. By having an appropriate acid value, it is possible to highly achieve both alkali developability and a good pattern shape of the developed pixel.

The alkali-soluble resin (F) can be used alone or in combination of two or more.

The content of the alkali-soluble resin (F) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the colorant. When an appropriate amount is contained, a film can be easily formed and good color characteristics can be easily obtained.

<Thiol chain transfer agent>
The photosensitive coloring composition may contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol chain transfer agent is used in combination with a photopolymerization initiator, chiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after light irradiation, and the sensitivity of the photosensitive coloring composition is improved.

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

Polyfunctional thiols include, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , Trimethylol Propanetristhioglycolate, Trimethylol Propanetristhiopropionate, Trimethylol Propantris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetrakissthiopropionate, 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, trimetylolpropantristhiopropionate, pentaerythritol tetrakisthiopropionate and the like.

The thiol 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 to 8% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the light sensitivity and the tapered shape are improved, and wrinkles are less likely to occur on the film surface.

<Polymerization inhibitor>
The photosensitive coloring composition may contain a polymerization inhibitor. This prevents the mask from being exposed to the diffracted light during exposure by the photolithography method, and makes it easier to obtain a good pattern shape.

Antipolymerization agents include, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2- Propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4- Alkylcatechol compounds such as tert-butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorsinol, 4-methylresorcinol, 2-ethylresorsinol, 4-ethylresorsinol, 2-propylreso Alkylresorcinol compounds such as lucinol, 4-propylresorcinol, 2-n-butylresorsinol, 4-n-butylresorsinol, 2-tert-butylresorsinol, 4-tert-butylresorsinol, methylhydroquinone, Alkylhydroquinone compounds such as ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone and 2,5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine. , Phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, fluoroglucin 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. When an appropriate amount is contained, a good pattern shape can be easily obtained.

<UV absorber>
The photosensitive coloring composition may contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds.

The benzotriazole-based compounds include, for example, 2- (5-methyl-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-t butyl-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-benzotriazole 2-yl)-(1, Mix of 1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester, 2- (2H-benzotriazole2-yl) -4,6-bis (1-methyl-1-phenylethyl) Phenol, 2- (2H-benzotriazole2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (3-) Reaction product of (2H-benzotriazole 2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300, 2- (2H-benzotriazole 2-yl) -4- (1,1,1) 3,3-Tetramethylbutyl) phenol, 2,2'-methylenebis [6- (2H-benzotriazole2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- ( 2H-benzotriazole 2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazole 2-yl) -6-t-butyl-4-methylphenol, 2- (3,5-di-t) -Amil-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-5-[2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, octyl-3- [3-tert-butyl-4- Hydroxy-5- (5-chloro-2H-benzotriazole2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole 2) -Il) phenyl] propionate can be mentioned.

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-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxy) Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate ester reaction product, 2,4-bis "2-hydroxy-4" -Butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-( Hexyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6- Tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine and the like can be mentioned.

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 Examples thereof include siloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

Examples of the salicylic acid ester compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate.

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

The content of the ultraviolet absorber is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerizable compound (C) and the ultraviolet absorber. When an appropriate amount is contained, the resolution after development is further improved.

The total content of the photopolymerizable compound (C) and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the adhesion between the substrate and the coating film is further improved, and good resolution can be obtained.

<Antioxidant>
The photosensitive coloring composition may contain an antioxidant. The antioxidant is a photopolymerization initiator or thermosetting compound contained in the photosensitive coloring composition, which prevents yellowing due to oxidation by heat curing or a thermal process during ITO annealing, and reduces the transmittance of the film. Can be suppressed. In particular, when the colorant concentration of the photosensitive coloring composition is high, the content of the photopolymerizable compound (D) decreases relatively. Therefore, if the amount of the photopolymerization initiator is increased or the thermosetting compound is blended, the film is formed. Is easy to yellow. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step and suppress a decrease in the transmittance of the coating film.

Examples of the antioxidant include hydride-based phenol-based, hydride-based amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present specification, the antioxidant is preferably a compound containing no halogen atom.

Among these, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, a hydride-based phenol-based antioxidant, a hydride-based amine-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant are preferable.

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

The content of the antioxidant is preferably 0.5 to 5% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the transmittance of the film, the spectral characteristics, and the sensitivity of the photosensitive coloring composition are further improved.

<Leveling agent>
The photosensitive coloring composition may contain a leveling agent. As a result, the wettability to the transparent substrate and the drying property of the coating film at the time of forming the coating film are further improved. Examples of the leveling agent include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and the like.

The surfactant 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 balance between the coatability of the photosensitive coloring composition, the pattern adhesion, and the transmittance is further improved.

<Storage stabilizer>
The photosensitive coloring composition may contain a storage stabilizer 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 phosphorous acid and their methyl ethers, organic acids such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples include phosphine and phosphite.

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

<Adhesion improver>
The photosensitive coloring composition may contain an adhesion improver. This further improves the adhesion between the coating film and the base material. In addition, it becomes easy to form a pattern having a narrow width by the photolithography method. Examples of the adhesion improver include a silane coupling agent and the like.

Examples of the silane coupling agent include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. (Meta) acrylic silanes such as 3-methacryloxypropyltriethoxysilane and 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-) Aminosilanes such as dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropyl Methyldimethoxysilane, mercaptos such as 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide and the like. Examples thereof include sulfides and isocyanates such as 3-isocyanapropyltriethoxysilane.

The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant (A). When an appropriate amount is contained, the light sensitivity of the photosensitive coloring composition is improved, the adhesion of the coating film is further improved, and the resolution of the pattern is further improved.

<Manufacturing method of photosensitive coloring composition>
The photosensitive coloring composition is subjected to dispersion treatment using, for example, an organic pigment (A), a dispersant (B), or the like to prepare a pigment dispersion. Then, the pigment dispersion, the binder resin (C), the photopolymerizable compound (D), and the photopolymerizable initiator (E) can be mixed and produced. When two or more kinds of organic pigments (A) are used, they can be mixed at the same time. It is also possible to separately prepare pigment dispersions and mix them. The dispersion aid is preferably used when producing a pigment dispersion.

For the dispersion treatment, for example, a disperser such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor can be used.

<Solvent>
The photosensitive coloring composition may contain a solvent. As a result, the viscosity of the photosensitive coloring composition can be easily adjusted, so that a film having a smooth surface can be easily formed. The solvent may be appropriately selected according to the purpose of use and may be contained in an appropriate amount.

As the solvent, a solvent usually used in the art can be used, and in consideration of performance such as boiling point, SP value, evaporation rate, viscosity, etc., it may be used alone or mixed as appropriate according to the coating conditions (speed, drying conditions, etc.). Is used.

Examples of the solvent include an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-), and an ether ester solvent. (Solvent containing -COO- and -O- in the molecule), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O −, −CO− and −COO− -free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

The solvent is preferably an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm from the viewpoint of coatability and drying property. Solvents are 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 preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferable.

<Removal of Coarse Particles> The photosensitive coloring composition is prepared by means such as centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration by a sintering filter or a membrane filter, and coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more. More preferably, it is preferable to remove coarse particles of 0.5 μm or more and mixed dust. As described above, it is preferable that the photosensitive coloring composition does not substantially contain particles having a size of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
The color filter of the present specification includes a substrate (also referred to as a substrate or a transparent substrate) and a filter segment formed from a photosensitive coloring composition. The color filter segment (hereinafter, also referred to as a filter segment) preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant to be used. Further, the color filter may have a magenta color filter segment, a cyan color filter segment, and a yellow filter segment instead of the color filter segment. A reflective substrate can be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate that uses an aluminum electrode or a metal thin film as a reflective surface.

<Manufacturing method of color filter>
It is preferable that the color filter first forms a black matrix on the base material and then forms a filter segment. A thin film transistor (TFT) can be formed in advance on the base material to form a color black matrix.
Examples of the black matrix include a multilayer film of chromium and chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed.

The filter segment can be formed by a photolithography method or the like.
In the photolithography method, for example, a photosensitive coloring composition containing a colorant having a certain color 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 film (hereinafter referred to as the first film) is exposed (irradiated with light) through a mask having a predetermined pattern. Then, the developing solution is immersed in a solvent or an alkaline developing solution, or the developing solution is sprayed by a spray or the like for development, and the uncured portion is removed to obtain a desired pattern. By performing this step in the same manner using a photosensitive coloring composition having a colorant having another color tone, a color filter having filter segments of each color can be produced. Further, a second film (oxygen blocking film) can be further formed on the first film before exposure by using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first film does not come into contact with oxygen, so that the exposure sensitivity is further improved. In addition, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment.

Examples of the coating apparatus include spray coating, spin coating, slit coating, roll coating and the like. A drying process can be performed during coating. Examples of the drying device include a hot air oven and an infrared heater.

Examples of the alkaline developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; and organic alkalis such as dimethylbenzylamine and triethanolamine. Examples of the developing solution include antifoaming agents and surfactants.

<Liquid crystal display device>
The display device of the present specification includes a color filter. The display device can be used for various purposes such as a liquid crystal display device, an organic EL display device, a solid-state image sensor, a quantum dot display device, electronic paper, and a head-mounted display. Among these, the liquid crystal display device will be described in this specification.

In the liquid crystal display device, the color filter is a color filter after forming the filter segment, which is bonded to the facing substrate by using a seal agent, and the liquid crystal is injected from the injection port provided in the seal portion, and then the injection port is opened. Seal. Further, if necessary, a polarizing film or a retardation film can be attached to the outside of the substrate to manufacture a liquid crystal display device.

The liquid crystal display device includes a light source in addition to the color filter. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED, but in the present specification, it is preferable to use a white LED in that the red reproduction region is widened. FIG. 1 is a schematic cross-sectional view of the liquid crystal display device 10. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged so as to be separated from each other, and a liquid crystal LC is enclosed between them.

The liquid crystal LC is oriented according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically CompensatedBirefringence). 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, for example, ITO is formed on the TFT (thin film transistor) array 12. An alignment layer 14 is provided on the transparent electrode layer 13. Further, 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 the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed over the color filter 22 as needed, and a transparent electrode layer 23 made of, for example, ITO is formed on the transparent protective film (not shown), and the alignment layer 24 covers the transparent electrode layer 23. Is provided.

Further, 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.

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

Specific examples of the LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

Specific examples of the LED2 include NSSW440 (manufactured by Nichia Corporation) and NSSW304D (manufactured by Nichia Corporation).

Hereinafter, the present invention will be described based on Production Examples and Examples. It goes without saying that the present invention is not limited to these. “Part” is “part by mass” and “%” is “% by mass”.

First, a method for calculating the weight average molecular weight of the resin and the method for measuring the acid value of the resin will be described.

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

(Acid value of resin)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the resin solution and stirred to uniformly dissolve the solution. Using a 0.1 mol / L KOH aqueous solution as a titrator, an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo Co., Ltd.) ) Was titrated, and the acid value (mgKOH / g) of the resin solution was measured. Then, the acid value per non-volatile component of the resin was calculated from the acid value of the resin solution and the non-volatile component concentration of the resin solution.

(Amine value of basic resin type dispersant)
The amine value of the basic resin type dispersant is a value obtained by converting the measured total amine value (mgKOH / g) into a non-volatile component according to the method of ASTM D 2074.

(Ammonium salt value (mgKOH / g))
The ammonium salt value is a value converted to the equivalent of potassium hydroxide after titration with a 0.1 N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and indicates the ammonium salt value of the non-volatile component.

<Miniaturization of diketopyrrolopyrrole red pigment>
The diketopyrrolopyrrole-based red pigments shown in Table 1 prepared in accordance with the examples of JP-A-2017-138417 were refined as follows, and the refined diketopyrrolops (A1-1) to (A1-8) were refined. A pyrrolop red pigment was obtained.

(Miniaturized diketopyrrolopyrrole red pigment (A1-1))
100 parts of diketopyrrolopyrrole red pigment (a1-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. for 10 hours. Next, the kneaded mixture was put into warm water and stirred for 1 hour while heating at about 80 ° C. to form a slurry, which was filtered and washed with water to remove salt and diethylene glycol, then dried at 80 ° C. for 24 hours and pulverized. By doing so, 96.9 parts of a finely divided diketopyrrolopyrrole red pigment (A1-1) was obtained.

(Miniaturized diketopyrrolopyrrole red pigments (A1-2) to (A1-8)
Except for changing the diketopyrrolopyrrole red pigment (a1-1) to the pigment shown in Table 1, miniaturization was performed in the same manner as the diketopyrrolopyrrole red pigment (A1-1). Ketopyrrolopyrrole red pigments (A1-2) to (A1-8) were obtained.

(Miniaturized diketopyrrolopyrrole red pigment (A1-9))
Diketopyrrolopyrrole red pigment (a1-1) was added to C.I. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by BASF Japan Ltd.) is replaced with finely divided diketopyrrolopyrrole red pigment (A1-1). A red pigment (A1-9) was obtained.

<Miniaturization of azo pigments>
The azo pigments shown in Tables 2-1 and 2-2 prepared according to the examples of Japanese Patent No. 6368844 were refined as follows to obtain (A2-1) to (A2-23).

(Manufacture of refined azo pigment A2-1)
80 parts of the azo pigment a1-1, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of a finely divided pigment (A2-1) was obtained.

(Manufacture of Finer Azo Pigment A2-2-23) Finer Azo Pigment Except for changing to the azo pigments (a2-2) to (a2-23) shown in Table 2 instead of the azo pigment a2-1. The fine pigments (A2-2) to (A2-23) were obtained in the same manner as in the production of the fine pigment (A2-1).

(Manufacturing of refined pigment A3-1)
C. I. Pigment Yellow 138 (PY138) (BASF Japan's "Pariotor Yellow K0960-HD"), 700 parts of sodium chloride, and 180 parts of diethylene glycol are charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. Kneaded for 6 hours. This mixture was put into 2000 parts of warm water and stirred for 1 hour while heating at 80 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent, and then dried at 80 ° C. for 24 hours to make a fine yellow pigment. (A3-1) was obtained.

<Manufacturing of refined pigments (A3-2) to (A3-4)>
The following quinophthalone compounds (a) to (c) were prepared according to the examples of JP2012-226110A.

(Manufacturing of refined pigment (A3-2))
100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 98 parts of micronized pigment (A3-2) was obtained.

(Manufacturing of refined pigment (A3-3))
100 parts of the quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was put into warm water and stirred for 1 hour while heating at about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. 98 parts of the refined pigment (A3-3) was obtained.

(Manufacturing of refined pigment (A3-4))
100 parts of the quinophthalone compound (c), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was put into warm water and stirred for 1 hour while heating at about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. 97 parts of the refined pigment (A3-4) was obtained.

(Manufacturing of refined pigment A3-5)
Isoindoline yellow pigment C.I. I. 100 parts of pigment yellow 139 (“Irgafore Yellow 2R-CF” manufactured by Ciba Japan), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader and kneaded at 60 ° C. for 10 hours. Next, this mixture was put into 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and solvent, and then 80. The mixture was dried at ° C. for one day and night to obtain a finely divided organic pigment (A3-5).

(Miniaturized organic pigment (A3-6))
100 parts of metal complex yellow pigment (CI pigment yellow 150, "Yellow Pigment E4GN" manufactured by LANXESS), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). It was kneaded at 60 ° C. for 10 hours. Next, this mixture was put into 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and solvent, and then 80. The mixture was dried at ° C. for one day and night to obtain a finely divided organic pigment (A3-6).

(Miniaturized organic pigment (A3-7))
Yellow pigment C.I. I. Pigment Yellow 185 (“Pariotol Yellow D1155” manufactured by Ciba Japan): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1-gallon kneader and kneaded at 120 ° C. for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , A finely divided organic pigment (A3-7) was obtained.

<Other colorants: Methods for producing resin salt products (a-1) to (a-3) of dyes>
Resin salts (a-1) to (a-3) of dyes were produced by using resin 1 having a cationic group in the following side chain and each dye.

(Resin 1 having a cationic group in the side chain)
67.3 parts of methyl ethyl ketone was placed in a 4-port separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised 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) ) Was made uniform in 6.5 parts and 25.1 parts of methyl ethyl ketone, charged in a dropping funnel, attached to a four-neck separable flask, and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed from the non-volatile content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added and reacted at 50 ° C. for 2 hours, then heated to 80 ° C. over 1 hour, and further reacted for 2 hours. In this way, a resin 1 having a cationic group in the side chain having a resin component of 47% by mass of an ammonium group was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

(Other colorants (a-1))
Resin 1 having a cationic group was added to 2000 parts of water in terms of non-volatile content in 30 parts of the side chain, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 90 parts of water and 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared, and the solution was added dropwise to the resin solution. After the dropping, the mixture was stirred at 60 ° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and using the point where the bleeding disappeared as the end point. After allowing to cool to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer. I. A colorant (AS-12), which is a salt-forming compound of Acid Red 52 and a resin 1 having a cationic group in the side chain, was obtained. At this time, C.I. I. The content of the active pigment component derived from Acid Red 52 was 25% by mass.

(Other colorants (a-2))
C. I. Acid Red 52 to C.I. I. Except for the change to Acid Red 289, the same procedure as in the production of the colorant (a-1) was carried out, and C.I. I. A colorant (a-2), which is a salt-forming compound of Acid Red 289 and a resin 1 having a cationic group in the side chain, was obtained. At this time, C.I. I. The content of the active pigment component derived from Acid Red 289 was 27% by mass.

(Other colorants (a-3))
In a 1 L stainless steel reaction vessel with a recirculation tube, under a nitrogen atmosphere, C.I. I. Dissolve 5.0 parts of Basic Violet 10 (BV10: manufactured by Taoka Chemical Co., Ltd .: Rodamine B) and 1.6 parts of hydroxyethyl methacrylate (HEMA) in 40 ml of dichloromethane, and dissolve 1- (3-dimethylaminopropyl) -3-ethyl. 2.2 parts of carbodiimide hydrochloride and 0.25 part of dimethylaminopyridine were added, and the mixture was stirred at room temperature for 24 hours. The obtained dichloromethane solution was washed with water, dried under reduced pressure, and then purified on a silica gel column to obtain a colorant (a-3).

(Manufacture of other coloring composition (dye: a'-1) solution)
The following mixture was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 5.0 μm to prepare a colored composition (a'-1) solution.
Colorant (a-1) 16.0 parts Propylene glycol monomethyl ether acetate 84.0 parts

(Other coloring compositions (dye solution: (a'-2), (a'-3) production)
Similar to the coloring composition (a-1), the coloring composition (a'-2) and (a'-3) solutions were prepared using the coloring agents (a-2) and (a-3), respectively. ..

Dye derivative (1)

Dye derivative (2)

Dye derivative (3)

<Manufacturing of resin type dispersant (B)>
(Manufacturing of resin type dispersant (B1-1) solution)
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of propylene glycol monomethyl ether acetate, 0.1 part of dimethylbenzylamine was charged. After replacement with nitrogen gas, the inside of the reaction vessel was heated to 120 ° C. and reacted at 120 ° C. for 4 hours, and then reacted at 80 ° C. for 2 hours. Furthermore, 30 parts of tertiary butyl acrylate, ETERNALCOLL OXMA (methyl methacrylate (3-ethyloxetane-3-yl), manufactured by Ube Industries, Ltd.) 20
5 parts, 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of propylene glycol monomethyl ether acetate were charged, and 15 parts of 2,2'-azobisisobutyronitrile 0.2 part was added while keeping the inside of the reaction vessel at 80 ° C. It was added in batches every 30 minutes. The non-volatile content was measured 1 hour after the final addition, and it was confirmed that 95% of the monomers had reacted. A resin type having a carboxyl group having an acid value of 51 mgKOH / g per non-volatile content and a weight average molecular weight (Mw) of 24,000 after diluting with propylene glycol monomethyl ether acetate so that the non-volatile content is 40% in the non-volatile content measurement. A dispersant (B1-1) solution was obtained.

(Manufacturing of resin type dispersant (B1-2-6) solution)
Resin-type dispersant (B1-2) to (B1-6) solutions were obtained by synthesizing and adjusting in the same manner as the resin-type dispersant (B1-1) solution except that the blending amounts were changed to those shown in Table 3. ..

<Abbreviations in the table>
PGMAC: Propylene glycol monomethyl ether acetate tBA: t-Butyl acrylate OXMA: ETERNALCOLL OXMA (methacrylic acid (3-ethyloxetane-3)
-Il) Methyl, manufactured by Ube Industries, Ltd.)
MAA: EA Methacrylic Acid: Ethyl Acrylate MMA: Methyl Methacrylate AIBN: 2,2'-Azobisisobutyronitrile

(Manufacturing of resin type dispersant (B1-7) solution)
In a reaction vessel equipped with a gas introduction 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), ETERNAL COLLOXMA ( 20 parts (manufactured by Ube Industries, Ltd.) and 100 parts of propylene glycol monomethyl ether acetate were charged and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2'-azobisisobutyronitrile in 14 parts of 2-mercapto-2-methyl-1,3-propanediol is added. Then, it reacted for 10 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. Next, BPAF: 9,9-bis (3,4-dicarboxyphenyl) fluorene diic anhydride (manufactured by JFE Chemical Co., Ltd.) 39 parts, C-1015N (bifunctional polycarbonate polyol, trade name Clare polyol C-1015N (trade name) 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 It was added and reacted at 100 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was harf esterified, and the reaction was terminated. The non-volatile content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a resin-type dispersant (B1-7) solution having an acid value of 94 mgKOH / g and a weight average molecular weight of 25,000.

(Basic resin type dispersant (B2-1) solution)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst, and charged at 50 ° C. while flowing nitrogen. The mixture was stirred with water for 1 hour, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate was charged as an initiator, 5.6 parts of cuprous chloride and 133 parts of PGMAc were charged as a catalyst, and the temperature was raised to 110 ° C. under a nitrogen stream in the first block (B block). Polymerization was 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 PGMAc, 40 parts of dimethylaminoethyl methacrylate and 10 parts of methacryloyloxyethyl benzyldimethylammonium chloride as the second block (A block) monomer were added to this reactor, and the temperature was maintained at 110 ° C. under a nitrogen atmosphere. The reaction was continued with stirring. Two hours after the addition, the polymerization solution was sampled and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of the non-volatile content, and the reaction solution was brought to room temperature. It was cooled to stop the polymerization. As a result of GPC measurement, the mass average molecular weight of the polymer was 20000, the molecular weight distribution Mw / Mn was 1.4, and the reaction conversion rate was 98.5%. In this way, a basic resin-type dispersant (B2-1) having an amine value of 169.8 mgKOH / g per non-volatile component was obtained. After cooling to room temperature, about 2 g of the resin-type dispersant solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content was added to the previously synthesized basic resin-type dispersant (B2-1). Propylene glycol monomethyl ether acetate (PGMAc) was added so that the content was 30% by mass to prepare a basic resin-type dispersant (B2-1) solution.

(Basic resin type dispersant (B2-2) solution)
133 parts of PGMAc was charged in a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110 ° C. while substituting with nitrogen. 177 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 2,2'-azobis (2,4-dimethylvalero) in the dropping tank. 6 parts of nitrile) was charged, stirred until uniform, and then added dropwise to the reaction vessel over 2 hours, after which the reaction was continued for 3 hours at the same temperature. In this way, a basic resin-type dispersant (B2-2) having an amine value of 201 mgKOH / g per non-volatile component and a number average molecular weight of 3,800 (Mn) was obtained. A solution of the basic resin type dispersant (B2-2) was prepared by diluting in the same manner as the solution of the basic resin type dispersant (B2-1).

(Salt (B3-1) solution of phenylphosphonic acid and a basic resin-type dispersant having an amino group)
In a 100 mL round bottom flask, 12.6 parts by mass of a basic resin-type dispersant (methyl methacrylate / dimethylaminoethyl methacrylate: composition ratio 5/3) is dissolved in 35 parts by mass of PGMAc, and phenyl as a salt-forming component is dissolved. By adding 2.4 parts by mass of phosphonic acid (0.5 molar equivalent to dimethylaminoethyl methacrylate) and stirring at a reaction temperature of 40 ° C. for 2 hours, a basic resin-type dispersion having phenylphosphonic acid and an amino group is performed. A solution of 30% by mass of the non-volatile content of the salt (B3-1) with the agent was prepared.

(Salt (B3-2) solution of phenylphosphonic acid, a basic resin-type dispersant having an amino group and an ammonium salt)
In a 100 mL round bottom flask, in 35 parts by mass of PGMAc, a basic resin type dispersant (methyl methacrylate / dimethylaminoethyl methacrylate / dimethylaminoethyl methyl methacrylate salt: composition weight ratio 3/3/2) 12.6 Phosphon is dissolved by dissolving parts by mass, adding 2.4 parts by mass of phenylphosphonic acid, which is a salt-forming component (0.5 molar equivalent to dimethylaminoethyl methacrylate), and stirring at a reaction temperature of 40 ° C. for 2 hours. A 30% by mass solution of a salt (B3-2) of a basic resin-type dispersant having a phosphonic acid, an amino group and an ammonium salt was prepared.

<Preparation of alkali-soluble resin (F) solution>
(Preparation of alkali-soluble resin (F-1) solution)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) , 2,2'-Azobisisobutyronitrile 1.1 parts mixture was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20%. A non-photosensitive alkali-soluble resin (F-1) solution was prepared. The weight average molecular weight (Mw) was 26000.

(Preparation of alkali-soluble resin (F-2) solution)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis. A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karens manufactured by Showa Denko Co., Ltd.). A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20%. A photosensitive alkali-soluble resin (F-2) was prepared. The weight average molecular weight (Mw) was 18,000.

(Preparation of alkali-soluble resin (F1-1) solution)
370 parts of cyclohexanone was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C. Milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.) 18 parts, benzyl methacrylate 10 parts, glycidyl methacrylate 18.2 parts, methyl methacrylate 25 parts, and 2,2'-azobisisobutyronitrile 2.0 The mixture of parts was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the above container at 120 ° C. The reaction was continued for 6 hours, and when the non-volatile acid value reached 0.5, the reaction was terminated to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were subsequently added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
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, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. A solution of the alkali-soluble resin (F1-1) of (I) was prepared. The weight average molecular weight (Mw) was 19000.

(Preparation of alkali-soluble resin (F1-2) solution)
333 g of propylene glycol monomethyl ether acetate was introduced into a 1 L flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping rotor and a gas introduction tube. Then, nitrogen gas was introduced into the flask through the gas introduction pipe. Then, the temperature of the solution in the flask was raised to 100 ° C., and 22.0 g of dicyclopentanyl methacrylate, 70.5 g of benzyl methacrylate, 43.0 g of methacrylic acid, 3.6 g of azobisisobutyronitrile and propylene glycol monomethyl ether acetylate. The mixture consisting of 164 g of the solution was added dropwise to the flask over 2 hours using a dropping rotor, and after the addition was completed, stirring was continued at 100 ° C. for 5 hours.
After the stirring is completed, air is introduced into the flask through a gas introduction tube, 35.5 g of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone are added into the flask, and the reaction is continued at 110 ° C. for 6 hours. , A resin solution having a non-volatile content and an acid value of 80 mgKOH / g 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, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. A solution of the alkali-soluble resin (F1-2) of (II) was prepared.

<Manufacturing method of coloring composition (single color)>
[Manufacturing Example 1]
(Preparation of coloring composition (R-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Aiga-Mill (“Mini Model M-250 MKII” manufactured by Aiga-Japan) using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a filter having a pore size of 5.0 μm to prepare a colored composition (R-1) having a non-volatile component of 24.3% by mass.
Pigment (A1-1): 20.5 parts Resin-type dispersant solution (B1-1: Non-volatile content 30%): 2.0 parts Alkali-soluble resin solution (F-1: Non-volatile content 20%): 16.0 parts Solvent (O): 61.5 parts The solvent (O) was prepared by mixing the following (O-1) to (O-6) in parts by mass.
(O-1) PGMAc 30 parts (O-2) Cyclohexanone 30 parts (O-3) Ethyl 3-ethoxypropionate 10 parts (O-4) Propylene glycol monomethyl ether 10 parts (O-5) Cyclohexanol acetate 10 parts (O-6) Diproprene glycol methyl ether acetate 10 parts

[Manufacturing Examples 2-53]
(Preparation of coloring compositions (R-2) to (R-53))
Colored compositions (R-2) to (R-53) were prepared in the same manner as in Production Example 1 except that the material types and masses were changed as shown in Table 4.

<Manufacturing method of coloring composition (mixing of coloring materials)>
[Manufacturing Example 101]
(Preparation of coloring composition (X-1))
The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a colored composition (X-1).
Coloring composition solution (R-1: non-volatile content 24.3%): 40 parts Coloring composition solution (R-46: non-volatile content 24.3%): 16 parts Alkali-soluble resin solution (F-1: non-volatile content 20) %): 32 parts Solvent (O): 12 parts

[Manufacturing Examples 102 to 155]
(Preparation of coloring compositions (X-2) to (X-55))
Colored compositions (X-2) to (X-55) were prepared in the same manner as in Production Example 101, except that the material types and masses were changed as shown in Table 5.

<Manufacturing method of photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition (Y-1))
The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y-1).
Coloring composition solution (R-1: non-volatile content 24.3%): 26.5 parts Alkali-soluble resin solution (F1-1: non-volatile content 20%): 22.0 parts Compound having an alicyclic epoxy group (E1) ): 1.8 parts Photopolymerizable compound (C): 3.2 parts Photopolymerizable initiator (D): 1.89 parts Sensitizer (G): 0.2 parts Thiol-based chain transfer agent (H) : 0.4 part Polymerization inhibitor (I): 0.01 part Ultraviolet absorber (J): 0.1 part Antioxidant (K): 0.1 part Leveling agent (L: Non-volatile content 3%): 1 .0 parts Storage stabilizer (M): 0.1 parts Silane coupling agent (N): 0.2 parts Solvent (O): 42.5 parts

[Examples 2 to 114, Comparative Examples 1 to 8]
(Preparation of Photosensitive Coloring Compositions (Y-2) to (Y-122))
The photosensitive coloring composition (Y-2) was carried out in the same manner as in Example 1 except that the types of the coloring composition and the binder resin solution of Example 1 were changed as shown in Tables 6-1 and 6-2. ~ (Y-122) were prepared respectively.

-Compounds having an alicyclic epoxy group: (E1-1) 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Co., Ltd .: seroxide 2021P, epoxy equivalent 128 to 145 g / eq) is added to PGMAc. It was dissolved in and adjusted to a non-volatile content of 40%.

-Compound having an alicyclic epoxy group: (E1-2) Synthesis and adjustment were carried out as follows.
In a flask equipped with a stirrer, 7.0 g of methyl methacrylate, 7.0 g of normalbutyl methacrylate, 1.4 g of 3,4-epoxycyclohexylmethyl methacrylate, and 2,2'-azobisisobutyronitrile. 227 mg and 559 mg of pyrazole 1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 mL of Toluen, and nitrogen bubbling was performed for 30 minutes. Then, with gentle stirring, the temperature of the reaction solution was raised to 57 ° C., and this temperature was maintained for 34 hours for living radical polymerization. Next, a solution prepared by dissolving 721 mg of 2,2'-azobisisobutyronitrile and 12.6 g of dimethylaminoethyl methacrylate in 20 mL of toluene and substituting nitrogen for 30 minutes was added to the above reaction solution, and the solution was added at 57 ° C. for 34 hours. Living radical polymerization was performed. Then, the solvent was removed by concentration under reduced pressure, and PGMAc was added to bring the non-volatile content to 40% by mass. In this way, a block copolymer composed of an A block having a repeating unit derived from dimethylaminoethyl methacrylate and a B block having a repeating unit derived from methyl methacrylate, normal butyl methacrylate and 3,4-epoxycyclohexylmethyl methacrylate is obtained. A solution containing 40% by mass was obtained. The polystyrene-equivalent Mw measured by GPC (eluting solvent: THF) of the obtained polymer was 8,000, and Mw / Mn was 1.3. The epoxy equivalent is 277 g / eq.

-Alicyclic epoxy group-free thermosetting compound (E2-1): Trichloroisocyanuric acid (manufactured by Nissan Chemical Industries, Ltd .: TEPIC-S, epoxy equivalent 99 g / eq) is dissolved in PGMAc and has a non-volatile content of 40%. Adjusted to.
-Alicyclic epoxy group-free thermosetting compound (E2-2): 2,2'-bis (hydroxymethyl) -1-butanol 1,2-epoxy-
A 4- (2-oxylanyl) cyclohexane adduct (manufactured by Daicel Corporation: EHPE3150, epoxy equivalent 170-190 g / eq) was dissolved in PGMAc to adjust the non-volatile content to 40%.

-Alicyclic epoxy group-free thermosetting compound (E2-3): Synthesized and adjusted as follows.
In a reaction vessel equipped with a gas introduction 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), ETERNAL COLLOXMA ( 20 parts (manufactured by Ube Industries, Ltd.) and 100 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2'-azobisisobutyronitrile in 14 parts of 2-mercapto-2-methyl-1,3-propanediol is added. Then, it reacted for 10 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. Next, BPAF: 9,9-bis (3,4-dicarboxyphenyl) fluorene diic anhydride (manufactured by JFE Chemical Co., Ltd.) 39 parts, C-1015N (bifunctional polycarbonate polyol, trade name Clare polyol C-1015N (trade name) 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 It was added and reacted at 100 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was harf esterified, and the reaction was terminated. The non-volatile content was adjusted to 40% with PGMAc to obtain a thermosetting compound (E2-3) solution having an acid value of 94 mgKOH / g and a weight average molecular weight of 25,000 and having no alicyclic epoxy group.

-Alicyclic epoxy group-free thermosetting compound (E2-4): 3-ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane is dissolved in PGMAc and has a non-volatile content of 40%. Adjusted to.

<Photopolymerizable compound (C)>
(C-1) Trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(C-2) Dipentaerythritol penta and hexaacrylate
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(C-3) Polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(C-4) Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

(C-5) Polyfunctional urethane acrylate according to the following. Pentaerythritol triacrylate (432 parts, hexamethylene diisocyanate 84 parts) was charged in a reaction vessel having a content of 1 liter and 5 mouths, and reacted at 60 ° C. for 8 hours. A product containing a polyfunctional urethane acrylate (C-5) having an acryloyl group was obtained. The proportion of the polyfunctional urethane acrylate (C-5) in the product was 70% by mass, and the balance was other light. It is occupied by polymerizable monomer. It was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

(C-6) Bifunctional bisphenol A type (meth) acrylate
[ABE-300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)]
(C-7) Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)]
As described above, (C-1) to (C-7) were mixed in the same amount to obtain a photopolymerizable compound (C).

<Photopolymerizable initiator (D)>
(D-1) 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropan-1-one
[Omnirad 907 (manufactured by IGM Resins)]
(D-2) 2- (Dimethylamino) -2-[(4-Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
[Omnirad 379EG (manufactured by IGM Resins)]
(D-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Omnirad TPO (manufactured by IGM Resins)]
(D-4) 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (manufactured by Kurokin Kasei Co., Ltd.)]
(D-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(D-6) Ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole 3-yl], 1- (O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan Ltd.)]
(D-7) 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one
[Omnirad 2959 (manufactured by IGM Resins)]
(D-8) Bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide
[Omnirad 819 (manufactured by IGM Resins)]
As described above, (D-1) to (D-8) were mixed in equal amounts to prepare a photopolymerization initiator (D).

<Sensitizer (G)>
(G-1) 2,4-diethylthioxanthone
[Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(G-2) 4,4'-bis (diethylamino) benzophenone
[CHEMARK DEABP (manufactured by Chemical)]
As described above, (G-1) and (G-2) were mixed in the same amount to prepare a sensitizer (G).

<Thiol chain transfer agent (H)>
(H-1) Trimethylolethane ethanetris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
(H-2) Trimethylolpropanetris (3-mercaptobutyrate)
[TPMB (manufactured by Showa Denko)]
(H-3) Pentaerythritol tetrakis (3-mercaptopropionate) [PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(H-4) Trimethylolpropane Tris (3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(H-5) Tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
As described above, (H-1) to (H-5) were mixed in the same amount to prepare a thiol-based chain transfer agent (H).

<Polymerization inhibitor (I)>
(I-1) 3-Methylcatechol (I-2) Methylhydroquinone (I-3) t-Butylhydroquinone or more, (I-1) to (I-3) are mixed in equal amounts, and a polymerization inhibitor is added. It was designated as (I).

<Ultraviolet absorber (J)>
(J-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 Ltd.)]
(J-2) 2- (2H-benzotriazole2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol
[TINUVIN900 (manufactured by BASF Japan Ltd.)]
As described above, (J-1) to (J-2) were mixed in the same amount to prepare an ultraviolet absorber (J).

<Antioxidant (K)>
(K-1) Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (K-2) 3,3'-dioctadecylthiodipropanoate (K-3) tris [2] , 4-Di- (t) -Butylphenyl] Phenylphosphine (K-4) Bis (2,2,6,6-Tetramethyl-4-piperidyl) Sevacate (K-5) Salicylic acid p-octylphenyl or more, (K-1) to (K-5) were mixed in the same amount to prepare an antioxidant (K).

<Leveling agent (L)>
Big Chemi-manufactured "BYK-330" 1 copy,
A mixed solution in which 1 part of "Mega Fvck F-551" manufactured by DIC and 1 part of "Emargen 103" manufactured by Kao Corporation are dissolved in 97 parts of PGMAc.

<Storage stabilizer (M)>
(M-1) 2,6-bis (1,1-dimethylethyl) -4-methylphenol (“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)
(M-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.)
As described above, (M-1) to (M-2) were mixed in the same amount to prepare a storage stabilizer (M).

<Adhesion improver (N)>
(N-1) 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicon Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(N-2) 3-Methacryloxypropyltriethoxysilane
[Shin-Etsu Silicon Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (N-3) N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane
[Shin-Etsu Silicon Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(N-4) 3-Mercaptopropyltrimethoxysilane
[Shin-Etsu Silicon Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
As described above, (N-1) to (N-4) were mixed in the same amount to prepare a silane coupling agent (N).

<Evaluation of photosensitive coloring composition>
Each test was performed by the following method. The test results are shown in Tables 7-1 and 7-2. The meaning of the evaluation rank is as follows.
◎: Extremely good 〇: Good △: Practical use ×: Not suitable for practical use

(Storage stability)
The storage stability of the obtained photosensitive coloring composition was evaluated by the following method.
Using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.), 25 The measurement was carried out at ° C. under the condition of a rotation speed of 50 rpm. From the values of the initial viscosity and the viscosity with time, the rate of change in viscosity with time was calculated by the following formula, and the storage stability was evaluated in two stages.
[Ratio of change in viscosity over time] = | ([Initial viscosity]-[Viscosity over time]) / [Initial viscosity] | × 100
〇: Change rate less than 5% Δ: Change rate 5% or more and less than 10% ×: Change rate 10% or more

(Solvent resistance evaluation)
A photosensitive coloring composition was applied on a 100 mm × 100 mm, 0.7 mm glass substrate so that the dry coating film had a thickness of about 2.0 μm, and prebaked at 90 ° C. for 120 seconds. Next, using an ultra-high pressure mercury lamp ^{, ultraviolet exposure was performed with an integrated light intensity of 150 mJ / cm 2} , and ultraviolet rays were exposed through a photomask having a 100 μm wide stripe pattern. Further, the coating substrate obtained by heat-treating at 230 ° C. for 1 hour in an oven is immersed in an N-methylpyrrolidone solution for 30 minutes, washed with ion-exchanged water, air-dried, and the pattern in the 100 μm photomask portion is optical. The evaluation was performed by observing with a microscope. The evaluation ranks are as follows.
〇: Good appearance and color without change
Δ: Wrinkles or the like occur in some parts, but the color does not change and is good.
×: Peeling and discoloration occur

(Heat resistance evaluation)
A photosensitive coloring composition is applied onto a 100 mm × 100 mm, 0.7 mm glass substrate so that the dry coating film is about 2.0 μm, then dried at 70 ° C. for 20 minutes and allowed to cool to obtain a coating film. A substrate was prepared. Use a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) to measure the chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film at the C light source. Measured using. After that, as a heat resistance evaluation, the mixture was heated at 230 ° C. for 1 hour, the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured, and the following formula was used. , Color difference ΔEab * was obtained and evaluated according to the following criteria.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
⊚: ΔEab * is less than 2 ◯: ΔEab * is 2-3
Δ: ΔEab * is 3 to 5
X: ΔEab * is 5 or more

(Evaluation of adhesion)
The obtained photosensitive coloring composition was applied onto a glass substrate of 100 mm × 100 mm and 0.7 mm so as to have a film thickness of 2.0 μm, and heat-treated at 230 ° C. for 20 minutes and at 240 ° C. for 60 minutes (post-baking). To obtain a cured film. A total of 100 grids were formed on the obtained cured film by using a cutter knife to form 1 × 1 (mm) size squares in 10 rows and 10 rows. This sample was subjected to a pressure cooker (PCT) test (condition: continuous treatment for 24 hours under the conditions of temperature 120 ° C. and humidity 100%), and then the grid was peeled off with tape. Adhesion was evaluated by counting the number of peeled grids.
⊚: 0 ◯: 1 or more and less than 5 Δ: 5 or more and less than 10 ×: 10 or more

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 Orientation layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims (6)

Organic pigment (A), resin-type dispersant (B), photopolymerizable compound (C), photopolymerizable initiator (D), compound having an alicyclic epoxy group (E1), and alkali-soluble resin (F). A photosensitive composition containing
The organic pigment (A) is one selected from the group consisting of the diketopyrrolopyrrole organic pigment (A1) and / or the organic pigment represented by the following general formula (1) and the organic pigment represented by the following general formula (2). A photosensitive coloring composition containing the above organic pigment (A2).
General formula (1)

[In the general formula (1), R ₁ is a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. Represents. R ₂ and R ₃ independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
Each of X _{1 to} X ₄ is independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group, a carboxyl group, or a sulfo group. , Or represents a halogen atom. ]
General formula (2)

[In the general formula (2), R ₄ is a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. Represents. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X _{5 to} X ₁₂ each independently contain a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group, or a halogen atom. Represent. A is a direct bond, an optionally substituted alkylene group, -O -, - S -, - CO -, - SO 2 -, - COO -, - CONH-, or a _-SO 2 NH- Represent. ] The photosensitive coloring composition according to claim 1, wherein the compound (E1) having an alicyclic epoxy group is contained in an amount of 0.01 to 10% by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition. The photosensitive coloring composition according to claim 1 or 2, wherein the compound (E1) having an alicyclic epoxy group has an epoxy equivalent of 160 g / eq or less. The claim that the alkali-soluble resin (F) is an alkali-soluble resin (F1) having a carboxyl group and a polymerizable unsaturated bond in the side chain, which is selected from the group consisting of the following resin (I) and resin (II). The photosensitive coloring composition according to any one of 1-3.
Resin (I) A resin resin obtained by further reacting a polybasic acid anhydride with a reaction product of an epoxy group in an epoxy group-containing monomer and a copolymer of other monomers and a carboxyl group of a carboxyl group-containing monomer ( II) A resin that is a reaction product of a carboxyl group in a carboxyl group-containing monomer and a copolymer of other monomers and an epoxy group of an epoxy group-containing monomer. A color filter comprising a base material and a color filter segment formed from the photosensitive coloring composition according to any one of claims 1 to 4. A display device comprising the color filter according to claim 5.

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