TW201740193A - Colored curable resin composition, color filter and display device containing the same - Google Patents

Abstract

Provided is a colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the colorant (A) contains a dye having a xanthene skeleton, and the polymerizable compound (C) contains a polymerizable compound having a hydroxyl value of 100 mg KOH/g or above.

Description

Colored curable resin composition, color filter, and display device containing the same

The present invention relates to a color-curable resin composition, and a color filter and a display device formed of the colored curable resin composition.

In recent years, development of a color-curable resin composition containing a dye as a colorant has been popular.

However, the heat resistance of the dye itself is not sufficient, and it is necessary to supplement the heat resistance with a transparent component other than the colorant.

Japanese Laid-Open Patent Publication No. 2009-237151 discloses a colored curable composition for a color filter, which comprises: (A) a colorant, (B) a binder resin, and (C) light having an ethylenically unsaturated bond. a polymerizable compound, (D) a photopolymerization initiator, (E) a solvent, (C) a photopolymerizable compound having an ethylenically unsaturated bond has a hydroxyl group, and the photopolymerizable compound has a hydroxyl value of from 90 mgKOH/g to 140 mgKOH /g. The numerical range of the hydroxyl value is considered to be in view of the developmental removability of the colored curable composition.

The present invention provides a colored curable resin composition, a color filter, and a display device shown below.

[1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant (A) comprises an oxygen The dye of the fluorene skeleton, the polymerizable compound (C) contains a polymerizable compound having a hydroxyl value of 100 mgKOH/g or more.

[2] The colored curable resin composition according to [1], wherein the polymerizable compound having a hydroxyl value of 100 mgKOH/g or more is pentaerythritol triacrylate.

[3] The colored curable resin composition according to any one of [1] to [3], wherein the ratio of the content of the polymerizable compound (C) to the content of the resin (B) (polymerizable compound (C) The content of the resin / the content of the resin (B) is 0.6 to 5 in terms of a mass ratio.

[4] The colored curable resin composition according to any one of [1] to [3] wherein the ratio of the content of the polymerizable compound (C) to the content of the resin (B) (polymerizable compound (C) The content of the resin / the content of the resin (B) is 0.75 to 5 in terms of a mass ratio.

[5] The colored curable resin composition according to any one of [1] to [4] wherein the colorant (A) further contains C.I. Pigment Blue 15:6.

[6] The colored curable resin composition according to any one of [1] to [5] wherein the colorant (A) has a xanthene skeleton dyed in 100% by mass The content of the material is from 1 to 50% by mass.

[7] The colored curable resin composition according to any one of [1] to [6], which contains a quinone compound as a polymerization initiator (D).

[8] A color filter comprising the color-curable resin composition according to any one of the above [1] to [7].

[9] A display device comprising the color filter of the above [8].

<Coloring curable resin composition>

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) contains a dye having a xanthene skeleton. Further, in the present invention, a polymerizable compound having a hydroxyl value of 100 mgKOH/g or more is contained as the polymerizable compound (C).

By the colored curable resin composition, good luminance can be exhibited, and a color filter excellent in heat resistance can be formed regardless of whether or not the dye is contained.

Further, the compounds which are the respective components are exemplified in the present specification, and may be used singly or in combination of plural kinds unless otherwise specified.

[1] Colorant (A)

The colorant (A) contains a dye.

The colored curable resin composition of the present invention contains a dye having a xanthene skeleton (hereinafter referred to as a xanthene dye) as the dye. Since the colored curable resin composition of the present invention contains a polymerizable compound and an oxonium dye which will be described later, good brightness can be obtained. Examples of xanthene dyes include: CI acid red 51, 52, 87, 92, 289, 388, CI acid violet 9, 30, CI alkaline red 8, CI mordant red 27, Bengal rose B, sulphur Sulfhodamine G, rhodamine 6G, xanthene dye described in JP-A-2010-32999, and xanthene dye described in Japanese Patent No. 4492760. The colorant (A) may contain one or more kinds of xanthene dyes.

Among them, the xanthene dye preferably contains a compound represented by the formula (1) (hereinafter also referred to as "compound (1)") as a main component:

In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or R ¹ and R ² and R ³ and R ⁴ respectively form together. A ring containing a nitrogen atom. The hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ^{10 is} substituted. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, -CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ .

m represents an integer from 0 to 5. When m is an integer of 2 or more, a plurality of R ⁵ may be the same or different.

R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

M ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ . X represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. a represents 0 or 1.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the -CH ₂ - contained in the saturated hydrocarbon group may be -S-, -O-, -CO- or -NR ¹¹ - substituted. R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. When there are a plurality of R ¹¹ , these may be all the same or a part of the same.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by -OH or a halogen atom, and the saturated aliphatic hydrocarbon group contains - CH ₂ - may be substituted by -S-, -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ may be bonded to each other to form a heterocyclic ring of 3 to 10 members containing a nitrogen atom. ring. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a tolylmethyl group, a xylyl group, a 2,4,6-trimethylphenyl group, a propylphenyl group, and a butyl group. Phenyl and the like.

a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ , the substituent having a group consisting of -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ and -SO ₂ NR ⁹ R ¹⁰ At least one selected from the group is preferable, and at least one selected from the group consisting of -SO ₃ ^- M ⁺ and -SO ₂ NR ⁹ R ¹⁰ is more preferable. At this time, -SO ₃ ^- M ^{+ is} preferably -[SO ₃ ^- ][ ⁺ N(R ¹¹ ) ₄ ]. When R ¹ to R ^{4 are} these groups, it is advantageous in forming a color filter excellent in heat resistance.

The ring formed by R ¹ and R ² together with the ring formed by R ³ and R ⁴ may, for example, be the following ring:

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, and a new one. Alkyl 1 to 20 alkyl group such as pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, decyl, dodecyl, hexadecanyl, and decyl; cyclopropyl, cyclopentyl a cycloalkyl group having 3 to 20 carbon atoms such as a cyclohexyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

With respect to R ⁸ , the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a hydrogen atom in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may, for example, be a phenyl group, a tolylmethyl group, a xylyl group or a 2, 4 group. 6-trimethylphenyl, propylphenyl and butylphenyl. Further, examples of the group in which -CH ₂ - in R ⁸ is substituted with -S-, -O-, -CO- or -NR ¹¹ - may, for example, be the following groups.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include those having 1 to 6 carbon atoms in the above-exemplified alkyl groups.

Examples of the group represented by -SO ₂ NR ⁹ R ¹⁰ include a group represented by the following formula.

In the above formula, X ¹ represents a halogen atom. The halogen atom in X ¹ may, for example, be a fluorine atom, a chlorine atom or a bromine atom.

The aralkyl group having 7 to 10 carbon atoms in R ¹¹ in the formula (1) may, for example, be a benzyl group, a phenylethyl group or a phenylbutyl group.

M ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ . ⁺ N(R ¹¹ ) ₄ is preferably one of four R ¹¹ groups, and at least two of the monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms are preferred. Further, the total carbon number of the four R ¹¹ is preferably from 20 to 80, more preferably from 20 to 60.

More preferably, the xanthene dye comprises a compound represented by the formula (2) as a main component:

In the formula (2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be -SO ₃ - , -SO ₃ ^- M ^a+ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ^{26 is} substituted. X represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A1 represents 0 or 1. M1 represents an integer from 0 to 5. When m1 is an integer of 2 or more, a plurality of R ²⁵ may be the same or different. M ^a+ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

R ²⁵ represents -SO ₃ ^- , -SO ₃ ^- M ^a+ , -SO ₃ H or SO ₂ NHR ²⁶ .

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The four R ²⁷ each independently represent a monovalent saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms.

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ in the formula (2) is the same as the group exemplified as the aromatic hydrocarbon group in R ¹ to R ⁴ . Wherein R ²¹ and R ²³ are a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and when the hydrogen atom contained in the aromatic hydrocarbon group is substituted, the substituted group is -SO ₃ ^- , -SO ₃ ^- M ⁺ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ are preferred. Further, more preferably, R ²¹ and R ²³ are a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be -SO ₃ ^- M ⁺ or -SO ₂ NHR ²⁶ substituent. When R ²¹ to R ^{24 are} these groups, it is advantageous in forming a color filter excellent in heat resistance.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ may be the same as those exemplified as the saturated hydrocarbon group in R ⁸ to R ¹¹ . -R ²⁶ in R ²¹ to R ²⁴ is preferably a hydrogen atom, a methyl group or an ethyl group, respectively.

As a -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ R ²⁶ in the number of branches based carbon chain alkyl group of 3-20 is preferred, C 6 branched chain alkyl group is more preferably of 12, 2-Ethylhexyl is more preferred.

M ^a+ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ . ⁺ N(R ²⁷ ) ₄ , preferably at least two of the four R ²⁷ are a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ²⁷ is preferably from 20 to 80, more preferably from 20 to 60.

The xanthene dye preferably contains any one or more of the compounds represented by the formula (1-1) to the formula (1-16) as a main component. Further, in the formula, Ra represents 2-ethylhexyl.

Among these compounds, a sulfonamide or a C.I. acid red 289 grade 4 ammonium salt of C.I. Acid Red 289 is more preferred. Examples of such a compound include compounds represented by the formula (1-1) to the formula (1-8), the formula (1-11), and the formula (1-12), respectively.

Further, in the same manner as described above, the dye produced by the method described in the upper right column to the lower left column of page 3 of JP-A No. 3-78702 can be produced by a method of reacting with an amine after chlorination.

Other preferred xanthene dyes include any one or more of the compounds represented by formula (1-17) to formula (1-31) as a main component.

The compound represented by the formula (1-17) to the formula (1-31) can be produced by the method described in the upper right column to the lower left column of page 3 of JP-A-3-78702. The method may, for example, be a method of reacting a compound represented by the formula (1a), a compound represented by the formula (1b) and a compound represented by the formula (1c). In the formulae (1b) and (1c), R ¹ to R ⁴ each have the same meaning as described above.

The colorant (A) may further contain a pigment in addition to a dye such as xanthene dye.

The pigments may, for example, be organic pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc.; and C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like. Among them, from the viewpoint of obtaining good brightness, the pigment is preferably at least one pigment selected from CI Pigment Violet 23, CI Pigment Blue 15:3, 15:6, and contains CI Pigment Blue 15:6. Better. The colorant (A) may contain one type or two or more types of pigments.

The pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment of a pigment surface by a polymer compound or the like, a sulfuric acid micronization method, or the like. The micronization treatment, the washing treatment by an organic solvent or water for removing impurities, the treatment for removing ionic impurities by an ion exchange method or the like, and the like.

The particle size of the pigment is preferably uniform. By containing a pigment dispersant and performing a dispersion treatment, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersing agents may be used alone or in combination of two or more.

When using a pigment dispersant, it is used in a quantity of pigment per 100 The parts by mass are preferably 100 parts by mass or less, more preferably 5 to 50 parts by mass. When the amount of the pigment dispersant used is in this range, there is a tendency that a pigment dispersion liquid having a uniform dispersion state can be obtained.

The content of the colorant (A) is usually from 1 to 70% by mass, preferably from 5 to 60% by mass, more preferably from 8 to 50% by mass, based on 100% by mass of the solid content of the colored curable resin composition. When the content of the colorant (A) is within the above range, a sufficient color density and mechanical strength are easily obtained when a color filter is produced. The "solid content of the colored curable resin composition" means the total of the components excluding the solvent (E) in the colored curable resin composition.

The content of the xanthene dye or the like in the colorant (A) is usually 1% by mass or more, preferably 3% by mass or more, preferably 5% by mass or more, more preferably 100% by mass of the coloring agent (A). It is 10% by mass or more. The content of the above dye may be 100% by mass in 100% by mass of the colorant (A).

The coloring agent (A) may contain a pigment. In this case, the content of the dye may be 90% by mass or less, or 80% by mass or less, or 70% by mass or less, based on 100% by mass of the coloring agent (A). It can be 50% by mass or less.

When the colorant (A) contains a pigment, the mass ratio of the content of the dye to the content of the pigment (content of the dye / content of the pigment) is usually from 1/99 to 99/1, preferably from 3/97 to 99/1, more The best is 3/97 to 70/30, and more preferably 3/97 to 50/50.

The mass ratio of the content of the dye to the content of C.I. Pigment Blue 15:6 when the C.I. Pigment Blue 15:6 containing the preferred pigment (the content of the dye) The content of /C.I. Pigment Blue 15:6) is preferably from 3/97 to 70/30, more preferably from 3/97 to 50/50. If the mass ratio is this range, it is advantageous to obtain high brightness and high contrast.

The colorant (A) may contain a pigment. As described above, the pigment preferably contains at least one pigment selected from CI Pigment Violet 23, CI Pigment Blue 15:3, 15:6, and preferably contains CI Pigment Blue 15:6. . From the viewpoint of obtaining good brightness, the content of CI Pigment Blue 15:6 in the pigment is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass in the pigment. More than %, more preferably 95% by mass or more, and most preferably 100% by mass.

[2] Resin (B)

The colored curable resin composition of the present invention contains one or more resins (B). The resin (B) is preferably an alkali-soluble resin. The alkali solubility means the property of a developer dissolved in an aqueous solution as an alkali compound. Examples of such an alkali-soluble resin include the following resins [K1] to [K6].

Resin [K1]: at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) [hereinafter sometimes referred to as "(a)") and cyclic ether having a carbon number of 2 to 4. The monomer (b) having a structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"). Copolymer.

Resin [K2]: (a), (b), and monomer (c) copolymerizable with (a) (except for (a) and (b)) (hereinafter sometimes referred to as "( Copolymer of c)").

Resin [K3]: a copolymer of (a) and (c).

Resin [K4]: a resin obtained by reacting the copolymer of (a) and (c) with (b).

Resin [K5]: a resin obtained by reacting the copolymer of (b) and (c) with (a).

Resin [K6]: a resin obtained by reacting the copolymer of (b) and (c) with (a) and reacting with a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid and antibutene; Acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2 , an unsaturated dicarboxylic acid such as 3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; methyl-5-northene-2, 3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methyl linkage Ring [2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]heptane- 2-olefin, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing a carboxyl group; maleic anhydride, citraconic anhydride, itaconic anhydride, 3- Vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Dimethyltetrahydrophthalic anhydride, dehydrogenation of 5,6-dicarboxybicyclo[2.2.1]hept-2-ene (seamic anhydride), etc. Unsaturated dicarboxylic acid anhydride; An unsaturated monovalent carboxylic acid of monovalent or higher bis(2-(methyl)propenyloxyethyl] succinate or mono[2-(methyl)propenyloxyethyl] phthalate (Meth)acryloxyalkylene ester; such as α-(hydroxymethyl)(meth)acrylic acid, unsaturated (meth)acrylic acid having a hydroxyl group and a carboxyl group in the same molecule.

Among them, (a) is preferably (meth)acrylic acid, maleic anhydride or the like from the viewpoint of copolymerization reactivity or solubility in an aqueous alkali solution.

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The notes on "(meth)acrylonitrile" and "(meth)acrylate" are also the same.

(b) means a cyclic ether structure having a carbon number of 2 to 4 (for example, at least 1 selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring). a polymerizable compound with an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether structure of 2 to 4 carbon atoms and a (meth) propylene decyloxy group.

(b) A monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), having an oxetane group and an ethylenically unsaturated bond The monomer (b2) (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)").

(b1) A monomer (b1-1) having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)"), and an unsaturated alicyclic hydrocarbon by epoxidation Constructed monomer (b1-2) [hereinafter sometimes referred to as "(b1-2)"].

(b1-1): glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, ortho -vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α- Methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-double (glycidyloxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-ginole (glycidol) Oxymethyl)styrene, 2,3,5-gin (glycidoxymethyl)styrene, 2,3,6-gin (glycidoxymethyl)styrene, 3,4,5-parameter (shrinkage) Glyceroloxymethyl)styrene, 2,4,6-gin (glycidoxymethyl)styrene, and the like.

(b1-2): vinylcyclohexene monooxide, 1,2-epoxy 4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Chemical Industry Co., Ltd.), (meth)acrylic acid 3 , 4-epoxycyclohexylmethyl ester (for example, Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; Daicel Chemical Industry Co., Ltd. A compound represented by the formula (I), a compound represented by the formula (II), and the like.

In the formulae (I) and (II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X ¹ and X ² each independently represent a single bond ^{system, * - R c -, *} - R c -O -, * - R c -S-, or * -R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the key with O.

The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a second butyl group or a t-butyl group.

The alkyl group in which a hydrogen atom is substituted with a hydroxyl group may, for example, be a methylol group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group or a 1-hydroxy-1 group. -methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

R ^a and R ^{b are} preferably a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group constituting R ^c include a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane- 1,5-diyl, hexane-1,6-diyl and the like.

X ¹ and X ^{2 are} preferably a single bond, a methylene group, an exoethyl group, a *-CH ₂ -O- (* represents a bond with O), a *-CH ₂ CH ₂ -O- group, It is preferably a single bond, *-CH ₂ CH ₂ -O- group.

Specific examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferred are formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15). More preferably, it is Formula (I-1), Formula (I-7), Formula (I-9), Formula (I-15).

Specific examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably, it is a formula (II-1), a formula (II-3), a formula (II-5), a formula (II-7), a formula (II-9), and a formula (II-11). To the formula (II-15), more preferred are the formula (II-1), the formula (II-7), the formula (II-9), and the formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. These lines can be mixed in any ratio. When mixing, the mixing ratio is based on the formula (I): formula (II) [mole ratio], preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and even more preferably It is 20:80 to 80:20.

The monomer (b2) having an oxetane group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth) acryloxy group. Preferred examples of (b2) include 3-methyl-3-(methyl)propenyl methoxymethyloxetane and 3-ethyl-3-(methyl)propenyl methoxymethyl group. Oxetane, 3-methyl-3-(meth)acryloyloxyethyloxetane, 3-ethyl-3-(methyl)propenyloxyethyloxetane alkyl.

The monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group.

Preferable examples of the (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Specific examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and (butyl) (meth)acrylate, and (methyl) Tert-butyl acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid ring Amyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth) acrylate In the technical field, the conventional name is "(meth)propylene dicyclopentanyl ester". Moreover, it is also called "tricyclodecyl (meth) acrylate", tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate [in the technical field, the conventional name is "Dicyclopentenyl (meth) acrylate"], dicyclopentyloxyethyl (meth) acrylate, isodecyl (meth) acrylate, adamantyl (meth) acrylate, (methyl) (meth) acrylate such as allyl acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate; (methyl) Hydroxy-containing (meth) acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, and itaconic acid Dicarboxylic acid diester such as ethyl ester; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1] Hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl) Bicyclo [2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5 , 6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclic ring [2 .2.1] Hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1] Hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5- Hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonyl Bicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonyl bicyclo [2.2.1] hept-2- Alkene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2 - olefinic and other bicyclic unsaturated compounds; N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-amber Imino-3-butylenediamine benzoate, N-succinimide-4-butylimide butyl ester, N-succinimide-6-cis a dicarbonyl group such as butylene diimide hexanoate, N-succinimide-3-butanediimide propionate, N-(9-acridinyl) maleimide Yttrium imide derivatives; styrene, α-methylstyrene, m-methylstyrene, -methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, (c) is benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, N-phenylbutylene Amidoxime, N-cyclohexylm-methylenediamine, N-benzylthene maleimide, bicyclo[2.2.1]hept-2-ene, and the like are preferred. Further, in terms of excellent developability at the time of pattern formation, (c) is preferably benzyl (meth)acrylate or tricyclodecyl (meth)acrylate.

In all the structural units constituting the resin [K1], the ratio of the structural units of each source in the resin [K1] is preferably in the following range.

The structural unit of the source (a): 2 to 50 mol% (more preferably 10 to 45 mol%), the structural unit of the source (b), in particular the structural unit of the source (b1): 50 to 98 Molar% (more preferably 55 to 90 mol%).

When the ratio of the structural unit of the resin [K1] is in the above range, the stability and the developability are excellent, and the solvent resistance of the obtainable pattern tends to be excellent.

Resin [K1] can be referred to the document "Experimental Method for Polymer Synthesis" (Dazu Takashi, Institute of Chemicals, Inc., 1st Edition, 1st Brush, issued on March 1, 1972) and the literature Citations Dedicated to manufacturing.

Specifically, a predetermined amount of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent, and the like are charged into a reaction container, and stirred and heated in an oxygen-free atmosphere. The method of insulation. Moreover, the polymerization initiator, solvent, and the like used herein are not particularly limited, and those generally used in the field can be used. Examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), and an organic peroxide ( Benzoyl peroxide, etc.). The solvent may be any one that dissolves each monomer, and a solvent (E) or the like described later may be used as a solvent for the colored curable resin composition.

The obtained copolymer may be used as it is, or may be used as a solid (powder) by reprecipitation or the like. In particular, by using the solvent (E) described later as the solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In all the structural units constituting the resin [K2], the ratio of the structural units of the respective sources in the resin [K2] is preferably in the following range.

The structural unit of (a) is: 4 to 45 mol% (more preferably 10 to 30 mol%), the structural unit of (b), especially the structural unit derived from (b1): 2 to 95 Molar% (more preferably 5 to 80 mol%), a structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%).

If the ratio of the structural unit of the resin [K2] is within the above range, it is preserved. The stability, developability, and the solvent resistance, heat resistance, and mechanical strength of the obtainable pattern tend to be excellent.

The resin [K2] can be produced in the same manner as the method described in the method for producing the resin [K1]. Specifically, a predetermined amount of (a), (b) (particularly (b1)) and (c), a polymerization initiator and a solvent are charged into a reaction container, and the mixture is carried out in an oxygen-free atmosphere. Stirring, heating, and heat preservation methods. As the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) may be used by reprecipitation or the like.

In all the structural units constituting the resin [K3], the ratio of the structural units of the respective sources in the resin [K3] is preferably in the following range.

The structural unit derived from (a): 2 to 55 mol% (more preferably 10 to 50 mol%), the structural unit derived from (c): 45 to 98 mol% (more preferably 50 to 90 mol) ear%).

The resin [K3] can be produced in the same manner as the method described in the method for producing the resin [K1].

The resin [K4] can be obtained by obtaining a copolymer of (a) and (c) and (b) a cyclic ether having a carbon number of 2 to 4, particularly (a) having an oxirane ring It is produced by (a) having a carboxylic acid and/or a carboxylic acid anhydride. Specifically, the copolymers of (a) and (c) are first produced in the same manner as the method described in the method for producing the resin [K1]. In this case, in all the structural units constituting the copolymer of (a) and (c), the ratio of the structural units of the respective sources is preferably in the following range.

From the structural unit of (a); 5 to 50 mol% (more preferably 10 to 45 mol%), derived from the structural unit of (c); 50 to 95 mol% (more preferably 55 to 90 mol) ear%).

Then, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with (b) a cyclic ether having a carbon number of 2 to 4, particularly with (b1) having an oxygen The cyclopropane ring reacts. Specifically, after the production of the copolymer of (a) and (c), the gas atmosphere in the flask is replaced by nitrogen to air, and (b) (particularly (b1)), a carboxylic acid or a carboxylic anhydride and a ring The reaction catalyst (such as dimethylaminomethyl phenol) and a polymerization inhibitor (hydroquinone or the like) of the ether structure are placed in a flask and reacted at 60 to 130 ° C for 1 to 10 hours. Resin [K4].

The amount of use (b), particularly the amount of (b1) used, is preferably 5 to 80 moles, more preferably 10 to 75 moles, relative to (a) 100 moles. By setting it as this range, the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to become favorable. Since the cyclic ether structure has high reactivity and does not easily remain unreacted (b), (b) used in the resin [K4] is preferably (b1), more preferably (b1-1).

The reaction catalyst is preferably used in an amount of from 0.001 to 5% by mass based on the total amount of (a), (b) (particularly (b1)) and (c). The polymerization inhibitor is preferably used in an amount of from 0.001 to 5% by mass based on the total amount of (a), (b) and (c).

The reaction conditions such as the charging method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production equipment, the calorific value caused by the polymerization, and the like. Moreover, the heat generated by the manufacturing equipment and the polymerization can be considered in the same manner as the polymerization conditions. The loading method and reaction temperature are appropriately adjusted.

The resin [K5] is a copolymer of (b) (particularly (b1)) and (c) in the same manner as in the production method of the resin [K1] in the first stage. Similarly to the above, the obtained copolymer may be directly used as a solution after the reaction, or a solution obtained by concentration or dilution, or may be taken out as a solid (powder) by reprecipitation or the like.

The ratio of the structural units derived from (b) (particularly (b1)) and (c) with respect to the total number of moles of all the structural units constituting the above copolymer is preferably in the following range.

The structural unit derived from (b), in particular the structural unit derived from (b1): 5 to 95 mol% (more preferably 10 to 90 mol%), the structural unit derived from (c): 5 to 95 Molar% (more preferably 10 to 90 mol%).

Further, the copolymer of (b) (particularly (b1)) and (c) has a cyclic ether structure derived from (b) and (a) under the same conditions as in the production method of the resin [K4]. The carboxylic acid or carboxylic acid anhydride is reacted, whereby the resin [K5] can be obtained. The amount of (a) to be reacted with the above copolymer is preferably from 5 to 80 moles, relative to (b) (particularly (b1)) 100 moles. Since the cyclic ether structure has high reactivity and does not easily remain unreacted (b), (b) used for the production of the resin [K5] is preferably (b1), and (b1-1) is more preferable. .

The resin [K6] is a resin obtained by further reacting a carboxylic anhydride with a resin [K5].

Hydroxyl groups produced by the reaction of a cyclic ether structure with a carboxylic acid or a carboxylic anhydride Base, reacting with a carboxylic anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetra. Hydrogen phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]g-2 - an alkenic anhydride (seamic anhydride) or the like.

Among the resins [K1] to [K6], the preferred resin as the resin (B) is [K1] or [K2]. The resin (B) may contain one type of resin, or may contain two or more types of resins.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000. When the molecular weight is in the above range, the unexposed portion has high solubility in the developer, and the residual film ratio and hardness of the obtained pattern tend to be high. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the solution of the resin (B) is preferably from 5 to 180 mg-KOH/g, more preferably from 10 to 100 mg-KOH/g, still more preferably from 12 to 50 mg-KOH/g. The acid value is a value obtained by measuring the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained, for example, by titration with an aqueous potassium hydroxide solution.

The content of the resin (B) in the solid content of the colored curable resin composition is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, still more preferably from 15 to 30% by mass. Resin (B) When the amount is in the above range, the solubility of the unexposed portion in the developer tends to be high.

[3] Polymerizable compound (C)

The polymerizable compound (C) is a compound obtained by polymerization of an active radical generated by a polymerization initiator (D) by irradiation with light or the like. The colored curable resin composition of the present invention contains a polymerizable compound having a hydroxyl value of 100 mgKOH/g or more in terms of the polymerizable compound (C). When the coloring-curable resin composition of the present invention contains the polymerizable compound (C), a color filter excellent in heat resistance can be formed regardless of whether or not the coloring agent (A) contains a dye.

The polymerizable compound (C) may contain one type of polymerizable compound having a hydroxyl value of 100 mgKOH/g or more, and may contain two or more kinds of polymerizable compounds having a hydroxyl value of 100 mgKOH/g or more. In addition, the polymerizable compound (C) may be one or two or more kinds of polymerizable compounds having a hydroxyl value of 100 mgKOH/g or more and one or two or more kinds of polymerizable compounds having a hydroxyl value of less than 100 mgKOH/g. mixture. In the case of the mixture, the polymerizable compound (C) is preferably a hydroxyl group value of the mixture of 100 mgKOH/g or more from the viewpoint of heat resistance. The hydroxyl value of the polymerizable compound (C) is preferably 110 mgKOH/g or more from the viewpoint of heat resistance. The hydroxyl value of the polymerizable compound (C) is usually 170 mgKOH/g or less. The hydroxyl value was measured in accordance with the description of the examples described later.

The polymerizable compound (C) is a compound having a polymerizable ethylenically unsaturated bond and a hydroxyl group. The polymerizable compound (C) is preferably one or more ethylenically unsaturated bonds in the molecule, and has three The above is better. Specific examples of the polymerizable compound having a hydroxyl value of 100 mgKOH/g or more include pentaerythritol triacrylate, pentaerythritol di(meth)acrylate, and ethoxylated pentaerythritol tri(meth)acrylic acid. Ester, propane oxidized neopentyl alcohol triacrylate, trimethylolpropane di(meth) acrylate, ethoxylated trimethylolpropane di(meth) acrylate, ethoxylated glycerol di(methyl) Acrylate, propane oxidized glycerol di(meth) acrylate, bis(trimethylol)propane tri(meth) acrylate, bis(trimethylol)propane tri(meth) acrylate, Propylene di(trimethylol)propane triacrylate or the like.

The content of the polymerizable compound (C) is usually a mass ratio (content of the polymerizable compound (C) / resin (B)) to the content of the resin (B) in the colored curable resin composition. 0.2 to 10, preferably 0.6 to 8, more preferably 0.6 to 5, still more preferably 0.75 to 5. When the mass ratio is within the above range, a colored coating film having better heat resistance can be obtained.

[4] Polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound which can initiate polymerization by the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include an anthraquinone compound such as an O-mercaptopurine compound, an alkylphenone compound, a biimidazole compound, and the like. a compound, a mercaptophosphine oxide compound or the like.

The polymerization initiator (D) can also take into account the shape of the sensitivity and the shape of the precise pattern. Two or more types are used together. The polymerization initiator (D system is preferably a ruthenium compound containing an O-fluorenyl ruthenium compound or the like) because it is advantageous in precisely producing the sensitivity and having a desired shape of the wire pattern.

The O-indenyl compound is a compound having a structure represented by the formula (d). Hereinafter, * indicates a keying key.

The O-indenyl compound is a compound represented by the formula (d1) (hereinafter sometimes referred to as "compound (d1)") or a compound represented by the formula (d2) (hereinafter sometimes referred to as "compound (d2)" At least one selected from the group consisting of the compound represented by the formula (d3) (hereinafter sometimes referred to as "compound (d3)") is preferred.

In the formulae (d1) to (d3), R ^d1 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, and a carbon number which may have a substituent a group having a substituent of an alkyl group or an aromatic hydrocarbon group of 1 to 15 and an alkanediyl group derived from the alkyl group, and a methylene group (-CH ₂ -) contained in the above alkyl group may also be substituted Is -O-, -CO-, -S-, -SO ₂ - or -NR ^d5 -.

R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms or an alkyl group having 1 to 10 carbon atoms, and R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. Or a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, R ^d4 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, The methylene group (-CH ₂ -) contained in the above aliphatic hydrocarbon group may be substituted with -O-, -CO- or -S-, and the methine group (-CH<) contained in the above aliphatic hydrocarbon group may be substituted with - PO ₃ <, the hydrogen atom contained in the above aliphatic hydrocarbon group may be substituted by an OH group.

R ^d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (-CH ₂ -) contained in the alkyl group may be substituted with -O- or -CO-.

The carbon number of the aromatic hydrocarbon group represented by R ^d1 is preferably from 6 to 15, more preferably from 6 to 12, still more preferably from 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, and a terphenyl group. The phenyl group and the naphthyl group are preferred, and the phenyl group is more preferred.

The aromatic hydrocarbon group represented by R ^d1 may have one or two or more substituents.

The substituent is preferably substituted at the α-position or the γ-position of the aromatic hydrocarbon group, and more preferably at the γ-position.

The substituent may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, an undecyl group, a dodecyl group, a thirteen group or a tetradecyl group An alkyl group having a carbon number of 1 to 15 such as a fifteen group; a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom; and the like.

The carbon number of the alkyl group as the above substituent is preferably from 1 to 10, more preferably from 1 to 7. The alkyl group as the substituent may be any of a linear chain, a branched chain, and a cyclic group, and may be a group in which a chain group and a cyclic group are combined. The methylene group (-CH ₂ -) contained in the alkyl group as the substituent may be substituted with -O- or -S-. Further, the hydrogen atom contained in the alkyl group may be substituted by a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom, and is preferably substituted by a fluorine atom.

The alkyl group which is a substituent in the aromatic hydrocarbon group represented by R ^d1 may, for example, be a group represented by the following formula. Where * represents a bond key.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^d1 include a group represented by the following formula. Where * represents a bond key.

The aromatic hydrocarbon group which may have a substituent represented by R ^d1 is preferably a group represented by the following formula.

(wherein R ^d6 represents an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom, and a hydrogen atom contained in R ^d6 may be substituted by a halogen atom. m2 represents an integer of 1 to 5.)

The alkyl group represented by R ^{d6 is the same} as the alkyl group exemplified as the substituent of the aromatic hydrocarbon group represented by R ^d1 . The carbon number of R ^d6 is preferably from 2 to 7, more preferably from 2 to 5. Further, the alkyl group represented by R ^d6 may be any of a linear chain, a branched chain, and a ring, and is preferably a chain.

The halogen atom in R ^d6 may, for example, be a fluorine atom, a chlorine atom, an iodine atom or a bromine atom, and is particularly preferably fluorine. It is preferred that two or more and ten or less hydrogen atoms contained in R ^d6 are substituted by a halogen atom, and it is preferred to substitute three or more and six or less hydrogen atoms. The substitution position of the R ^d6 O-group is preferably in the ortho position and the para position, and is particularly preferable in the alignment. The m2 is preferably 1 to 2, and particularly preferably 1.

The carbon number of the heterocyclic group represented by R ^d1 is preferably from 3 to 20, more preferably from 3 to 10, still more preferably from 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, a decyl group, a benzofuranyl group, and a carbazolyl group.

The heterocyclic group represented by R ^d1 may have one or two or more substituents. The substituent is the same as the group exemplified as the substituent which the aromatic hydrocarbon group represented by R ^d1 may have.

The number of carbon atoms of the alkyl group represented by R ^d1 is preferably from 1 to 12. The alkyl group represented by R ^d1 may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an eleven group, a dodecyl group or a thirteen group group. , fourteen bases and fifteen bases, etc. The alkyl group may be any of a linear chain, a branched chain, and a cyclic group, or may be a group in which a chain group and a cyclic group are combined. Further, in the alkyl group represented by R ^d1 , the methylene group (-CH ₂ -) may be substituted with -O-, -CO-, -S-, -SO ₂ - or -NR ^d5 -, and the hydrogen atom may be OH. Substituted or SH group substituted.

R ^d5 represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be in the form of a chain (linear or branched chain), or may be in the form of a ring, a linear chain, a branched chain, or a ring, or may be a combination of a chain group and a cyclic group. The basis. In the alkyl group of R ^d5 , the methylene group (-CH ₂ -) may be substituted with -O- or -CO-.

The alkyl group which may have a substituent represented by R ^{d1 is} specifically a group represented by the following formula. * indicates the key combination.

Further, the carbon number of the combination of the aromatic hydrocarbon group and the alkanediyl group shown by R ^d1 is preferably from 7 to 33, more preferably from 7 to 18, still more preferably from 7 to 12. The group of the combination may have one or two or more substituents, and the substituent may be the same as the group exemplified as the aromatic hydrocarbon group or the substituent which the alkyl group may have. The group represented by the above-mentioned R ^d1 in which the aromatic hydrocarbon group and the alkanediyl group are combined may, for example, be an aralkyl group. Specific examples thereof include a group represented by the following formula. Where * represents a bond key.

Among them, R ^d1 is preferably an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have a substituent.

The carbon number of the aromatic hydrocarbon group represented by R ^d2 is preferably from 6 to 15, more preferably from 6 to 12, still more preferably from 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, and a terphenyl group.

The carbon number of the heterocyclic group represented by R ^d2 is preferably from 3 to 20, more preferably from 3 to 10, still more preferably from 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, a decyl group, a benzofuranyl group, and a carbazolyl group.

The carbon number of the alkyl group represented by R ^d2 is preferably from 1 to 7, more preferably from 1 to 5, still more preferably from 1 to 3. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group. The alkyl group may be any of a linear chain, a branched chain, and a cyclic group, or may be a group in which a chain group and a cyclic group are combined.

R ^d2 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, still more preferably a chain alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group.

The carbon number of the aromatic hydrocarbon group represented by R ^d3 is preferably from 6 to 15, more preferably from 6 to 12, still more preferably from 6 to 10. The aromatic hydrocarbon group may, for example, be a phenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a biphenyl group or a terphenyl group, and more preferably a phenyl group or a naphthyl group.

The aromatic hydrocarbon group represented by R ^d3 may have one or two or more substituents. The substituent is preferably substituted at the α-position or the γ-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a decyl group. And an alkyl group having a carbon number of 1 to 15 such as a mercapto group; a carbon number such as an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a nonenyl group, and a nonenyl group; Alkenyl to 15; etc.

The aromatic hydrocarbon group represented by R ^d3 may have an aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has a carbon number of from 1 to 7, and the aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic group, or may be a combination of a chain group and a cyclic group. base. Further, the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group may be substituted with -O-, -CO- or -S-, and the methine group (-CH<) may be substituted with -N<.

Examples of the aliphatic hydrocarbon group include a group represented by the following formula. Where * represents a bond key.

The aromatic hydrocarbon group which may have a substituent represented by R ^d3 may, for example, be a group represented by the following formula. Where * represents a bond key.

The carbon number of the heterocyclic group represented by R ^d3 is preferably from 3 to 20, more preferably from 3 to 10, still more preferably from 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, a decyl group, a benzofuranyl group, and a carbazolyl group. In addition, the heterocyclic group represented by R ^d3 may have one or two or more substituents, and the substituent may be the same as those exemplified as the substituent which the aromatic hydrocarbon group represented by R ^d1 may have.

Wherein R ^d3 is preferably an aromatic hydrocarbon group having a substituent which is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms), and a substituent group The number is preferably two or more and five or less.

The carbon number of the aromatic hydrocarbon group represented by R ^d4 is preferably from 6 to 15, more preferably from 6 to 12, still more preferably from 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group and a terphenyl group. The phenyl group and the naphthyl group are more preferably a phenyl group. Further, the aromatic hydrocarbon group represented by R ^d4 may have one or two or more substituents. The substituent may be the same as the substituent which the aromatic hydrocarbon group of R ^d1 may have.

The carbon number of the aliphatic hydrocarbon group represented by R ^d4 is preferably from 1 to 13, more preferably from 2 to 10, still more preferably from 4 to 9. The aliphatic hydrocarbon group represented by R ^d4 may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an eleven group, a dodeca group or a thirteen group. An alkyl group of a group, a tetradecyl group, and a fienyl group; a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, Alkenyl groups such as hexenyl, dodecenyl, tridecenyl, tetradecenyl and pentadecenyl; and the like. These aliphatic hydrocarbon groups may be in the form of a chain (linear or branched chain), may be cyclic, or may be a group in which a chain group and a cyclic group are combined. In the aliphatic hydrocarbon group of R ^d4 , the methylene group (-CH ₂ -) may be substituted with -O-, -CO- or -S-, and the methine group (-CH<) may be substituted with -PO ₃ <, the above fat The hydrogen atom contained in the group hydrocarbon group may also be substituted with an OH group.

The aliphatic hydrocarbon group which may have a substituent represented by R ^d4 may, for example, be a group represented by the following formula. Where * represents a bond key.

R ^d4 is preferably a chain-like aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituent, and more preferably a branched chain alkyl group having no substituent.

The compound (d1) is a compound represented by the formula (d1), specifically a compound represented by the formula (d1) having each substituent described in the column (d1-1) to have a (d1-67)- The compound represented by the formula (d1) of each substituent described in the column. In Tables 1 to 7, * indicates a bonding key.

Among them, a compound having a substituent described in the column (d1-3) is preferably a compound having a substituent described in the column (d1-6), and a compound having a substituent described in the column (d1-18). a compound having a substituent described in the column (d1-52), a compound having a substituent described in the column (d1-55), a compound having a substituent described in the column (d1-56), and having (d1-60) a compound of the substituent described in the column, a compound having a substituent described in the column (d1-61); more preferably a compound having a substituent described in the column (d1-3) to have a (d1-6)- a compound of the substituent described in the column, having (d1-18) a compound having a substituent described in the column to a compound having a substituent described in the column (d1-41), more preferably a compound having a substituent described in the column (d1-24), having a column (d1-36) The compound of the substituent described above is a compound having a substituent described in the column (d1-40), and particularly preferably a compound having a substituent described in the column (d1-24).

The compound (d1) can be produced, for example, by the production method described in JP-A-2014-500852.

Compound (d2) is preferably: R ^d1 alkyl group may have a substituent group of carbon number 1 to 15, R ^d2 is an alkyl group having 1 to 10 carbons, R ^d3 may have a substituent group of carbon number 6 to 18 aromatic a compound having a hydrocarbon group and R ^d4 which may have a substituent of an aliphatic hydrocarbon group having 1 to 15 carbon atoms; more preferably: R ^d1 represents a methyl group, an ethyl group or a propyl group, and R ^d2 represents a methyl group, an ethyl group or a propyl group. R ^d3 represents a phenyl group substituted by a methyl group, and R ^d4 is a compound of a methyl group, an ethyl group or a propyl group, and more preferably: R ^d1 and R ^d2 are a methyl group, R ^d3 is an o-tolyl group and R ^d4 is Ethyl compound.

The compound (d3) is preferably a compound wherein R ^d1 is an alkyl group having 1 to 15 carbon atoms which may have a substituent, and R ^d2 is an aromatic hydrocarbon group having 6 to 18 carbon atoms; more preferably: R ^d1 is a hexyl group and R ^D2 is a compound of phenyl.

Examples of such an O-indenyl hydrazine compound include N-benzylideneoxy-1-(4-phenylhydrothiophenyl)butan-1-ol-2-imine and N-benzidine. Oxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylhydrothiophenyl)- 3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3 -yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Cyclopentyloxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2- Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylidene-1-(9-ethyl-6-(2) -Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercial products such as IRGACURE OXE01, OXE02, OXE03 (above, BASF) and N-1919 (made by ADEKA) can also be used. In the case of these O-fluorenyl ruthenium compounds, there is a tendency to obtain a color filter excellent in etching performance.

The alkylphenone compound is a compound having a structure represented by the formula (d4) or a structure represented by the formula (d5). In these configurations, the benzene ring may have a substituent.

As a compound having a structure represented by the formula (d4), 2-methyl-2-morpholine-1-(4-methylhydrothiophenyl)propan-1-one, 2-dimethylamine can be mentioned. 1-(4-morpholinylphenyl)-2-benzylidenebutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]- 1-[4-(4-morpholino)phenyl]butan-1-one or the like. IRGACURE 369, 907, 379 can also be used (above BASF) Commercial products such as company system).

The compound having a structure represented by the formula (d5) may, for example, be 2-hydroxy-2-methyl-1-phenylpropan-1-one or 2-hydroxy-2-methyl-1-[4-(2) -hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Polymer, α,α-diethoxyacetophenone, benzyldimethylketal, and the like.

In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d4).

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2,3-dichlorobenzene). -4,4',5,5'-tetraphenylbiimidazole (for example, see JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-double (2- Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis (2 -Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, see JP-A-48-38403, JP-A-62-174204, etc.) An imidazole compound in which a phenyl group at the 4,4', 5, and 5'-position is substituted with an alkoxycarbonyl group (for example, see JP-A-7-10913, etc.). Among them, a compound represented by the following formula or a mixture thereof is preferred.

three The compound can be exemplified by 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-three. 2,4-bis(trichloromethyl)-6-(4-methoxynaphthalene)-1,3,5-three , 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-tri , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri Wait.

The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or the like.

Further examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Compounds; benzophenone, methyl o-benzhydrylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3' a benzophenone compound such as 4,4'-tetra(t-butylcarbonyl peroxide) benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2- An anthraquinone compound such as ethyl hydrazine or camphor quinone; 10-butyl-2-chloroacridone, benzil, methyl benzhydrazide, a titanium ruthenium compound, and the like. These are related to

It is preferred to use a combination of a polymerization starting assistant (D1) (particularly an amine).

The content of the polymerization initiator (D) is preferably from 0.1 to 30 parts by mass, more preferably from 5 to 25 parts by mass, even more preferably 100 parts by mass based on the total amount of the resin (B) and the polymerizable compound (C). It is 10 to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is high and the exposure time tends to be shortened, so that the productivity of the color filter tends to be improved.

[5] Polymerization start aid (D1)

The polymerization initiation aid (D1) is a compound or a sensitizer used to promote polymerization of a polymerizable compound which starts polymerization by a polymerization initiator. When the polymerization initiation aid (D1) is contained, it can be used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include an amine compound, an alkoxy fluorene compound, a thioxanthone compound, and a carboxylic acid compound. Among them, a thioxanthone compound is preferred. Two or more kinds of polymerization starting aids (D1) may also be used in combination.

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethylamino group. Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'- Bis(dimethylamino)benzophenone (commonly known as miconesone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamine) Benzophenone, etc., of which 4,4'-bis(diethylamine) Benzo) benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

The alkoxy ruthenium compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl-9. 10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthiaxanone, and 2,4-dichlorothiazepinone. , 1-chloro-4-propoxy thioxanthone and the like.

The carboxylic acid compound may, for example, be phenylhydrothioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid or dimethylphenylthioacetic acid. , methoxyphenyl thioacetic acid, dimethoxyphenyl thioacetic acid, chlorophenyl thioacetic acid, dichlorophenyl thioacetic acid, N-phenylglycine, phenoxyacetic acid , naphthothioacetic acid, N-naphthalene acid, naphthoxyacetic acid, and the like.

The content of the polymerization initiation aid (D1) is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiation aid (D1) is within the above range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

[6] thiol compound (T)

The colored curable resin composition of the present invention may contain a thiol compound (T), and the thiol compound (T) may contain one or more thiol compounds. When the polymerization initiator (D) is an O-mercaptopurine compound or the like In the case of a compound and/or a biimidazole compound, it is particularly preferred to use a thiol compound (T). The thiol compound (T) is a compound having at least one thiol group (-SH) in the molecule. The thiol compound (T) is preferably a compound having one thiol group in the molecule.

As a compound having one hydrogenthio group in the molecule, a 2-hydrogenthio group is exemplified. Oxazole, 2-hydrothiothiazole, 2-hydrothiobenzimidazole, 2-hydrothiobenzothiazole, 2-hydrothiobenzoate Oxazole, 2-hydrothionicotinic acid, 2-hydrothiopyridine, 2-hydrothiopyridin-3-ol, 2-hydrothiopyridine-N-oxide, 4-amino-6-hydroxy- 2-Hydroxythiopyrimidine, 4-amino-6-hydroxy-2-hydrothiopyrimidine, 4-amino-2-hydrothiopyrimidine, 6-amino-5-nitroso-2-thiourea Pyridinium, 4,5-diamino-6-hydroxy-2-hydrothiopyrimidine, 4,6-diamino-2-hydrothiopyrimidine, 2,4-diamino-6-hydroxythio Pyrimidine, 4,6-dihydroxy-2-hydrothiopyrimidine, 4,6-dimethyl-2-hydrothiopyrimidine, 4-hydroxy-2-hydrothio-6-methylpyrimidine, 4-hydroxyl -2-Hexylthio-6-propylpyrimidine, 2-hydrothio-4-methylpyrimidine, 2-hydrothiopyrimidine, 2-thioureapyrimidine, 3,4,5,6-tetrahydropyrimidine 2-thiol, 4,5-diphenylimidazole-2-thiol, 2-hydrothioimidazole, 2-hydrothio-1-methylimidazole, 4-amino-3-indolyl-5 -Hexylthio-1,2,4-triazole, 3-amino-5-hydroxythio-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole- 3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-hydrothio 1H-1,2,4-triazole-3-thiol, 2-amine 5--5-hydroxythio-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-dihydrothio-1,3 , 4-thiadiazole, (furan-2-yl) Mercaptan, 2-hydrothio-5-thiazolone, 2-hydrothiothiazoline, 2-hydrothio-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5- Mercaptan, 2-quinoline thiol, 2-hydrothio-5-methylbenzimidazole, 2-hydrothio-5-nitrobenzimidazole, 6-amino-2-hydrothiobenzoate Thiazole, 5-chloro-2-hydrothiobenzothiazole, 6-ethoxy-2-thiothiobenzothiazole, 6-nitro-2-hydrothiobenzothiazole, 2-hydrothionaphthalene Imidazole, 2-hydrothionaphthyl Oxazole, 3-hydrothio-1,2,4-triazole, 4-amino-6-hydrothiopyrazole [2,4-d]pyridine, 2-amino-6-anthracenethiol, 6 - Hydrogenthioguanidine and 4-hydrothio-1H-pyrazole [2,4-d]pyrimidine and the like.

Examples of the compound having two or more hydrogenthio groups in the molecule include hexane dithiol, decane dithiol, 1,4-bis(methylhydrothio)benzene, butanediol bis (3- Hydrogenthiopropionate), butanediol bis(3-hydrothioacetate), ethylene glycol bis(3-hydrothioacetate), trimethylolpropane ginseng (3-hydrogen sulfide) Base acetate), butanediol bis(3-hydrothiopropionate), trimethylolpropane ginseng (3-hydrothiopropionate), trimethylolpropane ginseng (3-hydrogen sulphide) Base acetate), neopentyl sterol oxime (3-hydrothiopropionate), neopentyl sterol oxime (3-hydrothioacetate), hydroxyethyl ginseng (3-hydrothiopropyl propyl) Acid ester), neopentyl sterol oxime (3-hydrothiobutyl butyl ester), and 1,4-bis(3-hydrothiobutyloxy) butane.

The content of the thiol compound (T) is preferably from 0.5 to 50 parts by mass, more preferably from 5 to 45 parts by mass, still more preferably from 10 to 40 parts by mass, per 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is within the above range, the sensitivity is high and the developability is good.

[7] Solvent (E)

The colored curable resin composition of the present invention preferably contains a solvent (E), and the solvent (E) preferably contains one or more solvents. Examples of the solvent (E) include an ester solvent (a solvent containing -COO-) and an ester solvent. Other ether solvents (solvent containing -O-), ether ester solvent (solvent containing -COO- and -O-), ketone solvent (solvent containing -CO-) other than ester solvent, alcohol solvent, aromatic hydrocarbon Solvent, guanamine solvent and dimethyl hydrazine.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ring Hexanol acetate and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3 -methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anise Ether, phenethyl ether and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. , ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy Ethyl 2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like.

The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 4-methyl-2-pentanone. , cyclopentanone, cyclohexanone and isophorone.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene. Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

The solvent (E) is preferably an organic solvent containing a boiling point of 120 ° C or more and 180 ° C or less in 1 atm from the viewpoint of coatability and drying property. Wherein the solvent (E) comprises propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone And at least one selected from the group consisting of N,N-dimethylformamide is preferred to comprise propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate More preferably, at least one selected from the group consisting of ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate is preferred.

The content of the solvent (E) in the colored curable resin composition It is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass. In other words, the solid content of the colored curable resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is improved, and the color density is not insufficient when the color filter is formed. Therefore, the display characteristics tend to be good.

[8] Leveling agent (F)

The colored curable resin composition of the present invention may contain one or more kinds of leveling agents (F). The leveling agent (F) may, for example, be a polyfluorene-based surfactant (having no fluorine atom), a fluorine-based surfactant, a polyfluorene-based surfactant having a fluorine atom, or the like. These may also have a polymerizable group in the side chain.

Examples of the polyoxymethylene-based surfactant include a surfactant having a decane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Dow Corning Toray Co., Ltd.) ; KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan Contract Company) System) and so on.

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, it can be cited as: Fluorad (registered trademark) FC430, FC431 of the same series (made by Sumitomo 3M Co., Ltd.); Mega Fac (registered trademark) F142D, F171 of the same series, F172 of the same series, F173 of the same series, F177 of the same series, F183 of the same series, the same series F554, the same series of R30, the same series of RS-718-K (made by DIC Corporation); F-top (registered trademark) EF301, the same series of EF303, the same series of EF351, the same series of EF352 (Mitsubishi Materials) Electronic Technology Co., Ltd.); SURFLON (registered trademark) S381, S382 of the same series, SC101 of the same series, SC105 of the same series (made by Asahi Glass Co., Ltd.), and E5844 (made by Daikin Fine Chemical Laboratory Co., Ltd.) .

The polyoxo-based surfactant having a fluorine atom may, for example, be a surfactant having a decane bond and a fluorocarbon chain in the molecule. Specific examples include Mega Fac (registered trademark) R08, BL20 of the same series, F475 of the same series, F477 of the same series, and F443 (made by DIC Corporation) of the same series.

In the coloring curable resin composition, the content of the leveling agent (F) is usually 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more, 0.1% by mass or less, more preferably 0.005% by mass or more, or 0.05. Below mass%. Further, the content does not include the content of the above pigment dispersant.

[9] Antioxidant (G)

From the viewpoint of improving heat resistance and light resistance of the colorant (A), it is preferred that the coloring curable resin composition contains an antioxidant. anti-oxidation The agent is not particularly limited as long as it is an antioxidant generally used in the industry, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, or the like can be used. Two or more kinds of antioxidants can also be used.

Examples of the phenolic antioxidant include Irganox 1010 (nepentaerythritol [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Co., Ltd.), Irganox 1330 (Irganox 1330: 3, 3', 3'',5,5',5''-hexa-t-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, BASF Co., Ltd.), Irganox 3114 (Irganox 3114: 1,3,5-gin (3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), Irganox 3790 (Irganox 3790: 1,3,5-paran ((4-tert-butyl-3-hydroxy-2) ,6-dimethylphenyl)methyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), Irganox 1035 (Irganox 1035: thiodiethylene bis[3-(3,5-di-t-butyl-4) -hydroxyphenyl)propionate], manufactured by BASF Co., Ltd., Irganox 1135 (Irganox 1135: phenylpropanic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyl, C7-C9 Side chain alkyl ester, manufactured by BASF Co., Ltd.), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Corporation), Irganox 3125 (Irganox 3125, limited by BASF) Company), Irganox565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy 3',5'-di-t-butylanilino)-1,3,5-three , BASF Co., Ltd.), ADKSTAB AO-80 (ADKSTAB AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)) Oxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, manufactured by ADEKA Co., Ltd.), Sumilizer BHT (Sumitomo Chemical Co., Ltd.) Company system), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (manufactured by Cytec Co., Ltd.), and Vitamin E (manufactured by Eisai Co., Ltd.).

Examples of the phosphorus-based antioxidant include Irgafos 168 (parameter (2,4-di-t-butylphenyl) phosphite, manufactured by BASF Co., Ltd.), Irgafos 12 (see [2-[[2, 4, 8) , 10-tetra-t-butyldibenzo[d,f][1,3,2] Phospho-6-yl]oxy]ethyl]amine, manufactured by BASF Co., Ltd., Irgafos 38 (bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl) Ethyl ester phosphoric acid (manufactured by BASF Corporation), ADKSTAB 329K (made by Adeka Co., Ltd.), ADKSTAB PEP36 (made by Adeka Co., Ltd.), ADKSTAB PEP-8 (made by Adeka Co., Ltd.), Sandstab P-EPQ ( Clariant Co., Ltd., Weston 618 (manufactured by GE), Weston 619G (manufactured by GE), Ultranox 626 (manufactured by GE), and Sumilizer GP (6-[3-(3-tert-butyl-4-hydroxy-5) -Methylphenyl)propanyloxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1.3.2]dioxaphosphanee) (Sumitomo Chemical Co., Ltd.) and so on.

Examples of the sulfur-based antioxidants include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and hydrazine [methylene (3-dodecyl thio) propyl). A β-alkylmercaptopropionate compound of a polyhydric alcohol such as methane.

[10] Other ingredients

The colored curable resin composition of the present invention may contain one or two or more kinds of fillers, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an anti-aggregation agent, and the like, as needed. Additives such as organic acids, organic amine compounds, and hardeners.

Examples of the filler include glass, cerium oxide, and aluminum oxide. Examples of the polymer compound other than the resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

Examples of the adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginate (2-methoxyethoxy) decane, and N-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidol Oxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropyl Methyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like.

Examples of the ultraviolet absorber include a benzotriazole compound such as 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole; 2-hydroxy-4-octyl Benzophenone-based compound such as oxybenzophenone; benzoic acid such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate Ester compound; 2-(4,6-diphenyl-1,3,5-three -2-yl)-5-hexyloxyphenol, etc. a compound; Examples of the anti-agglomerating agent include sodium polyacrylate.

The organic acid is used to adjust the developability and the like, and specific examples thereof include aliphatic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethyl acetic acid, heptanoic acid, and octanoic acid. Monocarboxylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, trisallic acid (brassylic acid), methyl propyl Diacid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, anti-butyl An aliphatic dicarboxylic acid such as enedic acid or mesaconic acid; an aliphatic tricarboxylic acid such as 1,2,3-propanetricarboxylic acid, aconitic acid or camohoronic acid; benzoic acid, methylbenzoic acid, An aromatic monocarboxylic acid such as anisic acid, 3,4-dimethylformic acid or mesitylene; an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid or terephthalic acid; An aromatic polycarboxylic acid such as acid, 1,3,5-benzenetricarboxylic acid, benzotetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid; and the like.

The organic amine compound may, for example, be n-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptyl a monoalkylamine such as an amine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine; cyclohexylamine, 2-methylcyclohexylamine, 3-methyl a monocyclic alkylamine such as cyclohexylamine or 4-methylcyclohexylamine; Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine a dialkylamine such as di-t-butylamine, di-tert-butylamine, di-n-pentylamine or di-n-hexylamine; a monoalkyl group such as methylcyclohexylamine or ethylcyclohexylamine Monocyclic alkylamine; dicycloalkylamine such as dicyclohexylamine; dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-positive Propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri- a trialkylamine such as a second butylamine, a tri-t-butylamine, a tri-n-pentylamine or a tri-n-hexylamine; a dialkyl group such as dimethylcyclohexylamine or diethylcyclohexylamine a cycloalkylamine; a monoalkylbicycloalkylamine such as methyldicyclohexylamine, ethyldicyclohexylamine or tricyclohexylamine; 2-aminoethanol, 3-amino-1-propanol, 1 - monoalkanolamines such as amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol; 4-amino-1 -cyclohexanol Monocycloalkanolamine; diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine, etc. Alkanolamine; dicycloalkanolamine such as bis(4-cyclohexanol)amine; triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri- a trialkanolamine such as n-pentanolamine or tri-n-hexanolamine; a tricycloalkanolamine such as tris(4-cyclohexanol)amine; 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butane Alkanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propane Aminoalkanediol such as alcohol, 2-diethylamino-1,3-propanediol; 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexane Aminocycloalkanediol such as alkanediol; amine group-containing cycloalkanone methanol such as 1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol; 1-aminocyclohexanone methanol, 4-amine Cyclohexanone methanol, 4-dimethylaminocyclopentane methanol, 4-diethylaminocyclopentane methanol, 4-dimethylaminocyclohexane methanol, 4-diethylamino ring Amine-containing cycloalkane methanol such as hexane methanol; β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-amino group Isobutyric acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexane Aminocarboxylic acid such as alkanoic acid; aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylbenzene Amine, p-n-propylaniline, p-isopropylaniline, p-n-butylaniline, p-t-butylaniline, 1-naphthylamine, 2-naphthylamine, N,N-dimethylaniline, An aromatic amine such as N,N-diethylaniline or p-methyl-N,N-dimethylaniline; o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-amino group Aminobenzyl alcohol such as benzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol; o-aminophenol, m-aminophenol, p- Aminophenol, p-dimethylaminophenol, Amino phenol such as p-diethylamino phenol; amino benzene such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid or p-diethylaminobenzoic acid Formic acid; etc.

Examples of the curing agent include a compound which can be reacted with a carboxyl group in the resin (B) by heating to crosslink the resin (B), a compound which can be polymerized by itself to cure the colored pattern, and the like, and examples thereof include an epoxy compound and oxygen. Heterocyclic butane compounds and the like. The curing agent may be used alone or in combination of two or more.

Examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, and other aromatics. Epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, glycidyl ester resin, glycidylamine resin, epoxidized oil, etc., and brominated derivatives of these epoxy resins An aliphatic, alicyclic or aromatic epoxy compound other than an epoxy resin or a brominated derivative thereof, an (epoxy) epoxide of butadiene (co)polymer, and (co)polymerization of isoprene An epoxide of a substance, a (co)polymer of glycidyl (meth)acrylate, triglycidyl isocyanate or the like. The commercially available product of the epoxy resin is an o-cresol novolac type epoxy resin, "SUMIEPOXY (registered trademark) ESCN-195XL-80" (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

The oxetane compound may, for example, be a dioxetane carbonate, a benzoyl dioxane, a dioxetane adipate or a dioxetane to benzene. Formate, cyclohexanedicarboxylic acid, dioxetane, and the like.

When the colored curable resin composition of the present invention contains an epoxy compound, an oxetane compound or the like as a curing agent, it may contain an epoxy group or an oxetane compound of an epoxy compound. A compound in which alkane skeleton is ring-opened and polymerized. Examples of the compound include a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, and an acid generator.

The polycarboxylic acid may, for example, be 3,4-dimethylphthalic acid, 1,2,4,5-benzenetetracarboxylic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3, An aromatic polycarboxylic acid such as 3',4,4'-benzophenonetetracarboxylic acid; an aliphatic polycarboxylic acid such as 1,2,3,4-butanetetracarboxylic acid; hexahydrophthalic acid, 3 , 4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexane An alicyclic polycarboxylic acid such as a carboxylic acid, a cyclopentane tetracarboxylic acid or a 1,2,4,5-cyclohexanetetracarboxylic acid;

Examples of the polycarboxylic acid anhydride include phthalic anhydride, 1,2,4,5-benzenetetracarboxylic anhydride, trimellitic anhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, and the like. Aromatic polycarboxylic acid anhydride; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecene succinic anhydride, 1,2,3-propane tricarboxylic anhydride, maleic anhydride, 1,2,3,4-butane IV An aliphatic polycarboxylic acid anhydride such as carboxylic acid dianhydride; hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2 , 4-cyclohexane tricarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, seamic anhydride, nadic acid anhydride, etc. Cyclic polycarboxylic anhydride; An carboxylic acid anhydride containing an ester group such as ethylene glycol bis(triphenylhexacarboxylate) or glycerol ginseng (triphenylhexahydride);

As the carboxylic acid anhydride, those commercially available as an epoxy resin hardener can also be used. For the epoxy resin curing agent, the product name "Adeka Hardener (registered trademark) EH-700" (made by ADEKA Co., Ltd.), the product name "RIKACID (registered trademark) HH" (manufactured by Shin-Nippon Chemical Co., Ltd.), and the product "MH-700" (manufactured by Nippon Chemical and Chemical Co., Ltd.).

The acid generator may, for example, be 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylhydrazine hexafluoroantimonate, 4-ethoxymethoxyphenyldimethylhydrazine p-toluene Sulfonate, 4-ethyloxyphenyl/methyl/benzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenylsulfonium An anthracene salt such as p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate, nitrobenzyl methyl tosylate or benzoin tosylate.

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention can be obtained by mixing a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and preferably a solvent (E), and optionally Modulated by other ingredients.

<Color filter and its manufacturing method, color filter, and display device>

The colored curable resin composition of the present invention is useful as a material for a color filter. The color filter formed of the colored curable resin composition of the present invention is also within the scope of the present invention. Color filters can also be shaped Into a colored pattern.

The method of producing a colored pattern by the colored curable resin composition of the present invention includes a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. The photo-etching method is a method in which a colored curable resin composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to be developed. In the photoetching method, a colored coating film which is a cured product of the colored composition layer can be formed by not using a photomask during exposure and/or without developing. The colored pattern and colored coating film formed from the colored curable resin composition of the present invention are the color filters of the present invention.

The substrate can be used: quartz glass, borosilicate glass, alumina silicate glass, glass plate coated with cerium oxide-coated soda lime glass, polycarbonate, polymethyl methacrylate, polyethylene terephthalate A resin plate such as a diester or the like, in which an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Additional color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates.

The formation of each color pixel by photolithography can be carried out by a known or conventional device or condition, and can be produced, for example, as will be described later. First, the colored curable resin composition is applied onto a substrate, dried by heating (prebaking) and/or dried under reduced pressure to remove volatile components such as a solvent, and dried to obtain a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit, and a spin coating method.

The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Moreover, the heating time is 10 seconds. It is preferable to have a clock of 5 minutes, preferably 30 seconds to 3 minutes. When drying under reduced pressure, it is preferably carried out at a temperature of from 20 to 25 ° C at a pressure of from 50 to 150 Pa. The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the color filter.

Then, the colored composition layer is exposed through a photomask for forming a color pattern of interest. The pattern on the photomask is not particularly limited, and a pattern for the purpose of use is used. The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, a filter that blocks the wavelength region can be used to cut off light that is less than 350 nm, or a band pass filter that takes out wavelengths of light near 436 nm, near 408 nm, and around 365 nm can be used, and 436 nm can be selectively taken out. Light near the vicinity of 408 nm and around 365 nm.

Specifically, examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, and the like.

The exposure system can uniformly illuminate the parallel light on the entire exposed surface or accurately align the mask with the substrate on which the colored composition layer is formed. Therefore, it is preferable to use an exposure apparatus such as a mask aligner or a stepper.

The colored composition layer after exposure is brought into contact with the developing solution to develop, whereby a colored pattern can be formed on the substrate. By development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed.

The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide. The concentration in the aqueous solution of the basic compound is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Furthermore, the developer may also contain interfacial activity Agent.

The development method may be any one of a puddle method, a dipping method, and a spray method. The substrate can also be tilted at any angle during further development. After development, it is preferably washed with water.

Further, it is preferred to post-bait the resulting colored pattern. The post-baking temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

The film thickness of the obtained color filter affects adjacent pixels, so it is preferable to be as thin as possible. In particular, when a thick film is formed, when a liquid crystal panel is produced, light of a light source may leak through two or more pixels, and when the panel is viewed obliquely, there is a fear that color is lost. The coating film after post-baking is generally preferably 3 μm or less, more preferably 2.8 μm or less. The lower limit of the coating film is not particularly limited, but is usually 1 μm or more, and may be 1.5 μm or more.

(Effect of the invention)

The color filter of the present invention can be used as a color filter used for display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

[Examples]

The following are examples and comparative examples to further specifically The present invention is not limited to these examples. In the examples, the content and the % and the amount of use are indicated, and unless otherwise stated, the mass basis is indicated.

<Synthesis Example 1: Modulation of xanthene dye>

40.5 parts of the compound represented by the above formula (1a) and 60.5 parts of 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed under a light-shielding condition, and 200 parts of N-methylpyridone in 150 parts. Stir at ° C for 8 hours. After the obtained reaction liquid was cooled to room temperature, it was added to a mixed liquid of 1200 parts of water and 75 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour, and then crystals were precipitated. The precipitated crystals were suction-filtered to obtain a residue, and the residue was washed with 100 parts of methanol, and then dried under reduced pressure at 60 ° C for one night to obtain 49 parts of the compound of the formula (1-2). The yield was 85%.

Then, 28.8 parts of the compound represented by the formula (1-2), 21.6 parts of 1-bromopropane and 24.2 parts of potassium carbonate were added to 144 parts of N-methylpyridone, and the mixture was stirred at 90 ° C for 4 hours. The obtained reaction liquid was cooled to room temperature, concentrated, added to 560 parts of water, and stirred at 10 to 15 ° C for 1 hour, and crystals were precipitated. The resulting crystals were suction-filtered to obtain a residue, and the residue was dried, washed with 1000 parts of ion-exchanged water, and then dried under reduced pressure at 60 ° C for 1 night to obtain the above formula (1-24). Compound 30.0 parts. Yield It is 91%.

[Identification of the compound represented by formula (1-24)]

(mass analysis) ionization mode = ESI +: m / z = [M + H] + 659.3 accurate mass (Exact Mass): 658.3

<Synthesis Example 2: Modulation of Resin (B)>

An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen gas atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was stirred and heated to 85 °C. Then, it took 4 hours to dissolve 54 parts of acrylic acid and 3,4-ethoxytricyclo[5.2.1.0 ^2,6 ]nonane-8- in 80 parts of propylene glycol monomethyl ether acetate. a mixture of acrylate and 3,4-ethoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate (containing 50:50 by molar ratio) of 225 parts A mixed solution prepared by mixing 81 parts of vinyl toluene (heterosome mixture) into the flask.

On the other hand, it took 5 hours to drip in 160 parts of propylene glycol monomethyl ether acetate, and dissolved 30 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile). Solution. After completion of the dropwise addition of the solution, the mixture was kept at 85 ° C for 4 hours, and then cooled to room temperature to obtain a solution of the resin (B). The solid solution of the solution of the resin (B) was 37.5%, and the viscosity measured by a Brookfield viscometer (23 ° C) was 246 mPa·s. The weight average molecular weight of the resin (B) was 1.06 × 10 ⁴ , the acid value in terms of solid content was 115 mg-KOH/g, and the molecular weight distribution was 2.01.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin (B) are determined by the GPC method as follows The conditions are carried out. The ratio (Mw/Mn) of the polystyrene-equivalent weight average molecular weight to the number average molecular weight obtained under the following conditions was taken as the molecular weight distribution.

Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.), column: TSK-GELG2000HXL, column temperature: 40 ° C, solvent: THF, flow rate: 1.0 mL/min, solid concentration of test liquid: 0.001 to 0.01% by mass Injecting amount: 50 μL, detector: RI, standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.).

The components used in the examples are as follows, and may be briefly shown below.

Coloring agent (A-1): Compound (dye) and coloring agent (A-2) represented by the formula (1-24) obtained in Synthesis Example 1: CI Pigment Blue 15:6 (pigment), coloring agent (A- 3): the compound shown below (thiazole dye),

Colorant (A-4): C.I. Solvent Blue 45; Savinyl Blue RS (manufactured by Clariant) (anthraquinone dye)

Resin (B): Resin (B) and polymerizable compound (C-1) contained in the resin solution obtained in Synthesis Example 2: pentaerythritol triacrylate (trade name "A", manufactured by Shin-Nakamura Chemical Co., Ltd. -TMM-3LM-N", hydroxyl value: 110 mgKOH/g), polymerizable compound (C-2): dipentaerythritol polyacrylate (trade name "A-9550" manufactured by Shin-Nakamura Chemical Co., Ltd. , hydroxyl value: 50 mgKOH/g), polymerizable compound (C-3): a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name of Nakamura Nakamura Chemical Co., Ltd.) A-9530", hydroxyl value: 40 mgKOH/g), polymerization initiator (D): N-benzylideneoxy-1-(4-phenylhydrothiophenyl)octane-1-one-2 -imine (trade name "IRGACURE OXE 01", manufactured by BASF Corporation), and polymerization starter: 2,4-diethylthiaxanthone (trade name "KAYACURE DETY-S" manufactured by Nippon Kayaku Co., Ltd. "), solvent (E): propylene glycol monomethyl ether acetate, Leveling agent (F): Polyether modified polysiloxane (trade name "Toray Silicone SH8400" manufactured by Dow Corning Toray Co., Ltd.).

(1) Modulation of coloring curable resin composition

<Examples 1 to 4 and Comparative Examples 1 to 4>

Each component described in Table 8 was mixed at the mixing ratio described in Table 8, and a colored curable resin composition was obtained. The unit of the blending amount of each component in Table 8 is "parts by mass", and the blending amount is a solid fraction converted.

<Example 5>

[Preparation of coloring curable resin composition]

The above components are mixed, and the pigment is sufficiently dispersed using a beads mill, and then the following components are mixed to obtain a colored curable resin composition.

<Comparative Examples 5 to 6>

The colored curable resin composition was prepared in the same manner as in Example 5 except that the composition of the formulation was changed as shown in Table 8.

(2) Determination of hydroxyl value of polymerizable compounds

According to JIS K 0070-1992, an acetamidine reagent was added to the sample, and the mixture was heated in a glycerin bath, and after cooling, a phenol porphyrin solution was added as an indicator, and the solution was titrated with a potassium hydroxide ethanol solution. The measurement results are as described above.

(3) Production of patterns

The colored curable resin composition was applied by spin coating to a glass substrate ("EAGLE XG" manufactured by Corning Co., Ltd.) of 2 inches square, and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer was formed and the mask made of quartz glass was 150 μm, and an exposure machine ("TME-150RSK" manufactured by TOPCON Co., Ltd.) was used, and in an atmospheric gas atmosphere, 50 mJ/ The exposure amount of cm ² (365 nm reference) was irradiated with light. The reticle uses a reticle formed with a line pattern of 100 μm line and space. The colored composition layer after light irradiation was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 60 seconds at 24 ° C for development, and after washing in an oven, 230 After baking at ° C for 20 minutes, a colored pattern was obtained.

(4) Film thickness measurement

For the obtained color pattern, a film thickness measuring device is used (Japan true) The film thickness was measured by "DEKTAK3" manufactured by Nippon Technology Co., Ltd.). The results of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 9, and the results of Example 5 and Comparative Examples 5 to 6 are shown in Table 10.

(5) Chroma evaluation

For the obtained color pattern, the color measurement was performed using a color measuring machine ("OSP-SP-200" manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinate (x, in the XYZ color system of CIE) was measured using the characteristic function of the C light source. y) and triple value Y. The larger the value of Y, the higher the brightness. The results of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 9, and the results of Table 5 and Comparative Examples 5 to 6 are shown in Table 10.

(6) Heat resistance evaluation

The resulting colored pattern was heated in an oven at 230 ° C for 3 hours. The xy chromaticity coordinates (x, y) and Y before and after heating were measured, and the color difference ΔEab* was calculated from the measured value in the manner described in JIS Z 8730:2009 (7. Method for calculating color difference). The results of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 9, and the results of Example 5 and Comparative Examples 5 to 6 are shown in Table 10. The smaller the ΔEab*, the smaller the color change. In addition, when the heat resistance of the colored coating film is good, it can be said that the colored pattern produced from the same colored curable resin composition is also excellent in heat resistance.

(industrial availability)

According to the colored curable resin composition of the present invention, it is possible to provide a color filter which can exhibit excellent brightness and excellent heat resistance, and a display device including the filter.

Claims (9)

A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D); and the colorant (A) comprises a xanthene skeleton In the dye, the polymerizable compound (C) contains a polymerizable compound having a hydroxyl value of 100 mgKOH/g or more. The colored curable resin composition according to claim 1, wherein the polymerizable compound having a hydroxyl value of 100 mgKOH/g or more is pentaerythritol triacrylate. The colored curable resin composition according to the first or second aspect of the invention, wherein the ratio of the content of the polymerizable compound (C) to the content of the resin (B) (content of the polymerizable compound (C) / resin ( The content of B) is 0.6 to 5 in terms of mass ratio. The colored curable resin composition according to the first or second aspect of the invention, wherein the ratio of the content of the polymerizable compound (C) to the content of the resin (B) (content of the polymerizable compound (C) / resin ( The content of B) is 0.75 to 5 in terms of mass ratio. The colored curable resin composition according to claim 1 or 2, wherein the colorant (A) further contains C.I. Pigment Blue 15:6. The colored curable resin composition according to the first or second aspect of the invention, wherein the content of the dye having a xanthene skeleton in 100% by mass of the colorant (A) is from 1 to 50% by mass. The colored curable resin composition according to claim 1 or 2, which contains a quinone compound as a polymerization initiator (D). A color filter formed by the color hardening resin composition according to claim 1 or 2. A display device comprising the color filter of claim 8 of the patent application.