KR20170003378A - Colored photosensitive resin composition, color filter and liquid crystal display device - Google Patents

Abstract

It is an object of the present invention to provide a colored curable resin composition which does not generate residues resulting from the peeling off of a part of the colored curable composition layer during development following exposure, and provides a color filter with a good pattern profile. To this end, the colored curable resin composition comprises: (Aa) a pigment; (B) a binder resin; (C) a polymerizable compound; and (D) a polymerization initiator, wherein the binder resin (B) is a copolymer having (b1) a constituent unit derived from at least one monomer selected from a group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, (b2) a constituent unit derived from a monomer having an ethylenically unsaturated bond and a cyclic ether structure, (b3) a constituent unit derived from a (meth)acrylic acid ester monomer containing a hydroxyl group, and (b4) a constituent unit derived from a monomer of a carbonyl imide derivative.

Description

[0001] The present invention relates to a coloring curable resin composition, a color filter, and a liquid crystal display device,

The present invention relates to a colored curable resin composition, a color filter, and a liquid crystal display device.

The colored curable resin composition is used for the production of a color filter used in a display device such as a liquid crystal display device, an electroluminescence display device, and a plasma display. As such a color-curable resin composition, there is known a colored curable resin composition comprising a blue, green or red pigment alone or a combination of Pigment Blue 15: 6 and a predetermined dye as a colorant (Patent Documents 1 and 2).

Japanese Laid-Open Patent Publication No. 10-31308 Japanese Laid-Open Patent Publication No. 2010-32999

However, in the above-mentioned colored curable resin composition, a part of the colored composition layer after exposure peeled off at the time of development to form a foreign substance, and the pattern shape was sometimes not good.

Accordingly, it is an object of the present invention to provide a colored curable resin composition which provides a color filter in which a part of the colored composition layer after exposure is peeled off at the time of development, and no foreign matter is formed, and the pattern shape is good.

The gist of the present invention is as follows.

[1] A binder resin composition comprising a dye (Aa), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the binder resin (B) is at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (B2) derived from a monomer having an ethylenic unsaturated bond and a cyclic ether structure, and a structural unit (b3) derived from a hydroxyl group-containing (meth) acrylic acid ester monomer, , And a structural unit (b4) derived from a monomer of a dicarbonylimide derivative.

[2] The colored curable resin composition according to [1], wherein the total amount of the hydroxyl group-containing (meth) acrylic acid ester monomer and the monomer of the dicarbonylimide derivative is 25% by mass or more and 90% by mass or less of 100% by mass of the total monomer.

[3] The acrylic pressure-sensitive adhesive composition according to [1] or [2], wherein the hydroxy group-containing (meth) acrylic acid ester monomer is a hydroxyalkyl (meth) acrylate ester having an alkyl group having 1 to 10 carbon atoms,

Wherein the monomer of the dicarbonyl imide derivative is an N-substituted maleimide having a hydrocarbon group of 4 to 20 carbon atoms.

[4] The colored curable resin composition according to any one of [1] to [3], further comprising a pigment (Ab).

[5] A dye according to any one of [1] to [4], wherein the dye (Aa) is an anion of a compound containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, A-II), and a cation having a dye skeleton. The colored curable resin composition according to claim 1, wherein the polymeric anion has a structural unit derived from an anion represented by the following formula (A-II).

[Chemical Formula 1]

[In the above formula (A-II), X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom.

Y represents a divalent aliphatic hydrocarbon group, an arylene group, or a combination thereof, and the methylene group constituting the aliphatic hydrocarbon group may be substituted with an oxygen atom or a nitrogen atom.

And R ⁶¹ represents a hydrogen atom or a methyl group.

[6] The colored curable resin composition according to any one of [1] to [5], wherein the dye (Aa) is a compound represented by the formula (A-I).

(2)

[In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms, which may have a substituent, and the oxygen atom An aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom. R ⁴¹ and R ⁴² may bond to form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may bond to form a ring together with the nitrogen atom to which they are bonded.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group. R ⁴⁸ and R ⁵² may combine with each other to form -NH-, -O-, -S- or -SO ₂ -.

Ring T ¹ represents an aromatic heterocycle which may have a substituent.

[Y] ^m- is at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and an optional m-valent anion containing oxygen or a structural unit derived from an anion represented by the formula (A-II) ≪ / RTI >

m represents an arbitrary natural number.

When a plurality of cations represented by the following formulas are contained in one molecule, they may have the same structure or different structures.

(3)

[Wherein, ring T ^1, R ⁴¹ To R ⁴⁴ And R ⁴⁷ To R < ⁵⁴ > are each as defined above]

[Chemical Formula 4]

[In the formula (A-II), X, Y and R ⁶¹ are each as defined above]]

[7] A color filter formed from the colored curable resin composition according to any one of [1] to [6].

[8] A liquid crystal display device comprising a color filter according to [7].

According to the colored curable resin composition of the present invention, it is possible to provide a color filter in which a part of the colored composition layer after exposure is peeled off at the time of development, and no foreign matter is formed, and the pattern shape is good.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram showing the evaluation of a pattern shape after a pattern is formed by applying a colored curable resin composition to a substrate. FIG.

The colored curable resin composition of the present invention contains a dye (Aa), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the binder resin (B) comprises an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (B2) derived from a monomer having an ethylenic unsaturated bond and a cyclic ether structure, and a structural unit (b2) derived from a hydroxyl group-containing (meth) acrylic acid ester monomer , And a structural unit (b4) derived from a monomer of a dicarbonylimide derivative.

The respective components of the dye (Aa), the binder resin (B), the polymerizable compound (C) and the polymerization initiator (D) will be described below.

The dye (Aa)

Examples of the dyes include azo dyes (for example, monoazo dyes, diazo dyes, triazo dyes, metal complex azo dyes and the like), anthraquinone dyes, indigo dyes, phthalocyanine dyes, pyrazolone dyes, stilbene dyes, carotenoid dyes, An azine dye, an azine dye, an azine dye, an oxazine dye, a cyanine dye, an indanamine dye, an indophenol dye, a naphthalene dyestuff, a quinoline dye, a diarylmethane dye, a triarylmethane dye, an acridine dye, A quinone dyestuff, a quinone imine dyestuff, a methine dyestuff, an azomethine dyestuff, a squarylium dyestuff, a styryl dyestuff, a coumarin dyestuff, a quinoline dyestuff, a tetraazaporphyrin dyestuff, a nitro dye, or a nitroso A dye, and the like, and they are preferably soluble in an organic solvent. These dyes may be used alone or in combination of two or more.

Among them, a cationic dye, a triarylmethane dye, an anthraquinone dye, a tetraazaporphyrin dye, an azo dye, a cyanine dye, a phthalocyanine dye, a naphthoquinone dye, a quinoneimine dye, a methine dye, an azomethine dye, , Acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes are preferable, and xanthine dyes, triarylmethane dyes, coumarin dyes, anthraquinone dyes, and tetraazaporphyrin dyes are more preferable, Dyes are particularly preferred.

Examples of the xanthene dyes include C.I. 52, 87, 92, 94, 388, C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red is omitted and only the numbers are described. Acid violet 9, 30C. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. Basic Red 10 (Rhodamine B), 11, C.I. Basic violet 10, 11, 25, C.I. Solvent Red 218, C.I. Modern Red 27, C.I. Reactive Red 36 (Rose Bengal B), sulfolodamine G, xanthene dyes described in Japanese Patent Application Laid-Open No. 2010-32999, and xanthene dyes described in Japanese Patent Publication No. 4,492,760.

The xanthene dye is more preferably a compound represented by the following formula (a1-1) (hereinafter also referred to as a compound (a1-1)). The compound (a1-1) may be a tautomer thereof.

[Chemical Formula 5]

[In the formula (a1-1), R < ^{1 >} To R ⁴ Each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and the methylene group ( -CH ₂ -) may be substituted with -O-, -CO- or -NR ¹¹ -. R ¹ and R ² may be bonded together to form a ring containing a nitrogen atom, and R ³ and R ⁴ may bond together to form a ring containing a nitrogen atom.

R ⁵ Is _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ .

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

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

a represents an integer of 0 or 1;

X represents a halogen atom.

Z ⁺ represents ⁺ N (R < ¹¹ >) ₄ , Na ⁺ or K ⁺ , and four R < ¹¹ > may be the same or different.

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 a halogen atom.

R ⁹ and R ¹⁰ independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - included in the saturated hydrocarbon group is -O-, -CO-, -NH - or -NR ⁸ -, and R ⁹ and R ¹⁰ may combine with each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

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.

The xanthene dye is also preferably a compound represented by the formula (a1-2) (hereinafter referred to as "the compound (a1-2)")). The compound (a1-2) may be a tautomer thereof.

[Chemical Formula 6]

In the formula (a1-2), R ²¹ and R ²² independently represent a monovalent saturated hydrocarbon group of 1 to 10 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon groups of R ²¹ and R ²² have 6 to 10 carbon atoms An aromatic hydrocarbon group or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ - included in the saturated hydrocarbon group of R ²¹ and R ²² is -O-, -CO- or -NR < ¹¹ > -.

R ²³ and R ²⁴ independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.

R ²¹ and R ²³ may be bonded together to form a ring containing a nitrogen atom, and R ²² and R ²⁴ may bond together to form a ring containing a nitrogen atom.

p and q independently represent an integer of 0 to 5; p is 2 or more, plural R ²³ may be the same or different and when q is 2 or more, plural R ²⁴ may be the same or different.

R ¹¹ is as defined above.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ²¹ and R ²² include groups having 1 to 10 carbon atoms among those represented by R ⁸ .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent include the same groups as those of R ¹ .

Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group and a propoxy group.

R ²¹ and R ²² are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms for R ²³ and R ²⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl and tert-butyl.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms for R ²³ and R ²⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group and an isopropylsulfanyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms for R ²³ and R ²⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.

R ²³ and R ²⁴ are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

p and q are preferably an integer of 0 to 2, and 1 or 2 is preferable.

The triarylmethane dye is preferably a dye comprising a compound having a structure in which three aromatic hydrocarbon groups are bonded to one carbon atom. The triarylmethane dyes include, for example, C. I. Solvent Blue 2, 4, 5, 43, 124; C. I. Basic Violet 3, 14, 25; C. I. Basic Blue 1, 5, 7, 11, 26, and triarylmethane dyes described in Japanese Patent Publication No. 4,492,760.

A coumarin dye is a dye containing a compound having a coumarin skeleton in its molecule. Coumarine dyes include, for example, C. I. Acid Yellow 227, 250; C. I. Disperse Yellow 82, 184; C. I. Solvent Orange 112; C. I. Solvent Yellow 160, 172; And coumarin dyes described in Japanese Patent Publication No. 1,299,948.

Examples of the anthraquinone dyes include C.I. Solvent Yellow 117 (hereinafter abbreviated to C.I.Solvent Yellow, and only numbers are given), 163, 167, 189,

C. I. Solvent Orange 77, 86,

C. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,

C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,

CI Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111 , 112, 122, 128, 132, 136, 139,

C. I. Solvent Green 3, 28, 29, 32, 33,

C. I. Acid Red 80,

C. I. Acid Green 25, 27, 28, 41,

C. I. Acid Violet 34,

C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112

C. I. Disperse Yellow 51,

C. I. Disperse Violet 26, 27,

C. I. Disperse Blue 1, 14, 56, 60,

C. I. Direct Blue 40,

C. I. Modern Red 3, 11,

C. I. Modern Blue 8 and the like.

Tetraaza porphyrin dyes are compounds having a tetraaza porphyrin skeleton in the molecule. Also, when the tetraazaporphyrin dye is an acidic or basic dye, it may form a salt with any cation or anion.

As other dyes, azo dyes, thiazole dyes, oxazine dyes, phthalocyanine dyes, quinophthalone dyes and the like can be used, and known dyes are used respectively.

As the azo dye, for example, CI direct yellow (hereinafter, the explanation about CI direct yellow will be omitted and only the numbers are described below, only the numbers will be described) 2, 33, 34, 35, 39, 50, 69, 70, 71, 86, 93 , 94, 95, 98, 102, 109, 129, 136, 141;

C. I. Direct Orange 41, 46, 56, 61, 64, 70, 96, 97, 106, 107;

CI Direct Red 79, 82, 83, 84, 97, 98, 99, 106, 107, 172, 173, 176, 177, 179, 181, 182, 204, 207, 211, 213, 218, 221, 222, 232 , 233, 243, 246, 250;

C. I. Direct Violet 47, 52, 54, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

CI Direct Blue 51, 57, 71, 81, 84, 85, 90, 93, 94, 95, 98, 100, 101, 113, 149, 150, 153, 160, 162, 163, 164, 166, 167, 170 , 172, 188, 192, 193, 194, 196, 198, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275;

C. I. Direct Green 27, 34, 37, 65, 67, 68, 69, 72, 77, 79, 82, etc .;

CI Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151 , 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337;

C. I. Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127;

C. I. Acid Violet 11, 56, 58;

C. I. Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151;

C. I. Acid Brown 2, 4, 13, 248;

C. I. Acid Blue 92, 102, 113, 117, etc.; For example, C. I. Basic Red 17, 22, 23, 25, 29, 30, 38, 39, 46, 46: 1, 82; C. I. Basic Orange 2, 24, 25; C. I. Basic Violet 18; C. I. Basic Yellow 15, 24, 25, 32, 36, 41, 73, 80; C. I. Basic Brown 1; C. I. Basic Blue 41, 54, 64, 66, 67, 129 and the like.

The thiazole dyes include C. I. Direct Yellow 54 and C. I. Basic Yellow 1. [

The jade photographic dyes include C. I. Direct Blue 97, 99, 106, 107, 108, 109, 190, 293 and the like.

The phthalocyanine dyes include C. I. Direct Blue 86, 87, 189, 199, C. I. Acid Blue 249, C. I. Basic Blue 3 and the like.

Quinophthalone dyes include C. I. Acid Yellow 3, C.I. Disperse Yellow 143 and the like. Examples of the cyanine dye include copper phthalocyanine (CI 74160) and the like.

Examples of quinone imine dyes include C. I. Basic Blue 3, C. I. Basic Blue 9, and the like.

Methine dyes include C.I. Basic Red 13, 14; C.I. Basic orange 21; C.I. Basic violet 16, 39; CI Basic Yellow 11, 13, 21, 23, 28 and the like.

Examples of the quinoline dyes include C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse Yellow 64 and the like.

Nitro dyes include C. I. Acid Yellow 1, C. I. Acid Orange 3 and C. I. Disperse Yellow 42 and the like.

The azine dyes include C.I. Acid Blue 59, and the like.

The indigo dyes include C.I. Acid Blue 74 and the like.

The dye (Aa) is preferably a polymer having an anion of a compound containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus or a constituent unit derived from an anion represented by the formula (A-II) (Hereinafter also referred to as a compound (AA)) formed of an anion and a cation having a dye skeleton.

The dye skeleton of the cation constituting the dye includes a dye skeleton having an onium structure such as an azo skeleton, a xanthene skeleton, an azine skeleton, a cyanine skeleton, an acridine skeleton, an anthraquinone skeleton, or a squaryllithium skeleton; Triarylmethane skeleton; And a pigment skeleton in which at least one of the aromatic hydrocarbon rings in the triarylmethane skeleton is an aromatic heterocycle. Among them, preferably at least one of a xanthene skeleton having an onium structure, a cyanine skeleton having an onium structure, a squarylium skeleton having an onium structure, a triarylmethane skeleton, and an aromatic hydrocarbon ring having a triarylmethane skeleton, And is a pigment skeleton in which at least one of aromatic hydrocarbon rings having a triarylmethane skeleton is an aromatic heterocycle. Examples of the anion include anion of a compound containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus or a polymer anion having a constituent unit derived from an anion represented by the formula (A-II) .

Specifically, the dye (Aa) is preferably a compound represented by the formula (A-I) (hereinafter also referred to as "compound (A-I)").

(7)

[In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms, which may have a substituent, and the oxygen atom An aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom. R ⁴¹ and R ⁴² may bond to form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may bond to form a ring together with the nitrogen atom to which they are bonded.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group. R ⁴⁸ and R ⁵² may combine with each other to form -NH-, -O-, -S- or -SO ₂ -.

Ring T ¹ represents an aromatic heterocycle which may have a substituent.

[Y] ^m- is at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and an optional m-valent anion containing oxygen or a structural unit derived from an anion represented by the formula (A-II) ≪ / RTI >

[Chemical Formula 8]

[In the above formula (A-II), X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom.

Y represents a divalent aliphatic hydrocarbon group, an arylene group, or a combination thereof, and the methylene group constituting the aliphatic hydrocarbon group may be substituted with an oxygen atom or a nitrogen atom.

And R ⁶¹ represents a hydrogen atom or a methyl group.

m represents an arbitrary natural number.

When a plurality of cations represented by the following formulas are contained in one molecule, they may have the same structure or different structures.

 [Chemical Formula 9]

[Wherein, the ring T ¹ , R ⁴¹ to R ⁴⁴ and R ⁴⁷ to R ⁵⁴ are each as defined above].

The aromatic heterocycle of ring T < ¹ > may be monocyclic or condensed. The aromatic heterocycle is preferably a 5- to 10-membered ring, more preferably a 5- to 9-membered ring. Examples of the monocyclic aromatic heterocycle include a 5-membered ring containing a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring and a thiazole ring; A 5-membered ring containing a nitrogen atom such as a furan ring or a thiophene ring; A 6-membered ring containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring and a pyrazine ring, and the aromatic heterocycle of the condensed ring includes an indole ring, a benzimidazole ring, a benzothiazole ring, a quinoline ring A condensed ring containing a nitrogen atom; And condensed rings containing no nitrogen atom such as benzofuran ring.

Examples of the substituent that the aromatic heterocycle of ring T ¹ may have include a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, And the like.

Among them, the aromatic heterocycle of ring T ¹ is preferably an aromatic heterocycle containing a nitrogen atom, and more preferably a five-membered aromatic heterocycle containing a nitrogen atom.

Further, it is more preferable that the ring T ¹ is a ring represented by the formula (Ab2-x1).

[Chemical formula 10]

[Ring T ² represents an aromatic heterocycle.

R ⁴⁵ and R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms, which may have a substituent, a group having an oxygen atom inserted between the methylene groups constituting the alkyl group, An aralkyl group which may have a substituent, or a hydrogen atom. R ⁴⁵ and R ⁴⁶ may combine to form a ring together with the nitrogen atom to which they are bonded.

R ⁵⁵ represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent.

k1 represents 0 or 1;

* Represents the bonding position with the carbanion.

The aromatic heterocycle of ring T ² may be the same ring as the aromatic heterocycle exemplified in ring T ¹ .

The ring T ¹ is particularly preferably a ring represented by the formula (Ab2-y1).

(11)

[R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent.

X2 represents an oxygen atom, -NR < ⁵⁷ > - or a sulfur atom.

R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ are as defined above.

* Represents the bonding position with the carbanion.

The ring T ¹ is also preferably a ring represented by the formula (Ab 2 -x 2).

[Chemical Formula 12]

[Ring T ³ represents an aromatic heterocycle having a nitrogen atom.

R ⁵⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent.

R ⁵⁹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group which may have a substituent or an aralkyl group which may have a substituent.

k2 represents 0 or 1;

* Represents the bonding position with the carbanion)

It is more preferable that the ring T ¹ is a ring represented by the formula (Ab2-y2).

[Chemical Formula 13]

[R ⁶⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent.

R ⁵⁹ is as defined above.

* Represents the bonding position with the carbanion.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ may be any of linear, branched and cyclic. Examples of the linear or branched saturated hydrocarbon group include straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl and eicosyl groups; And branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl and 2-ethylhexyl groups. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.

The cyclic saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 6 to 10 carbon atoms.

The saturated hydrocarbon group of R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ may be substituted with a halogen atom or an amino group which may be substituted. Examples of the amino group which may be substituted include an amino group; And an alkylamino group such as a dimethylamino group and a diethylamino group. Examples of the halogen atom include chlorine, fluorine, bromine and iodine. When the halogen atom is a fluorine atom, it is preferable that a halogen atom is substituted such as to form a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, or a heptafluoropropyl unit.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms having a substituent include groups represented by the following formulas. In the following formula, * represents a bonding position with a nitrogen atom.

[Chemical Formula 14]

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ include groups having 1 to 8 carbon atoms in the linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ⁴¹ .

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ include a group having 1 to 10 carbon atoms in the straight-chain or branched-chain saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ⁴¹ .

The alkyl group represented by R ⁴¹ to R ⁵⁴ may have an oxygen atom inserted between the carbon atoms. The alkyl group preferably has 2 to 10 carbon atoms, and more preferably 2 to 8 carbon atoms. When the oxygen atom is inserted, the number of carbon atoms between the terminal and the oxygen atom or between the oxygen atom and the oxygen atom is, for example, 1 to 5, preferably 2 to 3, and more preferably 2. Examples of the group in which an oxygen atom is inserted between carbon atoms of such a saturated hydrocarbon group include, for example, an alkoxyalkyl group; A polyalkoxyalkyl group such as an (alkoxyalkoxy) alkyl group, an (alkoxyalkoxyalkoxy) alkyl group, an (alkoxyalkoxyalkoxyalkoxy) alkyl group, an (alkoxyalkoxyalkoxyalkoxy) alkyl group and an (alkoxyalkoxyalkoxyalkoxyalkoxy) The number of repeating alkoxy units is, for example, 1 to 6, preferably 1 to 4, more preferably 1 to 2. More preferred specific examples include groups represented by the following formulas. In the following formula, * represents a bonding position with a nitrogen atom.

[Chemical Formula 15]

The aromatic hydrocarbon group which may have a substituent group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, Preferably 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group and the like, preferably a phenyl group, a naphthyl group, a tolyl group, And particularly preferably a phenyl group. The aromatic hydrocarbon group may have one or two or more substituents, and examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; A haloalkyl group having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; An alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; A hydroxy group; A sulfamoyl group; An alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; An alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group, and the like. Specific examples of the aromatic hydrocarbon group which may be substituted include, for example, groups represented by the following formulas. In the following formula, * represents a bonding position with a nitrogen atom.

[Chemical Formula 16]

Examples of the aralkyl group which may have a substituent group represented by R ⁴¹ to R ⁴⁶ and R ⁵⁹ include a group in which an alkanediyl group having 1 to 5 carbon atoms such as a methylene group, an ethylene group and a propylene group is bonded to the group described as the aromatic hydrocarbon group .

R ⁴¹ and R ⁴² are bonded to form a ring together with the nitrogen atom to which they are bonded, a ring formed by R ⁴³ and R ⁴⁴ together with the nitrogen atom to which they are bonded, and R ⁴⁵ and R ⁴⁶ are bonded to form a bond Examples of the ring formed together with the nitrogen atom include a nitrogen-containing nonaromatic 4- to 7-membered ring such as a pyrrolidine ring, a morpholine ring, a piperidine ring and a piperazine ring, preferably a pyrrolidine ring, a piperidine ring Or a 4 to 7-membered ring having only one nitrogen atom as a hetero atom.

Of these, preferred as R ⁴¹ to R ⁴⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁸ and R ⁵⁹ are a saturated hydrocarbon group of 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent, and each independently represents saturated More preferably a hydrocarbon group or an aromatic hydrocarbon group represented by the following formula. R < ⁵⁵ > is still more preferably an aromatic hydrocarbon group represented by the following formula: In the following formula, * represents a bonding position with a nitrogen atom.

[Chemical Formula 17]

R ⁴⁵ to R ⁴⁶ are each independently an oxygen atom is inserted between the alkyl group having a carbon number of 1 saturated hydrocarbon group of 1 to 20, having 2 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent group, or R ⁴⁵ and And R < ⁴⁶ > are bonded to form a ring together with the nitrogen atom to which they are bonded. More preferred forms are those wherein R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an aromatic hydrocarbon group represented by the following formula: or R ⁴⁵ and R ⁴⁶ are bonded to form one Form a 4- to 7-membered ring having only a nitrogen atom. In the following formula, * represents a bonding position with a nitrogen atom.

[Chemical Formula 18]

In addition, R ⁴⁷ to R ⁵⁴ C 1 -C 8 alkyl group represented by, and having 2 to 8 carbon atoms as the group which is inserted an oxygen atom between carbon atoms, alkyl group of carbon atoms from groups corresponding to the above R ⁴¹ to R ⁴⁶ 8 or less May be exemplified, and more preferably, groups represented by the following formulas can be mentioned. In the following formula, * represents a bonding position with a carbon atom.

[Chemical Formula 19]

Each of R ⁴⁷ to R ⁵⁴ is preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and each independently is a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, from the standpoint of ease of synthesis.

Examples of the cation moiety of the formula (Ab2) include a cation 1 to a cation 14 represented by the formula (Ab2-1) as shown in Table 1 below. In the table, * indicates the bonding position.

[Chemical Formula 20]

(Table 1)

In Table 1, Ph1 to Ph9 are taken to mean groups represented by the following formulas. In the formula, * represents a bonding position.

Examples of the cation moiety of the formula (Ab2) include a cation 15 to a cation 18 represented by the formula (Ab2-2) as shown in Table 2 below. In the table, * indicates the bonding position.

[Chemical Formula 22]

(Table 2)

In Table 2, Ph1, Ph10 and Ph11 are taken to mean groups represented by the following formulas. In the formula, * represents a bonding position.

(23)

Particularly, the cation portion of the formula (Ab2) is preferably a cation 1 to a cation 6, a cation 11 to a cation 14, and particularly preferably a cation 1, a cation 2, or a cation 12 to a cation 14, and most preferably a cation 12.

[Y] ^m- may also be a polymer having a constituent unit derived from an anion represented by the formula (A-II) (hereinafter sometimes referred to as "anion (A-II)").

≪ EMI ID =

[In the above formula (A-II), X represents an alkyl group having 8 or less carbon atoms in which a part of the hydrogen atoms may be substituted with a fluorine atom. Y represents a divalent aliphatic hydrocarbon group, an arylene group, or a combination thereof, and the methylene group constituting the aliphatic hydrocarbon group and the arylene group may be substituted with an oxygen atom or a nitrogen atom. R ⁶¹ represents a hydrogen atom or a methyl group. ]

In the formula (A-II), X is preferably a perfluoroalkyl group in which all the hydrogen atoms are substituted with fluorine atoms from the viewpoint of enhancing the acidity of imidic acid, and examples thereof include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ halo _{fluoro-CF 2 CF 3, -CF (CF} 3) 2, -CF 2 CF 2 CF 2 CF such as _{3, -CF 2 CF (CF 3} ) 2, -C (CF 3) 3 containing from 1 to 8 carbon atoms in the Alkyl group. The carbon number of X is 2 or more and 8 or less, more preferably 3 or more, and further preferably 4 or more.

As the divalent group of Y, a linear or branched alkylene group, an arylene group, or an arylenealkylene group is preferable. Also, Y preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Specifically, the straight-chain or branched-chain alkylene group preferably has 1 to 10 carbon atoms, the arylene group preferably has 6 to 20 carbon atoms, and the arylenealkylene group preferably has 7 to 20 carbon atoms.

The alkylene group may be either linear or branched, and examples thereof include a methylene group, an ethylene group, an n-propylene group, an isopropylene group and a butyl group.

Examples of the arylene group include a phenylene group and a naphthylene group.

Examples of the arylene alkylene group include an arylene methylene group, an aryleneethylene group, an arylene propylene group, an arylene butylene group, an arylene pentylene group, and an arylene hexylene group. And is preferably bonded to the sulfur atom on the aryl group side of the arylene alkylene group.

The methylene group constituting the alkylene group and the arylenealkylene group may be substituted with an oxygen atom or a nitrogen atom. Among them, Y is preferably an arylene group or an arylenealkylene group having 7 to 10 carbon atoms, and among these, an arylene group, an arylmethylene group, an arylethylene group, an arylpropylene group, an arylenebutylene group, an arylenepentylene group, More preferably a silylene group, still more preferably an arylene group, and particularly preferably a phenylene group.

Examples of the anionic compound include anionic compounds represented by the following formulas (A-II-1) to (A-II-6).

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These anions (A-II) may be used alone or in combination of two or more.

[Y] ^m- corresponding to the anion is preferably an anion containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus. Compounds using such anions can improve heat resistance and solvent resistance.

[Y] ^m- is an anion of a heteropoly acid or isopoly acid containing tungsten, particularly an anion of tungstic acid, silicotungstic acid and tungsten-based isopoly acid.

Examples of the anions of the heteropoly acid or isopoly acid containing tungsten include tungstate ion α- [PW ₁₂ O ₄₀ ] ^3- , Kggin type, tungstate ion α- [PW ₁₂ O ₄₀ ] ^3- , Dawson type, [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , keel type silico tungstate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^{4 _{-, γ- [SiW 12 O 40}} ] 4-, [P 2 W 17 O 61] 10-, [P 2 W 15 O 56] 12-, [H 2 P 2 W 12 O 48] 12-, [NaP ^{_{5 W 30 O 110] 14-,}} α- [SiW 9 O 34] 10-, γ- [SiW 10 O 36] 8-, α- [SiW 11 O 39] 8-, β- [SiW 11 O 39] ^8- , [W ₆ O ₁₉ ] ^{2 -} , [W ₁₀ O ₃₂ ] ^{4 -} , WO ₄ ^{2 -} and mixtures thereof.

[Y] ^m- is preferably an anion composed of at least one element selected from the group consisting of silicon and phosphorus and oxygen.

At least one element selected from the group consisting of silicon and phosphorus, and the anion composed of oxygen include SiO ₃ ^{2 -} and PO ₄ ^3- .

From the ease of synthesis and post-treatment, tungstate anion such as tungstate ion of the keel type and tungstate ion of the Dowson type; The cake ginhyeong silicotungstic acid ion such as silicotungstic acid anion, [W ₁₀ O _32] tungsten-based anions such as ^4-isopropyl polyacid is preferred. Particularly preferred are tungstic acid anion and tungsten-based isopoly acid anion.

As the dye (Aa), for example, a compound represented by the following formula can be given.

(Table 3)

(Table 4)

Among them, the compound (A-I) is preferably a compound represented by the formula (Aa2-53).

The content of the dye (Aa) in the colored curable resin composition is usually 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 60% by mass or less, more preferably 10% 60 mass% or less, particularly preferably 15 mass% or more and 50 mass% or less. If the content of the dye (Aa) is within the above range, the desired spectral or color density can be obtained more easily. In the present specification, the term "total amount of solids" refers to the total amount of components excluding the solvent from the colored curable resin composition of the present invention. The total amount of the solid content and the content of each component in the total amount can be measured by a known analytical method such as liquid chromatography or gas chromatography.

The compound represented by the formula (AI) is preferably 50 mass% or more, more preferably 60 mass% or more, even more preferably 70 mass% or more, still more preferably 80 mass% or more in 100 mass% % Or more, particularly preferably 90 mass% or more, and most preferably 100 mass%.

The dye (preferably a xanthene dye) other than the compound (AI) is preferably not less than 0.1% by mass and not more than 30% by mass, more preferably not less than 0.5% by mass and not more than 20% by mass in 100% by mass of the dye (Aa) And more preferably 1.0 mass% or more and 10 mass% or less.

Compound (A-I) can be produced according to the method described in Japanese Patent Application Laid-Open No. 2015-28121.

Colored dispersion

In the present invention, a compound comprising an anion of a compound containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and a cation having a dye skeleton (hereinafter referred to as a compound (AA) ) Is mixed with a solvent to obtain a colored dispersion. (B), the polymerizable compound (C), the polymerization initiator (D), and the like to form a colored curable resin composition, the heat resistance of the color filter can be further increased.

Any solvent which can be used as the solvent (E) for the colored curable resin composition can be used as the solvent. Particularly excellent solvents for the purpose of dispersing compound (AA) are, for example, ether ester solvents, more preferably one hydroxy group of alkylene glycol or polyalkylene glycol is etherified, and the remaining hydroxy groups are esterified 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 monoethyl ether acetate, diethylene glycol monoethyl ether acetate, Ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like. These may be singular or plural.

The amount of the solvent is usually 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 10 parts by mass based on 1 part by mass of the compound (AA).

In preparing the colored dispersion, it is preferable to use a dispersant. As the dispersing agent, for example, known pigment dispersing agents such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic and the like can be used. These pigment dispersants may be used alone or in combination of two or more. (Manufactured by Shinetsu Kagaku Kogyo Co., Ltd.), fluorene (manufactured by Kyoritsu Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by BASF) , Aji Spa (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), and the like.

The amount of the dispersant is usually 1 to 1000 parts by mass, preferably 3 to 100 parts by mass, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 30 parts by mass with respect to 100 parts by mass of the compound (AA).

When the dye-curable resin composition described later contains a dye (Aa) other than the compound (AA), the colored dispersion may contain a part or all, preferably all, of the dye (Aa) other than the compound (AA) May be included in advance. The amount of the dye (Aa) other than the compound (AA) in the coloring dispersion is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 10 parts by mass, 5 parts by mass.

The colored dispersion may include a part or all, preferably a part of the binder resin (B) used in the colored curable resin composition, if necessary. When the binder resin (B) is previously contained in the colored curable resin composition, the dispersibility can be further improved. The solid content of the binder resin (B) in the colored dispersion is usually 1 to 300 parts by mass, preferably 10 to 100 parts by mass, more preferably 20 to 70 parts by mass, based on 100 parts by mass of the compound (AA).

In the preparation of the dispersion, it is preferable to finely disperse the dispersion by appropriately adding necessary components and then using a dispersing device. As the dispersion apparatus, a bead mill apparatus can be used. As the beads to be used, hard beads such as zirconia beads are generally used. The particle size thereof is selected, for example, in the range of 0.05 mm or more and 20 mm or less, preferably 0.1 to 10 mm, and more preferably 0.1 to 0.5 mm .

The content of the dye (Aa) in the colored curable resin composition (when the composition contains the pigment) is usually 1% by mass or more and 45% by mass or less, preferably 2% by mass or more and 40% by mass or less based on the total amount of solid matter, More preferably 3 mass% or more and 35 mass% or less, and particularly preferably 5 mass% or more and 30 mass% or less. If the content of the dye (Aa) is within the above range, a desired brightness can be obtained more easily.

The colored curable resin composition of the present invention may further comprise a pigment (Ab).

Pigment (Ab)

The pigment is not particularly limited and a known pigment can be used. For example, pigments classified as pigments in the color index (published by The Society of Dyers and Colourists) can be used alone or in combination of two or more kinds.

Specifically, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, , 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194 and 214;

Orange pigments such as C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, Pigments;

Blue pigments such as C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C. I. violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

Green pigments such as C.I. Pigment Green 7, 36, 58;

. Among them, C. I. Pigment Blue 15: 6 is preferable.

The pigment may be subjected to a surface treatment using a rosin treatment, an acidic group or a pigment derivative in which a basic group is introduced, a graft treatment on a pigment surface by a polymer compound or the like, an atomization treatment by a sulfuric acid atomization method or the like, Or the like, a removal treatment with an ion exchange method of ionic impurities, or the like can be carried out. The particle size of the pigment is preferably substantially uniform. The pigment can be a pigment dispersion in a state of being uniformly dispersed in the pigment dispersant solution by containing a pigment dispersant and performing a dispersion treatment. Each of the pigments may be dispersed singly or mixed with a plurality of dispersed pigments.

Examples of the pigment dispersant include surfactants and the like, and they can be any of cationic, anionic, nonionic, and amphoteric surfactants. Specific examples thereof include surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include, but are not limited to, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), propylene (manufactured by Kyowa Chemical Industry Co., Ltd.), Solsperse (manufactured by Zeneca) (Manufactured by BASF), Ajisap (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.) and Disperbyk (registered trademark) manufactured by BYK-Chemie.

When a pigment dispersant is used, its amount to be used is preferably 100 parts by mass or less, more preferably 0 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the pigment. When the amount of the pigment dispersant is within the above range, a more uniform dispersion state of the pigment dispersion tends to be obtained.

When the pigment (Ab) is contained, the content of the pigment (Ab) is preferably 1% by mass or more and 90% by mass or less, more preferably 2% by mass or more and 85% Is not less than 5 mass% and not more than 80 mass%.

The binder resin (B)

The binder resin (B) comprises a constituent unit (b1) derived from at least one kind of monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and a constituent unit (b1) derived from a monomer having an ethylenic unsaturated bond and a cyclic ether structure (b3) derived from a hydroxyl group-containing (meth) acrylic acid ester monomer, and a structural unit (b4) derived from a monomer of a dicarbonylimide derivative.

The binder resin (B) of the present invention may contain other constituent units as long as the constituent units (b1) to (b4) are included. With the binder resin of the present invention, the pattern shape can be made good and the generation of foreign matter can be reduced.

Examples of the at least one monomer selected from the group consisting of the unsaturated carboxylic acid and the unsaturated carboxylic acid anhydride constituting the structural unit (b1) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p- Monocarboxylic acids;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyloctanoic acid, 4-vinyloctanoic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid , Unsaturated dicarboxylic acids such as dimethyltetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

2,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hept- Carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept- 1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl butanoic anhydride, 4-vinyl butanoic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydro Unsaturated dicarboxylic acid anhydrides such as phthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hept-2-enoic anhydride.

In addition, unsaturated mono [(meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] ] Esters; and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as? - (hydroxymethyl) acrylic acid.

Among them, the monomer constituting the structural unit (b1) is preferably an unsaturated monocarboxylic acid, more preferably acrylic acid or methacrylic acid.

In the present specification, the notation such as "(meth) acrylic acid" and "(meth) acrylate" represents at least one kind selected from the group consisting of acrylic acid (acrylate) and methacrylic acid (methacrylate).

The monomer having an ethylenic unsaturated bond and a cyclic ether structure constituting the constituent unit (b2) is, for example, an ethylenically unsaturated bond and a cyclic ether structure having 2 to 4 carbon atoms (for example, an oxirane ring, And at least one member selected from the group consisting of tetrahydrofuran rings).

Examples of the constituent unit (b2) include a monomer (b2-1) having an oxirane group and an ethylenic unsaturated bond (hereinafter sometimes referred to as "(b2-1)"), an oxetanyl group and an ethylenically unsaturated (B2-2) (hereinafter also referred to as "(b2-2)"), a monomer (b2-3) having a tetrahydrofuryl group and an ethylenically unsaturated bond ) And the like.

The constituent unit (b2-1) is, for example, a monomer (b2-1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(b2-1-1)" ) And a monomer (b2-1-2) having an epoxidized alicyclic unsaturated hydrocarbon (hereinafter sometimes referred to as "(b2-1-2)").

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o -Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-m-vinylbenzyl glycidyl (Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) ) Styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- And the like.

(b2-1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000 manufactured by Daicel Co.), 3,4 - epoxycyclohexylmethyl (meth) acrylate (for example, CYCLOMER A400 manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, M100 manufactured by Daicel Co., Ltd.), a compound represented by formula (I) and a compound represented by formula (II).

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[In the formulas (I) and (II), R ^b1 and R ^b2 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 hydroxy group.

X ^b1 and X ^b2 represent a single bond, -R ^b3- , * -R ^b3 -O-, * -R ^b3 -S- or * -R ^b3 -NH-.

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents the bonding position with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.

R ^b1 and R ^b2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, , 6-diyl group, and the like.

X ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, more preferably a single bond, * - CH ₂ CH ₂ -O-. * Represents the bonding position with O.

Examples of the compound represented by the formula (I) include a compound represented by any one of the formulas (I-1) to (I-15). (I-1), (I-3), (I-5), (I-7), (I- Is preferably a compound represented by the formula (I-1), (I-7), (I-9) or (I-15)

(27)

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Examples of the compound represented by the formula (II) include a compound represented by any one of the formulas (II-1) to (II-15). Particularly, the compound represented by the formula (II-1), the compound represented by the formula (II-3), the compound represented by the formula (II-5), the compound represented by the formula (II- Is preferably a compound represented by the formula (II-1), (II-7), (II-9) or (II-15).

[Chemical Formula 29]

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The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used together, the content ratio of the compound represented by the formula (I): the compound represented by the formula (II) Preferably from 5:95 to 95: 5, more preferably from 20:80 to 80:20.

(b2-2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is preferable. (b2-2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3- 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

(b2-3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of the compound (b2-3) include tetrahydrofurfuryl acrylate (for example, Viscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate. .

The structural unit (b2) is preferably (b2-1) in that the reliability of heat resistance, chemical resistance and the like of the obtained cured film can be enhanced. (B2-1-2) is more preferable, and the compound represented by the formula (I) and the compound represented by the formula (II) are more preferable because the storage stability of the curable resin composition is excellent. -1), and the compound represented by the formula (II-1) are even more preferable.

Examples of the hydroxy group-containing (meth) acrylic acid ester monomer constituting the constituent unit (b3) include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate, (Meth) acrylic acid esters having a hydroxyl group such as acrylate and the like.

The hydroxy group-containing (meth) acrylic acid ester monomer is preferably a hydroxyalkyl (meth) acrylate ester having an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms Still more preferably a hydroxy group-containing (meth) acrylic acid ester having an alkyl group having 1 to 4 carbon atoms.

Among them, the monomer constituting the structural unit (b3) is preferably at least one monomer selected from the group consisting of hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylate is particularly preferable, and 2-hydroxyethyl (meth) acrylate is most preferable.

Examples of the monomer of the dicarbonylimide derivative constituting the constituent unit (b4) include dicarbonylimide having an aromatic carbon ring group such as N-phenylmaleimide and N-tolylmaleimide, N-cyclohexylmaleimide, N - dicarbonylimides having alicyclic hydrocarbon groups such as cycloheptylmaleimide, N-cyclooctylmaleimide and N-cyclododecylmaleimide, aralkyl groups such as N-benzylmaleimide and N-phenethylmaleimide, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimide having N-succinimidyl- Dicarbonylimide having a condensed heterocyclic group such as dicarbonylimide having a succinimidyl group such as dicyclohexylmethyldithiocarbamate and succinimidyl group such as dicyclohexylmethyldithiocarbamate and dicyclohexylmethyldipropylate, and dicarbonylimide having a condensed heterocyclic group such as N- (9-acridinyl) have.

The monomer of the dicarbonylimide derivative is preferably an N-substituted maleimide having a hydrocarbon group of 4 to 20 carbon atoms, more preferably an alicyclic hydrocarbon group of 4 to 20 carbon atoms, an aromatic hydrocarbon group, an aralkyl group, An imidyl group, a condensed heterocyclic group and the like.

More preferably 4 to 16 carbon atoms, still more preferably 4 to 12 carbon atoms, and particularly preferably 4 to 8 carbon atoms.

The hydrogen atom contained in the hydrocarbon group may be substituted with an amino group, an alkoxy group having 1 to 5 carbon atoms, a phenylamino group, a halogen atom, a hydroxy group, and the like.

Among them, the monomer of the dicarbonylimide derivative is more preferably an N-substituted maleimide having an alicyclic hydrocarbon group having 4 to 20 carbon atoms, and still more preferably N-cyclohexylmaleimide, N-cycloheptylmaleimide , N-cyclooctyl maleimide, N-cyclododecyl maleimide, particularly preferably N-cyclohexyl maleimide.

The binder resin (B) of the present invention may contain other structural units in addition to the structural units (b1) to (b4) by using the following monomers.

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cyclohexylboricyclo [2.2.1] hept-2-ene, (Cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (tert- butoxycarbonyl) bicyclo [2.2.1] hept- Bicyclic unsaturated compounds such as ene;

Vinyl group-containing aromatic compounds such as styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; Vinyl group-containing nitriles such as acrylonitrile and methacrylonitrile; Halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; Vinyl group-containing amides such as acrylamide and methacrylamide; Esters such as vinyl acetate; 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene diene;

At least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, still more preferably 2 to 30% by mass, 5 to 30 mass%.

The monomer having an ethylenically unsaturated bond and a cyclic ether structure is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, and still more preferably 5 to 30% by mass, based on 100% by mass of the total monomer.

The hydroxy group-containing (meth) acrylic acid ester monomer is preferably 1 to 35 mass%, more preferably 2 to 30 mass%, and still more preferably 3 to 25 mass%, of 100 mass% of the total monomer.

The monomer of the dicarbonyl imide derivative is preferably 25 to 80 mass%, more preferably 35 to 75 mass%, still more preferably 45 mass% or more, further preferably By mass is not less than 50% by mass.

The total amount of the hydroxy group-containing (meth) acrylic acid ester monomer and the monomer of the dicarbonylimide derivative is preferably 25 mass% or more and 90 mass% or less, more preferably 50 mass% or more, in 100 mass% , Further more preferably not less than 55 mass%, further still more preferably not less than 60 mass%.

Examples of the binder resin (B) include 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2- (Copolymer (B0)), and the like.

The binder resin (B) may contain other binder resins as long as they exhibit the effects of the present invention.

The other binder resin may be a resin different from the copolymer (B0), for example, a copolymer having the constituent unit (b1) and the constituent unit (b2), the copolymer comprising the constituent unit (b1), the constituent unit (b2) ), A copolymer having a constituent unit (b1), a constituent unit (b2) and a constituent unit (b4), a copolymer having a constituent unit (b1) and a constituent unit (b2) a copolymer having a structural unit (b1) and a structural unit having an ethylenically unsaturated bond, a copolymer having a structural unit (b1) and a structural unit having an ethylenic unsaturated bond, and the like .

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acryloyl group. The resin having such a structural unit is obtained by allowing a polymer having a structural unit derived from the structural unit (b1) or the structural unit (b2) to react with a group capable of reacting with a group having the structural unit (b1) And then adding a monomer having a bond.

Examples of such structural units include structural units obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid unit, structural units obtained by adding 2-hydroxyethyl (meth) acrylate to a maleic anhydride unit, glycidyl And structural units obtained by adding (meth) acrylic acid to an acrylate unit. When these structural units have a hydroxyl group, the structural unit to which the carboxylic acid anhydride is further added may also be exemplified as a structural unit having an ethylenically unsaturated bond.

(Meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / A resin [K1] such as a (meth) acrylic acid copolymer; (Meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 (meth) acrylate / glycidyl etc. .1.0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (meth) acrylic acid / styrene copolymer of Resin [K2]; A resin such as benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) ]; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (K4) such as a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) A resin [K5] such as a resin obtained by reacting (meth) acrylic acid with a copolymer; A resin such as a resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and tetrahydrophthalic anhydride in addition to the resin [K6] have.

The weight average molecular weight of the resin (B) in terms of polystyrene is usually 3,000 to 100,000, preferably 4,000 to 50,000, more preferably 5,000 to 35,000, even more preferably 5,000 to 30,000, and particularly preferably 5,500 To 30,000. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film rate is high, the unexposed portion has good solubility in the developing solution, and the resolution of the coloring pattern tends to be improved.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4, further preferably 1.3 to 3.

The acid value (in terms of solid content) of the resin (B) is preferably 1 to 170 mg-KOH / g, more preferably 5 to 170 mg-KOH / g, More preferably from 15 to 170 mg-KOH / g, even more preferably from 150 mg-KOH / g to 135 mg-KOH / g.

Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, and particularly preferably 13 to 60% by mass, based on the total amount of the solid components, And preferably from 17 to 60 mass%. When the content of the resin (B) is in the above range, coloring pattern formation is easy, and the resolution and residual film ratio of the coloring pattern tend to be improved.

The polymerizable compound (C)

The polymerizable compound is a compound that can be polymerized by an active radical and / or an acid generated from a polymerization initiator, and includes, for example, a polymerizable compound having an ethylenically unsaturated bond, and a compound having a (meth) acrylic acid ester structure . The polymerizable compound is preferably a polymerizable compound having three or more ethylenic unsaturated bonds, more preferably a polymerizable compound having 5 to 6 ethylenic unsaturated bonds.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N -Vinylpyrrolidone, the above-mentioned (a), (b) and (c). Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di Acrylate, bis (acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Examples of the polymerizable compound having three or more ethylenic unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (metha) acrylate, tripentaerythritol hepta (metha) acrylate, tetrapentaerythritol deca (Meth) acrylate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (metha) acrylate, propylene glycol-modified pentaerythritol Tetra (meth) acrylate, propylene glycol-modified dipentaerythritol (Meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) in the colored curable resin composition of the present invention is usually 1 to 60% by mass, preferably 5 to 50% by mass, more preferably 10 to 40% by mass, based on the total amount of solids , Still more preferably from 12 to 35 mass%. The content ratio of the binder resin (B) to the polymerizable compound (C) (binder resin (B): polymerizable compound (C)) is usually 20:80 to 80:20, preferably 35:65 ~ 80: 20. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the coloring pattern and the chemical resistance of the color filter tend to be improved.

The polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as far as it is a compound capable of generating an active radical or an acid by the action of light or heat and capable of initiating polymerization, and a known polymerization initiator can be used.

The polymerization initiator (D) is preferably a polymerization initiator comprising at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and nonimidazole compounds, Preferably a polymerization initiator comprising an O-acyloxime compound.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- -Acetoxy-l- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl -9-ethyl-6- (2-methylbenzoyl) - < / RTI > 3-yl] -3-cyclopentylpropan-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2- methylbenzoyl) -9H- 3-cyclopentylpropan-1-one-2-imine. Commercially available products such as IRGACURE (registered trademark) OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may also be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 1- (4-phenylsulfanylphenyl) -Imine and at least one member selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2- - (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable.

The alkylphenone compound is preferably a 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- -1-one and 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one. IRGACURE 369, 907 and 379 (manufactured by BASF) can be used.

The alkylphenone compound may be selected from the group consisting of 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl- 1- [4- (2-hydroxyethoxy) phenyl] Oligomers of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one,?,? - diethoxyacetophenone and benzyldimethylketone It may be a ride.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) 2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. A commercially available product such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis Phenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) bimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid- , An imidazole compound in which the phenyl group at the 4'5,5'-position is substituted by a carboalkoxy group (see, for example, JP-A-07-010913). Among them, compounds represented by the following formulas and mixtures thereof are preferable.

(31)

Other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and camphorquinone; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiator (specifically, an amine polymerization initiator) described below.

The content of the polymerization initiator (D) is generally from 0.1 to 40 parts by mass, preferably from 0.1 to 30 parts by mass, more preferably from 1 to 30 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) To 30 parts by mass, particularly preferably 1 to 20 parts by mass.

<Polymerization Initiator>

The polymerization initiation aid is a compound or sensitizer used for promoting the polymerization of the polymerizable compound (C) initiated by the polymerization initiator (D). When the color-curable resin composition of the present invention contains a polymerization initiator, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiator include an amine-based polymerization initiator, an alkoxyanthracene-based polymerization initiator, a thioxanone-based polymerization initiator, and a carboxylic acid-based polymerization initiator.

Examples of the amine-based polymerization initiator include alkanolamines such as triethanolamine, methyldiethanolamine and triisopropanolamine; Amino benzoic acid esters such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; N, N-dimethyl para-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly referred to as Michler's ketone) 4'-bis (ethylmethylamino) benzophenone. Of these, alkylaminobenzophenones such as 4,4'-bis (diethylamino) benzophenone are preferable. Among them, alkylaminobenzophenone is preferable, and 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene-based polymerization initiator include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thioxanthone polymerization initiator include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1- And propoxythioxanthone.

Examples of the carboxylic acid-based polymerization initiator include phenylsulfanyl acetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, Phenylsulfanyl acetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

When a polymerization initiator is used, its content is preferably 0.1 to 30 parts by mass, more preferably 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 initiator is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

&Lt; Solvent (E) >

The solvent (E) is not limited, and solvents commonly used in the field may be used alone or in combination of two or more. Specifically, an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester solvent (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent (containing OH in the molecule and -O -, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and? -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, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, .

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, Methyl propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 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 and dipropylene glycol methyl ether acetate.

Examples of the ketone solvent include diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4- - 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 solvents include benzene, toluene, xylene, and mesitylene.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

These solvents may be used in combination of two or more kinds

Among the above-mentioned solvents, an organic solvent having a boiling point of 120 deg. C or more and 210 deg. C or less at 1 atm is preferable from the viewpoint of coatability and drying property. Particularly, it is preferable to use propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Dipropylene glycol methyl ether acetate, 3-methoxybutylacetate, 3-methoxy-1-butanol, 4-hydroxy-4 methyl-2-pentanone, diacetone alcohol, N, Propyleneglycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, diacetone alcohol, 3-methoxybutyl acetate, 3-methoxybutyl acetate, -Methoxy-1-butanol, ethyl 3-ethoxypropionate, N, N-dimethylformamide and N- This pyrrolidone is more preferred.

The content of the solvent (E) is usually 45 to 95 mass%, preferably 50 to 90 mass%, and more preferably 50 to 85 mass%, based on the total amount of the colored curable resin composition. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and when the color filter is formed, the color density tends not to be insufficient and the display characteristics tend to be good

<Leveling agent>

Examples of the leveling agent include a silicone surfactant, a fluorine surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specific examples thereof include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicon DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Toray Dow Corning 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 (manufactured by Momentive Performance Materials Japan KK) ).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples of the fluorophores include FLUORAD (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by DIC Corporation), Megafac F557, Megapack F554, Megapack R30, Megapack RS-718- Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Mitsubishi Chemical Corporation) Manufactured by Kinki Fine Chemical Research Institute).

Examples of the silicon-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megapac (registered trademark) R08, Megapack BL20, Megapack F475, Megapack F477, and Megapack F443 (manufactured by DIC Corporation) can be mentioned.

The content of the leveling agent is usually 0.0005 mass% or more and 0.6 mass% or less, preferably 0.001 mass% or more and 0.5 mass% or less, more preferably 0.001 mass% or more and 0.2 mass% or less based on the total amount of the colored curable resin composition , Still more preferably 0.002 mass% or more and 0.1 mass% or less, and particularly preferably 0.005 mass% or more and 0.07 mass% or less. When the content of the leveling agent is within the above range, the flatness of the color filter can be improved.

The content of the leveling agent is usually 0.001 to 2.0% by mass, preferably 0.002 to 1.5% by mass, more preferably 0.004 to 1.0% by mass, based on the total solid content of the colored curable resin composition Still more preferably 0.008 mass% or more and 0.5 mass% or less, and particularly preferably 0.01 mass% or more and 0.3 mass% or less.

<Other ingredients>

The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and the like, if necessary.

&Lt; Process for producing colored curable resin composition >

The colored curable resin composition of the present invention can be obtained, for example, by mixing a dye (Aa), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E) And other components. In addition to the dye (Aa), a colorant such as a pigment may be further mixed. The pigment is preferably used in the form of a pigment dispersion in which the pigment is mixed with a part or the whole of the solvent (E) and the pigment is dispersed using a bead mill or the like until the average particle size of the pigment becomes about 0.2 탆 or less. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended.

After mixing, the colored curable resin composition is preferably filtered with a filter having a pore diameter of about 0.01 to 10 mu m.

<Manufacturing Method of Color Filter>

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. In particular, a photolithography method is preferable. The photolithography method is a method in which a colored curable resin composition is applied to a substrate, followed by drying to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film which is a cured product of the colored composition layer can be formed without using a photomask and / or not developing at the time of exposure. The thus formed colored pattern or colored coating film is the color filter of the present invention.

The film thickness of the color filter to be manufactured can be suitably adjusted according to the purpose or use, and is usually 0.1 to 30 탆, preferably 0.1 to 20 탆, more preferably 0.5 to 6 탆.

As the substrate, glass, a resin plate, silicon, and a substrate on which aluminum, silver, silver / copper / palladium alloy thin film and the like are formed are used. A separate color filter layer, a resin layer, a transistor, a circuit, and the like may be formed on these substrates.

The formation of each color pixel by a photolithography method can be performed by known or conventional equipment and conditions. For example, it can be produced as follows.

First, a colored curable resin composition is coated on a substrate and dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer. Examples of the application method include a spin coating method, a slit coating method, and a slit and spin coating method.

Next, the coloring composition layer is exposed through a photomask to form a desired coloring pattern. It is preferable to use an exposure apparatus such as a mask aligner and a stepper because it is possible to uniformly irradiate the entire surface of the exposure surface with parallel rays and accurately align the substrate on which the coloring composition layer is formed. After the exposure, the coloring composition layer is brought into contact with a developing solution to develop a coloring pattern on the substrate. The unexposed portion of the colored composition layer is dissolved and removed in the developer by the development. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The developing method may be any one of paddle method, dipping method and spray method. Further, the substrate can be neglected at an arbitrary angle at the time of development. It is preferable to rinse after development.

The post-baking is further preferably performed on the obtained coloring pattern. The color filter having the coloring pattern or the colored coating film thus obtained may be further provided for the surface coating treatment in order to give various characteristics.

The color filter formed of the colored curable resin composition of the present invention is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid state image sensor.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples,% and parts representing the content or amount are based on mass unless otherwise specified.

Synthesis Example 1

The following reaction was carried out in a nitrogen atmosphere. 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide were fed into a flask equipped with a cooling tube and a stirrer, and then the mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice-cooling, and the mixture was stirred for 1 hour while being warmed to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the reaction solution, and the mixture was stirred at room temperature for 24 hours. The reaction solution was added to 200 parts of ice water and allowed to stand at room temperature for 15 hours. When water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to the viscous solid, the mixture was stirred at room temperature for 15 hours. The precipitated solid was separated by filtration and then purified by column chromatography. The purified light yellow solid was dried at 60 캜 under reduced pressure to obtain 9.8 parts of a compound represented by the formula (C-I-18).

(32)

The following reaction was carried out in a nitrogen atmosphere. 8.2 parts of the compound represented by the formula (BI-7), 10 parts of the compound represented by the formula (CI-18) and 20 parts of toluene were charged into a flask equipped with a stirrer, a condenser and a cooling tube, and then 12.2 parts of phosphorus oxychloride And the mixture was stirred at 95 to 100 DEG C for 3 hours. The reaction mixture was then cooled to room temperature and then diluted with 170 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300 parts of saturated saline, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Subsequently, stirring was stopped, and the mixture was allowed to stand for 30 minutes to separate into an organic layer and a water layer. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, followed by stirring for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated with an evaporator to obtain a bluish-purple solid. The violet solid was further dried at 60 DEG C under reduced pressure to obtain 18.4 parts of a compound represented by the formula (A-II-18).

(33)

The following reaction was carried out in a nitrogen atmosphere. 8 parts of the compound represented by the formula (A-II-18) and 396 parts of methanol were put in a flask equipped with a stirrer, a cooling tube and a stirrer, and stirred at room temperature for 30 minutes to prepare a blue solution. Subsequently, 396 parts of water was added to the blue solution, and further stirred at room temperature for 30 minutes to obtain a reaction solution.

To 53 parts of water in a beaker, 11.8 parts of tungstic acid (manufactured by Aldrich) and 53 parts of methanol were added into the water and mixed at room temperature in an air atmosphere to prepare a tungstic acid solution.

The resulting tungstic acid solution was added dropwise over 1 hour to the previously prepared reaction solution. The mixture was further stirred at room temperature for 30 minutes, and then filtered to obtain a blue solid. The resulting blue solid was added to 200 parts of methanol, dispersed for 1 hour, and then filtered twice. The blue solid obtained by the above operation was added to 200 parts of water, dispersed for 1 hour, and then filtrated. This operation was repeated twice. The blue solid obtained by the above operation was dried at 60 캜 under reduced pressure to obtain 17.1 parts of a compound represented by the formula (A-I-18).

(34)

Synthesis Example 2

An appropriate amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the flask was purged with nitrogen atmosphere. Then, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85 DEG C with stirring. Then, 38 parts of acrylic acid, ^3.0 parts of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II- 50), 137 parts of cyclohexyl maleimide, 50 parts of 2-hydroxyethyl methacrylate and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution of 5 parts of 2,2-azobisisobutyronitrile and 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the completion of the dropwise addition, the mixture was maintained at the same temperature for 4 hours and cooled to room temperature to obtain a copolymer (resin (B-1)) having a B-type viscosity (23 캜) of 22 mPas, a solid content of 25.5% and a solution acid value of 28 mg- . The resulting copolymer had a weight average molecular weight Mw of 7700 and a molecular weight distribution of 2.1.

(35)

Synthesis Example 3

A proper amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the flask was purged with nitrogen atmosphere. Then, 153 parts of ethyl lactate and 145 parts of propyleneglycol monomethyl ether acetate were added and heated to 90 DEG C with stirring. Next, 17 parts of acrylic acid, 3, 4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by the above formula (I-1) and the compound represented by the formula ), 144 parts of cyclohexylmaleimide, 46 parts of 2-hydroxyethylmethacrylate, and 381 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution obtained by dissolving 3 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-2)) having a B-type viscosity (23 캜) of 15 mPas, a solid content of 24.6%, and a solution acid value of 24 mg- . The resulting copolymer had a weight average molecular weight Mw of 5500 and a molecular weight distribution of 1.8.

Synthesis Example 4

A proper amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the mixture was purged with a nitrogen atmosphere. To the flask, 69 parts of ethyl lactate and 127 parts of propyleneglycol monomethylether acetate were added and heated to 85 deg. Then, 35 parts of acrylic acid, 30 parts of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by the above formula (I-1) and the compound represented by the formula ), 115 parts of cyclohexyl maleimide, 12 parts of 2-hydroxyethyl methacrylate and 482 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution of 3 parts of 2,2-azobisisobutyronitrile and 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the completion of the dropwise addition, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-3)) having a B-type viscosity (23 캜) of 19 mPas, a solid content of 24.5% and a solution acid value of 26 mg- . The resulting copolymer had a weight average molecular weight Mw of 7900 and a molecular weight distribution of 2.1.

Synthesis Example 5

A proper amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the flask was purged with nitrogen atmosphere. Then, 114 parts of ethyl lactate and 247 parts of propyleneglycol monomethylether acetate were added and heated to 85 캜 with stirring. Then 48 parts of acrylic acid, 3,4-epoxytricyclo [5.2. 1.0 ^2.6 ] decyl acrylate (a mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) in a molar ratio of 50:50), 120 parts of cyclohexylmaleimide, 48 parts of hydroxyethyl methacrylate, and 318 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution of 3 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 78 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the completion of the dropwise addition, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-4)) having a B-type viscosity (23 캜) of 29 mPas, a solid content of 25.6% and a solution acid value of 38 mg- . The resulting copolymer had a weight average molecular weight Mw of 9400 and a molecular weight distribution of 2.4

Synthesis Example 6

A proper amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the flask was purged with nitrogen atmosphere. 38 parts of ethyl lactate and 184 parts of propyleneglycol monomethylether acetate were added and heated to 85 캜 with stirring. Subsequently, 61 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1. 1.0 ^2.6 ] decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) in a molar ratio of 50:50), 123 parts of cyclohexylmaleimide, 23 parts of hydroxyethyl methacrylate, and 343 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution of 7 parts of 2,2-azobisisobutyronitrile and 198 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was maintained at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-5)) having a B-type viscosity (23 캜) of 27 mPas, a solid content of 25.0% and a solution acid value of 47 mg-KOH / g. The resulting copolymer had a weight average molecular weight Mw of 9400 and a molecular weight distribution of 2.4.

Synthesis Example 7

Nitrogen was introduced at 0.02 L / min into a flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel to make a nitrogen atmosphere, and 268 parts of ethyl lactate was added and heated to 70 캜 with stirring. Subsequently, 55 parts of acrylic acid, 81 parts of N-cyclohexylmaleimide, 3,4-epoxytricyclo [5.2.1. 1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a compound represented by the formula (II-1) in a molar ratio of 50:50) and tricyclo [5.2.1.1 ^{( 6} ) decen-8-yl acrylate (the compound represented by the formula (c-1) and the compound represented by the formula (c-2) in a molar ratio of 50:50) was added to 140 parts of ethyl lactate To prepare a solution, and the solution was dropped into a flask kept at 70 캜 for 4 hours using a dropping funnel. On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was added dropwise to the flask over 4 hours using another dropping funnel. After the dropping of the polymerization initiator solution was completed, the solution was kept at 70 캜 for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B) having a weight average molecular weight Mw of 11.2 x 10 ³ , a solid content of 36.7% and a solution acid value of 44 mg- -6)) solution. The solid content of the solid content and the solution acid value was calculated to be 119 mg-KOH / g.

(36)

Synthesis Example 8

20 parts of a compound represented by the formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light shielding conditions and the resulting solution was stirred at 110 ° C for 6 hours Respectively. The resulting reaction solution was cooled to room temperature, added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were collected as a residue of suction filtration and dried to obtain a compound represented by the formula (1-32).

(37)

Synthesis Example 9

A proper amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the flask was purged with nitrogen atmosphere. 190 parts of ethyl lactate was added and heated to 65 캜 with stirring. Then, 38 parts of acrylic acid, 30 parts of 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the above formula (I-1) and the compound represented by the formula , 175 parts of cyclohexyl maleimide, 12 parts of 2-hydroxyethyl methacrylate, 295 parts of ethyl lactate and 180 parts of propylene glycol monomethyl ether acetate was added dropwise over 3 hours. On the other hand, a mixed solution of 5 parts of polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 80 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-7)) solution having a B-type viscosity (23 캜) of 26 mPas, a solid content of 25.4% by mass and a solution acid value of 28 mg- &Lt; / RTI &gt; The resulting copolymer had a weight average molecular weight Mw of 7600 and a molecular weight distribution of 2.2.

Synthesis Example 10

An appropriate amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the flask was purged with nitrogen atmosphere. Then, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85 DEG C with stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1. 0) ^2.6 ] decyl acrylate (a mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) in a molar ratio of 50:50), 137 parts of cyclohexylmaleimide, 50 parts of hydroxyethyl methacrylate and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution of 5 parts of polymerization initiator 2,2-azobisisobutyronitrile and 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-8)) solution having a B-type viscosity (23 캜) of 23 mPas, a solid content of 25.6% by mass and a solution acid value of 28 mg- &Lt; / RTI &gt; The resulting copolymer had a weight average molecular weight Mw of 8,000 and a molecular weight distribution of 2.1.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin were measured by the GPC method under the following conditions.

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Test liquid concentration; 25 mg / mL (solvent; THF)

Flow rate; 1.0 mL / min

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH CORPORATION)

The ratio of the weight average molecular weight to the number average molecular weight in terms of polystyrene obtained above was defined as a molecular weight distribution (Mw / Mn).

Synthesis Example 11

11.0 parts of 2,3,3-trimethylindolenine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 19.4 parts of 4-fluorobenzyl bromide were added to 100 parts of toluene, and the mixture was heated to reflux for 14 hours. The precipitate formed after cooling was collected by filtration, washed with 50 parts of chloroform and dried at 60 DEG C for 24 hours to obtain 17.7 parts of a compound represented by the following formula (d-1).

(XX)

Identification of the compound represented by the formula (d-1)

(Mass analysis) Ionization mode = ESI +: m / z = 268.1 [M-Br] ⁺

Exact Mass: 347.1

Subsequently, 6.0 parts of the compound represented by the formula (d-1), 0.95 part of squalic acid, 63 parts of 1-butanol and 7.0 parts of pyridine were mixed and heated and stirred at 115 캜 for 16 hours. The precipitate formed after cooling was collected by filtration and dried at 60 DEG C for 24 hours to obtain 2.3 parts of a compound represented by the formula (SQ-1).

[Chemical formula SQ-1]

Identification of the compound represented by the formula (SQ-1)

(Mass analysis) Ionization mode = ESI +: m / z = 611.3 [MH] ⁺

Exact Mass: 612.3

Synthesis Example 12

2.0 parts of the compound represented by the formula (SQ-1) and 2.0 parts of methyl trifluoromethane sulfonate were added to 14 parts of methylene chloride, and the mixture was stirred at 20 to 30 캜 for 3 hours. Then, 50 parts of a 5% aqueous solution of sodium hydrogencarbonate was added and the mixture was separated with chloroform. The chloroform was distilled from the organic layer and the remaining residue was dried at 60 DEG C for 24 hours to obtain 2.5 parts of a compound represented by the formula (SQ-1K).

[Chemical formula SQ-1K]

Identification of a compound represented by the formula (SQ-1K)

(Mass Spec.) Ionization mode = ESI +: m / z = 627.3 [M-CF 3 SO 3] +

Exact Mass: 776.3

Synthesis Example 13

To 7.7 parts of the compound represented by the formula (SQ-1K), 400 parts of methanol was added, and the mixture was stirred at 20 to 30 DEG C for 1 hour to obtain a solution. 400 parts of ion-exchanged water was added to this solution and stirred for 2 hours to obtain a solution (SQ-1KA). On the other hand, 28.8 parts of ion-exchanged water was added to 9.6 parts of Phosphorus 12 tungstate hydrogencarbonate, stirred at 20 ° C to 30 ° C for 1 hour, then 28.8 parts of methanol was added and stirred for 2 hours to obtain a solution (SQ- . The solution (SQ-1KB) was added to the solution (SQ-1KA) and stirred at 20 ° C to 30 ° C for 12 hours. The resulting precipitate was collected by filtration, washed twice with 200 parts of ion-exchanged water, and then washed twice with 200 parts of methanol. The crystals collected by filtration were dried at 60 DEG C for 24 hours to obtain 11.5 parts of a compound represented by the formula (SQ-1P).

[Chemical formula SQ-1P]

Synthesis Example 14

To 5.0 parts of the compound represented by the formula (1-1), 400 parts of methanol was added, and the mixture was stirred at 20 캜 to 30 캜 for 1 hour to obtain a solution. 400 parts of ion-exchanged water was added to this solution, and the mixture was stirred for 2 hours to obtain a solution (1-1A). On the other hand, 28.8 parts of ion-exchanged water was added to 9.6 parts of phosphorus tris (3-hydroxyanaphthalate), and the mixture was stirred at 20 to 30 DEG C for 1 hour. Then, 28.8 parts of methanol was added, . To the solution (1-1A) was added the solution (1-1B) and barium chloride (1.0 part), and the mixture was stirred at 20 ° C to 30 ° C for 24 hours. The resulting precipitate was collected by filtration, washed twice with 200 parts of ion-exchanged water, and then washed twice with 200 parts of methanol. The crystals collected by filtration were dried at 60 DEG C for 24 hours to obtain 6.3 parts of a compound represented by the formula (1-1P).

[Formula 1-1]

[Chemical Formula 1-1P]

Synthesis Example 15

10 parts of the compound represented by the formula (AXa-1), 300 parts of chloroform and 5.7 parts of N, N-dimethylformamide were fed into a flask equipped with a stirrer, a condenser and a cooling tube, 12.6 parts were added dropwise, and the mixture was allowed to react for 5 hours. Thereafter, a mixed solution of 6.7 parts of 2-ethylhexylamine and 11.5 parts of triethylamine was added dropwise while maintaining the temperature at 20 占 폚 or lower while stirring. Thereafter, the reaction was carried out by stirring at the same temperature for 5 hours. Then, the solvent was distilled off using a rotary evaporator, and a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 10.7 parts of a compound represented by the formula (AXa-1a).

[Formula AXa-1a]

Identification of the compound represented by the formula (AXa-1a)

(Mass analysis) Ionization mode = ESI +:

m / z = 701.9 [M-Cl] ^&lt; ^{+ &} gt ^;

Exact Mass: 736.4

Methanol (400 parts) was added to 7.3 parts of the compound represented by the formula (AXa-1a), and the mixture was stirred at 20 to 30 ° C for 1 hour to obtain a solution. 400 parts of ion-exchanged water was added to this solution, and the mixture was stirred for 2 hours to obtain a solution (AXa-1aKA).

On the other hand, 28.8 parts of ion-exchanged water was added to 9.6 parts of phosphorus tris (3-hydroxyanaphthalate), and the mixture was stirred at 20 to 30 ° C for 1 hour. Then, 28.8 parts of methanol was added and stirred for 2 hours to obtain a solution (AXa- &Lt; / RTI &gt; The solution (AXa-1aKB) was added to the solution (AXa-1aA), and the mixture was stirred at 20 ° C to 30 ° C for 12 hours. The resulting precipitate was collected by filtration, washed twice with 200 parts of ion-exchanged water, and then washed twice with 200 parts of methanol. The crystals collected by filtration were dried at 60 DEG C for 24 hours to obtain 10.2 parts of a compound represented by the formula (AXa-1A).

[Chemical Formula AXa-1A]

Examples 1 to 12 and Comparative Examples 1 to 2

The respective components were mixed so as to have the composition shown in Table 5-7 to obtain a colored curable resin composition.

(Table 5)

(Table 6)

(Table 7)

¹⁾ A1-1 is used to mix the amount of propylene glycol monomethyl ether acetate according to the dispersing agent B-1 ⁶⁾ and E-1 ⁸⁾ it is, and the dispersion in advance.

²⁾ A1-2 is an acryl-based pigment dispersant, and B-6 ⁷⁾ and propylene glycol monomethyl ether acetate in the amount described in E- ¹⁸⁾ are mixed and dispersed in advance.

³⁾ represents the sum of the content of resin B-1.

⁴⁾ Represents the sum of resin B-6 content.

⁵⁾ represents the total content of propylene glycol monomethyl ether acetate.

In addition, in Table 5-7, each component indicates the following. The binder resin (B) represents a part by mass in terms of solid content.

Colorant (A); 1-1; The compound represented by the formula (1-32)

Colorant (A); A1-1; The compound represented by A-I-18

Colorant (A); A1-2; C. I. Pigment Blue 15: 6

Colorant (A); Pigment dispersion A: The pigment dispersion A

Dispersant: (BYK (registered trademark) -LPN6919 (manufactured by Big Chem Japan)

A binder resin (B); B-1; Resin (B-1) (in terms of solid content)

A binder resin (B); B-2; Resin (B-2) (in terms of solid content)

A binder resin (B); B-3; Resin (B-3) (in terms of solid content)

A binder resin (B); B-4; Resin (B-4) (in terms of solid content)

A binder resin (B); B-5; Resin (B-5) (in terms of solid content)

A binder resin (B); B-6; Resin (B-6) (in terms of solid content)

A binder resin (B); B-7; Resin (B-7) (in terms of solid content)

A binder resin (B); B-8; Resin (B-8) (in terms of solid content)

Polymerizable compound (C); C-1; Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Gyaku Co., Ltd.)

Polymerization initiator (D); D-1; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure OXE 01;

Polymerization initiator (D); D-2; Methylphenyl) propane-1-one (Irgacure 907, an alkylphenone compound manufactured by BASF)

Polymerization initiator (D); D-3: 2-Dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure 369;

Polymerization initiator; D1-1; 2,4-diethylthioxanthone (KAYACURE DETX; manufactured by Nippon Gakkai Co., Ltd., thioxane compound)

Solvent (E); E-1; Propylene glycol monomethyl ether acetate

Solvent (E); E-2; Propylene glycol monomethyl ether

Solvent (E); E-3; Dipropylene glycol methyl ether acetate

Solvent (E); E-4; Diacetone alcohol

Solvent (E); E-5; Ethyl lactate

Surfactant (F); F-1; Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Preparation of Pigment Dispersion A]

C. I. Pigment Blue 15: 6 10.0 parts

Acrylic pigment dispersant 7.5 parts

Propylene glycol monomethyl ether acetate 77.5 parts

Ethyl lactate 5.0 parts

And the pigment was thoroughly dispersed using a bead mill to obtain a pigment dispersion A.

Examples 13 to 15

Each component was mixed so as to have the composition shown in Table 8 to obtain a colored photosensitive resin composition.

(Table 8)

²⁾ represents the total content of propylene glycol monomethyl ether acetate.

⁴⁾ A1-3 was previously dispersed by mixing an acrylic dispersant, a dispersion resin and propylene glycol monomethyl ether acetate in an amount described in E- ¹³⁾ .

⁵⁾ A1-4 was preliminarily mixed with an acrylic dispersant, a dispersion resin and an amount of propylene glycol monomethyl ether acetate as described in E- ¹³⁾ .

⁶⁾ represents the sum of the resin B1 content.

Further, in Table 8, each component represents the following. The binder resin (B) represents a part by mass in terms of solid content.

Colorant (A); 2- (1); A compound represented by the formula (SQ-1P)

Colorant (A); 3- (1); The compound represented by the formula (1-1P)

Colorant (A); 4- (1); The compound represented by the formula (AXa-1A)

Colorant (A); A1-3; C. I. Pigment Yellow 138

Colorant (A); A1-4; C. I. Pigment Red 254

A binder resin (B); (B-1); The resin (B-1) solution

Polymerizable compound (C); (C-1); Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Yakuza Co., Ltd.)

Polymerization initiator (D); (D-1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure OXE 01;

Solvent (E); (E-1); Propylene glycol monomethyl ether acetate

Solvent (E); (E-4); 4-hydroxy-4-methyl-2-pentanone

Surfactant (F); (F-1); Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

&Lt; Fabrication of coloring pattern &

Each of the colored curable resin compositions of Examples 1 to 12 and Comparative Examples 1 and 2 was applied by spin coating onto a 5 cm square glass substrate (Eagle 2000; Corning), prebaked at 100 ° C for 3 minutes, To form a composition layer. After cooling, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 80 mu m, exposure was performed at an exposure amount of 35 mJ / cm &lt; ² &gt; (365 nm) using an exposure machine (TME- ). The photomask used was a 50 μm line and space pattern. After the light irradiation, the colored composition layer was immersed in a developing solution (an aqueous solution containing 0.05% of potassium hydroxide and 0.2% of sodium naphthalenesulfonate in mass fraction) at 25 DEG C for 60 seconds, Post-baking was performed for 30 minutes to obtain a colored pattern.

&Lt; Measurement of film thickness &

The obtained coloring pattern was measured for thickness using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.). The results are shown in Tables 9 and 10.

&Lt; Evaluation of color &

(X, y) and lightness (x, y) in the CIE XYZ color coordinate system using the characteristic function of the C light source, and the spectral intensity was measured using a colorimetric apparatus (OSP- Y was measured. The results are shown in Tables 8 and 9.

<Evaluation of Shape of Coloring Pattern>

The obtained coloring pattern was observed using a scanning electron microscope (S-4000; manufactured by Hitachi High-Technologies Corporation). (P1) (a so-called net taper shape),? Indicates a shape represented by (p2), and? Indicates a shape represented by (p3). (p1), cracking or peeling tends to be less likely to occur when the inorganic film is laminated on the colored pattern. The results are shown in Tables 8 and 9.

[Fabrication of pattern and observation of peeling piece]

The colored curable resin composition was coated on a 2 inch square glass substrate (Eagle 2000; Corning) by spin coating, and then prebaked at 100 占 폚 for 3 minutes to form a colored composition layer. After cooling, the substrate with the colored composition layer formed thereon and a quartz glass photomask having a pattern were exposed at an exposure dose of 150 mJ / cm ² (manufactured by TOPCON CORPORATION) using an exposure machine (TME-150RSK; 365 nm). After the light irradiation, the colored composition layer was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 23 DEG C for 80 seconds, developed and washed with water. After washing with water, the substrate was observed with a microscope (magnification: 500x; VF-7510; manufactured by KYENCE INC.), And foreign matter derived from the peeling piece was observed at a portion corresponding to the non-exposed portion of the colored composition layer formed on the substrate Respectively. In the case where no foreign substance is recognized, it is indicated by ○, and when it is recognized, it is shown by ×, and it is shown in Tables 9 and 10.

Thereafter, post-baking was performed in an oven at 230 캜 for 30 minutes to obtain a colored pattern.

<Evaluation of Solubility>

A 2 inch square glass substrate (Eagle 2000; Corning) was sequentially washed with neutral detergent, water and ethanol and dried. The colored curable resin composition was spin-coated on the glass substrate, and then pre-baked at 100 캜 for 3 minutes in a clean oven to form a colored composition layer.

Subsequently, the substrate on which the colored composition layer was formed was immersed in a developing solution (aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate in a mass fraction respectively) at a liquid temperature of 25 캜 and developed, The dissolution time was defined as the dissolution time, and the results are shown in Tables 9, 10, and 11. The shorter the dissolution time, the better the solubility.

[Production of coloring pattern]

The colored curable resin compositions of Examples 10 to 12 and Comparative Example 2 were respectively applied to a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by spin coating, and then prebaked at 100 ° C for 3 minutes to prepare a colored composition Layer. The spacing and after cooling, the colored composition is formed, the substrate and the quartz glass photomask as 100μm, the exposure system; the amount of exposure (365nm reference) of 150mJ / cm ² under an air atmosphere using a (TME-150RSK Topcon Co., Ltd.) Light irradiation. The photomask used was a mask formed with a 100 μm line and space pattern. After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 24 DEG C for 60 seconds. After washing with water, post-baking was carried out in an oven at 230 DEG C for 30 minutes to give a colored pattern .

(Table 9)

(Table 10)

(Table 11)

According to the colored curable resin composition of the present invention, it is possible to provide a color filter in which a part of the colored composition layer after exposure is peeled off at the time of development, and no foreign matter is formed, and the pattern shape is good.

Claims (8)

(A), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D)
The binder resin (B)
A constituent unit (b1) derived from at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride,
A constituent unit (b2) derived from a monomer having an ethylenically unsaturated bond and a cyclic ether structure,
, And a structural unit (b3) derived from a hydroxy group-containing (meth) acrylic acid ester monomer and a structural unit (b4) derived from a monomer of a dicarbonylimide derivative. The colored curable resin composition according to claim 1, wherein the total amount of the hydroxyl group-containing (meth) acrylic acid ester monomer and the dicarbonyl imide derivative monomer is 25% by mass or more and 90% by mass or less, based on 100% by mass of the total monomer. 3. The method according to claim 1 or 2,
The hydroxy group-containing (meth) acrylic acid ester monomer is a hydroxyalkyl (meth) acrylic acid ester having an alkyl group having 1 to 10 carbon atoms,
Wherein the monomer of the dicarbonyl imide derivative is an N-substituted maleimide having a hydrocarbon group of 4 to 20 carbon atoms. The colored curable resin composition according to any one of claims 1 to 3, further comprising a pigment (Ab). The method according to any one of claims 1 to 4, wherein the dye (Aa) is an anion of a compound containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, ), And a cation having a dye skeleton. The colored curable resin composition according to any one of claims 1 to 3, wherein the polymer anion has a structural unit derived from an anion represented by the following formula (1).
[Chemical Formula 1]

[In the above formula (A-II), X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom.
Y represents a divalent aliphatic hydrocarbon group, an arylene group, or a combination thereof, and the methylene group constituting the aliphatic hydrocarbon group may be substituted with an oxygen atom or a nitrogen atom.
And R ⁶¹ represents a hydrogen atom or a methyl group. The colored curable resin composition according to any one of claims 1 to 5, wherein the dye (Aa) is a compound represented by the formula (AI).
(2)

[In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms, which may have a substituent, and the oxygen atom An aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom. R ⁴¹ and R ⁴² may bond to form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may bond to form a ring together with the nitrogen atom to which they are bonded.
R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group. R ⁴⁸ and R ⁵² may combine with each other to form -NH-, -O-, -S- or -SO ₂ -.
Ring T ¹ represents an aromatic heterocycle which may have a substituent.
[Y] ^m- is at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and an optional m-valent anion containing oxygen or a structural unit derived from an anion represented by the formula (A-II) &Lt; / RTI &gt;
m represents an arbitrary natural number.
When a plurality of cations represented by the following formulas are contained in one molecule, they may have the same structure or different structures.
(3)

[Wherein, ring T ^1, R ⁴¹ To R ⁴⁴ And R ⁴⁷ To R &lt; ⁵⁴ &gt; are as defined above.
[Chemical Formula 4]

[In the formula (A-II), X, Y and R ⁶¹ are each as defined above.]] A color filter formed from the colored curable resin composition according to any one of claims 1 to 6. A liquid crystal display device comprising the color filter according to claim 7.

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