KR102077702B1 - Colored photosensitive resin composition, color filter and liquid crystal display device - Google Patents

Abstract

This invention makes it a subject to provide the coloring curable resin composition which does not form a foreign material by peeling at the time of image development, and a part of after-exposure coloring composition layer provides a color filter with a favorable pattern shape, A dye (Aa) and binder resin Structural unit (b1) containing (B), a polymeric compound (C), and a polymerization initiator (D), and binder resin (B) derived from at least 1 sort (s) of monomer chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride. ), A structural unit (b2) derived from a monomer having an ethylenically unsaturated bond and a cyclic ether structure, a structural unit (b3) derived from a hydroxy group-containing (meth) acrylic acid ester monomer, and a monomer of a carbonylimide derivative It is a copolymer which has a derived structural unit (b4), The coloring curable resin composition characterized by the above-mentioned is provided.

Description

Colored curable resin composition, color filter and liquid crystal display device

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

Colored curable resin composition is used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display device, an electroluminescence display device, and a plasma display. As such a colored curable resin composition, the colored curable resin composition containing blue, green, or a red pigment alone or the combination of pigment blue 15: 6 and a predetermined dye is known as a coloring agent (patent document 1, 2).

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

However, in the said colored curable resin composition, a foreign material was formed by peeling a part of post-exposure coloring composition layer at the time of image development, and the pattern shape might not be favorable.

Therefore, an object of this invention is to provide the colored curable resin composition which does not form a foreign material by peeling a part of the coloring composition layer after exposure at the time of image development, and provides a color filter with a favorable pattern shape.

The gist of the present invention is as follows.

[1] at least one containing a dye (Aa), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the binder resin (B) is selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides Structural unit (b1) derived from the monomer of a species, structural unit (b2) derived from the monomer which has an ethylenically unsaturated bond and a cyclic ether structure, and the structural unit (b3) derived from a hydroxy group containing (meth) acrylic acid ester monomer. And it is a copolymer which has a structural unit (b4) derived from the monomer of a dicarbonyl imide derivative, The colored curable resin composition characterized by the above-mentioned.

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

[3] The hydroxy group-containing (meth) acrylic acid ester monomer according to [1] or [2], which is a hydroxyalkyl (meth) acrylic acid ester having an alkyl group having 1 to 10 carbon atoms,

The colored curable resin composition whose monomer of a dicarbonyl imide derivative is N substituted maleimide which has a C4-C20 hydrocarbon group.

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

[5] The anion or chemical formula of a compound according to any one of [1] to [4], wherein the dye (Aa) is a compound containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus ( Colored curable resin composition which is a compound which consists of a polymer anion which has a structural unit derived from the anion represented by A-II), and a cation which has a pigment skeleton.

[Formula 1]

[In Formula (A-II), X represents an alkyl group having 1 or more and 8 or less carbon atoms which may be substituted with a hydrogen atom or 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.

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).

[Formula 2]

[In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, and an oxygen atom between the methylene groups constituting the alkyl group. The group inserted, the aromatic hydrocarbon group which may have a substituent, the aralkyl group which may have a substituent, or a hydrogen atom are shown. R ⁴¹ and R ⁴² may be bonded to form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may be bonded 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 a structural unit derived from at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and any m-valent anion containing oxygen or an anion represented by the formula (A-II) A polymer anion having

m represents any natural number.

In addition, when one molecule contains a plurality of cations represented by the following formulas, they may have the same structure or different structures.

[Formula 3]

[In the above formula, ring T ¹ , R ⁴¹ To R ⁴⁴ And R ⁴⁷ To R ⁵⁴ are the same as defined above]

[Formula 4]

[Wherein, Ｘ, Ｙ and R ⁶¹ are the same as defined above in the formula (A-II)]]

[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 the color filter described in [7].

According to the colored curable resin composition of this invention, a part of the after-exposure coloring composition layer peels at the time of image development, and a foreign substance is not formed and a color filter with a favorable pattern shape can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which applies colored curable resin composition to a board | substrate, and shows evaluation of a pattern shape after pattern formation.

The colored curable resin composition of this invention contains dye (Aa), binder resin (B), a polymeric compound (C), and a polymerization initiator (D), and binder resin (B) consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride. Derived from a structural unit (b1) derived from at least one monomer selected from the group, a structural unit (b2) derived from a monomer having an ethylenically unsaturated bond and a cyclic ether structure, and a hydroxy group-containing (meth) acrylic acid ester monomer It is a copolymer which has a structural unit (b3) and the structural unit (b4) derived from the monomer of a dicarbonyl imide derivative to be characterized.

Hereinafter, each component of dye (Aa), binder resin (B), a polymeric compound (C), and a polymerization initiator (D) is demonstrated.

Dye (Aa)

Examples of the dyes include azo dyes (for example, monoazo dyes, diazo dyes, triazo dyes, metal complex salt azo dyes, etc.), anthraquinone dyes, indigo dyes, phthalocyanine dyes, pyrazolone dyes, stilbene dyes, carotenoid dyes, Thiazole dye, quinoline dye, diaryl methane dye, triaryl methane dye, acridine dye, xanthene dye, azine dye, tarazine dye, oxazine dye, cyanine dye, indamine dye, indophenol dye, naphthal Imide dye, perylene dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, styryl dye, coumarin dye, quinoline dye, tetraaza porphyrin dye, nitro dye, or nitroso Dye etc. are mentioned, It is preferable that these are organic solvent soluble. These dyes can be used individually or in combination of 2 or more types.

Among them, xanthene dye, triarylmethane dye, anthraquinone dye, tetraaza porphyrin dye, azo dye, cyanine dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye , Acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes are preferred, xanthine dyes, triaryl methane dyes, coumarin dyes, anthraquinone dyes, and tetraazaporphyrin dyes are more preferred, and xanthene Dyestuffs are particularly preferred.

As xanthene dye, C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red is omitted and only numbers are described. Others are the same), 52, 87, 92, 94, 388, and C.I. 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), sulforhodamine G, the xanthene dye of Unexamined-Japanese-Patent No. 2010-32999, the xanthene dye of Unexamined-Japanese-Patent No. 4,492,760, etc. are mentioned.

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

[Formula 5]

[In the formula (a1-1), R ¹ To R ⁴ Are independently 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 is a methylene group included in the saturated hydrocarbon 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 be bonded 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> is shown.

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

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

a represents the 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 included in the saturated hydrocarbon group may be substituted with a halogen atom.

R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or 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 be bonded to each other to form a 3 to 10 membered heterocycle including 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.

Moreover, as xanthene dye, the compound represented by general formula (a1-2) (Hereinafter, it may be called "compound (a1-2)") is also preferable. Compound (a1-2) may be a tautomer thereof.

[Formula 6]

[In the formula (a1-2), R ²¹ and R ²² are independently represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms from each other, hydrogen atoms included in the groups saturated hydrocarbon R ^21, R ²² is C 6 -C 10 It may be substituted with an aromatic hydrocarbon group or a halogen atom of, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, -CH ₂ -in the saturated hydrocarbon group of R ²¹ , R ²² is It may be substituted with -O-,-CO- or -NR ^11- .

R ²³ and R ²⁴ independently of each other represent an alkyl group having 1 to 4 carbon atoms, an alkylsulyl 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 be bonded together to form a ring containing a nitrogen atom.

p and q represent the integer of 0-5 independently of each other. When p is 2 or more, the plurality of R ²³ may be the same or different, and when q is 2 or more, the plurality of R ²⁴ may be the same or different.

R ¹¹ is as defined above].

As a C1-C10 monovalent saturated hydrocarbon group in R <^21> and R <^22> , a C1-C10 group is mentioned among the thing in R <^8> .

As a C6-C10 aromatic hydrocarbon group which can have as a substituent, the group similar to the thing in R <^1> is mentioned.

As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group etc. are mentioned, for example.

It is preferable that 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 in R ²³ and R ²⁴ include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, sec-butyl group and tert-butyl group.

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

Examples of the alkyl sulfonyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, and the like.

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

As for p and q, the integer of 0-2 is preferable, and 1 or 2 is preferable.

The triarylmethane dye is preferably a dye containing a compound having a structure in which three aromatic hydrocarbon groups are bonded to one carbon atom. As triarylmethane dyes, 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 the triaryl methane dye of Unexamined-Japanese-Patent No. 4,492,760 are mentioned.

Coumarin dyes are dyes comprising a compound having a coumarin skeleton in its molecule. Coumarin 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; The coumarin dye of Unexamined-Japanese-Patent No. 1,299,948 etc. are mentioned.

As the anthraquinone dye, C. I. Solvent Yellow 117 (hereinafter, the description of C.I. Solvent Yellow is omitted and only numbers are listed), 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;

Tetraa porphyrin dyes are compounds having a tetraaza porphyrin skeleton in the molecule. In addition, when the tetraaza porphyrin dye is an acid dye or a 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 an azo dye, for example, CI direct yellow (hereinafter, description of CI direct yellow is omitted and only numbers are 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 and the like;

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 and the like; 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, etc. are mentioned.

Examples of thiazole dyes include C. I. Direct Yellow 54 and C. I. Basic Yellow 1.

Examples of the oxazine dyes include C. I. Direct Blue 97, 99, 106, 107, 108, 109, 190, and 293.

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 etc. are mentioned. Copper phthalocyanine (C.I.74160) etc. are mentioned as a cyanine dye.

As quinone imine dye, C. I. basic blue 3, C. I. basic blue 9, etc. are mentioned.

Methine dyes include C.I Basic Red 13, 14; C.I Basic Orange 21; C.I Basic Violet 16, 39; C.I Basic Yellow 11, 13, 21, 23, 28, etc. are mentioned.

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, C. I. Disperse Yellow 42, and the like.

As the azine dye, C.I. Acid blue 59, 102, and the like.

Indigo dyes include C.I. And acid blue 74.

In the dye (Aa), a polymer having a structural unit derived from an anion of a compound containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus or an anion represented by the formula (A-II) Compounds formed from anions and cations having a dye skeleton (hereinafter may be referred to as compound (AA)) may be included.

As a pigment | dye skeleton which the cation which comprises a dye has, the pigment skeleton which has onium structure among azo skeleton, xanthene skeleton, azine skeleton, cyanine skeleton, acridine skeleton, anthraquinone skeleton, squarylium skeleton, etc .; Triaryl methane backbone; The pigment skeleton etc. which made one or more of the aromatic hydrocarbon rings of a triaryl methane frame | skeleton into an aromatic heterocycle are mentioned. Among them, preferably, at least one of the aromatic hydrocarbon rings of the xanthene skeleton incorporating the onium structure, the cyanine skeleton incorporating the onium structure, the squarylium skeleton incorporating the onium structure, the triaryl methane skeleton, and the triaryl methane skeleton are aromatic. It is a pigment skeleton made into a heterocycle, More preferably, it is a pigment skeleton which made one or more of the aromatic hydrocarbon rings of a triaryl methane skeleton an aromatic heterocycle. As the anion, at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an anion of a compound containing oxygen or a polymer anion having a structural unit derived from an anion represented by the formula (A-II) Can be mentioned.

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

[Formula 7]

[In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, and an oxygen atom between the methylene groups constituting the alkyl group. The group inserted, the aromatic hydrocarbon group which may have a substituent, the aralkyl group which may have a substituent, or a hydrogen atom are shown. R ⁴¹ and R ⁴² may be bonded to form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may be bonded 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, 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 a structural unit derived from at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and any m-valent anion containing oxygen or an anion represented by the formula (A-II) A polymer anion having

[Formula 8]

[In Formula (A-II), X represents an alkyl group having 1 or more and 8 or less carbon atoms which may be substituted with a hydrogen atom or 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.

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

m represents any natural number.

In addition, when one molecule contains a plurality of cations represented by the following formula, they may be the same structure or different structures.

 [Formula 9]

[Wherein, the rings 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. Moreover, it is preferable that an aromatic heterocycle is a 5-10 membered ring, and it is more preferable that it is a 5-9 membered ring. As a monocyclic aromatic heterocycle, For example, 5-membered ring containing nitrogen atoms, such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, a thiazole ring; 5-membered ring containing nitrogen atoms, such as a furan ring and a thiophene ring; 6-membered rings containing nitrogen atoms, such as a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, etc. are mentioned, As an aromatic heterocyclic ring of a condensed ring, an indole ring, a benzimidazole ring, a benzothiazole ring, a quinoline ring Condensed rings containing nitrogen atoms such as these; Condensed rings which do not contain nitrogen atoms, such as a benzofuran ring, etc. are mentioned.

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 a substituent. And an amino group.

Especially, the aromatic heterocycle of the ring T ¹ is preferably an aromatic heterocycle containing a nitrogen atom, and more preferably a 5-membered aromatic heterocycle containing a nitrogen atom.

In addition, the ring T ¹ is more preferably a ring represented by the formula (Ab2-x1).

[Formula 10]

[Ring T ² represents an aromatic heterocycle.

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

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

k1 represents 0 or 1.

* Represents a bonding position with a carbo cation.

The aromatic heterocycle of the ring T ^{2 includes} the same ring as the aromatic heterocycle exemplified in the ring T ¹ .

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

[Formula 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 is an oxygen atom, -NR ⁵⁷ - or represents 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 a bonding position with a carbo cation.

In addition, the ring T ¹ is also preferably a ring represented by the formula (Ab2-x2).

[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.

* Indicates the bonding position with the carbo cation]

In addition, the ring T ¹ is more preferably a ring represented by the formula (Ab2-y2).

[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 a bonding position with a carbo cation.

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 linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and eicosyl group; And branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group. The saturated hydrocarbon group is preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, 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. As said cyclic saturated hydrocarbon group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc. are mentioned. 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 amino groups which may be substituted include amino groups; Alkylamino groups, such as a dimethylamino group and a diethylamino group, are mentioned. Further, examples of the halogen atom include chlorine, fluorine, bromine and iodine. Moreover, when a halogen atom is a fluorine atom, it is preferable that the halogen atom is substituted like perfluoroalkyl unit, such as a trifluoro methyl unit, a pentafluoroethyl unit, and a heptafluoropropyl unit.

As a C1-C20 saturated hydrocarbon group which has a substituent, group represented by a following formula is mentioned, for example. In the following formulae, * represents a bonding position with a nitrogen atom.

[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 .

In addition to the alkyl group having 1 to 10 carbon atoms represented by R ^57, there may be mentioned groups having 1 to 10 carbon atoms of the saturated hydrocarbon groups of straight or branched chain saturated hydrocarbon group exemplified as the groups represented by R ^41.

The alkyl group represented by R ⁴¹ to R ⁵⁴ may have an oxygen atom inserted between carbon atoms. Preferable carbon number of an alkyl group is 2-10, More preferably, it is 2-8. 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 in which an oxygen atom is inserted between carbon atoms of such a saturated hydrocarbon group include, for example, an alkoxyalkyl group; Or polyalkoxyalkyl groups such as (alkoxyalkoxy) alkyl group, (alkoxyalkoxyalkoxy) alkyl group, (alkoxyalkoxyalkoxyalkoxyalkoxy) alkyl group, (alkoxyalkoxyalkoxyalkoxyalkoxy) alkyl group, (alkoxyalkoxyalkoxyalkoxyalkoxyalkoxyalkoxy) alkyl group, etc. The repeating number of the alkoxy units is, for example, 1 to 6, preferably 1 to 4, more preferably 1 to 2. More preferable examples include groups represented by the following formulas. In the following formulae, * represents a bonding position with a nitrogen atom.

[Formula 15]

In addition, R ⁴¹ to R ^46, R ^55, R aromatic hydrocarbon group which may have a substituent represented by ⁵⁶ and R ⁵⁸ to R ⁶⁰ is preferably a group having 6 to 20 carbon atoms, more preferably having 6 to 15, more Preferably it is 6-12 carbon atoms. As said aromatic hydrocarbon group, a phenyl group, a toryl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, etc. are mentioned, Preferably a phenyl group, a naphthyl group, a toryl group, xylyl Group, and particularly preferably, it is 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 fluorine atom, chlorine atom, iodine atom and bromine atom; Haloalkyl groups having 1 to 6 carbon atoms, such as a chloromethyl group and a trifluoromethyl group; Alkoxy groups having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; Hydroxyl group; Sulfamoyl group; Alkyl sulfonyl groups having 1 to 6 carbon atoms such as methyl sulfonyl group; C1-C6 alkoxy carbonyl groups, such as a methoxy carbonyl group and an ethoxy carbonyl group, etc. are mentioned. As a specific example of the aromatic hydrocarbon group which can be substituted, group represented by a following formula is mentioned, for example. In the following formulae, * represents a bonding position with a nitrogen atom.

[Formula 16]

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

A ring in which R ⁴¹ and R ⁴² are bonded to form together with the nitrogen atom to which they are bonded, a ring in which R ⁴³ and R ⁴⁴ are bonded together to form together with the nitrogen atom to which they are bonded, and R ⁴⁵ and R ⁴⁶ are bonded to which they are bonded As a ring formed with a nitrogen atom, nitrogen containing non-aromatic 4-7 membered rings, such as a pyrrolidine ring, a morpholine ring, a piperidine ring, a piperazine ring, are mentioned, Preferably a pyrrolidine ring and a piperidine ring As a hetero atom, the 4-7 membered ring which has only one nitrogen atom is mentioned.

Among these, as R ⁴¹ to R ⁴⁴ , R ⁵⁵ , R ⁵⁶ , R ^58, and R ⁵⁹ , a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent is preferable, and each independently has 1 to 8 saturated carbon atoms. It is more preferable that it is a hydrocarbon group or the aromatic hydrocarbon group represented by a following formula. R ⁵⁵ is even more preferably an aromatic hydrocarbon group represented by the following formula. In the following formulae, * represents a bonding position with a nitrogen atom.

[Formula 17]

R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom inserted between carbon atoms of an alkyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having a substituent, or R ⁴⁵ and It is preferable that R ⁴⁶ combines to form a ring together with the nitrogen atom to which they are bonded. A more preferable form is that 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 one another as a hetero atom. It is a form which forms the 4-7 membered ring which has only a nitrogen atom. In the following formulae, * represents a bonding position with a nitrogen atom.

[Formula 18]

Moreover, as group which the oxygen atom is inserted between the C1-C8 alkyl group represented by R <^47> -R <^54> , and the carbon atom of a C2-C8 alkyl group, it is C8 or less from the corresponding group of said R <^41> -R <^46> . The group which selected the thing of can be illustrated, More preferably, group represented by a following formula is mentioned. In the following formulae, * represents a bonding position with a carbon atom.

[Formula 19]

R ⁴⁷ to R ^{54 preferably} each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably each independently represent a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

As a cation part of general formula (Ab2), cation 1 thru | or cation 14 etc. which are represented by general formula (Ab2-1) as shown in following Table 1 are mentioned. In the table, * indicates the bonding position.

[Formula 20]

Table 1

In Table 1, Ph1 to Ph9 shall mean a group represented by the following formula. In the formula, * represents a bonding position.

Moreover, as a cation part of general formula (Ab2), cation 15-cation 18 etc. represented by general formula (Ab2-2) are mentioned, as shown in following Table 2. In the table, * indicates the bonding position.

[Formula 22]

Table 2

In Table 2, Ph1, Ph10, Ph11 shall mean a group represented by the following formula. In the formula, * represents a bonding position.

[Formula 23]

In particular, the cation moiety of the formula (Ab2) is preferably cation 1 to cation 6, cation 11 to cation 14, cation 1, cation 2 or cation 12 to cation 14 is particularly preferred, most preferably cation 12.

[Y] ^m- can also represent the polymer which has a structural unit derived from the anion represented by general formula (A-II) (Hereinafter, it may be called "anion (A-II).").

[Formula 24]

[In the 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 fluorine atoms. 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 perfluoro alkyl group in which all of the hydrogen atoms are substituted with fluorine atoms from the viewpoint of increasing the acidity of the imide acid, for example, -CF ₃ , -CF ₂ CF ₃ , -CF ₂ Halofluoro with 1 to 8 carbon atoms, such as CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ) ₂ , -C (CF ₃ ) ₃ Alkyl group is mentioned. Moreover, carbon number of X is two or more and 8 or less, More preferably, it is three or more, More preferably, it is four or more.

As a divalent group of Y, a linear or branched alkylene group, an arylene group, and an arylene alkylene group are preferable. Moreover, it is preferable that Y is C1-C20, More preferably, it is C1-C10. Specifically, the linear or branched alkylene group is preferably 1 to 10 carbon atoms, the arylene group is preferably 6 to 20 carbon atoms, and the arylene alkylene group is preferably 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.

A phenylene group, a naphthylene group, etc. are mentioned as an arylene group.

Moreover, as an arylene alkylene group, an arylene methylene group, an arylene ethylene group, an arylene propylene group, an arylene butylene group, an arylene pentylene group, an arylene hexylene group, etc. are mentioned. It is preferable to couple | bond with the sulfur atom on the aryl group side of an arylene alkylene group.

Moreover, the methylene group which comprises the said alkylene group and arylene alkylene group may be substituted by the oxygen atom or the nitrogen atom. Among these, as Y, an arylene group or an arylene alkylene group having 7 to 10 carbon atoms is preferable, and in particular, an arylene group, an aryl methylene group, an aryl ethylene group, an aryl propylene group, an arylene butylene group, an arylene pentylene group, and an arylene hex Silylene groups are more preferred, arylene groups are even more preferred, and phenylene groups are particularly preferred.

As an anionic compound, the anionic compound represented by following General formula (A-II-1)-a formula (A-II-6) is mentioned, for example.

[Formula 25]

These anions (A-II) may be used independently and may be used in combination of 2 or more type.

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

[Y] ^m- is preferably an anion of a heteropoly acid or isopoly acid containing tungsten, in particular an anion of phosphorus tungstic acid, silico tungstic acid and tungsten-based isopoly acid.

As an anion of a tungsten-containing heteropoly acid or isopoly acid, for example, Keggin type tungstate ion α- [PW ₁₂ O ₄₀ ] ^3- , Dawson type tungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin 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オ₅₆ ] ^12- , [H ₂ P ₂ Ｗ ₁₂オ₄₈ ] ^12- , [NFP ₅ Ｗ ₃₀ O ₁₁₀ ] ^14- , α- [Sii ₉ O ₃₄ ] ^10- , γ- [Sii ₁₀ O ₃₆ ] ^8- , α- [Sii ₁₁ O ₃₉ ] ^8- , β- [Sii ₁₁ O ₃₉ ] ^{_{8-, [W 6 O 19]}} 2-, [W 10 O 32] 4-, WO 4 2 - and mixtures thereof.

[Y] ^m- is also preferably an anion consisting 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 an anion consisting of oxygen include SiO ₃ ^{2 -} and PO ₄ ^3- .

Phosphoric tungstate anions such as Keggin phosphorus tungstate ions and Dawson phosphorus tungstate ions for ease of synthesis and post-treatment; 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. In particular, a phosphorus tungstate anion and a tungsten type isopoly acid anion are especially preferable.

As dye (Aa), the compound represented by a following formula is mentioned, for example.

Table 3

Table 4

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

The content rate of the dye (Aa) in a colored curable resin composition is 1 mass% or more and 70 mass% or less normally with respect to the total amount of solid content, Preferably it is 5 mass% or more and 60 mass% or less, More preferably, it is 10 mass% or more It is 60 mass% or less, Especially preferably, it is 15 mass% or more and 50 mass% or less. If the content rate of the dye (Aa) is within the above range, the desired spectroscopic or color concentration is more easily obtained. In addition, in this specification, "a total amount of solid content" means the total amount of the component except the solvent from the colored curable resin composition of this invention. The total amount of solids and the content of each component thereof can be measured, for example, by known analytical methods such as liquid chromatography and gas chromatography.

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

Dye other than compound (AI) (preferably xanthene dye) is 0.1 mass% or more and 30 mass% or less in 100 mass% of dye (Aa), More preferably, it is 0.5 mass% or more and 20 mass% or less, More preferably, they are 1.0 mass% or more and 10 mass% or less.

Compound (A-I) can be manufactured according to the method of Unexamined-Japanese-Patent No. 2015-28121.

Coloring dispersion

In the present invention, a compound composed of an anion of a compound containing oxygen and at least one element selected from tungsten, molybdenum, silicon and phosphorus and a cation having a dye skeleton (hereinafter referred to as compound (AA)) Is preferably mixed with a solvent to obtain a colored dispersion. After setting it as a colored dispersion liquid and mixing with a binder resin (B), a polymeric compound (C), a polymerization initiator (D), etc., and forming a colored curable resin composition, the heat resistance at the time of using a color filter can be improved further.

As the solvent, any solvent can be used as long as it can be used as the solvent (E) of the colored curable resin composition. Solvents which are particularly good for the purpose of dispersing compound (AA) are, for example, ether ester solvents, more preferably one hydroxyl group of an alkylene glycol or polyalkylene glycol is etherified, and the remaining hydroxyl group is esterified. Solvents such as 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, di Ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, etc. are mentioned. These may include single or plural species.

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 with respect to 1 part by mass of the compound (AA).

It is preferable to use a dispersing agent in manufacturing colored dispersion. As the dispersant, for example, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic can be used. These pigment dispersants can be used individually or in combination of 2 or more types. As the pigment dispersant, KP (produced by Shin-Etsu Chemical Co., Ltd.), Fren (Produced by Kyoeisha Chemical Co., Ltd.), Solsperse (Geneca Co., Ltd.), EFKA (produced by BASF) And Azispa (manufactured by Ajinomodo Fine Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie).

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, particularly preferably 10 to 30 parts by mass with respect to 100 parts by mass of the compound (AA).

In addition, when dye (Aa) other than a compound (AA) is contained in the colored curable resin composition mentioned later, a coloring dispersion liquid may partially or all, preferably all, dye (Aa) other than a compound (AA) as needed. It may include in advance. The amount of the dye (Aa) other than the compound (AA) in the colored dispersion is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 1 with respect to 100 parts by mass of the compound (AA). 5 parts by mass.

The said colored dispersion liquid can contain a part or all part, Preferably a part is previously used for the binder resin (B) used for a colored curable resin composition as needed. The binder resin (B) is included beforehand and dispersibility can be further improved when the colored curable resin composition is used. Solid content conversion amount of binder resin (B) in a coloring dispersion liquid is 1-300 mass parts normally with respect to 100 mass parts of compound (AA), Preferably it is 10-100 mass parts, More preferably, it is 20-70 mass parts.

In preparing a dispersion, it is preferable to finely disperse using a dispersing apparatus after appropriately adding necessary components. As the dispersing device, a bead mill device can be used. As the beads to be used, hard beads such as zirconia beads are generally used, and the particle diameter thereof is, for example, selected from 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 rate (when the composition contains a pigment) of the dye (Aa) in the colored curable resin composition is usually 1% by mass to 45% by mass, preferably 2% by mass to 40% by mass, More preferably, they are 3 mass% or more and 35 mass% or less, Especially preferably, they are 5 mass% or more and 30 mass% or less. When the content rate of the dye (Aa) is within the above range, the desired brightness becomes more easily obtained.

The colored curable resin composition of this invention can further contain a pigment (Ab).

Pigment (Ab)

It does not specifically limit as a pigment, A well-known pigment can be used. Examples include pigments classified as pigments in the color index (Published by The Society of Dyers and Colourists), and these may be used alone or in combination of two or more thereof.

Specifically, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129 Yellow pigments such as, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like;

CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Pigments;

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

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;

Can be mentioned. Especially, C. I. pigment blue 15: 6 is preferable.

Pigments may be rosin-treated, surface-treated with a pigment derivative having an acidic or basic group introduced therein, graft treatment on the surface of the pigment with a polymer compound, atomization by sulfuric acid atomization or the like, or an organic solvent or water for removing impurities. The washing treatment by, etc., the removal treatment by the ion exchange method of ionic impurities, etc. can be performed. It is preferable that the particle diameter of a pigment is substantially uniform. A pigment can be made into the pigment dispersion liquid of the state disperse | distributed uniformly in the pigment dispersant solution by containing and disperse | distributing a pigment dispersant. A pigment may be disperse | distributed individually, respectively, and may mix and disperse multiple types.

Surfactant etc. are mentioned as a pigment dispersant, It can be any of surfactant, cationic, anionic, nonionic, and amphoteric. Specifically, surfactant, such as polyester type, polyamine type, and acryl type, etc. are mentioned. These pigment dispersants may be used alone or in combination of two or more thereof. As a pigment dispersant, if it shows by brand name, KP (made by Shin-Etsu Chemical Co., Ltd.), Proren (made by Kyoeisha Chemical Co., Ltd.), Solsperth (registered trademark) (made by Geneka Co., Ltd.), EFKA (registered trademark) ) (Manufactured by BASF Corporation), Ajispa (registered trademark) (manufactured by Ajinomodo Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie), and the like.

When using a pigment dispersant, the usage-amount is 100 mass parts or less with respect to 100 mass parts of pigments, More preferably, they are 0 mass part or more and 80 mass parts or less. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency which can obtain the pigment dispersion liquid of a more uniform dispersion state.

When it contains a pigment (Ab), it is preferable that the content rate of the pigment (Ab) is 1 mass% or more and 90 mass% or less with respect to the total amount of dye and pigment, More preferably, it is 2 mass% or more and 85 mass% or less, More preferably, Preferably it is 5 mass% or more and 80 mass% or less.

Binder Resin (B)

The binder resin (B) is a structural unit derived from a monomer having at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and monomers having an ethylenically unsaturated bond and a cyclic ether structure. (b2), a copolymer having 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 dicarbonyl imide derivative.

The binder resin (B) of this invention may also contain another structural unit, as long as it contains the structural unit of said (b1)-(b4). With the binder resin of this invention, it becomes possible to make a pattern shape favorable and to reduce generation | occurrence | production of a foreign material.

As at least 1 type of monomer chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride which comprise a structural unit (b1), Unsaturation, such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinyl benzoic acid, is carried out. Monocarboxylic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid Unsaturated dicarboxylic acids such as dimethyl tetrahydro phthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5 -Carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2 .1] bicyclo unsaturated compounds containing carboxyl groups such as hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydro phthalic anhydride, 1,2,3,6-tetrahydro And unsaturated dicarboxylic anhydrides such as phthalic anhydride, dimethyltetra hydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride.

In addition, unsaturated mono [(meth) acryloyloxyalkyl of a bivalent or more polyvalent carboxylic acid, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ] Esters; Unsaturated acrylate etc. which contain a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid, can also be used.

Especially, it is preferable that the monomer which comprises a structural unit (b1) is unsaturated monocarboxylic acid, More preferably, it is acrylic acid and methacrylic acid.

In addition, in this specification, notation, such as "(meth) acrylic acid" and "(meth) acrylate", represents at least 1 sort (s) chosen from the group which consists of acrylic acid (acrylate) and methacrylic acid (methacrylate).

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

As the structural unit (b2), for example, a monomer (b2-1) (hereinafter sometimes referred to as "(b2-1)") having an oxiranyl group and an ethylenically unsaturated bond, an oxetanyl group and an ethylenically unsaturated Monomer (b2-2) having a bond (hereinafter sometimes referred to as "(b2-2)"), monomer (b2-3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter "(b2-3)" May be referred to).

The structural 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 monomers (b2-1-2) (hereinafter sometimes referred to as "(b2-1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

As (b2-1-1), glycidyl (meth) acrylate, (beta) -methyl glycidyl (meth) acrylate, (beta)-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o -Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl Ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (gly Cydyloxymethyl) 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-tris (glycidyloxymethyl) styrene Etc. can be mentioned.

As (b2-1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; Daicel Corporation make), 3,4 -Epoxycyclohexyl methyl (meth) acrylate (e.g., CYCLOMER A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (e.g., cycloma M100; Daicel Corporation), the compound represented by general formula (I), the compound represented by general formula (II), etc. are mentioned.

[Formula 26]

[In 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 included 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.

* Indicates a bonding position with O.]

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

As an alkyl group in which the hydrogen atom was substituted by hydroxy, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy A hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

R ^b1 and R ^b2 are preferably hydrogen atoms, methyl groups, hydroxymethyl groups, 1-hydroxyethyl groups and 2-hydroxyethyl groups, and more preferably hydrogen atoms and methyl groups.

Examples of the alkanediyl group include a methylene group, an ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1 And a 6-diyl group.

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-, and more preferably a single bond, *- CH ₂ CH ₂ -O- may be mentioned. * Indicates a bonding position with O.

As a compound represented by general formula (I), the compound etc. which are represented by either of general formula (I-1)-general formula (I-15) are mentioned. In particular, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) The compound represented by is preferable, and the compound represented by general formula (I-1), general formula (I-7), general formula (I-9) or general formula (I-15) is more preferable.

[Formula 27]

[Formula 28]

Examples of the compound represented by the formula (II) include a compound represented by any one of the formulas (II-1) to (II-15). In particular, the formulas (II-1), (II-3), (II-5), (II-7), (II-9) or (II-11) to (II-15) The compound represented by is preferable, and the compound represented by general formula (II-1), general formula (II-7), general formula (II-9) or general formula (II-15) is more preferable.

[Formula 29]

[Formula 30]

The compound represented by the formula (I) and the compound represented by the formula (II) may each be used alone or in combination of two or more thereof. When the compound represented by the formula (I) and the compound represented by the formula (II) are used together, the content ratio thereof [the compound represented by the formula (I): the compound represented by the formula (II)] is on a molar basis. Preferably it is 5: 95-95: 5, More preferably, it is 20: 80-80: 20.

As (b2-2), the monomer which has an oxetanyl group and a (meth) acryloyloxy group is preferable. Examples of (b2-2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyl oxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxy methyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-metha Cryloyl oxyethyl oxetane, 3-ethyl-3- acryloyloxy ethyl oxetane, etc. are mentioned.

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

As a structural unit (b2), it is preferable that it is (b2-1) from the point which can raise reliability, such as heat resistance and chemical-resistance of the cured film obtained. Moreover, from the point which is excellent in the storage stability of curable resin composition, (b2-1-2) is more preferable, the compound represented by general formula (I) and the compound represented by general formula (II) are more preferable, and general formula (I) Even more preferred are compounds represented by -1) and compounds represented by formula (II-1).

As a hydroxy group containing (meth) acrylic acid ester monomer which comprises a structural unit (b3), hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth And hydroxyl group-containing alkyl (meth) acrylic acid esters such as acrylate.

The hydroxy group-containing (meth) acrylic acid ester monomer is preferably a hydroxyalkyl (meth) acrylic acid 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. Even more preferred is a hydroxy group-containing (meth) acrylic acid ester having an alkyl group having 1 to 4 carbon atoms.

Among these, the monomer which comprises a structural unit (b3) is hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (Meth) acrylate is especially preferable, and most preferably 2-hydroxyethyl (meth) acrylate.

As a monomer of the dicarbonyl imide derivative which comprises a structural unit (b4), dicarbonyl imide which has aromatic carbon-hydrogen groups, such as N-phenyl maleimide and N-tolyl maleimide, N-cyclohexyl maleimide, N Aralkyl groups, such as dicarbonyl imide which has alicyclic hydrocarbon groups, such as -cycloheptyl maleimide, N-cyclooctyl maleimide, and N-cyclododecyl maleimide, N-benzyl maleimide, and N-phenethyl maleimide Having dicarbonyl imide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimi Dicarbonyl imide which has condensed heterocyclic groups, such as dicarbonyl imide which has succinimidyl groups, such as di--3- maleimide propionate, and N- (9-acridinyl) maleimide, etc. are mentioned. have.

It is preferable that the monomer of the said dicarbonyl imide derivative is N substituted maleimide which has a C4-C20 hydrocarbon group, More preferably, a C4-C20 alicyclic hydrocarbon group, an aromatic hydrocarbon group, an aralkyl group, and succinate N substituted maleimide which has an imidyl group, a condensed heterocycle, etc.

It is more preferable that it is C4-C16, More preferably, it is 4-12, Especially preferably, it is 4-8.

The hydrogen atom contained in a hydrocarbon group may be substituted by an amino group, a C1-C5 alkoxy group, a phenyl amino group, a halogen atom, a hydroxyl group, etc.

Among these, as the monomer of the dicarbonyl imide derivative, N-substituted maleimide having an alicyclic hydrocarbon group having 4 to 20 carbon atoms is even more preferable, and still more preferably N-cyclohexyl maleimide and N-cycloheptyl maleimide , N-cyclooctyl maleimide, N-cyclododecyl maleimide, and particularly preferably N-cyclohexyl maleimide.

The binder resin (B) of this invention may also contain another structural unit using the following monomers other than the said structural unit (b1)-(b4).

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybi Cyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2 -Ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept 2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyl oxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxy Cycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2- Bicyclo unsaturated compounds, such as ene;

Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxy styrene; 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;

It is preferable that the at least 1 sort (s) of monomer chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride is 1-40 mass% in 100 mass% of all monomers, More preferably, it is 2-35 mass%, More preferably, 5-30 mass%.

As for the monomer which has an ethylenically unsaturated bond and a cyclic ether structure, 1-40 mass% is preferable in 100 mass% of all monomers, More preferably, it is 2-30 mass%, More preferably, it is 5-30 mass%.

It is preferable that a hydroxy-group containing (meth) acrylic acid ester monomer is 1-35 mass% in 100 mass% of all monomers, More preferably, it is 2-30 mass%, More preferably, it is 3-25 mass%.

It is preferable that the monomer of a dicarbonyl imide derivative is 25-80 mass% in 100 mass% of all monomers, More preferably, it is 35-75 mass%, More preferably, it is 45 mass% or more, Further more preferable Preferably it is 50 mass% or more.

It is preferable that the total amount of the said hydroxyl group containing (meth) acrylic acid ester monomer and the monomer of the said dicarbonyl imide derivative is 25 mass% or more and 90 mass% or less in 100 mass% of all monomers, More preferably, it is 50 mass% or more , Still more preferably 55% by mass or more, still more preferably 60% by mass or more.

As the binder resin (B), 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexyl maleimide / 2-hydroxyethyl (meth) acrylic And late copolymers (copolymers (B0)).

Binder resin (B) can contain other binder resin as long as the effect of this invention is exhibited.

As other binder resin, what is necessary is just a resin different from a copolymer (B0), For example, the copolymer which has a structural unit (b1) and a structural unit (b2), a structural unit (b1), a structural unit (b2), and a structural unit (b3). Copolymer having a structural unit (b1) and a structural unit (b2) and a structural unit (b4), a copolymer having a structural unit (b1) and a structural unit (b2) and other structural units, a structural unit (b1) and the copolymer which has a structural unit which has an ethylenically unsaturated bond with a structural unit (b4), the copolymer which has a structural unit which has an ethylenically unsaturated bond with a structural unit (b1), etc. are mentioned. .

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 ethylenically unsaturated to a group capable of reacting with a group having a structural unit (b1) or a structural unit (b2) in a polymer having a structural unit derived from the structural unit (b1) or the structural unit (b2). It can obtain by adding the monomer which has a bond.

As such a structural unit, the structural unit which added glycidyl (meth) acrylate to the (meth) acrylic acid unit, the structural unit which added 2-hydroxyethyl (meth) acrylate to the maleic anhydride unit, glycidyl (meth) Structural units etc. which added (meth) acrylic acid to the acrylate unit are mentioned. Moreover, when these structural units have a hydroxyl group, the structural unit which further added the carboxylic anhydride can also be enumerated as a structural unit which has an ethylenically unsaturated bond.

As binder resin (B), 3, 4- epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic acid copolymer, 3, 4- epoxy citricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / Resins such as (meth) acrylic acid copolymers [K1]; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer Resin [K2]; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [K3] ]; Resin which glycidyl (meth) acrylate was added to the benzyl (meth) acrylate / (meth) acrylic acid copolymer, and glycidyl (meth) to the tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin, such as resin which added the acrylate, and resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; Of resin which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins [K5] such as resins in which (meth) acrylic acid is reacted with a copolymer; Resin [K6] etc., such as resin which made tetrahydrophthalic anhydride react with the resin which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, can also be used. have.

The weight average molecular weight in terms of polystyrene of the resin (B) is usually 3,000 to 100,000, preferably 4,000 to 50,000, more preferably 5,000 to 35,000, still more preferably 5,000 to 30,000, particularly preferably 5,500 To 30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film rate is high, the solubility in the developer of the unexposed portion is good, and the resolution of the colored 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 (solid content conversion) of resin (B) becomes like this. Preferably it is 1-170 mg-KOH / g, More preferably, it is 5-170 mg-KOH / g, Especially, 10-170 mg-KOH / g is preferable, The Especially, 15-170 mg-KOH / g is preferable, 150 mg-KOH / g or less is more preferable, 135 mg-KOH / g or less is further more preferable.

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

The content of the resin (B) is preferably 7 to 65% by mass, particularly preferably 10 to 60% by mass, and particularly preferably 13 to 60% by mass, with respect to the total amount of solids. Preferably it is 17-60 mass%. When content of resin (B) exists in the said range, formation of a coloring pattern is easy and there exists a tendency for the resolution and the residual film ratio of a coloring pattern to improve.

Polymerizable Compound (C)

A polymeric compound is a compound which can superpose | polymerize with the active radical and / or acid which generate | occur | produced from the polymerization initiator, For example, the polymeric compound which has an ethylenically unsaturated bond is mentioned, The compound which has a (meth) acrylic acid ester structure This is preferred. It is preferable that a polymeric compound is a polymeric compound which has three or more ethylenically unsaturated bonds, and it is more preferable that it is a polymeric compound which has 5-6 ethylenically unsaturated bonds.

As a polymeric compound which has one ethylenically unsaturated bond, nonylphenyl carbitol acrylate, 2-hydroxy-3- phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N -Vinylpyrrolidone, and (a), (b) and (c) mentioned above are mentioned. Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexane diol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth). ) Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate are mentioned. Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. , Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritolhepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylic Ethylurethane, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol Tetra (meth) acrylate, propylene glycol modified dipenta Lisitol hexa (meth) acrylate, a caprolactone modified pentaerythritol tetra (meth) acrylate, and a caprolactone modified dipentaerythritol hexa (meth) acrylate are mentioned.

Among these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

Content of the polymeric compound (C) of the colored curable resin composition of this invention is 1-60 mass% normally with respect to the total amount of solid content, Preferably it is 5-50 weight%, More preferably, it is 10-40 mass% And still more preferably 12 to 35 mass%. The content ratio (binder resin (B): polymerizable compound (C)) of the binder resin (B) and the polymerizable compound (C) is usually 20:80 to 80:20 by mass, preferably 35:65 80: 20. When content of a polymeric compound (C) exists in the said range, there exists a tendency for the chemical-resistance of the residual film ratio at the time of coloring pattern formation, and a color filter to improve.

Polymerization initiator (D)

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

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

As the O-acyl oxime compound, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 -One-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6 -(2-methyl benzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl -2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] And 3-cyclopentyl propane-1-one-2-imine. Commercial items, such as Irgacure (IRGACURE (trademark) OXE01, OXE02 (above, BASF Corporation), N-1919 (made by ADEKA Corporation)), can also be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2 At least one selected from the group consisting of -imines and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imines is preferred, and N-benzoyloxy-1 More preferred is-(4-phenylsulfanylphenyl) octan-1-one-2-imine.

The alkylphenone compound is 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane -1-one and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one. Commercial items, such as Irgacure 369, 907, 379 (above, BASF Corporation), can also be used.

The alkylphenone compound is 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane-1- Oligomers of on, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone and benzyldimethylke It may be a mask.

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

Acyl phosphine oxide compounds include 2,4,6-trimethylbenzoyl diphenylphosphine oxide. Commercial items, such as Irgacure 819 (made by BASF Corporation), can also be used.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, see Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra ( Alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chloro Phenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, eg, JP-A-48-38403, JP-A-62-174204, etc.) and 4 The imidazole compound (For example, refer Unexamined-Japanese-Patent No. 07-010913 etc.) in which the phenyl group of a 4'5,5 'position is substituted by the carboalkoxy group. Among them, compounds represented by the following formulae and mixtures thereof are preferable.

[Formula 31]

As another polymerization initiator, Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, methyl o-benzoyl benzoate, 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-ethylanthraquinone and camphorquinone; And 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound and the like. It is preferable to use these in combination with the polymerization start adjuvant (especially an amine polymerization start adjuvant) mentioned later.

Content of a polymerization initiator (D) is 0.1-40 mass parts normally with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), Preferably it is 0.1-30 mass parts, More preferably, 1 It is 30 mass parts, Especially preferably, it is 1-20 mass parts.

Polymerization Aids

A polymerization start adjuvant is a compound or a sensitizer used in order to accelerate superposition | polymerization of the polymeric compound (C) by which polymerization was initiated by the polymerization initiator (D). When the colored curable resin composition of this invention contains a polymerization start adjuvant, it is normally used in combination with a polymerization initiator (D).

Examples of the polymerization start aid include amine polymerization start aids, alkoxy anthracene polymerization start aids, thioxanthone polymerization start aids, and carboxylic acid polymerization start aids.

As an amine polymerization start adjuvant, Alkanolamine, such as a triethanolamine, a methyl diethanolamine, a triisopropanolamine; Amino benzoic acid esters such as methyl 4-dimethylamino benzoate, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoic acid isoamyl, benzoic acid 2-dimethylamino ethyl, and 4-dimethylamino benzoic acid 2-ethylhexyl; N, N-dimethylpara toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly referred to as Michler's ketone), 4,4'-bis (diethylamino) benzophenone and 4, 4'-bis (ethylmethylamino) benzophenone is mentioned, Especially, alkylamino benzophenone, such as 4,4'-bis (diethylamino) benzophenone, is preferable. Especially, alkylamino benzophenone is preferable and 4,4'-bis (diethylamino) benzophenone is preferable. Commercial items, such as EAB-F (made by Hodogaya Chemical Co., Ltd.), can also be used.

Alkoxy anthracene-based polymerization initiators include 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 9, 10-dibutoxy anthracene and 2-ethyl-9,10-dibutoxy anthracene.

Examples of the thioxanthone polymerization start adjuvant include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone and 1-chloro-4- Propoxy thioxanthone.

Carboxylic acid polymerization initiation aids include phenylsulfanyl acetic acid, methylphenyl sulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, mephenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chloro Phenylsulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthylthio acetic acid, N-naphthyl glycine and naphthoxy acetic acid.

When using a polymerization start adjuvant, its content becomes like this. Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C). . When content of a polymerization start adjuvant exists in this range, a coloring pattern can be formed with high sensitivity, and there exists a tendency for the productivity of a color filter to improve.

<Solvent (E)>

Solvent (E) is not limited, The solvent generally used in the said field can be used individually or in combination of 2 or more types. Specifically, an ester solvent (a solvent containing -COO- in a molecule and no -O-), an ether solvent (a solvent containing -O- in a molecule and no -COO-), an ether ester solvent (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O Solvents containing no-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxy isobutane, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl aceto acetate, ethyl aceto acetate, cyclohexanol acetate and γ-butyrolactone.

As an ether solvent, 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 Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol and methyl anisole Can be mentioned.

As an ether ester solvent, methoxy methyl acetate, methoxy ethyl acetate, methoxy acetate butyl, ethoxy methyl acetate, ethoxy acetate ethyl, 3-methoxy propionate methyl, 3-methoxy propionic acid ethyl, 3-ethoxy propionic acid Methyl, 3-ethoxy propionate, 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxy propionic acid propyl, 2-ethoxy propionate methyl, 2-ethoxy propionate ethyl, 2-methoxy-2 -Methyl methyl propionate, 2-ethoxy-2-methyl ethyl 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.

As the ketone solvent, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 -Pentanone, cyclopentanone, cyclohexanone and isophorone.

Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

Examples of the amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl pyrrolidone.

These solvents can also combine two or more types.

Among the solvents described above, organic solvents having a boiling point of 120 ° C or more and 210 ° C or less at 1 atm are preferable from the viewpoint of coating properties and drying properties. In particular, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy propionate ethyl, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Dipropylene glycol methyl ether acetate, 3-methoxy butyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4 methyl-2-pentanone, diacetone alcohol, N, N-dimethyl formamide and N -Methyl pyrrolidone is preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methylether acetate, ethyl lactate, diacetone alcohol, 3-methoxy butyl acetate, 3 -Methoxy-1-butanol, 3-ethoxy propionate, N, N-dimethyl formamide and N-meth This pyrrolidone is more preferred.

Content of a solvent (E) is 45-95 mass% normally with respect to the total amount of colored curable resin composition, Preferably it is 50-90 mass%, More preferably, it is 50-85 mass%. When the content of the solvent (E) is in the above range, the flatness at the time of coating becomes good, and since the color density is not insufficient when the color filter is formed, the display characteristics tend to be good.

<Leveling agent>

As a leveling agent, silicone type surfactant which has a silicone type surfactant, a fluorine type surfactant, and a fluorine atom is mentioned. These may have a polymeric group in a side chain.

As silicone type surfactant, surfactant which has a siloxane bond in a molecule | numerator is mentioned. Specifically, Toray Silicone DC3PA, Toray Silicon SH7PA, Toray Silicon DC11PA, Toray Silicon SH21PA, Toray Silicon SH28PA, Toray Silicon SH29PA, Toray Silicon SH30PA, Toray Silicon SH8400 (manufactured by Toray Dow Corning), 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 Co., Ltd.) ).

As a fluorine type surfactant, surfactant which has a fluorocarbon chain in a molecule | numerator is mentioned. Specifically, Fluorad (FLUORAD (registered trademark)) FC430, Fluoride FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega pack (Megafac, registered trademark) F142D, Mega pack F171, Mega pack F172, Mega pack F173, Mega pack F177, Megapack F183, Megapack F554, Megapack R30, Megapack RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, Ftop EF303, Ftop EF351, Ftop EF352 (Made by Mitsubishi Material Electronics Chemical Co., Ltd.), Suflon (Surflon (registered trademark)) S381, Suflon S382, Suflon SC101, Suflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 Keen Fine Chemical Research Institute) is mentioned.

Silicone surfactants having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, Mega Pack (R) R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, and Mega Pack F443 (manufactured by DIC Corporation) are mentioned.

The content of the leveling agent is usually 0.0005% by mass or more and 0.6% by mass or less, preferably 0.001% by mass or more and 0.5% by mass or less, and more preferably 0.001% by mass or more and 0.2% by mass or less based on the total amount of the colored curable resin composition. More preferably, they are 0.002 mass% or more and 0.1 mass% or less, Especially preferably, they are 0.005 mass% or more and 0.07 mass% or less. If 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% by mass or more and 2.0% by mass or less, preferably 0.002% by mass or more and 1.5% by mass or less, and more preferably 0.004% by mass or more and 1.0% by mass or less, based on the total amount of solids of the colored curable resin composition. More preferably, they are 0.008 mass% or more and 0.5 mass% or less, Especially preferably, they are 0.01 mass% or more and 0.3 mass% or less.

<Other Ingredients>

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

<Method for producing colored curable resin composition>

The colored curable resin composition of this invention is a dye (Aa), resin (B), a polymeric compound (C), a polymerization initiator (D), a solvent (E), and a leveling agent and a polymerization start adjuvant as needed, for example. And other components can be prepared. In addition to the dye (Aa), coloring agents, such as a pigment, can also be mixed further. It is preferable to use the pigment in the state of the pigment dispersion liquid disperse | distributed using the bead mill etc. until it mixes previously with some or all of the solvent (E), and until the average particle diameter of a pigment becomes about 0.2 micrometer or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed.

After mixing, it is preferable to filter the colored curable resin composition with a filter having a pore diameter of about 0.01 to 10 μm.

<Method of manufacturing color filter>

As a method of manufacturing a coloring pattern from the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. In particular, the photolithography method is preferable. The photolithography method is a method of applying a colored curable resin composition to a substrate, drying to form a colored composition layer, and exposing and developing the colored composition layer through a photomask. In the photolithography method, the colored coating film which is the hardened | cured material of the said coloring composition layer can be formed by not using a photomask and / or developing at the time of exposure. The coloring pattern and coloring film which were formed in this way are the color filter of this invention.

The film thickness of the produced color filter can be suitably adjusted according to the objective, a use, etc., and is 0.1-30 micrometers normally, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers.

As a board | substrate, what formed aluminum, silver, a silver / copper / palladium alloy thin film, etc. on glass, a resin board, silicon, and the said board | substrate is used. Separate color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

Formation of each color pixel by the photolithography method can be performed under known or conventional equipment and conditions. For example, it can manufacture as follows.

First, a coloring curable resin composition is apply | coated on a board | substrate, and it heat-drys (prebakes) and / or dries under reduced pressure, removes and dries volatile components, such as a solvent, and obtains a smooth coloring composition layer. Coating methods include spin coating, slit coating and slit and spin coating.

Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. It is preferable to use exposure apparatuses, such as a mask aligner and a stepper, since it can irradiate a parallel light beam uniformly to the whole exposure surface, and can precisely align the board | substrate with a photomask and a coloring composition layer. After exposure, a coloring pattern layer is formed by contacting and developing a coloring composition layer on a board | substrate. By development, the unexposed part of a coloring composition layer melt | dissolves in a developing solution and is removed. As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethyl ammonium hydroxide, is preferable. The developing method may be any one of a paddle method, a dipping method, and a spray method. In addition, during development, the substrate can be tempered off at any angle. It is preferable to wash with water after image development.

It is preferable to post-bake to the obtained coloring pattern further. In order to provide various characteristics, the color filter which has the coloring pattern and colored coating film obtained in this way may be further provided to the surface coating process.

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

EXAMPLE

Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited by these Examples. In the examples,% and parts representing the content to the amount of use are based on mass unless otherwise specified.

Synthesis Example 1

The following reaction was carried out under a nitrogen atmosphere. 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide were added to a flask equipped with a cooling tube and a stirring device, and the mixed solution was ice-cooled. Under ice-cooling, 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes, and then stirred for 1 hour while the temperature was raised to room temperature. 10.4 parts of 4,4'-difluoro benzophenone (made by Tokyo Chemical Industry Co., Ltd.) was added little by little to the reaction liquid, and it stirred at room temperature for 24 hours. After adding the reaction liquid to 200 parts of ice water little by little, it left still at room temperature for 15 hours, and when water was removed by decantation, the viscous solid was obtained as a residue. 60 parts of methanol was added to the viscous solid, followed by stirring at room temperature for 15 hours. The precipitated solid was filtered off and purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ° C. to obtain 9.8 parts of the compound represented by the formula (C-I-18).

[Formula 32]

The following reaction was performed in nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 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 added thereto, followed by addition of 12.2 parts of phosphorus oxychloride. And stirred at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300 parts of saturated saline solution, and then 100 parts of toluene was added and stirred for 30 minutes. Then, stirring was stopped and left still for 30 minutes, and the organic layer and the water layer were separated. After discarding the water layer by separation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was solvent evaporated with an evaporator to obtain a blue violet solid. Furthermore, a blue-purple solid was dried at 60 degreeC under reduced pressure, and 18.4 parts of compounds of formula (A-II-18) were obtained.

[Formula 33]

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

Into a beaker was added 53 parts of water, 11.8 parts of kegin-type phosphorus tungstic acid (manufactured by Aldrich) and 53 parts of methanol were added to the water, and mixed under an air atmosphere at room temperature to prepare a solution of phosphorus tungstic acid.

The obtained phosphorus tungstic acid solution was dripped over 1 hour in the reaction solution prepared previously. Furthermore, after stirring at room temperature for 30 minutes, it filtered and obtained the blue solid. The obtained blue solid was thrown in 200 parts of methanol, and it disperse | distributed for 1 hour, and the operation to filter was repeated twice. The blue solid obtained by the said operation was thrown in 200 parts of water, and it disperse | distributed for 1 hour, and the operation to filter was repeated twice. The blue solid obtained by the said operation was dried at 60 degreeC under reduced pressure, and 17.1 parts of compounds represented by general formula (A-I-18) were obtained.

[Formula 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 replaced with a nitrogen atmosphere. Then, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85 ° C while stirring. Subsequently, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) are molar ratios of 50: Mixed solution of 25 parts, cyclohexyl maleimide, 137 parts, 2-hydroxy ethyl methacrylate 50 parts, and 338 parts of propylene glycol monomethyl ether acetate were added dropwise over 5 hours. On the other hand, 5 parts of 2, 2- azobis isobutyronitrile and the mixed solution which melt | dissolved in 88 parts of propylene glycol monomethyl ether acetate were dripped over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, cooled to room temperature, and a copolymer (resin (B-1)) having a form B viscosity (23 ° C) of 22 mPas, a solid content of 25.5%, and a solution acid value of 28 mg-KOH / g. Got it. The weight average molecular weight Mw of the produced copolymer was 7700, and molecular weight distribution 2.1.

[Formula 35]

Synthesis Example 3

An appropriate amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace with a nitrogen atmosphere, and 153 parts of ethyl lactate and 145 parts of propylene glycol monomethyl ether acetate were added and heated to 90 ° C while stirring. Then, 17 parts of acrylic acid, 3,4-epoxy tricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) in a molar ratio of 50:50 Mixed solution of 23 parts, 144 parts of cyclohexyl maleimide, 46 parts of 2-hydroxyethyl methacrylate, and 381 parts of propylene glycol monomethyl ether acetate were added dropwise over 5 hours. On the other hand, the mixed solution which melt | dissolved 3 parts of 2, 2- azobis isobutyronitrile in 88 parts of propylene glycol monomethyl ether acetates was dripped 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)) of 15 mPas of B-type viscosity (23 ° C), 24.6% of solid content, and 24 mg-KOH / g of solution acid value. . The weight average molecular weight Mw of the produced copolymer was 5500, and molecular weight distribution 1.8.

Synthesis Example 4

An appropriate amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and replaced with a nitrogen atmosphere. 69 parts of ethyl lactate and 127 parts of propylene glycol monomethyl ether acetate were added and heated to 85 ° C while stirring. Subsequently, 35 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) are molar ratios of 50:50. Mixed solution of 69 parts, 115 parts of cyclohexyl maleimide, 12 parts of 2-hydroxy ethyl methacrylate, and 482 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, 3 parts of 2, 2- azobis isobutyronitrile and the mixed solution which melt | dissolved in 88 parts of propylene glycol monomethyl ether acetate were dripped 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 of B-type viscosity (23 ° C) of 19 mPas, solid content of 24.5%, and solution acid value of 26 mg-KOH / g (resin (B-3)). Got it. The weight average molecular weight Mw of the produced copolymer was 7900, and molecular weight distribution 2.1.

Synthesis Example 5

An appropriate amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer and replaced with a nitrogen atmosphere. 114 parts of ethyl lactate and 247 parts of propylene glycol monomethyl ether acetate were added and heated to 85 ° C while stirring. Then 48 parts of acrylic acid, 3,4-epoxy tricyclo [5.2. 1.0 ^2.6 ] decyl acrylate (mixing the compound represented by the formula (I-1) and the compound represented by the formula (II-1) in a molar ratio of 50: 50) 24 parts, cyclohexyl maleimide 120 parts, 2- A mixed solution of 48 parts of hydroxy ethyl methacrylate and 318 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, the mixed solution dissolved in 3 parts of 2, 2- azobis (2, 4- dimethyl valeronitrile) in 78 parts of propylene glycol monomethyl ether acetate was dripped 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-4)) of 29 mPas of B-type viscosity (23 ° C), 25.6% of solid content, and 38 mg-KOH / g of solution acid value. . The weight average molecular weight Mw of the produced copolymer was 9400, and molecular weight distribution 2.4.

Synthesis Example 6

An appropriate amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace with a nitrogen atmosphere, and 38 parts of ethyl lactate and 184 parts of propylene glycol monomethyl ether acetate were added and heated to 85 ° C while stirring. Then 61 parts of acrylic acid, 3,4-epoxy tricyclo [5.2.1. 1.0 ^2.6 ] decyl acrylate (mixing the compound represented by the formula (I-1) and the compound represented by the formula (II-1) in a molar ratio of 50: 50) 23 parts, cyclohexyl maleimide 123 parts, 2- A mixed solution of 23 parts of hydroxyethyl methacrylate and 343 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, the mixed solution which melt | dissolved 7 parts of 2, 2- azobis isobutyronitrile in 198 parts of propylene glycol monomethyl ether acetate was dripped 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-5)) having a form B viscosity (23 ° C) of 27 mPas, a solid content of 25.0%, and a solution acid value of 47 mg-KOH / g. The weight average molecular weight Mw of the produced copolymer was 9400, and molecular weight distribution 2.4.

Synthesis Example 7

Nitrogen was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooler and a dropping funnel at 0.02 L / min to form a nitrogen atmosphere, and 268 parts of ethyl lactate was added thereto and heated to 70 ° C while stirring. 55 parts acrylic acid, 81 parts N-cyclohexyl maleimide, 3,4-epoxy tricyclo [5.2.1. 1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) in a molar ratio of 50:50) 224 parts, and tricyclo [5.2.1.1.0 ^{2. 6} ] decene-8-yl acrylate (mixing the compound represented by the formula (c-1) and the compound represented by the formula (c-2) in a molar ratio of 50:50) 7 parts to 140 parts of ethyl lactate It melt | dissolved, the solution was prepared, and the said solution was dripped in the flask heated to 70 degreeC over 4 hours using the dropping funnel. On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 parts of ethyl lactates was dripped in the flask over 4 hours using the other dropping funnel. After completion of the dropwise addition of the polymerization initiator solution, the mixture was maintained at 70 ° C. for 4 hours, cooled to room temperature, and the weight average molecular weight Mw was 11.2 × 10 ³ , a solid content of 36.7%, a solution acid value of 44 mg-KOH / g, a copolymer (resin (B -6)) a solution was obtained. When the solid acid value of the solid content and the solution acid value was calculated, it was 119 mg-KOH / g.

[Formula 36]

Synthesis Example 8

20 parts of the compound represented by the formula (1x) and 200 parts of N-propyl-2,6-dimethyl aniline (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. It was. After cooling the obtained reaction liquid to room temperature, it added in the liquid mixture of 800 parts of water and 50 parts of 35% hydrochloric acid, stirred at room temperature for 1 hour, and precipitated the crystal | crystallization. The precipitated crystals were obtained as a residue of suction filtration and dried to obtain a compound represented by the formula (1-32).

[Formula 37]

Synthesis Example 9

An appropriate amount of nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, replaced with a nitrogen atmosphere, 190 parts of ethyl lactate was added thereto, and the mixture was heated to 65 ° C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) in a molar ratio of 50:50 Mixed solution of 25 parts, cyclohexyl maleimide, 175 parts, 2-hydroxy ethyl methacrylate, 12 parts of 2-hydroxyethyl methacrylate, 295 parts of ethyl lactate, and 180 parts of propylene glycol monomethyl ether acetate were added dropwise over 3 hours. On the other hand, 5 parts of polymerization initiator 2, 2- azobis (2, 4- dimethylvaleronitrile) were dripped at the mixed solution which melt | dissolved in 80 parts of propylene glycol monomethyl ether acetates over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain 26 mPas of B-type viscosity (23 ° C), 25.4 mass% of solid content, and a solution of the acid value of 28 mg-KOH / g (resin (B-7)). Got. The weight average molecular weight Mw of the produced copolymer was 7600, and molecular weight distribution 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 to replace with a nitrogen atmosphere, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85 ° C while stirring. Then 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1. 0 ^2.6 ] decyl acrylate (compound 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) 25 parts, cyclohexyl maleimide 137 parts, 2- A mixed solution of 50 parts of hydroxy ethyl methacrylate and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, 5 parts of polymerization initiator 2, 2- azobis isobutyronitrile were dripped at the mixed solution which melt | dissolved in 88 parts of propylene glycol monomethyl ether acetate over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature, and a copolymer (resin (B-8)) solution having a B viscosity (23 ° C) of 23 mPas, a solid content of 25.6 mass%, and a solution acid value of 28 mg-KOH / g Got. The weight average molecular weight Mw of the produced copolymer was 8000, and molecular weight distribution 2.1.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the said binder resin was performed on condition of the following using GPC method.

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

Detectors; 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 and number average molecular weight of polystyrene conversion obtained above was made into molecular weight distribution (Mw / Mn).

Synthesis Example 11

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

[Formula XX]

Identification of Compounds Represented by Formula (d-1)

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

Exact Mass: 347.1

Next, 6.0 parts of compounds represented by the formula (d-1), 0.95 parts of squariaic acid, 63 parts of 1-butanol and 7.0 parts of pyridine were mixed and stirred by heating at 115 ° C. for 16 hours. The precipitate produced after cooling was collected by filtration and dried at 60 ° C. for 24 hours to obtain 2.3 parts of a compound represented by Chemical Formula (SQ-1).

[Formula SQ-1]

Identification of Compounds Represented by Formula (SQ-1)

(Mass spectrometry) 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 trifluoro methanesulfonic acid methyl were added in 14 parts of methylene chloride and stirred at 20 to 30 ° C. for 3 hours. Thereafter, 50 parts of 5% aqueous sodium hydrogen carbonate solution was added, the mixture was separated with chloroform, and chloroform was distilled from the organic layer, and the remaining residue was dried at 60 ° C. for 24 hours to obtain 2.5 parts of a compound represented by the formula (SQ-1K).

Formula SQ-1K]

Identification of Compounds Represented by Formula (SQ-1K)

(Mass spectrometry) ionization mode = ESI +: m / z = 627.3 [M-CF ₃ SO ₃ ] ⁺

Exact Mass: 776.3

Synthesis Example 13

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

Formula SQ-1P]

Synthesis Example 14

400 parts of methanol was added to 5.0 parts of the compound represented by the formula (1-1), and stirred at 20 ° C to 30 ° C for 1 hour to obtain a solution. 400 parts of ion-exchange water was added to this solution, and it stirred for 2 hours, and obtained the solution (1-1A). Meanwhile, 28.8 parts of ion-exchanged water was added to 9.6 parts of phospho 12 tungstic acid tritium, stirred at 20 ° C. to 30 ° C. for 1 hour, and then 28.8 parts of methanol was added, and stirred for 2 hours to give a solution (1-1B). Got. To the solution (1-1A) was added solution (1-1B) and barium chloride 1.0 part, and stirred at 20 ° C to 30 ° C for 24 hours. The resulting precipitate was collected by filtration by filtration, washed twice with 200 parts of ion-exchanged water, and then twice with 200 parts of methanol. The crystals collected by filtration were dried at 60 ° C. for 24 hours to obtain 6.3 parts of the compound represented by the formula (1-1P).

[Formula 1-1]

[Formula 1-1P]

Synthesis Example 15

10 parts of a compound represented by the formula (AXa-1), 300 parts of chloroform and 5.7 parts of N, N-dimethyl formamide were charged into a flask equipped with a cooling tube and a stirring device, and thionyl chloride was maintained at 20 ° C. or lower under stirring. 12.6 parts were added dropwise, and maintained for 5 hours to react. Thereafter, a mixture of 6.7 parts of 2-ethylhexyl amine and 11.5 parts of triethylamine was added dropwise while maintaining the temperature at 20 ° C. or lower while stirring. Thereafter, the reaction was stirred at the same temperature for 5 hours. Subsequently, the solvent was distilled off from the reaction mixture by a rotary evaporator, and then a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to the liquid mixture of 375 parts of ion-exchange water, stirring, and the crystal | crystallization was deposited. 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 the compound represented by the chemical formula (AXa-1a).

[Formula AXa-1a]

Identification of Compounds Represented by Formula (AXa-1a)

(Mass spectrometry) ionization mode = ESI +:

m / z = 701.9 [M-Cl] ⁺

Exact Mass: 736.4

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

Meanwhile, 28.8 parts of ion-exchanged water was added to 9.6 parts of phospho 12 tungstic acid tritium, stirred at 20 ° C. to 30 ° C. for 1 hour, and then 28.8 parts of methanol was added, and stirred for 2 hours to give a solution (AXa-1aKB). Got. To the solution (AXa-1aA) was added the solution (AXa-1aKB) 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 with 200 parts of methanol. The crystals collected by filtration were dried at 60 ° C. for 24 hours to obtain 10.2 parts of the compound represented by the formula (AXa-1A).

[Formula AXa-1A]

Examples 1 to 12 and Comparative Examples 1 to 2

Each component was mixed so that it might become a composition shown in Table 5-7, and the colored curable resin composition was obtained.

Table 5

Table 6

Table 7

¹⁾ A1-1 is used by mixing and dispersing propylene glycol monomethyl ether acetate in the amount described in the dispersing agents B-1 ⁶⁾ and E-1 ⁸⁾ .

²⁾ A1-2 is mixed with an acrylic pigment dispersant, B-6 ⁷⁾ and E-1 ⁸⁾ in the amount of propylene glycol monomethyl ether acetate, and dispersed beforehand.

³⁾ The sum total of resin B-1 content is shown.

⁴⁾ The sum total of resin B-6 content is shown.

⁵⁾ The sum total of propylene glycol monomethyl ether acetate content is shown.

In addition, in Table 5-7, each component shows the following. In addition, binder resin (B) shows the mass part of solid content conversion.

Colorant (A); 1-1; Compound represented by formula (1-32)

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

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

Colorant (A); Pigment Dispersion A: Pigment Dispersion A Obtained Below

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

Binder resin (B); B-1; Resin (B-1) (solid content conversion)

Binder resin (B); B-2; Resin (B-2) (solid content conversion)

Binder resin (B); B-3; Resin (B-3) (solid content conversion)

Binder resin (B); B-4; Resin (B-4) (solid content conversion)

Binder resin (B); B-5; Resin (B-5) (solid content conversion)

Binder resin (B); B-6; Resin (B-6) (solid content conversion)

Binder resin (B); B-7; Resin (B-7) (solid content conversion)

Binder resin (B); B-8; Resin (B-8) (solid content conversion)

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

Polymerization initiator (D); D-1; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure OXE 01; manufactured by BASF; oxime compound)

Polymerization initiator (D); D-2; 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (irgacure 907; manufactured by BASF; alkylphenone compound)

Polymerization initiator (D); D-3; 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (irgacure 369; manufactured by BASF; alkylphenone compound)

Polymerization initiation aids; D1-1; 2,4-diethyl thioxanthone (KAYACURE DETX; Nippon Kayaku 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 (Torre Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Preparation of Pigment Dispersion A]

C. I. Pigment Blue 15: 6 10.0 parts

7.5 parts of acrylic pigment dispersant

Propylene Glycol Monomethyl Ether Acetate 77.5 Parts

Ethyl lactate5.0parts

Were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion A.

Examples 13-15

Each component was mixed so that it might become the composition shown in Table 8, and the coloring photosensitive resin composition was obtained.

Table 8

²⁾ The sum total of propylene glycol monomethyl ether acetate content is shown.

⁴⁾ A1-3 was previously dispersed by mixing an acrylic dispersant, a dispersing resin, and propylene glycol monomethyl ether acetate in the amount described in the E-1 ³⁾ column.

⁵⁾ A1-4 was previously dispersed by mixing an acrylic dispersant, a dispersing resin, and propylene glycol monomethyl ether acetate in the amount described in the E-1 ³⁾ column.

⁶⁾ The sum total of resin B1 content is shown.

In addition, in Table 8, each component represents the following. In addition, binder resin (B) shows the mass part of solid content conversion.

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

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

Colorant (A); 4- (1); 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

Binder resin (B); (B-1); Resin (B-1) solution

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

Polymerization initiator (D); (D-1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure OXE 01; manufactured by BASF; oxime compound)

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 (Toresilicon SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Production of colored pattern>

After coating each of the colored curable resin compositions of Examples 1 to 12 and Comparative Examples 1 and 2 on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Corporation) by spin coating, prebaking was performed at 100 ° C. for 3 minutes for coloring. The composition layer was formed. After cooling, the distance between the substrate on which this coloring composition layer was formed and the quartz glass photomask was set to 80 µm, and an exposure amount of 35 mJ / cm ² in an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) (365 nm standard) ) Was irradiated with light. As the photomask, a 50 μm line and space pattern was formed. After light irradiation, the coloring composition layer was immersed in a developing solution (aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butyl naphthalene sulfonate each by mass fraction) at 25 ° C. for 60 seconds, and washed with water at 230 ° C. in an oven. Post-baking was performed for 30 minutes, and the coloring pattern was obtained.

<Measurement of film thickness>

About the obtained coloring pattern, thickness was measured using the film thickness measuring apparatus (DEKTAK3; the Japan vacuum technology company make). The results are shown in Tables 9 and 10.

<Color evaluation>

About the obtained coloring pattern, spectroscopic measurement was carried out using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y) and brightness in the CIE XYZ colorimeter using the characteristic function of the C light source. Y was measured. The results are shown in Tables 8 and 9.

<Evaluation of Colored Pattern Shapes>

The shape was observed for the obtained coloring pattern using the scanning electron microscope (S-4000; the Hitachi Hi-Tech Co., Ltd. product). If it was a shape shown by (p1) of FIG. 1 (so-called forward taper shape), it was set as (circle), and if it was a shape shown by (p2), it was set as (triangle | delta), and if it was a shape shown by (p3), it was set as x. If it is a shape shown by (p1), it exists in the tendency which a crack or peeling hardly arises when laminating an inorganic film on a coloring pattern. The results are shown in Tables 8 and 9.

[Production of pattern and observation of peeling fragment]

The colored curable resin composition was applied by spin coating onto a 2-inch square glass substrate (Eagle 2000; manufactured by Corning), and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, the exposure amount of 150 mJ / cm ² under an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) as an interval of 100 µm between the substrate on which this coloring composition layer was formed and the quartz glass photomask having a pattern ( Light emission at 365 nm). After light irradiation, the coloring composition layer was immersed in 23 degreeC for 80 second in aqueous developing solution containing 0.12% of nonionic surfactant and 2% of sodium carbonate, and it developed and washed with water. After washing with water, the substrate was observed using a microscope (magnification of 500 times; VF-7510; manufactured by Keyence Co., Ltd.), and foreign matters derived from the peeling pieces were observed in portions corresponding to the non-exposed portions of the colored composition layer formed on the substrate. It was. When foreign matter was not recognized, (circle), and when it recognized, it is shown by Table 9 and 10.

Then, it post-baked for 30 minutes at 230 degreeC in oven, and obtained the coloring pattern.

Solubility Assessment

A 2 inch square glass substrate (Eagle 2000; manufactured by Corning) was washed sequentially with a neutral detergent, water and ethanol and dried. The colored curable resin composition was spin-coated on this glass substrate, and then prebaked for 3 minutes at 100 degreeC in the clean oven, and the coloring composition layer was formed.

Subsequently, the substrate on which the coloring composition layer was formed was immersed and developed in a developing solution having a liquid temperature of 25 ° C. (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butyl naphthalene sulfonate in mass fractions respectively) and 10 mm from the center of the substrate. The time which complete | finishes this melt | dissolution was made into melt | dissolution time, and the result was shown to Table 9, 10, and 11. The shorter the dissolution time, the better the solubility.

[Production of colored pattern]

After apply | coating the colored curable resin composition of Examples 10-12 and the comparative example 2 on the 2-inch square glass substrate (Eagle XG; Corning Corporation make), respectively, by a spin coat method, it prebaked for 3 minutes at 100 degreeC, and colored composition. A layer was formed. After cooling, the distance between the substrate on which the coloring composition was formed and the quartz glass photomask was 100 μm, and the exposure amount (365 nm standard) was 150 mJ / cm ² under an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Light irradiation. In addition, the mask which used the 100-micrometer line and space pattern was used for the photomask. After irradiation with light, the coating film was immersed in an aqueous developer containing 0.12% of nonionic surfactant and 2% of sodium carbonate at 24 ° C. for 60 seconds. After washing with water, post-baking was carried out in an oven at 230 ° C. for 30 minutes to produce a colored pattern. Got it.

Table 9

Table 10

Table 11

According to the colored curable resin composition of this invention, when a part of post-exposure coloring composition layer peels at the time of image development, a foreign material is not formed and a color filter with a favorable pattern shape can be provided.

Claims (8)

It contains dye (Aa), binder resin (B), a polymeric compound (C), and a polymerization initiator (D),
Binder resin (B)
Structural unit (b1) derived from at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides,
A structural unit (b2) derived from a monomer having an ethylenically unsaturated bond and a cyclic ether structure,
It is a copolymer which has a structural unit (b3) derived from a hydroxy group containing (meth) acrylic acid ester monomer, and a structural unit (b4) derived from the monomer of a dicarbonyl imide derivative,
The monomer which has the said ethylenically unsaturated bond and cyclic ether structure contains the compound represented by following formula (I) and formula (II), The coloring curable resin composition characterized by the above-mentioned.
[Formula 26]

[In 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 included 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.
* Indicates a bonding position with O.] The colored curable resin composition of Claim 1 whose total amount of the hydroxyl group containing (meth) acrylic acid ester monomer and the monomer of a dicarbonyl imide derivative is 25 mass% or more and 90 mass% or less in 100 mass% of all monomers. The method of claim 1,
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,
The colored curable resin composition whose monomer of a dicarbonyl imide derivative is N substituted maleimide which has a C4-C20 hydrocarbon group. The colored curable resin composition according to claim 1, further comprising a pigment (Ab). 2. The dye (Aa) according to claim 1, wherein the dye (Aa) is derived from an anion of a compound containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus or an anion represented by the formula (A-II) Colored curable resin composition which is a compound which consists of a polymer anion which has a structural unit to make, and a cation which has a pigment skeleton.
[Formula 1]

[In Formula (A-II), X represents an alkyl group having 1 or more and 8 or less carbon atoms which may be substituted with a hydrogen atom or 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.
R ⁶¹ represents a hydrogen atom or a methyl group.] The colored curable resin composition according to claim 1, wherein the dye (Aa) is a compound represented by the formula (AI).
[Formula 2]

[In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, and an oxygen atom between the methylene groups constituting the alkyl group. The group inserted, the aromatic hydrocarbon group which may have a substituent, the aralkyl group which may have a substituent, or a hydrogen atom are shown. R ⁴¹ and R ⁴² may be bonded to form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may be bonded 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 a structural unit derived from at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and any m-valent anion containing oxygen or an anion represented by the formula (A-II) A polymer anion having
m represents any natural number.
In addition, when one molecule contains a plurality of cations represented by the following formulas, they may have the same structure or different structures.
[Formula 3]

[In the above formula, the rings T ¹ , R ⁴¹ to R ⁴⁴ and R ⁴⁷ to R ⁵⁴ are as defined above, respectively.]
[Formula 4]

[In the formula (A-II), X represents an alkyl group having 1 or more and 8 or less carbon atoms which may be substituted with a hydrogen atom or 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.
R ⁶¹ represents a hydrogen atom or a methyl group.]] The color filter formed from the colored curable resin composition in any one of Claims 1-6. A liquid crystal display device comprising the color filter according to claim 7.

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