KR102555424B1 - Colored curable resin composition - Google Patents

Abstract

(Problem) A problem is to obtain a color filter having an excellent pattern shape.
(Solution) The colored curable resin composition of the present invention contains a colorant, a resin, a polymerizable compound and a polymerization initiator, contains a dye and a pigment as the colorant, and the polymerization initiator is a compound represented by the following formula (d1) includes
[Formula 1]

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

Colored curable resin composition is used for manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays. As such a colored curable resin composition, a colored curable resin composition containing N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine as an initiator is known (Patent Document 1).

Further, as a highly sensitive photoinitiator in a photopolymerizable composition, an oxime ester derivative of a benzocarbazole compound has been proposed (Patent Document 2).

Japanese Unexamined Patent Publication No. 2010-32999 Japanese Patent Publication No. 2014-500852

In this invention, it makes it a subject to obtain the color filter excellent in pattern shape.

The present invention includes the following inventions.

[1] containing a colorant, a resin, a polymerizable compound and a polymerization initiator;

As the colorant, dyes and pigments are included,

The colored curable resin composition in which the said polymerization initiator contains the compound represented by following formula (d1).

[Formula 1]

[In formula (d1),

R ^d1 is an aromatic hydrocarbon group which may have a substituent of 6 to 18 carbon atoms, a heterocyclic group which may have a substituent of 3 to 36 carbon atoms, an alkyl group which may have a substituent of 1 to 15 carbon atoms, or a carbon number which may have a substituent represents an aralkyl group of 7 to 33, and the methylene group (-CH ₂ -) contained in the alkyl group or aralkyl group is -O-, -CO-, -S-, -SO ₂ - or -N(R ^d5 ) may be substituted with -.

R ^d2 represents an aromatic hydrocarbon group of 6 to 18 carbon atoms, a heterocyclic group of 3 to 36 carbon atoms, or an alkyl group of 1 to 10 carbon atoms.

R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.

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

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

[2] The colored curable resin composition according to [1], wherein the dye contains at least one dye selected from the group consisting of xanthene dyes, triarylmethane dyes, compounds represented by Formula (Ab2), and coumarin dyes.

[Formula 2]

[In formula (Ab2), R ⁴¹ to ^{R 44} are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent represents an aralkyl group of 7 to 30, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and the number of carbon atoms in the saturated hydrocarbon group In the case of 2 to 20, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. R ⁴¹ and R ⁴² may be bonded together to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded together with the nitrogen atom to which they are bonded to form a ring.

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 when the alkyl group has 2 to 8 carbon atoms, the methylene group constituting the alkyl group is It may be substituted with an oxygen atom or -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or SO ₂ -.

Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms which may have a substituent.

[Y] ^m- represents an arbitrary m-valent anion.

m represents any natural number.]

[3] The colored curable resin composition according to [1] or [2], containing a phthalocyanine pigment as the coloring agent.

[4] The colored curable resin composition according to any one of [1] to [3], wherein the pigment content is 1% by mass or more and 50% by mass or less with respect to the total amount of solid content.

[5] The colored curable resin composition according to any one of [1] to [4], wherein the content ratio of the polymerization initiator to the polymerizable compound (polymerization initiator/polymerizable compound) is 4/1000 or more and 35/100 or less on a mass basis. .

[6] A color filter formed from the colored curable resin composition according to any one of [1] to [5].

[7] A liquid crystal display device comprising the color filter according to [6].

ADVANTAGE OF THE INVENTION According to the colored curable resin composition of this invention, the color filter excellent in pattern shape can be formed.

1 is a schematic diagram illustrating the cross-sectional shape of a coloring pattern.
2 is a schematic diagram illustrating the cross-sectional shape of a coloring pattern.

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).

In this specification, the compound illustrated as each component can be used individually or in combination of multiple types, unless otherwise indicated.

<Colorant (A)>

The colored curable resin composition of the present invention contains a dye and a pigment as a coloring agent (A).

The dye is at least one dye selected from the group consisting of a xanthene dye (Aa), a triarylmethane dye (Ab), a compound represented by formula (Ab2), and a coumarin dye (Ac) (hereinafter referred to as "dye (A1)" ”) is preferable, and it is more preferable that a xanthene dye (Aa) is included.

In this specification, a dye refers to a dye soluble in a solvent.

A xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in its molecule. As the xanthene dye (Aa), for example, C.I. C.I. acid red dye; C.I. Acid Violet 9, 30, 102 and the like C.I. acid violet dye; C.I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, 10 (Rhodamine B), 11, etc. C.I. basic red dye; C.I. Basic Violet 10, 11, 25, etc. C.I. basic violet dye; C.I. C.I., such as solvent red 218. solvent red dye; C.I. Modern Tread 27 and other C.I. Mordant Red dye; C.I. C.I., such as Reactive Red 36 (Rose Bengal B). reactive red dye; sulforhodamine G; xanthene dyes described in Japanese Unexamined Patent Publication No. 2010-32999; and the xanthene dyes described in Japanese Patent No. 4492760; etc. can be mentioned. As the xanthene dye (Aa), it is preferable to dissolve in an organic solvent.

Among these, as xanthene dye (Aa), a dye containing a compound represented by formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable. Compound (1a) may be its tautomer. When using the compound (1a), the content of the compound (1a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more. In particular, as the xanthene dye (Aa), it is preferable to use only the compound (1a).

[Formula 4]

[In Formula (1a), R ¹ to ^{R 4} are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or 1 carbon number 6 to 10 which may have a substituent It represents a valent aromatic hydrocarbon group, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be substituted with -O-, -CO-, or -N(R ¹¹ )-. R ¹ and R ² may combine to form a ring containing a nitrogen atom, and R ³ and R ⁴ may combine 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 N(R ⁹ )(R ¹⁰ ).

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

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

a represents an integer of 0 or 1.

X represents a halogen atom.

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

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated aliphatic hydrocarbon group is -O-, -CO It may be substituted with -, -NH- or -N(R ⁸ )-, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.]

In formula (1a), when -SO ₃ ^- exists, the number is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to ^{R 4} include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group and a butylphenyl group.

As a substituent ^which the said aromatic hydrocarbon group may have, a halogen atom, ^-R8 , -OH, ^-OR8 , _-SO3- , _-SO3H , _-SO3 ^- Z ⁺ , _-CO2H , _-CO2R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ N(R ⁹ )(R ¹⁰ ), wherein these substituents replace hydrogen atoms contained in the aromatic hydrocarbon group. desirable. Among these, as a substituent, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^{-Z +} , -SO ₃ R ⁸ and -SO ₂ N(R ⁹ )(R ¹⁰ ) are preferable, and -SO ₃ ^{-Z +} and -SO ₂ N(R ⁹ )(R ¹⁰ ) are more preferred. As -SO ₃ ^{-Z +} in this case, -SO ₃ ^-+ N(R ¹¹ ) ₄ is preferable. As -SO ₂ N(R ⁹ )(R ¹⁰ ), -SO ₂ NHR ⁹ is preferable. When R ¹ to ^{R 4} are these groups, the colored curable resin composition of the present invention containing the compound (1a) can form a color filter with less generation of foreign matter and excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ¹ to ^{R 4} and R ⁸ to ^{R 11} include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and jade. straight-chain alkyl groups such as a ethyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, and an icosyl group; branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; and cyclic alkyl groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group.

The hydrogen atom contained in the saturated hydrocarbon group in R ¹ to ^{R 4} may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom as a substituent. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may substitute the hydrogen atom of the saturated hydrocarbon group of R ¹ to R ⁴ include the same groups as those exemplified as the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to ^{R 4} . can

The hydrogen atom contained in the saturated hydrocarbon group in R ⁹ and R ¹⁰ may be substituted with, for example, a hydroxy group or a halogen atom as a substituent.

Examples of the ring formed by combining R ¹ and R ² and the ring formed by combining R ³ and R ⁴ include the following, and more preferably do not contain a double bond.

[Formula 5]

Examples of -OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an icosyloxy group. An alkyloxy group etc. are mentioned.

Examples of -CO ₂ R ⁸ include alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group, and icosyloxycarbonyl group.

Examples of -SR ⁸ include alkylsulfanyl groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group, and icosylsulfanyl group.

As _-SO2R8 , ^{alkylsulfonyl} groups, such as a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group, etc. are mentioned, for example.

Examples of -SO ₃ R ⁸ include alkyloxy sulfonyl groups such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group, and icosyloxysulfonyl group. A phonyl group etc. are mentioned. As R ⁸ of -SO ₃ R ⁸ , a branched chain alkyl group having 3 to 20 carbon atoms is preferable, a branched chain alkyl group having 6 to 12 carbon atoms is more preferable, and a 2-ethylhexyl group is still more preferable. It is possible to form a color filter with less generation of foreign matter.

Examples of -SO ₂ N(R ⁹ )(R ¹⁰ ) include a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butyl alcohol Pamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(1, 2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- ( 3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamoyl group diyl group, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl) N-1-substituted sulfamoyl groups such as sulfamoyl group, N-(1,5-dimethylhexyl)sulfamoyl group, and N-(1,1,2,2-tetramethylbutyl)sulfamoyl group;

N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N, such as a N,N-tert-butylmethylsulfamoyl group, a N,N-butylethylsulfamoyl group, a N,N-bis(1-methylpropyl)sulfamoyl group, a N,N-heptylmethylsulfamoyl group, An N-2 substituted sulfamoyl group etc. are mentioned.

In the N-1 substituted sulfamoyl group, as R ⁸ , a branched chain alkyl group of 3 to 20 carbon atoms is preferable, a branched chain alkyl group of 6 to 12 carbon atoms is more preferable, and a 2-ethylhexyl group is still more preferable. It is possible to form a color filter with less generation of foreign matter.

As R ⁵ , -CO ₂ H, -CO ₂ ^{-Z +} , -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ ^{-Z +} , -SO ₃ H or -SO ₂ NHR ⁹ are preferable, and -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or -SO ₂ NHR ⁹ are more preferred.

1-4 are preferable and, as for m, 1 or 2 is more preferable.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include those having 1 to 6 carbon atoms among the above-mentioned alkyl groups. Especially, as ^R6 and ^R7 , a hydrogen atom is preferable.

As a C7-C10 aralkyl group in R ^<11> , a benzyl group, a phenylethyl group, a phenylbutyl group, etc. are mentioned.

As R ¹¹ , a saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group is preferable.

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ .

As said ⁺ N(R ¹¹ ) ₄ , it is preferable that at least two of the four R ¹¹ are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Moreover, 20-80 are preferable and, as for the total number of carbon atoms of 4 R ^<11> , 20-60 are more preferable. When ⁺ N(R ¹¹ ) ₄ exists in compound (1a), if R ¹¹ is these groups, a color filter with few foreign substances can be formed from the colored curable resin composition of the present invention containing compound (1a). .

1-4 are preferable and, as for m, 1 or 2 is more preferable.

As a combination of R ¹ to ^{R 4} , a combination in which R ¹ and R ³ are hydrogen atoms and R ² and R ⁴ are an aromatic hydrocarbon group having a monovalent substituent having 6 to 10 carbon atoms is preferable. As a substituent of the aromatic hydrocarbon group, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^{-Z +} , -SO ₃ R ⁸ or -SO ₂ NHR ⁹ is preferable, and -SO ₃ ^{-Z +} or -SO ₂ NHR ⁹ is more preferred. These substituents substitute the hydrogen atom contained in the aromatic hydrocarbon group.

As the combination of R ¹ to ^{R 4} , a combination in which all of R ¹ to ^{R 4} are monovalent saturated hydrocarbon groups is also preferable. In this case, the saturated hydrocarbon group is preferably a methyl group or an ethyl group.

Further, as a combination of R ¹ to ^{R 4} , a combination in which R ¹ and R ³ are saturated hydrocarbon groups having 1 to 10 carbon atoms which may have substituents, and R ² and R ⁴ are phenyl groups which may have substituents is also preferable.

In this case, R ¹ may form a ring with the substituent substituting the phenyl group of R ² , and R ³ may form a ring with the substituent substituting the phenyl group of R ⁴ .

In addition, it is preferable that the number of carbon atoms in R ¹ and R ³ is 1 to 3 independently of each other. As a substituent for the hydrogen atom contained in the saturated hydrocarbon group of R ¹ and R ³ , an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with an alkoxy group having 1 to 3 carbon atoms or a halogen atom is preferable.

Moreover, as a substituent which the phenyl group of ^R2 and ^R4 may have, a C1-C4 alkyl group, a C1-C4 alkylsulfanyl group, or a C1-C4 alkylsulfonyl group is preferable, and a C1-C4 alkyl group is more preferable, and a methyl group is still more preferable. The number of substituents substituting the phenyl groups of R ² and R ⁴ is 0 to 5, preferably 0 to 2, and more preferably 0 or 1.

Examples of the alkyl group having 1 to 4 carbon atoms that may be substituted for the phenyl group of R ² and R ⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl and the like. can

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms which may be substituted for the phenyl groups of R ² and R ⁴ include methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl and isopropylsulfanyl.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms which may be substituted for the phenyl group of R ² and R ⁴ include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropylsulfonyl.

As a compound (1a), the compound represented by Formula (1-1) - Formula (1-43) is mentioned, for example. In the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms, preferably a branched chain alkyl group of 6 to 12 carbon atoms, more preferably a 2-ethylhexyl group.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

Examples of the xanthene dye (Aa) include compounds having a structure in which an aromatic heterocycle having 3 to 9 carbon atoms is bonded to the 9-position carbon of the xanthene ring. The aromatic ring may have a substituent.

As the xanthene dye (Aa), compounds represented by formulas (1-1) to (1-8), C.I. A quaternary ammonium salt of Acid Red 289 (for example, a compound represented by formula (1-11) or formula (1-12)), C.I. Sulfonamides of Acid Violet 102 and C.I. The quaternary ammonium salt of Acid Violet 102 is preferable, and compounds represented by formulas (1-1) to (1-8) and compounds represented by formulas (1-11) and (1-12) are preferable.

In view of the excellent solubility in organic solvents, compounds represented by any of formulas (1-24) to (1-33) are also preferable.

Xanthene dye (Aa) is a commercially available xanthene dye (eg, "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Kasei Co., Ltd., "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.) ) can be used. Moreover, it is also compoundable with reference to Unexamined-Japanese-Patent No. 2010-32999 using commercially available xanthene dye as a starting material.

The content of the xanthene dye (Aa) is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, still more preferably 90 parts by mass or more, particularly preferably 99 parts by mass or more, based on 100 parts by mass of the dye (A1). It is more than a mass part, and it is preferable that it is 100 mass parts or less.

Triarylmethane dye (Ab) is a dye containing a compound having a structure in which three aromatic groups are bonded to one carbon atom. As the said aromatic group, an aromatic hydrocarbon group is specifically mentioned.

As the triarylmethane dye (Ab), for example, C.I. Solvent Blue 2, 4, 5, 43, 124; C.I. Basic Violet 3, 14, 25; C.I. Basic Blue 1, 5, 7, 11, 26 and triarylmethane dyes described in Japanese Patent No. 4492760; and the like. It is preferable to dissolve in an organic solvent.

Among these, as triarylmethane dye (Ab), a dye containing a compound represented by formula (Ab1) (hereinafter sometimes referred to as “compound (Ab1)”) is preferable.

[Formula 14]

[In formula (Ab1), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or a saturated hydrocarbon group having 1 to 20 carbon atoms, and the saturated hydrocarbon group having 2 to 20 carbon atoms. In the case of , the methylene group constituting the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-.

R ^9A to R ^12A are each independently a hydrogen atom, a saturated hydrocarbon group of 1 to 20 carbon atoms, an aromatic hydrocarbon group of 6 to 20 carbon atoms which may have a substituent, or an aralkyl group of 7 to 30 carbon atoms which may have a substituent , the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or halogen atom, and when the carbon number of the saturated hydrocarbon group is 2 to 20, the methylene group contained in the saturated hydrocarbon group is an oxygen atom or - It may be substituted with CO-. R ^9A and R ^10A may combine to form a ring with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may bond to form a ring with the nitrogen atom to which they bond.

A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted.

[G] ^g- represents an arbitrary g valency counter anion. g represents 0 or any natural number.]

In addition, in formula (Ab1), when g is a natural number of 2 or more, the cations in formula (Ab1) may have the same structure or different structures.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^1A to ^{R 12A} may be linear, branched or cyclic, preferably chain. Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^1A to R ^12A include the same groups as those exemplified as the saturated hydrocarbon group for R ¹ . As for carbon number of the saturated hydrocarbon group represented by ^R1A - ^R12A , it is more preferable that it is 1-10, and it is still more preferable that it is 1-8.

When the saturated hydrocarbon group represented by R ^1A to ^{R 12A} has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-, preferably with an oxygen atom. In addition, an oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group. The number of carbon atoms in the saturated hydrocarbon group in which the methylene group may be substituted with an oxygen atom or -CO- is preferably 2 to 10, more preferably 2 to 8, still more preferably 2 to 6. As the saturated hydrocarbon group in which the methylene group may be substituted with an oxygen atom, a linear or branched saturated hydrocarbon group (i.e., a linear or branched chain alkyl group) is preferable, and a linear saturated hydrocarbon group (i.e., linear alkyl group) is more preferable. do.

Further, when the methylene group is substituted with an oxygen atom or -CO-, the number of carbon atoms between the terminal and the oxygen atom or -CO- or between the oxygen atom or -CO- and the oxygen atom or -CO- is preferably 1 to 4 And, 2-3 are more preferable.

Examples of the substituted or unsubstituted amino group that the alkyl group of R ^9A to R ^12A may have include an amino group; N-methylamino group, N-ethylamino group, N-phenylamino group, N,N-dimethylamino group, N,N-diethylamino group, etc. are mentioned. Moreover, as a halogen atom which the saturated hydrocarbon group of ^R9A - ^R12A may have, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

The number of carbon atoms in the aromatic hydrocarbon group represented by R ^9A to R ^12A is preferably 6 to 20, more preferably 6 to 15, still more preferably 6 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a toluyl group, a xylyl group, a naphthyl group, anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. Moreover, the said aromatic hydrocarbon group may have 1 or 2 or more substituents, As said substituent, Halogen atoms, such as a fluorine atom, a chlorine atom, an iodine atom, a bromine atom; alkoxy groups having 1 to 6 carbon atoms, such as a methoxy group and an ethoxy group; hydroxy group; sulfamoil group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group; alkoxycarbonyl groups having 2 to 6 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group; etc. can be mentioned.

The number of carbon atoms in the aralkyl group represented by R ^9A to R ^12A is 7 to 30, more preferably 7 to 20, still more preferably 7 to 17. Examples of the aralkyl group represented by R ^9A to ^{R 12A} include groups in which an alkanediyl group having 1 to 5 carbon atoms, such as a methylene group, an ethylene group, or a propylene group, is bonded to the groups described as the aromatic hydrocarbon groups for R 9A to ^R 12A.

Among them, as R ^1A to R ^8A , a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group) is preferable, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.

R ^9A to ^{R 12A} are each independently preferably a saturated hydrocarbon group (preferably an alkyl group) having 1 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent. .

As an aromatic hydrocarbon group represented by A, C6-C20 aromatic hydrocarbon groups, such as a phenyl group, a toluyl group, a xylyl group, a naphthyl group, anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, are mentioned.

As a substituent which the aromatic hydrocarbon group represented by A may have, For example, Halogen atoms, such as a fluorine atom, a chlorine atom, and an iodine atom; A substituted or unsubstituted amino group; hydroxy group; sulfo group; -SO ₃ ^- ; -SO ₃ J etc. are mentioned. As a substituent which may substitute the said amino group, C1-C20 alkyl group which may be substituted by the amino group or a halogen atom; Aryl groups, such as a phenyl group which may be substituted by the alkoxy group of 1-10 carbon atoms; etc. can be mentioned.

Especially, as A, the aromatic hydrocarbon group which may have a substituent is preferable.

Examples of J include inorganic cations and organic cations. Specifically, the same cation as Z ⁺ in the above compound (1a), a cation of the following formula, and the like are exemplified.

[Formula 16]

[G] ^g- represents a g-valent anion. g may be 0, and is usually 1 to 14, preferably 1 to 12, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 4. [G] Examples of ^{g -} include an anion represented by formula (y1), formula (y2) or formula (y3).

[Formula 17]

[In formula, R ^B1 represents a monovalent organic group.

R ^B2 and R ^B3 represent a halogen atom or a halogenated hydrocarbon group, and R ^B2 and R ^B3 may combine with each other to form a ring containing -SO ₂ ^-N -SO ₂ -. R ^B4 and R ^B5 represent a divalent organic group.

M1 represents an aluminum atom or a boron atom.]

The halogenated hydrocarbon group represented by R ^B2 or R ^B3 is preferably a fluorinated hydrocarbon group, and more preferably a perfluoroalkyl group.

The divalent organic group represented by R ^B4 or R ^B5 is preferably a divalent aromatic hydrocarbon group.

Examples of the anion represented by formula (y1) include methanesulfonic acid anion, toluenesulfonic acid anion, dodecylbenzenesulfonic acid anion, trifluoromethanesulfonic acid anion, and perfluorobutanesulfonic acid anion.

As an anion represented by formula (y2), the anion represented by the following formula, etc. are mentioned.

[Formula 18]

As an anion represented by formula (y3), the anion represented by the following formula, etc. are mentioned.

[Formula 19]

[G] ^g- includes, for example, a halide ion, a resin having a sulfonic acid anion, and a trisperfluoroalkylsulfonylmethide anion.

As a compound represented by Formula (Ab1), the compound represented by the following formula is mentioned. In the following formula, J has the same meaning as described above.

[Formula 20]

[Formula 21]

[Formula 22]

When the triarylmethane dye (Ab) is included, the content is preferably 1 part by mass or more and 99 parts by mass or less with respect to 100 parts by mass of the dye (A1).

The compound represented by formula (Ab2) (hereinafter sometimes referred to as compound (Ab2)) includes its tautomer.

[Formula 23]

[In formula (Ab2), R ⁴¹ to ^{R 44} are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and a carbon number which may have a substituent In the saturated hydrocarbon group having 7 to 30 aralkyl groups and having 1 to 20 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with substituted or unsubstituted amino groups or halogen atoms, and the number of carbon atoms in the saturated hydrocarbon group is In the case of 2 to 20, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. R ⁴¹ and R ⁴² may be bonded together to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded together with the nitrogen atom to which they are bonded to form a ring.

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 when the alkyl group has 2 to 8 carbon atoms, the methylene group constituting the alkyl group is It may be substituted with an oxygen atom or -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or SO ₂ -.

Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms which may have a substituent.

[Y] ^m- represents an arbitrary m-valent anion.

m represents any natural number.

In the formula (Ab2), when m is 2 or more, the cations in the formula (Ab2) may have the same structure or different structures.

The aromatic heterocycle of the ring T ¹ may be a monocyclic ring or a condensed ring. The number of carbon atoms of the aromatic heterocycle represented by ring T ¹ is 3 to 10, preferably 3 to 8. Moreover, it is preferable that it is a 5-10 membered ring, and, as for an aromatic heterocycle, it is more preferable that it is a 5-9 membered ring. As a monocyclic aromatic heterocycle, For example, 5-membered rings containing nitrogen atoms, such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; 5-membered rings that do not contain nitrogen atoms such as furan rings and thiophene rings; 6-membered rings containing nitrogen atoms such as pyridine rings, pyrimidine rings, pyridazine rings, and pyrazine rings; Examples of the aromatic heterocycle of the condensed ring include condensed rings containing a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring; Rings containing no nitrogen atom, such as a benzofuran ring; etc. can be mentioned.

As the substituent which the aromatic heterocycle of ring T ¹ may have, a halogen atom, a cyano group, a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 20 carbon atoms) which may have a substituent, and a substituent which may have An aromatic hydrocarbon group having 6 to 20 carbon atoms, or a substituted or unsubstituted amino group, and the like, preferably a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 20 carbon atoms), a substituted or unsubstituted amino group, Or the C6-C20 aromatic hydrocarbon group which may have a substituent is mentioned.

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

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

[Formula 25]

[In formula (Ab2-x1),

Ring T ² represents an aromatic heterocycle having 3 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent In the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the The methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. R ⁴⁵ and R ⁴⁶ may be bonded together to form a ring together with the nitrogen atom to which they are bonded.

R ⁵⁵ represents a saturated hydrocarbon group of 1 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 20 carbon atoms which may have a substituent.

k1 represents 0 or 1.

* represents a bond with a carbocation.]

Moreover, it is especially preferable that ring ^T1 is a ring represented by formula (Ab2-y1).

[Formula 26]

[In Formula (Ab2-y1),

R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

X2 represents an oxygen atom, -N(R ⁵⁷ )-, or a sulfur atom.

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

R ⁴⁵ and R ⁴⁶ have the same meaning as described above.

* represents a bond with a carbocation.]

In the above formula, examples of the aromatic heterocycle of ring T ² include the same rings as the aromatic heterocycles exemplified for ring T ¹ .

Further, the case where ring T ¹ is a ring represented by the formula (Ab2-x2) is also preferable.

[Formula 27]

[In formula (Ab2-x2),

Ring T ³ represents an aromatic heterocycle having 3 to 10 carbon atoms and having a nitrogen atom.

R ⁵⁸ represents a saturated hydrocarbon group of 1 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 20 carbon atoms 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 having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent.

k2 represents 0 or 1.

* represents a bond with a carbocation.]

Ring T ¹ is also more preferably a ring represented by formula (Ab2-y2).

[Formula 28]

[In formula (Ab2-y2),

R ⁶⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

R ⁵⁹ has the same meaning as described above.

* represents a bond with a carbocation.]

The saturated hydrocarbon groups represented by R ⁴¹ to ^{R 46} , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to ^{R 60} may be linear, branched or cyclic. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 4. Examples of 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} include the same groups as those exemplified as the saturated hydrocarbon group represented by R ¹ . The chain saturated hydrocarbon group (alkyl group) has preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms. The number of carbon atoms of the saturated cyclic hydrocarbon group (alicyclic saturated hydrocarbon group) is preferably 3 to 10, more preferably 6 to 10.

In the case where the saturated hydrocarbon group represented by R ⁴¹ to ^{R 46} has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-, preferably with an oxygen atom. . In addition, an oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (ie, a linear or branched alkyl group), and more preferably a linear saturated hydrocarbon group (ie, a linear alkyl group). The number of carbon atoms in the saturated hydrocarbon group in which the methylene group may be substituted with an oxygen atom or -CO- is preferably 2 to 10, more preferably 2 to 8. Further, when the methylene group is substituted with an oxygen atom or -CO-, the number of carbon atoms between the terminal and the oxygen atom or -CO- or between the oxygen atom or -CO- and the oxygen atom or -CO- is preferably 1 to 4 And, 2-3 are more preferable.

The saturated hydrocarbon group represented by R ⁴¹ to ^{R 46} , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to ^{R 60} may be substituted with a substituted or unsubstituted amino group or a halogen atom. As a substituted amino group, alkylamino groups, such as a dimethylamino group and a diethylamino group, are mentioned, for example. Moreover, as a halogen atom, fluorine, chlorine, bromine, and iodine are mentioned. When the halogen atom is a fluorine atom, the saturated hydrocarbon group substituted with a halogen atom (fluorine atom) represented by R ⁴¹ to ^{R 46} , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to ^{R 60} is a trifluoromethyl group, a pentafluoroethyl group, It is preferable that it is a perfluoroalkyl group, such as a heptafluoropropyl group.

As a substituent which the alkyl group represented by ^R59 may have, a halogen atom, a cyano group, etc. are mentioned.

Examples of the optionally substituted aromatic hydrocarbon group represented by R ⁴¹ to ^{R 46} , R ⁵⁵ , R ⁵⁶ , and R ⁵⁸ to R ⁶⁰ include the same groups as the optionally substituted aromatic hydrocarbon group represented by R ^9A . It is preferable that it is 6-20, and, as for carbon number of the said aromatic hydrocarbon group, it is 6-10 more preferably. As the said aromatic hydrocarbon group, a phenyl group, a toluyl group, a xylyl group, and a naphthyl group are preferable. Moreover, the said aromatic hydrocarbon group may have 1 or 2 or more substituents.

Examples of the optionally substituted aralkyl group represented by R ⁴¹ to R ⁴⁶ and R ⁵⁹ include the same groups as the optionally substituted aralkyl group represented by R ^9A .

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ include straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms as exemplified for R ^9A .

Among the groups represented by R ⁴¹ to ^{R 46} , R ⁵⁵ , R ⁵⁶ , and R ⁵⁸ to ^{R 60} , as the substituent in the aromatic hydrocarbon group and the aralkyl group, a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, a methoxy group Alkoxy groups having 1 to 6 carbon atoms such as groups and ethoxy groups; hydroxy group; C1-C6 alkyl groups, such as a methyl group and an ethyl group; sulfamoil group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group; and alkoxycarbonyl groups having 1 to 6 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group.

The alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to ^{R 54} may be linear, branched or cyclic, preferably a chain, and among the linear, branched and cyclic alkyl groups exemplified for R ¹ , 1 to 8 carbon atoms may be used. 8, and so on.

When the alkyl group represented by R ⁴⁷ to ^{R 54} has 2 to 8 carbon atoms, the methylene group constituting the alkyl group is substituted with an oxygen atom or -CO- (preferably a group substituted with an oxygen atom). Groups having 8 or less carbon atoms are selected from groups in which the methylene group constituting the alkyl group having 2 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ is substituted with an oxygen atom or -CO-. In the group, an oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group.

Among them, examples of R ⁴¹ to ^{R 44} , R ⁵⁵ , R ⁵⁶ , R ⁵⁸ , and R ⁵⁹ include an aliphatic hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group) and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. desirable.

Further, as R ⁴⁷ to ^{R 54} , a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms is independently preferred, and a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom is particularly preferred independently of each other.

As R ⁵⁶ , a saturated hydrocarbon group having 1 to 10 carbon atoms (preferably an alkyl group) or an aromatic hydrocarbon group which may have a substituent is preferable, more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms (preferably an alkyl group). alkyl group), or an aromatic hydrocarbon group which may be substituted with a halogen atom, a haloalkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, a hydroxy group, an alkyl group of 1 to 4 carbon atoms, or a methylsulfonyl group.

As R ⁵⁷ , a hydrogen atom or an alkyl group having 1 to 8 carbon atoms is preferable.

As a cation in formula (Ab2), it is a cation represented by formula (Ab2-I), and cation 1 - cation 12 etc. which have a substituent shown in Table 1 are mentioned. In the table, * represents a binding hand.

[Formula 29]

In Table 1, Ph1 to Ph9 mean groups represented by the following formula. In the formula, * represents a bonding hand.

[Formula 30]

Examples of the cation in the formula (Ab2) include cations 13 to 16 having substituents shown in Table 2 as cations represented by formula (Ab2-II). In the table, * represents a binding hand.

[Formula 31]

In Table 2, Ph1, Ph10, and Ph11 mean groups represented by the following formula. In the formula, * represents a bonding hand.

[Formula 32]

As a cation of formula (Ab2), cation 1-6, cation 11, or cation 12 is preferable, and cation 1, cation 2, or cation 12 is more preferable.

[Y] ^m- represents an m-valent anion. m may be 0, preferably 1 to 14, more preferably 1 to 12, still more preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4 particularly preferred. As [Y] ^{m -} , the anion illustrated as [G] ^g- can be mentioned, and also the anion represented by formula (y4), formula (y5), and formula (y6) is mentioned.

[Formula 33]

[In formula, R ^B6 represents a divalent organic group. R ^B7 represents a trivalent aromatic hydrocarbon group. n represents a natural number.]

Examples of the anion represented by formula (y4) include methanedisulfonic acid anion, propanedisulfonic acid anion, toluene disulfonic acid anion, naphthalene disulfonic acid anion, and anion represented by the following formula. .

[Formula 34]

As an anion represented by formula (y6), the anion represented by the following formula, etc. are mentioned. In formula, n represents a natural number.

[Formula 35]

As the anion in the formula (Ab2), it is preferable to select a boron-containing anion, an aluminum-containing anion, and a fluorine-containing anion from the viewpoint of heat resistance among the anions exemplified above.

As a compound (Ab2), the compound represented by the following formula is mentioned, for example.

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

When containing the compound represented by Formula (Ab2), it is preferable that the content is 1 mass part or more and 99 mass parts or less in 100 mass parts of dye (A1).

A coumarin dye (Ac) is a dye containing a compound having a coumarin skeleton in its molecule. As the coumarin dye (Ac), 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; coumarin dyes described in Japanese Patent No. 1299948; etc. can be mentioned. It is preferable to dissolve in an organic solvent.

Among these, as a coumarin dye, for example, a compound represented by formula (Ac1) (hereinafter sometimes referred to as "compound (Ac1)") is preferable.

[Formula 43]

[In Formula (Ac1), X ^C represents an oxygen atom or a sulfur atom.

R ^1C each independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group constituting the saturated hydrocarbon group may be substituted with an oxygen atom.

R ^2C to R ^13C are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group, an amino group, and 1 carbon atom. represents a monovalent hydrocarbon group of to 20, and the methylene group constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N(R ^14C )-, a sulfonyl group, or a carbonyl group, and the hydrogen atom contained in the hydrocarbon group is It may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxy group, a formyl group or an amino group.

R ^14C represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^14C groups exist, they may be the same or different.

M represents a hydrogen atom or an alkali metal atom.

L ^C represents a divalent hydrocarbon group or sulfonyl group having 1 to 20 carbon atoms.]

The saturated hydrocarbon group of 1 to 20 carbon atoms for R ^1C may be linear, branched or cyclic, preferably chain. Specifically, groups similar to the groups exemplified as the saturated hydrocarbon group having 1 to 20 carbon atoms for R ¹ can be exemplified.

In the case where the saturated hydrocarbon group represented by R ^1C has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom. In addition, an oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group.

Examples of the monovalent hydrocarbon group of 1 to 20 carbon atoms for R ^2C to ^{R 14C} include a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms, a monovalent unsaturated aliphatic hydrocarbon group of 1 to 20 carbon atoms, and a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms. etc. can be mentioned. Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include groups similar to those exemplified as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ¹ . Examples of the monovalent unsaturated hydrocarbon group having 1 to 20 carbon atoms include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group. group, a linear alkenyl group such as a hexadecenyl group, an octadecenyl group, and an icocenyl group; cycloalkenyl groups such as a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group; etc. can be mentioned. Moreover, as said C6-C10 monovalent aromatic hydrocarbon group, the same group as the group illustrated as a C6-C10 aromatic hydrocarbon group in R ^<1> is mentioned.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms for ^LC include a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, a divalent unsaturated hydrocarbon group having 1 to 20 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and a group in which one hydrogen atom contained in a monovalent hydrocarbon group having 1 to 20 carbon atoms in R ^2C is used as a bonding hand.

In addition, it is preferable that a plurality of R ^1C to R ^13C are the same group respectively.

Especially, as R ^1C , a C1-C20 chain alkyl group is preferable, and a C1-C10 chain alkyl group is more preferable.

As R ^2C to ^{R 6C} , a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms is preferable, a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable, a hydrogen atom or a chain alkyl group having 1 to 5 carbon atoms is more preferable

As R ^7C to ^{R 13C} , a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms is preferable, and a hydrogen atom is particularly preferable.

As L ^C , a saturated hydrocarbon group having 1 to 20 carbon atoms, such as a sulfonyl group or a methylene group or a propanediyl group, is preferable. In addition, the divalent hydrocarbon group of ^LC preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

Moreover, as X ^C , an oxygen atom is particularly preferable.

As a compound (Ac1), the compound represented by the following formula is mentioned, for example.

[Formula 44]

[Formula 45]

When the coumarin dye (Ac) is included, the content thereof is preferably 1 part by mass or more and 99 parts by mass or less with respect to 100 parts by mass of the dye (A1).

As dyes other than dye (A1), for example, compounds classified as having color other than pigments in the color index (published by The Society of Dyers and Colourists), and those described in dyeing notes (Shikisensha) Well-known dyes are mentioned. In addition, according to the chemical structure, azo dyes, cyanine dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, quinoline dyes and nitro dyes; and the like. Among these, those dissolved in organic solvents are preferred.

Specifically, C.I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;

C.I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 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;

C.I. 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 1, 3, 5, 28, 29, 32, 33; Etc. C.I. solvent dyes,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 1 84, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

C.I. Acid Red 73, 80, 91, 97, 138, 151, 211, 274;

C.I. Acid Green 3, 5, 9, 25, 27, 28, 41;

C.I. Acid Violet 34, 120;

C.I. Acid Blue 25, 27, 40, 45, 78, 80, 112; Etc. C.I. acid dyes,

C.I. Basic Green 1; Etc. C.I. basic dye,

C.I. Reactive Yellow 2, 76, 116;

C.I. Reactive Orange 16; Etc. C.I. reactive dyes,

C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;

C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Blue 40; Etc. C.I. direct dye,

C.I. Disperse Yellow 51, 54, 76;

C.I. Disperse Violet 26, 27;

C.I. Disperse Blue 1, 14, 56, 60; Etc. C.I. disperse dye,

C.I. As a mordant dye, C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; Etc. C.I. mordant Dye,

C.I. C.I. from Bat Green 1 and more. Vat dye etc. are mentioned.

The content of the dye (A1) in the dye is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 85 It is mass % or more and 100 mass % or less.

The coloring agent (A) further contains a pigment (A2). As the pigment (A2), known pigments that are not particularly limited can be used, and examples thereof include pigments classified as pigments in the color index (published by The Society of Dyers and Colourists). Or it can use in combination of 2 or more types.

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

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

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 ;

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

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

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

C.I. brown pigments such as Pigment Brown 23 and 25;

C.I. Black pigments, such as Pigment Black 1 and 7, etc. are mentioned.

Among them, the pigment is preferably a phthalocyanine pigment, more preferably a copper phthalocyanine pigment and a zinc phthalocyanine pigment, still more preferably a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment, and particularly preferably a halogenated copper phthalocyanine pigment.

Moreover, as a pigment, a blue pigment and a green pigment are preferable, and a blue pigment is more preferable.

Specifically, C.I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, and 60 are preferred, and C.I. Halogenated copper phthalocyanine blue pigments such as Pigment Blue 15, 15:3, 15:4, and 15:6 are preferred, and C.I. Pigment Blue 15:6 is particularly preferred. By including the pigment, the transmission spectrum is easily optimized, and the light resistance and chemical resistance of the color filter are improved.

The pigment is, if necessary, rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced therein, grafting treatment to the surface of the pigment with a polymer compound or the like, atomization treatment by a sulfuric acid atomization method, or the like, or for removing impurities. A washing treatment with an organic solvent or water, a treatment for removing ionic impurities by an ion exchange method, or the like may be performed.

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

As said pigment dispersant, surfactant is mentioned, for example, Any cationic, anionic, nonionic, and amphoteric surfactant may be used. Specifically, surfactants, such as a polyester type, a polyamine type, and an acrylic type, etc. are mentioned. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Corporation) are commercially available. , Ajisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemie Co., Ltd.), and the like.

When the pigment dispersion liquid contains a pigment dispersant, the content thereof is preferably 1% by mass or more and 500% by mass or less, more preferably 5% by mass or more and 300% by mass or less with respect to the total amount of the pigment (A2). When the content of the pigment dispersant is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The content ratio of the dye (A1) and the pigment (A2) (dye (A1):pigment (A2)) is 1:99 to 89:11 on a mass basis, preferably 1:99 to 70:30, More preferably, it is 1:99 to 50:50, and still more preferably 5:95 to 50:50.

The content of the pigment is preferably 1% by mass or more, more preferably 1.5% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass with respect to the total amount of solid content. It is more preferable that it is below. When the content rate of the pigment is within the above range, a color filter with good chromaticity can be obtained.

In the coloring agent (A), examples of combinations of the dye (A1) and the pigment (A2) include the following.

As a combination in the case of preparing the colored curable resin composition of this invention as a red colored curable resin composition, a coumarin dye (Ac), a red pigment, etc. are mentioned.

As a combination in the case of preparing colored curable resin composition of this invention as a green colored curable resin composition, combination of a coumarin dye (Ac) and a green pigment; a combination of a coumarin dye (Ac) and a triarylmethane dye (Ab) with a green pigment; A combination of a coumarin dye (Ac), a compound represented by Formula (Ab2), and a green pigment, and the like are exemplified.

As a combination in the case of preparing the colored curable resin composition of this invention as a blue colored curable resin composition, the combination of a xanthene dye (Aa), a triarylmethane dye (Ab), and a blue pigment; a combination of a xanthene dye (Aa), a compound represented by Formula (Ab2), and a blue pigment; a combination of a xanthene dye (Aa) and a blue pigment; a combination of a xanthene dye (Aa) and a blue pigment and a violet pigment; a combination of a triarylmethane dye (Ab) and a violet pigment; a combination of a compound represented by formula (Ab2) and a violet pigment; etc. can be mentioned. In this case, the dye preferably contains at least one selected from the group consisting of a triarylmethane dye (Ab) and a compound represented by the formula (Ab2), and is represented by the triarylmethane dye (Ab) and the formula (Ab2). It is more preferable to contain at least 1 sort(s) selected from the group which consists of compounds which appear, and also a xanthene dye (Aa). The content of at least one selected from the group consisting of triarylmethane dyes (Ab) and compounds represented by formula (Ab2) is preferably 40% by mass or more, more preferably 50% by mass, in dye (A1). More than that.

The content of the coloring agent (A) is preferably 1% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 55% by mass or less, still more preferably 5% by mass, based on the total amount of solid content. or more and 50% by mass or less. When the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and a necessary amount of resin or polymerizable compound can be contained in the composition, so that a colored pattern having sufficient mechanical strength can be formed. there is. Here, "the total amount of solid content" in this specification means the quantity remove|excluding content of the solvent from the total amount of colored curable resin composition. The total amount of solid content and the content of each component thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Suji (B)>

The resin (B) is preferably an alkali-soluble resin, and is derived from at least one (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as "(a)"). It is preferable that it is a polymer which has the structural unit which does.

The copolymer having the structural unit derived from (a) is derived from the monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. It is preferable that it is a copolymer which has at least 1 sort(s) selected from the group which consists of a structural unit and a structural unit which has an ethylenically unsaturated bond. The copolymer may further have other structural units. Examples of other structural units include structural units derived from monomer (c) copolymerizable with (a) (however, it is different from (a) and (b). Hereinafter, it may be referred to as "(c)"). . The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group as a side chain. A resin having such a structural unit is obtained by adding a group capable of reacting with the group of (a) or (b) and a monomer having an ethylenically unsaturated bond to a polymer having a structural unit derived from (a) or (b). lose

Examples of such a structural unit include a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit obtained by adding (a) to a structural unit derived from (b). Moreover, when these structural units have a hydroxyl group, structural units to which a carboxylic acid anhydride is further added are also exemplified as structural units having an ethylenically unsaturated bond.

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic 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, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic 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-carboxymethylbicyclo[2.2.1]hept-2-ene, 5-carboxyethylbicyclo[2.2.1]hept-2-ene, and the like;

carboxylic acid anhydrides such as anhydrides of the above unsaturated dicarboxylic acids excluding fumaric acid and mesaconic acid;

Unsaturated mono[(meth)acryloyloxyalkyl] of divalent or higher polyhydric carboxylic acids such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalate mono[2-(meth)acryloyloxyethyl] esters;

and unsaturated acrylates containing a hydroxyl group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the viewpoint of the copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

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

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (b2) (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), and the like.

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)"), alicyclic unsaturated and a monomer (b1-2) having a structure in which a hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Specifically as (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, Vinylbenzyl glycidyl ether, α-methylvinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyl Oxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene ) Styrene etc. are mentioned.

As (b1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclo Hexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) ) M100;(manufactured by Daicel Co., Ltd.), compounds represented by formula (BI) and compounds represented by formula (BII), and the like.

[Formula 46]

[In Formula (BI) and Formula (BII), ^Rb1 and ^Rb2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group do.

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

R ^b3 represents a C1-C6 alkanediyl group.

* represents a bonding hand with O.]

As a C1-C4 alkyl group of ^Rb1 and ^Rb2 , a methyl group, an ethyl group, etc. are mentioned.

A hydroxymethyl group, a hydroxyethyl group, etc. are mentioned as an alkyl group in which the hydrogen atom of ^{Rb1 and Rb2} was substituted by the hydroxyl group.

As ^Rb1 and ^Rb2 , a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms is preferable, more preferably a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, still more preferably A hydrogen atom and a methyl group are mentioned.

Examples of the alkanediyl group for R ^b3 include a linear or branched alkanediyl group, and specifically, a methylene group and an ethylene group.

As X ^b1 and X ^b2 , a single bond, *-R ^b3 -, or *-R ^b3 -O- is preferable, more preferably a single bond or *-R ^b3 -O-, still more preferably a single bond bonds, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, and particularly preferably single bonds, *-CH ₂ CH ₂ -O- (* is a bond with O). hand).

As a compound represented by formula (BI), the compound etc. represented by any of formula (BI-1) - formula (BI-15) are mentioned. Among them, Formula (BI-1), Formula (BI-3), Formula (BI-5), Formula (BI-7), Formula (BI-9), or Formula (BI-11) to Formula (BI-15) ) is preferable, and a compound represented by formula (BI-1), formula (BI-7), formula (BI-9) or formula (BI-15) is more preferable.

[Formula 47]

[Formula 48]

As a compound represented by Formula (BII), the compound etc. represented by any of Formula (BII-1) - Formula (BII-15) are mentioned. Among them, formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formula (BII-11) to formula (BII-15 ) is preferred, and compounds represented by formula (BII-1), formula (BII-7), formula (BII-9) or formula (BII-15) are more preferred.

[Formula 49]

[Formula 50]

The compound represented by formula (BI) and the compound represented by formula (BII) may be used independently, respectively, or may use 2 or more types together. When the compound represented by formula (BI) and the compound represented by formula (BII) are used together, the content ratio [compound represented by formula (BI):compound represented by formula (BII)] is preferably 5: It is 95 to 95:5, more preferably 20:80 to 80:20.

As said (b2), the monomer which has an oxetanyl group and (meth)acryloyloxy group is more preferable. As (b2), 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acrylo Iloxyethyl oxetane, 3-ethyl-3-(meth)acryloyloxyethyl oxetane, etc. are mentioned.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, tricyclo[5.2.1.0 ^{2, 6} ] Decan-8-yl (meth)acrylate (In the technical field, it is called "dicyclopentanyl (meth) acrylate" as a common name. Also, in the case of "tricyclodecyl (meth) acrylate" ), tricyclo[5.2.1.0 ^2,6 ]decan-9-yl(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate (the related art ), tricyclo[5.2.1.0 ^2,6 ]decen-9-yl(meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate. )Acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate (meth)acrylic acid esters such as acrylate and benzyl (meth)acrylate;

hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxy ratio Cyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -N, 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 -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-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy Cicarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxy bicyclounsaturated compounds such as ccarbonyl)bicyclo[2.2.1]hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl- dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide;

vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, and p-methoxystyrene; vinyl group-containing nitriles such as (meth)acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl group-containing amides such as (meth)acrylamide; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene; etc. can be mentioned.

Among these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and the like are preferable. do.

The reaction sequence is not limited, and monomer (a) and at least one of monomers (b) and (c) may be copolymerized at one time. In the case of using all of the monomers (a) to (c), the monomer (c) may be reacted after copolymerizing the monomer (a) and the monomer (b), or copolymerization of the monomer (a) and the monomer (c). After that, the monomer (b) may be reacted. Moreover, you may make a monomer (a) react with the copolymer of a monomer (b) and a monomer (c), and may further react with a carboxylic acid anhydride.

The polymerization initiator and solvent are not particularly limited, and those commonly used in the field can be used. For example, as a polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or organic peroxides (benzoyl peroxide, etc.) ) can be mentioned, and the solvent may be one that dissolves each monomer, and the solvent (E) described later as the solvent (E) of the colored curable resin composition of the present invention.

In addition, the obtained copolymer may use the solution after reaction as it is, may use a concentrated or diluted solution, or may use what was taken out as a solid (powder) by methods, such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during this polymerization, since the solution after the reaction can be used as it is for preparation of the colored curable resin composition of the present invention, the colored curable resin of the present invention The manufacturing process of the composition can be simplified.

Moreover, you may use a reaction catalyst (for example, tris (dimethylaminomethyl) phenol etc.) of carboxylic acid or a carboxylic acid anhydride and a cyclic ether, a polymerization inhibitor (for example, hydroquinone etc.), etc. as needed.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 - Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. are mentioned. The amount of carboxylic acid anhydride used is preferably 0.5 to 1 mole per 1 mole of (a).

Specifically as the resin (B), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/( copolymers having structural units derived from (a) and (b), such as meth)acrylic acid copolymers; 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 acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, etc. copolymers having structural units derived from (a), (b) and (c) of; copolymers having structural units derived from (a) and (c), such as benzyl (meth)acrylate/(meth)acrylic acid copolymers and styrene/(meth)acrylic acid copolymers; Resin obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate to tricyclodecyl(meth)acrylate/styrene/(meth)acrylic acid copolymer ) Acrylate-added resins, tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymers with glycidyl (meth)acrylate added, etc. derived from (a) a polymer having a structural unit in which (b) is added to the structural unit; A resin made by reacting (meth)acrylic acid with a copolymer of tricyclodecyl(meth)acrylate/glycidyl(meth)acrylate, tricyclodecyl(meth)acrylate/styrene/glycidyl(meth)acrylate polymers having a structural unit obtained by adding (a) to a structural unit derived from (b), such as a resin obtained by reacting (meth)acrylic acid with a copolymer; A structural unit derived from (b), such as a resin obtained by reacting a copolymer of tricyclodecyl(meth)acrylate/glycidyl(meth)acrylate with (meth)acrylic acid and further reacting with tetrahydrophthalic anhydride. and a copolymer having a structural unit derived from (c) and a structural unit in which (a) is added to and a carboxylic acid anhydride is added.

Especially, as resin (B), the copolymer which has structural units derived from (a) and (b), and the copolymer which has structural units derived from (a), (b) and (c) are preferable.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the color filter tends to have improved hardness, a high film remaining rate, good solubility in the developing solution of unexposed areas, and improved color pattern resolution.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of Resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

The solid dispersion value of Resin (B) is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150 mg-KOH/g, still more preferably 70 to 135 mg-KOH/g. Here, the solid dispersion 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, for example, by titrating with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass with respect to the total amount of solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and remaining film rate of the colored pattern tend to be improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (D), examples of which include compounds having polymerizable ethylenically unsaturated bonds, etc., preferably More specifically, it is a (meth)acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl compounds having one ethylenically unsaturated bond such as pyrrolidone and compounds exemplified as (Ba), (Bb) and (Bc) described above;

1,6-Hexanedioldi(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyl) of bisphenol A compounds having two ethylenically unsaturated bonds such as yloxyethyl) ether and 3-methylpentanediol di(meth)acrylate;

compounds having three ethylenically unsaturated bonds such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(2-(meth)acryloyloxyethyl) isocyanurate;

Ethylenically unsaturated bonds such as pentaerythritol tetra(meth)acrylate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, etc. A compound having 4;

compounds having 5 ethylenically unsaturated bonds such as dipentaerythritol penta(meth)acrylate;

dipentaerythritol hexa(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. compounds having 6 ethylenically unsaturated bonds;

having 7 or more ethylenically unsaturated bonds such as tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, and tetrapentaerythritol deca(meth)acrylate compound; etc. can be mentioned.

Especially, it is preferable that it is a polymeric compound which has 3 or more ethylenically unsaturated bonds, and, as for a polymeric compound (C), it is more preferable that it is a polymeric compound which has 5-6 ethylenically unsaturated bonds. Specifically, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable.

As a typical polymerizable compound (C) in the present invention, KAYARAD (registered trademark) DPHA (Nippon Kayak Co., Ltd.), A-TMM-3LM-N (Shin Nakamura Chemical Industry Co., Ltd.) and A9550 (Shin Nakamura Chemical Co., Ltd.) Industrial Co., Ltd.) and the like.

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.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass with respect to the total amount of solid content. When the content rate of the polymerizable compound (C) is within the above range, the remaining film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

The content ratio of the resin (B) and the polymerizable compound (C) [resin (B):polymerizable compound (C)] is preferably 20:80 to 80:20 on a mass basis, more preferably is 35:65 to 80:20.

<Polymerization initiator (D)>

The polymerization initiator (D) is a compound capable of initiating polymerization by generating active radicals under the action of light or heat. The colored curable resin composition of the present invention contains a compound represented by the following formula (d1) (hereinafter sometimes referred to as "compound (d1)") as a polymerization initiator.

[Formula 51]

[In formula (d1),

R ^d1 is an aromatic hydrocarbon group which may have a substituent of 6 to 18 carbon atoms, a heterocyclic group which may have a substituent of 3 to 36 carbon atoms, an alkyl group which may have a substituent of 1 to 15 carbon atoms, or a carbon number which may have a substituent represents an aralkyl group of 7 to 33, and the methylene group (-CH ₂ -) contained in the alkyl group or aralkyl group is -O-, -CO-, -S-, -SO ₂ - or -N(R ^d5 ) may be substituted with -.

R ^d2 represents an aromatic hydrocarbon group of 6 to 18 carbon atoms, a heterocyclic group of 3 to 36 carbon atoms, or an alkyl group of 1 to 10 carbon atoms.

R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.

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

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

The number of carbon atoms of the aromatic hydrocarbon group represented by ^Rd1 is preferably 6 to 15, more preferably 6 to 12, still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, more preferably a phenyl group and a naphthyl group, and particularly preferably a phenyl group.

Moreover, the aromatic hydrocarbon group represented by ^Rd1 may have 1 or 2 or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group, and more preferably at the γ-position. Examples of the substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, butadecyl, pentadecyl, etc. an alkyl group having 1 to 15 carbon atoms; Halogen atoms, such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; etc. can be mentioned.

It is preferable that it is 1-10, and, as for carbon number of the alkyl group as the said substituent, it is more preferable that it is 1-7. The alkyl group as the substituent may be either linear, branched or cyclic, or may be a combination of a chain and a cyclic group. The methylene group (-CH ₂ -) contained in the alkyl group as the substituent may be substituted with -O- or -S-. The hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, or a bromine atom, and is preferably substituted with a fluorine atom.

As an alkyl group as a substituent of the aromatic hydrocarbon group represented by ^Rd1 , the group etc. represented by the following formula are mentioned, for example. In the formula, * represents a bonding hand.

[Formula 52]

[Formula 53]

Examples of the aromatic hydrocarbon group which may have a substituent represented by ^Rd1 include a group represented by the following formula. In the formula, * represents a bonding hand.

[Formula 54]

[Formula 55]

As an aromatic hydrocarbon group which may have a substituent represented by ^Rd1 , a group represented by the following formula is preferable.

[Formula 56]

[Wherein, R ^d6 represents an alkyl group having 1 or more and 10 or less carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom. m2 represents an integer of 1 to 5.]

Examples of the alkyl group represented by ^Rd6 include the same groups as the alkyl groups exemplified as substituents of the aromatic hydrocarbon group represented by ^Rd1 . It is preferable that they are 2 or more and 7 or less, and, as for carbon number of the alkyl group represented by ^Rd6 , it is more preferable that they are 2 or more and 5 or less. In addition, the alkyl group represented by ^Rd6 may be linear, branched or cyclic, preferably a chain.

As a halogen atom which may substitute the hydrogen atom contained in ^Rd6 , a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom are mentioned, and fluorine is especially preferable. Moreover, it is preferable that 2 or more and 10 or less of the hydrogen atoms contained in R ^d6 are substituted with halogen atoms, and it is preferable that 3 or more and 6 or less are substituted with halogen atoms. The substitution position of the R ^d6 O- group is preferably an ortho position and a para position, and particularly preferably a para position.

Moreover, as for m2, it is preferable that it is 1-2, and it is especially preferable that it is 1.

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

Moreover, the heterocyclic group represented by ^Rd1 may have 1 or 2 or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent the aromatic hydrocarbon group represented by ^Rd1 may have.

It is preferable that the carbon number of the alkyl group represented by ^Rd1 is 1-12. Examples of the alkyl group represented by R ^d1 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, butadecyl group, and pentadecyl group. A decyl group etc. are mentioned. These alkyl groups may be linear, branched or cyclic, or may be a group in which a chain group and a cyclic group are combined. Further, in the alkyl group represented by R ^d1 , the methylene group (-CH ₂ -) may be substituted with -O-, -CO-, -S-, -SO ₂ - or -N(R ^d5 )-; The hydrogen atom may be substituted with an OH group or an SH group.

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

As an alkyl group which may have a substituent represented by ^Rd1 , the group etc. specifically represented by the following formula are mentioned. * represents a bonding hand.

[Formula 57]

The aralkyl group that may have a substituent represented by ^Rd1 is preferably a group obtained by combining the aromatic hydrocarbon group represented by ^Rd1 and a divalent group derived from the alkyl group represented by ^Rd1 . The number of carbon atoms in the aralkyl group is preferably 7 to 33, more preferably 7 to 18, still more preferably 7 to 12. The aralkyl group may have one or two or more substituents, and examples of the substituent include the same groups as those exemplified as the aromatic hydrocarbon group represented by ^Rd1 and the substituent the alkyl group represented by ^Rd1 may have. As a group combining the divalent group derived from the aromatic hydrocarbon group represented by ^Rd1 and the alkyl group represented by ^Rd1 , specifically, a group represented by the following formula is exemplified. In the formula, * represents a bonding hand.

[Formula 58]

As R ^d1 , an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a substituent is preferable, an aromatic hydrocarbon group which may have a substituent is more preferable, and a phenyl group which may have a substituent is more preferable. As substituents in the aromatic hydrocarbon group and the phenyl group, an alkoxy group having 4 to 9 carbon atoms, an alkoxy group having 4 to 9 carbon atoms having a halogen (preferably a fluorine atom), and 1 to 3 methylene groups are substituted with an ether bond An alkoxy group having 5 to 9 carbon atoms is preferred. It is preferable that all of these substituents have a branched structure.

The number of carbon atoms of the aromatic hydrocarbon group represented by ^Rd2 is preferably 6 to 15, more preferably 6 to 12, still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.

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

The number of carbon atoms in the alkyl group represented by R ^d2 is preferably 1 to 7, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. The alkyl group concerned may be either linear, branched or cyclic, or may be a group in which a chain-like group and a cyclic group are combined.

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

The number of carbon atoms of the aromatic hydrocarbon group represented by ^Rd3 is preferably 6 to 15, more preferably 6 to 12, still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, and a phenyl group and a naphthyl group are more preferable.

In addition, the aromatic hydrocarbon group represented by ^Rd3 may have one or two or more substituents. It is preferable that the substituent is substituted at the α-position or γ-position of the aromatic hydrocarbon group. As the substituent, an aliphatic hydrocarbon group having 1 to 15 carbon atoms is preferable. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a carbon number 1 such as a decyl group -15 alkyl groups; alkenyl groups having 1 to 15 carbon atoms, such as an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a nonenyl group, and a decenyl group; etc. can be mentioned.

As for carbon number of the aliphatic hydrocarbon group as the said substituent, it is more preferable that it is 1-7. Further, the aliphatic hydrocarbon group as the substituent may be either linear, branched or cyclic, or may be a combination of a chain and a cyclic group. In addition, in the aliphatic hydrocarbon group as the substituent, the methylene group (-CH ₂ -) may be substituted with -O-, -CO-, or -S-, and the methine group (-CH<) is -N< may be substituted.

Examples of the aliphatic hydrocarbon group as a substituent for the aromatic hydrocarbon group represented by ^Rd3 include groups represented by the following formula. In the formula, * represents a bonding hand.

[Formula 59]

As an aromatic hydrocarbon group which may have a substituent represented by ^Rd3 , the group etc. represented by the following formula are mentioned, for example. In the formula, * represents a bonding hand.

[Formula 60]

The number of carbon atoms of the heterocyclic group represented by R ^d3 is preferably 3 to 20, more preferably 3 to 10, still more preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.

The heterocyclic group represented by ^Rd3 may have one or two or more substituents, and examples of the substituent include the same groups as those exemplified as the substituents the aromatic hydrocarbon group represented by ^Rd1 may have.

As R ^d3 , an aromatic hydrocarbon group having a substituent is preferable, and a phenyl group having a substituent is more preferable.

As the substituent, a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms) is preferable, and the number of substituents is preferably 2 or more and 5 or less.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d4 is preferably 6 to 15, more preferably 6 to 12, still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, more preferably a phenyl group and a naphthyl group, and particularly preferably a phenyl group.

Moreover, the aromatic hydrocarbon group represented by ^Rd4 may have 1 or 2 or more substituents. Examples of the substituent include the same substituents that the aromatic hydrocarbon group represented by ^Rd1 may have.

The number of carbon atoms of the aliphatic hydrocarbon group represented by R ^d4 is preferably 1 to 13, more preferably 2 to 10, still more preferably 4 to 9. Examples of the aliphatic hydrocarbon group represented by R ^d4 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, and butadecyl group. , an alkyl group such as a pentadecyl group; Ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, butadecenyl group, pentadecenyl alkenyl groups such as groups; etc. can be mentioned. These aliphatic hydrocarbon groups may be chain (linear or branched) or cyclic, or may be a combination of chain and cyclic groups. In addition, in the aliphatic hydrocarbon group represented by R ^d4 , the methylene group (-CH ₂ -) may be substituted with -O-, -CO-, or -S-, and the methine group (-CH<) is -PO ₃ may be substituted with <. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.

Examples of the aliphatic hydrocarbon group which may have a substituent represented by R ^d4 include groups represented by the following formula. In the formula, * represents a bonding hand.

[Formula 61]

As R ^d4 , it is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group, still more preferably a branched chain alkyl group of 4 to 9 carbon atoms.

Examples of the compound (d1) include compounds (d1-1) to (d1-67) having substituents shown in Tables 3 to 9 below. In the table, * represents a binding hand.

Among them, compounds (d1-3) to (d1-6), (d1-18) to (d1-52), (d1-55), (d1-56), (d1-60), (d1-61) ) are preferred, more preferably compounds (d1-3) to (d1-6) and (d1-18) to (d1-41), still more preferably compounds (d1-24) and (d1-36) ) to (d1-40), particularly preferably compound (d1-40).

The content of the compound (d1) is preferably 30 parts by mass or more and 100 parts by mass or less, more preferably 50 parts by mass or more, still more preferably 80 parts by mass or more, based on 100 parts by mass of the polymerization initiator (D). More preferably, it is 90 mass parts or more.

Compound (d1) can be produced by the production method described in Japanese Patent Publication No. 2014-500852.

In addition, the polymerization initiator (D) may further contain polymerization initiators other than the compound (d1). These are not particularly limited, and known polymerization initiators can be used.

Examples of the polymerization initiator generating active radicals include O-acyloxime compounds other than the compound (d1), biimidazole compounds, alkylphenone compounds, triazine compounds, and acylphosphine oxide compounds.

The O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane- 1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl- 6-(2-methylbenzoyl)-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-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- yl] -3-cyclopentylpropan-1-one-2-imine, etc. are mentioned. You may use commercial items, such as Irgacure (trademark) OXE01, OXE02 (above, made by BASF Corporation), and N-1919 (made by ADEKA Corporation). Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine and N-acetyloxy-1-[4- At least one selected from the group consisting of {4-(2-hydroxyethoxy)phenyl}sulfanylphenyl]-propan-1-one-2-imine is preferred, and N-benzoyloxy-1-(4-phenyl) Sulfanylphenyl)octan-1-one-2-imine and N-acetyloxy-1-[4-{4-(2-hydroxyethoxy)phenyl}sulfanylphenyl]-propan-1-one-2- At least one selected from the group consisting of imines is more preferred. If it is these O-acyl oxime compounds, there exists a tendency for the color filter of high brightness to be obtained.

As a biimidazole compound, specifically, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'- tetraphenyl biimidazole, 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-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, Japanese Patent Publication No. 48-38403, Japanese Unexamined Patent Publication No. 62- 174204, etc.), an imidazole compound in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (for example, see Japanese Patent Laid-Open No. 7-10913, etc.) etc. can be mentioned.

Especially, the compound represented by Formula (d4) is preferable.

[Formula 63]

[In formula (d4), R ^d13 to ^{R d16} each independently represent a hydrogen atom or an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group). R ^d17 and R ^d18 each independently represent a hydrogen atom or a halogen atom (preferably a chlorine atom).]

The alkylphenone compound is a compound having a partial structure represented by formula (d5) or a partial structure represented by formula (d6). Among these partial structures, the benzene ring may have a substituent.

[Formula 65]

Examples of the compound having a partial structure represented by formula (d5) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl] Butan-1-one etc. are mentioned. You may use commercial items, such as Irgacure 369, 907, and 379 (above, BASF Corporation make).

Examples of the compound having a partial structure represented by formula (d6) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4-( Oligomer of 2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one , α,α-diethoxyacetophenone, benzyldimethylketal, and the like.

From the point of sensitivity, as an alkylphenone compound, the compound which has a partial structure represented by Formula (d5) is preferable.

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(trichloromethyl)-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, 2,4-bis(trichloro romethyl) -6- [2- (3,4-dimethoxy phenyl) ethenyl] -1,3,5-triazine; and the like.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. You may use commercial items, such as Irgacure (trademark) 819 (made by BASF Corporation).

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoylmethylbenzoate, 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; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly amines) described later.

Among them, when two or more polymerization initiators are used, a combination of a compound (d1) and a biimidazole compound, a combination of a compound (d1) and a biimidazole compound and a thiol compound described later, or a combination of a compound (d1) and an alkylphenone Combinations of compounds and the like are preferred.

The content of the polymerization initiator (D) is preferably 0.1 parts by mass or more, more preferably 3 parts by mass or more, and still more preferably based on 100 parts by mass in total of the resin (B) and the polymerizable compound (C). It is preferably 5 parts by mass or more and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 27 parts by mass or less, still more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less below the mass part. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is improved.

In addition, the content ratio of the polymerization initiator (D) and the polymerizable compound (C) (polymerization initiator (D)/polymerizable compound (C)) is preferably 1/1000 or more, and 4/1000 or more on a mass basis. More preferably, it is preferably 40/100 or less, and more preferably 35/100 or less. When the content ratio (polymerization initiator (D)/polymerizable compound (C)) is within the above range, a color filter having excellent lightness (brightness) can be obtained.

<Polymerization initiation aid (D1)>

The polymerization initiating aid (D1) is a compound or a sensitizer used to promote polymerization of a polymerizable compound whose polymerization is initiated by a polymerization initiator. When a polymerization initiation aid (D1) is included, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiating aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds.

Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; aminobenzoic acid esters such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 2-ethylhexyl 4-dimethylaminobenzoate; N,N-dimethylparatoluidine; Alkylamino such as 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone benzophenone; These etc. are mentioned, Among these, alkylamino benzophenone is preferable, and 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

Examples of the alkoxy anthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- Dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene, etc. are mentioned.

Examples of the thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxy. Citioxanthone etc. are mentioned.

As said carboxylic acid compound, phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chloro Phenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenyl glycine, phenoxy acetic acid, naphthyl thioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, etc. are mentioned.

As the polymerization initiation aid (D1), a thioxanthone compound is preferable.

When using these polymerization initiation aids (D1), the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). is the mass part. In the case of using the polymerization initiation aid (D1), the content thereof is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, and still more preferably 100 parts by mass of the total amount of the polymerization initiator (D). It is preferably 15 to 55 parts by mass. When the amount of the polymerization initiating aid (D1) is within this range, it is possible to form a colored pattern with higher sensitivity and the productivity of the color filter tends to be improved.

<Thiol compound (T)>

It is preferable that the colored curable resin composition of this invention further contains a thiol compound (T).

The thiol compound (T) is a compound having a sulfanyl group (-SH) in the molecule.

Examples of the compound having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, and 2-sulfanylbenzo Oxazole, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine , 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6 -Hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine, 4,6-dihydroxy-2-sul Panylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2 -Sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2 - Thiol, 2-sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino- 5-sulfanyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3- Thiol, 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3,4- Thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl)methanethiol, 2-sulfanyl-5-thiazolidone, 2-sulfanyl Thiazoline, 2-sulfanyl-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2-sulfur Panyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro- 2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyrazolo[ 2,4-d] pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo[2,4-d]pyrimidine, and the like.

Examples of the compound having two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediolbis(3-sulfanylpropionate), butanediolbis(3-sulfanyl) Panyl Acetate), Ethylene Glycol Bis (3-Sulfanyl Acetate), Trimethylol Propane Tris (3-Sulfanyl Acetate), Butanediol Bis (3-Sulfanyl Propionate), Trimethylol Propane Tris (3-Sulfanyl Propio nate), trimethylolpropanetris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl tris (3-sulfanyl acetate) panylpropionate), pentaerythritol tetrakis(3-sulfanylbutyrate), 1,4-bis(3-sulfanylbutyloxy)butane, and the like.

As the thiol compound (T), a compound having one sulfanyl group in the molecule is preferable, and 2-sulfanylbenzthiazole is particularly preferable.

The content of the thiol compound (T) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is within this range, the sensitivity tends to increase and the developability tends to improve.

<Solvent (E)>

It is preferable that the colored curable resin composition of the present invention further contains a solvent (E).

The solvent (E) is not particularly limited, and solvents commonly used in the field can be used. For example, ester solvents (solvents that contain -COO- in the molecule and do not contain -O-), ether solvents (solvents that contain -O- and do not contain -COO- in the molecule), ether esters Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not -COO- in the molecule), alcohol solvents (containing OH in the molecule, - solvents that do not contain O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

As the 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, diethylene glycol monobutyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methylanisole etc. can be mentioned.

As the ether ester solvent, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-ethoxyethylpropionate, 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropylpropionate, 2-ethoxymethylpropionate, 2-ethoxyethylpropionate, 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 mono propyl 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, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, di Acetone alcohol, cyclopentanone, cyclohexanone, isophorone, etc. are mentioned.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

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

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

Among the above solvents, organic solvents having a boiling point of 120°C or more and 180°C or less at 1 atm are preferable from the viewpoint of coating properties and drying properties. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionate ethyl, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diacetone alcohol and 3-ethoxypropionic acid Ethyl is more preferred.

The content rate of the solvent (E) is preferably 35 to 95% by mass, more preferably 40 to 92% by mass with respect to the total amount of the colored curable resin composition of the present invention. In other words, the total amount of solid content of the colored curable resin composition is preferably 5 to 65% by mass, more preferably 8 to 60% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of application becomes good, and the display characteristics tend to be good because the color density is not insufficient when the color filter is formed.

<Leveling agent (F)>

The colored curable resin composition of the present invention may also contain a leveling agent (F).

As a leveling agent (F), a silicone type surfactant, a fluorochemical surfactant, etc. are mentioned. These may have a polymeric group in a side chain.

Examples of silicone surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Joint Stock Company) ) and the like.

As said fluorochemical surfactant, surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Florad (registered trademark) FC430, the same FC431 (made by Sumitomo Sieem Co., Ltd.), Megapack (registered trademark) F142D, the same F171, the same F172, the same F173, the same F177, the same F183, the same F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, same EF303, same EF351, same EF352 (manufactured by Mitsubishi Material Electron Chemical Co., Ltd.), Suffron (registered trademark) ) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute).

As a silicone type surfactant, the silicone type surfactant which has said fluorine atom is mentioned further. Examples of silicone surfactants having a fluorine atom include Megapack (registered trademark) R08, Copper BL20, Copper F475, Copper F477 and Copper F443 (manufactured by DIC Corporation).

The content rate of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass, with respect to the total amount of the colored curable resin composition. It is more than 0.05 mass % or less. In addition, the content rate of the said pigment dispersant is not included in this content rate. When the content rate of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

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

<Method for producing colored curable resin composition>

The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and optionally a solvent (E), a leveling agent ( It can be prepared by mixing F), polymerization initiation aid (D1), thiol compound (T), and other components.

When using the pigment (A2), it is preferable to mix it with part or all of the solvent (E) in advance and disperse it using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. At this time, you may mix|blend a part or all of the said pigment dispersant and resin (B) as needed. The target colored curable resin composition can be prepared by mixing the remaining components with the pigment dispersion obtained in this way so as to have a predetermined concentration.

The dye (A1) may be dissolved in part or all of the solvent (E) beforehand to prepare a solution. It is preferable to filter the said solution with the filter of about 0.01-1 micrometer of pore size.

It is preferable to filter the colored curable resin composition after mixing with a filter having a hole diameter of about 0.01 to 10 μm.

<Method of manufacturing color filter and liquid crystal display device>

As a method of forming a color filter with the colored curable resin composition of the present invention, a photolithography method, a method using an inkjet machine, and the like are exemplified. In the photolithography method, for example, the colored curable resin composition of the present invention is applied onto a substrate, and volatile components such as a solvent are removed and dried to form a colored composition layer, and the colored composition layer is formed through a photomask. It is a method of exposing and developing a layer. After development, a colored pattern can be formed by heating as needed. In the method for forming the colored pattern, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask at the time of exposure and/or not developing. The color pattern and color coating film obtained in this way can be used as a color filter.

As the substrate, a glass plate, a resin plate, silicon, or a substrate in which aluminum, silver, or a silver/copper/palladium alloy thin film or the like is formed is used. On these substrates, other color filter layers, resin layers, transistors, circuits and the like may be formed.

The film thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted depending on the intended use and the like, and is, for example, 0.1 to 30 µm, preferably 1 to 20 µm, and more preferably 1 to 6 µm. am.

Formation of each color pixel by the photolithography method can be performed using known or common equipment and conditions. For example, it is producible as follows.

First, a colored curable resin composition is applied on a substrate, dried by heating (prebaking) and/or reduced pressure drying to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer.

Examples of the coating method include spin coating, slit coating, and slit and spin coating.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper because it is possible to uniformly irradiate the entire exposure surface with parallel light rays and perform accurate alignment of the photomask and the substrate on which the coloring composition layer is formed.

A colored pattern is formed on the substrate by developing the colored composition layer after exposure in contact with a developing solution. By developing, the unexposed part of the coloring composition layer dissolves in a developing solution and is removed. As a developing solution, the aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, is preferable, for example.

The developing method may be any of a puddle method, a dipping method, and a spray method. Further, the substrate may be tilted at an arbitrary angle during development.

After image development, it is preferable to wash with water.

Moreover, it is preferable to post-bake the obtained coloring pattern.

ADVANTAGE OF THE INVENTION According to the colored curable resin composition of this invention, the color filter especially excellent in pattern shape can be produced. The color filter is useful as a color filter used for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is, of course, not limited by the following examples, and it is also possible to add and implement appropriate changes within the range that can be suitable for the purpose of the foregoing and later. Of course, it is possible, and they are all included in the technical scope of the present invention. In addition, in the following, "part" means "mass part" and "%" means "mass %" unless otherwise indicated.

[Synthesis Example 1]

In a flask equipped with a cooling tube and a stirring device, 15 parts of a mixture of the compound represented by the formula (A0-1) and the compound represented by the formula (A0-2) (trade name Chugai Aminol Fast Pink R; manufactured by Chugai Chemicals) were mixed with 150 parts of chloroform. And 8.9 parts of N,N-dimethylformamide were introduced, and 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature at 20°C or less under stirring. After completion of the dropwise addition, the temperature was raised to 50°C, maintained at the same temperature for 5 hours for reaction, and then cooled to 20°C. A liquid mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise to the reaction solution while maintaining the cooled reaction solution at 20°C or less under stirring. Then, it was stirred and reacted at the same temperature for 5 hours. Subsequently, after solvent-distilling the obtained reaction mixture with a rotary evaporator, a small amount of methanol was added to the solvent-distilled reaction mixture, followed by vigorous stirring. The obtained mixture was added while stirring to a liquid mixture of 375 parts of ion-exchanged water to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60°C to obtain dye (Aa-1) (a mixture of compounds represented by formulas (A1-1) to (A1-8)) 11.3 got rich

[Formula 66]

[Formula 67]

[Synthesis Example 2]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was flowed at 0.02 L/min to create a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were placed and stirred. It was heated to 70°C. Then, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate (molar ratio of the compound represented by formula (BI-1) and the compound represented by formula (BII-1) , A mixture of 50:50.) 240 parts by mass was dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the dissolved solution was poured into a flask kept at 70°C for 4 hours using a dropping funnel. Dropped. On the other hand, a solution in which 30 parts by mass of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of 3-methoxybutyl acetate was added dropwise into the flask over 4 hours using another dropping funnel. . After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 70° C. for 4 hours, and then cooled to room temperature to obtain a solution of Resin B′1 having a solid content of 32.6 mass% and an acid value of 110 mg-KOH/g (solid content conversion). Got it. The weight average molecular weight Mw of obtained resin Aa was 13,400, and molecular weight distribution was 2.50.

[Formula 68]

Measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin obtained in the Synthesis Example was performed under the following conditions using the GPC method.

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

column temperature; 40℃

menstruum; Tetrahydrofuran (THF)

flow rate; 1.0mL/min

detector; RI

calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-228, A-2500, A-500 (manufactured by Tosoh Corporation)

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

Examples 1 to 6, Comparative Examples 1 to 5

[Preparation of colored curable resin composition]

Each component was mixed so that it might become the composition shown in Table 10, and the colored curable resin composition was obtained.

In Table 10, "P1-1" was mixed with the acrylic pigment dispersant and propylene glycol monomethyl ether acetate in the amount described in "E-1 (Note 2)", and used what was previously dispersed.

The column "E-1 (note 1)" shows the total content of propylene glycol monomethyl ether acetate including (note 2).

Colorant (A): Aa-1: Dye (Aa-1)

Colorant (A): P1-1:C.I. Pigment Blue 15:6 (pigment) Resin (B): Resin B'1 (solid content conversion)

Polymerizable compound (C): C-1: KAYARAD (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd.)

Polymerizable compound (C): C-2: NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

Polymerizable compound (C): C-3: NK ester A-9550 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

Polymerization initiator (D): D-1: compound represented by formula (d1-40)

[Formula 69]

Polymerization initiator (D): D-2: 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime) (trade name Irgacure OXE01, Ciba Specialty Chemicals) Priests)

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

Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.)

According to the method described in Japanese Patent Publication No. 2014-500852, a compound represented by the formula (d1-40) was prepared.

[Formation of coating 1]

A 2-inch square glass substrate (Eagle XG; manufactured by Corning Co., Ltd.) was sequentially washed with neutral detergent, water and alcohol, and then dried. On this glass substrate, each of the colored curable resin compositions of Examples 1 and 2 and Comparative Example 1 obtained above was spin-coated so that the film thickness after post-baking was 3.0 µm, and then in a clean oven at 190°C. Prebaked for 3 minutes. Then, it heated at 230 degreeC for 20 minutes, and obtained the coating film.

[Formation of coating film 2]

A 2-inch square glass substrate (Eagle XG; manufactured by Corning Co., Ltd.) was sequentially washed with neutral detergent, water and alcohol, and then dried. On this glass substrate, the colored curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 6 obtained above were spin-coated so that the film thickness after post-baking was 2.5 μm, and then in a clean oven, 190 It prebaked at °C for 3 minutes. Then, it heated at 230 degreeC for 20 minutes, and obtained the coating film.

[Pattern production 1]

On a 2-inch square glass substrate (Eagle 2000; manufactured by Corning), the colored curable resin compositions of Examples 1 and 2 and Comparative Example 1 were applied by spin coating so that the film thickness after post-baking was 2.0 μm, respectively. After coating, it was prebaked at 100°C for 3 minutes to form a composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) with an interval of 80 μm between the substrate on which the composition layer was formed and the quartz glass photomask, an exposure amount of 40 mJ / cm 2 (365 nm) standard) was irradiated with light. Moreover, as a photomask, the one in which the line-and-space pattern of 50 micrometers was formed was used. The composition layer after light irradiation was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25°C for 60 seconds, developed, washed with water, and then post-baked at 230°C for 20 minutes in an oven, got a pattern About the obtained pattern, as a result of measuring the film thickness using the film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), it was confirmed that it was 2.0 micrometers.

[Pattern production 2]

On a 2-inch square glass substrate (Eagle 2000; manufactured by Corning), the colored curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 6 were spin-coated so that the film thickness after post-baking was 2.5 µm. After applying by the method, it prebaked at 100 degreeC for 3 minutes, and formed the composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) with an interval of 80 μm between the substrate on which the composition layer was formed and the quartz glass photomask, an exposure amount of 40 mJ / cm 2 (365 nm) standard) was irradiated with light. Moreover, as a photomask, the one in which the line-and-space pattern of 50 micrometers was formed was used. The composition layer after light irradiation was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25°C for 60 seconds, developed, washed with water, and then post-baked at 230°C for 20 minutes in an oven, got a pattern About the obtained pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

[Evaluation of colored pattern shape 1]

For the colored patterns of Examples 1 and 2 and Comparative Example 1 obtained in Pattern Production 1, the shapes were observed using a scanning electron microscope (S-4000; manufactured by Hitachi High-Technologies, magnification: 10000 times). In FIG. 1, when it is the shape (○) shown by (p1), when an inorganic film is laminated|stacked on a colored pattern, there exists a tendency for cracks and peeling to occur in an inorganic film less easily. The results are shown in Table 11.

[Evaluation of colored pattern shape 2]

For the colored patterns obtained from the respective compositions of Examples 1 to 7 and Comparative Examples 1 to 6 obtained in Pattern Production 2, a scanning electron microscope (S-4000; manufactured by Hitachi High Technologies Co., Ltd., magnification: 10000 times) was used to observe the shape. In FIG. 2 , in the shape (◯) shown in (p3), when the inorganic film is laminated on the colored pattern, there is a tendency that cracks or peeling are less likely to occur in the inorganic film. The results are shown in Table 12.

<Chromaticity Evaluation>

For the color pattern obtained by each composition of Examples 5 to 7, spectroscopy was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the CIE XYZ color system was obtained using the characteristic function of the C light source. The xy chromaticity coordinates (x, y) and the tristimulus value Y in were measured. The higher the value of Y, the higher the brightness. The results are shown in Table 12.

From said results, it was confirmed that the pattern formed with the colored curable resin composition of this invention was excellent in pattern shape. From this, it turns out that according to this invention, the colored curable resin composition which can manufacture the display apparatus excellent in display characteristics was able to be provided.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the colored curable resin composition which can form a favorable colored pattern.

Patterns and coating films obtained from the colored curable resin composition of the present invention are transparent films, patterns, photo spacers, overcoats, insulating films, projections for controlling liquid crystal alignment, microlenses, coating layers, etc. constituting a part of a color filter substrate and/or an array substrate. Color filter substrates, array substrates, etc., which are useful as a component and have these coating films or patterns as part of their constituent parts, and display devices equipped with these color filter substrates and/or array substrates, for example, liquid crystal display devices; It can be suitably used for organic EL devices, electronic paper, and the like.

Claims (7)

containing a colorant, a resin, a polymerizable compound and a polymerization initiator;
As the colorant, dyes and pigments are included,
As the dye, at least one dye selected from the group consisting of xanthene dyes, triarylmethane dyes, compounds represented by Formula (Ab2), and coumarin dyes is included,
As the pigment, including a phthalocyanine pigment,
The content ratio (dye:pigment) of the dye and the pigment is 5:95 to 70:30 on a mass basis,
A colored curable resin composition containing a compound represented by the following formula (d1) as the polymerization initiator.

[In formula (Ab2), R ⁴¹ to ^{R 44} are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent In the saturated hydrocarbon group having 7 to 30 aralkyl groups and having 1 to 20 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with substituted or unsubstituted amino groups or halogen atoms, and the number of carbon atoms in the saturated hydrocarbon group is In the case of 2 to 20, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. R ⁴¹ and R ⁴² may be bonded together to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded together with the nitrogen atom to which they are bonded to form a ring.
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 when the alkyl group has 2 to 8 carbon atoms, the methylene group constituting the alkyl group is It may be substituted with an oxygen atom or -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or SO ₂ -.
Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms which may have a substituent.
[Y] ^m- represents an arbitrary m-valent anion.
m represents any natural number.]

[In formula (d1),
R ^d1 is an aromatic hydrocarbon group which may have a substituent of 6 to 18 carbon atoms, a heterocyclic group which may have a substituent of 3 to 36 carbon atoms, an alkyl group which may have a substituent of 1 to 15 carbon atoms, or a carbon number which may have a substituent represents an aralkyl group of 7 to 33, and the methylene group (-CH ₂ -) contained in the alkyl group or aralkyl group is -O-, -CO-, -S-, -SO ₂ - or -N(R ^d5 ) may be substituted with -.
R ^d2 represents an aromatic hydrocarbon group of 6 to 18 carbon atoms, a heterocyclic group of 3 to 36 carbon atoms, or an alkyl group of 1 to 10 carbon atoms.
R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.
R ^d4 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, and the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group is It may be substituted with -O-, -CO-, or -S-, and the methine group (-CH<) contained in the aliphatic hydrocarbon group may be substituted with -PO ₃ <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
R ^d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (-CH ₂ -) contained in the alkyl group may be substituted with -O- or -CO-.] delete delete According to claim 1,
The colored curable resin composition whose content rate of a pigment is 1 mass % or more and 50 mass % or less with respect to the total amount of solid content. According to claim 1,
A colored curable resin composition in which the content ratio of the polymerization initiator to the polymerizable compound (polymerization initiator/polymerizable compound) is 4/1000 or more and 35/100 or less on a mass basis. A color filter formed from the colored curable resin composition according to any one of claims 1, 4 and 5. A liquid crystal display device comprising the color filter according to claim 6.

Images