KR20160117271A - Olored curable resin composition - Google Patents

Abstract

The present invention relates to a color filter having an excellent pattern shape. A colored curable resin composition of the present invention comprises: a coloring agent; a resin; a polymerizable compound; and a polymerization initiator, wherein the coloring agent comprises a dye and the content of the dye is 90 parts by weight or more with respect to 100 parts by weight of the coloring agent. In addition, the polymerization initiator comprises a compound represented by chemical formula (d1).

Description

OLEDED CURABLE RESIN COMPOSITION [0001]

The present invention relates to a colored curable resin composition.

The colored curable resin composition is used for the production of a color filter used in a display device such as a liquid crystal display device, an electroluminescence display device, and a plasma display. Patent Document 1 discloses a photosensitive coloring composition comprising a salt-forming compound comprising a triarylmethane-based basic dye and a counter compound, and an oxime ester-based photopolymerization initiator (Patent Document 1).

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

Japanese Laid-Open Patent Publication No. 2014-170098 Japanese Patent Publication No. 2014-500852

Conventionally known photosensitive color compositions are not sufficiently satisfactory in the obtained color pattern, that is, the shape of the color filter. Accordingly, an object of the present invention is to obtain a color filter having an excellent pattern shape.

However, Patent Document 2 teaches the use of oxime ester derivatives of benzocarbazole compounds as photoinitiators in photopolymerizable compositions, but no change in pattern shape when the composition contains a colorant has not been taught at all.

The present invention includes the following inventions.

[1] A colorant comprising a colorant, a resin, a polymerizable compound and a polymerization initiator,

And a dye as the coloring agent,

The content of the dye is 90 parts by mass or more in 100 parts by mass of the colorant,

Wherein the polymerization initiator comprises a compound represented by the following formula (d1).

[Chemical Formula 1]

[In the formula (d1)

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

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

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 -) included in the aliphatic hydrocarbon group is -O -, -CO- or -S-, the methine group (-CH <) included in the aliphatic hydrocarbon group may be substituted with -PO ₃ <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be replaced 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 coloring agent does not contain a pigment.

[3] The dyeing composition according to [1] or [2], wherein the dye is selected from the group consisting of xanthene dyes, triarylmethane dyes, compounds represented by formula (Ab2), coumarin dyes, anthraquinone dyes, and tetraazaporphyrin dyes And at least one kind of dye selected from the group consisting of dyes.

(2)

(In the formula (Ab2), each of R ⁴¹ to R ⁴⁴ independently represents 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, A saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom 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 is 2 to 20 , The methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the terminal methylene group is not substituted with an oxygen atom or -CO-. R ⁴¹ and R ⁴² may bond to form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may bond to form a ring together with the nitrogen atom to which they are attached.

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 an oxygen atom Or -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or -SO ₂ -. However, adjacent methylene groups in the alkyl group are not simultaneously substituted with oxygen atoms, and the terminal methylene group is not substituted with an oxygen atom or -CO-.

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

[Y] ^m- represents an anion of any m-valence.

[4] A colored curable resin composition according to any one of [1] to [3], which comprises a xanthene dye as the dye and a compound represented by the formula (Ab2).

[5] A color filter formed from the colored curable resin composition according to any one of [1] to [4].

[6] A liquid crystal display device comprising a color filter according to [5].

According to the colored curable resin composition of the present invention, a color filter excellent in shape can be formed.

1 is a schematic view for explaining a cross-sectional shape of a colored pattern.

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

The compounds exemplified as the respective components in the present specification may be used alone or in combination of several kinds unless otherwise specified.

&Lt; Colorant (A) >

In the colored curable resin composition of the present invention, a dye is included as the colorant (A).

Examples of the dyes include compounds classified in the color index (published by The Society of Dyers and Colourists) as having a color other than pigment, and known dyes described in dyeing notes (color dyeing). According to the chemical structure, it is also possible to use 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. Among them, it is preferable to be dissolved in an organic solvent.

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, 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, 112, 122, 128, 132, 136, 139;

C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33; 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, 112, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 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; C.I. Acid dyes,

C.I. Basic Green 1; C.I. Basic dyes,

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

C.I. Reactive Orange 16; 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, 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; C.I. Direct dyes,

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

C.I. Disperse Violet 26, 27;

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

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

C.I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; C.I. Modern dyes,

C.I. C.I. Vat dyes and the like.

Among them, the dyes are preferably selected from the group consisting of xanthene dyes (Aa), triarylmethane dyes (Ab), compounds represented by the formula (Ab2), coumarin dyes (Ac), anthraquinone dyes (Ad), and tetraazaporphyrin dyes (Ae) (Hereinafter sometimes referred to as "dye (A1)"), and at least one kind of dye selected from the group consisting of xanthine dyes (Aa), triarylmethane dyes (Ab) Ab2), more preferably at least one dye selected from the group consisting of a xanthene dye (Aa), a triarylmethane dye (Ab) or a compound represented by the formula (Ab2) , And it is particularly preferable to include a xanthene dye and a compound represented by the formula (Ab2).

In this specification, a dye means a dye which is soluble in a solvent.

The xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in its molecule. Examples of the xanthene dyes (Aa) include C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red is omitted and only the numbers are described, and the other is the same), C.I. 52, 87, 92, 94, 289, Acid Red Dyes; C.I. Acid violet 9, 30, 102, etc. C.I. Acid Violet Dyes; C.I. Basic Red 1 (Rhodamine 6G), 2,3, 4,8, 10 (Rhodamine B), 11, etc. C.I. Basic red dyes; C.I. Basic violet 10, 11, 25, etc. C.I. Basic violet dyes; C.I. C.I. Solvent red dyes; C.I. C.I. Modern tread dyes; C.I. Reactive Red 36 (Rose Bengal B). Reactive red dyes; Sulfoladamin G; Xanthene dyes described in JP-A-2010-32999; And the xanthene dyes described in Japanese Patent Publication No. 4492760; And the like. The xanthene dye (Aa) is preferably dissolved in an organic solvent.

Among them, the xanthene dye (Aa) is preferably a dye containing a compound represented by the formula (1a) (hereinafter occasionally referred to as "compound (1a)"). The compound (1a) may be a tautomer thereof. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye (Aa) is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more. It is particularly preferable to use only the compound (1a) as the xanthene dye (Aa).

(3)

[In the formula (1a), R ¹ to R ⁴ independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon having 6 to 10 carbon atoms which may have a substituent And the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be substituted with -O-, -CO-, or -NR ¹¹ -. R ¹ and R ² may be taken together to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be taken together to form a ring containing a nitrogen atom.

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

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

m represents an integer of 0 to 5; When m is 2 or more, plural 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 four R ^{11 s} may be the same or different.

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

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

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

When -SO ₃ ^- is present in the formula (1a), 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 mesyl group, a propylphenyl group and a butylphenyl group.

As the substituent which may have aromatic hydrocarbon groups wherein the halogen ^{atoms, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ , and it is preferable that such a substituent substitutes a hydrogen atom contained in an aromatic hydrocarbon group. Among these, as the substituent is _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z +, -SO 3 R 8 and -SO ₂ NR ⁹ R ¹⁰ are preferred, and -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R &lt; ¹⁰ &gt; is more preferable. In this case, -SO ₃ ^- Z ⁺ is preferably -SO ₃ ^{- +} N (R ¹¹ ) ₄ . And -SO ₂ NR ⁹ R ¹⁰ is preferably -SO ₂ NHR ⁹ . When R ¹ to R ⁴ are these groups, a colored filter having less occurrence of foreign matter and excellent in heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (1a).

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

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 or a halogen atom having 6 to 10 carbon atoms as a substituent. R include ¹ ~ R ⁴ can be substituted with a hydrogen atom from a saturated hydrocarbon group having 6 to 10 of the aromatic hydrocarbon group R ¹ ~ R ⁴ the same group a group exemplified as the aromatic hydrocarbon group having 6 to 10 in which the have.

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 R ¹ and R ² together and the ring formed by R ³ and R ⁴ together include the following, and more preferably, no double bond.

[Chemical Formula 4]

Examples of -OR ⁸ include alkyloxyl such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and icosyloxy Time and so on.

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

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

Examples of -SO ₂ R ⁸ include alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and icosylsulfonyl groups.

Examples of -SO ₃ R ⁸ include alkyloxonylphenyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butyloxycarbonyl group, a hexyloxyl group, And the like. R ⁸ of R ⁸ -SO ₃ roneun a branched chain alkyl group having 3 to 20 carbon atoms are preferred, the branched chain alkyl group having a carbon number of 6-12, and more preferably, is more preferably a 2-ethylhexyl group. It is possible to form a color filter with less generation of foreign matter.

Group -SO ₂ NR ⁹ R ¹⁰ as for example a sulfamoyl;

N-ethylsulfamoyl group, N-ethylsulfamoyl group, N-ethylsulfamoyl group, N-isopropylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N- isobutylsulfamoyl group, N-sec- (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, (2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, an N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) An N-1 substituted sulfamoyl group such as a sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group and N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;

An N, N-dimethylsulfamoyl group, an N, N-dimethylsulfamoyl group, an N, N-ethylmethylsulfamoyl group, N, N-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group and the like.

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

Roneun 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 preferred, -SO ₃ ^-, -SO ₃ ^- is Z ^+, -SO ₃ H or -SO ₂ NHR ⁹ is more preferable.

m is preferably 1 to 4, more preferably 1 or 2.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include those having 1 to 6 carbon atoms in the alkyl groups listed above. Among them, R ⁶ and R ⁷ are preferably hydrogen atoms.

Examples of the aralkyl group having 7 to 10 carbon atoms for R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

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

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

The N ⁺ (R ¹¹⁾ ₄ roneun four of R ^11, at least two of the monovalent saturated hydrocarbon group having a carbon number of 5-20 is preferable. The total carbon number of four R &lt; ¹¹ &gt; is preferably 20 to 80, more preferably 20 to 60. [ In the case where ⁺ N (R ¹¹ ) ₄ exists in the compound (1a), when R ¹¹ is such a group, a color filter having few foreign matters can be formed from the colored curable resin composition containing the compound (1a).

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

A combination of R ¹ ~ R ⁴ are also preferably R ¹ ~ R ⁴ are both monovalent saturated hydrocarbon group in combination. In this case, the saturated hydrocarbon group is preferably a methyl group or an ethyl group.

Also, as a combination of R ¹ to R ⁴ , it is preferable that R ¹ and R ³ are a saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ² and R ⁴ are a phenyl group which may have a substituent.

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 .

The number of carbon atoms of R ¹ and R ³ is preferably independently from 1 to 3. As the substituent of 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.

The substituent that the phenyl group of R ² and R ⁴ may have is preferably an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms More preferred is a methyl group. The number of substituents replacing the phenyl group of R ² and R ⁴ is 0 to 5, preferably 0 to 2, more preferably 0 or 1.

Examples of the alkyl group having 1 to 4 carbon atoms which may substitute the phenyl group of R ² and R ⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, .

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms for substituting the phenyl group of R ² and R ⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group and an isopropylsulfanyl group.

Furthermore, examples of the alkylsulfonyl group having 1 to 4 carbon atoms which may substitute the phenyl group of R ² and R ⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.

Examples of the compound (1a) include compounds represented by the formulas (1-1) to (1-43). In the formulas, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, more preferably a 2-ethylhexyl group.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

Further, in the formula (Ab2) to be described later, a compound in which R &lt; ⁴⁸ &gt; and R &lt; ⁵² &gt; bind to each other to form -O- can also be referred to as xanthene dye (Aa).

Among these, C.I. Sulfonamides of Acid Red 289, C.I. Quaternary ammonium salts of Acid Red 289, C.I. Sulfonamides of Acid Violet 102 or C.I. Quaternary ammonium salts of Acid Violet 102 are preferred. Examples of such a compound include compounds represented by formulas (1-1) to (1-8), (1-11), and (1-12).

The compounds represented by any one of formulas (1-24) to (1-33) are also preferable in that they are excellent in solubility in an organic solvent.

The xanthan dyes (Aa) are commercially available xanthene dyes (for example, " Chugai Aminol Fast Pink RH / C ", manufactured by Dai-Ichi Kagaku Kogyo Co., Ltd., "Rhodamin 6G & Can be used. It is also possible to synthesize a commercially available xanthene dye as a starting material by referring to Japanese Laid-Open Patent Publication No. 2010-32999.

When the xanthene dye (Aa) is contained, the content thereof is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, particularly preferably 18 parts by mass or more, Preferably not more than 50 parts by mass, more preferably not more than 40 parts by mass, and even more preferably not more than 35 parts by mass.

A triarylmethane dye (Ab) is a dye comprising a compound having a structure in which three aromatic groups are bonded to one carbon atom. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the triarylmethane dye (Ab) include C.I. Solvent Blue 2, 4, 5, 43, 124; C.I. Basic Violet 3, 14, 25; C.I. Basic Blue 1, 5, 7, 11, 26, and triarylmethane dyes described in Japanese Patent Publication No. 4492760, and the like. It is preferable that it is dissolved in an organic solvent.

Among them, the triarylmethane dye (Ab) preferably contains a compound represented by the formula (Ab1) (hereinafter sometimes referred to as a "compound (Ab1)").

[Chemical Formula 13]

[In formula (Ab1), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or a saturated hydrocarbon group having 1 to 20 carbon atoms, and when the number of carbon atoms in the saturated hydrocarbon group is 2 to 20 , The methylene group constituting the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the terminal methylene group is not substituted with an oxygen atom or -CO-.

R ^9A to R ^12A each independently represent 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 and may have a substituent, The hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and when the number of carbon atoms in the saturated hydrocarbon group is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be an oxygen atom or -CO- . &Lt; / RTI &gt; However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the terminal methylene group is not substituted with an oxygen atom or -CO-. R ^9A and R ^10A may form a ring together with the nitrogen atom to which they are bonded, and R ^11A and R ^12A may bond to form a ring together with the nitrogen atom to which they are attached.

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

[G] ^g- represents an anion of any g-valence. g represents 0 or any natural number.]

When a plurality of cations represented by the following formulas are contained in one molecule in the formula (Ab1), they may have the same structure or different structures.

[Chemical Formula 14]

^Wherein A and R ^1A to R ^12A each have the same meaning as defined above.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^1A to R ^12A may be any of straight chain, branched chain and cyclic, and is preferably chain-like. The saturated hydrocarbon group of R ^1A to R ^12A preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Examples of the linear or branched saturated hydrocarbon group (alkyl group) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group and a decyl group. The number of carbon atoms of the chain saturated hydrocarbon group (alkyl group) is preferably 1 to 10, more preferably 1 to 8, and still more preferably 1 to 6.

The cyclic saturated hydrocarbon group (alicyclic saturated hydrocarbon group) represented by R ^1A to R ^12A may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group (alicyclic saturated hydrocarbon group) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and an adamantyl group. The number of carbon atoms of the cyclic saturated hydrocarbon group (alicyclic saturated hydrocarbon group) is preferably 3 to 10 carbon atoms, more preferably 6 to 10 carbon atoms.

Specific examples of the saturated hydrocarbon group represented by R ^1A to R ^12A include groups represented by the following formulas. In the following formulas, * represents a bonding position.

[Chemical Formula 15]

When the number of carbon atoms of the saturated hydrocarbon group represented by R ^1A to R ^12A is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-, and preferably substituted with an oxygen atom. In addition, oxygen atoms may be inserted between the methylene groups constituting the saturated hydrocarbon group. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the terminal methylene group is not substituted with an oxygen atom or -CO-. The saturated hydrocarbon group in which the methylene group may be replaced by an oxygen atom or -CO- preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 2 to 6 carbon atoms. The saturated hydrocarbon group in which the methylene group may be substituted with an oxygen atom is preferably a straight chain or branched chain saturated hydrocarbon group (i.e., a straight chain or branched chain alkyl group), and more preferably a straight chain saturated hydrocarbon group (i.e., a straight chain alkyl group). Examples of the group include groups represented by the following formulas. In the following formulas, * represents a bonding position.

[Chemical Formula 16]

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, 2 to 3 are more preferable.

^Examples of the substituted or unsubstituted amino group that the saturated hydrocarbon 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 and N, N-diethylamino group. ^Examples of the halogen atom which the saturated hydrocarbon group of R ^9A to R ^12A may have include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^9A to R ^12A is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a toluyl group, an ethylphenyl group, a propylphenyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group. Phenyl group, naphthyl group and the like are preferable. The aromatic hydrocarbon group may have one or two or more substituents, and examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; A haloalkyl group having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; An alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; A hydroxy group; A sulfamoyl group; An alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; An alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; And the like.

Furthermore, the number of carbon atoms of the aralkyl group represented by R ^9A to R ^12A is 7 to 30, more preferably 7 to 20, and even more preferably 7 to 17. R ^9A ~ R aralkyl group represented by ^12A, may be mentioned include groups alkanediyl group of R ^9A ~ R methylene groups described for ^12A aromatic hydrocarbon group, an ethylene group, a propylene group and the like having 1 to 5 carbon atoms in the combined .

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

R ^9A to R ^12A each independently represent a saturated hydrocarbon group having 1 to 10 carbon atoms (preferably an alkyl group), an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 7 to 20 carbon atoms, (Preferably an alkyl group) having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, a phenyl group having a methyl group, a naphthyl group having a methyl group, and a naphthyl group having a methyl group; An unsubstituted aralkyl group or an aralkyl group substituted by at least one member selected from the group consisting of a halogen atom, a methoxy group, an ethoxy group, a sulfamoyl group, a methylsulfonyl group, a methoxycarbonyl group and an ethoxycarbonyl group And it is more preferably each independently a linear alkyl group having 1 to 4 carbon atoms.

Examples of the aromatic hydrocarbon group represented by A include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, toluyl, ethylphenyl, xylyl, naphthyl, anthryl, phenanthryl, biphenyl and terphenyl.

Examples of the substituent which the aromatic hydrocarbon group represented by A may have include halogen atoms such as a fluorine atom, a chlorine atom and an iodine atom; An alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; A hydroxy group; A sulfamoyl group; An alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; An alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; An amino group which may be substituted; A sulfo group; -SO ₃ ^-; -SO ₃ J, and the like. Examples of the substituent capable of substituting the amino group include an alkyl group having 1 to 20 carbon atoms such as a methyl group which may be substituted with an amino group or a halogen atom; An aryl group such as an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a SO ₃ ^- group, a methylsulfonyl group, a dialkylamino group or a phenyl group which may be substituted with an alkoxy group having 1 to 10 carbon atoms; And the like.

Among them, A is preferably an aromatic hydrocarbon group which may have a substituent.

J may be an inorganic cation or an organic cation. Specifically, the same cation as Z ⁺ in the above-mentioned compound (1a) and cation of the following formula can be mentioned.

[Chemical Formula 17]

Specific examples of the aromatic hydrocarbon group which may have a substituent include the groups represented by the following formulas. In the following formulas, * represents a bonding position.

Specific examples of the aralkyl group which may have a substituent include a group in which a methylene group is bonded to a bonding position of each specific example of the following aromatic hydrocarbon group.

[Chemical Formula 18]

[Chemical Formula 19]

Examples of the aromatic hydrocarbon group which may have a substituent in A include groups represented by the following formulas. * Indicates the binding position.

[Chemical Formula 20]

Among them, groups represented by formulas (A1-1) and (A1-3) are preferable.

[G] ^g- represents an anion of g-valence. g may be 0, usually 1 to 14, preferably 1 to 12, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1 to 4. [G] ^g- may be a known anion, and may be a halide ion such as F ^- , Cl ^- , or Br ^- . In view of heat resistance, a boron anion, an aluminum anion, and a fluorine anion are preferable.

Examples of the boron anion and the aluminum anion include an anion represented by the following formula (y4).

[Chemical Formula 21]

[In the formula (y4), W ¹ and W ² each independently represent a group having two substituents formed by releasing a proton from a monovalent proton donating substituent. M3 represents boron or aluminum.]

Examples of the group having two substituents formed by releasing a proton from a monovalent proton donating substituent include a group having two proton donating substituents from a compound having at least two monovalent proton donating substituents (for example, a hydroxy group, a carboxylic acid group, etc.) And a group in which protons are released from the proton. Examples of the compound include catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, 3-hydroxy-2 Naphthoic acid, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent, Salicylic acid which may have a substituent, benzylic acid which may have a substituent, or mandelic acid which may have a substituent.

Examples of the substituent in the above-exemplified compounds include a saturated hydrocarbon group (e.g., an alkyl group, a cycloalkyl group, etc.), a halogen atom, a haloalkyl group, a hydroxyl group, an amino group, a nitro group and an alkoxy group.

Examples of the salicylic acid which may have a substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, Monoaminosalicylic acid such as salicylic acid, 3-amino salicylic acid, 4-amino salicylic acid, 5-amino salicylic acid and 6-amino salicylic acid; (2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), 6-hydroxysalicylic acid Monohydroxysalicylic acid such as hydroxysalicylic acid (2,6-dihydroxybenzoic acid); Dihydroxysalicylic acid such as 4,5-dihydroxysalicylic acid and 4,6-dihydroxysalicylic acid; Monohalosilicic acid such as 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid and 6-bromosalicylic acid; Dihalosalicylic acids such as 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid and 3,5-diiodo salicylic acid; Trihalosalicylic acid such as 3,5,6-trichlorosalicylic acid; And the like.

As the benzylic acid which may have a substituent

[Chemical Formula 22]

As the mandelic acid which may have a substituent

(23)

And the like.

Preferred anions among the anions represented by formula (y4) include anions (BC-1) to anions (BC-24) having substituents described in Table 1 and anions (BC- Anion (BC-25) to anion (BC-28) represented by the formula (BC-26), the formula (BC-27) and the formula (BC-28).

&Lt; EMI ID =

(Table 1)

(In the table above, the anion is anion.)

(25)

Anions (BC-1), anions (BC-2), anions (BC-3), anions (BC-25), anions (BC-26) More preferably an anion (BC-1), an anion (BC-2) and an anion (BC-25), and more preferably an anion (BC-1) and an anion (BC-2). By using these anions as [G] ^g- , the dye represented by formula (Ab2) tends to have excellent solubility in an organic solvent.

Examples of fluorine anions include anions represented by the following formulas (y6), (y7), (y8), and (y9).

(26)

[In the formula (y6), W ³ and W ⁴ each independently represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms, or W ³ and W ⁴ together form a fluorinated alkanediyl group having 1 to 4 carbon atoms can do.]

(27)

Equation (y7) of the, W ⁵ ~ W ⁷ represents a fluorinated alkyl group having a fluorine atom or a group having from 1 to 4 carbon atoms each independently;

(28)

[In the formula (y8), Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms.]

[Chemical Formula 29]

[Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms]

As the fluorinated alkyl group having 1 to 4 carbon atoms in the formulas (y6) and (y7), a perfluoroalkyl group is preferable. As in the perfluoroalkyl group is _{-CF 3, -CF 2 CF 3,} -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3 ), and the _2, -C (CF _{3) 3.}

Equation (y6) by fluoride in alkanediyl group having from 1 to 4 carbon atoms is preferably a perfluoroalkyl roal alkanediyl group, and _{-CF 2 -, -CF 2 CF 2} -, -CF 2 CF 2 CF 2 -, -C (CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ - and the like.

As the fluorinated alkanediyl group having 1 to 4 carbon atoms in the formula (y8), a perfluoroalkanediyl group is preferred. Examples of the perfluoroalkanediyl group include -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -C (CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ - .

As the fluorinated alkyl group having 1 to 4 carbon atoms in the formula (y9), a perfluoroalkyl group is preferable. Examples of the perfluoroalkyl group include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ) _2, and the like -C (CF _{3) 3.}

The anions represented by the formulas (6-1) to (6-6) (hereinafter referred to as "anions 6-1 (6-1) ) "To" anion (6-6) ").

(30)

The anion represented by the formula (y7) (hereinafter sometimes referred to as "anion (7)") includes the anion (7-1) represented by the following formula.

(31)

The anions represented by the formulas (8-1) to (8-4) (hereinafter, referred to as "anions (8-1 ) "To" anion (8-4) ").

(32)

Anions represented by formulas (9-1) to (9-4) (hereinafter referred to as "anions (9-1 ) "To" anion (9-4) ").

(33)

At least one anion selected from the group consisting of anion 6, anion 7, anion 8 and anion 9 (i.e., a fluorine anion, hereinafter referred to as "anion 6" to "9" , The solubility of the dye represented by the formula (Ab2) in an organic solvent can be improved. Among them, the anions 6 and 7 are preferable, and the anion 6-1, the anion 6-2 and the anion 7-1 are more preferable, and the anion 6-2 is particularly preferable.

A commercially available alkali metal salt of an anion represented by the formula (6), the formula (7), the formula (8) or the formula (9) may be used, and in International Publication No. 2008/075672 or Japanese Patent Application Laid- And the like.

As the compound represented by the formula (Ab1), for example, a compound represented by the following formula can be given. J is the same as defined above.

(34)

(35)

(36)

When the triarylmethane dye (Ab) is contained, the content thereof is preferably 1 part by mass or more, more preferably 50 parts by mass or more, further preferably 60 parts by mass or more, and still more preferably 1 part by mass or more in 100 parts by mass of the dye (A1) More preferably not more than 95 parts by mass, more preferably not more than 90 parts by mass, still more preferably not more than 85 parts by mass, particularly preferably not more than 82 parts by mass.

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

(37)

(In the formula (Ab2), each of R ⁴¹ to R ⁴⁴ independently represents 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, A saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom 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 is 2 to 20 , The methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the terminal methylene group is not substituted with an oxygen atom or -CO-. R ⁴¹ and R ⁴² may bond to form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may bond to form a ring together with the nitrogen atom to which they are attached.

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 contained in the alkyl group may be an oxygen atom Or -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or -SO ₂ -. Provided that the methylene group adjacent to the alkyl group is not simultaneously substituted with an oxygen atom, and the methylene group at the terminal is not substituted with an oxygen atom or -CO-.

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

[Y] ^m- represents an anion of any m-valence.

m represents an arbitrary natural number.]

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

(38)

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

The aromatic heterocycle of ring T ¹ may be monocyclic or condensed. The number of carbon atoms of the aromatic heterocyclic ring represented by ring T ¹ is 3 to 10, preferably 3 to 8. The aromatic heterocycle is preferably a 5- to 10-membered ring, more preferably a 5- to 9-membered ring. Examples of the monocyclic aromatic heterocycle include a 5-membered ring containing nitrogen atom such as pyrrole ring, oxazole ring, pyrazole ring, imidazole ring, thiazole ring and the like; A 5-membered ring which does not contain a nitrogen atom such as a furan ring, a chroman ring or a thiophene ring; A 6-membered ring containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring; The aromatic heterocycle of the condensed ring may be a condensed ring containing a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring or a quinoline ring; A ring containing no nitrogen atom such as benzofuran ring; And the like.

Examples of the substituent that the aromatic heterocycle of ring T ¹ may have include 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), a substituted or unsubstituted amino group , An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, 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, And an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

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

It is more preferable that the ring T ¹ is a ring represented by the formula (Ab 2 -x 1).

[Chemical Formula 39]

[Of the formula (Ab2-x1)

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

R ⁴⁵ and R ⁴⁶ each independently represent 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 and may have a substituent, In the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and when the number of carbon atoms in the saturated hydrocarbon group is 2 to 20, The included methylene group may be substituted with an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the terminal methylene group is not substituted with an oxygen atom or -CO-. R ⁴⁵ and R ⁴⁶ may combine to form a ring together with the nitrogen atom to which they are attached.

R ⁵⁵ represents 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.

k1 represents 0 or 1;

* Represents the bonding position with the carbanion.]

Furthermore, it is particularly preferable that the ring T ¹ is a ring represented by the formula (Ab2-y1).

(40)

[In the 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 and may have a substituent.

X2 represents an oxygen atom, -NR &lt; ⁵⁷ &gt; - or a sulfur atom.

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

R ⁴⁵ and R ⁴⁶ are as defined above.

* Represents the bonding position with the carbanion.]

In the formula, an aromatic heterocyclic ring of T ² may be the same ring and summoned aromatic heterocyclic ring exemplified in T ^1.

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

(41)

[Of the formula (Ab2-x2)

The ring T ³ represents an aromatic heterocycle having 3 to 10 carbon atoms having a nitrogen atom.

R ⁵⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms and 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 the bonding position with the carbanion.]

And the ring T ¹ is a ring represented by the formula (Ab2-y2).

(42)

[Of the 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 and may have a substituent.

R ⁵⁹ has the same meaning as described above.

* Represents the bonding position with the carbanion.]

The saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ may be any of linear, branched and cyclic. 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 number of carbon atoms of the chain saturated hydrocarbon group (alkyl group) is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4. The number of carbon atoms of the cyclic saturated hydrocarbon group (alicyclic hydrocarbon group) is preferably 3 to 10, more preferably 6 to 10.

When the number of carbon atoms of the saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-, and preferably substituted with an oxygen atom. In addition, oxygen atoms may be inserted between the methylene groups constituting the saturated hydrocarbon group. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the terminal methylene group is not substituted with an oxygen atom or -CO-. In this case, the saturated hydrocarbon group is preferably a straight chain or branched chain saturated hydrocarbon group (that is, a straight chain or branched chain alkyl group), and more preferably a straight chain saturated hydrocarbon group (i.e., a straight chain alkyl group). The saturated hydrocarbon group in which the methylene group may be substituted with an oxygen atom or -CO- preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms. 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, 2 to 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. Examples of the substituted amino group include alkylamino groups such as dimethylamino group and diethylamino group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. 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, And a perfluoroalkyl group such as a heptafluoropropyl group.

^Examples of the substituent which the alkyl group represented by R ⁵⁹ may have include a halogen atom, cyano group and the like.

^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 group as the aromatic hydrocarbon group which may be substituted and represented by R ^9A . The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 10. The aromatic hydrocarbon group is preferably a phenyl group, a toluyl group, a xylyl group or a naphthyl group. The aromatic hydrocarbon group may have one or two or more substituents.

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

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ include a group having 1 to 10 carbon atoms in the linear or branched alkyl group exemplified for R ^9A .

Examples of the substituent in the aromatic hydrocarbon group and the aralkyl group in the groups represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ include a halogen atom such as a fluorine atom, a chlorine atom and iodine; An alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; A hydroxy group; An alkyl group having 1 to 6 carbon atoms such as methyl group and ethyl group; A sulfamoyl group; An alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; And alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group.

R ⁴⁷ ~ R having a carbon number of alkyl group of 1-8 represented by ⁵⁴ is a straight-chain, branched chain and may be of any ring, chain and the type is preferable, a straight-chain exemplified in R ^1, carbon atoms of the branched chain and cyclic alkyl group having 1 ~ 8 period.

A group in which the methylene group constituting the alkyl group having 2 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ is substituted with an oxygen atom or -CO- (preferably a group substituted with an oxygen atom, provided that the methylene group adjacent to the alkyl group is simultaneously The methylene group constituting the alkyl group having 2 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ is an oxygen atom or -CO-, Is a group selected from those having 8 or less carbon atoms.

Among them, R ⁴¹ to R ⁴⁴ , R ⁵⁵ , R ⁵⁸ and R ⁵⁹ are preferably a saturated hydrocarbon group (preferably an alkyl group) having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms and may have a substituent.

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

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

Examples of the cation moiety of the formula (Ab2) include a cation 1 to a cation 12 represented by the formula (Ab2-I) as shown in Table 2 below. In the table, * indicates the bonding position.

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(Table 2)

(In the above table, the cation 1 -> cation 1, cation 2 -> cation 2, cation 3 -> cation 3, cation 4 -> cation 4, cation 5 -> cation 5, cation 6 -> cation 6, > Cation 7, Cation 8-> Cation 8, Cation 9-> Cation 9, Cation 10-> Cation 10, Cation 11-> Cation 11, Cation 12-> Cations 12)

In Table 2, Ph1 to Ph9 means a group represented by the following formula. In the formulas, * represents a bonding position.

(44)

Examples of the cation moiety of the formula (Ab2) include a cation 13 to a cation 16 represented by the formula (Ab2-II) as shown in Table 3 below. In the table, * indicates the bonding position.

[Chemical Formula 45]

(Table 3)

(In the above table, cation 13 -> cation 13, cation 14 -> cation 14, cation 15 -> cation 15, cation 16 -> cation 16).

In Table 3, Ph1, Ph10, and Ph11 mean the groups represented by the following formulas. In the formulas, * represents a bonding position.

(46)

Among them, the cation moiety of the formula (Ab2) is preferably a cation 1 to a cation 6, a cation 11, or a cation 12, and particularly preferably a cation 1, a cation 2, or a cation 12.

[Y] ^m- includes the above ^- mentioned known anions, and further includes anions represented by the formulas (y10) and (y11).

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^Wherein 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 the formula (y10) include methane disulfonic acid anion, propane disulfonic acid anion, toluene disulfonic acid anion, naphthalene disulfonic acid anion, and anions represented by the following formulas.

(48)

The anion represented by the formula (y11) includes, for example, an anion represented by the following formula. In the formula, n represents a natural number.

(49)

Preferred anions in terms of heat resistance are boron anions, aluminum anions, and fluorine anions.

The compound (Ab2) includes, for example, a compound represented by the following formula.

(50)

(51)

(52)

(53)

(54)

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When the compound represented by the formula (Ab2) is contained, the content thereof is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and even more preferably 65 parts by mass or more in 100 parts by mass of the dye (A1) More preferably 90 parts by mass or less, still more preferably 85 parts by mass or less, particularly preferably 82 parts by mass or less.

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 Publication No. 1299948; And the like. It is preferable that it is dissolved in an organic solvent.

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

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[In the 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 number of carbon atoms in the saturated hydrocarbon group is 2 to 20, the methylene group constituting the saturated hydrocarbon group may be substituted with an oxygen atom. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the terminal methylene group is not substituted with an oxygen atom.

R ^2C to R ^13C each independently represent 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, , 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 may be a halogen atom, A nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group or an amino group.

R ^14C represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and when a plurality of R ^14C 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 having 1 to 20 carbon atoms or a sulfonyl group.

The saturated hydrocarbon group having 1 to 20 carbon atoms of R ^1C may be any of straight chain, branched chain, and cyclic groups, and is preferably chain-like. Specifically, the same groups as the groups exemplified as the saturated hydrocarbon groups of 1 to 20 carbon atoms represented by R ¹ can be mentioned.

When the number of carbon atoms of the saturated hydrocarbon group represented by R ^1C is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom. In addition, oxygen atoms may be inserted between the methylene groups constituting the saturated hydrocarbon group. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the terminal methylene group is not substituted with an oxygen atom.

Examples of the monovalent hydrocarbon group of 1 to 20 carbon atoms represented by R ^2C to R ^14C include a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, a monovalent unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms . Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include the same groups as those exemplified as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in 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, A straight chain alkenyl group such as a hexadecenyl group, an octadecenyl group and an icosenyl group; Cycloalkenyl groups such as cyclopentenyl, cyclohexenyl and cycloheptenyl; And the like. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include groups similar to those exemplified as the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ .

A divalent hydrocarbon group of 1 to 20 carbon atoms of L ^C may be a divalent aromatic hydrocarbon group having from 1 to 20 carbon atoms a divalent saturated hydrocarbon groups, having 1 to 20 carbon atoms a divalent unsaturated hydrocarbon group having 6 to 10 of the, R ^{And a} group in which one hydrogen atom contained in a monovalent hydrocarbon group having 1 to 20 carbon atoms in ^2C is bonded.

Furthermore, it is preferable that plural R ^1C to R ^13C are the same group respectively.

Among them, R ^1C is preferably a chain alkyl group having 1 to 20 carbon atoms, more preferably a chain alkyl group having 1 to 10 carbon atoms.

As R ^2C to R ^6C , a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms is preferable, and a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable, and 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.

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

As X &lt; ^{C &} gt ;, an oxygen atom is particularly preferable.

The compound (Ac1) includes, for example, a compound represented by the following formula.

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[Chemical Formula 59]

When the coumarin dye (Ac) is contained, the content thereof is preferably 1 part by mass or more, more preferably 50 parts by mass or more, further preferably 80 parts by mass or more and 100 parts by mass in 100 parts by mass of the dye (A1) And preferably 99 parts by mass or less.

As the anthraquinone dye (Ad), known materials may be used. As the anthraquinone dye (Ad), for example,

C.I. Solvent Yellow 117 (hereinafter referred to only as "CI Solvent Yellow"), 163, 167, 189,

C.I. Solvent Orange 77, 86,

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

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

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, 112, 122, 128, 132, 136, 139,

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

C.I. Acid Red 80,

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

C.I. Acid Violet 34,

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

C.I. Disperse Yellow 51,

C.I. Disperse Violet 26, 27,

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

C.I. Direct Blue 40,

C.I. Modern Red 3, 11,

C.I. Modern Blue 8

And the like. The anthraquinone dye (Ad) is preferably dissolved in an organic solvent, and a blue, violet or red anthraquinone dye is more preferable.

Among these, the anthraquinone dye (Ad) is preferably a compound represented by the formula (1d) (hereinafter sometimes referred to as "compound (1d)").

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[In the formula (1d), R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent,

Equation (1d ')

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(Formula (1d ') of, R ⁹³ is an alkyl group having 1 to 6 carbon atoms, a halogen _{atom, -SO 3 H, -CO 2 H} , -CO 2 R 94, -NHCOR 94, -SO 3 R 94 or -SO ₂ NR ⁹⁴ R ⁹⁵ .

R ⁹⁴ represents an aliphatic hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxy group or an amino group, or an alicyclic hydrocarbon group of 3 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxy group or an amino group.

R ⁹⁵ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.

r represents an integer of 0 to 5; When R is 2 or more, plural R ⁹³ may be the same or different.

X ⁹¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.)

Represents a group represented by the formula:

When compound (1d) has -SO ₃ H and / or -CO ₂ H, they can form salts (for example Na or K salt).

Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms for R ⁹¹ and R ⁹² , R ⁹⁴ and R ⁹⁵ 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, Isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl groups.

Examples of the substituent that the aliphatic hydrocarbon group may have include a hydroxy group, a halogen atom, and an amino group, and a hydroxy group or a halogen atom is preferable.

Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ⁹¹ , R ⁹² and R ⁹⁴ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group .

Examples of the substituent that the alicyclic hydrocarbon group may have include a hydroxy group, a halogen atom or an amino group, and a hydroxy group or a halogen atom is preferable.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁹³ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, Isopentyl group, neopentyl group and the like.

Examples of -CO ₂ R ⁹⁴ include a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and eicosyloxycarbonyl group.

Examples of -NHCOR ⁹⁴ include an N-acetylamino group, an N-propanylamino group, an N-butyrylamino group, an N-isobutyrylamino group and an N-pivaloylamino group.

Examples of -SO ₃ R ⁹⁴ include a methoxy group, an ethoxy group, an ethoxy group, an ethoxy group, a propoxy group, a tert-butoxy group, a hexyloxy group, and an eicosyloxy group.

Examples of -SO ₂ NR ⁹⁴ R ⁹⁵ include N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1- (2-methylpropyl) sulfamoyl group, N- (2-methylpropyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-cyclohexylsulfamoyl group, an N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) Sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N- heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group , An N-octylsulfamoyl group, an N- (2-ethylhexyl) sulfamoyl group, an N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) A mono group, N- (5-aminopentyl) sulfa Substituted N-1, such as a sulfamoyl group; An N, N-dimethylsulfamoyl group, an N, N-dimethylsulfamoyl group, an N, N-ethylmethylsulfamoyl group, N, N-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group and the like.

Examples of the alkanediyl group having 1 to 6 carbon atoms in X ⁹¹ include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, 1-yl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1-yl group, , 2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group and the like.

R ⁹³ is preferably an alkyl group having 1 to 5 carbon atoms which may have a hydroxyl group, -SO ₃ R ⁹⁴ or -SO ₂ NR ⁹⁴ R ⁹⁵ , more preferably -SO ₂ NR ⁹⁴ R ⁹⁵ , -SO ₂ NHR ⁹⁴ ( ^Wherein R ⁹⁴ and R ⁹⁵ are as defined above).

Examples of the compound (1d) include compounds represented by the formulas (3-1) to (3-11).

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The anthraquinone dye (Ad) is preferably a compound represented by the formula (1d) wherein R ⁹¹ and R ⁹² are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group optionally having a halogen atom, , And compounds represented by formulas (3-4) and (3-11) are more preferable. With such anthraquinone dyes, it is possible to form a coating film or pattern of high contrast, and also to form a coating film or pattern with less occurrence of foreign matter and excellent light resistance.

When the anthraquinone dye (Ad) is contained, the content thereof is preferably 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the dye (A1).

The tetraazaporphyrin dye (Ae) is a compound having a tetraaza porphyrin skeleton in its molecule. When the tetraazaporphyrin dye (Ae) is an acidic dye or a basic dye, it may form a salt with any cation or anion.

Among them, as the tetraazaporphyrin dye (Ae), a dye containing a structure represented by the formula (1e) (hereinafter sometimes referred to as a compound (1e)) is preferable.

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[Wherein R ⁷¹ to R ⁷⁸ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group , A substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyloxy group, or a substituted or unsubstituted amino group, M4 represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent A substituted metal atom, or a metal oxide.

In the formula (1e), the aryl group is an aromatic hydrocarbon group having 6 to 30 carbon atoms such as a phenyl group or a naphthyl group; A heterocyclic group having 3 to 20 carbon atoms such as a furyl group, a thienyl group and a pyridyl group, and is preferably an aromatic hydrocarbon group.

In the formula (1e), R ⁷¹ to R ⁷⁸ each independently preferably represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted 1 to 24 carbon atom A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 4 to 30 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms, or a substituted or unsubstituted aralkyloxy group having 1 to 30 carbon atoms Lt; / RTI &gt;

More preferably, R ⁷¹ to R ⁷⁸ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 16 carbon atoms A substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 24 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 24 carbon atoms, or a substituted or unsubstituted aryl group having 1 to 16 carbon atoms Amino group.

More preferably, R ⁷¹ to R ⁷⁸ each independently represent a hydrogen atom, a fluorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, A substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 16 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 16 carbon atoms, or a substituted amino group having 1 to 12 carbon atoms.

In the formula (1e), specific examples of R ⁷¹ to R ⁷⁸ are shown below.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the unsubstituted alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n- Ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, n-decyl group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group, N-hexadecyl group, n-heptadecyl group, 1-octylnonyl group, n-octadecyl group, 1-nonyldecyl group, 1-decylundecyl group, n- Branched or cyclic group consisting of only carbon atoms and hydrogen atoms such as a dodecyl group, a dodecyl group, a dodecyl group, a docosyl group, an n-tetradecyl group, a 1-adamantyl group, a cyclopentyl group, It can kill the group.

Examples of the substituent in the alkyl group include an alkyloxy group having 1 to 16 carbon atoms, an alkyloxyalkyloxy group, an aralkyloxy group, an aryloxy group, an alkylthio group, a halogen atom and a halogenoalkyloxy group.

Specific examples of the alkyl group having a substituent include a methoxymethyl group, an ethoxymethyl group, an n-butoxymethyl group, an n-hexyloxymethyl group, a (2-ethylbutyloxy) methyl group, 2-n-butoxyethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2-n-pentyloxyethyl group, (2'-ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-octyloxyethyl group, 2- a 3-methoxypropyl group, a 3-ethoxypropyl group, a 3-n-propyl group, a 2-n-propyloxyethyl group, Propyl group, 3- (n-pentyloxy) propyl group, 3- (n-hexyloxy) propyl group, 3- Propyl group, 3- (n-octyloxy) propyl group, 3- (2'-ethylhexyloxy) (n-dodecyloxy) propyl group, a 3- (n-dodecyloxy) propyl group, a 3-cyclohexyloxypropyl group, 4-n-butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-pentyloxybutyl group, , 4-n-decyloxybutyl, 4-n-dodecyloxybutyl, 5-methoxypentyl, 5-ethoxypentyl, 5-n-propoxypentyl, Hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-ethoxyheptyl group, 6-n-butoxyhexyl group, Butoxydecyl group, 12-ethoxydodecyl group, 12-isopropoxydodecyl group, tetrahydrofurfuryl group, 2-methoxybutyl group, An alkyl group having an alkyloxy group such as a lyryl group;

(2-methoxyethoxy) methyl group, (2-ethoxyethoxy) methyl group, (2-n-butyloxyethoxy) (3-n-butyloxypropyloxy) methyl, (4-methoxybutyloxy) methyl, (3-n-butyloxypropyloxy) Ethoxyethoxy) ethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-methoxyethoxy) ethoxyethoxy) propyl group, 3- (2'-methoxypropoxy) propyl group, 3- (2'-isopropyloxypropoxy) An alkyl group having an alkyloxyalkyloxy group such as a propyl group, a 3- (3'-methoxypropyloxy) propyl group and a 3- (3'-ethoxypropyloxy) propyl group;

For example, a benzyloxymethyl group, a 2-benzyloxyethyl group, a 2-phenethyloxyethyl group, a 2- (4'-methylbenzyloxy) (4'-methoxybenzyloxy) ethyl group, 2- (4'-chlorobenzyloxy) ethyl group, 3- An alkyl group having an aralkyloxy group such as a benzyloxymethoxy) ethyl group and a 2- (4'-methylbenzyloxymethoxy) ethyl group;

A 2-methylphenyloxymethyl group, a 4-methoxyphenyloxymethyl group, a 4-fluorophenyloxymethyl group, a 4-chlorophenyloxymethyl group, a 2-chlorophenyloxy group, Methylphenyloxy) ethyl group, 2- (4'-methoxyphenyloxy) ethyl group, 2- (4'- (2'-naphthyloxy) ethyl group, a 3-phenyloxypropyl group, a 2- (2'-naphthyloxy) Butylphenyloxy group, a 3- (2'-naphthyloxy) propyl group, a 4-phenyloxybutyl group, a 4- (2'-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3'-chlorophenyloxy) , A 3- (2'-phenyloxyethoxy) propyl group, and a 4- (2'-phenyloxyethoxy) butyl group;

butylthioethyl group, 2-n-hexylthioethyl group, 2-n-octylthioethyl group, 2-n-butylthiomethyl group, 2-methylthioethyl group, n-butylthioethyl group, 4-n-propylthiobutyl group, 4-n-butylthio group, An alkylthio group-containing alkyl group such as a thiobutyl group, a 5-ethylthiopentyl group, a 6-methylthiohexyl group, a 6-ethylthiohexyl group, a 6-n-butylthiohexyl group and an 8-methylthiooctyl group;

Fluorohexyl group, 8-fluorooctyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-purple Perfluoro-n-propyl group, 1,1-dihydro-perfluoro-n-propyl group, n-butyl group, 1,1-dihydro-perfluoro-n-pentyl group, 1,1-dihydroperfluoro-n-hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl Perfluoro-n-decyl group, 1,1-dihydro-perfluoro-n-decyl group, 1,1-dihydro- N-hexadecyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentadecyl group, perfluoro-n- N-hexyl group, 2,2-bis (trifluoromethyl) propyl group, dichloromethyl group, 2-chloroethyl group, 3- chloropropyl group, An alkyl group having a halogen atom such as a 4-chlorocyclohexyl group, a 7-chloroheptyl group, an 8-chlorooctyl group, or a 2,2,2-trichloroethyl group;

Fluoro-n-hexyloxymethyl group, trifluoromethyloxymethyl group, 1,1-dihydro-perfluoroethyloxymethyl group, 1-fluoro-n-propyloxymethyl group, Perfluoro-n-propyloxymethyl group, 2-hydro-perfluoro-2-propyloxymethyl group, 1,1-dihydroperfluoro-n-butyloxymethyl group, 1,1-dihydro- Perfluoro-n-pentyloxymethyl group, 1,1-dihydro-perfluoro-n-hexyloxymethyl group, 1,1-dihydro- perfluoro- (Trifluoromethyl) propyloxymethyl group, a 3-methyl-3-methyl-3-pentyloxy group, (1,1-dihydro-perfluoroethyloxy) ethyl group, 2- (1,1,3-tetrahydro-naphthyloxy) ethyl group, Trihydro-perfluoro-n-propyloxy) ethyl group, 2- (1,1-dihydro-perfluoro-n (Pentyloxy) ethyl group, 2- (6-fluoro-n-hexyloxy) Perfluoro-n-dodecyloxy) propyl group, 3- (1,1-dihydro-perfluoroethyloxy) (Perfluoro-n-hexyloxy) butyl group, 4- (1,1-dihydro-perfluoroethyloxy) butyl group, 6- An alkyl group having a halogenoalkyloxy group such as a 1,1-dihydro-perfluoroethyloxy) hexyl group;

4-tert-butylphenyloxymethyl group, 4-n-butylphenyloxymethyl group, 4-tert-butylphenyloxymethyl group, 4-methylphenyloxymethyl group, 4-n-hexylphenyloxymethyl group, 4-n-octylphenyloxymethyl group, 4-n-decylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-ethoxyphenyloxymethyl group, 4 -Butoxyphenyloxymethyl, 4-n-pentyloxyphenyloxymethyl, 4-fluorophenyloxymethyl, 3-fluorophenyloxymethyl, 2-fluorophenyloxymethyl, 3,4-difluorophenyloxy 2-naphthyloxymethyl group, 2-furyloxymethyl group, 1-phenyloxyethyl group, 2-naphthyloxymethyl group, 2-naphthyloxymethyl group, (4'-n-hexylphenyloxy) ethyl group, 2- (4'-methoxyphenyloxy) ethyl group, 2- (4'-fluorophenyloxy) ethyl group, 2- (4'-chlorophenyloxy) ethyl group, 2- (4'- (2'-naphthyloxy) ethyl group, 2-phenyloxypropyl group, 3-phenyloxypropyl group, 3- (4'-naphthyloxy) (2'-ethylphenyloxy) propyl group, a 3- (2'-naphthyloxy) propyl group, a 4-phenyloxybutyl group, (2'-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenylphenyloxyphenyl group, And an alkyl group having an aryloxy group such as an oxydecyl group and a 10- (3'-methylphenyloxy) decyl group.

Examples of the unsubstituted alkoxy group include an alkoxy group derived from a specific example of the above alkyl group. The substituent in the substituted alkoxy group includes the same substituent as the substituent in the alkyl group.

Examples of the unsubstituted aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-anthracenyl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, A 2-perylenyl group, a 3-perylenyl group, a 2-fluoranthenyl group, a 3-fluoranthenyl group, a 7-fluoranthenyl group and an 8-fluoranthenyl group.

Examples of the substituent in the substituted aryl group include an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryloxy group, an aryl group, and a halogen atom.

Specific examples of the substituted aryl group include a 1-methyl-2-pyrenyl group, a 2-methylphenyl group, a 4-ethylphenyl group, a 4-tert- butylphenyl group, a 4- (4'-tert- butylcyclohexyl) An aryl group having an alkyl group such as a hexylphenyl group, a 2-cyclohexylphenyl group, a 4-ethyl-1-naphthyl group, a 6-n-butyl-2-naphthyl group and a 2,4-dimethylphenyl group;

Propoxyphenyl group, a 4-isopropoxyphenyl group, a 3-isopropoxyphenyl group, a 2-ethoxyphenyl group, a 3-n-propoxyphenyl group, An alkoxy group such as an isopropoxyphenyl group, a 2-sec-butoxyphenyl group, a 4-n-pentyloxyphenyl group, a 4-isopentyloxyphenyl group, a 2-methyl-5-methoxyphenyl group, An aryl group having a group;

Phenyl-1-naphthyl group, 1-phenyl-2-naphthyl group, 2-phenyl-2-naphthyl group, An aryl group having an aryl group such as a t-butyl group, a 7-phenyl-1-pyrenyl group and the like;

Bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2-methylphenyl group, 2-chlorophenyl group, An aryl group having a halogen atom such as a 3-chlorophenyl group, a 2-methoxy-4-fluorophenyl group, or a 2-fluoro-4-methoxyphenyl group;

Further preferred examples thereof include a 2-trifluoromethylphenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, a 3,5-bistrifluoromethylphenyl group, a 4-perfluoroethylphenyl group, Phenyl group, 4-ethylthiophenyl group, 4-cyanophenyl group, 3-cyanophenyl group and the like.

Examples of the unsubstituted aryloxy group include an aryloxy group derived from a specific example of the aryl group. The substituent in the substituted aryloxy group includes the same substituent as the substituent in the aryl group.

Examples of the substituted or unsubstituted aralkyloxy group include benzyloxy group,? -Methylbenzyloxy group, phenethyloxy group,? -Methylphenethyloxy group,?,? -Dimethylbenzyloxy group,?,? - dimethylphenethyloxy group, An aralkyloxy group having an unsubstituted or alkyl group such as a 4-methylphenethyloxy group, a 4-methylbenzyloxy group and a 4-isopropylbenzyloxy group;

An aralkyloxy group having an aryl group or an aralkyl group such as a 4-benzylbenzyloxy group, a 4-phenethylbenzyloxy group or a 4-phenylbenzyloxy group; 4-methoxycarbonyloxy group, 4-methoxybenzyloxy group, 4-n-tetradecyloxybenzyloxy group, 4-n-heptadecyloxybenzyloxy group, An aralkyloxy group having a substituted oxy group such as a vinyloxymethylbenzyloxy group, a 4-benzyloxybenzyloxy group and a 4-phenethyloxybenzyloxy group;

An aralkyloxy group having a hydroxyl group such as a 4-hydroxybenzyloxy group and a 4-hydroxy-3-methoxybenzyloxy group; An aralkyloxy group having a halogen atom such as a 4-fluorobenzyloxy group, a 3-chlorobenzyloxy group, or a 3,4-dichlorobenzyloxy group;

2-furfuryloxy group, diphenylmethyloxy group, 1-naphthylmethyloxy group, 2-naphthylmethyloxy group and the like.

Specific examples of the amino group having a substituent include an amino group having an alkyl group such as N-methylamino group, N-ethylamino group, N-n-butylamino group, N-cyclohexylamino group, Nn-octylamino group or Nn-decylamino group;

(4-methylphenyl) amino group, N- (4-n-butylphenyl) amino group, N- (4-methoxyphenyl) amino group, An amino group having an aralkyl group or an aryl group such as an N- (3-fluorophenyl) amino group, an N- (4-chlorophenyl) amino group, an N- (1-naphthyl) amino group, ;

N, N-di-n-hexylamino group, N, N-di-n-octylamino group, N, N-diethylamino group, N-methyl-N-ethylamino group, N-ethyl-N-butylamino group, N-methyl-N-phenylamino group, N- An amino group having two alkyl groups such as an ethyl-N-phenylamino group and an N-butyl-N-phenylamino group or an aralkyl group as a substituent;

(4-methylphenyl) amino group, N, N-di (4-ethylphenyl) amino group, N, N-di (4-tert-butylphenyl) amino group, an N, N-di (4-n-hexylphenyl) amino group, (1-naphthyl) amino group, N, N-di (4-n-butoxyphenyl) amino group, (4-methylphenyl) amino group, N-phenyl-N- (4-octylphenyl) amino group, (4-methoxyphenyl) amino group, an N-phenyl-N- (4-methoxyphenyl) amino group, (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group, N-phenyl- Phenylphenyl) amino group, and an N-phenyl-N- (4-phenylphenyl) amino group, and the like can be given .

In formula (1e), M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, or a metal oxide metal, more preferably two hydrogen atoms, Or a metal oxide metal atom, more preferably a divalent metal atom or a metal oxide metal atom.

Examples of the monovalent metal atom represented by M include Na, K, and Li.

Examples of the divalent metal atom represented by M include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, have.

The trivalent substituted metal atom represented by M is preferably one selected from the group consisting of Al-Cl, Ga-Br, Ga-I, In-Cl, Al-C ₆ H ₅ , In-C ₆ H ₅ , Mn ₃ ) ₃ ], Fe-Cl, and the like.

Examples of the metal oxide atom represented by M include VO, MnO, TiO, and the like.

In the formula (1e), M is more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, VO and TiO, more preferably Cu, Ni, Pd and VO, VO.

Specific examples of the compound (1e) include compounds represented by the formulas (2-1) to (2-38).

&Lt; EMI ID =

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The tetraazaporphyrin dye (Ae) is preferably a compound represented by the formula (2-29).

When the tetraazaporphyrin dye (Ae) is contained, the content thereof is preferably 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the dye (A1).

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, further preferably 85% by mass or more and 100% Or less.

The content of the dye in the colorant (A) is 90 parts by mass or more, preferably 93 parts by mass or more, more preferably 95 parts by mass or more, and further preferably 99 parts by mass or more, and 100 parts by mass or more, , That is, not containing a pigment is particularly preferable.

The colorant (A) may further contain the pigment (A2). The pigment (A2) is not particularly limited, and known pigments can be used. Examples thereof include pigments classified as pigments in the color index (The Society of Dyers and Colourists), and these pigments can be used singly or in combination Two or more species can be used in combination.

The content of the colorant (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, and still more preferably 5% by mass or more and 50% by mass or less, based on the total amount of solid matter. When the content of the colorant (A) is within the above range, the color density when formed into a color filter is sufficient and the resin or a polymerizable compound can be contained in a required amount in the composition, . Here, the "total amount of solid content" in the present specification means the amount excluding the content of the solvent in the total amount of the colored curable resin composition. The total amount of the solid content and the content of each component thereof can be measured by a known analytical means such as liquid chromatography or gas chromatography.

&Lt; Resin (B) >

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and is preferably a polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. The monomer (a) is copolymerized with at least one of a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond and a monomer (c) copolymerizable with the monomer (a) .

The order of the reaction is not limited, and at least one of the monomer (a) and the monomers (b) and (c) may be copolymerized at a time. When all of the monomers (a) to (c) are used, the monomer (a) may be reacted with the monomer (b) after the copolymerization of the monomer (a) The post monomer (b) may also be reacted. Further, the monomer (a) may be reacted with the copolymer of the monomer (b) and the monomer (c), and further the carboxylic acid anhydride may be reacted.

(a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p-vinylbenzoic acid;

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

5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- , 5-carboxymethylbicyclo [2.2.1] hept-2-ene, and 5-carboxyethylbicyclo [2.2.1] hept-2-ene;

Carboxylic anhydrides such as the anhydrides of the unsaturated dicarboxylic acids except for fumaric acid and mesaconic acid; And the like.

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono Esters;

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

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoints of copolymerization reactivity and the solubility of the resulting resin in an aqueous alkali solution.

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

(b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter may be referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (b2) "), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter occasionally referred to as" (b3) "), and the like.

(b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)"), an alicyclic unsaturated hydrocarbon having an epoxy (B1-2) (hereinafter may be referred to as "(b1-2)").

The monomer (b1-1) is preferably a monomer having a glycidyl group and an ethylenic unsaturated bond. (meth) acrylate,? -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, vinylbenzyl glycidyl (meth) acrylate, (Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxy) styrene, Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) Styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) .

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000 manufactured by Daicel Co.), 3,4-epoxycyclohexyl (Meth) acrylate (for example, Cyclomer (registered trademark) A400 manufactured by Daicel Co.), 3,4-epoxycyclohexylmethyl (meth) acrylate (Manufactured by Daicel Co., Ltd.), a compound represented by formula (BI) and a compound represented by formula (BII).

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[In the formula (BI) and the formula (BII), R ^b1 and R ^b2 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 hydroxy group.

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

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

* Represents the bonding position with O.]

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^b1 and R ^b2 include a methyl group and an ethyl group.

Examples of the alkyl group in which the hydrogen atom of R ^b1 or R ^b2 is substituted with a hydroxyl group include a hydroxymethyl group and a hydroxyethyl group.

R ^b1 and R ^b2 are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, Methyl group.

As the alkanediyl group for R ^b3 , a straight chain or branched chain alkanediyl group can be enumerated, and specifically, a methylene group and an ethylene group can be exemplified.

X ^b1 and X ^b2 are preferably a single bond, * -R ^b3- , or * -R ^b3 -O-, more preferably a single bond or * -R ^b3 -O-, more preferably a single bond, -CH ₂ -O- and * -CH ₂ CH ₂ -O-, and particularly preferably a single bond, * -CH ₂ CH ₂ -O- (* represents the bonding position with O) .

Examples of the compound represented by the formula (BI) include a compound represented by any one of the formulas (BI-1) to (BI-15). Among them, the expression (BI-1), the expression (BI-3), the expression (BI-5), the expression (BI- (BI-1), a compound represented by the formula (BI-7), a compound represented by the formula (BI-9) or a compound represented by the formula (BI-15) are more preferable.

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Examples of the compound represented by formula (BII) include compounds represented by any one of formulas (BII-1) to (BII-15). Among them, BII-1, BII-3, BII-5, BII-7, BII-9 or BII- (BII-1), a compound represented by the formula (BII-7), a compound represented by the formula (BII-9) or a compound represented by the formula (BII-15) are more preferable.

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

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

(meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- ethyl hexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] (Meth) acrylate (also referred to in the art as "dicyclopentanyl (meth) acrylate", sometimes referred to as "tricyclodecyl (meth) acrylate" tricyclo [5.2.1.0 ^2,6] decane-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate (in the art as the trivial name "DC (Meth) acrylate "), tricyclo [5.2.1.0 ^2,6 ] decen-9-yl (meth) acrylate (Meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate, isobonyl (meth) acrylate, adamantyl (meth) acrylate, allyl (Meth) acrylic acid esters such as naphthyl (meth) acrylate and benzyl (meth) acrylate;

(Meth) acrylic acid esters having a hydroxy group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

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

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like such as bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept- Cyclounsaturated compounds;

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

Vinyl group-containing aromatic compounds such as styrene,? -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; And the like.

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

The polymerization initiator and the solvent are not particularly limited and those generally used in the field can be used. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), organic peroxides (such as benzoyl peroxide) And the solvent may be one which dissolves the respective monomers, and examples of the solvent (E) of the colored curable resin composition of the present invention include a solvent described later and the like.

As the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) extracted by re-precipitation or the like may be used. In particular, since the solution after the reaction can be used as it is in the production of the colored curable resin composition of the present invention by using a solvent contained in the colored curable resin composition of the present invention as a solvent in such polymerization, the production of the colored curable resin composition Can be simplified.

If necessary, a reaction catalyst of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (e.g., tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (e.g., hydroquinone) may be used.

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

Examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate / A resin [K1] such as an acrylic acid copolymer; (Meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 (meth) acrylate / glycidyl .1.0 ^2,6] decyl acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (meth) acrylic acid / styrene copolymers, etc. Of resin [K2]; Resins [K3] such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (K4) such as a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) A resin [K5] such as a resin obtained by reacting (meth) acrylic acid with a copolymer; A resin such as a resin obtained by reacting a (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and tetrahydrophthalic anhydride in addition to the resin [K6] have.

Among them, the resin (B) is preferably a resin [K1] and a resin [K2].

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, and still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer is good, and the resolution of the coloring pattern tends to be improved.

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

The solids content of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and even more preferably 70 to 135 mg-KOH / g. Here, the solid content is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass with respect to the total amount of the solid components. When the content of the resin (B) is in the above range, a coloring pattern can be formed, and the resolution and residual film ratio of the coloring pattern tends to be improved.

&Lt; Polymerizable compound (C) >

The polymerizable compound (C) is a compound capable of polymerizing with an active radical and / or an acid generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenically unsaturated bond, Methacrylate ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of such a polymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- A compound having one ethylenically unsaturated bond such as the compound exemplified as (a), (b) and (c) above;

(Meth) acrylates such as 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di Oxyethyl) ether and 3-methylpentanediol di (meth) acrylate;

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

(Meth) acrylate such as pentaerythritol tetra (meth) acrylate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate and caprolactone modified pentaerythritol tetra A compound having four ethylenically unsaturated bonds;

Compounds having five ethylenic unsaturated bonds such as dipentaerythritol penta (meth) acrylate;

Acrylate, dipentaerythritol hexa (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (metha) acrylate, propylene glycol modified dipentaerythritol hexa (metha) acrylate, caprolactone modified dipentaerythritol hexa A compound having 6 ethylenic unsaturated bonds such as acrylate;

Ethylenically unsaturated bonds such as tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (metha) acrylate, A compound having 7 or more carbon atoms; And the like.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds, more preferably a polymerizable compound having five to six ethylenic unsaturated bonds. Particularly preferred are dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

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

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total solid content. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a coloring pattern and the chemical resistance of the color filter tend to be improved.

The content ratio of the resin (B) to the polymerizable compound (C) is preferably 20:80 to 80:20, 80:20.

&Lt; Polymerization initiator (D) >

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

&Lt; EMI ID =

[In the formula (d1)

R ^d1 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, an alkyl group having 1 to 15 carbon atoms which may have a substituent, And the methylene group (-CH ₂ -) included in the alkyl group or the aralkyl group may be substituted with -O-, -CO-, -S-, -SO ₂ - or -NR ^d5 - have.

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

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 -) included in the aliphatic hydrocarbon group is -O -, -CO- or -S-, the methine group (-CH <) included in the aliphatic hydrocarbon group may be substituted with -PO ₃ <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be replaced 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 R ^d1 is preferably 6 to 15, more preferably 6 to 12, and 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, a terphenyl group and the like, with a phenyl group and a naphthyl group being more preferable and a phenyl group being particularly preferable.

The aromatic hydrocarbon group represented by R ^d1 may have one or two or more substituents. The substituent is preferably substituted at the? -Position or? -Position of the aromatic hydrocarbon group, and more preferably substituted at the? -Position. Examples of the substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, An alkyl group having 1 to 15 carbon atoms; A halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; And the like.

The alkyl group as the substituent preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms. The alkyl group as the substituent may be any of straight chain, branched chain, and cyclic groups, or may be a combination of a chain group 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.

Examples of the alkyl group as a substituent of the aromatic hydrocarbon group represented by R ^d1 include groups represented by the following formulas. In the formulas, * represents a bonding position.

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[Formula 76]

^Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^d1 include groups represented by the following formulas. In the formulas, * represents a bonding position.

[Formula 77]

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As the aromatic hydrocarbon group which may have a substituent represented by R ^d1 , a group represented by the following formula is preferable.

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

The alkyl group represented by R ^d6 includes the same group as the alkyl group exemplified as the substituent of the aromatic hydrocarbon group represented by R ^d1 . The number of carbon atoms of the alkyl group represented by R ^d6 is preferably 2 or more and 7 or less, and more preferably 2 or more and 5 or less. The alkyl group of R ^d6 may be any of straight chain, branched chain and cyclic groups, and is preferably chain-like.

^Examples of the halogen atom capable of substituting the hydrogen atom contained in R ^d6 include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom, and a fluorine atom is particularly preferable. It is preferable that at least 2 to 10 hydrogen atoms contained in R ^d6 are substituted with a halogen atom, and it is preferable that 3 or more and 6 or less hydrogen atoms are substituted with a halogen atom. The substitution position of the R ^d6 O- group is preferably an ortho or para position, and particularly preferably a para position.

M2 is preferably 1 to 2, and particularly preferably 1.

The carbon number of the heterocyclic group represented by R ^d1 is preferably 3 to 20, more preferably 3 to 10, and 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 of R ^d1 may have one or two or more substituents. Examples of the substituent include the same groups as the groups exemplified as substituents that the aromatic hydrocarbon group represented by R ^d1 may have.

The alkyl group represented by R ^d1 preferably has 1 to 12 carbon atoms. The alkyl group represented by R ^d1 includes 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 decyl group, an undecyl group, a dodecyl group, And pentadecyl group. Such an alkyl group may be any of straight chain, branched chain, and cyclic groups, or may be a combination of a chain group and a cyclic group. The methylene group (-CH ₂ -) in the alkyl group of R ^d1 may be substituted with -O-, -CO-, -S-, -SO ₂ - or -NR ^d5- , and the hydrogen atom may be substituted with OH group or SH Lt; / RTI &gt;

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

^Examples of the alkyl group which may have a substituent represented by R ^d1 include specifically groups represented by the following formulas. * Indicates the binding position.

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In addition to the aromatic hydrocarbon groups resulting from a combination of the alkanediyl group derived from a group represented by the R ^d1 it is represented by ^d1 R aralkyl group which may have a substituent represented by R ^d1 is preferred. The number of carbon atoms of the aralkyl group is preferably 7 to 33, more preferably 7 to 18, and even more preferably 7 to 12. The aralkyl group may have a substituent one or two or, as the substituent there may be mentioned the same groups a group exemplified as the substituent that the alkyl group represented by an aromatic hydrocarbon group, and R ^d1 is represented by the R ^d1 can have. A group derived from a combination of divalent groups represented by the R ^d1 aromatic hydrocarbon group represented by the R ^d1 may include groups represented by the following formula in detail. In the formulas, * represents a bonding position.

[Formula 81]

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

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d2 is preferably 6 to 15, more preferably 6 to 12, and 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, a terphenyl group, and the like.

The heterocyclic group represented by R ^d2 preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 3 to 5 carbon atoms. 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 alkyl group represented by R ^d2 preferably has 1 to 7 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. 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 may be any of straight chain, branched chain, and cyclic groups, or may be a combination of a chain group and a cyclic group.

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

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d3 is preferably 6 to 15, more preferably 6 to 12, and 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, a terphenyl group and the like, and a phenyl group and a naphthyl group are more preferable.

The aromatic hydrocarbon group represented by R ^d3 may have one or two or more substituents. The substituent is preferably substituted at the [alpha] or [gamma] position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group of 1 to 15 carbon atoms and more preferably an aliphatic hydrocarbon group of 1 to 15 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, An alkyl group; An alkenyl group having 1 to 15 carbon atoms such as an ethynyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a nonenyl group and a decenyl group; And the like.

The aliphatic hydrocarbon group as the substituent preferably has 1 to 7 carbon atoms. The aliphatic hydrocarbon group as the substituent may be a straight chain, branched chain or cyclic group, or may be a combination of a chain group and a cyclic group. The methylene group (-CH ₂ -) in the aliphatic hydrocarbon group as the substituent may be substituted with -O-, -CO- or -S-, and the methine group (-CH <) may be substituted with -N < .

Examples of the aliphatic hydrocarbon group as a substituent of the aromatic hydrocarbon group represented by R ^d3 include groups represented by the following formulas. In the formulas, * represents a bonding position.

(82)

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^d3 include groups represented by the following formulas. In the formulas, * represents a bonding position.

(83)

The carbon number of the heterocyclic group represented by R ^d3 is preferably 3 to 20, more preferably 3 to 10, and 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 R ^d3 may have one or two or more substituents. Examples of the substituent include the same groups as those exemplified as the substituents that the aromatic hydrocarbon group represented by R ^d1 may have.

Among them, R ^d3 is preferably an aromatic hydrocarbon group having a substituent, and the substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms), and the number of substituents is 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, and 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, a terphenyl group and the like, with a phenyl group and a naphthyl group being more preferable and a phenyl group being particularly preferable.

The aromatic hydrocarbon group represented by R ^d4 may have one or two or more substituents. As the substituent, the same group as the substituent that the aromatic hydrocarbon group of R ^d1 may have may be mentioned.

The aliphatic hydrocarbon group represented by R ^d4 preferably has 1 to 13 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 4 to 9 carbon atoms. ^Examples of the aliphatic hydrocarbon group represented by R ^d4 include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, An alkyl group such as a decyl group; An alkenyl group, an alkenyl group, an alkenyl group, an alkynyl group, an alkenyl group, an alkynyl group, an alkenyl group, an alkynyl group, An alkenyl group such as a group; And the like. The aliphatic hydrocarbon group may be a chain (straight chain or branched chain) or a cyclic group, or a combination of a chain group and a cyclic group. The methylene group (-CH ₂ -) in the aliphatic hydrocarbon group represented by R ^d4 may be replaced by -O-, -CO- or -S-, and the methine group (-CH <) is replaced by -PO ₃ < . 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 formulas. In the formulas, * represents a bonding position.

(84)

R ^d4 is preferably a chain type aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group which does not have a substituent, more preferably a branched chain alkyl group which does not have a substituent.

Examples of the compound (d1) include the compounds (d1-1) to (d1-67) represented by the formula (d1) as shown in Tables 4 to 10 below. In the table, * indicates the bonding position.

(85)

(Table 4)

(Table 5)

(Table 6)

(Table 7)

(Table 8)

(Table 9)

(Table 10)

Among them, the compounds (d1-3) to (d1-6), (d1-18) to (d1-52), (d1-55), (d1-56), (d1-60) (D1-24), (d1-36) to (d1-24) are more preferable, and the compounds (d1-3) to (d1-6) d1-40), particularly preferably the compound (d1-24).

The content of the compound (d1) in the 100 parts by mass of the polymerization initiator (D) is preferably 2 parts by mass or more and 100 parts by mass or less, more preferably 30 parts by mass or more, further preferably 40 parts by mass or more, More preferably not more than 90 parts by mass, more preferably not more than 70 parts by mass, and even more preferably not more than 60 parts by mass.

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

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

Examples of the polymerization initiator that generates an active radical include O-acyloxime compounds, imidazole compounds, alkylphenone compounds, triazine compounds, and acylphosphine oxide compounds other than the compound (d1). Among them, the polymerization initiator (D) preferably contains a nonimidazole compound or an alkylphenone compound in addition to the compound (d1), and preferably contains a nonimidazole compound.

Examples of the O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3- Dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ ) -9H-carbazol-3-yl] -3-cyclopentylpropan- 1-imine, N-benzoyloxy- Yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure (registered trademark) OXE 01, OXE 02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may also be used. Among them, the O-acyloxime compound is preferably selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- - (2-hydroxyethoxy) phenyl} sulfanylphenyl] -propan-1-one-2-imine is preferable and at least one member selected from the group consisting of N-benzoyloxy- 1-one-2-imine and N-acetyloxy-1- [4- {4- (2- hydroxyethoxy) phenyl} sulfanylphenyl] More preferably at least one kind selected from the group consisting of When such an O-acyloxime compound is used, a color filter with a high lightness tends to be obtained.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A 6-75372, JP-A 6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'- (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis 4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, ', An imidazole compound in which the phenyl group at the 5,5'-position is substituted by a carboalkoxy group (see, for example, JP-A-7-10913).

Among them, the compound represented by the formula (d4) is preferable.

&Lt; EMI ID =

[In the 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).

Examples of the compound represented by the formula (d4) include compounds represented by the following formulas, and mixtures thereof are preferable.

[Chemical Formula 87]

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 88]

Examples of the compound having a partial structure represented by the formula (d5) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) Butane-1-one and the like. IRGACURE 369, 907 and 379 (all manufactured by BASF) can be used.

Examples of the compound having a partial structure represented by the formula (d6) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one, 1-hydroxycyclohexylphenylketone and 2-hydroxy- ,?,? -diethoxyacetophenone, and benzyl dimethyl ketal.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d5).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

Further, 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, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, camphorquinone, etc .; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator D1 (particularly amines) to be described later.

Among them, when two or more polymerization initiators are used, a combination of a compound (d1) and a nonimidazole compound, a combination of a compound (d1) and a nonimidazole compound and a thiol compound described below, And the like are preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, still more preferably 2 to 15 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C) Mass part. When the content of the polymerization initiator (D) is within the above range, the sensitivity of the color filter tends to be shortened because the sensitivity is increased and the exposure time is shortened.

&Lt; Polymerization initiator (D1) >

The polymerization initiator (D1) is a compound or a sensitizer used for promoting polymerization of the polymerizable compound initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiator (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

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-dimethyl para-toluidine; Alkylamino such as 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone and 4,4'- Benzophenone; Among them, alkylaminobenzophenone is preferable, and 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, Dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Citoxanthone and the like.

When the thioxanthone compound is included, the content thereof is preferably 50 parts by mass or more and 100 parts by mass or less, more preferably 70 parts by mass or more and 99 parts by mass or less, based on 100 parts by mass of the polymerization initiator.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

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

When such a polymerization initiator (D1) is used, 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) .

When the polymerization initiator (D1) is used, the content thereof is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, still more preferably 15 to 250 parts by mass based on 100 parts by mass of the total amount of the polymerization initiator (D) Mass part. When the amount of the polymerization initiator (D1) is within this range, coloring patterns can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

&Lt; Thiol compound (T) >

The colored curable resin composition of the present invention preferably further contains a thiol compound (T).

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

Examples of the compound having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylpyridine-3-ol, 2-sulfanylpyridine-N-oxide, 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-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2- 4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole- Thiol, 2-sulfa Imidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino- Methyl-4H-1,2,4-triazole, 3-thiol, 3-sulfanyl 1H- Amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 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, Sulfanyl benzothiazole, 6-ethoxy-2-sulfanyl benzothiazole, 6-nitro-2-sulfanyl benzothiazole, , 2-sulfanylnaphthoimidazole, 2-sulfanil naphthoxazole, 3-sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyrazolo [2,4- 2-amino-6-purine It may include all, such as 6-sulfanyl-purine, 4-sulfanyl -1H- pyrazolo [2,4-d] pyrimidine.

Examples of the compound having two or more sulfanyl groups in the molecule include hexane dithiol, decane dithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis Trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropane tris (3-sulfanyl propionate) (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl tris (3 -Sulfanylpropionate), pentaerythritol tetrakis (3-sulfanylbutyrate), and 1,4-bis (3-sulfanylbutyloxy) butane.

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

The content of the thiol compound is preferably 0.5 part by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, in 100 parts by mass of the polymerization initiator. When the content of the thiol compound is within this range, the sensitivity tends to be high and the developing property tends to be good.

&Lt; Solvent (E) >

The colored curable resin composition of the present invention preferably further contains a solvent (E).

The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used. For example, an ester solvent (a solvent containing -COO- and -O- in the molecule), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester solvent ( (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- and -COO- in the molecule), alcohol solvent (containing OH in the molecule and -O-, CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, Butyl propionate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetone and? -Butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, And the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , Di, and the like ethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

Examples of the ketone solvent include 4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4- Acetone alcohol, cyclopentanone, cyclohexanone and isophorone.

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

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

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

An organic solvent having a boiling point at 1 atm of not less than 120 ° C and not more than 180 ° C is preferable from the standpoint of coatability and drying property of the above-mentioned solvent. Examples of the solvent include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diacetone alcohol, 4-methyl-2-pentanone and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diacetone alcohol and 3-ethoxypropionic acid Ethyl is more preferable.

The content of the solvent (E) is preferably 35 to 95% by mass, and more preferably 40 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total amount of solids in the colored curable resin composition is preferably 5 to 65% by mass, and 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 coating becomes good, and when the color filter is formed, the color density tends not to be insufficient and the display characteristics tend to be good.

&Lt; Leveling agent (F) >

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

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

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, TORAY silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name: (Manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, KP321, And TSF4460 (manufactured by Momentive Performance Materials Japan Joint Corporation).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Concretely, it is preferable to use a mixture of FLORAD (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (registered trademark) F142D, copper (equivalent) F171, copper (same) F-177, F183, F554, R30, RS-718-K (manufactured by DIC), F-TOP (registered trademark) EF301, (Trade name) EF303, EF351 and EF352 (manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd.), Surflon (registered trademark) S381, S382, S1002, ) SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Co., Ltd.).

Examples of the silicon-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapac (registered trademark) R08, Dongbang BL20, Dongbu F475, Dongbu F477 and Dongbu F443 (manufactured by DIC Corporation).

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

&Lt; Other components >

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

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (2-aminoethyl) (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methoxysilane and the like.

&Lt; Process for producing colored curable resin composition >

The coloring curable resin composition of the present invention may contain a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E) , A polymerization initiator (D1), and other components.

The dye can be dissolved in a part or all of the solvent (E) beforehand to prepare a solution. It is preferable to filter the solution with a filter having a pore size of about 0.01 to 1 mu m.

It is preferable to filter the mixed colored curable resin composition with a filter having a pore size of about 0.01 to 10 mu m.

&Lt; Color filter and manufacturing method of liquid crystal display device >

Examples of the method for forming a color filter using the colored curable resin composition of the present invention include a method using a photolithography method and an ink jet apparatus. In the photolithography method, for example, a colored curable resin composition of the present invention is coated on a substrate, and a volatile component such as a solvent is removed or dried to form a colored composition layer. The colored composition layer is exposed through a photomask, . After development, a colored pattern can be formed by heating as required. In the method for forming a coloring pattern, a colored coating film which is a cured product of the colored composition layer can be formed without using a photomask and / or not developing at the time of exposure. The coloring pattern and the colored coating film thus obtained can be made into color filters.

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

The thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted according to the intended use. For example, it is 0.1 to 30 탆, preferably 1 to 20 탆, more preferably 1 to 6 탆.

The formation of each color pixel by the photolithographic method can be performed by a known or common apparatus or condition. For example, as follows.

First, the colored curable resin composition is coated on a substrate, and then heated and dried (pre-baked) and / or reduced-pressure dried to remove volatile components such as a solvent and dried to obtain a smooth colored composition layer.

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

The coloring composition layer is then exposed through a photomask to form the desired coloring pattern.

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

A coloring pattern is formed on the substrate by developing the exposed coloring composition layer in contact with a developing solution. By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developer. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable.

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

It is preferable to rinse after development.

Further, post-baking is preferably performed on the obtained coloring pattern.

According to the colored curable resin composition of the present invention, a color filter having particularly excellent shape can be produced. The color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image pickup device.

The present invention will be described in more detail with reference to the following examples, but it should be understood that the present invention is not limited by the following examples in any way, and may be appropriately changed within the scope of the present invention. All of which are included in the technical scope of the present invention. In the following, "part" means "part by mass" and "%" means "% by mass" unless otherwise specified.

In the following Synthesis Examples, the compounds were identified by mass analysis (LC: Agilent 1200 type, MASS: Agilent LC / MSD type) or elemental analysis (VARIO-EL;

[Synthesis Example 1]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added, Lt; 0 &gt; C. Subsequently, 60 parts by mass of methacrylic acid, and 30 parts by mass of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the molar ratio of the compound represented by formula (I-1) 50: 50) was dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution. The solution was added dropwise into a flask kept at 70 DEG C over 4 hours using a dropping funnel. On the other hand, a solution prepared by dissolving 30 parts by weight of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by weight of 3-methoxybutyl acetate was added to a flask . After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 DEG C for 4 hours and then cooled to room temperature to obtain a resin B'1 solution having a solid content of 32.6% by mass and an acid value of 110 mg-KOH / g (in terms of solid content) . The obtained resin B'1 had a weight average molecular weight Mw of 13,400 and a molecular weight distribution of 2.50.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in Synthesis Example 1 were measured by the GPC method under the following conditions.

Device; K2479 (manufactured by Shimadzu Seisakusho Co., Ltd.)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 mL / min

Detector; RI

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

The ratio (Mw / Mn) of the polystyrene reduced weight average molecular weight to the number average molecular weight obtained above was used as the molecular weight distribution.

[Examples 1 to 3 and Comparative Examples 1 to 4]

The respective components were mixed so as to obtain the composition shown in Table 11 to obtain a colored curable resin composition.

(Table 11)

The components in Table 11 are as follows.

Colorant (A-1): A compound represented by the formula (1)

(89)

Colorant (A-2): A compound represented by the formula (2)

(90)

Colorant (A-3): Basic Blue 7 (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

[Formula 91]

Colorant (A-4): A compound represented by the formula (Ac1-1)

&Lt; EMI ID =

Resin (B): Resin B'1 obtained in Synthesis Example 1

Polymerizable compound (C): (trade name: A-TMM-3LM-N, Shin Nakamura Kagaku Kogyo Co., Ltd.)

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

&Lt; EMI ID =

Polymerization initiator (D-2): 1,2-octadione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (trade name: Irgacure OXE 01,

Polymerization initiator (D-3): N-Acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- , Manufactured by BASF)

Polymerization initiator (D-4): 2,4-Diethylthioxanthone (KAYACURE (registered trademark) DETX-2: manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (D-5): 2,2 ', 4-tris (2-chlorophenyl) -5- (3,4-dimethoxyphenyl) -4,5- (Trade name: TCDM, manufactured by CHEMBRIDGE INTERNATIONAL CORPORATION)

Thiol compound (T-1): 2-mercaptobenzothiazole (trade name: SANCELLER M, manufactured by SANSHIN KAGAKU KOGYO CO., LTD.)

Leveling agent (F): polyether-modified silicone oil

    (TORAY Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.)

Additive (G): 3-methacryloxypropyltrimethoxysilane

             (KBM-503: Shin-Etsu Chemical Co., Ltd.)

Solvent (E): Propylene glycol monomethyl ether acetate

The compound represented by the above formula (d1-40) was prepared according to the method described in Japanese Laid-Open Patent Publication No. 2014-500852.

[Formation of coating film]

A glass substrate (Eagle XG; manufactured by Corning Incorporated) having a 2-inch square was sequentially washed with a neutral detergent, water and alcohol, and then dried. The colored curable resin composition obtained above was spin-coated on the glass substrate such that the film thickness after post-baking was 3.0 占 퐉, and then prebaked in a clean oven at 90 占 폚 for 3 minutes. Thereafter, the coating film was heated at 230 DEG C for 20 minutes to obtain a coating film.

[Production of pattern]

The colored curable resin composition was applied on a 2 inch square glass substrate (Eagle 2000; Corning) by spin coating so as to have a post-baked film thickness of 2.0 占 퐉, and then prebaked at 100 占 폚 for 3 minutes to form a composition layer did. After cooling, the exposure dose (365 nm) of 40 mJ / cm ² was measured under an atmospheric environment using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) with an interval of 80 mu m between the substrate on which the composition layer was formed and the quartz glass photomask Standard). As the photomask, a 50 占 퐉 line and space pattern was formed. After the light irradiation, the composition layer was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 캜 for 60 seconds to perform development. After washing with water, post-baking was performed in an oven at 230 캜 for 20 minutes Pattern. The obtained pattern was measured for film thickness using a film thickness measuring device (DEKTAK3; manufactured by Nihon Vacuum Technology Co., Ltd.), and it was confirmed that it was 2.0 탆.

The shapes of the coloring patterns obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were observed using a scanning electron microscope (S-4000; manufactured by Hitachi High-Technologies Corporation). In the case of the shape shown by (p1) in Fig. 1 (so-called net taper shape) (p1), cracks and peeling tend not to occur in the inorganic film when the inorganic film is laminated on the colored pattern, which is good. The results are shown in Table 12.

(Table 12)

According to the present invention, it becomes possible to provide a colored curable resin composition capable of forming a good colored pattern.

The pattern and coating film obtained from the colored curable resin composition of the present invention can be used as a transparent film, a pattern, a photo spacer, an overcoat, an insulating film, a projection for controlling liquid crystal orientation, a micro lens, a coating layer or the like constituting a part of a color filter substrate and / A color filter substrate, an array substrate, and the like having such a coating film or pattern as a part of their constituent parts, and further a display device including these color filter substrates and / or array substrates, for example, a liquid crystal display, , Electronic paper, and the like.

Claims (6)

A colorant, a resin, a polymerizable compound and a polymerization initiator,
And a dye as the coloring agent,
The content of the dye is 90 parts by mass or more in 100 parts by mass of the colorant,
Wherein the polymerization initiator comprises a compound represented by the following formula (d1).
[Chemical Formula 1]

[In the formula (d1)
R ^d1 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, an alkyl group having 1 to 15 carbon atoms which may have a substituent, And the methylene group (-CH ₂ -) contained in the alkyl group or the aralkyl group is -O-, -CO-, -S-, -SO ₂ - or -N (R ^d5 ) - .
R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
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 -) included in the aliphatic hydrocarbon group is -O -, -CO- or -S-, the methine group (-CH <) included in the aliphatic hydrocarbon group may be substituted with -PO ₃ <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be replaced 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 colored curable resin composition according to claim 1, which does not contain a pigment as the colorant. 3. The method according to claim 1 or 2,
Wherein the dye is at least one dye selected from the group consisting of xanthene dyes, triarylmethane dyes, compounds represented by formula (Ab2), coumarin dyes, anthraquinone dyes, and tetraazaporphyrin dyes. Composition.
(2)

(In the formula (Ab2), each of R ⁴¹ to R ⁴⁴ independently represents 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, A saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom 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 is 2 to 20 , The methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the terminal methylene group is not substituted with an oxygen atom or -CO-. R ⁴¹ and R ⁴² may bond to form a ring together with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may bond to form a ring together with the nitrogen atom to which they are attached.
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 an oxygen atom Or -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or -SO ₂ -. However, adjacent methylene groups in the alkyl group are not simultaneously substituted with oxygen atoms, and the terminal methylene group is not substituted with an oxygen atom or -CO-.
Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms which may have a substituent.
[Y] ^m- represents an anion of any m-valence. 4. The method according to any one of claims 1 to 3,
A xanthene dye as said dye, and a compound represented by said formula (Ab2). A color filter formed from the colored curable resin composition according to any one of claims 1 to 4. A liquid crystal display device comprising the color filter according to claim 5.

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