KR102276924B1 - Colored curable resin composition - Google Patents

Abstract

The present invention relates to a colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant comprises a xanthene dye, a triarylmethane dye and a pigment, and the content of the triarylmethane dye is that of the xanthene dye. It is 1 mass part or more and 100 mass parts or less with respect to 100 mass parts of content.

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

A colored curable resin composition is used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display panel, an electroluminescent panel, and a plasma display panel. As such a colored curable resin composition, as a coloring agent, a xanthene dye and C.I. A colored curable resin composition containing only Pigment Blue 15:6 is known (JP2010-32999-A).

As for said colored curable resin composition known conventionally, the contrast of the color filter obtained by this colored curable resin composition was not necessarily fully satisfactory.

The present invention includes the following inventions.

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

the colorant comprises xanthene dyes, triarylmethane dyes and pigments;

Content of triarylmethane dye is 1 mass part or more and 100 mass parts or less with respect to content of 100 mass parts of xanthene dye.

[2] The colored curable resin composition according to [1], wherein the content of the xanthene dye is 0.1 mass% or more and 70 mass% or less with respect to the total amount of the colorant.

[3] A color filter formed of the colored curable resin composition according to [1] or [2].

[4] A display device including the color filter according to [3].

ADVANTAGE OF THE INVENTION According to the colored curable resin composition of this invention, a color filter with high contrast can be formed.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram explaining the manufacturing method of the color filter of this invention.
2 is a schematic diagram illustrating a method for manufacturing a color filter of the present invention.
3 is a schematic diagram illustrating a method for manufacturing a color filter of the present invention.

The colored curable resin composition of this invention contains a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D).

The colorant (A) includes a xanthene dye (Aa), a triarylmethane dye (Ab) and a pigment (Ad). The colorant (A) may further contain a dye different from the xanthene dye (Aa) and the triarylmethane dye (Ab) (hereinafter sometimes referred to as “dye (Ac)”).

It is preferable that the colored curable resin composition of this invention contains a solvent (E) and/or a leveling agent (F) further.

The colored curable resin composition of this invention may contain the polymerization initiation auxiliary|assistant (D1).

The colored curable resin composition of this invention can manufacture a color filter with high contrast by including a xanthene dye (Aa), a triarylmethane dye (Ab), and a pigment (Ad) as a coloring agent (A).

<Colorant (A)>

A xanthene dye (Aa) is a dye containing the compound which has a xanthene skeleton in a molecule|numerator. As the xanthene dye (Aa), for example, C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red is omitted and described only by numbers. Others are the same), 52, 87, 92, 94, 289, 388, C.I. Acid Violet 9, 30, 102, C.I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. Basic Red 10 (Rhodamine B), 11, C.I. Basic Violet 10, 11, 25, C.I. Solvent Red 218, C.I. Modern Red 27, C.I. Reactive Red 36 (Rose Bengal B), sulforodamine G, the xanthene dye described in JP2010-32999-A and the xanthene dye described in JP4492760-B, and the like. It is preferable to dissolve in an organic solvent.

Among these, as the xanthene dye (Aa), a dye containing a compound represented by the general formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable. 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, still more preferably 90 mass% or more. . In particular, it is preferable to use only compound (1a) as the xanthene dye (Aa).

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

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

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

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

a represents an integer of 0 or 1.

X represents a halogen atom.

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

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

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

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

The aromatic hydrocarbon group which may have as substituents 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 ,} and -SO ₂ NR ⁹ R ¹⁰ . Among these, as the substituent _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ are preferred, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ more preferably is Do. In this case, -SO ₃ ^- Z ⁺ as -SO ₃ ^- is N ⁺ (R ¹¹⁾ ₄ are preferred. If R ¹ ~R ⁴ is these groups, less generation of foreign matter from the colored curable resin composition of the present invention, including the compound (1a), can also form a color filter having excellent heat resistance.

Examples of the ring formed by R ¹ and R ² together with the nitrogen atom and the ring formed by R ³ and R ⁴ together with the nitrogen atom include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ⁸ to ^{R 11} 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, a decyl group, and a dodecyl group. straight-chain alkyl groups such as , hexadecyl group and icosyl group; branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group.

The hydrogen atom contained in the said saturated hydrocarbon group may be substituted with a C6-C10 aromatic hydrocarbon group or a halogen atom, for example.

-OR ⁸ includes, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, an icosyloxy group, and the like.

Examples of -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosylcarbonyl group.

Examples of -SR ⁸ include 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 a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

-SO ₂ NR ⁹ R ¹⁰ may include, for example, a sulfamoyl group;

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

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

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in ^{R 9} and R ^{10 may have a substituent.} A hydroxyl group and a halogen atom are mentioned as this substituent.

R ⁵ is ^{_{-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 - Z +, -SO 3}} H or SO ₂ NHR ⁹ is more preferable.

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

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

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.

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

The N ⁺ (R ¹¹⁾ roneun _4, it is preferred that at least two of the four R ¹¹ dogs a monovalent saturated hydrocarbon group having a carbon number of 5 to 20. Moreover, 20-80 are preferable and, as for total carbon number of four R<^{11>, 20-60 are more preferable.} When in the compound ^{(1a) + N (R 11} ) 4 is present, R ¹¹ is these groups, if, from the colored curable resin composition of the present invention containing compound (1a), it is possible to form a small foreign body color filter .

As the compound (1a), a compound represented by the general formula (2a) (hereinafter sometimes referred to as “compound (2a)”) is preferable. Compound (2a) may be a tautomer thereof.

[In formula (2a), R ²¹ to ^{R 24} each independently represent a hydrogen atom, —R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R ²¹ and R ²² may form a ring containing a nitrogen atom together with a nitrogen atom, and R ²³ and R ²⁴ may form a ring containing a nitrogen atom together with a nitrogen atom.

R ²⁵ is -SO ₃ ^- shows the Z1 ⁺ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.

m1 represents the integer of 0-5. When m1 is 2 or more, a plurality of R ²⁵ may be the same or different.

a1 represents an integer of 0 or 1.

X1 represents a halogen atom.

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

Z1 ⁺ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , and four R ²⁷ may be the same or different.

R ²⁷ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms for R ²¹ to ^{R 24} include the same groups as those exemplified as the aromatic hydrocarbon group for ^{R 1} to ^{R 4 above.} Hydrogen atoms contained to said aromatic hydrocarbon is -SO ₃ ^- may be substituted with Z1 ^+, -SO ₃ R ²⁶ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.

As the combination of R ²¹ ~R ^24, R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ is an 1-valent aromatic hydrocarbon group having a carbon number of 6-10, hydrogen atom is contained the aromatic hydrocarbon groups -SO ₃ ^-, -SO ₃ H, -SO ₃ ^- as Z1 ^+, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ is preferably substituted. A more preferred combination, R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ is an 1-valent aromatic hydrocarbon group having a carbon number of 6-10, hydrogen atom is contained the aromatic hydrocarbon groups -SO ₃ ^- Z1 ^+, or -SO ₂ is substituted with NHR ^{26 .}

R ^21, if ~R ²⁴ is these groups, from the colored curable resin composition of the present invention containing compound (2a), it is possible to form a color filter having excellent heat resistance.

As ^{a ring containing a nitrogen atom which R 21} and R ²² form together with a nitrogen atom and a ring containing a nitrogen atom which R ²³ and R ²⁴ form together with a nitrogen atom, R ¹ and R ² are formed together with a nitrogen atom The same thing as the ring to be mentioned can be mentioned. Especially, an aliphatic heterocyclic ring is preferable. Examples of the aliphatic heterocycle include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ²⁶ and R ²⁷ include the same groups as those exemplified as ^{the saturated hydrocarbon group for R 8 to R 11 .}

When R ²¹ to ^{R 24} are -R ²⁶ , it ^{is preferable that -R 26} each independently represent a methyl group or an ethyl group. In addition, as -SO ₃ R ^26, and -SO ₂ NHR ²⁶ R ²⁶ in and a branched alkyl group of 3 to 20 carbon atoms are preferred, more preferably a branched alkyl group having a carbon number of 6 to 12, the 2-ethylhexyl group, more preferably. If R ²⁶ is these groups, a color filter with little generation|occurrence|production of a foreign material can be formed from the colored curable resin composition of this invention containing a compound (2a).

Z1 ⁺ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ .

The N ⁺ (R ²⁷⁾ Examples _4, it is preferred that at least two of the four R ²⁷ dogs a monovalent saturated hydrocarbon group having a carbon number of 5 to 20. Further, the total carbon number of R 4 is ²⁷ 20 to 80 are preferred, and more preferably 20 to 60 a. When ⁺ N(R ²⁷ ) ₄ is present in the ^{compound (2a), if R 27} is these groups, a color filter with less foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a). can

1-4 are preferable and, as for m1, 1 or 2 are more preferable.

Further, as the compound (1a), a compound represented by the general formula (3a) [hereinafter sometimes referred to as “compound (3a)”] is also preferable. Compound (3a) may be a tautomer thereof.

[In formula (3a), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group is substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ - contained in the saturated hydrocarbon group is substituted with -O-, -CO- or -NR ^{11 -} good to be

R ³³ and R ³⁴ each independently represent 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.

R ³¹ and R ³³ may form a ring containing a nitrogen atom together with a nitrogen atom, and R ³² and R ³⁴ may form a ring containing a nitrogen atom together with a nitrogen atom.

p and q each independently represent an integer of 0-5. When p is 2 or more, a plurality of R ³³ may be the same or different, and when q is 2 or more, a plurality of R ³⁴ may be the same or different.

R ¹¹ has the same meaning as above.]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms for R ³¹ and R ³² include a group having 1 to 10 carbon atoms among those ^{for R 8 .}

As a C6-C10 aromatic hydrocarbon group which you may have as a substituent, the group same as that in R<^1> is mentioned.

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

R ³¹ and R ³² are each independently preferably a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.

R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

The integers of 0-2 are preferable and, as for p and q, 0 or 1 is preferable.

Examples of the compound (1a) include compounds represented by formulas (1-1) to (1-43). In the formula, 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, and more preferably a 2-ethylhexyl group.

Among the above compounds, compounds represented by formulas (1-1) to (1-23) or formulas (1-37) to (1-43) correspond to compound (2a), and formula (1-24) - A compound represented by any one of formulas (1-36) corresponds to compound (3a).

Among these, C.I. The sulfonamidide of Acid Red 289, C.I. The quaternary ammonium salt of Acid Red 289, C.I. Sulfonamidide of Acid Violet 102 or C.I. The quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such compounds include compounds represented by formulas (1-1) to (1-8), (1-11) or (1-12).

Further, a compound represented by any one of the formulas (1-24) to (1-33) is also preferable from the viewpoint of excellent solubility in organic solvents.

The xanthene dye (Aa) is a commercially available xanthene dye (eg, "Chugai Aminol Fast Pink RH/C" manufactured by Chugai Kasei Co., Ltd., "Rhodamin 6G" manufactured by Daoka Chemical Industries, Ltd.). is available. In addition, it is also possible to synthesize a commercially available xanthene dye as a starting material with reference to JP2010-32999-A.

A triarylmethane dye (Ab) is a dye containing the compound which has a triarylmethane skeleton in a molecule|numerator. As the triarylmethane dye (Ab), for example,

C.I. Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72,

C.I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 22, 24, 26, 34, 38, 48, 75, 83, 84, 86, 88, 90, 90:1, 91, 93, 93:1, 99, 100, 103, 104, 108, 109, 110, 119, 123, 147, 213, 269,

C.I. Acid Green 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 50, 50:1,

C.I. Basic Blue 7, 81, 83, 88, 89,

C.I. basic violet 2,

C.I. Basic Red 9,

C.I. Direct Blue 1, 3, 28, 29, 41, 42, 47, 52, 55,

C.I. food violet 3,

C.I. Modern Red 29, 42, 52, 62, 76, 78,

C.I. Mordant Violet 1, 1:1, 3, 6, 8, 10, 11, 15, 16, 17, 18, 19, 21, 23, 27, 28, 33, 36, 39, 49,

C.I. Modern Green 3, 13, 21, 23, 31,

C.I. Mordant Brown 26 etc. are mentioned. In addition, when the triarylmethane dye is an acid dye or a basic dye, you may form the salt with arbitrary cations or anions. It is preferable to melt|dissolve a triarylmethane dye (Ab) in an organic solvent. In particular, when preparing the colored curable resin composition of the present invention as a blue colored curable resin composition, the triarylmethane dye is preferably at least one dye selected from the group consisting of blue, violet and red.

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

[In formula (1b), R ⁴¹ to ^{R 46} independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a benzyl group which may have a substituent.

W ¹ represents a group represented by the formula (Z1) or the formula (Z2).

R ⁴⁷ to ^{R 49} each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, or a halogen atom.

t1 to t3 each independently represent an integer of 0 to 4. When t1 is 2 or more, a plurality of R ⁴⁷ may be the same or different, when t2 is 2 or more, a plurality of R ⁴⁸ may be the same or different, and when t3 is 2 or more, a plurality of R ⁴⁹ may be the same or different.

b represents an integer of 0 or 1.

Xb ^- represents a halide ion or an organometallic anion.]

The aliphatic hydrocarbon group having 1 to 6 carbon atoms includes, for example, an aliphatic group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group. saturated hydrocarbon group; Aliphatic unsaturated hydrocarbon groups, such as a propenyl group and a hexenyl group, are mentioned.

Examples of the halide ion include a fluoride ion, a chloride ion, a bromide ion and an iodide ion.

Examples of the substituent that the aliphatic hydrocarbon group having 1 to 6 carbon atoms in R ⁴¹ to ^{R 46} , the phenyl group and benzyl group and the aliphatic hydrocarbon group having 1 to 6 carbon atoms in ^{R 47} to ^{R 49} _{may have include -SO 3} ^- , - there may be mentioned such as Zb ^{+ -} SO ₃ H, -SO _3.

In addition, Zb ⁺ represents ⁺ N(R ⁵⁰ ) ₄ , Na ⁺ or K ⁺ . R ⁵⁰ 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, and ⁺ N(R ⁵⁰ ) ₄ ^{is +} N(R ¹¹ ) _{4 in the} formula (1a) and the same can be mentioned.

The aliphatic hydrocarbon group for R ⁴¹ to ^{R 46} is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.

The aliphatic hydrocarbon group for R ⁴⁷ to ^{R 49} is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and more preferably a methyl group.

t1 to t3 are preferably 0 or 1 independently of each other.

The ^{organometallic anion in Xb −} is an anion having a structure in which a metal atom capable of forming a divalent or higher metal ion and an organic compound are bonded by an ionic bond or a coordination bond.

Al, Cr, Co, Fe, Cu, Ni, Co, Zn, Mg, Ca, Ba, etc. are mentioned as a metal atom which can form a divalent or more metal ion. Among them, Al, Cr and Co are preferable.

Examples of the organic compound include salicylic acids, benzyl acids, mandelic acids, picolinic acids, and compounds having a plurality of carboxymethyl groups bonded to nitrogen atoms. Especially, salicylic acids are preferable.

Examples of the salicylic acid include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-aminosalicylic acid, 3-chlorosalicylic acid, 4-bromosalicylic acid, 3-methoxysalicylic acid, 2-hydroxysalicylic acid, 3- Nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-dibromosalicylic acid, 3,5-dichlorosalicylic acid, 3,5,6-trichlorosalicylic acid, 4- Hydroxysalicylic acid, 5-hydroxysalicylic acid, etc. are mentioned.

Examples of the benzyl acids include the following compounds.

Examples of the mandelic acids include the following compounds.

Examples of the picolinic acids include the following compounds.

Examples of the compound having a plurality of carboxymethyl groups bonded to the nitrogen atom described above include the following compounds.

As said organometallic anion, the following anion etc. are mentioned, for example.

Examples of the compound (1b) include compounds represented by formulas (2-1) to (2-12).

As the triarylmethane dye (Ab), C.I. Acid Blue 90 [compound represented by formula (2-1)] and C.I. Acid Blue 104 [the compound represented by the formula (2-2)] is preferable. With these triarylmethane dyes, a high-contrast coating film and pattern can be formed, and there is little generation of foreign substances.

The dye (Ac) is not particularly limited as long as it is a different dye from the xanthene dye (Aa) and the triarylmethane dye (Ab), and an oil-soluble dye, an acid dye, a basic dye, a direct dye, a mordant dye, or an acid dye. and dyes such as amine salts or sulfonamide derivatives of acid dyes. For example, in the color index (published by The Society of Dyers and Colorists), dyes, i.e. CI A compound classified as having a color other than a pigment, and a known dye described in a dyeing note (Skisensha) can be mentioned. Further, according to the chemical structure, azo dyes, cyanine dyes, anthraquinone dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, and coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferable.

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

C.I. Solvent Red 45, 49, 125, 130;

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

C.I. Solvent Blue 4, 5, 25, 35, 37, 45, 67, 70, 90;

C.I. Solvent Green 1, 4, 5, 7, 34, 35, etc. C.I. solvent dyes,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 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 Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 57, 66, 73, 80, 81, 82, 83, 88, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 356, 382, 383, 394, 401, 412, 417, 418, 422, 426;

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

C.I. acid violet 6B, 7, 17, 19, 29, 31, 33, 34, 36, 36:1, 39, 41, 42, 43, 47, 48, 51, 63, 76, 103, 109, 118, 126;

C.I. Acid Blue 2, 8, 14, 18, 23, 25, 27, 29, 35, 37, 41, 42, 43, 45, 47, 49, 50, 51, 52, 53, 55, 56, 57, 58, 59, 60, 62, 62:1, 63, 64, 65, 68, 69, 70, 72, 74, 78, 79, 80, 81, 81:1, 82, 87, 92, 96, 102, 111, 113, 117, 120, 122, 124, 126, 127, 127:1, 129, 129:1, 130, 131, 137, 138, 140, 142, 143, 145, 145:1, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 176, 182, 183, 184, 187, 192, 198, 199, 203, 204, 205, 208, 210, 220, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;

C.I. Acid Green 1, 58, 63, 65, 80, 104, 105, 106, 109, etc. C.I. acid dye,

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

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

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

C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

C.I. Direct Blue 2, 6, 8, 15, 22, 25, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. C.I. direct dye,

C.I. Basic Blue 1, 3, 5, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;

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

C.I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

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

C.I. Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C.I. Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 , 74, 77, 83, 84;

C.I. C.I. of Mordant Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. Mordant dye etc. are mentioned.

It does not specifically limit as a pigment (Ad), A well-known pigment can be used, For example, the pigment classified as a pigment by the color index (The Society of Dyers and Colorists publication) is mentioned.

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

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

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

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

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

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

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

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

As a pigment, C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 60; C.I. Violet pigments, such as Pigment Violet 1, 19, 23, 29, 32, 36, 38, are preferable, and C.I. Pigment Blue 15:3, 15:6 and C.I. Pigment violet 23 is more preferable, and C.I. Pigment Blue 15:6 is more preferred. By including said pigment, optimization of a transmission spectrum is easy and the light resistance and chemical-resistance of a color filter become favorable.

The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group has been introduced, graft treatment to the pigment surface with a polymer compound, etc., atomization treatment by sulfuric acid atomization method, etc., or to remove impurities if necessary. Washing treatment with an organic solvent, water, etc., removal treatment of ionic impurities by an ion exchange method, etc. may be performed.

It is preferable that a pigment has a uniform particle size. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was uniformly disperse|distributed in the solution can be obtained.

Examples of the pigment dispersant described above include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used independently and may be used in combination of 2 or more type. As a pigment dispersant, as a brand name, KP [manufactured by Shin-Etsu Chemical Co., Ltd.], Floren [manufactured by Kyoei Shaka Chemical Co., Ltd.], Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Aji Spur (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by Big Chemi Corporation), and the like.

When using a pigment dispersant, the usage-amount becomes like this. Preferably it is 1 mass % or more and 100 mass % or less with respect to the total amount of a pigment (Ad), More preferably, they are 5 mass % or more and 50 mass % or less. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency for the pigment dispersion liquid of a uniformly dispersed state to be obtained.

0.1 mass % or more and 70 mass % or less are preferable with respect to the total amount of a coloring agent (A), and, as for content of a xanthene dye (Aa), 0.5 mass % or more and 50 mass % or less are more preferable.

1 mass part or more and 100 mass parts or less are preferable with respect to 100 mass parts of xanthene dye (Aa), and, as for content of a triarylmethane dye (Ab), 20 mass parts or more and 100 mass parts or less are more preferable.

10 mass % or more and 99.9 mass % or less are preferable with respect to the total amount of a coloring agent (A), and, as for content of a pigment (Ad), 30 mass % or more and 99 mass % or less are more preferable.

When the colorant (A) contains the dye (Ac), the content of the dye (Ac) is preferably 0.1 mass% or more and 50 mass% or less, and 0.5 mass% or more and 30 mass% or less with respect to the total amount of the colorant (A). more preferably.

The colorant (A) is preferably a colorant comprising a xanthene dye (Aa), a triarylmethane dye (Ab) and a pigment (Ad). In this case, their content is each with respect to the total amount of the colorant (A).

xanthene dyes (Aa); 0.1 mass% or more and 70 mass% or less

triarylmethane dyes (Ab); 0.1 mass% or more and 70 mass% or less

pigment (Ad); It is preferable that it is 29.9 mass % or more and 99.8 mass % or less,

xanthene dyes (Aa); 0.5 mass% or more and 50 mass% or less

triarylmethane dyes (Ab); 0.5 mass% or more and 50 mass% or less

pigment (Ad); It is more preferable that they are 49.5 mass % or more and 99 mass % or less.

Preferably content of a coloring agent (A) is 5-60 mass % with respect to the total amount of solid content, More preferably, it is 8-55 mass %, More preferably, it is 10-50 mass %. When the content of the colorant (A) is within the above range, the color density when the color filter is used is sufficient, and the composition can contain the resin (B) or the polymerizable compound (C) in a required amount, so that the mechanical strength is reduced Sufficient patterns can be formed. Here, the "total amount of solid content" in this specification means the quantity remove|excluding content of the solvent from the total amount of colored curable resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

<Resin (B)>

Although resin (B) is not specifically limited, It is preferable that it is alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1] at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (a) [hereinafter sometimes referred to as “(a)”], a cyclic ether structure having 2 to 4 carbon atoms, a copolymer with a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);

Resin [K2] (a) and (b), and a monomer (c) copolymerizable with (a) [however, different from (a) and (b)] [hereinafter referred to as “(c)” in some cases] copolymers with;

resin [K3] copolymer of (a) and (c);

Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c);

Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c);

Resin [K6] Resin in which (a) was made to react with the copolymer of (b) and (c), and carboxylic anhydride was further reacted.

Specific examples of (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, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene , 5-Carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxy group, such as [2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;

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

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

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity and the solubility point with respect to the aqueous alkali solution of resin obtained.

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

In addition, in this specification, "(meth)acrylic acid" shows 1 or more types chosen from the group which consists of acrylic acid and methacrylic acid. Notations such as “(meth)acryloyl” and “(meth)acrylate” have the same meaning.

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter referred to as "(b1)") "(b2)" may be referred to], a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc. are mentioned.

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

As (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxy) methyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc. are mentioned. can

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane [eg, Celoxide 2000; manufactured by Daicel Co., Ltd.], 3,4-epoxycyclohexylmethyl (meth)acrylate [eg, cyclomer A400; manufactured by Daicel Co., Ltd.], 3,4-epoxycyclohexylmethyl (meth)acrylate [eg, cyclomer M100; manufactured by Daicel Co., Ltd.], the compound represented by the formula (I), the compound represented by the formula (II), and the like.

[In formulas (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^a and X ^b represent a single bond, -R ^c -, *-R ^c -O-, *-R ^c -S- or *-R ^c -NH-.

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

* indicates the number of bonds with O.]

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

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

R ^a and R ^b preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

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

X ^a and X ^b include preferably a single bond, a methylene group, an ethylene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, More preferably, a single bond, *-CH ₂ CH ₂ -O- (* indicates the number of bonds with O).

Examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-15). Preferably, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) ) can be mentioned. More preferably, a compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15) is mentioned.

Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15). Preferably, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) ) can be mentioned. More preferably, the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), or Formula (II-15) is mentioned.

Each of the compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. In addition, they can be mixed in any ratio. In the case of mixing, the mixing ratio is in a molar ratio, preferably 5:95 to 95:5, more preferably 10:90 to 90:10, still more preferably 20: in formula (I):formula (II): It is 80-80:20.

As (b2), the monomer which has an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo yloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. are mentioned.

As (b3), the monomer which has a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by Osaka Yuki Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), it is preferable that it is (b1) from the point which reliability, such as heat resistance of the color filter obtained and chemical-resistance, can be improved more. Moreover, (b1-2) is more preferable at the point that it is excellent in the storage stability of colored curable resin composition.

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (called "dicyclofentanyl (meth) acrylate" as a common name in the art. In addition, sometimes referred to as "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (as a common name in the technical field, "dicyclophene" tenyl (meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propar (meth)acrylic acid esters, such as gil (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

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

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

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

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

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

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

In the resin [K1], the ratio of the structural units derived from each of the total structural units constituting the resin [K1],

a structural unit derived from (a); 2-60 mol%

the structural unit derived from (b); It is preferable that it is 40-98 mol%,

a structural unit derived from (a); 10-50 mol%

the structural unit derived from (b); It is more preferable that it is 50-90 mol%.

When the ratio of the structural unit of resin [K1] exists in the said range, there exists a tendency excellent in the storage stability of a colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance of the color filter obtained.

Resin [K1] is, for example, the method described in the document "Experimental Methods for Polymer Synthesis" [written by Takayuki Otsu, Hatkyosho Co., Ltd., 1st edition, 1st edition, published on March 1, 1972] and the cited references described in this document. It can be prepared as a reference.

Specifically, there is a method in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, for example, oxygen is replaced with nitrogen to create a deoxidized atmosphere, and heating and warming while stirring is mentioned. . In addition, the polymerization initiator, a solvent, etc. used here are not specifically limited, Those normally used in the said field|area can be used. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) What is necessary is just to melt|dissolve each monomer as a solvent, The solvent etc. which are mentioned later as a solvent (E) of the colored curable resin composition of this invention are mentioned.

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

In the resin [K2], the ratio of the structural units derived from each of the total structural units constituting the resin [K2],

a structural unit derived from (a); 2-45 mol%

the structural unit derived from (b); 2-95 mol%

the structural unit derived from (c); It is preferable that it is 1-65 mol%,

a structural unit derived from (a); 5-40 mol%

the structural unit derived from (b); 5-80 mol%

the structural unit derived from (c); It is more preferable that it is 5-60 mol%.

When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability in forming a colored pattern, and the solvent resistance, heat resistance and mechanical strength of the resulting color filter tend to be excellent. .

The resin [K2] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

In the resin [K3], the ratio of the structural units derived from each of the total structural units constituting the resin [K3],

a structural unit derived from (a); 2-60 mol%

the structural unit derived from (c); It is preferable that it is 40-98 mol%,

a structural unit derived from (a); 10-50 mol%

the structural unit derived from (c); It is more preferable that it is 50-90 mol%.

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

Resin [K4] is prepared by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms in (b) to the carboxylic acid and/or carboxylic anhydride in (a). can do.

First, a copolymer of (a) and (c) is prepared in the same manner as described as a method for producing the resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the same ratio as what was exemplified in the resin [K3].

Next, the C2-C4 cyclic ether which (b) has is made to react with a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the said copolymer.

Following the preparation of the copolymer of (a) and (c), the atmosphere in the flask is substituted with air from nitrogen, and (b), a reaction catalyst of a carboxylic acid or carboxylic acid anhydride and a cyclic ether [such as tris(dimethylamino) methyl) phenol, etc.] and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted at, for example, 60° C. to 130° C. for 1 to 10 hours, thereby preparing the resin [K4].

As for the usage-amount of (b), 5-80 mol is preferable with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of the storage stability of colored curable resin composition, the developability at the time of forming a pattern, and solvent resistance, heat resistance, mechanical strength, and sensitivity of the pattern obtained to become favorable. Since the reactivity of a cyclic ether is high and unreacted (b) hardly remains, as (b) used for resin [K4], (b1) is preferable and (b1-1) is more preferable.

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b), and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b), and (c).

Reaction conditions, such as an injection method, reaction temperature, and time, can be adjusted suitably in consideration of manufacturing equipment, the amount of heat generated by polymerization, and the like. In addition, similarly to polymerization conditions, the injection method and reaction temperature can be suitably adjusted in consideration of manufacturing equipment, the amount of heat generated by polymerization, etc.

The resin [K5] is a first step, and a copolymer of (b) and (c) is obtained in the same manner as in the production method of the above-mentioned resin [K1]. Similarly to the above, the obtained copolymer may be used as it is after the reaction, a concentrated or diluted solution, or extracted as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is, respectively, with respect to the total number of moles of all the structural units constituting the copolymer.

the structural unit derived from (b); 5-95 mol%

the structural unit derived from (c); It is preferable that it is 5-95 mol%,

the structural unit derived from (b); 10-90 mol%

the structural unit derived from (c); It is more preferable that it is 10-90 mol%.

Further, the carboxylic acid or carboxylic acid anhydride of (a) is added to the cyclic ether derived from (b) in the copolymer of (b) and (c) under the same conditions as in the method for producing the resin [K4]. By reacting, resin [K5] can be obtained.

As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of a cyclic ether is high and unreacted (b) hardly remains, as (b) used for resin [K5], (b1) is preferable and (b1-1) is more preferable.

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

A carboxylic acid anhydride is reacted with a hydroxyl group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride), etc. are mentioned. As for the usage-amount of carboxylic anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amounts of (a).

Specifically as the resin (B), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decylacrylate/(meth) resins such as acrylic acid copolymer [K1]; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 ^{.1.0 2.6} ]Resins such as decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer [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, and glycidyl (meth) to a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer ) Resin to which acrylate was added, resin [K4], such as a resin which added glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer; A resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate resin [K5] such as a resin obtained by reacting (meth)acrylic acid with a copolymer; and resin [K6] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting tetrahydrophthalic anhydride. .

Especially, as resin (B), resin [K1] and resin [K2] are preferable.

Preferably the weight average molecular weight of polystyrene conversion of resin (B) is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is also high, the solubility in the developing solution of the unexposed part is good, and the resolution of the coloring pattern tends to be improved.

Preferably the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of resin (B) is 1.1-6, More preferably, it is 1.2-4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150 mg-KOH/g, still more preferably 70 to 135 mg-KOH/g. Here, an acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), For example, it can obtain|require by titrating using potassium hydroxide aqueous solution.

Preferably content of resin (B) is 7-65 mass % with respect to the total amount of solid content, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %. When content of resin (B) exists in said range, a coloring pattern can be formed and there exists a tendency for the resolution and residual film rate of a coloring pattern to improve.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized with an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, preferably It is a (meth)acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more ethylenically unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa. (meth)acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (Meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate , propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

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

The weight average molecular weight of a polymeric compound (C) becomes like this. Preferably it is 150 or more and 2,900 or less, More preferably, it is 250-1,500 or less.

It is preferable that content of a polymeric compound (C) is 7-65 mass % with respect to the total amount of solid content, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %. When content of a polymeric compound (C) exists in said range, there exists a tendency for the residual-film rate at the time of coloring pattern formation and the chemical-resistance of a color filter to improve.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids, etc. under the action of light or heat, and a known polymerization initiator can be used.

As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a biimidazole compound is preferable, and O - The polymerization initiator containing an acyl oxime compound is more preferable.

The O-acyloxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents the number of bonds.

Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3, 3-Dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-) Methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-3-cyclopentylpropan-1-one-2-imine; and the like. You may use commercial items, such as Ilgacure OXE01, OXE02 (above, BASF company make), and N-1919 (made by ADEKA company). Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane At least one selected from the group consisting of -1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferable , N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine is more preferable. If it is these O-acyl oxime compounds, there exists a tendency for a high-brightness color filter to be obtained.

The alkylphenone compound is a compound having a partial structure represented by Formula (d2) or a partial structure represented by Formula (d3). Among these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-( 4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane -1-one and the like. You may use commercial items, such as Ilgacure 369, 907, 379 (above, BASF Corporation make).

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4-(2). -hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one; α,α-diethoxyacetophenone, benzyl dimethyl ketal, and the like.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the general formula (d2).

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -(4-Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine etc. are mentioned.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound. You may use commercial items, such as Ilgacure (trademark) 819 (made by BASF).

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro) Phenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis(2-chlorophenyl)-4 ,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2 '-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5, 5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JPS48-38403-B, JPS62-174204-A, etc.), the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group imidazole compounds (for example, refer to JPH07-10913-A etc.) etc. are mentioned.

Moreover, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone , benzophenone compounds such as 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization initiation adjuvant (D1) (especially amines) mentioned later.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl/methyl/benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate Onium salts, such as phenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

Preferably content of a polymerization initiator (D) is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), More preferably, it is 1-20 mass parts. When content of a polymerization initiator (D) exists in an above-mentioned range, since there exists a tendency for it to become highly sensitive and exposure time to shorten, productivity of a color filter improves.

<Polymerization initiation aid (D1)>

A polymerization initiation adjuvant (D1) is a compound used in order to accelerate|stimulate superposition|polymerization of the polymeric compound which superposition|polymerization was started by a polymerization initiator, or a sensitizer. When a polymerization initiator auxiliary (D1) is included, it is used in combination with a polymerization initiator (D) normally.

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminomethylbenzoate, 4-dimethylaminoethylbenzoate, 4-dimethylaminobenzoate isoamyl, benzoate 2-dimethylaminoethyl, 4-dimethyl 2-ethylhexyl aminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4, 4'-bis(ethylmethylamino)benzophenone etc. are mentioned, Especially, 4,4'-bis(diethylamino)benzophenone is preferable. You may use a commercial item, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- Dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

As the thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxy City oxanthon etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

When using these polymerization initiation adjuvant (D1), the content becomes like this with respect to 100 mass parts of total amounts of resin (B) and polymeric compound (C), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. is wealth When the amount of the polymerization initiation auxiliary (D1) is within this range, a coloring pattern can be formed with a higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not specifically limited, The solvent normally used in this field|area can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents ( Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (containing OH in the molecule, -O- , -CO- and -COO--free solvent), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc. are mentioned.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, gamma -butyrolactone, etc. are mentioned.

Ether solvents 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. Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol, methylanisole and the like.

Ether ester solvents include methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxy propionate, ethyl 3-methoxy propionate, and methyl 3-ethoxy propionate. , 3-Ethoxy ethyl propionate, 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxy propyl propionate, 2-ethoxy methyl propionate, 2-ethoxy propionate ethyl, 2-methoxy-2- Methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono and propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo pentanone, cyclohexanone, isophorone, and the like.

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

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

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

Among the above-described solvents, organic solvents having a boiling point of 120°C or higher and 180°C or lower at 1 atm are preferable from the viewpoint of coating properties and drying properties. As a solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydro Roxy-4-methyl-2-pentanone and N,N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and ethyl 3-ethoxypropionate are more preferable.

Preferably content of a solvent (E) is 70-95 mass % with respect to the total amount of the colored curable resin composition of this invention, More preferably, it is 75-92 mass %. In other words, the total amount of solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass %, More preferably, it is 8-25 mass %. When content of a solvent (E) exists in said range, since the flatness at the time of application|coating becomes favorable and color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

<Leveling agent (F)>

As the leveling agent (F), a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom, etc. are mentioned. These may have a polymerizable group in a side chain.

Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Tore Silicone DC3PA, Tore Silicone SH7PA, Toore Silicone DC11PA, Toore Silicone SH21PA, Toore Silicone SH28PA, Toore Silicone SH29PA, Toore Silicone SH30PA, Toore Silicone SH8400 [brand name: Ltd.], KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momen) TV Performance Materials Japan Kodo Co., Ltd.) and the like.

Examples of the fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (registered trademark) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183 , Megapack F554, Megapack R30, Megapack RS-718-K [manufactured by DIC Corporation], Ftop (registered trademark) EF301, Ftop EF303, Ftop EF351, Ftop EF352 [Mitsubishi Materials Denshi Kasei] Co., Ltd.], Sufflon (registered trademark) S381, Sufflon S382, Sufflon SC101, Sufflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemicals, Genkyusho Co., Ltd.), etc. can be heard

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

Preferably content of a leveling agent (F) is 0.001 mass % or more and 0.2 mass % or less with respect to the total amount of colored curable resin composition, Preferably they are 0.002 mass % or more and 0.1 mass % or less, More preferably, they are 0.01 mass % or more and 0.05 mass% or less. When content of a leveling agent (F) exists in an above-described range, the flatness of a color filter can be made favorable.

<Other ingredients>

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

<Method for producing colored curable resin composition>

The colored curable resin composition of the present invention includes, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as needed, a leveling agent (F), It can prepare by mixing a polymerization start adjuvant (D1) and other components.

A solution may be prepared by dissolving the xanthene dye (Aa), the triarylmethane dye (Ab), and the dye (Ac) to be used as necessary in part or all of the solvent (E) in advance. It is preferable to filter this solution through a filter with a pore diameter of about 0.01 to 1 m.

It is preferable to mix the pigment (Ad) with a part or all of the solvent (E) beforehand, and to disperse it using a bead mill etc. until the average particle diameter of a pigment becomes about 0.2 micrometer or less. At this time, you may mix|blend a part or all of the said pigment dispersant and resin (B) as needed. The target colored curable resin composition can be prepared by mixing a remaining component with the pigment dispersion liquid obtained in this way so that it may become predetermined density|concentration.

It is preferable to filter the colored curable resin composition after mixing with a filter of about 0.01-10 micrometers in pore diameter.

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

As a method of forming a color filter with the colored curable resin composition of this invention, the method of using a photolithography method and an inkjet apparatus, etc. are mentioned. In the photolithography method, for example, the colored curable resin composition of the present invention is applied on a substrate, volatile components such as a solvent are removed or dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to develop. way to do it After image development, a coloring pattern can be formed by heating as needed. In the formation method of the said coloring pattern, the colored coating film which is hardened|cured material of the said coloring composition layer can be formed by not using and/or not developing a photomask at the time of exposure. The colored pattern and colored coating film obtained in this way can be used as a color filter.

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or silica-coated soda-lime glass, a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate, silicone, or on the substrate What formed the thin film of aluminum, silver, silver/copper/palladium alloy, etc. is used. Another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed on these board|substrates.

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

Next, a method of forming a pattern on a glass substrate on which a thin film transistor (hereinafter referred to as "TFT") is formed will be described.

Specifically, a plurality of TFTs 22 are formed for each pixel on the glass substrate 21 by a known method such as a photolithography technique (see Fig. 1). The TFT 22 is formed of, for example, molybdenum (Mo) on a glass substrate 21 and includes a gate electrode 22a constituting a part of the gate line, and a nitride film (SiN _x ) formed on the gate electrode 22a, for example. A gate insulating film 22b made of a lamination film of a peroxide film (SiO ₂ ), a polysilicon film 22c formed on the gate insulating film 22b, and, for example, a lamination film of an _{oxide film (SiO 2} ) and a nitride film (SiN _{x )} is constituted by a protective film 22d formed by A region of the polysilicon film 22c opposite to the gate electrode 22a serves as a channel region of the TFT 22, and regions on both sides of the channel region serve as a source region or a drain region. The source region of the polysilicon film 22c is electrically connected to a signal line 27 formed of, for example, aluminum (Al) through a connection hole (contact hole) formed in the protective film 22d. Further, the drain region of the polysilicon film 22c is electrically connected to the pixel electrode 24 through a connection hole (contact hole) 201 as will be described later.

When forming the plurality of TFTs 22 for each pixel on the glass substrate 21 , an alignment mark (not shown) is formed on the glass substrate 21 simultaneously with the TFT 22 . This alignment mark becomes a reference|standard of the alignment in the formation process of the color filter layer 23 so that it may mention later. Moreover, these alignment marks can also be used as the mark used as a reference|standard for bonding of a drive board|substrate and an opposing board|substrate. The alignment mark can be formed by the same process using at least one layer when forming a metal layer such as wiring or a polysilicon layer in the manufacturing process of the TFT 22 .

Next, on the TFT 22 and the glass substrate 21 in which the alignment mark was formed, the colored curable resin composition of this invention is apply|coated, and volatile components, such as a solvent, are removed by heat-drying (pre-baking) and/or drying under reduced pressure. and dried to form a coloring composition layer having a film thickness of 0.5 to 5.0 µm, for example, 1.0 µm.

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

30 degreeC - 120 degreeC are preferable and, as for the temperature in the case of heat-drying, 60 degreeC - 110 degreeC are more preferable. Moreover, as heating time, it is preferable that they are 10 second - 60 minutes, and it is more preferable that they are 30 second - 30 minutes.

When drying under reduced pressure, it is preferable to carry out under a pressure of 50 to 150 Pa at a temperature range of 20°C to 25°C.

Next, the color composition layer is irradiated with ultraviolet light through a photomask (not shown), and an unnecessary portion is selectively removed with a developing solution, whereby a connection hole (contact hole) reaching the drain region of the polysilicon film 22c. After obtaining the coloring composition layer shape|molded by the pixel in which ) (201) was formed, it washes with water.

By image development, the unexposed part of a coloring composition layer melt|dissolves in a developing solution, and is removed. As a developing solution, the aqueous solution of basic compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, is preferable, for example. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%. Moreover, the developing solution may contain surfactant.

Any of a puddle method, a dipping method, a spray method, etc. may be sufficient as a developing method. Moreover, you may incline a board|substrate at any angle at the time of development.

Then, in order to reflow (reflow) the coloring composition layer in which the connection hole (contact hole) 201 was formed, and/or in order to harden the polymeric compound (C) etc. contained in this coloring composition layer, 100 degreeC, for example. Heating is carried out at a temperature of -300°C, preferably 150°C-230°C, for example 1 to 120 minutes, preferably 10 to 60 minutes. In this way, the colored curable resin composition layer 23A which is a coloring pattern is formed. This colored curable resin composition layer 23A respond|corresponds to the color filter of this invention.

By repeating this operation and forming the colored curable resin composition layer 23A from red colored curable resin composition, green colored curable resin composition, and blue colored curable resin composition, respectively, correspondingly for every pixel row, the red filter 23a, a green filter A color filter layer 23 including 23b and a blue filter 23c is formed (see Fig. 2). The area between each filter of the color filter layer 23 becomes a mixed area of adjacent colors, but since this area is a light-shielding area facing the signal line 27, there is no particular problem in quality. In addition, you may make it so that the area|region between each of these filters is not colored.

Subsequently, the photosensitive resin film 29 as a protective film with a film thickness of, for example, 0.3 to 2.0 mu m is formed so as to cover the color filter layer 23 by, for example, spin coating. Subsequently, the polysilicon film is irradiated with ultraviolet light to the photosensitive resin film 29 through a photomask (not shown), and the region corresponding to the connection hole 201 and the unnecessary portion are selectively removed with a developer solution. After forming the connection hole (contact hole) 202 reaching the drain region of (22c), it is washed with water. Thereafter, the photosensitive resin film 29 is heated at a temperature in the range of 100 DEG C to 300 DEG C, for example, 200 DEG C for reflow (reflow). Subsequently, in order to remove residues such as dye and organic matter deposited in the contact hole 202, etching is performed with oxygen plasma, and further, in order to remove the oxide film formed by oxygen plasma, for example, dilute hydrofluoric acid is etched. .

Next, a transparent conductive material, for example, ITO (Indium-Tin Oxide: oxide mixed film of indium and tin) is formed on the photosensitive resin film 29 by, for example, sputtering, and this ITO film is formed by photolithography and etching. A transparent pixel electrode 24 is formed by patterning (refer to FIG. 3). Note that the pixel electrode 24 may be formed of a metal such as aluminum (Al) or silver (Ag) depending on the device to be manufactured. After that, after forming an alignment film by a known method, a liquid crystal display device can be manufactured by bonding this drive board|substrate and a counter board|substrate.

According to the colored curable resin composition of this invention, especially the color filter excellent in contrast can be produced. This color filter is useful as a color filter used for a display device (for example, a liquid crystal display device, an organic electroluminescent device, electronic paper, etc.) and a solid-state image sensor.

Example

Hereinafter, the colored curable resin composition of this invention is demonstrated in detail by an Example.

"%" and "part" in the examples are mass% and parts by mass, unless otherwise specified.

In the following synthesis examples, the compound is analyzed by mass spectrometry (LC; Agilent type 1200, MASS; Agilent LC/MSD type) or elemental analysis [VARIO-EL; Elemental Co., Ltd.] was identified.

[Synthesis Example 1]

20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was stirred at 110° C. for 6 hours. After cooling the resulting reaction solution to room temperature, it was added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were obtained as a residue of suction filtration and dried to obtain 24 parts of a compound represented by the formula (1-24) (hereinafter referred to as "xanthene dye 1"). The yield was 80%.

Identification of a compound represented by the formula (1-24);

(mass spectrometry) ionization mode=ESI+: m/z=[M+H] ⁺ 603.4

Exact Mass: 602.2

[Synthesis Example 2]

A mixture of the compound represented by the formula (A0-1) and the compound represented by the formula (A0-2) (trade name Chugai Aminol Fast Pink R; manufactured by Chugai Kasei) was placed in a flask equipped with a cooling tube and a stirring device 15 , 150 parts of chloroform and 8.9 parts of N,N-dimethylformamide were charged, and 10.9 parts of thionyl chloride were added dropwise while maintaining 20°C or lower under stirring. After completion of the dropwise addition, the temperature was raised to 50°C, the reaction was maintained at the same temperature for 5 hours, and then cooled to 20°C. The mixture solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise to the reaction solution after cooling, maintaining at 20 degrees C or less under stirring. Thereafter, the reaction was stirred at the same temperature for 5 hours. Subsequently, the solvent was distilled off of the obtained reaction mixture by a rotary evaporator, and after adding a small amount of methanol, it was stirred vigorously. This mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60° C., and xanthene dye 2 [a mixture of compounds represented by formulas (Aa-1-1) to (Aa-1-8)] 11.3 copies were obtained.

[Synthesis Example 3]

A solution (s1) was prepared by dissolving 1.0 parts of the compound represented by the formula (f-1) [BONTRON (registered trademark) E-108, manufactured by Orient Chemical Co., Ltd.] in 70 parts of N,N-dimethylformamide. . Separately, a solution (t1) in which 3.92 parts of a compound represented by the formula (2-5) (Victoria Pure Blue BO, manufactured by Aldrich) was dissolved in 90 parts of N,N-dimethylformamide was prepared. The solution (t1) was added to the solution (s1) at 25 °C, and then the temperature was raised to 80 °C and stirred for 8 hours. After cooling this liquid mixture to room temperature, 100 parts of saturated saline solution and 1000 parts of ion-exchange water were then added, and it stirred for 1 hour further. Thereafter, the precipitate was collected by suction filtration and washed with 100 parts of ion-exchanged water and 100 parts of hexane to obtain 1.70 parts of a compound represented by the formula (2-9) (hereinafter referred to as “triarylmethane dye 1”).

Identification of a compound represented by the formula (2-9);

(Elemental Analysis) C: 75.6 H: 7.9 N: 4.2

[Synthesis Example 4]

3-bromofluorobenzene [manufactured by Tokyo Kasei Kogyo Co., Ltd.] 3.30 parts, diethylamine 6.00 parts, copper powder [manufactured by Kanto Chemical Co., Ltd.] 0.064 parts, copper (I) iodide 0.19 parts, tripotassium phosphate 9.20 parts of n-hydrate (manufactured by Kanto Chemical Co., Ltd.) and 20.0 parts of 2-(dimethylamino)ethanol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed at room temperature, heated to 80°C, and stirred for 72 hours. After cooling this liquid mixture to room temperature, 200 parts of water and 150 parts of chloroform were added and liquid-separated, the chloroform layer was acquired, and it dehydrated with magnesium sulfate. From the solution obtained by removing magnesium sulfate, chloroform was distilled off under reduced pressure to obtain 2.06 parts of a compound represented by the following formula (gx-1).

16.30 parts of N,N-diethyl-3-methylaniline (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 19.00 parts of dimethoxymethane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 100 parts of acetic acid were mixed. 300 parts of acetic acid/98% sulfuric acid (1/1) mixture was dripped at this mixed solution, and it stirred at room temperature for 10 minutes. The precipitate was collected by suction filtration and washed with 1000 parts of ion-exchanged water to obtain 10.04 parts of a compound represented by the following formula (gx-2).

6.70 parts of the compound represented by the formula (gx-2), 20 parts of potassium permanganate (manufactured by Kanto Chemical Co., Ltd.), and 20 parts of copper(II) sulfate pentahydrate (manufactured by Kanto Chemical Co., Ltd.) were mixed and mixed at room temperature for 6 hours stirred for a while. 200 parts of chloroform was added to the reaction mixture, and the chloroform-extracted solution was filtered off. Chloroform was distilled off under reduced pressure to obtain 6.20 parts of a compound represented by the following formula (gx-3).

14.10 parts of the compound represented by the formula (gx-3), 34.50 parts of the compound represented by the formula (gx-1), and 50 parts of phosphorus oxychloride [manufactured by Kanto Chemical Co., Ltd.] were mixed at room temperature, and the temperature was raised to 100 ° C. Stirred for 3 hours. After the mixture was cooled to room temperature, it was added to a mixed solvent of 120 parts of ethyl acetate/10 parts of perchloric acid and stirred for 1 hour. The precipitate was collected by suction filtration and washed with 200 parts of ethyl acetate to obtain 8.64 parts of a salt represented by the following formula (g-1).

A solution (s2) was prepared in which 1.54 parts of the compound represented by the formula (f-1) [BONTRON (registered trademark) E-108, manufactured by Orient Chemical Co., Ltd.] was dissolved in 61 parts of N,N-dimethylformamide. . Separately, a solution (t2) in which 1.50 parts of the salt represented by the formula (g-1) was dissolved in 15 parts of N,N-dimethylformamide was prepared. The solution of (t2) was added to (s2) at 25°C and stirred for 2 hours. 382 parts of ion-exchanged water was added to this mixture, and the mixture was stirred for 1 hour more. Thereafter, the precipitate was collected by suction filtration and washed with 127 parts of ion-exchanged water to obtain 1.78 parts of a compound represented by the formula (2-10) (hereinafter referred to as “triarylmethane dye 2”).

Identification of a compound represented by the formula (2-10);

(Elemental Analysis) C: 73.7 H: 8.4 N: 4.1

[Synthesis Example 5]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was flowed at a rate of 0.02 L/min to form a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was added and heated to 70° C. while stirring.

Subsequently, 46 parts by mass of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decylacrylate [the compound represented by the formula (I-1) and the compound represented by the formula (II-1) are mixed in a molar ratio of 50 Mix at 50] 240 parts by mass and 185 parts by mass of ethyl lactate to prepare a solution, and the solution was added dropwise to a flask kept at 70°C over 4 hours using a dropping funnel.

On the other hand, a solution obtained by dissolving 30 parts by mass of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was added dropwise to the flask over 4 hours using a separate dropping funnel. After the polymerization initiator solution was dropped, it was maintained at 70° C. for 4 hours, and then cooled to room temperature so that the weight average molecular weight (Mw) was 9.1×10 ³ , the molecular weight distribution was 2.1, the solid content was 26% by mass, and the solid content was acid value 120. A solution of mg-KOH/g Resin B1 was obtained. Resin B1 has the structural unit shown below.

[Synthesis Example 6]

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube, the atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. acrylate 70.5 g (0.40 mol), methacrylic acid 43.0 g (0.5 mol), tricyclodecane skeleton monomethacrylate [dicyclopentanyl methacrylate; FA-513M manufactured by Hitachi Kasei Co., Ltd.] 22.0 g (0.10 mol) and 136 g of propylene glycol monomethyl ether acetate was added dropwise with a solution containing 3.6 g of 2,2'-azobisisobutyronitrile, Moreover, stirring was continued at 100 degreeC.

Next, the atmosphere in the flask was changed from nitrogen to air, and glycidyl methacrylate 35.5 g [0.25 mol, (50 mol% based on the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0.9 g And 0.145 g of hydroquinone was put into the flask, and the reaction was continued at 110° C. to obtain a resin B2 solution having a solid content of 29% and an acid value of a solid content of 79 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,000.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by the synthesis example was performed on condition of the following using the GPC method.

Device; K2479 [manufactured by Shimadzu Corporation]

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]

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

[Example 1]

(Preparation of colored curable resin composition)

(A) Colorant: C.I. Pigment Blue 15:6 (pigment) 16 parts

3.9 parts of acrylic pigment dispersant

130 parts of propylene glycol monomethyl ether acetate

to sufficiently disperse the pigment using a bead mill, and then,

(A) Colorant: xanthene dye 1 2.2 parts

(A) Colorant: C.I. Acid Blue 104 (Daiwa BLUE 300; manufactured by Daiwa Kasei Co., Ltd.: Triarylmethane dye) 0.9 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

[Kayarad (registered trademark) DPHA; Nihon Kayaku Co., Ltd.] 50 copies

(D) polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine [Ilgacure (registered trademark) OXE01; Manufactured by BASF] 10 copies

(F) Leveling agent: polyether-modified silicone oil [Toore Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.] 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

<Production of coloring pattern>

After applying the colored curable resin composition by spin coating on a square glass substrate having a side of 5 cm (Eagle 2000; manufactured by Corning), it was prebaked at 100°C for 3 minutes to obtain a colored layer.

After cooling, the interval between the substrate on which the colored layer was formed and the photomask made of quartz glass was set to 100 μm, and the exposure machine [TME-150RSK; Topcon Co., Ltd.] was used to irradiate the light with an exposure dose of 150 mJ/cm 2 (based on 365 nm) under an atmospheric atmosphere. As a photomask, a 100 m line and space pattern formed thereon was used. The colored layer after light irradiation was immersed in an aqueous developer solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24° C. for 60 seconds, washed with water, and then post-baked at 230° C. in an oven for 30 minutes to perform a colored pattern. got

<Measurement of film thickness>

About the obtained coloring pattern, the film thickness was measured with a film thickness measuring apparatus [DEKTAK3; Nippon Shinkugi Jutsu Co., Ltd.] was used for measurement.

<Chromaticity evaluation>

About the obtained coloring pattern, a colorimeter [OSP-SP-200; Spectroscopy was measured using Olympus Co., Ltd.], and the xy chromaticity coordinates (x, y) and tristimulus value Y in the XYZ colorimetric system of CIE were measured using the characteristic function of the C light source. It shows that the brightness is so high that the value of Y is large. A result is shown in Table 1.

<Contrast evaluation>

Except not using a photomask at the time of exposure, operation similar to preparation of a coloring pattern was performed, and the colored coating film was produced. About the obtained colored coating film, the contrast system [CT-1; The Tsubosaka Electric Co., Ltd. color difference meter BM-5A; manufactured by Topcon, light source; F-10, polarizing film; Tsubosaka Denki Co., Ltd.] was used, the blank value was set to 30000, and the contrast was measured. When the contrast in a coating film is high, also in a coloring pattern, it can be said that contrast is high similarly. A result is shown in Table 1.

[Example 2]

C.I. Acid Blue 104 was mixed with C.I. Except changing to Acid Blue 90, operation similar to Example 1 was performed, and the colored curable resin composition was obtained. Evaluation similar to Example 1 was performed about this colored curable resin composition. A result is shown in Table 1.

[Example 3]

(Preparation of colored curable resin composition)

(A) Colorant: C.I. Pigment Blue 15:6 (pigment) 17 parts

4.2 parts of acrylic pigment dispersant

141 parts of propylene glycol monomethyl ether acetate

to sufficiently disperse the pigment using a bead mill, and then,

(A) Colorant: C.I. Acid Red 52

[Manufactured by Tokyo Kasei Kogyo Co., Ltd.; xanthene dye] 2.5 parts

(A) Colorant: Triphenylmethane dye 1 1.0 part

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

[Kayarad (registered trademark) DPHA; Nihon Kayaku Co., Ltd.] 50 copies

(D) polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine [Ilgacure (registered trademark) OXE01; Manufactured by BASF] 10 copies

(F) Leveling agent: polyether-modified silicone oil [Toore Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.] 0.1 part

(E) solvent: 559 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

are mixed to obtain a colored curable resin composition.

About this colored curable resin composition, operation similar to Example 1 was performed, and the same evaluation was performed. A result is shown in Table 1.

[Example 4]

Except having changed the triphenylmethane dye 1 into the triphenylmethane dye 2, operation similar to Example 3 was performed and the colored curable resin composition was obtained. Evaluation similar to Example 1 was performed about this colored curable resin composition. A result is shown in Table 1.

[Comparative Example 1]

(A) Colorant: C.I. Pigment Blue 15:6 (pigment) 20 parts

5 parts of acrylic pigment dispersant

137 parts of propylene glycol monomethyl ether acetate

to sufficiently disperse the pigment using a bead mill, and then,

(A) Colorant: xanthene dye 2 3.5 parts

(B) Resin: 157 parts of resin B2 solution

(C) Polymerizable compound: dipentaerythritol hexaacrylate

[Manufactured by Nihon Kayaku Co., Ltd.] 50 copies

(D) polymerization initiator: OXE 01 (manufactured by BASF) 15 parts

(E) solvent: 289 parts of 4-hydroxy-4-methyl-2-pentanone

was mixed to obtain a colored curable resin composition. Evaluation similar to Example 1 was performed about this colored curable resin composition. A result is shown in Table 1.

[Table 1]

[Example 5]

(Preparation of colored curable resin composition)

(A) Colorant: C.I. Pigment Blue 15:6 (pigment) 24 parts

6.1 parts of acrylic pigment dispersant

163 parts of propylene glycol monomethyl ether acetate

to sufficiently disperse the pigment using a bead mill, and then,

(A) Colorant: xanthene dye 2 1.8 parts

(A) Colorant: C.I. Acid Blue 104 [Daiwa BLUE 300;

Daiwakasei Co., Ltd. product: triarylmethane dye] 1.8 parts

(B) Resin: 60 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

[Kayarad (registered trademark) DPHA; Nihon Kayaku Co., Ltd.] 40 copies

(D) polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine [Ilgacure (registered trademark) OXE 01; Manufactured by BASF] 5 copies

(F) Leveling agent: polyether-modified silicone oil [Toore Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.] 0.08 parts

(E) solvent: ethyl lactate 682 parts

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

are mixed to obtain a colored curable resin composition.

It evaluates similarly to Example 1 about this colored curable resin composition, and confirms that the color filter of high contrast can be obtained.

According to the colored curable resin composition of an Example, it was confirmed that the obtained colored coating film shows high contrast. From this, the colored coating film and coloring pattern obtained from the colored curable resin composition of this invention are useful as a color filter with high contrast, and it turns out that the liquid crystal display device containing this color filter is excellent in display characteristics.

ADVANTAGE OF THE INVENTION According to the colored curable resin composition of this invention, a color filter with high contrast can be formed.

21: glass substrate
22: TFT (switching element)
22a: gate electrode
22b: gate insulating film
22c: polycrystalline silicon film
22d: Shield
23: color filter layer
23A: colored curable resin composition layer (color filter)
23a: red filter
23b: green filter
23c: blue filter
24: pixel electrode
27: signal line
29: photosensitive resin film (protective film)
201, 202: connection hole

Claims (5)

A colored curable resin composition, wherein the colored curable resin composition comprises a colorant, a resin, a polymerizable compound, and a polymerization initiator;
the colorant includes xanthene dyes, triarylmethane dyes and pigments;
The content of the pigment is 83.8 mass% or more and 99 mass% or less with respect to the total amount of the colorant,
The triarylmethane dye is selected from the group consisting of compounds represented by the following formulas (2-2) to (2-4) and (2-6) to (2-12),
Colored curable resin composition:

. The colored curable resin composition according to claim 1, wherein the content of the triarylmethane dye is 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the xanthene dye. The colored curable resin composition according to claim 1, wherein the content of the xanthene dye is 0.5 mass% or more and 50 mass% or less with respect to the total amount of the colorant. The color filter formed with the colored curable resin composition in any one of Claims 1-3. A display device comprising the color filter according to claim 4 .

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