KR101632461B1 - Colored curable resin composition - Google Patents

Abstract

The present invention provides a colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant comprises a xanthene dye and an anthraquinone dye.

Description

COLORED CURABLE RESIN COMPOSITION [0002]

The present invention relates to a colored curable resin composition.

The colored curable resin composition is used for the production of color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. Examples of such a color-curable resin composition include xanthene dyes and C.I. A pigmented curable resin composition containing only Pigment Blue is known (JP2010-32999-A).

The conventionally known coloring curable resin composition does not necessarily satisfy the contrast of the color filter obtained by the coloring curable resin composition.

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 includes a xanthene dye and an anthraquinone dye.

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

[3] The colored curable resin composition according to [1] or [2], wherein the colorant further comprises a pigment.

[4] A color filter formed by the colored curable resin composition according to any one of [1] to [3].

[5] A display device comprising the color filter according to [4].

According to the colored curable resin composition of the present invention, a color filter with high contrast can be formed.

1 is a schematic view for explaining a method of manufacturing a color filter of the present invention.
2 is a schematic view for explaining a method of manufacturing a color filter of the present invention.
3 is a schematic view for explaining a method of manufacturing a color filter of the present invention.

The colored curable resin composition of the present invention is a colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the colorant (A) ) And anthraquinone dyes (Ab). It is also preferable to include a solvent (E) and / or a leveling agent (F).

The colored curable resin composition of the present invention contains a xanthene dye (Aa) and an anthraquinone dye (Ab) as a colorant (A), thereby making it possible to produce a color filter of high contrast.

≪ Colorant (A) >

The colorant (A) includes a xanthene dye (Aa) and an anthraquinone dye (Ab). It is preferable to further include a pigment (Ad). Further, it may contain a dye different from the xanthene dye (Aa) and the anthraquinone dye (Ab) (hereinafter sometimes referred to as "dye (Ac)").

The xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in its molecule. As the xanthene dye (Aa), for example, C.I. 52, 87, 92, 94, 289, 388, C.I. Acid Red 51 (hereinafter, the description of C.I. acid red is omitted and only the numbers are described. Acid Violet 9, 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), Sulfolodamine G, the xanthene dyes described in JP2010-32999-A, and the xanthene dyes described in JP4492760-B. It is preferable to dissolve in an organic solvent.

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

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

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

m represents an integer of 0 to 5; When m is an integer of 2 or more, a plurality of R ^{5 s} may be the same or different. Provided that when R ⁵ is -SO ₃ ^- , m is 1.

a represents an integer of 0 or 1;

X represents a halogen atom.

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.

Z ⁺ represents ⁺ N (R < ¹¹ >) ₄ , Na ⁺ or K ⁺ .

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

R ¹¹ independently 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 which represent 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.

Examples of the aromatic hydrocarbon groups, even if having 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 , -SO ₂ NR ⁹ R ¹⁰ , and the like. 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 than the ₂ NR ⁹ R ¹⁰ desirable. In this case, -SO ₃ ^- Z ⁺ is preferably -SO ₃ ^{- +} N (R ¹¹ ) ₄ . When R ¹ to R ⁴ are these groups, a color filter having less occurrence of foreign matter and excellent in heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (1a).

A ring containing a nitrogen atom formed by R ¹ and R ² together with a nitrogen atom, and R ³ And the ring containing R < ⁴ > together with the nitrogen atom include a nitrogen atom, for example, the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by 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 straight chain alkyl group having 1 to 20 carbon atoms such as a hexadecyl group and an icosyl group; A branched chain alkyl group having 3 to 20 carbon atoms such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group; An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.

Examples of -OR ⁸ include a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group .

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 icosyloxycarbonyl 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.

Examples of -SO ₂ NR ⁹ R ¹⁰ include a sulfamoyl group;

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N-methylpyrrolyl group, N- (2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) An N-1-substituted sulfamoyl group such as a sulfamoyl group, N- (1,5-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-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group, and the like.

Examples of the substituent which may have a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and represent R ⁹ and R ¹⁰ include a hydroxyl group and a halogen atom.

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 .

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

R represents the alkyl group having 1 to 6 carbon atoms ⁶ and R ^7, include those of the exemplary group in the above, the group having 1 to 6 carbon atoms.

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

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

As the ⁺ N (R ¹¹ ) ₄ , it is preferable that at least two of the four R ^{11 s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R < ¹¹ > s is preferably from 20 to 80, more preferably from 20 to 60. [ In the case where ⁺ N (R ¹¹ ) ₄ is present in the compound (1a), if R ¹¹ is these groups, a color filter having few foreign matters can be formed from the colored curable resin composition containing the compound (1a).

As the compound (1a), a compound represented by the formula (2a) (hereinafter also referred to as "compound (2a)") is more preferable. The compound (2a) may be a tautomer thereof.

When the compound (2a) is used, the content of the compound (2a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, furthermore preferably 90% by mass or more.

[In the formula (2a), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or an aromatic hydrocarbon group which may have a substituent and may have a monovalent substituent having 6 to 10 carbon atoms.

R ²¹ and R ²² may form a ring including a nitrogen atom together with a nitrogen atom, and R ²³ and R ²⁴ may form a ring including 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 an integer of 0 to 5; If m1 is an integer of 2 or more, plural R ²⁵ it is the same or different. Provided that when R ²⁵ is -SO ₃ ^- , m 1 is 1.

a1 represents an integer of 0 or 1;

X1 represents a halogen atom.

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

Z 1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

And R < ²⁷ > each independently represent 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 which represent R ²¹ to R ²⁴ include groups as exemplified as aromatic hydrocarbon groups in R ¹ to R ⁴ . Hydrogen atoms contained to said aromatic hydrocarbon is -SO ₃ ^- good even if they are 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 a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10 valency, hydrogen atoms contained groups are aromatic hydrocarbon -SO ₃ ^-, -SO ₃ H, -SO ₃ ^- as Z1 ^+, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ is preferably substituted. More preferred combinations are those wherein R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group are -SO ₃ ^- Z 1 ⁺ or -SO ₂ NHR < ^{26 &} gt ;.

When R ²¹ to R ²⁴ are these groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).

R ²¹ and R ²² the ring containing the nitrogen atom to form together with the nitrogen atom, and, R ²³ and R ²⁴ are as the ring containing the nitrogen atom to form together with the nitrogen atom, R ¹ and R ² is a nitrogen atom And rings formed together. Of these, aliphatic heterocyclic rings are preferred. The aliphatic heterocycle includes, for example, the following.

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

When R ²¹ to R ²⁴ are -R ²⁶ , -R ²⁶ is preferably independently a methyl group or an ethyl group. In addition, as -SO ₃ R ^26, and -SO ₂ NHR ²⁶ R ²⁶ in, a branched chain alkyl group of 3 to 20 carbon atoms are preferable and, a branched chain alkyl group having a carbon number of 6 to 12 and more preferably a 2-ethylhexyl group Is more preferable. When R < ²⁶ > is one of these groups, it is possible to form a color filter which generates less foreign matter from the colored curable resin composition of the present invention containing the compound (2a).

Z 1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .

As the ⁺ N (R ²⁷ ) ₄ , it is preferable that at least two of the four R ^{27 s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total carbon number of the four R < ²⁷ > s is preferably from 20 to 80, more preferably from 20 to 60. [ In the case where ⁺ N (R ²⁷ ) ₄ is present in the compound (2a), a color filter having less foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a) wherein R ²⁷ is these groups.

m1 is preferably 1 to 4, more preferably 1 or 2.

As the compound (1a), a dye containing a compound represented by the formula (3a) (hereinafter also referred to as "compound (3a)") is more preferable. The compound (3a) may be a tautomer thereof. When the compound (3a) is used, the content of the compound (3a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, furthermore preferably 90% by mass or more.

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

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

p and q independently represent an integer of 0 to 5; When p is 2 or more, plural R ^{33 s} may be the same or different, and when q is 2 or more, plural R ^{34 s} may be the same or different.

R ¹¹ has the same meaning as above.]

As the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ³² , a group having 1 to 10 carbon atoms among those represented by R ⁸ can be exemplified.

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

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

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

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

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms for R 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 in 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, and more preferably a methyl group.

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

Examples of the compound (1a) include compounds represented by the formulas (1-1) to (1-42), respectively. In the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, more preferably a 2-ethylhexyl group. The compound represented by formula (1-1) to formula (1-29) corresponds to compound (2a), and the compound represented by formula (1-30) to formula (1-42) corresponds to compound (3a) do.

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

The compounds represented by formulas (1-30) to (1-39) are preferable from the standpoint of excellent solubility in organic solvents.

Examples of the xanthene dye (Aa) include commercially available xanthene dyes (for example, " Chudai Aminol Fast Pink RH / C ", manufactured by Juagai Kagaku Co., Ltd., " Rhodamin 6G " Can be used. Also, a commercially available xanthene dye can be used as a starting material and synthesized by referring to Japanese Patent Application Laid-Open No. 2010-32999.

The anthraquinone dye (Ab) is a dye containing a compound having an anthraquinone skeleton in the molecule. As the anthraquinone dye (Ab), for example,

C.I. Solvent Yellow 117, 163, 167, 189,

C.I. Solvent Orange 77, 86,

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

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

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

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

C.I. Acid Red 80,

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

C.I. Acid Violet 34,

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

C.I. Disperse Yellow 51,

C.I. Disperse Violet 26, 27,

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

C.I. Direct Blue 40,

C.I. Modern Red 3, 11,

C.I. Modern Blue 8

And the like. The anthraquinone dye (Ab) is preferably dissolved in an organic solvent, and blue, violet or red anthraquinone dyes are more preferred.

Among them, as the anthraquinone dye (Ab), a dye containing a compound represented by the formula (1b) (hereinafter occasionally referred to as "compound (1b)") is preferable. When the compound (1b) is used, the content of the compound (1b) in the anthraquinone dye (Ab) is preferably 50% by mass or more, more preferably 70% by mass or more, furthermore preferably 90% by mass or more. In particular, it is preferable to use only compound (1b) as the anthraquinone dye (Ab).

[In the formula (1b), A represents a hydroxy group or -NH-R ⁵² .

R ⁵¹ and R ⁵² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent,

(In the formula (1b '), R ⁵³ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, -SO ₃ H, -CO ₂ H, -CO ₂ R ⁵⁴ , -NHCOR ⁵⁴ , -SO ₃ R ⁵⁴ or -SO ₂ NR ⁵⁴ R ⁵⁵ .

R ⁵⁴ represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an amino group.

R ⁵⁵ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.

r represents an integer of 0 to 5; When r is 2 or more, a plurality of R ⁵³ may be the same or different.

X ⁵¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.)

Represents a group represented by the formula:

When the compound (1b) has -SO ₃ H and / or -CO ₂ H, they may form a salt (for example, a Na salt or a K salt).

Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms for R ⁵¹ and R ⁵² 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, , Isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group.

Examples of the substituent which the aliphatic hydrocarbon group may have include a hydroxyl group, a halogen atom and the like.

Examples of the cycloaliphatic hydrocarbon group having 3 to 10 carbon atoms for R ⁵¹ and R ⁵² include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

Examples of the substituent which the alicyclic hydrocarbon group may have include a hydroxyl group and a halogen atom.

Examples of the alkyl group having 6 to 10 carbon atoms for R ⁵³ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, T-butyl, neopentyl and the like.

Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ⁵⁴ and R ⁵⁵ include linear hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, An alkyl group; A branched chain alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group; A saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

Examples of -CO ₂ R ⁵⁴ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an icosyloxycarbonyl group.

Examples of -NHCOR ⁵⁴ include an N-acetylamino group, an N-propanoylamino group, an N-butyrylamino group, an N-isobutyrylamino group and an N-pivaloylamino group.

Examples of -SO ₃ R ⁵⁴ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group.

Examples of -SO ₂ NR ⁵⁴ R ⁵⁵ include N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, Butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethyl (2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-dimethylpropyl) sulfamoyl group, (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-cyclohexylsapamoyl group, N-hexylsulfamoyl group, N- (1,3- (1-methylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethyl Butyl) sulfamoyl group, N- (5-amino Pentyl) sulfamoyl group, and other N-1 substituted sulfamoyl groups;

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

Examples of the alkanediyl group having 1 to 6 carbon atoms for X ⁵¹ include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, -1,6-diyl group, ethane-1,1-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2- Propane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group and the like.

Examples of the compound (1b) include compounds represented by the formulas (2-1) to (2-13).

Examples of the anthraquinone dyes (Ab) include C.I. Solvent Blue 35 (a compound represented by the formula (2-4)), C.I. Solvent Blue 45, C.I. Acid Blue 80 (a compound represented by the formula (2-11)), C.I. Solvent Blue 104 (a compound represented by the formula (2-12)) and C.I. Solvent Blue 122 (a compound represented by the formula (2-13)) is preferable. When these anthraquinone dyes are used, a high-contrast coating film or pattern can be formed, and generation of foreign matter is also small.

The dyes (Ac) are not particularly limited as long as they are different from the xanthene dyes (Aa) and the anthraquinone dyes (Ab), and can be an oil dyes, acid dyes, basic dyes, direct dyes, mordant dyes, A sulfonamide derivative of a dye, and the like. For example, a dye, i.e., a compound other than pigment in the color index (published by The Society of Dyers and Colourists), a dyeing note (Shikisensha Co., Ltd.) , And the like. According to the chemical structure, the azo dye, the cyanine dye, the triphenylmethane dye, the phthalocyanine dye, the naphthoquinone dye, the quinoneimine dye, the methine dye, the azomethine dye, the squarylium dye, the acridine dye, , Coumarin dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

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, 37, 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, 112, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 57, 66, 73, 80, 88, 91, 215, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 173, 145, 150, 151, 158, 176, 182, 183, 344, 382, 383, 394, 401, 412, 314, 315, 316, 339, 341, 345, 346, 346, 268, 270, 274, 277, 280, 281, 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;

C.I. Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;

C.I. C.I., such as Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, Acid dyes,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 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, 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 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 198, 199, 200, 201, 202, 203, 207, 209, 210, 202, 203, 207, 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, Direct dyes,

C.I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;

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

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

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

C.I. 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. CI. 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, And modern dyes.

The pigment (Ad) is not particularly limited and known pigments can be used. For example, the pigment is classified into pigments in the color index (The Society of Dyers and Colourists).

As the pigment, 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 and 214;

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

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

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

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

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. Pigment black 1, pigment black 7, and the like.

As the pigment, C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; C.I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like 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 preferable. In the case of preparing the colored curable resin composition of the present invention as a blue colored curable resin composition, by including the above-mentioned pigment. The transmission spectrum is easily optimized, and the light resistance and chemical resistance of the color filter are improved.

These pigments may be used singly or in combination of two or more kinds.

The pigment may be subjected to surface treatment using a rosin treatment, a pigment derivative in which an acidic group or a basic group is introduced, graft treatment on the surface of a pigment with a polymer compound or the like, atomization treatment using a sulfuric acid atomization method or the like, A cleaning treatment with an organic solvent or water, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.

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

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include trade name KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (manufactured by Kyoeisha Chemical Co., Ltd.), Solspers (manufactured by Zeneca), EFKA (manufactured by CIBA), AJISPAR (Manufactured by Fine Techno Co., Ltd.), and Disperbyk (manufactured by Vickers).

When a pigment dispersant is used, its amount to be used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (Ad). When the amount of the pigment dispersant is within the above range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state.

The content of the xanthene dye (Aa) is preferably not less than 0.1 mass% and not more than 70 mass%, more preferably not less than 0.5 mass% nor more than 50 mass%, based on the total amount of the colorant (A).

The content of the anthraquinone dye (Ab) is preferably from 0.1 mass% to 70 mass%, more preferably from 0.5 mass% to 50 mass%, based on the total amount of the colorant (A).

When the colorant (A) contains the pigment (Ad), the content of the pigment (Ad) is preferably 10 mass% or more and 99.8 mass% or less, more preferably 30 mass% or more and 99 mass% Or less.

When the colorant (A) contains the dye (Ac), the content of the dye (Ac) is preferably from 0.1 mass% to 50 mass%, more preferably from 0.5 mass% to 30 mass% Or less.

When the colorant (A) is a colorant comprising a xanthene dye (Aa), an anthraquinone dye (Ab) and a pigment (Ad), the content ratio thereof is

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

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

Pigment (Ad); 29.9% by mass or more and 99.8% by mass or less

, ≪ / RTI >

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

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

Pigment (Ad); 49.5 mass% or more and 99 mass% or less

Is more preferable.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, and still more preferably from 10 to 50% by mass, based on the total amount of solid matter. When the content of the colorant (A) is in the above range, the color density when the color filter is used is sufficient, and the resin (B) or the polymerizable compound (C) can be contained in a required amount in the composition. A sufficient pattern can be formed. Here, the "total amount of solid content" in the present specification means the amount excluding the content of the solvent in the total amount of the colored curable resin composition. The total amount of the solid content and the content of each component in the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

≪ Resin (B) >

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

(A) (hereinafter may be referred to as "(a)") selected from the group consisting of a resin [K1] unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having a carbon number of 2 to 4 (B) (hereinafter also referred to as "(b)") having an ethylenically unsaturated bond;

(Hereinafter sometimes referred to as "(c)") of the resin [K2] (a) and (b) and the monomer (c) copolymerizable with the monomer (a) Copolymer;

Resin [K3] Copolymer of (a) and (c);

Resin [K4] Resin (b) is reacted with a copolymer of (a) and (c);

Resin [K5] Resin (a) is reacted with a copolymer of (b) and (c);

Resin [K6] Resin (a) is reacted with a copolymer of (b) and (c) and the carboxylic acid anhydride is further reacted.

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

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

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept- 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept- Cyclo [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 dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride;

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

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

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

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

In the present specification, "(meth) acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

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

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

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrenes such as 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, (Glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) .

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000 manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl Acrylate (for example, Cyclomer M100, manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A100 manufactured by Daicel Chemical Industries, Ltd.) I), a compound represented by the formula (II), and the like.

[In the 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 hydroxy group.

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

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

* Represents the number of bonds with O.]

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

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

Preferable examples of R ^a and R ^b are a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

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

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

Examples of the compound represented by formula (I) include compounds represented by formulas (I-1) to (I-15). (I-1), (I-3), (I-5), ). ≪ / RTI > More preferably, the compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) can be mentioned.

Examples of the compound represented by formula (II) include compounds represented by formulas (II-1) to (II-15). (II-1), II-3, II-5, II-7, II-9 or II- ). ≪ / RTI > The compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferred.

The compound represented by formula (I) and the compound represented by formula (II) may be used alone. They may be mixed at an arbitrary ratio. When mixing, the mixing ratio is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, and even more preferably from 20: 80 to 80:20.

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

As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.

Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V # 150, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) and tetrahydrofurfuryl methacrylate.

(b) is preferably (b1) in that the reliability of the obtained color filter can be further improved, such as heat resistance and chemical resistance. Further, (b1-2) is more preferable because the storage stability of the colored curable resin composition is excellent.

(meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (referred to in the art as "dicyclopentanyl (meth) acrylate" (Also referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (Also referred to as " chloropentenyl (meth) acrylate "), (Meth) acrylate, naphthyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, (Meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and benzyl (meth) acrylate;

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

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

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

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N- Dicarbonylimide derivatives such as 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

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

In the resin [K1], the proportion of the structural unit derived from each of the resins [K1]

(a); 2 to 60 mol%

(b); 40 to 98 mol%

, ≪ / RTI >

(a); 10 to 50 mol%

(b); 50 to 90 mol%

Is more preferable.

When the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency that storage stability of the colored curable resin composition, developability in forming a colored pattern, and solvent resistance of the resulting color filter are excellent.

The resin [K1] can be synthesized by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, First Edition, issued March 1, 1972, Reference can be made to references.

Concretely, there is a method of placing a predetermined amount of (a) and (b), a polymerization initiator and a solvent in a reaction vessel and replacing oxygen by nitrogen, for example, . On the other hand, the polymerization initiator and the solvent to be used herein are not particularly limited, and those generally used in the field can be used. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), organic peroxides (such as benzoyl peroxide) The solvent may be any one that dissolves the respective monomers, and examples of the solvent (E) of the colored curable resin composition of the present invention include a solvent described later and the like.

On the other hand, as the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) extracted by re-precipitation or the like may be used. Particularly, since the solution after the reaction can be used as it is to prepare the colored photosensitive resin composition of the present invention by using a solvent contained in the colored photosensitive resin composition of the present invention as a solvent in the polymerization, the colored photosensitive resin The manufacturing process of the composition can be simplified.

In the resin [K2], the proportion of the structural units derived from each other is preferably from 1 to 100,

(a); 2 to 45 mol%

(b); 2 to 95 mol%

(c); 1 to 65 mol%

, ≪ / RTI >

(a); 5 to 40 mol%

(b); 5 to 80 mol%

(c); 5 to 60 mol%

Is more preferable.

When the proportion of the structural unit of the resin [K2] is in the above-mentioned range, there is a tendency that the storage stability of the colored curable resin composition, developability in forming a colored pattern and solvent resistance, heat resistance and mechanical strength of the resulting color filter are excellent .

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

In the resin [K3], the ratio of the respective structural units derived from each other is preferably selected from the group consisting of the total structural units constituting the resin [K3]

(a); 2 to 60 mol%

(c); 40 to 98 mol%

, ≪ / RTI >

(a); 10 to 50 mol%

(c); 50 to 90 mol%

Is more preferable.

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

Resin [K4] is obtained by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms of (b) to a carboxylic acid and / or carboxylic acid anhydride having (a) Can be manufactured.

First, a copolymer of (a) and (c) is prepared in the same manner as the method described as the method for producing the resin [K1]. In this case, the proportion of the structural units derived from each of them is preferably the same as that in the resin [K3].

Subsequently, a cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer.

Subsequent to the preparation of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air at nitrogen, (b), a reaction catalyst of carboxylic acid or carboxylic acid anhydride with cyclic ether (Aminomethyl) phenol, etc.) and a polymerization inhibitor (e.g., hydroquinone) are placed in a flask and reacted at 60 to 130 DEG C for 1 to 10 hours, for example.

(b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting the content in this range, the storage stability of the colored curable resin composition, the developability in forming the pattern, and the balance between solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern tends to be good. (B1) is more preferable, and (b1-1) is more preferable for the resin (K4) because the reactivity of the cyclic ether is high and unreacted (b)

The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c).

The reaction conditions such as the preparation method, the reaction temperature and the time can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization. On the other hand, as in the case of the polymerization conditions, the preparation method and the reaction temperature can be appropriately adjusted in consideration of the production facilities and the amount of heat generated by polymerization.

Resin [K5] is a first step, and a copolymer of (b) and (c) is obtained in the same manner as in the above-mentioned production method of Resin [K1]. Similarly to the above, the resulting copolymer may be used as it is, or may be a concentrated or diluted solution, or may be a solution extracted as a solid (powder) by re-precipitation or the like.

the proportion of the structural units derived from the structural units (b) and (c) is preferably in the range of the total number of moles of the total structural units constituting the copolymer

(b); 5 to 95 mol%

(c); 5 to 95 mol%

, ≪ / RTI >

(b); 10 to 90 mol%

(c); 10 to 90 mol%

Is more preferable.

Furthermore, by reacting the carboxylic acid anhydride of (a) with a cyclic ether derived from (b) in the copolymer of (b) and (c) under the same conditions as in the production of resin [K4] [K5] can be obtained.

The amount of (a) to be reacted with the above copolymer is preferably 5 to 80 moles per 100 moles of (b). (B1) is more preferable, and (b1-1) is more preferable for the resin (K5) because the reactivity of the cyclic ether is high and the unreacted (b)

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

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

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) Resin [K1] such as coalescence; (Meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2.6] decyl acrylate / (meth) resins such as acrylic acid / N- cyclohexyl maleimide copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (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 a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (meth) ) Resin, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) A resin [K5] such as a resin obtained by reacting a (meth) acrylic acid with a copolymer; A resin such as a resin obtained by further reacting a resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and tetrahydrophthalic anhydride, and the like .

These resins may be used alone or in combination of two or more.

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

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility in the developing solution of the unexposed portion is good, and the resolution of the coloring pattern tends to be improved.

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

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

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

≪ Polymerizable compound (C) >

The polymerizable compound (C) is a compound which can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, Meth) acrylate ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. As such a polymerizable compound, there may be mentioned, for example, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, (Meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra , Propylene glycol-modified dipentaerythritol hexa (meth) acrylate , Caprolactone and the like can be modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate. The polymerizable compounds may be used alone or in combination of two or more.

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

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

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

≪ Polymerization initiator (D) >

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating an active radical or acid by 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 member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and nonimidazole compounds is preferable, and O -Acyloxime compound is more preferable.

The O-acyloxime compound is a compound having a partial structure represented by formula (d1).

Herein, * represents the number of bonds.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3 -Dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ Benzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan- 1-imine, N-benzoyloxy- -Yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as IRGACURE (registered trademark) OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used.

Among them, the O-acyloxime compound is preferably an N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan- 1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- , And N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine are more preferable. If these O-acyloxime compounds are used, a color filter of high brightness tends 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). Of 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- (4-morpholinyl) phenyl] butane-1-one, 2- (dimethylamino) -1-one. Commercially available products such as IRGACURE (registered trademark) 369, 907 and 379 (manufactured by BASF) may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy- -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy- ?,? - diethoxyacetophenone, and benzyl dimethyl ketal.

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

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

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. IRGACURE (registered trademark) 819 (manufactured by BASF), or the like may be used.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- ) -4,4 ', 5,5'-tetraphenylbiimidazole (see JPH06-75372-A, JPH06-75373-A and the like), 2,2'-bis (2-chlorophenyl) 4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (4-chlorophenyl) Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis -Tetra (trialkoxyphenyl) biimidazole (see, for example, JPS48-38403-B, JPS62-174204-A and the like), the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group Imidazole compounds (see JPH07-10913-A and the like), and the like.

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

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, di Onium salts such as phenyl iodonium hexafluoroantimonate, and nitrobenzyl tosylates and benzoin tosylates.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is in the above range, the productivity of the color filter is improved because the sensitivity is increased and the exposure time is shortened.

The polymerization initiator (D) may further comprise a polymerization initiator (D1). The polymerization initiator (D1) is a compound or a sensitizer used for promoting polymerization of a polymerizable compound initiated polymerization by a polymerization initiator.

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, '-Bis (ethylmethylamino) benzophenone, among which 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

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

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

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

The polymerization initiator may be used alone or in combination of two or more.

When these polymerization initiator (D1) is used, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) to be. When the amount of the polymerization initiator (D1) is in this range, it is possible to form a colored pattern with higher sensitivity, and the productivity of the color filter tends to be improved.

≪ Solvent (E) >

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

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

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

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

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

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

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.

These solvents may be used alone or in combination of two or more.

Among these solvents, an organic solvent having a boiling point of 120 占 폚 or more and 180 占 폚 or less at 1 atm is preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 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.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total amount of solids in the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color characteristic is not insufficient when the color filter is formed, so that the display characteristic tends to be good.

≪ Leveling agent (F) >

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

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

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Concretely, FLUORAD (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), MEGAFAC (registered trademark) F142D, copper F171, copper F172, copper Fl73, copper F177, copper F183, copper F554, copper R30, (Registered trademark) S381 (trade name) manufactured by Mitsubishi Materials Corporation), RS-718-K (manufactured by DIC Corporation), EFTOT (registered trademark) EF301, EF303, EF351 and EF352 , S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Co., Ltd.).

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

These surfactants may be used singly or in combination of two or more kinds.

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, and still more preferably 0.01% by mass or less, relative to the total amount of the colored curable resin composition % To 0.05% by mass or less. When the content of the leveling agent (F) is in the above range, the flatness of the color filter can be improved.

≪ Other components >

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

≪ Process for producing colored curable resin composition >

The colored curable resin composition of the present invention can be obtained by using the colorant (A), the resin (B), the polymerizable compound (C) and the polymerization initiator (D), the solvent (E) , A polymerization initiator (D1), and other components.

The solution of the xanthene dye (Aa), the anthraquinone dye (Ab) and the dye (Ac) to be used as needed may be previously dissolved in a part or all of the solvent (E).

It is preferable to filter the solution with a filter having a pore diameter of about 0.01 to 1 mu m.

When the pigment (Ad) is contained, the pigment (Ad) is mixed with a part or the whole of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less desirable. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended. The remainder of the colorant (A), the remainder of the resin (B), the polymerizable compound (C), the polymerization initiator (D) and the remainder of the solvent (E) and the leveling agent (F) , The polymerization initiator (D1), and other components are mixed so as to have a predetermined concentration, whereby a desired colored curable resin composition can be prepared.

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

≪ Color filter and manufacturing method of liquid crystal display device >

Examples of the method for forming the color filter using the colored curable resin composition of the present invention include a method using a photolithographic method and an inkjet apparatus. In the photolithographic method, for example, the colored curable resin composition of the present invention is applied on a substrate, and dried by removing volatile components such as a solvent to form a colored composition layer, and the colored composition layer is exposed through a photomask And then developed. After development, a colored pattern can be formed by heating as required. In the method for forming a coloring pattern, a colored coating film which is a cured product of the colored composition layer can be formed by not using a photomask when exposed, and / or not developing it. The coloring pattern and the colored coating film thus obtained can be used as a color filter.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass and soda lime glass whose surface is coated with silica, resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate, silicon, , Silver, silver / copper / palladium alloy thin film, or the like is formed. On these substrates, a separate color filter layer (for example, a color filter layer formed on the substrate by a colored curable resin composition), a resin layer, a transistor, a circuit, and the like may be formed.

The film thickness of the color filter to be produced is not particularly limited and may be suitably adjusted in accordance with the intended use. For example, it is 0.1 to 30 탆, preferably 1 to 20 탆, more preferably 1 to 6 탆.

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 a glass substrate 21 by a known method such as a photolithography technique (see FIG. 1). TFT (22) includes a glass substrate 21, a gate electrode (22a) constituting, for example molybdenum (Mo) a portion at the same time the gate line is formed by a phase and, for example, the nitride film formed on the gate electrode (22a) (SiN _x ) and oxide film (SiO ₂₎ and of the laminated film gate insulation film (22b) formed of a polysilicon film (22c formed on the gate insulating film (22b)) and, for example, an oxide film (SiO ₂₎ and a nitride film (SiN _x) and And a protective film 22d formed of a laminated film of the same. The region of the polysilicon film 22c opposed to the gate electrode 22a is the channel region of the TFT 22 and the region on both sides of the channel region is the source region or the 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. On the other hand, the drain region of the polysilicon film 22c is electrically connected to the pixel electrode 24 through a connection hole (contact hole) 201 as described later.

Alignment marks (not shown) are formed on the glass substrate 21 simultaneously with the TFTs 22 when a plurality of TFTs 22 are formed on the glass substrate 21 for each pixel. This alignment mark is used as an alignment reference in the color filter layer 23 forming process as will be described later. On the other hand, these alignment marks can also be used as a mark serving as a bonding reference between the driving substrate and the counter substrate. The alignment mark can be formed in the same process using at least one layer when forming a metal layer such as wiring or a polycrystalline silicon layer in the manufacturing process of the TFT 22. [

Subsequently, the colored photosensitive resin composition of the present invention is coated on the TFT 22 and the glass substrate 21 on which the alignment mark is formed, and the volatile components such as a solvent are removed by heating and drying (prebaking) and / And dried to form a coloring composition layer having a film thickness of 0.5 to 5.0 mu m, for example, 1.0 mu m.

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

The temperature in the case of heat drying is preferably 30 to 120 占 폚, more preferably 60 to 110 占 폚. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

In the case of performing the reduced-pressure drying, it is preferable that the drying is carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa.

Subsequently, the coloring composition layer is irradiated with ultraviolet rays through a photomask (not shown), and unnecessary portions are selectively removed by a developing solution to form a connection hole (contact hole) reaching the drain region of the polysilicon film 22c, The formed coloring composition layer is formed on the pixel on which the pixel electrode 201 is formed, and then the pixel is washed with water.

By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developer. As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant.

The developing method may be any of a puddle method, a dipping method and a spraying method. Further, the substrate may be inclined at an arbitrary angle at the time of development.

Thereafter, in order to reflow the colored composition layer in which the connection hole (contact hole) 201 is formed, and / or to cure the polymerizable compound (C) contained in the colored composition layer, At a temperature of 100 to 300 캜, preferably 150 to 230 캜, for example, for 1 to 120 minutes, preferably 10 to 60 minutes. Thus, the colored curable resin composition layer 23A as a coloring pattern is formed. This colored curable resin composition layer 23A corresponds to the color filter of the present invention.

This operation is repeated to form the colored curable resin composition layer 23a from the red colored curable resin composition, the green colored curable resin composition and the blue colored curable resin composition, respectively, so that the red filter 23a, A color filter layer 23 including a blue filter 23b and a blue filter 23c is formed (see Fig. 2). The region between the filters of the color filter layer 23 is a mixed region of adjacent colors. This region is a light shielding region opposed to the signal line 27, so there is no particular problem in terms of quality. On the other hand, the area between the filters may not be colored.

Next, for example, a photosensitive resin film 29 as a protective film having a film thickness of 0.3 to 2.0 mu m is formed so as to cover the color filter layer 23 by, for example, a spin coating method. Subsequently, the photosensitive resin film 29 is irradiated with ultraviolet rays through a photomask (not shown), and a region corresponding to the connection hole 201 and unnecessary portions are selectively removed by a developing solution, thereby forming a polycrystalline silicon film (Contact hole) 202 reaching the drain region of the gate insulating film 22c. Thereafter, for reflow (reflow) of the photosensitive resin film 29, it is heated at a temperature ranging from 100 to 300 캜, for example, 200 캜. Subsequently, in order to remove residues such as dyes and organic substances deposited in the contact holes 202, etching is performed by oxygen plasma, and in order to remove the oxide film formed by the oxygen plasma, for example, Etching.

Subsequently, a transparent conductive material such as ITO (indium-tin oxide: mixed oxide film of indium and tin) is formed on the photosensitive resin film 29 by, for example, sputtering, and this ITO film is subjected to photolithography and etching And patterned to form a transparent pixel electrode 24 (see FIG. 3). On the other hand, the pixel electrode 24 may be formed of a metal such as aluminum (Al) or silver (Ag), depending on the device to be manufactured. Thereafter, an alignment film is formed by a known method, and then the liquid crystal display device can be manufactured by bringing the drive substrate and the counter substrate into contact with each other.

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

Example

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples.

In the examples, "% " and " part " are by mass% and mass part, respectively, unless otherwise specified.

In the following synthesis examples, the compound was identified by elemental analysis (VARIO-EL; manufactured by Elementar Co., Ltd.).

[Synthesis Example 1]

15 parts of a mixture of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (trade name: Chugai Aminol Fast Pink R; manufactured by Juga Igasai) was placed in a flask equipped with a stirrer, , 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added and 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature below 20 占 폚 with stirring. After completion of the dropwise addition, the temperature was raised to 50 占 폚, and the reaction was continued at the same temperature for 5 hours and then cooled to 20 占 폚. The cooled reaction solution was added dropwise with a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine while maintaining the temperature at 20 캜 or lower with stirring. Thereafter, the reaction was carried out by stirring at the same temperature for 5 hours. Subsequently, the obtained reaction mixture was distilled off with a rotary evaporator, methanol was added in small amount and stirred vigorously. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. (A-1) (a mixture of the compounds represented by the formulas (Al-1) to (A1-8)) by filtration, 11.3 parts were obtained.

[Synthesis Example 2]

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. The obtained reaction solution was cooled to room temperature, added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were collected as a residue of suction filtration and dried to obtain 24 parts of a compound represented by the formula (1-30). The yield was 80%.

The structure of the compound represented by the formula (1-30) was confirmed by mass analysis (LC: manufactured by Agilent 1200 type, MASS: manufactured by Agilent LC / MSD type).

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 603.4

 Exact Mass: 602.2

[Synthesis Example 3]

(1-38) was obtained in the same manner as in Synthesis Example 1, except that N-propyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of the compound represented by the formula (1-38)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 659.9

Exact Mass: 658.9

[Synthesis Example 4]

12 parts of the compound represented by the formula (1x), 60 parts of N-methyl-2-pyrrolidone and 12.6 parts of piperidine (manufactured by TOKYO KASEI KOGYO CO., LTD.) Were mixed and the resulting mixture was stirred at 60 ° C for 5 hours did. The reaction solution was cooled to room temperature, added to a mixed solution of 600 parts of water and 100 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were obtained as a residue of suction filtration and dried to obtain 12.4 parts of a compound represented by the formula (1-27). The yield was 83%.

Identification of the compound represented by the formula (1-27)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 503.4

Exact Mass: 502.2

[Synthesis Example 5]

15 parts of the compound represented by the formula (1x), 75 parts of N-methyl-2-pyrrolidone and 25.8 parts of decahydroquinoline (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and the resulting mixture was stirred at 110 ° C for 24 hours did. The reaction solution was cooled to room temperature, added to a mixed solution of 600 parts of water and 100 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were collected as a residue of suction filtration and dried to obtain 19.5 parts of the compound represented by the formula (1-29). The yield was 86%.

Identification of the compound represented by the formula (1-29)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 611.4

Exact Mass: 610.3

[Synthesis Example 6]

Nitrogen was flowed at 0.02 L / min in a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was added and heated to 70 캜 with stirring.

Subsequently, 46 parts by mass of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II- 50) and 185 parts by mass of ethyl lactate to prepare a solution. This solution was dropped into a flask kept at 70 캜 for 4 hours by using a dropping funnel.

On the other hand, a solution prepared by dissolving 30 parts by mass of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was dropped into the flask over 4 hours using a separate dropping funnel. After the completion of the dropwise addition of the polymerization initiator solution, the mixture was maintained at 70 占 폚 for 4 hours and then cooled to room temperature. The weight average molecular weight (Mw) was 9.1 占⁰³ , the molecular weight distribution was 2.1, the solid content was 26% A resin B1 solution of 120 mg-KOH / g was obtained. Resin B1 has the following structural unit.

[Synthesis Example 7]

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, the atmosphere in the flask was changed to nitrogen in air, 22.0 g (0.10 mol) of 70.5 g (0.40 mol) of acrylate, 43.0 g (0.5 mol) of methacrylic acid and monometacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., And 136 g of methyl ether acetate, to which 3.6 g of 2,2'-azobisisobutyronitrile had been added was further added dropwise, followed by further stirring at 100 ° C.

Subsequently, 35.5 g (0.25 mol) of glycidyl methacrylate (50 mol% with respect to the carboxyl group of the methacrylic acid used in the present reaction)), 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone was charged into the flask, and the reaction was continued at 110 캜 to obtain a resin B2 solution having a solid content of 29% and a solid acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,000.

[Synthesis Example 8]

Nitrogen was flowed at 0.02 L / min in a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel to make a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added and heated to 70 캜 with stirring. Subsequently, 60 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) ) And 140 parts of propylene glycol monomethyl ether acetate to prepare a solution. The solution was dropped into a flask kept at 70 캜 for 4 hours using a dropping funnel.

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 70 占 폚 for 4 hours and then cooled to room temperature. The weight average molecular weight (Mw) was 9.1 占⁰³ , the molecular weight distribution was 2.16, the solid content was 34.8% A resin B3 solution having an acid value of 81 mgKOH / g was obtained. Resin B3 has the following structural unit.

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

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

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 mL / min

Detector; RI

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

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

[Example 1]

(Preparation of colored curable resin composition)

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

Acrylic pigment dispersant 6.1 parts

Propylene glycol monomethyl ether acetate 163 parts

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

(A) Colorant: Dye (A1-a) (xanthene dye) 1.8 parts

(A) Colorant: C.I. Solvent Blue 35

(Sudan Blue II; manufactured by Aldrich; anthraquinone dye) 1.8 parts

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 40 parts

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-

(IRGACURE (registered trademark) OXE 01, manufactured by BASF) 5 parts

(F) Leveling agent: polyether-modified silicone oil

(TORAY SILICONE SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.08 part

(E) Solvent: Ethyl lactate 682 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 8 parts

Were mixed to obtain a colored curable resin composition.

≪ Fabrication of coloring pattern &

The colored curable resin composition was applied on a glass substrate (Eagle 2000; Corning) having a size of 5 cm square by spin coating, and then pre-baked at 100 占 폚 for 3 minutes to obtain a colored composition layer. After cooling down, an exposure amount of 150 mJ / cm < 2 > (manufactured by TOPCON CO., LTD.) Was applied to the surface of the substrate on which the colored composition layer was formed and the quartz glass photomask at an interval of 100 mu m using an exposure machine 365 nm). As the photomask, a photomask having a 100 占 퐉 line and space pattern was used. After the light irradiation, the coloring composition layer was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 DEG C for 60 seconds, washed with water and then postbaked at 230 DEG C for 30 minutes in an oven To obtain a colored pattern.

≪ Measurement of film thickness &

With respect to the obtained coloring pattern, the film thickness was measured by using a film thickness measuring device (DEKTAK3; manufactured by Nihon Shinku Jujutsu Co., Ltd.).

≪ Evaluation of color &

The obtained coloring pattern was measured for spectroscopy using a colorimeter (OSP-SP-200, manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) in the CIE XYZ color system using the characteristic function of the C light source ) And three stimulus values Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Tables 3 and 4.

<Evaluation of contrast>

Except that a photomask was not used at the time of exposure, a colored coating film was produced by operating in the same manner as the production of a colored pattern. Using a contrasting system (CT-1; manufactured by Tsubosaka KK, color chromaticity meter BM-5A; TOPCON, light source: F-10, polarizing film; manufactured by Tsubosaka Denki Co., Ltd.) And the blank value was set to 30000, and the contrast was measured. If the contrast in the colored coating film is high, the coloring pattern can also be said to have high contrast. The results are shown in Tables 3 and 4.

[Comparative Example 1]

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

Acrylic pigment dispersant 5 parts

Propylene glycol monomethyl ether acetate 137 parts

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

(A) Colorant: Dye (Aa-1) (xanthene dye) 3.5 parts

(B) Resin: Resin B2 Solution 157 parts

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Manufactured by Nihon Kayaku Co., Ltd.) 50 parts

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

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

Were mixed to obtain a colored curable resin composition.

Examples 2 to 15

The procedure of Example 1 was repeated to obtain the compositions shown in Tables 1 and 2 to obtain a colored curable resin composition.

On the other hand, in Table 1 and Table 2, "Ad-11 ⁾ " was preliminarily mixed with an acrylic pigment dispersant and propylene glycol monomethyl ether acetate in an amount described in "E- ¹³⁾ ".

Quot; E-1 ²⁾ &quot; represents the total content of propylene glycol monomethyl ether acetate.

In Table 1 and Table 2, each component represents the following. The resin (B) represents a part by mass in terms of solid content.

Xanthene dye (Aa): Aa-1: dye (Aa-1)

Xanthene dye (Aa): Aa-2: Compound represented by formula (1-30)

Xanthene dye (Aa): Aa-3: Compound represented by formula (1-38)

Xanthene dye (Aa): Aa-4: C.I. Acid Red 52 (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

Xanthene dye (Aa): Aa-5: Compound represented by formula (1-27)

Xanthene dye (Aa): Aa-6: Compound represented by formula (1-29)

Anthraquinone dye (Ab): Ab-1: C.I. Solvent Blue 35 (Sudan Blue II; Aldrich)

Anthraquinone dye (Ab): Ab-2: C.I. Solvent Blue 45 (Savinyl Blue RS; Clariant)

Anthraquinone dye (Ab): Ab-3: C.I. Acid Blue 80 (Coomassie (registered trademark) Blue B 150 (manufactured by ICI)

Anthraquinone dye (Ab): Ab-4: C.I. Solvent Blue 104 (Polysynthrene Blue RBL P; manufactured by Clariant)

Anthraquinone dye (Ab): Ab-5: C.I. Solvent Blue 122 (Polysynthrene Blue R; Clariant)

Pigment (Ad): Ad-1: C.I. Pigment Blue 15: 6

Resin (B): B-1: Resin B1

Resin (B): B-2: Resin B2

Resin (B): B-3: Resin B3

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (D): D-1: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IRGACURE (registered trademark) OXE 01; Oxime compounds)

Polymerization initiator (D): D-2: 2-Methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (IRGACURE (registered trademark) 907; )

Polymerization initiator D1: 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nihon Kayaku Co., Ltd., thioxanthone compound)

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

Solvent (E): E-2: Ethyl lactate

Solvent (E): E-3: Propylene glycol monomethyl ether

Solvent (E): E-4: 4-Hydroxy-4-methyl-2-pentanone

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

The colored curable resin compositions of Examples 2 to 15 and Comparative Example 1 obtained as described above were evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4.

According to the colored curable resin composition of the examples, it was confirmed that the obtained coating film exhibited a high contrast. From this, it can be seen that the colored coating film or the colored pattern obtained from the colored curable resin composition of the present invention is useful as a high-contrast color filter, and the liquid crystal display device including the color filter has excellent display characteristics.

According to the colored curable resin composition of the present invention, a color filter of high contrast can be formed.

21: glass substrate 22: TFT (switching element)
22a: gate electrode 22b: gate insulating film
22c: polycrystalline silicon film 22d: protective film
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 holes

Claims (5)

A colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator,
Wherein the colorant comprises a xanthene dye and an anthraquinone dye,
Wherein the anthraquinone dye comprises a compound represented by the following formula (1b).

[In the formula (1b), A represents -NH-R ⁵² .
R ⁵¹ and R ⁵² each independently represents a group represented by formula (1b '):

(In the formula (1b '), R ⁵³ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, -CO ₂ H, -CO ₂ R ⁵⁴ , -NHCOR ⁵⁴ , -SO ₃ R ⁵⁴ or -SO ₂ NR ⁵⁴ R ⁵⁵ .
R ⁵⁴ represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an amino group.
R ⁵⁵ represents a hydrogen atom.
r represents an integer of 0 to 5; When r is 2 or more, a plurality of R ⁵³ may be the same or different.
X ⁵¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.)
Lt; / RTI &gt;
When -CO ₂ H is present in the formula (1b), it may form a salt.] The colored curable resin composition according to claim 1, wherein the content of the anthraquinone dye is 0.1% by mass or more and 70% by mass or less based on the total amount of the colorant. The colored curable resin composition according to claim 1 or 2, wherein the colorant further comprises a pigment. A color filter formed by the colored curable resin composition according to claim 1 or 2. A display device comprising the color filter according to claim 4.

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