KR102024938B1 - Colored curable resin composition - Google Patents

Abstract

PROBLEM To provide the colored curable resin composition which can obtain the high contrast color filter.
[Solution] Includes a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent,
The colorant is a colorant containing an organic solvent soluble dye and a pigment,
The solvent is a solvent containing cyclohexanone,
The colored curable resin composition whose viscosity in 23 degreeC is 4.2 mPa * s or more and 10 mPa * s or less when adjusting solid content of colored curable resin composition to 15 mass%.

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

A color filter is used for display apparatuses, such as a liquid crystal display device, an electroluminescent display device, a plasma display, and an electronic paper, and is manufactured by colored curable resin composition. As such colored curable resin composition, the colored curable resin composition containing propylene glycol monomethyl ether, ethyl lactate, and propylene glycol monomethyl ether acetate as a solvent is known (patent document 1).

[Patent Document 1] Japanese Unexamined Patent Publication No. 2010-211198

The color filter formed from the said colored curable resin composition conventionally known may not fully satisfy contrast.

The present invention includes the following inventions.

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

The colorant is a colorant containing an organic solvent soluble dye and a pigment,

The solvent is a solvent containing cyclohexanone,

The colored curable resin composition whose viscosity in 23 degreeC is 4.2 mPa * s or more and 10 mPa * s or less when the solid content of colored curable resin composition is adjusted to 15 mass%.

[2] The colored curable resin composition according to the above [1], wherein the solvent further includes a solvent having a hydroxyl group in the molecule.

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

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

According to the colored curable resin composition of this invention, the color filter with high contrast can be obtained.

Hereinafter, the present invention will be described in detail.

The colored curable resin composition of this invention contains a coloring agent (A).

The coloring agent (A) used for the colored curable resin composition of this invention is a coloring agent containing organic solvent soluble dye (A1) (hereinafter may be called "dye (A1)") and pigment (A2).

The dye (A1) is not particularly limited as long as it is a dye soluble in an organic solvent, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Such dyes (A1) include, for example, compounds classified as dyes in the Color Index (Published by The Society of Dyers and Colourists), and known dyes described in dyeing notes (Shiksensha). Specifically, C.I. Solvent Yellow 4 (hereinafter, the description of CI solvent yellow is omitted, only the number is described, and the same applies to the dye described later), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98 , 99, 117, 162, 163, 167, 189;

C.I. Solvent red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

C.I. Solvent orange 2, 7, 11, 15, 26, 56, 77, 86;

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

C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. C.I. Solvent dyes,

C.I. Acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

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

C.I. Acid violet 6B, 7, 9, 17, 19, 30, 34, 102;

C.I. Acid blue 1, 7, 9, 15, 18, 22, 23, 25, 27, 29, 40, 41, 42, 43, 45, 51, 54, 59, 60, 62, 70, 72, 74, 78, 80, 82, 83, 86, 87, 90, 92, 93, 96, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 229, 234, 236, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;

C.I. C.I. such as acid green 1, 3, 5, 9, 16, 25, 27, 28, 41, 50, 58, 63, 65, 80, 104, 105, 106, 109 and the like. 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, 102, 108, 109, 129, 136, 138, 141;

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

C.I. Direct orange 26, 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, 40, 41, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. Direct dyes,

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

C.I. Disperse violet 26, 27;

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

C.I. Basic red 1, 10;

C.I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68;

C.I. C.I. of Basic Green 1 et al. Basic Dye,

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

C.I. Reactive orange 16;

C.I. C.I. of Reactive Red 36 et al. Reactive dyes,

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

C.I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 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. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84;

C.I. Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. Modern Dye,

C.I. C.I. of Bat Green 1 et al. Bat dye etc. are mentioned.

In the colored curable resin composition of this invention, these dyes can be suitably selected and used according to the spectral spectrum of a desired color filter. In addition, these dyes may be used independently and may be used in combination of 2 or more type.

As the dye (A1), xanthene dye (Aa) dissolved in an organic solvent is preferable. Xanthene dye (Aa) is a dye containing the compound which has a xanthene frame | skeleton in a molecule | numerator.

Xanthene dyes (Aa) are for example C.I. Acid red 51 (hereinafter, the description of C.I. acid red is omitted, only the numbers are used, and others are the same), 52, 87, 91, 92, 94, 95, 98, 289, 388, C.I. Acid violet 9, 30, 102, C.I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. Basic Red 1, 10 (Rhodamine B), 11, C.I. Basic Violet 10, 11, 25, C.I. Solvent Red 218, C.I. Modern Red 27, C.I. Reactive red 36 (rose bengal B), sulforhodamine G, the xanthene dye of Unexamined-Japanese-Patent No. 2010-32999, the xanthene dye of Unexamined-Japanese-Patent No. 4452760, etc. are mentioned.

Among these, as xanthene dye (Aa), the dye containing the compound represented by General formula (1a) (Hereinafter, it may be called "compound (1a)") is preferable. When using compound (1a), content of compound (1a) in xanthene dye (Aa) becomes like this. Preferably it is 50 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.

In particular, it is preferable to use only compound (1a) as xanthene dye (Aa).

[In formula (1a), R ¹ ~R ⁴ are each independently a hydrogen atom, -R ⁸ or a substituent monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms good. R <^1> and R <^2> may form the ring containing a nitrogen atom together, and R <^3> and R <^4> may form the ring containing a nitrogen atom together.

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

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

m represents the integer of 0-5. When m is an integer of 2 or more, some R <^5> may be the same and may differ.

a represents the integer of 0 or 1.

X represents a halogen atom.

R <^8> represents a C1-C20 monovalent saturated hydrocarbon group, and the hydrogen atom contained in this saturated hydrocarbon group may be substituted by the halogen atom.

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

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

Each 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 C6-C10 monovalent aromatic hydrocarbon group representing R ¹ to R ⁴ include a phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.

Group is a monovalent aromatic hydrocarbon having a carbon number of 6 to 10 that represents the R ¹ ~R ^4, hydrogen atoms are halogen atoms included since this is an aromatic ^{hydrocarbon, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, Or may be substituted with -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ^8, or -SO ₂ NR ⁹ R ¹⁰ . Among these substituent _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z + and -SO ₂ NR ⁹ at least one element selected from the group consisting of R ¹⁰ are preferred, and -SO ₃ ^- Z ⁺ and -SO One or more types selected from the group consisting of ₂ NR ⁹ R ¹⁰ are more preferable. In the case of -SO ₃ ^- Z ⁺ roneun -SO ₃ ^- is N ⁺ (R ¹¹⁾ ₄ are preferred. If R <^1> -R <^4> is these groups, the color filter which has little generation | occurrence | production of a foreign material and is excellent in heat resistance can be formed from the colored curable resin composition of this invention containing a compound (1a).

R ¹ and R ² and R ³ and R ⁴ may each together form a ring containing a nitrogen atom. As a ring containing this nitrogen atom, the following are mentioned, for example.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ⁸ to R ¹¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and hexa Linear alkyl groups such as decyl group and isocyl group; Branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group.

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

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

Examples of -SR ⁸ include methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group, and isocylsulfanyl group.

Examples of —SO ₂ R ⁸ include methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group, and isocylsulfonyl group.

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

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

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

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

Also, -CH ₂ R ^9, and which includes carbon atoms, a monovalent saturated hydrocarbon group of 1 to 20 represent the R ^10, hydrogen atoms may be substituted by -OH or halogen atoms included in the groups, saturated hydrocarbon, the saturated hydrocarbon groups - is - O-, -CO-, -NH- or -NR ⁸ -may be substituted.

R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered heterocycle including a nitrogen atom. As this heterocycle, the following are mentioned, for example.

As a C1-C6 alkyl group which shows R <^6> and R <^7> , a C1-C6 thing is mentioned among the linear alkyl group and branched alkyl group mentioned above.

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

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

As said ⁺ N (R <^11> ) ₄ , it is preferable that two or more of four R <^11> is a C5-C20 monovalent saturated hydrocarbon group. Moreover, 20-80 are preferable and, as for the total carbon number of four R <^11> , 20-60 are more preferable. When ⁺ N (R ¹¹ ) ₄ is present in the compound (1a), if R ¹¹ is these groups, a color filter with less foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (1a). .

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

It is preferable that compound (1a) is a compound represented by General formula (2a) (Hereinafter, it may be called "compound (2a)."), As xanthene dye (Aa), it is a dye containing compound (2a). More preferred. When using compound (2a), 50 mass% or more of content of compound (2a) in xanthene dye (Aa) is preferable, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.

[In the formula (2a), R ²¹ ~R ²⁴ are each independently a hydrogen atom, or a substituent -R ²⁶ represents a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms good. R ²¹ and R ²² may together form a ring containing a nitrogen atom, and R ²³ and R ²⁴ together may form a ring containing a nitrogen atom.

R ²⁵ represents —SO ₃ ^— , —SO ₃ H, —SO ₃ ^— Z 1 ^+, or —SO ₂ NHR ²⁶ .

m1 represents the integer of 0-5. When m1 is an integer of 2 or more, some R <^25> may be the same and may differ.

a1 represents the integer of 0 or 1.

X1 represents a halogen atom.

R <^26> represents a C1-C20 monovalent saturated hydrocarbon group.

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

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

As a C6-C10 monovalent aromatic hydrocarbon group which shows R <^21> -R <^24> , the group similar to what was mentioned as an aromatic hydrocarbon group in said R <^1> -R <^4> is mentioned. Hydrogen atoms contained groups are aromatic hydrocarbon is -SO ₃ ^- may be substituted with Z1 ^+, -SO ₃ R ²⁶ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.

As a combination of R <^21> -R <^24> , Preferably R <^21> and R <^23> is a hydrogen atom, R <^22> and R <^24> is a C6-C10 monovalent aromatic hydrocarbon group, The hydrogen atom contained in this aromatic hydrocarbon group- _{^{SO 3 -, -SO 3 H,}} -SO 3 - Z1 +, -SO 3 R 26 or -SO ₂ NHR ²⁶ may be substituted with. More preferably, 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- It may be substituted by SO ₂ NHR ²⁶ . If R <^21> -R <^24> is these groups, the color filter excellent in heat resistance can be formed from the colored curable resin composition of this invention containing a compound (2a).

As a C1-C20 monovalent saturated hydrocarbon group which shows R <^26> and R <^27> , the group similar to what was mentioned as a saturated hydrocarbon group in R <^8> -R <^11> is mentioned.

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

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

To the ⁺ N (R ²⁷⁾ ₄ roneun four R ²⁷ 2 or more is a monovalent saturated hydrocarbon group having a carbon number of 5 to 20 is preferred. Moreover, 20-80 are preferable and, as for the sum total carbon number of four R <^27> , 20-60 are more preferable. When ⁺ N (R ²⁷ ) ₄ is present in the compound (2a), a color filter with less generation of foreign matters can be formed from the colored curable resin composition of the present invention in which R ²⁷ contains a compound (2a) in which these groups are present. .

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

Examples of the compound (2a) include compounds represented by any one of formulas (1-1) to (1-23), formulas (1-37), and formulas (1-41) to formulas (1-45). . 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 2-ethylhexyl group. Among these, sulfonamides of CI acid red 289, quaternary ammonium salts of CI acid red 289, sulfonamides of CI acid violet 102 or quaternary ammonium salts of CI acid violet 102 are preferable. Examples of such compounds include compounds represented by the formulas (1-1) to (1-8), the formulas (1-11), and the formulas (1-12).

Moreover, as xanthene dye (Aa), the dye containing the compound represented by General formula (3a) (hereinafter may be called "compound (3a)") is also preferable. When using compound (3a), 50 mass% or more of content of compound (3a) in xanthene dye (Aa) is preferable, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.

In Formula (3a), R ³¹ and R ³² independently represent an alkyl group having 1 to 8 carbon atoms. R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms. R ³¹ and R ³³ may together form a ring containing a nitrogen atom, and R ³² and R ³⁴ together may form a ring containing a nitrogen atom.

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

Examples of the alkyl group having 1 to 8 carbon atoms for R ³¹ , R ³² , R ³³ and R ³⁴ include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and hex A real group, an octyl group, 2-ethylhexyl group, etc. are mentioned.

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

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

It is preferable that R <^31> and R <^32> are mutually independently a C1-C4 alkyl group, It is more preferable that it is a C1-C3 alkyl group, It is still more preferable that it is a methyl group, an ethyl group, or an isopropyl group. It is preferable that R <^33> and R <^34> are a C1-C4 alkyl group, and it is more preferable that it is a methyl group.

It is preferable that p and q are the integers of 0-2 independently from each other, and it is more preferable that it is 1 or 2.

Examples of the compound (3a) include compounds represented by formulas (1-24) to (1-36), respectively. Among them, compounds represented by any one of the formulas (1-24) to (1-30), the formulas (1-34) and the formulas (1-35) are preferable in view of excellent solubility in an organic solvent.

Moreover, as a compound (1a), the compound represented by any one of general formula (1-38)-general formula (1-40) is mentioned.

Xanthene dye which is marketed as xanthene dye (Aa) [for example, "Chugai Aminol Fast Pink RH / C" of Chugaikasei Co., Ltd., "Rhodamin 6G" of Taokakagaku Kogyo Co., Ltd. product] Can be used. Moreover, you may synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using commercially available xanthene dye as a starting material.

Colorant (A) contains pigment (A2).

The pigment (A2) is not particularly limited, and known pigments can be used, and examples thereof include compounds classified as pigments in the Color Index (Published by The Society of Dyers and Colourists).

Specifically, for example, C.I. Pigment Yellow 1 (hereinafter, the description of CI Pigment Yellow is omitted and only the numbers are described, and the same applies to the pigments described later), 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, 180, 185, 194, 214, 219, etc. Yellow pigments;

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

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Red pigment;

C. I. blue pigments such as Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, 80 and the like;

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

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

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

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

Especially, it is preferable to include 1 or more types chosen from the group which consists of a blue pigment and a violet pigment as a pigment (A2), It is more preferable to contain a blue pigment, It is further more preferable to include only a blue pigment. . As a blue pigment, C.I. Pigment blue 15: 6, and C.I. More preferably only Pigment Blue 15: 6. Violet pigments include C.I. It is preferred to include pigment violet 23. By including said pigment, optimization of a transmission spectrum becomes easy. These pigments may be used independently and may be used in combination of 2 or more type.

If necessary, the pigment may be a rosin treatment, surface treatment using a pigment derivative having an acid group or a basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound or the like, atomization treatment by a sulfuric acid atomization method or the like to remove impurities. Cleaning treatment with an organic solvent, water, or the like, removal treatment by an ion exchange method of ionic impurities, or the like may be performed.

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

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used independently and may be used in combination of 2 or more type. As the pigment dispersant, for example, KP [manufactured by Shin-Etsukagaku Kogyo Co., Ltd.], Floren [manufactured by Kyoeisha Kagaku Co., Ltd.], Solsperth [manufactured by Geneka Co., Ltd.], EFKA (manufactured by CIBA), Aji Spur (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by Vikchem Co., Ltd.) and the like.

When using a pigment dispersant, the usage-amount is 100 mass parts or less with respect to 100 mass parts of pigments (A2), More preferably, it is 5 mass parts or less. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency which can obtain the pigment dispersion liquid of a uniform dispersion state.

As a solvent which disperse | distributes a pigment (A2), the solvent containing the ether ester solvent mentioned later is preferable, and the solvent containing a cyclohexanone and an ether ester solvent is more preferable. 100-2500 mass parts is preferable with respect to 100 mass parts of pigments (A2), and, as for the usage-amount of a solvent, the quantity of 500-1500 mass parts is more preferable. By performing the dispersion treatment under such conditions, there is a tendency to obtain a pigment dispersion having excellent viscosity stability over time.

The content of the dye (A1) and the pigment (A2) of the colored curable resin composition of the present invention is based on the total amount of the colorant (A), respectively.

Dyes (A1); 1 to 99 mass%

Pigment (A2); It is preferable that it is 1-99 mass%,

Dyes (A1); 1 to 60 mass%

Pigment (A2); It is more preferable that it is 40-99 mass%,

Dyes (A1); 3-40 mass%

Pigment (A2); It is more preferable that it is 60-97 mass%. If the content of the dye (A1) and the pigment (A2) is within the above range, desired spectroscopy and color concentration can be obtained.

The total amount of the coloring agent (A) is preferably 4 to 60% by mass, more preferably 5 to 50% by mass, still more preferably 7 to 40% by mass relative to the total amount of solids of the colored curable resin composition. If content of a coloring agent (A) exists in the said range, desired spectroscopy and color concentration can be obtained. Here, the "total amount of solid content" in this specification means the quantity which subtracted content of a solvent from the total amount of colored curable resin composition. The total amount of solids and the content of each component thereof can be measured by known analysis means such as liquid chromatography or gas chromatography, for example.

The colored curable resin composition of this invention contains resin (B). Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin. Here, alkali-soluble means the property melt | dissolved in the developing solution which is the aqueous solution of an alkali compound. Examples of the resin (B) include the following resins [K1] to [K6].

[K1] at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)"), a cyclic ether structure having 2 to 4 carbon atoms, and ethylene Copolymer with the monomer (b) (Hereinafter, it may be called "(b)") which has a sex unsaturated bond.

[K2] Monomer (c) copolymerizable with (a) and (b) and (a) and (b) (but different from (a) and (b)) (hereinafter referred to as "(c)" Copolymers).

[K3] A copolymer of (a) and (c).

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

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

[K6] A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting a carboxylic anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid;

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

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2- N, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methyl ratio Bicyclo unsaturated compounds containing carboxyl groups such as 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-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl of a divalent or higher polyhydric carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ] Esters;

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

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

(b) means the polymerizable compound which has an ethylenically unsaturated bond with a C2-C4 cyclic ether structure (for example, 1 or more types chosen from the group which consists of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring). As for (b), the monomer which has a C2-C4 cyclic ether structure and a (meth) acryloyloxy group is preferable.

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

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)") and a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter "( b2) ", and the monomer (b3) which may have a tetrahydrofuryl group and ethylenically unsaturated bond (Hereinafter, it may be called" (b3) ").

(b1) is a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and unsaturated to the bond constituting the ring. The monomer (b1-2) (Hereinafter, it may be called "(b1-2)") in which the alicyclic unsaturated hydrocarbon which has a bond was epoxidized is mentioned.

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether and o-vinyl benzyl. Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxy Methyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, and 2,4,6-tris (glycidyloxymethyl) styrene Can be.

(b1-2) include, for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane [eg, ceoxide 2000; Daicel Kagaku Kogyo Co., Ltd. product, 3, 4- epoxycyclohexyl methyl (meth) acrylate [for example, cyclomer A400; Daicel Kagaku Kogyo Co., Ltd.], 3, 4- epoxycyclohexyl methyl (meth) acrylate [for example, cyclomer M100; Daicel Kagaku Kogyo Co., Ltd.], the compound represented by general formula (I), the compound represented by general formula (II), etc. are mentioned.

[Formula (I) and Formula (II), R ^<a> and R <^b> represent a hydrogen atom or a C1-C4 alkyl group, and the hydrogen atom contained in the said alkyl group may be substituted by the hydroxy group.

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

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

* Represents the number of bonds with O.]

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

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

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

Alkanediyl groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1 And a 6-diyl group.

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

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

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

The compound represented by general formula (I) and the compound represented by general formula (II) can be used independently, respectively. In addition, these can be mixed and used in arbitrary ratios. When mixed and used, the mixing ratio is in a molar ratio, preferably in the general formula (I): general formula (II), 5:95 to 95: 5, more preferably 10:90 to 90:10, still more preferably Is 20:80 to 80:20.

As a monomer (b2) which has an oxetanyl group and ethylenically unsaturated bond, the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo Iloxy ethyl oxetane, 3-ethyl-3- acryloyloxy ethyl oxetane, etc. are mentioned.

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

Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Yukikagaku Kogyo Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

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

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (commonly known in the art as "dicyclopentanyl (meth) acrylate"). In addition, it may be called "tricyclodecyl (meth) acrylate", and tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (it is common name in the art as "dicyclophene.""Tenyl (meth) acrylate"), dicyclopenta Neyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naph (Meth) acrylic acid esters such as methyl (meth) acrylate and benzyl (meth) acrylate;

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

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

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

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

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

Among these, styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [2.2.1] hept-2-ene, etc. are preferable at the point of copolymerization reactivity and heat resistance.

In resin [K1], the ratio of the structural unit derived from each is in all the structural units which comprise resin [K1],

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

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

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

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

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

Resin [K1] is, for example, the method described in the document "Experimental method of polymer synthesis" (by Takayuki Otsu, first publication, March 1, 1972 issued by Hakko Sho Chemical Co., Ltd.) and the citations described in this document. It can be prepared with reference to.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, oxygen is replaced with nitrogen to form a deoxygen atmosphere, and a method of heating and keeping warm while stirring is given. Can be. In addition, the polymerization initiator, solvent, etc. which are used here are not specifically limited, What is normally used in the said field | area can be used. For example, as a polymerization initiator, an azo compound [2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.] and an organic peroxide (benzoyl peroxide etc.) are mentioned. As a solvent, what is necessary is just to melt | dissolve each monomer, and the solvent (F) mentioned later as a solvent of colored curable resin composition is mentioned.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was extracted as solid (powder) by methods, such as reprecipitation. In particular, by using the solvent (F) mentioned later as a solvent at the time of this superposition | polymerization, the solution after reaction can be used as it is, and a manufacturing process can be simplified.

In resin [K2], the ratio of the structural unit derived from each is in the whole structural unit which comprises resin [K2],

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

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

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

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

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

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

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

Resin [K2] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

In resin [K3], the ratio of the structural unit derived from each is in the whole structural unit which comprises resin [K3],

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

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

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

Structural unit derived from (c): It is more preferable that it is 50-90 mol%.

Resin [K3] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

Resin [K4] obtains the copolymer of (a) and (c), and adds the C2-C4 cyclic ether which (b) has to the carboxylic acid and / or carboxylic anhydride which (a) has It can manufacture.

First, the copolymer of (a) and (c) is manufactured similarly to the method described as a manufacturing method of resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the ratio similar to what was illustrated by resin [K3].

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

Subsequent to the preparation of the copolymer of (a) and (c), the atmosphere in the flask was replaced with nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride with a cyclic ether [such as tris (dimethyl Aminomethyl) phenol and the like] and a polymerization inhibitor (for example, hydroquinone and the like) and the like are placed in a flask and reacted at 60 ° C to 130 ° C for 1 to 10 hours, for example, to prepare a resin [K4].

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

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

The reaction conditions such as the injection method, the reaction temperature and the time can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, polymerization and the like. In addition, similarly to the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production facility, polymerization, and the like.

Resin [K5] is carried out similarly to the manufacturing method of resin [K1] mentioned above as a 1st step, and obtains the copolymer of (b) and (c). As mentioned above, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was extracted as solid (powder) by methods, such as reprecipitation.

It is preferable that the ratio of the structural unit derived from (b) and (c) exists in the following ranges with respect to the total mole number of all the structural units which comprise said copolymer.

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

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

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

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

Moreover, the carboxylic acid or carboxylic anhydride which (a) has in the cyclic ether derived from (b) which the copolymer of (b) and (c) has on the same conditions as the manufacturing method of resin [K4] Resin [K5] can be obtained by making it react.

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

Resin [K6] is resin which made carboxylic anhydride further react with resin [K5]. The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic anhydride.

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid Resins such as copolymers [K1]; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2.6 ] decylacrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decylacrylate / (meth) acrylic acid / vinyltoluene copolymer, 3 , 4-epoxytricyclo [5.2.1.0 ^2.6 ] decylacrylate / (meth) acrylic acid / tricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate copolymer, 3-methyl-3- (meth) acryloyl Resin [K2], such as an oxymethyl oxetane / (meth) acrylic acid / styrene copolymer, and 3-methyl- 3- (meth) acryloyl oxymethyl oxetane / (meth) acrylic acid / N-cyclohexyl maleimide copolymer ; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; Resin which glycidyl (meth) acrylate was added to the benzyl (meth) acrylate / (meth) acrylic acid copolymer, and glycidyl (meth) to the tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin [K4], such as resin which added the acrylate, and resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; Of resin, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate Resins [K5], such as resin which made (meth) acrylic acid react with the copolymer; Resin [K6], such as resin which further made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid reacted with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, is mentioned. .

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

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

The weight average molecular weight of polystyrene conversion of resin (B) becomes like this. Preferably it is 3,000-100,000 or less, More preferably, it is 4,000 or more and 30,000 or less, More preferably, it is 5,000 or more and 12,000 or less. When resin (B) contains several types of resin, it is preferable that the weight average molecular weight of what mixed these is in the said range. When the molecular weight of resin (B) exists in the said range, there exists a tendency for the solubility to the developing solution of an unexposed part to be high, and the residual film ratio and contrast of the pattern obtained are high.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4. When the molecular weight distribution of the resin (B) is in the above-described range, there is a tendency for excellent developability.

The acid value of resin (B) becomes like this. Preferably it is 20-180 mg-KOH / g, More preferably, it is 50-150 mg-KOH / g, More preferably, it is 70-135 mg-KOH / g. When resin (B) contains several types of resin, it is preferable that the acid value of what mixed these is in the said range. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

Content of resin (B) is 7-65 mass% with respect to solid content of colored curable resin composition, More preferably, it is 13-55 mass%, More preferably, it is 17-45 mass%. When content of resin (B) exists in the said range, there exists a tendency for the solvent resistance of the pattern obtained to be high.

The colored curable resin composition of this invention contains a polymeric compound (C). The polymerizable compound (C) is a compound which can be polymerized by active radicals and / or acids generated from the polymerization initiator (D) by the action of light or heat, and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. And, preferably, a (meth) acrylic acid ester compound.

Especially, as a polymeric compound (C), it is preferable that it is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri Pentaerythritol octa (meth) acrylate, tripentaerythritolhepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) Acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate , Propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra ( Agent) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Especially, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable. These polymeric compounds may be used independently and may be used in combination of 2 or more type.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 55% by mass, still more preferably 17 to 45% by mass based on the total amount of solids of the colored curable resin composition. %to be. When content of said polymeric compound (C) exists in the said range, since hardening arises sufficiently, the sensitivity at the time of pattern formation is high, and there exists a tendency for the solvent resistance of the pattern obtained to be high.

The colored curable resin composition of this invention contains a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it can generate active radicals by the action of light or heat and can initiate polymerization of the polymerizable compound (C), and known radical polymerization initiators can be used.

Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds, biimidazole compounds and the like.

As a polymerization initiator (D), the compound which generate | occur | produces an active radical by the action of light is preferable, and is selected from the group which consists of an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, an O-acyl oxime compound, and a biimidazole compound. The polymerization initiator containing 1 or more types is more preferable, and the polymerization initiator containing an O-acyl oxime compound is further more preferable.

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

Hereinafter, * represents a bond number.

As the O-acyl oxime compound, for example, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3- Dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl ) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- And the like] -3-cyclopentylpropane-1-one-2-imine. You may use commercially available products, such as Ilgacure (registered trademark) OXE01, OXE02 (above BASF Corporation make), and N-1919 (ADEKA Corporation make). Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2 -Imines and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imines are preferred. When using 1 or more types of these O-acyl oxime compounds, the brightness of the color filter obtained tends to become high.

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

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

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

In view of sensitivity, a compound having a partial structure represented by the general formula (d2) is preferable as the alkylphenone compound.

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

2,4,6-trimethyl benzoyl diphenyl phosphine oxide etc. are mentioned as an acyl phosphine oxide compound. You may use a commercial item, such as Ilgacure (trademark) 819 (made by BASF Corporation).

Biimidazole compounds include, for example, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl ) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, eg, Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.) and 4, The imidazole compound (For example, refer Unexamined-Japanese-Patent No. 7-10913 etc.) in which the phenyl group of a 4'5,5'-position is substituted by the carboalkoxy group.

Moreover, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 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-ethylanthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization start adjuvant (E) (especially amines) mentioned later.

Content of a polymerization initiator (D) becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), More preferably, it is 5-25 mass parts. When content of a polymerization initiator (D) exists in the said range, a pattern can be formed with high sensitivity, and the pattern obtained tends to be excellent in solvent resistance, mechanical strength, and surface smoothness.

The colored curable resin composition of this invention may further contain the polymerization start adjuvant (E) with a polymerization initiator (D). A polymerization start adjuvant (E) is a compound or sensitizer used in order to accelerate superposition | polymerization of the photopolymerizable compound in which superposition | polymerization was started with a polymerization initiator.

An amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned as a polymerization start adjuvant (E), Preferably it is a thioxanthone compound.

As the amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminoisobenzoic acid isoamyl, 2-dimethylaminoethyl benzoate, 4-dimethylamino 2-ethylhexyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4 '-Bis (ethylmethylamino) benzophenone and the like can be cited, and among these, 4,4'-bis (diethylamino) benzophenone is preferable. You may use a commercial item, such as EAB-F (made by Hodogaya Kagaku Kogyo Co., Ltd.).

Alkoxy anthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibu Methoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene, and the like.

Thioxanthone compounds include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone and 1-chloro-4-propoxy Orcanthone etc. are mentioned.

These polymerization start adjuvant (E) may be used independently and may be used in combination of 2 or more type.

When using a polymerization start adjuvant (E), the usage-amount is preferably 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), More preferably, it is 1-20 It is a mass part. Moreover, with respect to 100 mass parts of content of a polymerization initiator (D), Preferably it is 20-100 mass parts, More preferably, it is 30-80 mass parts. When the amount of the polymerization start aid (E) is within this range, a pattern can be formed with high sensitivity, and the pattern obtained tends to be excellent in solvent resistance, mechanical strength, and surface smoothness.

The colored curable resin composition of this invention contains a solvent (F), and a solvent (F) contains cyclohexanone. In the present invention, the solvent (F) is preferably a mixed solvent containing cyclohexanone.

The solvent combined with cyclohexanone is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (solvent containing -COO- in a molecule and no -O-), an ether solvent (solvent containing -O- in a molecule and not containing -COO-), an ether ester solvent ( Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-; except cyclohexanone), alcohol solvents (molecules) OH in the solvent, and none of -O-, -CO-, and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, and the like.

These solvents may be used independently and may be used in combination of 2 or more type.

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

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

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxy propionate, ethyl 3-methoxy propionate, and methyl 3-ethoxy propionate , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2- Methyl methyl propionate, 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 And di, and the like ethylene glycol monobutyl ether acetate.

As ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo Pentanone, isophorone, etc. are mentioned.

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

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

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

Moreover, it is preferable that the solvent (F) contained in the colored curable resin composition of this invention contains the solvent which has a hydroxyl group in a molecule | numerator. Examples of such solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and diol. Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1 Butanol, 3-methoxy-3-methylbutanol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and 4-hydride Hydroxy-4-methyl-2-pentanone, and the like. Especially, ethyl lactate, propylene glycol monomethyl ether, and 4-hydroxy-4-methyl- 2-pentanone are preferable. By including these solvents, a color filter with few foreign substances can be obtained.

It is more preferable that the solvent (F) further contains an ether ester solvent. When an ether ester solvent is included, it is preferable that an ether ester solvent is 1 or more types chosen from the group which consists of propylene glycol monomethyl ether acetate, 3-ethoxy propionate, and 3-methoxybutyl acetate. By including these solvents, the dispersion state of a pigment can be stabilized and the viscosity increase with time of a colored curable resin composition can be suppressed.

Content of cyclohexanone in a solvent (F) becomes like this. Preferably it is 1-90 mass%, More preferably, it is 4-70 mass%. When content of cyclohexanone exists in the said range, the color filter obtained has high contrast and it exists in the tendency for generation | occurrence | production of a foreign material to be small.

When a solvent (F) contains the solvent which has a hydroxyl group in a molecule | numerator, the content is preferably 10-90 mass% in solvent (F), More preferably, it is 15-80 mass%.

As a solvent which has a hydroxyl group in a molecule | numerator, it is especially preferable to contain 1 or more types chosen from the group which consists of ethyl lactate and propylene glycol monomethyl ether, and it is more preferable to contain ethyl lactate.

In a more preferable aspect, the solvent (F) may contain only ethyl lactate as a solvent which has a hydroxyl group in a molecule | numerator, but may contain ethyl lactate and propylene glycol monomethyl ether. When the solvent (F) contains ethyl lactate and propylene glycol monomethyl ether, the content of propylene glycol monomethyl ether in the solvent (F) is preferably 1 to 120 to 100 parts by mass of ethyl lactate. It is mass part, More preferably, it is 1-87 mass part. If content of propylene glycol monomethyl ether exists in the said range, there exists a tendency for there to be few foreign substances on the color filter obtained.

When a solvent (F) contains an ether ester solvent, the content is preferably 1-50 mass% in a solvent (F), More preferably, it is 1-35 mass%, More preferably, 1 It is -25 mass%. When content of an ether ester solvent exists in the said range, the dispersion state of a pigment will be stabilized and the viscosity increase over time of a colored curable resin composition can be suppressed effectively, but when it exceeds too much above the said range, the color filter obtained There exists a possibility that the foreign material which arises in a phase may increase.

In especially preferable embodiment of this invention, in order to obtain the colored curable resin composition of this invention, a solvent (F) is prepared by mixing the following solvent species by the following ratio.

Preferably,

Cyclohexanone: 4 to 70%

Solvent having a hydroxyl group in the molecule: 15 to 80%

Ether ester solvent: 1 to 35%

More preferably,

Cyclohexanone: 5-60%

Solvent having a hydroxyl group in the molecule: 20 to 75%

Ether ester solvent: 10-25%

More preferably,

Cyclohexanone: 4 to 70%

Ethyl lactate: 10-80%

Propylene glycol monomethyl ether: 0-40%

Ether ester solvent: 1 to 35%

Particularly preferably,

Cyclohexanone: 5-60%

Ethyl lactate: 20-75%

Propylene Glycol Monomethyl Ether: 0-30%

Ether ester solvent: 10-25%

Content of a solvent (F) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of colored curable resin composition, More preferably, it is 75-92 mass%. In other words, solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass%, More preferably, it is 8-25 mass%.

When content of the solvent (F) exists in the said range, flatness at the time of application | coating will become favorable, and when a color filter is formed, there exists a tendency for display characteristics to become favorable because color concentration does not run short.

It is preferable that the viscosity at 23 degrees C of a solvent (F) is 1.8 mPa * s or more and 3.7 mPa * s or less, More preferably, it is 1.8 mPa * s or more and 3.1 mPa * s or less, More preferably, it is 2.0 mPa * s. It is more than 2.5 mPa * s. In the case where the solvent (F) is a mixed solvent composed of plural kinds of solvents, it is preferable that the viscosity measured at 23 ° C. becomes the above value after mixing all the solvents constituting the mixed solvent in a predetermined content ratio.

The viscosity of a solvent (F) is the value measured using the rotary viscometer by the measuring method based on JISZ8803 "Viscosity-measuring method of a liquid." As the rotary viscometer for measuring the viscosity, for example, a type B (spindle type) or type E (cone plate type) rotary viscometer can be used.

If the viscosity of a solvent (F) exists in the said range, the color filter obtained will have high contrast. If the viscosity is too low, the contrast of the color filter obtained will not become sufficiently high. On the other hand, if the viscosity is too high, streaks of streaks will occur on the film after application, or cloud-like stains or dolby on the film after solvent removal. (bumping) There may be a hole.

It is preferable that the colored curable resin composition of this invention contains surfactant (G) further. As surfactant (G), silicone type surfactant, a fluorine-type surfactant, the silicone type surfactant which has a fluorine atom, etc. are mentioned. These may have a polymeric group in a side chain.

As silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. Specifically, doyle silicon DC3PA, doyle silicon SH7PA, doyle silicon DC11PA, doyle silicon SH21PA, doyle silicon SH28PA, doyle silicon SH29PA, doyle silicon SH30PA, doyle silicon SH8400 [Doray Dow Corning Co., Ltd.] Manufacture], KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsukagaku Kogyo Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (momentary performance) Materials Japan Kogyo Co., Ltd.) etc. are mentioned.

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, fluoride (trademark) FC430, fluoride FC431 (manufactured by Sumitomo 3M Co., Ltd.), megapack (registered trademark) F142D, megapack F171, megapack F172, megapack F173, megapack F177, megapack F183, Megapack F554, Megapack R30, Megapack RS-718-K, Megapack F554 (manufactured by DIC Corporation), F-Top® EF301, F-top EF303, F-top EF351, F-top EF352 [Mitsubishi Material Denshi Kasei Co., Ltd.], Supron (registered trademark) S381, Supron S382, Supron SC101, Supron SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (Daikin Fine Chemical Co., Ltd.) Kyusho Corporation) etc. are mentioned.

As a silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned. Specifically, Mega Pack (R) R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, Mega Pack F443 (manufactured by DIC Corporation), and the like.

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

The content of the surfactant (G) is preferably 0.001% by mass or more and 0.2% by mass or less with respect to the total amount of the colored curable resin composition, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more and 0.05. It is mass% or less. If content of surfactant (G) exists in the said range, the coating film with high flatness can be obtained. This content does not contain the pigment dispersant mentioned above.

The colored curable resin composition of this invention may contain various additives, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, a chain transfer agent, as needed.

<Viscosity of Colored Curable Resin Composition>

When the colored curable resin composition of this invention adjusts solid content of colored curable resin composition to 15 mass%, the viscosity in 23 degreeC is 4.2 mPa * s or more and 10 mPa * s or less, Preferably it is 4.2 mPa * s It is 8 mPa * s or more, More preferably, they are 4.2 mPa * s or more and 6 mPa * s or less. If the viscosity is within the above range, the color filter obtained has high contrast. When the viscosity at 23 degreeC exceeds 10 mPa * s when the solid content of colored curable resin composition is adjusted to 15 mass%, applicability | paintability with respect to a board | substrate falls, and the unevenness | corrugation of a line | wire pattern to the film after application | coating There exists a possibility that it may generate | occur | produce or a cloud-shaped stain and a dolby hole may arise in the film | membrane after solvent removal. Moreover, when it is less than 4.2 mPa * s, the contrast of the color filter obtained will become low.

The said viscosity prescribed | regulated in the colored curable resin composition of this invention is the value measured using the rotary viscometer by the measuring method based on JISZ8803 "Viscosity-measuring method of a liquid." Examples of the rotary viscometer for measuring the viscosity include VISCOMETER TV-30 (manufactured by Toki Sangyo Co., Ltd.) and the like, and a type B (spindle type) or an E type (corn plate type) rotary viscometer can be used. .

Specifically, for example, the solid content of the colored curable resin composition of the present invention is adjusted to 15% by mass, and rotor No. 1 is used as the E-type rotational viscometer using VISCOMETER TV-30 (manufactured by Toki Sangyo Co., Ltd.). It can measure by 23 degreeC of measurement temperature in ° 34'xR24 and rotation speed 100rpm. In addition, measurement temperature 23 degreeC means the temperature of the colored curable resin composition to measure.

Adjustment of solid content of colored curable resin composition is performed by adjusting the quantity of a solvent (F).

For example, when solid content of the colored curable resin composition obtained by mixing each component is higher than 15 mass%, adjustment is performed by adding the solvent (F) to the obtained colored curable resin composition so that the solid content may be 15 mass%. At this time, when the solvent (F) which comprises a colored curable resin composition is a mixed solvent, it adjusts so that solid content of the colored curable resin composition used for viscosity measurement may be 15 mass%, maintaining the mixing ratio of each solvent. . That is, the solvent which consists of the same composition (mixing ratio) as the solvent (F) which comprises colored curable resin composition is used for solid content adjustment. Specifically, first, the solvent species contained in the obtained colored curable resin composition and the content ratio thereof are analyzed by gas chromatography, and the solid content of the colored curable resin composition is heated as a residue according to JIS K5602-1-2. Obtain Subsequently, the solvent of the kind calculated | required by the said analysis is mixed at the content rate calculated | required, the mixed solvent is prepared, and solid content of a colored curable resin composition is adjusted to 15 mass% by adding a required amount of this mixed solvent.

On the other hand, when solid content of the colored curable resin composition obtained by mixing each component is less than 15 mass%, adjustment is performed by evaporating the solvent contained in a colored curable resin composition. Specifically, the obtained colored curable resin composition is placed in a container without a lid, and the solvent is heated until the solid content of the colored curable resin composition is 15% by mass in an oven at 150 ° C. Solid content of the colored curable resin composition which evaporated the solvent can be calculated | required as a heating residue according to the method based on JISK5601-1-2.

<The manufacturing method of colored curable resin composition>

The colored curable resin composition of this invention can be prepared as follows, for example.

First, the pigment (A2) of a coloring agent (A) is previously mixed with one part or all of the solvent (F), and is disperse | distributed using a bead mill etc. until the average particle diameter of a pigment becomes about 0.2 micrometer or less. At this time, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. In the obtained pigment dispersion liquid, the remainder of the coloring agent (A), the remainder of the resin (B), the polymerizable compound (C), the polymerization initiator (D), the remainder of the solvent (F), and other components to be used as required are prescribed contents. The desired colored curable resin composition can be obtained by mixing so that it may become.

In addition, it is preferable to dissolve dye (A1) in one part or all part of solvent (F) in advance, and to prepare a solution, and to use this solution for preparation of colored curable resin composition. It is preferable to filter this solution with the filter of about 0.01-1 micrometer of pore diameters before using for preparation of colored curable resin composition.

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

<Method of manufacturing color filter>

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

The film thickness of the pattern to produce is not specifically limited, It can adjust suitably according to the objective, a use, etc., for example, 0.1-30 micrometers, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers.

As a board | substrate, glass plates, such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass which silica-coated the surface, resin plates, such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and aluminum on the said board | substrate , Silver, and a silver / copper / palladium alloy thin film or the like are used. Separate color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

Formation of each color pixel by the photolithographic method can be performed by a well-known or usual apparatus and conditions. For example, it can produce as follows.

First, a coloring curable resin composition is apply | coated on a board | substrate, volatile components, such as a solvent, are removed and dried by heat drying (prebaking) and / or drying under reduced pressure, and a smooth composition layer is obtained. As a coating method, a spin coat method, the slit coat method, the slit and spin coat method, etc. are mentioned.

30 degreeC-120 degreeC is preferable, and, as for the temperature at the time of heat-drying, 50 degreeC-110 degreeC is more preferable. Moreover, as heating time, it is preferable that it is for 10 second-60 minutes, and it is more preferable that it is for 30 seconds-30 minutes. When drying under reduced pressure, it is preferable to carry out in the temperature range of 20 degreeC-25 degreeC under the pressure of 50-150 Pa.

The film thickness of a composition layer is not specifically limited, According to the material, a use, etc. which are used, it can adjust suitably, For example, it is 0.1-20 micrometers, Preferably it is 0.5-6 micrometers.

The composition layer is then exposed through a photomask for forming the desired pattern. The pattern on the said photomask is not specifically limited, The pattern according to the intended use is used.

As a light source used for exposure, the light source which produces the light of 250-450 nm wavelength is preferable. For example, the light of 350 nm or less is cut using the filter which cuts this wavelength range, or the light of 436 nm, 408 nm, and 365 nm vicinity is used the bandpass filter which extracts these wavelength ranges. It may be taken out selectively. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

Since it is possible to irradiate parallel light rays uniformly to the entire exposure surface or to accurately position the photomask and the substrate, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

The pattern is formed on a board | substrate by developing the composition layer after exposure contacting with a developing solution. By development, the unexposed part of a composition layer melt | dissolves in a developing solution and is removed. As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, is preferable, for example. The density | concentration in the aqueous solution of these alkaline compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%. In addition, the developing solution may contain surfactant.

The developing method may be any of a puddle method, a dipping method and a spray method. In addition, you may tilt the board | substrate at arbitrary angles at the time of image development. It is preferable to wash with water after image development.

Moreover, it is preferable to post-bake on the obtained pattern. 150 degreeC-250 degreeC is preferable, and, as for post-baking temperature, 160 degreeC-235 degreeC is more preferable. 1-120 minutes are preferable and, as for post-baking time, 10 to 60 minutes are more preferable.

The pattern and coating film obtained in this way are useful as a color filter.

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

Example

Next, an Example is given and this invention is demonstrated further more concretely. "%" And "part" in an example are mass% and a mass part unless there is particular notice.

Synthesis Example 1

In a flask equipped with a cooling tube and a stirring device, 15 parts of a mixture of the compound represented by the formula (A0-1) and the compound represented by the formula (A0-2) (manufactured by Chugaikasei), 150 parts of chloroform and N 8.9 parts of, N-dimethylformamide were added thereto, and 10.9 parts of thionyl chloride were added dropwise while maintaining the temperature at 20 ° C. or lower under stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C, held at the same temperature for 5 hours for reaction, and then cooled to 20 ° C. A mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise while maintaining the reaction solution after cooling at 20 ° C. or lower under stirring. Thereafter, the reaction was stirred at the same temperature for 5 hours. Subsequently, the obtained reaction mixture was distilled off the solvent by a rotary evaporator, and a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to the liquid mixture of 375 parts of ion-exchange water, stirring, and the crystal | crystallization was deposited. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C. to obtain 11.3 parts of dye A1 [mixture of compounds represented by formula (A1-1) to formula (A1-8)].

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. After cooling the obtained reaction liquid to room temperature, it added to the liquid mixture of 800 parts of water and 50 parts of 35% hydrochloric acid, and stirred for 1 hour at room temperature, and crystal | crystallization precipitated. The precipitated crystals were obtained as a residue of suction filtration, and then dried to obtain 24 parts of the compound represented by the formula (1-24). Yield 80%.

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

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

                        Exact Mass: 602.2

Synthesis Example 3

A compound represented by the formula (1-30) was obtained in the same manner as in Synthesis example 2 except that N-isopropyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of Compounds Represented by Formula (1-30)

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 659.4

                        Exact Mass: 658.3

Synthesis Example 4

A compound represented by the formula (1-35) was obtained in the same manner as in Synthesis example 2 except that N-propyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of Compounds Represented by Formula (1-35)

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 659.4

                        Exact Mass: 658.3

Synthesis Example 5

Into a four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, the following monomer, 134 parts of ethyl lactate, and 1.4 parts of azobisisobutyronitrile were injected, and the internal temperature was maintained at 85 ° C to 95 ° C under a nitrogen stream, The reaction was stirred for an hour to obtain a resin B1 solution having a solid content of 32%. The weight average molecular weight of obtained resin B1 was 7.8x10 <^3> , molecular weight distribution was 2.2, and solid content acid value was 84 mg-KOH / g.

Methacrylic acid 7.8 parts

N-cyclohexylmaleimide 22.7 parts

3-ethyl-3-methacryloyloxymethyloxetane 26.7 parts

Resin B1 has the following structural unit.

Synthesis Example 6

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 220 parts of ethyl lactate was added and heated to 70 ° C while stirring. Subsequently, 84 parts of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate [a compound represented by the formula (I-1) and a compound represented by the formula (II-1) are molar ratios. , 50:50] 336 parts were dissolved in 140 parts of ethyl lactate to prepare a solution, and the solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping funnel.

On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 95 parts of ethyl lactates was dripped in the flask over 4 hours using the other dropping funnel. After completion of dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight (Mw) was 8.0 × 10 ³ , the molecular weight distribution was 2.5, the solid content was 48%, and the solid content. Resin B2 solution having an acid value of 104 mg-KOH / g was obtained. Resin B2 has the following structural unit.

About the measurement of the polystyrene conversion weight average molecular weight of the said resin, it carried out on condition of the following using GPC method. In addition, ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight of polystyrene conversion was made into molecular weight distribution.

Device; K2479 [manufactured by Shimadzu Seisakusho Corporation]

column; SHIMADZU Shim-pack GPC-80 M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Test liquid solids concentration; 0.001-0.01%

Injection amount; 50 μl

Detectors; RI

Calibration standards; TSK STANDARD POLYSTYRENE

                  F-40, F-4, F-288, A-2500, A-500

                  [Tosho Corporation]

Examples 1 to 19, Comparative Example 1, Comparative Example 2 and Reference Example 1

Each component was mixed so that it might become the composition shown in Tables 1-3, and the colored curable resin composition was obtained. On the other hand, the solvent (F) was mixed so that solid content of colored curable resin composition might become "solid content (%)" in a table | surface, and the breakdown of a solvent (F) became the mass ratio shown to (F1)-(F4). In addition, surfactant (G) was mixed so that the density | concentration in colored curable resin composition may become the ratio shown in a table | surface.

TABLE 1

TABLE 2

TABLE 3

In addition, in Tables 1-3, each component shows the following. In addition, resin (B) showed the mass part of conversion of solid content.

Colorant (A): (A1): Dye 1 (organic solvent soluble dye)

Colorant (A): 1-24: Compound represented by the formula (1-24) (organic solvent soluble dye)

Colorant (A): 1-30: Compound represented by the general formula (1-30) (organic solvent soluble dye)

Colorant (A): 1-35: Compound represented by the formula (1-35) (organic solvent soluble dye)

Colorant (A): 1-37: Compound represented by formula (1-37): C.I. Acid Red 52 (organic solvent soluble dye)

Colorant (A): (A2): C.I. Pigment Blue 15: 6 (pigment)

Resin (B): (B1): Resin B1

Resin (B): (B2): Resin B2

Resin (B): (B3): A copolymer of methacrylic acid and benzyl methacrylate [acid value: 157 mg-KOH / g, polystyrene conversion weight average molecular weight: 1.1 × 10 ⁴ ]

Polymerizable Compound (C): (C1): dipentaerythritol hexaacrylate [KAYARAD DPHA; Nihon Kayaku Co., Ltd.]

Polymerization initiator (D): (D1): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE 01; Manufactured by BASF Corporation; O-acyl oxime compound)

Polymerization initiator (D): (D2): 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one [Igure Cure® 907; Manufactured by BASF Corporation; Alkylphenone Compound]

Polymerization start aid (E): (E1): 2,4-diethyl thioxanthone [Kayacure® DETX-S; Nihon Kayaku Co., Ltd. product; Thioxanthone compound]

Solvent (F): (F1): Cyclohexanone

Solvent (F): (F2): Propylene glycol monomethyl ether

Solvent (F): (F3): ethyl lactate

Solvent (F): (F4): Propylene glycol monomethyl ether acetate

Surfactant (G): (G1): polyether-modified silicone oil [doresilicon SH8400; Toore Dow Corning Co., Ltd.]

[Viscosity Measurement of Solvent (F)]

The viscosity of the solvent (F) contained in the colored curable resin composition of each Example, a comparative example, and a reference example was measured with a viscometer [model: VISCOMETER TV-30; Toki Sangyo Co., Ltd. make, rotor No. 1 degrees 34'x R24, rotation speed 100rpm, measurement temperature: 23 degreeC]. The results are shown in Table 4.

TABLE 4

[Viscosity Measurement of Colored Curable Resin Composition]

The solid content of the colored curable resin composition of Examples 1-19, Comparative Example 1, Comparative Example 2, and Reference Example 1, and the colored curable resin composition of Examples 12-19, and Comparative Example 2 is adjusted to 15 mass%, and is adjusted. The viscosity of the colored curable resin composition was measured by a viscometer [model; VISCOMETER TV-30; It was measured using Toki Sangyo Co., Ltd. make, rotor No. 1 degrees 34'xR24, rotation speed 100rpm, measurement temperature 23 degreeC]. The results are shown in Tables 5 and 6.

[Creation of pattern]

The colored curable resin composition was apply | coated by the spin coat method on the square glass substrate (Eagle 2000; Corning Co., Ltd.) whose one side is 2 inches, and it prebaked at 100 degreeC for 3 minutes, and the composition layer was formed. After cooling, the interval between the substrate on which the composition layer was formed and the photomask made of quartz glass was set to 100 m, and an exposure machine [TME-150RSK; Topcon Co., Ltd.] was irradiated with light at an exposure dose of 365 mJ / cm 2 (365 nm standard) in an air atmosphere. As the photomask, one having a 100 µm line and space pattern was used. The composition layer after light irradiation was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds and developed. After washing with water, post-baking was carried out at 200 ° C. for 30 minutes in an oven. A pattern was obtained. After cooling, the film thickness of the obtained pattern was measured by a film thickness measuring apparatus [DEKTAK3; It was 2.2 micrometers when it measured using Nihon Shinku Co., Ltd. product.

[Color evaluation]

For the obtained pattern, a colorimeter [OSP-SP-200; Spectrophotometry was measured using Olympus Co., Ltd., and the xy chromaticity coordinates (x, y) and tristimulus values Y in the XYZ colorimeter of CIE were measured using the characteristic function of the C light source. The larger the value of Y, the higher the brightness.

The results are shown in Tables 5 and 6.

[Production of film and measurement of film thickness]

The colored curable resin composition was apply | coated by the spin coat method on the square glass substrate (Eagle 2000; Corning Corporation) whose one side is 5 cm, and it prebaked at 100 degreeC for 3 minutes, and the composition layer was formed. After cooling, an exposure machine [TME-150RSK; Topcon Co., Ltd.] was irradiated with light at an exposure amount (365 nm standard) of 150 mJ / cm 2 in an air atmosphere. After light irradiation, the coating film was obtained by performing post-baking at 220 degreeC for 20 minutes in oven. After cooling, the film thickness of the obtained coating film was measured by a film thickness measuring apparatus [DEKTAK3; Nippon Shinkujuju Co., Ltd. product] was used for the measurement. The results are shown in Tables 5 and 6.

[Contrast evaluation; Condition 1]

With respect to the coating films obtained in Examples 1 to 15, Comparative Example 1 and Comparative Example 2, the contrast system [color chrominance system BM-5A; Topcon Co., Light Source; F-10, polarizing film; The Tsubasa Kadenki Co., Ltd. product] was made the blank value 10000, and the contrast was measured. The glass substrate in which the said coating film was formed was sandwiched between polarizing films (POLAX-38S; Lukeo Co., Ltd.) as a measurement sample. The results are shown in Table 5.

[Contrast evaluation; Condition 2]

For Examples 16 to 19 and Reference Example 1, the resulting coating film was a contrast system [color chrominance system BM-5A; Topcon Co., Light Source; F-10, polarizing film; The Tsubasa Kadenki Co., Ltd. product] used the blank value as 30000, and measured the contrast. The glass substrate in which the said coating film was formed was sandwiched between polarizing films (POLAX-38S; Lukeo Co., Ltd.) as a measurement sample. The results are shown in Table 6.

[Observation of foreign objects]

The obtained coating film was observed at 250 times magnification using a surface shape measurement microscope (VF-7510; manufactured by Keyence). If the number of foreign objects of black or white spots in the microscope field is 30 or less, ◎, more than 30 and 80 or less, ○, more than 80 and less than 120, △, if more than 120, evaluated as × Was performed. The results are shown in Tables 5 and 6.

TABLE 5

TABLE 6

From the said result, it was confirmed that the pattern formed with the colored curable resin composition of this invention is excellent in contrast. From this, according to the colored curable resin composition of this invention, it turns out that the color filter excellent in color performance can be manufactured.

According to the colored curable resin composition of this invention, a pattern with high contrast can be formed.

Claims (5)

It contains a coloring agent, resin, a polymeric compound, a polymerization initiator, and a solvent,
The colorant is a colorant containing an organic solvent soluble dye and a pigment,
The solvent is a solvent containing cyclohexanone, a solvent having a hydroxy group in the molecule, and an ether ester solvent, the content of the ether ester solvent in the solvent is 1 to 25% by mass,
The colored curable resin composition whose viscosity in 23 degreeC is 4.2 mPa * s or more and 10 mPa * s or less when the solid content of colored curable resin composition is adjusted to 15 mass%. The coloring of Claim 1 whose content of cyclohexanone is 5-60 mass%, the content of the solvent which has a hydroxyl group in a molecule | numerator is 20-75 mass%, and content of an ether ester solvent is 10-25 mass% in a solvent. Curable Resin Composition. The color filter formed with the colored curable resin composition of Claim 1 or 2. The display device containing the color filter of Claim 3. The coloring curable resin composition of Claim 1 in which the solvent which has a hydroxyl group in a molecule contains ethyl lactate.