KR102003237B1 - Colored photosensitive resin composition - Google Patents

Abstract

There is provided a colored photosensitive resin composition which is free from the occurrence of peeling flakes derived from a colored photosensitive resin composition in a developing solution after development. The colored photosensitive resin composition of the present invention comprises a colorant, a binder resin, a polymerizable compound, a polymerization initiator and a solvent, wherein the colorant is a colorant containing a dye, the binder resin has a weight average molecular weight of from 3,000 to less than 15,000, (B2) a resin having a weight average molecular weight of 15,000 or more and 100,000 or less and an acid value of 20 mgKOH / g or more and 200 mgKOH / g or less; Is a binder resin containing a resin.

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a colored photosensitive resin composition.

The colored photosensitive resin composition is used for producing a color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, and a plasma display panel. As this colored photosensitive resin composition, a colored photosensitive resin composition containing a copolymer of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate as a resin is known (Patent Document 1).

Japanese Patent Application Laid-Open No. 2010-211198 Japanese Patent Application Laid-Open No. 2010-224204

When the pattern is formed by the photolithography method, when the colored photosensitive resin composition layer on the substrate is peeled off and removed by the developing solution at the time of development, there is a fear that the peeling pieces are adhered as foreign matters on the pattern or the pipe through which the developing solution flows after development have. The above-mentioned developability of the above-mentioned colored photosensitive resin composition, which is conventionally known, can not always be sufficiently satisfied.

The present invention provides the following [1] to [6].

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

Wherein the coloring agent is a coloring agent comprising a dye,

Wherein the binder resin is a binder resin comprising the following (B1) and (B2).

(B1) a resin having a weight average molecular weight of 3,000 or more and less than 15,000, and having an acid value of 20 mgKOH / g or more and 200 mgKOH / g or less

(B2) a resin having a weight average molecular weight of 15,000 or more and 100,000 or less and an acid value of 20 mg-KOH / g or more and 200 mg-KOH / g or less

[2] The thermosetting resin composition as described in [1], wherein (B1) is a copolymer comprising a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, A colored photosensitive resin composition comprising a structural unit derived from a monomer having an unsaturated bond.

[3] The colored photosensitive resin composition according to [1] or [2], wherein the polymerization initiator is a polymerization initiator comprising an oxime compound.

[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the colorant is a colorant comprising a dye and a pigment.

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

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

(Effects of the Invention)

According to the colored photosensitive resin composition of the present invention, the occurrence of peeling fragments derived from the colored photosensitive resin composition in the developing solution after development is small.

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

And the binder resin (B) is a binder resin comprising the following (B1) and (B2).

(B1) a resin having a weight average molecular weight of 3,000 or more and less than 15,000, and having an acid value of 20 mgKOH / g or more and 200 mgKOH / g or less

(B2) a resin having a weight average molecular weight of 15,000 or more and 100,000 or less and an acid value of 20 mg-KOH / g or more and 200 mg-KOH / g or less

The colored photosensitive resin composition of the present invention comprises a colorant (A), and the colorant (A) comprises a dye (A1). Examples of the dye (A1) include dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes and sulfonamide derivatives of acid dyes. For example, in the color index (The Society of Dyers and Colourists) A compound which is classified as having a color other than the dye, and a known dye described in dyeing notes (Shikisensa). According to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes and phthalocyanine dyes can be mentioned. These dyes may be used alone or in combination of two or more. Of these, organic solvent-soluble dyes are preferred.

Specifically, CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, and the description is made only by numbers), 14, 15, 23, 24, 38, 62, 63, 68, 82 , 94, 98, 99, 117, 162, 163, 167, 189;

CI 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;

CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 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; CI. ≪ / RTI > solvent dyes,

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

C.I. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 76, 188, 195, 176, 182, 183, 195, 183, 183, 143, 145, 150, 151, 158, 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;

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

C. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 28, 41, 50, 58, 63, 65, 80, 104, 105, 106, 109; C.I. acid dye,

CI 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;

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

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

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

CI Direct Blue 1, 2, 6, 8, 15, 22, 25, 40, 41, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 198, 199, 200, 201, 202, 193, 194, 195, 196, 198, 199, 200, 201, 202, 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; C.I. direct dye,

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

C. I. Disperse Violet 26, 27;

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

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

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

C.I. Reactive Orange 16;

C.I. Reactive Red 36; C.I. reactive dyes such as < RTI ID = 0.0 >

CI. 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;

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;

CI. Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53; C.I.Modent dyes and the like

And C.I. bat dyes such as C. I. Bat Green 1 and the like.

As the dye (A1), a xanthene dye (Aa) is preferable.

The xanthene dye (Aa) is a dye comprising a compound having a xanthene skeleton.

Examples of the xanthene dye (Aa) include C.I. acid red 51, 52, 87, 92, 94, 289, 388, C.I. acid violet 9,30, 102, C.I. (Rhodamine 6G), 2,3,4,8, C. I. Basic Red 10 (Rhodamine B), 11, C. I. Basic Violet 10,11, 25, C.I. Solvent Red 218, C.I. I. Moderntred 27, C.I. Reactive Red 36 (Rose Bengal B), Sulfolodamine G, the xanthene dyes disclosed in Japanese Patent Application Laid-Open No. 2010-32999, and the xanthene dyes described in Japanese Patent No. 4492760 And the like.

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

[In the formula (1), each of R ¹ to R ⁴ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is halogen ^{atoms, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - M +, -CO 2 H, -CO 2 - M +, -CO 2 R 8, - SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ^8, or -SO ₂ NR ⁹ R ¹⁰ . The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and the saturated hydrocarbon group -CH ₂ - included therein may be substituted with -O-, -CO- or -NR ¹¹ -. R ¹ and R ² may be united to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be united to form a ring containing a nitrogen atom.

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

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

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

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

X represents a halogen atom.

a represents an integer of 0 or 1;

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

R 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.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a hydroxyl group or a halogen atom, and the saturated aliphatic hydrocarbon group contained in the saturated aliphatic hydrocarbon group, CH ₂ - may be substituted with -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ are bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom good]

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

As R ¹ ~R ⁴ carbon atoms, 6 to 10 of 1-valent aromatic hydrocarbon group substituents in the _{^{-SO 3 -, -SO 3 H,}} -SO 3 - M + and -SO selected from the group consisting of ₂ NR ⁹ R ¹⁰ preferably has at least one kind, and, -SO ₃ ^- and more preferably that has at least one member selected from the group consisting of M ⁺ and -SO ₂ NR ⁹ R ^10. In this case, -SO ₃ ^- M ⁺ is preferably -SO ₃ ^{- +} N (R ¹¹ ) ₄ . When R ¹ to R ⁴ are these groups, a color filter having less occurrence of foreign matter and excellent in heat resistance can be formed from the colored photosensitive resin composition containing the compound (1) of the present invention.

Examples of the ring formed by the combination of R ¹ and R ² and the ring formed by combining R ³ and R ⁴ include the following.

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

Examples of -OR ⁸ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and eicosyloxy. have.

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

Examples of -SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group and an eicosylsulfanyl group.

Examples of -SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group and an eicosylsulfonyl group.

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

Examples of -SO ₂ NR ⁹ R ¹⁰ include sulfamoyl groups; N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N-methylpyrrolyl group, N- (2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) An N-1-substituted sulfamoyl group such as a sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group and N- (1,1,2,2-tetramethylbutyl) sulfamoyl group; N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group, and the like.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which represents R ⁹ and R ¹⁰ may have a hydrogen atom contained in the saturated hydrocarbon group substituted with -OH or a halogen atom, and -CH ₂ - included in the saturated hydrocarbon group may be replaced with -O- , -CO-, -NH-, or -NR ⁸ -.

R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. Examples of the heterocyclic ring include the following.

R ⁵ is ^{_{-CO 2 H, -CO 2 R 8}} , -SO 3 -, -SO 3 - M +, -SO 3 H or SO ₂ NHR ⁹ are _{^{preferred, SO 3 -, -SO 3 -}} M +, -SO ₃ H or SO ₂ NHR ⁹ is more preferable.

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

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include those having 1 to 6 carbon atoms in the alkyl groups listed above.

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

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

^{As +} N (R ¹¹ ) _4, it is preferable that at least two of the four R ^{11 s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of four R < ¹¹ > is preferably 20 to 80, more preferably 20 to 60. [ When ⁺ N (R ¹¹ ) ₄ is present in the compound (1), a colored filter having few foreign matters can be formed from the colored photosensitive resin composition containing the compound (1), provided that R ¹¹ is a group of these.

The compound (1) is preferably a compound represented by the formula (2) (hereinafter sometimes referred to as "compound (2)"), and the xanthene dye (Aa) . The compound (2) may be a tautomer thereof. When the compound (2) is used, the content of the compound (2) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, furthermore preferably 90% by mass or more. In particular, it is preferable to use only the compound (2) as the xanthene dye (Aa).

[In the formula (2), each of R ²¹ to R ²⁴ independently represents a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -SO ₃ ^- ₃ ^- Ma ⁺ , -SO ₃ H, -SO ₃ R ^26, or -SO ₂ NHR ²⁶ .

X ^a represents a halogen atom.

a ¹ represents an integer of 0 or 1;

m1 represents an integer of 0 to 5; When m1 is 2 or more integer, a plurality of R ²⁵ are the same or different.

M ^{a +} represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

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

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

R ²⁷ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group;

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ include groups similar to those listed as the aromatic hydrocarbon group in R ¹ to R ⁴ .

Among them, R ²¹ ~R ²⁴ combined as a preferably R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ has 6 to 10 carbon atoms and of 1-valent aromatic hydrocarbon group, hydrogen atoms contained to said aromatic hydrocarbon It is -SO ₃ ^- may be substituted by _{^{M +, -SO 3 H, -SO}} 3 R 26 or _{^{-SO 2 NHR 26 -, -SO 3}} . More preferably, R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -SO ₃ ^- M ⁺ or - SO ₂ NHR ²⁶ . When R ²¹ to R ²⁴ are these groups, a color filter having excellent heat resistance can be formed from the colored photosensitive resin composition of the present invention containing the compound (2).

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ include the same groups as those listed as the saturated hydrocarbon groups in R ⁸ to R ¹¹ .

When R ²¹ to R ²⁴ are -R ²⁶ , -R ²⁶ is preferably independently a hydrogen atom, a methyl group or an ethyl group.

-SO ₃ R ^26, and -SO ₂ NHR ²⁶ R ²⁶ as a branched chain alkyl group of 3 to 20 carbon atoms are preferred, and the carbon number of 6 to 12 branch chain alkyl group, and more preferably, is more preferably a 2-ethylhexyl group in the Do. When R < ²⁶ > is a group of these, the colored photosensitive resin composition containing the compound (2) can form a color filter with less foreign matter.

M ^{a +} is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .

^{As the +} N (R ²⁷ ) _4, it is preferable that at least two of the four R ^{27 s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total carbon number of the four R < ²⁷ > s is preferably from 20 to 80, more preferably from 20 to 60. In the presence of ⁺ N (R ²⁷ ) ₄ in the compound (2), a color filter having less foreign matter can be formed from the colored photosensitive resin composition containing the compound (2) wherein R ²⁷ is a group of these compounds.

Examples of the compound (1) include compounds represented by the formulas (1-1) to (1-30). In the following formulas, Ra represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, more preferably a 2-ethylhexyl group. Among these, the sulfonamides of C. I. Acid Red 289, the quaternary ammonium salts of C. I. Acid Red 289, the sulfonamides of C. I. Acid Violet 102 or the quaternary ammonium salts of C. I. Acid Violet 102 desirable. Examples of such a compound include compounds represented by formulas (1-1) to (1-8), (1-11), and (1-12).

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

[In the formula (3), R ³¹ and R ³² independently represent an alkyl group having 1 to 10 carbon atoms. R ³³ and R ³⁴ independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms. R ³¹ and R ³³ may be united to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be united to form a ring containing a nitrogen atom.

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

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ³¹ and R ³² include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, , Nonyl group, decyl group and the like. Examples of the alkyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include groups having up to 4 carbon atoms.

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

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

R ³¹ and R ³² are preferably independently of each other a methyl group, an ethyl group, a propyl group or an isopropyl group. R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

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

Examples of the compound (3) include compounds represented by the formulas (1-31) to (1-43), respectively. Among them, compounds represented by formulas (1-31) to (1-40) are preferable because they are excellent in solubility in an organic solvent.

Examples of the xanthene dye (Aa) include commercially available xanthene dyes (e.g., " Chugai Aminol Fast Pink RH / C ", manufactured by Chugai Chemical Industry Co., Ltd., " Rhodamin 6G " May be used. Further, commercially available xanthene dyes can also be synthesized by referring to Japanese Patent Application Laid-Open No. 2010-32999 as a starting material.

The colorant (A) preferably also contains the pigment (A2) together with the dye (A1).

The pigment is not particularly limited, and known pigments can be used, and compounds classified as pigments in the color index (published by The Society of Dyers and Colourists), for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 154, 166, 173, 194 and 214;

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

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

Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

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

Green pigments such as CI Pigment Green 7, 36, 58;

Brown pigments such as CI Pigment Brown 23 and 25;

And C.I. Pigment Black 1 and Black Pigment 7 and the like.

Among them, CI Pigment Yellow 138, 139, 150, CI Pigment Red 177, 209, 242, 254, CI Pigment Violet 23, CI Pigment Blue 15: 3, 15: 6 and CI Pigment Green 7, 36, 58 are preferred. Examples of pigments used in the colored photosensitive resin composition of the present invention include CI Pigment Blue 15: 6, CI Pigment Red 254, CI Pigment Red 242, CI Pigment Red 177, More preferably at least one pigment selected from the group consisting of CI Pigment Green 58, CI Pigment Yellow 150 and CI Pigment Yellow 138 is more preferable. By including the pigment, the transmission spectrum can be easily optimized and the chemical resistance can be improved.

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

If necessary, the pigment may be subjected to a surface treatment using a rosin treatment, a pigment derivative into which an acidic group or a basic group has been introduced, a graft treatment to the surface of the pigment with a polymer compound or the like, an atomization treatment using a sulfuric acid atomization method or the like, A cleaning treatment with water or the like, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.

The pigment preferably has a uniform particle size. A pigment dispersion may be obtained by dispersing the pigment in the solution by dispersing the pigment dispersion.

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

When a pigment dispersant is used, its amount to be used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment (A2). When the amount of the pigment dispersant is within the above range, a pigment dispersion in a uniformly dispersed state tends to be obtained.

When the pigment (A2) is contained, the content ratio (A1 (A2)) of the pigment (A1) to the pigment (A2) is preferably 1:99 to 99: 1, 10 is more preferable. By making this ratio, it is easy to optimize the transmission spectrum, and the obtained color filter tends to be excellent in contrast, brightness, heat resistance and chemical resistance.

Particularly, when the colored photosensitive resin composition of the present invention is prepared as a blue colored photosensitive resin composition, the colorant (A) is preferably a colorant containing a xanthene dye and a blue pigment, and a colorant containing a xanthene dye and C.I. Pigment Blue 15 : 6 is more preferable. The content ratio of the xanthene dye to the blue pigment is preferably 3: 97 to 90: 10, more preferably 3: 97 to 70: 30, more preferably 3: 97 to 50: 50, More preferably 95 to 30:70. By incorporating these colorants as the above content, a high-definition blue color filter can be obtained.

The content of the colorant (A) is preferably from 5 to 60 mass%, more preferably from 8 to 55 mass%, further preferably from 10 to 50 mass%, particularly preferably from 5 to 60 mass%, based on the solid content in the colored photosensitive resin composition Is from 12 to 30 mass%. When the content of the colorant (A) is within the above range, desired spectral and color density can be obtained when the color filter is used, and since a required amount of binder resin or polymerizable compound can be contained in the composition, can do. Here, the solid content refers to the total amount of the components excluding the solvent from the colored photosensitive resin composition of the present invention. The solid content and the content of each component in the solid content can be measured by known analytical means such as liquid chromatography or gas chromatography.

The colored photosensitive resin composition of the present invention comprises a binder resin (B), and the binder resin (B) includes the following (B1) and (B2). By combining these resins, it is possible to suppress the occurrence of peeling-off points derived from the colored photosensitive resin composition in the developer after development.

(B1) a resin having a weight average molecular weight of 3,000 or more and less than 15,000, and having an acid value of 20 mgKOH / g or more and 200 mgKOH / g or less

(B2) a resin having a weight average molecular weight of 15,000 or more and 100,000 or less and an acid value of 20 mg-KOH / g or more and 200 mg-KOH / g or less

In the present specification, the weight average molecular weight refers to a value obtained as a weight average molecular weight in terms of polystyrene by gel permeation chromatography. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin, and is a value obtained by titration using an aqueous potassium hydroxide solution.

(B1) has a weight average molecular weight of 3,000 or more and less than 15,000, preferably 4,000 or more and 11,000 or less, more preferably 5,000 or more and 10,000 or less. (Weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (B1) is preferably 1.1 to 6, and more preferably 1.2 to 4.

KOH / g to 170 mg-KOH / g, more preferably 60 mg-KOH / g to 200 mg-KOH / g, g or more and 150 mg-KOH / g or less, and more preferably 80 mg-KOH / g or more and 120 mg-KOH / g or less.

(B2) has a weight average molecular weight of 15,000 or more and 100,000 or less, preferably 18,000 or more and 50,000 or less, and more preferably 20,000 or more and 30,000 or less. (Weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (B2) is preferably 1.1 to 6, and more preferably 1.2 to 4.

KOH / g to 170 mg-KOH / g, more preferably 80 mg-KOH / g to 200 mg-KOH / g, g or more and 160 mg-KOH / g or less, and more preferably 100 mg-KOH / g or more and 150 mg-KOH / g or less. (B2) is preferably higher than the acid value of (B1) used together.

The chemical structures of (B1) and (B2) are not particularly limited, and examples thereof include the following resins [K1] to [K6].

(A) (hereinafter may be referred to as "(a)") selected from the group consisting of [K1] unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, And a monomer (b) having an unsaturated bond (hereinafter sometimes referred to as " (b) ").

(A) and (b)) (hereinafter sometimes referred to as "(c)") of the monomer (c) copolymerizable with [K2] (a) and (b) coalescence

[K3] The copolymer of (a) and (c)

[K4] Resin obtained by reacting the copolymer (a) and (c) with (b).

[K5] Resin obtained by reacting the copolymer (b) and (c) with (a).

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

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

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

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- , 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

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

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

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

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

(b) is, for example, a polymer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of oxirane rings, oxetane rings, and tetrahydrofuran rings) Compound. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

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

(b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (B2) "), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as" (b3) ") and the like.

(b1-1) (hereinafter may be referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized and an ethylenically unsaturated bond and a structure, And a monomer (b1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1-2)").

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl- Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- ) Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5- , 3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) have.

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000 manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexyl (Meth) acrylates such as methyl (meth) acrylate (for example, Cyclomer A400, manufactured by Daicel Chemical Industries Ltd.), 3,4-epoxycyclohexylmethyl A compound represented by the formula (I) and a compound represented by the formula (II).

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

X ¹ and X ² independently 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 of 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, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, 1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.

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, more preferably a hydrogen atom or a methyl group.

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

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- (* represents the number of bonds of O) group, * -CH ₂ CH ₂ -O- group , More preferably a single bond, * -CH ₂ CH ₂ -O- group.

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

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

The compound represented by formula (I) and the compound represented by formula (II) may be used alone. Also, they can be mixed at any ratio. The mixing ratio thereof is preferably from 5: 95 to 95: 5, more preferably from 10: 90 to 90: 10, and even more preferably from 20: 80 to 90: 10 in the formula (I) 80:20.

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

As the monomer (b3) having a tetrahydrofuryl group and an ethylenic unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

(b) is preferably (b1) in that reliability of heat resistance, chemical resistance, etc. of the obtained color filter can be further enhanced. Further, (b1-2) is more preferable in view of good storage stability of the colored photosensitive resin composition.

(meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- (Meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (Meth) acrylate (also referred to in the art as dicyclopentanyl (meth) acrylate) in the prior art, and (meth) acrylic acid esters such as methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan- Dicyclopentanyloxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (referred to in the art as dicyclopentenyl (meth) acrylate ), Isobonyl (meth) acrylate, adamantyl (Meth) acrylate such as methyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl Ryu;

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

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

2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] 2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cicarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene, Cyclo-unsaturated compounds;

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

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

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

The ratio of the respective structural units derived from the resin [K1] is preferably in the following range among the total structural units constituting the resin [K1].

a structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 40 mol%)

(b); 50 to 98 mol% (more preferably 60 to 90 mol%),

When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored photosensitive resin composition, developability and solvent resistance of the color filter tends to be excellent.

Resin [K1] can be prepared by, for example, the method described in the "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, 1st Edition, March 1, 1972) As a reference.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator and a solvent are placed in a reaction vessel, and oxygen is replaced by, for example, nitrogen, thereby heating and keeping the vessel in a deoxygenated atmosphere with stirring have. The polymerization initiator, solvent and the like to be used herein are not particularly limited, and any of those conventionally used in the field can be used. Examples of the polymerization initiator include azo compounds (such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (such as benzoyl peroxide) . Any solvent may be used as long as it dissolves the respective monomers. As the solvent (E) of the colored photosensitive resin composition of the present invention, a solvent described later or the like may be used.

The resulting copolymer may be a solution after the reaction as it is, or a concentrated or diluted solution may be used, or it may be drawn out as a solid (powder) by re-precipitation or the like. Particularly, since the solution after the reaction can be used as it is for the preparation of the colored photosensitive resin composition of the present invention by using a solvent contained in the colored photosensitive resin composition of the present invention as a solvent in the polymerization, the production of the colored photosensitive resin composition of the present invention The process can be simplified.

The ratio of the respective structural units derived from the resin [K2] is preferably within the following range among the total structural units constituting the resin [K2].

a structural unit derived from (a); 4 to 45 mol% (more preferably 10 to 30 mol%)

(b); 2 to 95 mol% (more preferably 5 to 80 mol%)

a structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%),

When the ratio of the structural unit of the resin [K2] is within the above range, there is a tendency that storage stability, developability, solvent resistance, heat resistance and mechanical strength of the colored photosensitive resin composition are excellent.

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

Specifically, a predetermined amount of the components (a), (b) and (c), a polymerization initiator and a solvent are placed in a reaction vessel and the mixture is heated and maintained in a deoxidized atmosphere by stirring, for example, by substituting oxygen with nitrogen . The obtained copolymer may be used as a solution for the preparation of the colored photosensitive resin composition of the present invention as the solution after the reaction, or a concentrated or diluted solution may be used, or a solution drawn out as a solid (powder) good.

The ratio of the respective structural units derived from the resin [K3] is preferably within the following range among the total structural units constituting the resin [K3].

(a) 2 to 50 mol%, more preferably 5 to 40 mol%

(c) 50 to 98 mol%, more preferably 60 to 95 mol%

The resin [K3] can be produced, for example, by a method described as a method of producing the resin [K1].

Resin [K4] can be prepared by obtaining a copolymer of (a) and (c) and adding (b).

First, the copolymer of (a) and (c) is prepared in the same manner as the method described as the production method of [K1]. In this case, the ratio of the respective derived structural units is preferably in the following range among the total structural units constituting the copolymer of (a) and (c).

(a) 5 to 50 mol%, more preferably 10 to 45 mol%

(c) 50 to 95 mol%, more preferably 55 to 90 mol%

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

Subsequent to the preparation of the copolymers of (a) and (c), the atmosphere in the flask is replaced by air from nitrogen and a reaction catalyst of carboxylic acid or carboxylic acid anhydride and cyclic ether (for example tris (dimethylaminomethyl) Phenol, etc.) in an amount of 0.001 to 5 mass% with respect to the total amount of (a), (b) and (c) and a polymerization inhibitor (such as hydroquinone) ) Is added to the flask in the range of 0.001 to 5 mass%, for example, at 60 to 130 캜 for 1 to 10 hours to obtain the resin (K4). Reaction conditions such as injection method, reaction temperature and time can be appropriately adjusted in consideration of the amount of heat generated by the production equipment or polymerization. In addition, as in the case of 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 equipment or polymerization.

In this case, the amount of (b) to be used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of the amount of (a). This range tends to improve the balance between storage stability, developability and solvent resistance of color filters, heat resistance, mechanical strength and sensitivity of the colored photosensitive resin composition.

(B1) is preferable and (b1-1) is more preferable as (b) used in the production of the resin [K4] since the reactivity of the cyclic ether is high and unreacted (b)

Resin [K5] is a first step, and the copolymer of (b) and (c) is obtained in the same manner as the above-mentioned method for producing resin [K1]. The solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or the solution may be withdrawn as a solid (powder) by re-precipitation or the like.

the proportion of the structural units derived from (b) and (c) is preferably within the following range with respect to the total number of moles of the total structural units constituting the copolymer.

(b); 5 to 95 mol% (more preferably 10 to 90 mol%)

a structural unit derived from (c); 5 to 95 mol% (more preferably 10 to 90 mol%)

The carboxylic acid or carboxylic acid anhydride of (a) in the cyclic ether derived from (b) of the copolymer (b) and (c) under the same conditions as in the production of the resin [K4] To obtain a resin [K5]. The carboxylic acid anhydride may be further reacted with the hydroxyl group generated by the reaction of the cyclic ether and the carboxylic acid or the carboxylic acid anhydride.

The amount of the component (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of the component (b). (B1) is more preferable and (b1-1) is more preferable as the component (b) used in the resin [K5] because the reactivity of the cyclic ether is high and the unreacted component (b) is difficult to remain.

Resin [K6] is a resin obtained by further reacting a resin [K5] with a carboxylic acid anhydride. A carboxylic acid anhydride is reacted with a hydroxyl group generated by the reaction of a cyclic ether and a carboxylic acid or carboxylic acid anhydride.

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

Specific examples of the binder resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) Resin [K1] such as a copolymer; (Meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 (meth) acrylate / glycidyl .1.0 ^2.6] decyl acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, the resin composition comprising 3,4-tricyclo [5.2.1.0 ^2.6] decyl acrylate / methacrylic acid / vinyl toluene copolymer, 3 Resins [K2] such as methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; Resins [K3] such as benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer and vinyl toluene / methacrylic acid copolymer; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (K4) such as a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate and glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting dicyclopentanyl (meth) acrylate / styrene / glycidyl A resin [K5] such as a resin obtained by reacting (meth) acrylic acid with a copolymer; (K6) such as a resin obtained by further reacting a resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and tetrahydrophthalic anhydride .

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

(B1) is a copolymer comprising a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a structure derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond Is preferably at least one member selected from the group consisting of a resin [K1] and a resin [K2], and the resin [K1] and (b1) containing a structural unit derived from (b1) More preferably at least one member selected from the group consisting of a resin [K2] containing a derived structural unit, and more preferably at least one member selected from the group consisting of resins [K1] and (b1-2) containing a structural unit derived from (b1-2) And a resin [K2] containing a structural unit which is a structural unit to be polymerized. Specific examples thereof include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / methacrylic acid / vinyltoluene copolymer and At least one member selected from the group consisting of 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer is preferable.

(B2) is preferably at least one member selected from the group consisting of resin [K1], resin [K2] and resin [K3], more preferably resin [K3]. Specifically, at least one member selected from the group consisting of benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer and vinyl toluene / methacrylic acid copolymer is preferable, Acrylate / (meth) acrylic acid copolymer is more preferable.

The content of the binder resin (B1) is preferably 5 to 95% by mass, more preferably 15 to 80% by mass, further preferably 20 to 70% by mass with respect to the content of the binder resin (B) Is 25 to 55 mass%.

(B2) is preferably 5 to 95% by mass, more preferably 20 to 85% by mass, still more preferably 30 to 80% by mass with respect to the content of the binder resin (B) Is 45 to 75 mass%.

(B1) and (B2) described above can be used to form a coloring pattern with less occurrence of peeling fragments derived from the colored photosensitive resin composition and excellent in shape in the developer after development.

The content of the binder resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 55% by mass, and still more preferably from 17 to 50% by mass, based on the solid content of the colored photosensitive resin composition. When the content of the binder resin (B) is within the above range, the solubility in the developing solution of the unexposed portion is high, and the occurrence of peeling fragments derived from the colored photosensitive resin composition in the developer after development tends to be small.

The colored photosensitive resin composition of the present invention comprises a polymerizable compound (C). The polymerizable compound (C) is a compound which can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenic unsaturated bond, (Meth) acrylic acid ester compounds.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, tripentaerythritol (Meth) acrylate, tris (2- (meth) acryloyloxyethyl) tetrapentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (Meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, ethylene glycol modified pentaerythritol tetra Methacrylate, caprolactone-modified pentaerythritol La (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable. These polymerizable compounds may be used singly or in combination of two or more.

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the solid content of the colored photosensitive resin composition. When the content of the polymerizable compound (C) is within the above range, the curing is sufficiently carried out, the residual film ratio in the development is improved, and the undercutting tends to be hardly caused in the coloring pattern, so that the adhesion tends to be good.

The colored photosensitive resin composition of the present invention comprises a polymerization initiator (D). As the polymerization initiator (D), any known polymerization initiator can be used without particular limitation, as long as it is a compound capable of initiating polymerization by generating an active radical or an acid by the action of light or heat.

The polymerization initiator (D) is preferably a compound which generates an active radical by the action of light, and is preferably at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds and non- Is more preferable, and a polymerization initiator containing an oxime compound is more preferable.

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

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-morpholinyl) phenyl] butane-1-one, 2- (dimethylamino) -1-one. And commercially available products such as Irgacure (registered trademark) 369, 907 and 379 (above, manufactured by BASF) may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy- -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan- ?,? - diethoxyacetophenone, and benzyl dimethyl ketal.

In view of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2), and 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- And 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one are more preferable.

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

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

The oxime compound is a compound having a partial structure represented by the formula (d1). Herein, * represents the number of bonds.

Examples of the oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 1- (4-phenylsulfanylphenyl) 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- -9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2-methyl-benzothiazol- (4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan- 1-imine, N-benzoyloxy- -Cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2- Imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine are preferable. When these oxime compounds are used, especially when the colored photosensitive resin composition of the present invention is prepared as a blue colored photosensitive resin composition, a color filter having high brightness tends to be obtained.

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

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

Examples of the acid generator which generates an acid by light include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfate P-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyl iodonium hexafluoroantimonate; nitrobenzyl tosylates, benzoin tosylates, and the like.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the binder resin (B) and the polymerizable compound (C). When the content of the photopolymerization initiator is within the above range, the coloring pattern can be formed with high sensitivity, so that the exposure time is shortened and the productivity is improved.

The colored photosensitive resin composition of the present invention may further comprise a polymerization initiator (D1). When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D). The polymerization initiator (D1) is a compound or a sensitizer used for promoting the polymerization of the polymerizable compound initiated by the polymerization initiator.

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

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

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

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

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

When the polymerization initiator (D1) is used, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the binder resin (B) and the polymerizable compound (C) Wealth. When the amount of the polymerization initiator (D1) is within this range, a colored pattern can be formed with high sensitivity, and the productivity of the colored pattern tends to be improved.

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

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

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

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

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Methoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, propyleneglycol monomethyl ether acetate, Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether And the like Le acetate, diethylene glycol monobutyl ether acetate.

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

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

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

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

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

Organic solvents having a boiling point of 120 캜 or more and 180 캜 or less at 1 atm are preferred from the standpoint of coatability and drying property among the above-mentioned solvents. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl Acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, Dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate.

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

The colored photosensitive resin composition of the present invention may further contain a surfactant (F). Examples of the surfactant (F) include a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond. Specific examples thereof include DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30Pa and Copper 8400 (manufactured by Toray Dow Corning), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan Co., Ltd.) .

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Concretely, there are fluororads (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554, R30, RS-718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, EF303, EF351 and EF352 (manufactured by Mitsubishi Materials Corporation), Surflon ) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Co., Ltd.).

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

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

The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or less based on the total amount of the colored photosensitive resin composition of the present invention % To 0.05% by mass or less. The content of the pigment dispersant is not included in the content. When the content of the surfactant (F) is within the above range, the flatness of the color filter can be improved.

The colored photosensitive resin composition of the present invention may contain various additives known in the art such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents (hereinafter referred to as " May be included.

The colored photosensitive resin composition of the present invention can be obtained, for example, by mixing a colorant (A), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D) ), A surfactant (F), and other components.

When the pigment (A2) is contained, it is preferable to mix the pigment (A2) with a part or the whole of the solvent (E) in advance and disperse with a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less Do. At this time, if necessary, a part or all of the pigment dispersant and the binder resin (B) may be blended. The desired colored photosensitive resin composition can be prepared by mixing the remaining components or the like to the obtained pigment dispersion to a predetermined concentration.

It is preferable that the dye (A1) is previously dissolved in a part or all of the solvent (E) to prepare a solution. It is preferable to filter the solution with a filter having a pore diameter of about 0.01 to 1 mu m.

It is preferable to filter the colored photosensitive resin composition prepared by mixing as described above with a filter having a pore diameter of about 0.01 to 10 mu m.

Examples of the method of forming a coloring pattern of a color filter using the colored photosensitive resin composition of the present invention include a photolithography method and an inkjet method. In order to form a colored pattern by a photolithography method, the colored photosensitive resin composition of the present invention is applied on a substrate or another resin layer (for example, another colored photosensitive resin composition layer previously formed on a substrate) The component is removed (dried) to form a coating film after drying, and the colored layer is exposed and developed through a photomask. In the photolithography method, the photomask is not used at the time of exposure and / or the development is not performed, whereby a colored coating film which is a cured product of the dried film can be formed. These coloring patterns and colored coating films can be used as color filters.

The film thickness of the color filter to be manufactured is not particularly limited and can be appropriately adjusted according to the material to be used and the intended use. For example, it is 0.1 to 30 탆, preferably 0.5 to 20 탆, more preferably 0.5 to 6 탆 .

The colored photosensitive resin composition is coated on a substrate and heated and dried (prebaking) and / or reduced-pressure drying to remove volatile components such as solvents to obtain a smooth and dried coating film.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass and soda lime glass whose surface is coated with a silica, resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate, silicon, , Silver / copper / palladium alloy thin film, or the like can be used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

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

The temperature for heating and drying is preferably 30 to 120 占 폚, more preferably 50 to 110 占 폚. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

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

The film thickness of the coated film after drying is not particularly limited and can be appropriately adjusted according to the materials to be used, applications, and the like.

After drying, the coating film is exposed through a photomask for forming a desired pattern. The pattern on the photomask at this time is not particularly limited, and the pattern according to the intended use is used.

As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light having a wavelength of less than 350 nm is cut using a filter that cuts the wavelength region, or a band-pass filter for extracting light in the vicinity of 436 nm, around 408 nm, and around 365 nm, . Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps.

It is preferable to use a mask aligner, a stepper, or the like in order to uniformly irradiate the entire exposure surface with a parallel light beam or to accurately align the mask and the substrate on which the coated film has been formed.

A coloring pattern can be obtained by contacting the developing solution after exposure and dissolving and removing (that is, developing) the unexposed portion. Examples of the developer include aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogencarbonate, tetramethylammonium hydroxide and the like. The concentration of the alkaline compound in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant.

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

It is preferable to rinse after development.

Post baking may be further performed if necessary. The post-baking temperature is preferably 150 to 250 占 폚, more preferably 160 to 235 占 폚. The post baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

According to the colored photosensitive resin composition of the present invention, a color filter can be produced with particularly high productivity. The color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper or the like) or a solid-state image pickup device.

Example

Hereinafter, the present invention will be described in more detail by way of examples. In the examples, "% " and " part " are parts by mass and parts by mass unless otherwise specified.

[Synthesis Example 1]

15 parts of a mixture of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (Chugai Chemical), 150 parts of chloroform and 50 parts of N, N- 8.9 parts of dimethylformamide was added, and 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature below 20 ° C with stirring. After completion of the dropwise addition, the temperature was raised to 50 占 폚, maintained at the same temperature for 5 hours and reacted, and then cooled to 20 占 폚. After cooling, the reaction solution was added dropwise with stirring to a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine while keeping the temperature at 20 ° C or lower. Then, the mixture was stirred at the same temperature for 5 hours for reaction. Then, the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and vigorously stirred. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water and dried under reduced pressure at 60 ° C to obtain 11.3 parts of a dye A1 (dye A1) (a mixture of compounds represented by formulas (A1-1) to (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. The obtained reaction solution was cooled to room temperature and then added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid. The mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were collected as a residue of suction filtration and dried to obtain 24 parts of a compound represented by the formula (1-31). The yield was 80%.

The structure of the compound represented by formula (1-31) was confirmed by mass analysis (LC: Agilent 1200 type, MASS: Agilent LC / MSD type).

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

                       Exact Mass: 602.2

[Synthesis Example 3]

Compound (1-39) was obtained in the same manner as in Synthesis Example 1 except that N-propyl-2,6-dimethyl aniline was used instead of N-ethyl-o-toluidine.

Identification of the compound represented by the formula (1-39)

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

                       Exact Mass: 658.9

[Synthesis Example 4]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 220 parts of ethyl lactate was added and heated to 70 캜 with stirring. Then, 84 parts of methacrylic acid, 3 parts of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by formula (I-1) and the compound represented by formula (II-1) : 50) was dissolved in 140 parts of ethyl lactate to prepare a solution. This solution was added dropwise to a flask maintained at 70 캜 for 4 hours using a dropping funnel.

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate was added dropwise to the flask over 4 hours using another dropping funnel. After the dropping of the polymerization initiator solution is completed for 4 hours, kept at 70 ℃, and thereafter by cooling to room temperature, a weight average molecular weight Mw of 8.0 × 10 ^3, the molecular weight distribution of 2.5, a solid content of 48%, a solution acid value of 50㎎ -KOH / g was obtained. The solid acid value calculated from the solid content and the solution acid value is 104 mg-KOH / g. Resin B1 has the following structural unit.

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

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 mL / min

Detector; RI

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

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

Examples 1 to 6 and Comparative Example 1

Each component was mixed so as to have the composition shown in Table 1 to obtain a colored photosensitive resin composition.

Each component in Table 1 indicates the following. The binder resin (B) represents a part by mass in terms of solid content.

Colorant (A); (A-1); C.I. Pigment Blue 15: 6

Colorant (A); (A-2); Dye A1

Colorant (A); (A-3); The compound represented by the formula (1-39)

A binder resin (B); (B1-1); Resin B1

A binder resin (B); (B2-1); The copolymer solution of methacrylic acid and benzyl methacrylate [the ratio of methacrylic acid unit to benzyl methacrylate unit (molar ratio) was 35:65, the acid value was 135 mg-KOH / g, the weight average molecular weight in terms of polystyrene was 25,000, The distribution is 2.2, the solid content is 34%, the solvent is propylene glycol monomethyl ether acetate]

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

Polymerization initiator (D); (D-1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01,

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

Solvent (E); (E-2); Propylene glycol monomethyl ether

Solvent (E); (E-3); Ethyl lactate

Surfactant (F); (F-1); Polyether-modified silicone oil (TORAYI Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.)

≪ Fabrication of coloring pattern &

The colored photosensitive resin composition was coated on a 5 cm x 5 cm glass substrate (Eagle 2000; made by Corning) by spin coating, pre-baked at 100 ° C for 3 minutes, and dried to form a coating film. After cooling, the substrate was dried and exposed to light at an exposure dose of 60 mJ / cm 2 (based on 365 nm) in an atmospheric environment using an exposure apparatus (TME-150RSK; Topcon Co., Ltd.) I investigated. As the photomask, a 100 μm line and space pattern was formed. After the light irradiation, the coated film was immersed in a developing solution (aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate in a mass fraction) at 25 캜 for 60 seconds, and after washing with water, Baking was carried out to obtain a colored pattern.

<Observation of separation>

In the production of the coloring pattern, the developing solution after development was visually observed. When the peeled piece derived from the colored photosensitive resin composition was not confirmed in the developer, the result was rated &quot; Good &quot;, and when the peeled piece was confirmed, it was rated &quot; If a peeled piece derived from the colored photosensitive resin composition is identified in a developing solution, it may adhere to the pattern as foreign matter and cause a defect, which is not preferable. The results are shown in Table 2.

&Lt; Measurement of film thickness &

The obtained coloring pattern was measured for film thickness using a film thickness measuring device (DEKTAK3, manufactured by Nippon Shokubi Jutsu Co., Ltd.)). The results are shown in Table 2.

&Lt; Evaluation of color &

(X, y) in the XYZ colorimetric system of CIE was measured using a characteristic function of the C light source, and the obtained coloring pattern was measured by using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation) And the three stimulus values Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 2.

<Evaluation of Shape of Coloring Pattern>

The shape of the obtained coloring pattern was observed using a scanning electron microscope (S-4000; Hitachi High Technologies Co., Ltd.). (P1) (so-called pure taper shape), the case was shown as (p2), the case was indicated as (p2), and the case shown by (p3) (p1), the inorganic film tends to be less likely to crack or peel off when the inorganic film is laminated on the colored pattern. The results are shown in Table 2.

Examples 7 to 9

A colored photosensitive resin composition was obtained in the same manner as in Examples 1 to 3 except that the compound represented by the formula (1-31) was used in place of the dye A1. It is confirmed that the release piece is not generated by performing the same operation as described above. Further, a coloring pattern excellent in brightness and shape is obtained.

From the above results, the colored photosensitive resin composition of the present invention was not found to have a peeled piece in the developer after development. In this respect, it can be seen that the color photosensitive resin composition of the present invention makes it possible to produce a color filter with a high product ratio.

According to the colored photosensitive resin composition of the present invention, the occurrence of peeling fragments derived from the colored photosensitive resin composition in the developing solution after development is small.

Claims (6)

A colorant, a binder resin, a polymerizable compound, a polymerization initiator and a solvent,
Wherein the colorant is a colorant comprising a dye,
The dye includes a compound represented by the following formula (3)

[In the formula (3), R ³¹ and R ³² independently represent an alkyl group having 1 to 10 carbon atoms. R ³³ and R ³⁴ independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms. R ³¹ and R ³³ may be united to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be united to form a ring containing a nitrogen atom.
p and q independently represent an integer of 0 to 5; When p is 2 or more, plural R ^{33 s} may be the same or different, and when q is 2 or more, plural R ^{34 s} may be the same or different)
The content of the coloring agent is 5 to 60 mass% with respect to the solid content in the colored photosensitive resin composition,
Wherein the binder resin includes the following (B1) and (B2), and the content of (B2) is from 20 to 85% by mass with respect to the content of the binder resin.
(B1) a resin having a weight average molecular weight of 3,000 or more and less than 15,000, and having an acid value of 20 mgKOH / g or more and 200 mgKOH / g or less
(B2) a resin having a weight average molecular weight of 15,000 or more and 100,000 or less and an acid value of 20 mg-KOH / g or more and 200 mg-KOH / g or less The method according to claim 1,
(B1) is a copolymer comprising a structural unit derived from at least one member selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond Wherein the photosensitive resin composition is a copolymer containing a structural unit. The method according to claim 1,
Wherein the polymerization initiator is a polymerization initiator comprising an oxime compound. The method according to claim 1,
Wherein the coloring agent is a coloring agent comprising a dye and a pigment. A color filter formed by the colored photosensitive resin composition according to any one of claims 1 to 4. A display device comprising the color filter according to claim 5.