KR20130038172A - Colored photosensitive resin composition - Google Patents

Abstract

PURPOSE: A colored photosensitive composition is provided to suppress the generation of dissected piece derived from the color photosensitive resin composition in the development liquid after development by including resin containing a structure unit derived from a specific monomer. CONSTITUTION: A colored photosensitive composition comprises a coloring agent, a B1-resin, a B2-resin, a polymerizable compound, and a polymerization initiator. The B1-resin comprises a structure unit-a and a structure unit-b. The B1-resin also comprises the structure unit-a and a structure unit-x, and in this case the B2 resin does not include the structure unit-b. The structure unit-a is derived from at least one kind selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride. The structure unit-b is derived from cyclic ether structure with 2-4 carbons and the monomer having ethyIene unsaturated bonding. The structure unit-x is derived from the monomer having alicyclic hydrocarbon structure. The colored photosensitive composition forms a layer(23A). [Reference numerals] (201) Connection hole; (22a) Gate electrode; (22b) Gate insulating film; (22c) Polycrystalline silicon film; (22d) Protective film; (27) Signal line;

Description

Colored photosensitive resin composition {COLORED PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a colored photosensitive resin composition.

The colored photosensitive resin composition is used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display panel, an electroluminescence panel, and a plasma display panel. As such a coloring photosensitive resin composition, the coloring photosensitive resin composition containing only the copolymer of methacrylic acid and 3, 4- epoxy cyclo [5.2.1.0 ^2.6 ] decyl acrylate as a resin is known (JP2010-211198-A). .

When forming a pattern by the photolithographic method, when the composition layer formed by apply | coating a coloring photosensitive resin composition to a board | substrate and drying is peeled at the time of image development, and it flows out into a developing solution, the peeling piece of this as a foreign material on a pattern There is a risk of sticking or clogging the piping of the developer waste liquid in the developer. The said colored photosensitive resin composition conventionally known may not fully be satisfied with respect to the above developability in some cases.

The present invention includes the following inventions.

[1] A colored photosensitive resin composition comprising (A), (X1), (B2), (C) and (D).

(A) Colorant

(Iii) a structural unit derived from one or more structural units selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and monomers having a C 2 to C 4 cyclic ether structure and an ethylenically unsaturated bond; Containing resin

(X2) Resin containing structural units derived from at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and structural units derived from monomers having alicyclic hydrocarbon structures (however, C2-4) Does not include structural units derived from monomers having two cyclic ether structures and ethylenically unsaturated bonds)

(C) polymerizable compound

(D) polymerization initiator

[2] The colored photosensitive resin composition as described in [1], wherein (b2) further includes a structural unit derived from a monomer having an aromatic hydrocarbon group.

[3] The colored photosensitive resin composition according to [1] or [2], wherein the content of (B2) is 10 to 90 mass% with respect to the total amount of (B1) and (B2).

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

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

According to the coloring photosensitive resin composition of this invention, generation | occurrence | production of the peeling piece derived from the coloring photosensitive resin composition in the developing solution after image development is few.

The coloring photosensitive resin composition of this invention contains the following (A), (X1), (X2), (C), and (D).

(A) a coloring agent;

(Iii) a structural unit derived from one or more structural units selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and monomers having a C 2 to C 4 cyclic ether structure and an ethylenically unsaturated bond; Resin (hereinafter, referred to as "resin (K1)");

(X2) Resin containing structural units derived from at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and structural units derived from monomers having alicyclic hydrocarbon structures (however, C2-4) Structural units derived from a monomer having two cyclic ether structures and an ethylenically unsaturated bond) (hereinafter referred to as "resin (X2)");

(C) polymeric compound;

(D) polymerization initiator.

It is preferable that the coloring photosensitive resin composition of this invention contains a solvent (E) further.

In addition, the coloring photosensitive resin composition of this invention may contain 1 or more types chosen from the group which consists of a polymerization initiator (D1) and surfactant (F) as needed.

Moreover, unless otherwise indicated, each component may be used individually by 1 type, and may use 2 or more types together.

<Coloring agent (A)>

Dye (A1) and a pigment (A2) are mentioned as a coloring agent (A).

Dye (A1) is not specifically limited, A well-known dye can be used, For example, a solvent dye, an acid dye, direct dye, a mordant dye, etc. are mentioned, The dye which is soluble in an organic solvent is preferable.

As dye (A1), the compound classified as dye in the color index (The Society of Dyers and Colourists), for example, and the well-known dye described in the dyeing note (Shishensha) are mentioned. In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes And styryl dyes, coumarin dyes, quinoline dyes, nitro dyes and the like. Among these, organic solvent soluble dye is preferable.

Specifically, C.I. Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted and only numbers are listed), 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, 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, Solvent dyes,

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

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 266, 268, 270, 274, 277, 280, 281, 272, 277, 278, 279, 252, 257, 258, 260, 261, 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, 136, 138, 141;

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

C.I. Direct Orange 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, Direct dyes,

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

C.I. Disperse violet 26, 27;

C.I. Disperse dyes such as 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. 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. 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 dyes,

C.I. C.I. Bat dye

And the like.

Such dye may be appropriately selected in accordance with the spectral spectrum of the desired color filter.

As dye (A1), xanthene dye (AA) is preferable.

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

Among these, as xanthene dye (Aa), the dye containing the compound represented by Formula (1a) (henceforth "compound (1a)") is preferable. When using compound (1a), content of the compound (1a) in xanthene dye (Aa) 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 the formula (1a), R ¹ to R ⁴ represents a group each independently represent a hydrogen atom, -R ^8, or C 6 -C 10 monovalent aromatic hydrocarbon group which may have a substituent. R ¹ and R ² may form a ring containing a nitrogen atom together with a nitrogen atom, and R ³ and R ⁴ may form a ring containing a nitrogen atom together with a nitrogen atom.

R ⁵ is _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ is 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> is the same or different. However, the R ⁵ -SO ₃ ^- If, m is 1.

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 the said 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, and R ⁹ and R ¹⁰ are bonded to each other to form a nitrogen containing compound of 3 to 10 membered rings together with a nitrogen atom. A summon may be formed.

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]

As a C6-C10 monovalent aromatic hydrocarbon group which shows R <^1> -R <^4> , a phenyl group, tolyl group, xylyl group, mesityl group, propylphenyl group, and butylphenyl group are mentioned, for example.

R ¹ to R ⁴ C 6 -C 10 monovalent aromatic hydrocarbon in the groups hydrogen atoms are halogen atoms contained to said aromatic ^{hydrocarbon, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, It may be substituted by -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₃ R ⁸ , -SO ₂ NR ⁹ R ¹⁰ . Among these substituent _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z + and -SO ₂ NR ⁹ R at least one member selected from the group consisting of ¹⁰ is preferred, and -SO ₃ ^- Z ⁺ and -SO More preferred is one or more selected from the group consisting of ₂ NR ⁹ R ¹⁰ . Examples of Z ⁺ -SO ₃ ^{- -} -SO ₃ in this case is N ⁺ (R ¹¹⁾ ₄ are preferred. When R <^1> -R <^4> is such a group, the coloring photosensitive resin composition containing a compound (1a) can form a color filter excellent in heat resistance and less in foreign material.

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

As a C1-C20 monovalent saturated hydrocarbon group which shows R <^8> -R <^11> , a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, hexa C1-C20 linear alkyl groups, such as a decyl group and an icosyl group; Branched alkyl groups having 3 to 20 carbon atoms such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group, are mentioned.

As -OR <^8> , a methoxy group, an ethoxy group, a propoxy group, butoxy group, a pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, and an icosyloxy group are mentioned, for example. have.

Examples of -CO ₂ R ^8, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a tert- butoxy group, a hexyloxy group and an oxycarbonyl group Aiko chamber.

Examples of -SR ⁸ include methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group, icosylsulfanyl group and the like.

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

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

As —SO ₂ NR ⁹ R ¹⁰ , 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.

In addition, R ^9, and C 1 -C 20 monovalent saturated hydrocarbon group representing R ¹⁰ is optionally substituted hydrogen atoms are -OH, or a halogen atom contained to said saturated hydrocarbon, -CH ₂ contained to said saturated hydrocarbon - is -O It may be substituted with-, -CO-, -NH- or -NR ^8- .

R ⁹ and R ¹⁰ may be bonded to each other to form a nitrogen-containing heterocycle of a 3 to 10 membered ring together with a nitrogen atom. As said heterocycle, the following are mentioned, for example.

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

As a C7-10 aralkyl group which shows R <^11> , a benzyl group, a phenylethyl group, a phenylbutyl group, etc. are mentioned.

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 pieces are preferable and, as for the sum total carbon number of four R <^11> , 20-60 pieces are more preferable. If R <^11> is such a group, the coloring photosensitive resin composition containing a compound (1a) can form a color filter with few foreign substances.

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

As xanthene dye (Aa), the dye containing the compound represented by Formula (2a) (henceforth "compound (2a)") is more preferable. When using compound (2a), content of the compound (2a) in xanthene dye (Aa) is 50 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.

In the formula (2a), R ²¹ to R ²⁴ represents an aromatic hydrocarbon group which may have a substituent each independently selected from hydrogen, -R ²⁶ or C 6 -C 10 monovalent. R ²¹ and R ²² may form a ring containing a nitrogen atom together with the nitrogen atom, and R ²³ and R ²⁴ may form a ring containing a nitrogen atom together with the 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> is the same or different. However, the R ²⁵ -SO ₃ ^- if, m1 is 1.

a1 represents the integer of 0 or 1.

X1 represents a halogen atom.

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

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

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 said aromatic hydrocarbon group in said R <^1> -R <^4> is mentioned. Hydrogen atoms contained to said aromatic hydrocarbon is -SO ₃ ^- or may be substituted with Z1 ^+, -SO ₃ R ²⁶ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.

And R ²¹ to R ²⁴ as a combination of R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ is a group having 6 to 10 carbon atoms of the monovalent aromatic hydrocarbon group, hydrogen atom is contained the aromatic hydrocarbon groups -SO ₃ ^{-, -} SO ₃ H, -SO ₃ ^- as Z1 ^+, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ is preferably substituted. Even more preferred combinations are those in which R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group are -SO ₃ ^- Z 1 ⁺ or -SO _2. NHR ²⁶ is substituted.

In addition, R ²¹ and R ²² that forms the summons aliphatic clothing having a nitrogen atom together with the nitrogen atom, it is also preferred that R ²³ and R ²⁴ to form a summons aliphatic clothing having a nitrogen atom together with the nitrogen atom.

When R <^21> -R <^24> is such group, the coloring photosensitive resin composition containing a compound (2a) can form the color filter excellent in heat resistance.

As said aliphatic heterocycle, the following are mentioned, for example.

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

R ²¹ to R ²⁴ -R ²⁶ in the are preferably each independently a hydrogen atom, methyl or ethyl. Also, -SO ₃ R ^26, and -SO ₂ NHR ²⁶ R ²⁶ as the carbon number of 3 to 20 branched alkyl group is preferable, and even more preferably having 6 to 12 branched chain alkyl group in, and is a 2-ethylhexyl group Even more preferred. When R <^26> is such a group, the coloring photosensitive resin composition containing a compound (2a) can form the color filter with little generation | occurrence | production of a foreign material.

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

The N ⁺ (R ²⁷⁾ R _4, as the four ²⁷ from two or more is 5 to 20 carbon atoms of the monovalent saturated hydrocarbon group is preferred. Moreover, 20-80 pieces are preferable and, as for the sum total carbon number of four R <^27> , 20-60 pieces are more preferable. The coloring photosensitive resin composition in which R <^27> contains the compound (2a) which is such a group can form the color filter with little generation | occurrence | production of a foreign material.

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

As compound (2a), the compound represented, for example by Formula (1-1)-Formula (1-25) is mentioned. Furthermore, in 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, even more preferably a 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. As such a compound, the compound etc. which are represented by Formula (1-1)-Formula (1-1), Formula (1-1), and Formula (1-12) are mentioned, for example.

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

[In formula (3a), R <^31> and R <^32> represents a C1-C4 alkyl group mutually independently.

R ³³ and R ³⁴ independently of each other represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.

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

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

Examples of the alkyl group having 1 to 4 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 the like. Can be.

As a C1-C4 alkylsulfanyl group which shows R <^33> and R <^34> , a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, an isopropylsulfanyl group, etc. are mentioned.

As a C1-C4 alkylsulfonyl group which shows R <^33> and R <^34> , a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, etc. are mentioned.

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

The integer of 0-2 is preferable, and, as for m and n, it is more preferable that it is 0 or 1.

As compound (3a), the compound shown, for example by Formula (1-2-6)-Formula (1-32) is mentioned, respectively. Among these, the compound represented by Formula (12-2) is preferable at the point which is excellent in solubility with respect to an organic solvent.

Xanthene dyes (Aa) are commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugaikasei Co., Ltd., "Rhodamin 6G" manufactured by Taoka Chemical Co., Ltd.) Can be used. Moreover, you may synthesize | combine with reference to JP2010-32999-A, using commercially available xanthene dye as a starting material.

As dye (A1), phthalocyanine dye (A ') is also preferable. The phthalocyanine dye (AZ) is preferably a compound represented by formula (4).

In the formula (4), G ¹ represents an alkanediyl group having 2 to 16 eggs, -CH ₂ contained in the alkanediyl group - may be substituted with -O-.

J ¹ is hydrogen, -NR ^a R ^b or -NR ^a R ^b H ⁺ Q ^- represents a.

R ^a and R ^b independently of one another represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Q ^- is a halide ion, BF ₄ ^- represents a _{^{-, PF 6 -, ClO 4}} -, X-CO 2 - , or Y-SO _3.

X and Y each independently represent a monovalent organic group.

p represents an integer of 1 to 4]

Equation (4) shows that it is replaced by a p-hydrogen atoms -SO ₂ -NH-G ¹ -J ¹ included in the compound represented by the formula (4-0). When p is 2 or more, a plurality of -SO ₂ -NH-G ¹ -J ¹ may be the same as or different from each other.

Examples of the alkanediyl group having 2 to 12 carbon atoms include methylene group, ethylene group, propanediyl group, butanediyl group and the like.

-CH ₂ - that it may be mentioned groups represented by the group, and formula (G-2) represented by a carbon number of 2 to 12 known at alkanediyl group formula (G-1) which is substituted with -O-.

[In Formula (XI-1) and Formula (XI-2), G <^2> -G <^5> represents a C1-C8 alkanediyl group each independently.

n1 represents the integer of 1-3.

n2 represents the integer of 0-3.

However, the total number of carbon atoms and oxygen atoms contained in the group represented by formula (VII-1) is 3-12, and the total number of carbon atoms and oxygen atoms contained in the group represented by formula (VII-2) is 2-12. to be.

* Represents a coupling arm with -NH-]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group and butyl group.

Examples of _{^{-SO 2 -NH-G 1 -J 1}} , there may be mentioned, for example to a group represented by the following formula.

In the case where G ¹ is a group represented by formula (VII-1), examples of -SO ₂ -NH-G ¹ -J ¹ include a group represented by the following formula.

In the case where G ¹ is a group represented by formula (VIII), examples of -SO ₂ -NH-G ¹ -J ¹ include a group represented by the following formula.

If the J ¹ is -NR ^a R ^b, as _{^{-SO 2 -NH-G 1 -J 1}} , there may be mentioned groups represented by the following formula for example.

The ^{J 1 -NR a R b H +} Q - if, as _{^{-SO 2 -NH-G 1 -NR a}} R b H +, there may be mentioned a group represented by formula e. G. To.

Q ^- is a halide ion, BF ₄ ^- represents a _{^{-, PF 6 -, ClO 4}} -, X-CO 2 - , or Y-SO _3.

X and Y represent monovalent organic group. As a monovalent organic group, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, the group which combined these, etc. are mentioned.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, hexyl group and decyl group.

Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and cyclodecyl group.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, naphthyl group and anthryl group.

X-CO ₂ ^- is an organic anion containing a CO ₂ ^- group, Y-SO ₃ ^- is an anion containing a SO ₃ ^- group, for example, an anion represented by formulas (VII-1) to (IV-4) Can be mentioned.

[R ^y represents an alkyl group having 1 to 20 carbon atoms.

n3 represents an integer of 0 to 5;

Q ^- as X-CO ₂ ^- and Y-SO ₃ ^- is preferable, and more preferable anions represented by the formula (Q-4). If it is such an anion, there exists a tendency for the solubility to the solvent of the compound represented by Formula (2) to become high.

As a compound represented by Formula (4), the compound of JP2011-28236-A is mentioned, for example. Among these, the compound represented by Formula (4-1)-Formula (4-5) is preferable, and the compound represented by Formula (4-2) and the compound represented by Formula (4-5) are more preferable.

Examples of the pigment (A2) include compounds classified as pigments in the color index (Published by The Society of Dyers and Colorists).

As the pigment, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 Yellow pigments such as, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194, 214, 219;

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

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, and 80;

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

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

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

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

When preparing the colored photosensitive resin composition of this invention as a blue coloring photosensitive resin composition, it is C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, etc. Blue pigment and C.I. Pigment violet 1, 19, 23, 29, 32, 36, 38, etc. Violet pigments are preferable, C.I. Pigment Blue 15: 3, 15: 6 and C.I. Pigment Violet 23 is more preferred, and C.I. Pigment Blue 15: 6 is even more preferred.

When preparing the colored photosensitive resin composition of this invention as a green coloring photosensitive resin composition, a pigment is C.I. Pigment green 7, 36, 58 and the like green pigments and C.I. Yellow pigments, such as Pigment Yellow 138, 139, 150, are preferable.

When preparing the colored photosensitive resin composition of this invention as a red coloring photosensitive resin composition, a pigment is C.I. Pigment Red 177, 209, 242, 254, 255, etc. Red pigment, C.I. Pigment Orange Orange pigments, such as 38, 43, 71 and C.I. Yellow pigments, such as Pigment Yellow 138, 139, 150, are preferable.

By including said pigment, optimization of a transmission spectrum is easy and the light resistance and chemical-resistance of a color filter become favorable.

Pigment (A2) is optionally treated with rosin treatment, surface treatment using a pigment derivative having an acid group or basic group introduced therein, graft treatment on the surface of the pigment with a polymer compound, atomization treatment by sulfuric acid atomization or the like, or In order to remove an impurity, you may perform the washing process by the organic solvent, water, etc., the removal process by the ion exchange method of an ionic impurity, etc.

It is preferable that pigment (A2) is uniform particle diameter. By carrying out a dispersion process by containing a pigment dispersant, the pigment dispersion liquid of the form which the pigment disperse | distributed uniformly in the solution can be obtained.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more thereof. As a pigment dispersant, brand names KP [made by Shin-Etsu Chemical Co., Ltd.], Floren [made by Kyoeisha Chemical Co., Ltd.], Solsperth [made by Geneka Co., Ltd.], EFKA (made by CIBA Corporation), Ajisper [Ajinomoto Fine Co., Ltd.] Techno Co., Ltd.], Disperbyk (made by BIC Chem), etc. are mentioned.

When using a pigment dispersant, its usage-amount is preferably 1 mass% or more and 100 mass% or less with respect to pigment (A2), More preferably, they are 5 mass% or more and 50 mass% or less. When the usage-amount of a pigment dispersant exists in said range, there exists a tendency for the pigment dispersion liquid of a uniform dispersion state to be obtained.

It is preferable that a coloring agent (A) contains dye (A1). By including the dye (A1), the optimization of the transmission spectrum is easy.

Moreover, it is more preferable that a coloring agent (A) contains dye (A1) and a pigment (A2). In this case, 1: 99-99: 1 are preferable on a mass basis, and, as for content ratio of dye (A1) and pigment (A2), 3: 97-90: 10 are more preferable. By setting it as such a ratio, optimization of a transmission spectrum becomes easy and the color filter obtained tends to be excellent in contrast, lightness, heat resistance, and chemical-resistance.

The dye (A1) is preferably a dye containing xanthene dye (AA), more preferably a dye containing xanthene dye (AA) and a phthalocyanine dye (AA). In this case, the content ratio of xanthene dye (AA) and phthalocyanine dye (AA) is preferably 5:95 to 95: 5, more preferably 20:80 to 80:20, and 40:60 to 65 on a mass basis. : 35 is even more preferable.

Especially as a coloring agent (A), the coloring agent containing xanthene dye (Aa) and a blue pigment is preferable, and xanthene dye (Aa) and C.I. More preferred are colorants comprising Pigment Blue 15: 6. The content ratio of the xanthene dye (AA) and the blue pigment is preferably 1:99 to 90:10, more preferably 2:98 to 70:30, even more preferably 2:98 to 50:50, on a mass basis. .

The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 50% by mass, still more preferably 10 to 40% by mass with respect to the total amount of solids. When content of a coloring agent (A) exists in the said range, since the color density at the time of setting it as a color filter can be sufficient, and a resin and a polymeric compound (C) can be contained in a composition, a color filter with sufficient mechanical strength can be used. Can be formed.

Here, the "total amount of solid content" in this specification means the quantity remove | excluding content of a solvent from the total amount of the coloring photosensitive resin composition of this invention. 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.

<Resin (Ｂ１)>

Resin (B1) is a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter referred to as "a"), a cyclic ether structure having 2 to 4 carbon atoms, and It is resin containing the structural unit derived from the monomer which has an ethylenically unsaturated bond (henceforth "(i)"). Resin (B1) may differ from (a) and (b) further, and may have a structural unit derived from the monomer which can copolymerize with these (henceforth "(c)").

Examples of the resin (B1) include the following resins [B1] and resins [B2].

Resin [XI1]: Copolymer of (a) and (iii);

Resin [B2]: Copolymer of (a), (b), and (c).

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, metaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetra Unsaturated dicarboxylic acids such as hydrophthalic 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] hepto-2-ene , 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxyl group such as [2.2.1] hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-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 anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl] of 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 them, (meth) acrylic acid, maleic anhydride, and the like are preferred, and (meth) acrylic acid is more preferable from the viewpoint of copolymerization reactivity and solubility in aqueous alkali solution.

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

(iii) represents, for example, an ethylenically unsaturated bond with a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) Eggplant refers to a polymerizable compound. (VIII) The monomer which has a C2-C4 cyclic ether and a (meth) acryloyloxy group is preferable.

As (iii), for example, a monomer (X1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(X1)") and a monomer (X2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, "(B2)", the monomer (3) (henceforth "(3)") etc. which have a tetrahydrofuryl group and ethylenically unsaturated bond are mentioned.

(X1) refers to, for example, a monomer having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (X1-1) (hereinafter referred to as "(X1-1)") and an unsaturated alicyclic hydrocarbon is epoxy. Monomer (X12) (hereinafter, referred to as "(X1-2)") having a structured structure is mentioned.

As (191-1) glycidyl (meth) acrylate, (beta) -methylglycidyl (meth) acrylate, (beta) -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and o-vinyl benzylglycol Cylyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α- Methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl ) 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 have.

Examples of (B1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane [for example, ceroxide 2000; Daicel Chemical Industries, Ltd.], 3, 4- epoxycyclohexylmethyl (meth) acrylate [for example, cyclomer A400; Daicel Chemical Industries, Ltd.], 3, 4- epoxycyclohexyl methyl (meth) acrylate [for example, cyclomer M100; Daicel Chemical Industry Co., Ltd.], the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

[Formula (I) and Formula (II), R <^b1> and R <^b2> 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 ^b1 and X ^b2 represents a single bond (單結合), -R ^b3 - represents the, -R * ^b3 -O-, -S- or ^b3 * -R * -R ^b3 -NH-.

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

* Represents the arm 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, tert-butyl group and the like.

As an alkyl group in which a hydrogen atom was substituted by hydroxy, it is a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy The -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

R ^b1 and R ^{b2 are} preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

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

X ^b1 and X ^{b2 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- (* represents a bonding arm with O).

As a compound represented by Formula (I), the compound etc. which are represented by either of Formula (II-1)-Formula (II-1) are mentioned. Among these, Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-V), and Formulas (I-1) to Formulas (I-15) The compound represented by either of them is preferable, and the compound represented by a formula (I-1), a formula (I-7), a formula (I-V), or a formula (I-15) is more preferable.

Examples of the compound represented by formula (II) include compounds represented by any one of formulas (II-1) to (II-15). Among these, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-X), and formulas (II-111) to formula (II-15) ), And the compound represented by any one of Formula (II-1), Formula (II-7), Formula (II-X) or Formula (II-15) is more preferable.

The compound represented by Formula (I) and the compound represented by Formula (II) may be used independently, respectively, and may mix and use in arbitrary ratios. When using in mixture, the content rate of the compound represented by Formula (I) and the compound represented by Formula (II) is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90: on a molar basis. 10, even more preferably 20:80 to 80:20.

As a monomer (X2) which has an oxetanyl group and ethylenically unsaturated bond, the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxy methyl oxetane, 3-methyl-3- acryloyloxy methyl oxetane, 3-ethyl-3-methacryloyloxy methyl oxetane, 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 (X3) 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 (iii) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(b) It is preferable that it is (b1) from the point which can further improve reliability, such as heat resistance and chemical-resistance of the color filter obtained. Furthermore, (b 1-2) is more preferable at the point which is excellent in the storage stability of a coloring photosensitive 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 (in the art, it is commonly known as "dicyclopentanyl (meth) acrylate" Also referred to as "tricyclodecyl (meth) acrylate", tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the art, the common name is "dicyclopentenyl ( Methacrylate)), dicycle Lofentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (Meth) acrylic acid esters such as naphthyl (meth) acrylate and benzyl (meth) acrylate;

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

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

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2 -Ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1 ] Hepto-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] Hepto-2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5 -Methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2. 1] hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5- Cyclohexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl Bicyclo unsaturated compounds, such as) bicyclo [2.2.1] hepto-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3-maleimide benzoate, 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, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide And vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

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

In resin [K1], the ratio of the structural unit derived from each monomer is with respect to the all the structural units which comprise resin [K1],

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

structural units derived from (iii); 40 to 98 mol%

Is preferred,

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

structural units derived from (iii); 50 to 90 mol%

Is more preferable.

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

Resin [1] is described, for example, in the method described in the document "Experimental method of polymer synthesis" (Otsu Takayuki, First Edition, First Edition, Issued March 1, 1972, issued by Chemical Industries, Ltd.). It may be prepared with reference to the cited literature.

Specifically, a method of heating and keeping warm while stirring in a deoxygen atmosphere by placing a predetermined amount of (a) and (iii), a polymerization initiator, a solvent, and the like into a reaction vessel and replacing oxygen with nitrogen, for example, is mentioned. . Moreover, 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.], an organic peroxide (benzoyl peroxide etc.) Examples of the solvent may be those obtained by dissolving each monomer, and examples thereof include a solvent (E) to be described later as a solvent of the colored photosensitive resin composition.

Moreover, the obtained resin may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what extracted as solid (powder) by methods, such as reprecipitation. In particular, since the solution after reaction can be used as it is for manufacture of a coloring photosensitive resin composition by using the solvent (E) mentioned later as a solvent at the time of this superposition | polymerization, the manufacturing process of a coloring photosensitive resin composition can be simplified.

In resin [K2], the ratio of the structural unit derived from each is in the all the structural units which comprise resin [K2],

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

structural units derived from (iii); 2 to 95 mol%

structural unit derived from (c); 1 to 65 mol%

Is preferably,

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

structural units derived from (iii); 5 to 80 mol%

structural unit derived from (c); 5 to 60 mol%

More preferably.

When the ratio of the structural unit of resin [2] is in the said range, there exists a tendency which is excellent in the storage stability of a coloring photosensitive resin composition, developability at the time of forming a coloring pattern, and the solvent resistance, heat resistance, and mechanical strength of the obtained coloring pattern. have.

Specific examples of the resin (3) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, and 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid. Resins such as coalescing [X1]; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxy cicyclo [5.2 .1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / vinyltoluene copolymer, 3 Resins such as -methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / N-cyclohexylmaleimide copolymer;

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

The weight average molecular weight of polystyrene conversion of resin (B1) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the molecular weight is in the above range, the hardness of the color filter is improved, the residual film ratio is also high, and the solubility in the developer of the unexposed part is good, so that the resolution tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (B1) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of the resin (XI) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, even more preferably 70 to 135 mg-KOH / g. Here, 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, for example, titration using an aqueous potassium hydroxide solution.

The content of the resin (B1) is preferably 10 to 90% by mass, more preferably 25 to 85% by mass, even more preferably 50 to 80% by mass relative to the total amount of the resin (B1) and the resin (B2). %to be.

<Resin>

Resin (K2) is resin containing (a) and the structural unit (henceforth "(i)") derived from the monomer which has an alicyclic hydrocarbon structure. However, resin (2) does not contain the structural unit derived from the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond. Resin (B2) may differ from (a), (b), and (b) further, and may have a structural unit derived from the monomer which can copolymerize with these (henceforth "(d)").

Examples of the resin (B2) include the following resins [K3] and [K4].

Resin [K3]: copolymer of (a) and (iii);

Resin [K4]: The copolymer of (a), (v) and (d).

As (a), the same thing as (a) of resin (VII) is mentioned. Among them, (meth) acrylic acid and maleic anhydride are preferable, and (meth) acrylic acid is more preferable from the viewpoint of copolymerization reactivity and solubility in aqueous alkali solution.

As (iii) (meth) which has monocyclic alicyclic hydrocarbon structures, such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-methylcyclohexyl (meth) acrylate, ) Acrylic acid esters;

Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate, dicyclopentanyloxyethyl (meth) (Meth) acrylic acid esters having a polycyclic alicyclic hydrocarbon structure such as acrylate, isobornyl (meth) acrylate and adamantyl (meth) acrylate;

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2 -Ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1 ] Hepto-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] Hepto-2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5 -Methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2. 1] hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5- Cyclohexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl Bicyclo unsaturated compounds, such as) bicyclo [2.2.1] hepto-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

N-substituted maleimide which has alicyclic hydrocarbon structures, such as N-cyclohexyl maleimide, etc. are mentioned.

Among these, (i) is preferably at least one selected from the group consisting of (meth) acrylic acid esters having an alicyclic hydrocarbon structure and bicyclo unsaturated compounds, and (meth) acrylic acid esters having an alicyclic hydrocarbon structure. It is more preferable, and (meth) acrylic acid ester which has a polycyclic alicyclic hydrocarbon structure is more preferable. When (b) is such a monomer, when manufacturing a coloring pattern from the coloring photosensitive resin composition of this invention containing resin (b2), generation | occurrence | production of the peeling piece originating from the coloring photosensitive resin composition in the developing solution after image development will reduce. Moreover, the foreign material by adhesion of such a peeling piece on a coloring pattern is also suppressed.

As (d), the thing except having corresponded to (b) in (c) of resin (K1) is mentioned, for example.

As (d), 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, aryl (meth) acrylate, propargyl (meth) acrylate, phenyl ( (Meth) acrylic acid esters such as metha) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

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

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

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

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

Among these, monomers having an aromatic hydrocarbon structure such as styrene, vinyltoluene, N-phenylmaleimide, N-benzylmaleimide, benzyl (meth) acrylate are preferred, and styrene, vinyltoluene and benzyl (meth) acrylate are preferred. More preferred. If (d) is such a monomer, since the viscosity of the resin (B2) solution during superposition | polymerization or after superposition | polymerization does not become high too much, it exists in the tendency to be easy to handle. Moreover, when resin (B2) containing the structural unit derived from such a monomer is used for a coloring photosensitive resin composition, generation | occurrence | production of the peeling piece at the time of image development can be further suppressed.

In resin [K3], the ratio of the structural unit derived from each monomer is with respect to the all the structural units which comprise resin [K3],

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

structural units derived from (iii); 40 to 98 mol%

Is preferred,

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

structural units derived from (iii); 50 to 90 mol%

Is more preferable.

When the ratio of the structural unit of resin [3] exists in the said range, there exists a tendency for the coloring pattern with a favorable shape to be obtained.

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

In resin [K4], the ratio of the structural unit derived from each is in the all the structural units which comprise resin [K4],

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

structural units derived from (iii); 2 to 95 mol%

structural unit derived from (d); 1 to 65 mol%

Is preferably,

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

structural units derived from (iii); 5 to 80 mol%

structural unit derived from (d); 5 to 60 mol%

More preferably.

When the ratio of the structural unit of resin [4] exists in the said range, there exists a tendency for the coloring pattern with a favorable shape to be obtained.

When (d) of resin [14] contains the structural unit derived from the monomer which has an aromatic-hydrocarbon structure [hereinafter, "(d ')",

structural unit derived from (a); 5 to 45 mol%

structural units derived from (iii); 5 to 80 mol%

structural unit derived from (d '); 30 to 65 mol%

Is preferably,

structural unit derived from (a); 10 to 40 mol%

structural units derived from (iii); 5 to 40 mol%

structural unit derived from (d '); 40 to 65 mol%

More preferably.

If resin [K4] is such a resin, generation | occurrence | production of the peeling piece by image development will become further smaller, and there exists a tendency for the coloring pattern with a favorable shape to be obtained.

Resin [K4] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

Specifically as resin (B2), a cyclohexyl (meth) acrylate / (meth) acrylic acid copolymer, a tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer, bicyclo [2.2.1] hepto-2- Resins such as ene / (meth) acrylic acid copolymers [X3]; Cyclohexyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, tricyclodecyl (meth ) Acrylic / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / vinyltoluene / (meth) acrylic acid copolymer, bicyclo [2.2.1] hepto-2-ene / styrene / (meth) Resin [K4], such as an acrylic acid copolymer, is mentioned.

Among these, resin [K4] is preferable as resin (K2).

The weight average molecular weight of polystyrene conversion of resin (B2) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 3,000-30,000, More preferably, it is 4,000-15,000. When the molecular weight is in the above range, the hardness of the color filter is improved, the residual film ratio is also high, and the solubility in the developer of the unexposed part is good, so that the resolution tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (B2) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of the resin (B2) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, still more preferably 70 to 135 mg-KOH / g. When an acid value exists in the said range, there exists a tendency for the coloring pattern with a favorable shape to be obtained. When the acid value is higher than the above range, undercut is likely to occur in the colored pattern, which causes pattern peeling. Moreover, when an acid value is low beyond the said range, there exists a possibility that a developing residue may arise. Here, 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, for example, titration using an aqueous potassium hydroxide solution.

The content of the resin (B2) is preferably 10 to 90% by mass, more preferably 15 to 75% by mass, even more preferably 50 to 80% by mass relative to the total amount of the resin (B1) and the resin (B2). %to be.

The total amount of the resin (B1) and the resin (B2) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, even more preferably 17 to 55% by mass relative to the total amount of solids. When the said total amount exists in the said range, there exists a tendency for the resolution and residual film rate of a coloring pattern to improve.

<Polymeric Compound (C)>

A polymerizable compound (C) is a compound which can superpose | polymerize with the active radical and / or acid which generate | occur | produce from heat or a polymerization initiator (D), For example, the compound etc. which have a polymerizable ethylenically unsaturated bond, etc. are mentioned, Preferably it is a (meth) acrylic acid ester compound.

Especially, as a polymeric compound (C), it is preferable that it is a polymeric compound which has three or more ethylenically unsaturated bonds. As such a polymeric compound, a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, for example , Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (Meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanate, 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 Y, a caprolactone modified pentaerythritol tetra (meth) acrylate, a caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

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

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

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

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited so long as it is a compound capable of generating an active radical, an acid, or the like by the action of light or heat and can initiate polymerization, and a known polymerization initiator 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. Among these, the polymerization initiator containing an O-acyl oxime compound is preferable, and the polymerization initiator containing an O-acyl oxime compound and an alkylphenone compound is more preferable.

The O-acyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a coupling arm.

As the O-acyl oxime compound, for example, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and 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-yl] -3-cyclopentylpropan-1-one-2-imine, etc. are mentioned. You may use commercially available products, such as Ilgacure (trademark) OXE01, OXE02 (above, BASF Corporation), and N-1919 (ADEKA Corporation).

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

As a compound which has a partial structure represented by a formula (d2), for example, 2-methyl- 2-morpholino- 1- (4-methylsulfanylphenyl) propane- 1-one, 2-dimethylamino-1- ( 4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane -1-one etc. are mentioned. You may use commercially available products, such as Ilgacure (trademark) 369, 907, and 379 (above, BASF Corporation make).

As a compound which has a partial structure represented by a formula (d3), for example, 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, (alpha), (alpha)-diethoxy acetophenone, benzyl dimethyl ketal, etc. are mentioned.

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

As the triazine compound, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc. are mentioned as an acyl phosphine oxide compound. You may use commercially available products, such as Monocure (registered trademark) 819 (made by BASF Corporation).

As a biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-dichloro, for example). Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, eg, JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis (2-chlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4' , 5,5'-tetra (trialkoxyphenyl) biimidazole (see, eg, JPS48-38403-B, JPS62-174204-A, etc.), phenyl group at 4,4 ', 5,5'-position And imidazole compounds substituted with carboalkoxy groups (see, for example, JPH07-10913-A).

Furthermore, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and campquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound and the like. It is preferable to use these in combination with the polymerization initiator adjuvant (D1) [especially amines] mentioned later.

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, Onium salts, such as diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylates, benzoin tosylate, etc. are mentioned.

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 (K1), resin (K2), and a polymeric compound (C), More preferably, it is 1-20 mass. It is wealth. When content of a polymerization initiator (D) exists in the said range, since it will become high sensitivity and an exposure time tends to be shortened, productivity improves.

The polymerization initiator (D1) may be further included together with the polymerization initiator (D). The polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of the photopolymerizable compound in which polymerization is initiated by the polymerization initiator.

As polymerization initiator (D1), an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned, Preferably it is a thioxanthone compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 2-dimethylaminoethyl benzoic acid and 4-dimethylaminobenzoic acid 2 -Ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone [commonly known as Michler's ketone], 4,4'-bis (diethylamino) benzophenone, 4,4 ' -Bis (ethylmethylamino) benzophenone etc. are mentioned, Among these, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Co., Ltd.).

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxy Anthracene, 2-ethyl-9, 10-dibutoxy anthracene, etc. are mentioned.

As a thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy city oxane Tone, etc. can be mentioned.

As the carboxylic acid compound, phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenyl sulfone Panyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthyl thioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, etc. are mentioned.

When using such a polymerization initiator (D1), its usage-amount is preferably 0.1-30 mass parts, More preferably, with respect to 100 mass parts of total amounts of resin (K1), resin (B2), and a polymeric compound (C). Preferably it is 1-20 mass parts. When the amount of the polymerization initiator (D1) is in this range, it is possible to form a coloring pattern with higher sensitivity, and the productivity of the color filter tends to improve.

<Solvent (E)>

The solvent (E) is not particularly limited, but a solvent commonly used in the art may be used. For example, an ester solvent (solvent containing -COO- in a molecule and not containing -O-), an ether solvent (solvent containing -O- in a molecule and not containing -COO-), ether ester Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and no -COO-), alcoholic solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl It can select from sulfoxide etc., and can use.

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, butyric acid Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, cyclohexanol acetate, gamma -butyrolactone, and the like.

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 methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl anisole, etc. Can be mentioned.

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate butyl, ethoxy acetate methyl, ethoxy acetate ethyl, 3-methoxy propionate methyl, 3-methoxy propionate ethyl, 3-ethoxy propionate methyl, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol mono Butyl ether and the like can be mentioned acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate.

As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentane Warm, cyclohexanone, isophorone and the like.

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

Benzene, toluene, xylene, mesitylene etc. are mentioned as an aromatic hydrocarbon solvent.

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

You may use these solvents individually or in combination of 2 or more types.

Among the solvents described above, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable from the viewpoint of applicability and drying properties. Examples of the solvent (E) include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and 4- Hydroxy-4-methyl-2-pentanone is preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferred.

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

<Surfactant (F)>

Examples of the surfactant (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymeric group in a side chain.

As silicone type surfactant, surfactant etc. which have a siloxane bond in a molecule | numerator are mentioned. Specifically, toray silicon DC3PA, toray silicon SH7PA, toray silicon DC11PA, toray silicon SH21PA, toray silicon SH28PA, toray silicon SH29PA, toray silicon SH30PA, toray silicon SH8400 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 [Momental Performance Materials Japan] Joint company], etc. are mentioned.

As said fluorine-type surfactant, surfactant etc. which have a fluoro carbon chain in a molecule | numerator are mentioned. Specifically, Floroid (registered trademark) FC430, Floride FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Pack (registered trademark) F142D, Mega Pack F171, Mega Pack F172, Mega Pack F173, Mega Pack F177, Mega Pack F183, Megapack F554, Megapack R30, Megapack RS-718-K [manufactured by DIC Corporation], FTOP® EF301, Ftop EF303, Ftop EF351, Ftop EF352 [Mitsubishi Material Electronic Chemicals ], Saffron (registered trademark) S381, Saffron S382, Saffron SC101, Saffron SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemical Research Institute, Inc.), etc. are mentioned. have.

As silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain in a molecule | numerator 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 (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, even more preferably 0.01% by mass relative to the total amount of the colored photosensitive resin composition. It is more than 0.05 mass% in%. Moreover, content of the said pigment dispersant is not included in this content. When content of surfactant (F) exists in said range, flatness of a color filter can become favorable.

<Other Ingredients>

The coloring photosensitive resin composition of this invention may contain additives known in the art, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, an optical stabilizer, a chain transfer agent, as needed.

<The manufacturing method of a coloring photosensitive resin composition>

The coloring photosensitive resin composition of this invention can be used, for example as a coloring agent (A), resin (B1), resin (B2), a polymeric compound (C), and a polymerization initiator (D), and a polymerization initiator as needed. It can prepare by mixing (D1), a solvent (E), surfactant (F), and another component.

When the pigment (A) is included as the coloring agent (A), the pigment (A2) is mixed with the solvent (E) in advance, and a beads mill or the like is added until the average particle diameter of the pigment is about 0.2 µm or less. It is preferable to disperse using. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant, resin (K1), or a part or all of resin (K2) as needed. Remainder of resin (X1), the remainder of resin (X2) and the polymeric compound (C), and the remainder of dye (A1), polymerization initiator (D), and solvent (E) which are used as needed in the obtained pigment dispersion liquid, and an interface The target coloring photosensitive resin composition can be prepared by mixing an active agent (F), other components, etc. in predetermined concentration.

The dye (A1) in the case of containing the dye (A1) may be dissolved in the solvent (E) in advance. The solution is preferably filtered with a filter having a pore diameter of about 0.01 to 1 m.

It is preferable to filter the coloring photosensitive resin composition after mixing with the filter of about 0.1-10 micrometers of pore diameters.

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

As a method of manufacturing the coloring patterning coating film (the "coloring patterning coating film" is simply described as a "coloring pattern") of a color filter from the coloring photosensitive resin composition of this invention, the photolithographic method and an inkjet Law, printing method and the like. Among these, the photolithographic method is preferable. The photolithographic method applies the colored photosensitive resin composition of this invention to a board | substrate, removes volatile components, such as a solvent, and dries to form a composition layer. Next, it is a method of exposing and developing the said composition layer by sandwiching a photomask. After image development, a coloring pattern can be formed by heating as needed. In the formation method of the said coloring pattern, the coloring coating film which is the hardened | cured material of the said composition layer can be formed by not using a photomask and / or developing at the time of exposure. The coloring patterning coating film and coloring coating film obtained in this way can be used as a color filter.

Although the film thickness of the produced color filter is not specifically limited, According to the objective, a use, etc., it can adjust suitably, For example, it is 0.1-30 micrometers, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass coated with silica on the surface, resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, and aluminum on the substrate. And silver, and the thing which formed the silver / copper / palladium alloy thin film etc. can be used. Another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed on such a board | substrate.

Next, the method of forming a pattern on the glass substrate in which the thin film transistor (henceforth "TFT") was formed is demonstrated.

Specifically, a plurality of TFTs 22 are formed for each pixel on the glass substrate 21 by a known method such as a photolithography technique (see FIG. 1). The TFT 22 is formed by, for example, molybdenum (Mo) on the glass substrate 21, and forms an example formed on the gate electrode 22a and part of the gate line 22a. For example, a gate insulating film 22b formed of a laminated film of a nitride film (SiN _x ) and an oxide film (SiO ₂ ), a polycrystalline silicon film 22c formed on the gate insulating film 22b, for example, an oxide film (SiO ₂ ), It is composed of a protective layer (22d) formed by a laminated film of a nitride film (SiN _x). The region facing the gate electrode 22a of the polycrystalline silicon film 22c is the channel region of the TFT 22, and the regions on both sides of the channel region are the source region or the drain region. The source region of the polycrystalline silicon film 22c is electrically connected to the signal line 27 formed of aluminum (Al), for example, via a connection hole (contact hole) provided in the protective film 22d. Further, the drain region of the polycrystalline silicon film 22c is electrically connected to the pixel electrode 24 via the connection hole (contact hole) 201 as described later.

When the plurality of TFTs 22 are formed for each pixel on the glass substrate 21, alignment marks (not shown) are formed on the glass substrate 21 simultaneously with the TFTs 22. This alignment mark becomes a reference of the alignment in the formation process of the color filter layer 23 as mentioned later. Moreover, such an alignment mark can also be used as a mark which becomes a reference | standard of the bonding of a drive board | substrate and an opposing board | substrate. Alignment mark can be formed in the same process using one or more layers, when forming metal layers, such as wiring, and a polycrystalline silicon layer in the manufacturing process of TFT22.

Subsequently, the coloring photosensitive resin composition of this invention is apply | coated on the TFT 22 and the glass substrate 21 in which the alignment mark was formed, and volatile components, such as a solvent, are dried by heat drying (prebake) and / or reduced pressure drying. It is removed and dried to form a composition layer having a film thickness of 0.5 to 5.0 mu m, for example 1.0 mu m.

As a coating method, the spin coat method, the slit coat method, the slit & spin coat method, etc. are mentioned.

30-120 degreeC is preferable and, as for the temperature in the case of heat-drying, 50-110 degreeC is more preferable. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferable to carry out in the temperature range of 20-25 degreeC under reduced pressure of 50-150 Pa.

Subsequently, a photomask (not shown) is inserted to irradiate ultraviolet rays to the composition layer, and furthermore, by selectively removing unnecessary portions (unexposed portions) with a developing solution, to the drain region of the polycrystalline silicon film 22c. After obtaining the composition layer formed in the pixel in which the contact hole [contact hole] 201 which reached is obtained, it wash | cleans with water.

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 concentration in the aqueous solution of such an alkaline compound is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain surfactant.

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

Thereafter, in order to reflow (reflow) and / or harden the composition layer in which the connection hole [contact hole] 201 is formed, it is the range of 150-250 degreeC, for example, 160-235 degreeC 1 to 120 minutes are preferable at the temperature of the range of, and it heats for 10 to 60 minutes. In this way, the coloring photosensitive resin composition layer 23A is formed. This colored photosensitive resin composition layer 23A corresponds to the color filter of this invention.

By repeating this operation, the colored photosensitive resin composition layer 23A is formed from the red colored photosensitive resin composition, the green colored photosensitive resin composition, and the blue colored photosensitive resin composition, respectively, so as to correspond to the red filter 23a for each column of pixels. ), A color filter layer 23 including a green filter 23b and a blue filter 23c is formed (see Fig. 2). The region between each filter of the color filter layer 23 becomes a mixed region of adjacent colors, but since this region is a light shielding region facing the signal line 27, there is no particular problem in quality. Furthermore, the area between each of these filters may not be colored.

Then, the photosensitive resin film 29 as a protective film with a film thickness of 0.3-2.0 micrometers is formed so that the color filter layer 23 may be covered, for example by the spin coat method. Subsequently, a photomask (not shown) is inserted to irradiate the photosensitive resin film 29 with ultraviolet rays, and further selectively remove regions and unnecessary portions corresponding to the connection holes 201 with the developer, thereby removing the polycrystalline silicon film ( The connection hole (contact hole) 202 reaching the drain region of 22c is formed and then washed with water. Then, for reflow (reflow) of the photosensitive resin film 29, it heats at the temperature of 100-300 degreeC, for example, 200 degreeC. Subsequently, in order to remove residues such as dyes and organic matter deposited in the contact hole 202, etching with oxygen plasma is performed, and further, in order to remove the oxide film formed by oxygen plasma, for example, in dilute hydrofluoric acid, By etching.

Subsequently, on the photosensitive resin film 29, a transparent conductive material, for example, ITO (Indium-Tin Oxide: an oxide mixed film of indium and tin), is formed by a sputtering method. The film is patterned by photolithography techniques and etching to form a transparent pixel electrode 24 (see FIG. 3). In addition, the pixel electrode 24 may be made of a metal such as aluminum (Al) or silver (Ag), depending on the device to be manufactured. Thereafter, after the alignment film is formed by a known method, the liquid crystal display device can be manufactured by bonding the drive substrate and the counter substrate.

According to the coloring photosensitive resin composition of this invention, since a high yield color filter with especially few surface foreign substances can be manufactured with good yield, the said color filter is a display apparatus (for example, a liquid crystal display device, an organic EL device, etc.), an electronic paper. It is useful as a color filter used for a solid-state image sensor etc.

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

Example

The present invention will be described more specifically with reference to the following examples. In the examples,% and parts indicating the content to the amount of use are based on mass unless otherwise specified.

Synthesis Example 1

In a flask equipped with a cooling tube and a stirring device, 15 parts of a mixture of a compound represented by the formula (A1-1a) and a compound represented by the formula (A1-1ｂ) (trade name Chugai Aminol Fast Pink R; manufactured by Chuga Kasei), chloroform 150 parts and 8.9 parts of N, N-dimethylformamide were added thereto, and 10.9 parts of thionyl chloride was 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. The mixture liquid of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was dripped, and added, maintaining the reaction solution after cooling at 20 degrees C or less under stirring. Thereafter, the reaction was stirred at the same temperature for 5 hours. Subsequently, the obtained reaction mixture was removed by evaporation of the solvent with a rotary evaporator, and then 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 dyes (A1-1) [formulas (A1-1-1) to (A1-1-1). Mixture of compounds represented by iv)] 11.3 parts was obtained.

[Synthesis Example 2]

In a 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 305 parts by mass of ethyl lactate was added thereto and heated to 70 ° C while stirring. Subsequently, 60 parts by mass of acrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate [compound represented by formula (I-1) and compound represented by formula (II-1) were molar ratios of 50:50. Mixing] 240 parts by mass were dissolved in 140 parts by mass 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 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of ethyl lactates was dripped in the flask over 4 hours using the other dropping funnel. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature. The weight average molecular weight (Mw) was 9.1 × 10 ³ , the molecular weight distribution was 2.1, solid content 26 mass%, and solid content. The resin (X11) solution having an acid value of 120 mg-KOH / g was obtained. Resin (XI1-1) has the following structural unit.

[Synthesis Example 3]

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 257 parts by mass of propylene glycol monomethyl ether acetate was added and heated to 70 ° C while stirring. Next, 57 parts by mass of acrylic acid, 83 parts of vinyltoluene, and 3,4-epoxycitcyclo [5.2.1.0 ^2.6 ] decyl acrylate [compound represented by formula (I-1) and compound represented by formula (II-1) are molar. Ratio of 50:50] 238 parts by mass was dissolved in 140 parts by mass of propylene glycol monomethyl ether acetate 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 flask which melt | dissolved the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of propylene glycol monomethyl ether acetates using a separate dropping funnel, over 4 hours It dripped in the inside. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature. The weight average molecular weight (Mw) was 9.9 × 10 ³ , solid content 37.5%, and solid acid value 112 mg-KOH / Resin (X12) solution which is g was obtained. Resin (B1-2) has the following structural units.

[Synthesis Example 4]

The flask equipped with the stirrer, the thermometer, the reflux cooling tube, the dropping funnel and the nitrogen inlet tube was placed in a nitrogen atmosphere, and 210 parts of propylene glycol monomethyl ether acetate was added thereto, and the temperature was raised to 100 ° C while stirring. Subsequently, 106 parts of benzyl methacrylate, 22 parts of acrylic acid and 22 parts of dicyclopentanyl methacrylate (FA-513M manufactured by Hitachikasei Co., Ltd.) were dissolved in 215 parts of propylene glycol monomethyl ether acetate, and further 2,2'- A solution prepared by dissolving 3.6 parts of azobisisobutyronitrile was added dropwise into the flask, followed by stirring at 100 ° C. for 5 hours, whereby the weight average molecular weight (Mw) was 1.00 × 10 ⁴ , solid content 34.1%, and solid acid value 109 mgKOH / g. Phosphorus resin (X21) solution was obtained. Resin (B2-1) has the following structural unit.

Synthesis Example 5

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 220 parts of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Subsequently, 84 parts of methacrylic acid and the compound represented by 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decyl acrylate [formula (II-1) and the compound represented by formula (II-1) are molar ratios of 50: Mixed with 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 the dropwise addition of the solution of the polymerization initiator, 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 solution. A resin solution (X13-3) having an acid value of 50 mg-KOH / g (the acid value in terms of solid content is 104 mgKOH / g) was obtained. Resin (13-3) has the following structural unit.

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

Equipment: K2479 [manufactured by Shimadzu Corporation]

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: THF (Tetrahydrofuran)

Flow rate: 1.0 mL / min

Detector: RI

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500

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

Examples 1 to 6, and Comparative Example 1

[Preparation of Colored Photosensitive Resin Composition]

Each component of the quantity shown in Table 1 was mixed, and the coloring photosensitive resin composition was obtained.

¹⁾ (A2-1) mixes a pigment dispersant, the propylene glycol monomethyl ether acetate of the amount described in (E-1) ⁵⁾ , and the propylene glycol monomethyl ether of the amount described in (E-2) ⁶⁾ , It was previously dispersed using a mill.

²⁾ (E-1) ²⁾ represents the sum total of propylene glycol monomethyl ether acetate content.

³⁾ (E-2) ³⁾ represents the sum total of propylene glycol monomethyl ether content.

⁴⁾ Resin (B1) ⁴⁾ shows content of solid content conversion.

Moreover, in Table 1, each component shows the following.

Coloring agent (A); (A1-1); Dye (A1-1)

Coloring agent (A); (A1-2); C.I. Salt [orient Chemical Co., Ltd. product] of direct blue 264 with dodecylbenzenesulfonic acid (dye)

Coloring agent (A); (A2-1); C.I. Pigment Blue 15: 6 (pigment)

Resin (B1); (1-1); Resin (B1-1)

Resin (B1); (V1-2); Resin (B1-2)

Resin (B1); (V1-3); Resin (13-1)

Resin (B2); (V2-1); Resin (B2-1)

Polymeric compound (C); Dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.]

Polymerization initiator (D); (D-1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE01; Manufactured by BASF Corporation; o-acyl oxime compound]

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

Polymerization initiation aid (D1); 2,4-diethyl thioxanthone [KAYACURE® DETX-S; Nihon Kayaku Co., Ltd. product; Thioxanthone compound]

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 oils [Torre Silicone SH8400; Torreda Corning Corporation]

[Evaluation of development]

After apply | coating the coloring photosensitive resin composition on the 2-inch square glass substrate (Eagle XG; product made by Corning Corporation) by the spin coat method, it prebaked at 100 degreeC for 3 hours, and formed the composition layer. The substrate on which the composition layer was formed was immersed at 25 ° C. for 120 seconds in a chalet containing 10 ml of an aqueous developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate, and after immersion, the developer was visually observed. When the peeling piece derived from the coloring photosensitive resin composition was not confirmed in the developing solution, it was judged that developability was favorable, and when (circle) and a peeling piece were confirmed, it was set as x. When the peeling piece derived from the coloring photosensitive resin composition is confirmed in a developing solution, since it adheres as a foreign material on a color filter and causes a defect, it is unpreferable. The results are shown in Table 2.

[Production of color filter]

After apply | coating the coloring photosensitive resin composition on the 2-inch square glass substrate (Eagle XG; product made by Corning Corporation) by the spin coat method, it prebaked at 100 degreeC for 3 hours, and formed the composition layer. After cooling, an exposure apparatus [TME-150RSK; was set at 200 mu m between the substrate on which the composition layer was formed and the quartz glass photomask having a pattern. Topcon Co., Ltd.] was used to irradiate light at an exposure dose (365 nm standard) of 40 mJ / cm 2 under an air atmosphere. Moreover, the light irradiation at this time was performed by the optical filter [UV-35; It was carried out by passing through Asahi Spectroscopy Co., Ltd. product. Further, light irradiation was performed by sandwiching a photomask in which a pattern (having a square light shield having one side of 30 µm and a square spacing of 100 µm) was formed on the same plane (hereinafter, corresponding to the light transmitting portion of the photomask). The part irradiated with light is referred to as the "exposed part", and the part which is not irradiated with the light shielding part of a photomask is called "unexposed part." After light irradiation, the coating film was developed by immersing in an aqueous developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 25 ° C. for 60 seconds, washed with water, and then postbaked at 230 ° C. for 20 minutes in an oven. ) To obtain a color filter in which a hole having a 30 μm angle is formed in the unexposed portion.

[Film thickness measurement]

In the exposure part of the obtained color filter, film thickness measuring apparatus [DEKTAK3; The film thickness was measured using Japan Vacuum Technology Co., Ltd. product. The results are shown in Table 2.

[Color evaluation]

In the exposure part of the obtained color filter, a colorimeter [OSP-SP-200; Spectrophotometry was measured using Olympus Co., Ltd., and the xy chromaticity coordinates (x, y) and tristimulus value Y in the XYZ colorimetric system of CIE were measured using the isochromatic coefficient of C light source. The larger the value of Y, the higher the brightness. The results are shown in Table 2.

In the coloring photosensitive resin composition of the Example, it was confirmed that generation | occurrence | production of the peeling piece by image development was not confirmed at the time of color filter formation. From this, a display device can be manufactured with a high yield by the color filter produced from the coloring photosensitive resin composition of this invention.

According to the coloring photosensitive resin composition of this invention, generation | occurrence | production of the peeling piece derived from the coloring photosensitive resin composition in the developing solution after image development is few.

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

Claims (5)

Colored photosensitive resin composition containing (A), (X1), (X2), (C), and (D).
(A) Colorant
(Iii) a structural unit derived from one or more structural units selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and monomers having a C 2 to C 4 cyclic ether structure and an ethylenically unsaturated bond; Containing resin
(X2) Resin containing structural units derived from at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and structural units derived from monomers having alicyclic hydrocarbon structures (however, C2-4) Does not include structural units derived from monomers having two cyclic ether structures and ethylenically unsaturated bonds)
(C) polymerizable compound
(D) polymerization initiator The method of claim 1,
The colored photosensitive resin composition which further contains the structural unit derived from the monomer which (b2) has an aromatic hydrocarbon group. 3. The method according to claim 1 or 2,
Colored photosensitive resin composition whose content of said (B2) is 10-90 mass% with respect to the total amount of (B1) and (B2). The color filter formed with the coloring photosensitive resin composition of any one of Claims 1-3. A display device comprising the color filter of claim 4.

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