KR20130036720A - Colored photosensitive resin composition - Google Patents

Abstract

A structural unit derived from at least one selected from the group consisting of a colorant, a resin, a polymerizable compound and a polymerization initiator, the colorant being a colorant comprising a dye, and the resin being an unsaturated carboxylic acid and an unsaturated carboxylic anhydride; It is resin containing the structural unit derived from the monomer which has a 2-4 cyclic ether structure and an ethylenically unsaturated bond, and the copolymer containing the structural unit derived from the monomer represented by Formula (i), The colored photosensitive resin composition whose content of the structural unit derived from the monomer represented by this is 0.1 mol% or more and 20 mol% or less with respect to the structural unit whole quantity which comprises the said copolymer. In formula (i), R <^a1> represents a hydrogen atom or a C1-C4 alkyl group. X ^a1 represents a single bond, -X ^a2- , * -X ^a2 -O-, * -X ^a2 -S- or * -X ^a2 -NH-. X ^a2 represents an alkanediyl group having 1 to 6 carbon atoms. * Represents the arm with O]

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 the copolymer of methacrylic acid and 3, 4- epoxy cyclo [5.2.1.0 ^2.6 ] decyl acrylate as a resin is known (JP 2010-211198-A). ).

To form a colored pattern using the colored photosensitive resin composition, the colored photosensitive resin composition is applied to a substrate to form a composition layer, and the photomask is sandwiched in the composition layer to be exposed and developed to obtain a pattern. Law is used. However, in the conventionally proposed colored photosensitive resin composition, a part of the unexposed part of the composition layer formed from the said colored photosensitive resin composition is peeled off at the time of image development, and its peeling piece adheres on a coloring pattern and becomes a foreign material. There was a case.

The present invention includes the following inventions.

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

Colorants include dyes,

Structural units derived from at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, structural units derived from monomers having 2 to 4 cyclic ether structures and ethylenically unsaturated bonds, Expression (ｘ)

In formula (i), R <^a1> represents a hydrogen atom or a C1-C4 alkyl group.

X ^a1 represents a single bond ^{(單結合), -X a2 -} , * represents an -X ^a2 -O-, -S- or ^a2 * -X * -X ^a2 -NH-.

X ^a2 represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents a coupling arm with O]

Containing a structural unit derived from a monomer represented by

The colored photosensitive resin composition whose content of the structural unit derived from the monomer represented by Formula (i) is 0.1 mol% or more and 20 mol% or less with respect to the structural unit whole quantity which comprises the said copolymer.

[2] The colored photosensitive resin composition as described in [1], wherein the coloring agent is a coloring agent further containing a pigment.

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

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

According to the coloring photosensitive resin composition of this invention, a part of unexposed part of the composition layer formed from the said coloring photosensitive resin composition can be prevented from peeling at the time of image development, and the foreign material on a coloring pattern can be reduced.

The coloring photosensitive resin composition of this invention contains a coloring agent (A), resin (i), a polymeric compound (C), and a polymerization initiator (D),

A coloring agent (A) is a coloring agent containing dye (A1),

The resin is a structure derived from a structural unit derived from at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and monomers having 2 to 4 cyclic ether structures and ethylenically unsaturated bonds. It is resin containing the copolymer of a unit and the structural unit derived from the monomer represented by Formula (i).

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, as long as there is no notice in particular, each said 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 , Styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. 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 3 to 10 membered ring nitrogen with an adjacent nitrogen atom. You may form the containing heterocycle.

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 group, the coloring photosensitive resin composition containing a compound (1a) can produce the color filter which is less likely to generate | occur | produce a foreign material and further excellent in heat resistance.

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 and icosylsulfanyl group.

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.

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, a pigment 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) 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 more excellent in contrast, brightness, heat resistance, and chemical-resistance.

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 in a required amount, mechanical strength is sufficient. Color filters 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 a coloring photosensitive resin composition. The total amount of solids and the content of each component thereof can be measured, for example, by known analysis means such as liquid chromatography or gas chromatography.

<Resin>

The resin 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 The structural unit derived from the monomer which has an ethylenically unsaturated bond (henceforth "(i)"), and a formula (i)

In formula (i), R <^a1> represents a hydrogen atom or a C1-C4 alkyl group.

X ^a1 represents a single bond, -X ^a2- , * -X ^a2 -O-, * -X ^a2 -S- or * -X ^a2 -NH-.

X ^a2 represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents the arm with O]

Content of the structural unit derived from (i), including the copolymer (henceforth "copolymer (VII)") which has a structural unit derived from the monomer (henceforth "(i)") represented by Is 0.1 mol% or more and 20 mol% or less, preferably 0.5 mol% or more and 15 mol% or less, and more preferably 1 mol% or more and 10 mol or less based on the total amount of the structural units constituting the copolymer (X1). % Or less

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

Examples of the alkanediyl group having 1 to 6 carbon atoms which represents X ^a2 include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, butane-1,4-diyl group, pentane-1, 5-diyl group, hexane-1, 6- diyl group, etc. are mentioned. X ^a2 is preferably an ethylene group.

R ^a1 is preferably a hydrogen atom or a methyl group.

X ^a1 is preferably a single bond, -X ^a2 -or * -X ^a2 -O-, and more preferably a single bond.

As (iii), for example, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the technical field, commonly referred to as "dicyclopentenyl (meth) acrylate") , 2- (tricyclo [5.2.1.0 ^2,6 ] decen-8-yloxy) ethyl (meth) acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] decene-8-ylsulfanyl) ethyl ( Meta) acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] decen-8-ylamino) ethyl (meth) acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] decene-8-ylsulphate Panyl) ethyl (meth) acrylate etc. are mentioned.

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, acrylic acid, methacrylic acid, maleic anhydride and the like are 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) is a monomer having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (X1-1) (hereinafter referred to as "(X11-1)"), and the 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 represent a single bond, -R ^b3- , * -R ^b3 -O-, * -R ^b3 -S- or * -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 these is preferable, and the compound represented by either of Formula (I-1), Formula (I-7), Formula (I-V), and 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) ) Is preferably a compound represented by any one, and more preferably a compound represented by any one of formulas (II-1), (II-7), (II-1) and (II-15).

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 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.

Furthermore, the copolymer (XI1) may have a structural unit derived from the monomer (hereinafter referred to as "(c)") different from (a), (iv), and (iv) and copolymerizable with these.

As (c), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, cyclo, for example Pentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art In the conventional name, it is called "dicyclopentanyl (meth) acrylate", "tricyclodecyl (meth) acrylate"), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) Acrylate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate (Meth) acrylic acid esters ;

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

Among them, in view of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] hepto 2-ene is preferred. Among these, vinyl toluene and N-cyclohexyl maleimide are more preferable because of excellent heat resistance.

When the copolymer (X1) is a copolymer composed of a structural unit derived from (i), a structural unit derived from (a) and a structural unit derived from (iii), the content ratio of the structural unit derived from each is Regarding the total amount of structural units constituting the coalescence,

structural units derived from (iii); 0.1 to 20 mol%

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

structural units derived from (iii); 35 to 95 mol%

Is preferred,

structural units derived from (iii); 1 to 10 mol%

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

structural units derived from (iii); 50 to 80 mol%

Is more preferable.

When the ratio of each structural unit is in the said range, since unexposed part peeling at the time of image development is suppressed in the composition layer formed from colored photosensitive resin composition, there exists a tendency for generation | occurrence | production of a foreign material to be small.

When copolymer (B1) is a copolymer which consists of a structural unit derived from (iii), the structural unit derived from (a), the structural unit derived from (iii), and the structural unit derived from (c), it originates in each The content rate of the structural unit to make is with respect to the total amount of the structural units which comprise the said copolymer,

structural units derived from (iii); 0.1 to 20 mol%

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

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

structural unit derived from (c); 2 to 80 mol%

Is preferred,

structural units derived from (iii); 1 to 10 mol%

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 65 mol%

Is more preferable.

When the ratio of each structural unit is in the said range, since unexposed part peeling at the time of image development is suppressed in the composition layer formed from colored photosensitive resin composition, there exists a tendency for generation | occurrence | production of a foreign material to be small.

The copolymer (B1) is described in, for example, the method described in the document "Experimental Method for Polymer Synthesis" (Otsu Takayuki, First Edition, First Edition, Issued March 1, 1972). It may be prepared with reference to the cited documents described.

Specifically, (a), (a), (iii) and, if necessary, a predetermined amount of (c), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, in a deoxygenated atmosphere by replacing oxygen with nitrogen. The method of heating and keeping warm while stirring 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 copolymer 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, by using the solvent (E) mentioned later as a solvent at the time of this superposition | polymerization, the solution after reaction can be used as it is, and a manufacturing process can be simplified.

The weight average molecular weight of polystyrene conversion of copolymer (X1) 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 the copolymer (B1) is preferably 1.1 to 6, more preferably 1.2 to 4.

The acid value of the copolymer (X1) 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 copolymer (X1) is preferably 2 to 65% by mass, more preferably 5 to 60% by mass, still more preferably 15 to 55% by mass relative to the total amount of solids.

When content of a copolymer (X1) exists in the said range, since the unexposed part peeling at the time of image development is suppressed in the composition layer formed from the coloring photosensitive resin composition, there exists a tendency for generation of a foreign material to be small.

Resin (B) may contain resin different from a copolymer (B1) (henceforth "resin (B2)"). Although resin (B2) is not specifically limited, It is preferable that it is alkali-soluble resin. Examples of the resin (B2) include the following resins [B1] to [B6] and the like.

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

Resin [2]: a copolymer of (a), (iii) and (c);

Resin [K3]: Copolymer with (a) and the monomer which can be copolymerized with (a) and differs from (a) and (v) (henceforth "(c ')");

Resin [K4]: Resin which (v) reacted with the copolymer of (a) and (c ');

Resin [K5]: Resin which (a) made to react the copolymer of (i) and (c ');

Resin [6]: Resin which (a) was made to react the copolymer of (i) and (c '), and the carboxylic anhydride was made to react.

Here, as (c '), the monomers illustrated by the above-mentioned (iv) and (c) are mentioned.

In resin [K1], the ratio of the structural unit derived from each 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 of resin [V1] 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 [K1] can be manufactured similarly to the method described as a manufacturing method of a copolymer (K1), for example.

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] 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, heat resistance, and mechanical strength of the obtained coloring pattern. have.

Resin [K2] can be manufactured similarly to the method described as a manufacturing method of a copolymer (X1), for example.

In resin [K3], the ratio of the structural unit derived from each is in the all the structural units which comprise resin [K3],

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

structural unit derived from (c '); 40 to 98 mol%

Is preferably,

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

structural unit derived from (c '); 50 to 90 mol%

More preferably.

Resin [K3] can be manufactured similarly to the method described as a manufacturing method of copolymer (X1), for example.

Resin [4] is obtained by obtaining the copolymer of (a) and (c '), and adding the C2-C4 cyclic ether which (b) has to the carboxylic acid and / or carboxylic anhydride which (a) has can do.

First, the copolymer of (a) and (c ') is manufactured similarly to the method described as a manufacturing method of copolymer (x1). In this case, it is preferable that the ratio of the structural unit derived from each is the same ratio as what was heard with resin [K3].

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

Subsequent to the preparation of the copolymer of (a) and (c '), the atmosphere in the flask was replaced with nitrogen from air, and (iii) a reaction catalyst of carboxylic acid or carboxylic anhydride with a cyclic ether [for example , Tris (dimethylaminomethyl) phenol and the like and a polymerization inhibitor (for example, hydroquinone) and the like are put in a flask and reacted at 60 to 130 ° C. for 1 to 10 hours to produce a resin [4]. can do.

The use amount of (iii) is preferably 5 to 80 moles, more preferably 10 to 75 moles, relative to 100 moles of (a). By setting it as this range, there exists a tendency for the balance of the storage stability of a coloring photosensitive resin composition, developability at the time of forming a coloring pattern, and the solvent resistance, heat resistance, mechanical strength, and the sensitivity of the coloring pattern obtained to become favorable. Since the reactivity of a cyclic ether is high and it is hard to remain unreacted (iv), as (v) used for resin [4], (b1) is preferable and (b1-1) is still more preferable.

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

Reaction conditions, such as a compounding method, reaction temperature, and time, can be suitably adjusted in consideration of the amount of heat generated by a manufacturing facility, polymerization, etc. In addition, the mixing method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, polymerization, and the like in the same manner as the polymerization conditions.

Resin [K5] obtains the copolymer of (b) and (c ') similarly to the method described as a manufacturing method of copolymer (x1) as a 1st step. In the same manner as described above, the obtained copolymer may be used as it is, the concentrated or diluted solution may be used, or the extracted copolymer may be used as a solid (powder) by a method such as reprecipitation.

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

structural units derived from (iii); 5 to 95 mol%

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

Is preferably,

structural units derived from (iii); 10 to 90 mol%

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

More preferably.

Furthermore, carboxylic acid or carboxylic anhydride which (a) has in the cyclic ether derived from (i) which the copolymer of (i) and (c ') has on the same conditions as the manufacturing method of resin [4]. By reacting, resin [K5] can be obtained.

As for the usage-amount of (a) made to react with said copolymer, 5-80 mol is preferable with respect to 100 mol of (iv). Since the reactivity of a cyclic ether is high and it is hard to remain unreacted, (b) is preferable as (b) used for resin [k5], and (b1-1) is still more preferable.

Resin [6] is resin which made carboxylic anhydride further react with resin [5]. The carboxylic anhydride is reacted with a hydroxy group generated by the reaction of the cyclic ether with carboxylic acid or carboxylic anhydride.

As the carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetra Hydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride), and the like. As for the usage-amount of carboxylic anhydride, 0.5-1 mol is preferable with respect to 1 mol of use of (a).

Specific examples of the resin (2) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymers, and 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid. Resins such as copolymers [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 ] decylacrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decylacrylate / (meth) acrylic acid / styrene copolymer, 3- Resins such as methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / N-cyclohexylmaleimide copolymer; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; Glycidyl (meth) to a resin in which glycidyl (meth) acrylate is added to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, and tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin, such as resin which added the acrylate and resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; Of resin which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins such as resins in which (meth) acrylic acid is reacted with a copolymer; Resins, such as resin which made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid reacted with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, etc. are mentioned. .

Such resin may be used independently or may use 2 or more types together.

Especially, as resin (B2), resin [K1], resin [K2], and resin [K3] are preferable.

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 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 (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.

Resin (B) may be only a copolymer (B1), but when it contains resin (B2), its content becomes like this. Preferably it is 1-95 mass% with respect to the total amount of resin, More preferably, it is 5- 90 mass%.

The content of the resin is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass relative to the total amount of solids. When content of resin 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. You may use a photopolymerizable compound (C) individually or in combination of 2 or more types.

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 and biimidazole compounds, and polymerization initiators containing O-acyl oxime compounds are preferable. More preferred are polymerization initiators comprising an O-acyl oxime compound and an alkylphenone compound.

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 (K) and a polymeric compound (C), More preferably, it is 1-20 mass parts. 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), the usage-amount thereof is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (K) and a polymeric compound (C), Preferably it is 1-20. It is a mass part. 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 Sulfoxide and the like.

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.

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. As such a solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionate ethyl, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and 4-hydride Roxy-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 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.). 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 R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, Mega Pack F443 (manufactured by DIC Corporation), and the like.

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, a coloring agent (A), resin (K), a polymeric compound (C), and a polymerization initiator (D), and a polymerization initiator (D1) and a solvent which can be used as needed. It can prepare by mixing (E), surfactant (F), and another component.

In the case of containing the pigment (A2), the pigment (A2) is previously mixed with the solvent (E), and dispersed using a beads mill or the like until the average particle diameter of the pigment is about 0.2 µm or less. desirable. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin as needed. The remainder of the resin (V) and the polymerizable compound (C), the remainder of the polymerization initiator (D), the solvent (E), the surfactant (F), other components, and the like, which are used as necessary, are obtained in the obtained pigment dispersion. By mixing, the desired colored photosensitive resin composition can be prepared.

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 0.01-10 micrometers of pore diameters.

<Manufacturing Method of Color Filter>

As a method of manufacturing the coloring patterning coating film (the "coloring patterning coating film" is simply described as "coloring pattern") of a color filter from the coloring photosensitive resin composition of this invention, the photolithographic method, the inkjet method, and the printing method Etc. can be mentioned. Among these, the photolithographic method is preferable. The photolithographic method is a method of applying the colored photosensitive resin composition to a substrate, drying to form a composition layer, exposing and developing the composition layer by sandwiching a photomask. In the photolithography method, the colored 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.

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.

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

First, a coloring photosensitive resin composition is apply | coated on a board | substrate, and volatile components, such as a solvent, are removed and dried by heat-drying (prebake) and / or vacuum drying, and a smooth composition layer is obtained.

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 the pressure of 50-150 Pa.

Although the film thickness of a composition layer is not specifically limited, It can adjust suitably according to the material to be used, the film thickness of a desired color filter, etc ..

Subsequently, the composition layer is exposed by sandwiching a photomask in order to form a target colored patterned coating film. Although the pattern on the said photomask is not specifically limited, The pattern according to the intended use can be used.

As a light source used for exposure, the light source which produces the light of the wavelength of 250-450 nm is preferable. For example, light below 350 nm can be cut using a filter that cuts this wavelength range, or a band pass filter can be used that extracts light around 436 nm, near 408 nm, and around 365 nm. May be selectively extracted. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

It is preferable to use exposure apparatuses, such as a mask aligner and a stepper, in order to irradiate a parallel light beam uniformly to the whole exposure surface or to perform the exact position combination of a photomask and a board | substrate.

A colored patterned coating film is formed on a board | substrate by developing the composition layer after exposure contacting with a developing solution. By development, the unexposed part of a composition layer melt | dissolves in a developing solution and is removed. As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, is preferable, for example. The 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, a spray method, and the like. Further, the substrate may be tilted at any angle during development.

It is preferable to wash with water after image development.

Furthermore, it is preferable to postbake to the obtained coloring pattern. 150-250 degreeC is preferable and, as for post-baking temperature, 160-235 degreeC is more preferable. The post-baking time is preferably 0.5 to 10 minutes, more preferably 1 to 5 minutes.

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

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

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. Then, it stirred for 5 hours and made it react at the same temperature. 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, dried under reduced pressure at 60 ° C, and dyes (A1-1) [formulas (A1-1-1) to (A2-2-2). Mixture of compounds represented by iv)] 11.3 parts was obtained.

Synthesis Example 2

In a flask equipped with a stirrer, a thermometer, a reflux cooler and a dropping funnel, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 268 parts of ethyl lactate was added thereto and heated to 70 ° C while stirring. Next, it is represented by 55 parts of acrylic acid, 81 parts of N-cyclohexyl maleimide, a compound represented by 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decyl acrylate [formula (I-1) and formula (II-1)] Compound at 50:50 in molar ratio] 224 parts and tricyclo [5.2.1.0 ^2.6 ] decen-8-ylacrylate [compound represented by formula (c-1) and compound represented by formula (c-2) Molar ratio of 50:50] 7 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 225 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 1.12 × 10 ⁴ , solid content 36.7%, and solid content acid value 119 mg-KOH / The copolymer solution (g11-1) which is g was obtained. The copolymer (XI1-1) has the following structural unit.

Synthesis Example 3

In a flask equipped with a stirrer, a thermometer, a reflux cooler and a dropping funnel, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 259 parts by mass of propylene glycol monomethyl ether acetate was added thereto and heated to 70 ° C while stirring. . Next, 56 parts by mass of acrylic acid, 83 parts of vinyltoluene, and 3,4-epoxy cicyclocyclo [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] 229 parts by mass and tricyclo [5.2.1.0 ^2.6 ] decen-8-ylacrylate [compound represented by formula (c-1) and compound represented by formula (c-2) in molar ratio 50:50] 8 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 the polymerization initiator solution dropwise addition has ended, 4 hours, kept at 70 ℃, cooled to room temperature Then, the weight average molecular weight (Mw) of 1.00 × 10 ^4, a solid content of 37.5% by weight and a solid content acid value of 107 mg-KOH The copolymer (X12) solution which is / g was obtained. The copolymer (X12) has the following structural unit.

Synthesis Example 4

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 263 parts by mass of ethyl lactate was added thereto and heated to 70 ° C while stirring. Subsequently, 67 parts by mass of methacrylic acid, 82 parts of N-cyclohexylmaleimide, a compound represented by 3,4-epoxycitcyclo [5.2.1.0 ^2.6 ] decyl acrylate [formula (I-1) and formula (II-1) ) 216 parts by mass] and tricyclo [5.2.1.0 ^2.6 ] decen-8-ylacrylate [compound represented by formula (c-1) and formula (c-2)] 7 parts by mass was dissolved in 140 parts by mass of ethyl lactate, 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 the polymerization initiator solution dropwise addition has ended, 4 hours, kept at 70 ℃, cooled to room temperature Then, the weight average molecular weight (Mw) of 9.8 × 10 ^3, the solid content 37.2% by weight and a solid content acid value of 110 mg-KOH A copolymer (X13-3) solution which was / g was obtained. The copolymer (13-3) has the following structural unit.

Synthesis Example 5

In a flask equipped with a stirrer, a thermometer, a reflux cooler, and a dropping funnel, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 258 parts by mass of propylene glycol monomethyl ether acetate was added thereto and heated to 70 ° C while stirring. . Next, 57 parts by mass of acrylic acid, 79 parts of vinyltoluene, and 3,4-epoxy cicyclocyclo [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] 222 parts by mass and tricyclo [5.2.1.0 ^2.6 ] decen-8-ylacrylate [compound represented by formula (c-1) and compound represented by formula (c-2) in molar ratio 50:50 mixed] 19 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 1.05 × 10 ⁴ , solid content 37.7 mass%, solid content acid value 106 mg-KOH The copolymer (X1-4) solution which is / g was obtained. The copolymer (X1-4) has the following structural unit.

Synthesis Example 6

In a flask equipped with a stirrer, a thermometer, a reflux cooler 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 thereto and heated to 70 ° C while stirring. . Next, 57 parts by mass of acrylic acid, 79 parts of vinyltoluene, and 3,4-epoxy cicyclocyclo [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] 204 parts by mass and tricyclo [5.2.1.0 ^2.6 ] decen-8-ylacrylate [compound represented by formula (c-1) and compound represented by formula (c-2) in molar ratio 50:50] 38 parts by mass of a propylene glycol monomethyl ether acetate was dissolved in 140 parts by mass 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 the polymerization initiator solution dropwise addition has ended, 4 hours, kept at 70 ℃, cooled to room temperature Then, the weight average molecular weight (Mw) of 1.10 × 10 ^4, a solid content of 37.8% by weight and a solid content acid value of 106 mg-KOH A copolymer (X1-5) solution which was / g was obtained. The copolymer (X1-5) has the following structural unit.

Synthesis Example 7

In a flask equipped with a stirrer, a thermometer, a reflux cooler and a dropping funnel, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 265 parts by mass of propylene glycol monomethyl ether acetate was added thereto and heated to 70 ° C while stirring. . Subsequently, 52 parts by mass of acrylic acid, 159 parts of benzyl methacrylate, 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decyl acrylate [a compound represented by formula (I-1) and a compound represented by formula (II-1) Mixed at a molar ratio of 50:50] 152 parts by mass and tricyclo [5.2.1.0 ^2.6 ] decen-8-ylacrylate [compound represented by formula (c-1) and compound represented by formula (c-2) Molar ratio of 50:50] 7 parts by mass was dissolved in 140 parts by mass of propylene glycol monomethyl ether acetate to prepare a solution. 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 1.10 × 10 ⁴ , solid content 37.0 mass%, solid content acid value 96 mg-KOH A copolymer (X16) solution which was / g was obtained. The copolymer (X16) has the following structural unit.

Synthesis Example 8

In a flask equipped with a reflux cooler, 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 (XII-1) solution having an acid value of 50 mg-KOH / g (the acid value in terms of solid content is 104 mgKOH / g) was obtained. Resin (B2-1) 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

[Preparation of Pigment Dispersion]

Colorant (A): C.I. Pigment Blue 15: 6 (pigment) 10.1 copies

6.5 parts of acrylic pigment dispersant

Solvent (E): 59 parts of propylene glycol monomethyl ether acetate

Solvent (E): 25 parts of ethyl lactate

Was mixed and the pigment dispersion liquid A was obtained by fully disperse | distributing a pigment using a bead mill.

[Preparation of Colored Photosensitive Resin Composition]

The components shown in Table 1 were mixed and the coloring photosensitive resin composition was obtained.

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

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

Coloring agent (A); (A2-1); Pigment Dispersion Obtained Above

Resin; (1-1); Copolymer (B1-1) solution

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

Resin; (V1-3); Copolymer (13) solution

Resin; (V1-4); Copolymer (X1-4) solution

Resin; (V1-5); Copolymer (B1-5) solution

Resin; (V1-6); Copolymer (B16) solution

Polymeric compound (C); (C-1); 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); (D1-1); 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); Ethyl lactate

Surfactant (F); (F-1); Polyether modified silicone oils [Torre Silicone SH8400; Torreda Corning Corporation]

Comparative example

C.I. Pigment Blue 15: 6 Part 20

Acrylic dispersant 5 parts

Propylene glycol monomethyl ether acetate 142 parts

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

Dye A1 3.5 parts

65 parts of resin solution

Dipentaerythritol hexaacrylate [KAYARAD (registered trademark) DPHA, manufactured by Nihon Kasei Co., Ltd.] 31 parts

N-benzoyloxy-1- (4-phenolsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE01; BASF Corporation] 9.3

136 parts ethyl lactate

Propylene glycol monomethyl ether 255 parts

By mixing, a coloring photosensitive resin composition was obtained.

Solubility Assessment

After apply | coating the coloring photosensitive composition by the spin coat method on a 2-inch square glass substrate (Eagle XG; the product made by Corning Corporation), a pressure reduction dryer [VCD; Microtech Co., Ltd.] was dried under reduced pressure at 50 Pa for 2 seconds. The aqueous developer containing 0.12% of nonionic surfactant and 2% of sodium carbonate was immersed in 23 degreeC for 20 second in the film | membrane after drying, and it wash | cleaned with water. The substrate after washing with water was subjected to a microscope [magnification 250 times; VF-7510; When the foreign material was not observed on the board | substrate after wash | cleaning with water made by Keyence Co., Ltd., and ○, the case where the foreign material was confirmed on the board | substrate after washing with water was shown in Table 2 as X. . If a foreign material is not confirmed on a board | substrate by this test, even if a colored pattern is formed on a board | substrate by the photolithographic method, it can be said that a foreign material was not confirmed on the board | substrate and a colored pattern.

[Production of colored pattern]

After apply | coating the coloring photosensitive resin composition on the 2-inch square glass substrate (Eggle XG; Corning Corporation make) by the spin coat method, it prebaked at 100 degreeC for 3 minutes, and formed the composition layer. After cooling, the interval between the substrate on which the composition layer was formed and the quartz glass photomask having a pattern was set to 100 m, and an exposure machine [TME-150RSK; Topcon Co., Ltd.] was used to irradiate light at an exposure amount (365 nm standard) of 150 mJ / cm 2 under an air atmosphere. Moreover, as a photomask, the mask in which the 100-micrometer line and space pattern was formed was used. The composition layer after light irradiation was developed by immersing in an aqueous developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 24 ° C. for 60 seconds, washed with water, and then post-baked at 230 ° C. for 30 minutes in an oven. , Coloring pattern was obtained.

[Film thickness measurement]

About the obtained coloring pattern, a film thickness was measured by a film thickness measuring apparatus [DEKTAK3; It was measured using Japan Vacuum Technology Co., Ltd. product. The results are shown in Table 2.

[Color evaluation]

About the coloring pattern on the obtained glass substrate, a colorimeter [OSP-SP-200; Spectroscopy was measured using Olympus Co., Ltd., and the xy chromaticity coordinates (x, y) and the brightness Y in the XYZ colorimeter of CIE were measured using the isochromatic coefficient of the C light source. The results are shown in Table 2.

[Production of Colored Coating Film]

After apply | coating the coloring photosensitive resin composition on the 2-inch square glass substrate (Eggle XG; Corning Corporation make) by the spin coat method, it prebaked at 100 degreeC for 3 minutes, and formed the composition layer. After cooling, the exposure machine [TME-150RSK; Topcon Co., Ltd.] was used to irradiate the entire surface with an exposure amount (365 nm standard) of 150 mJ / cm 2 under an air atmosphere. The composition layer after light irradiation was post-baked at 230 degreeC for 30 minutes in oven, and the coloring coating film was obtained.

[Heat resistance evaluation]

The obtained colored coating film was heated at 230 degreeC in oven for 2 hours. The xy chromaticity coordinates (x, y) and brightness Y are measured before and after heating, and the color difference ΔEab * is calculated from the measured value by the method described in JIS Z 8730: 2009 (7.Calculation method of color difference), and the results are shown in Table 2. Indicated. The smaller the value of ΔEab *, the smaller the color change.

In the coloring photosensitive resin composition of the Example, peeling by image development was suppressed at the time of colored pattern formation, and it was confirmed that a foreign material was not confirmed on the board | substrate after colored pattern formation. From this, a display device can be manufactured with high yield by using the coloring pattern obtained from the coloring photosensitive resin composition of this invention as a color filter.

According to the coloring photosensitive resin composition of this invention, a part of unexposed part of the composition layer formed from the said coloring photosensitive resin composition can be prevented from peeling at the time of image development, and the foreign material on a coloring pattern can be reduced.

Claims (4)

Containing a colorant, a resin, a polymerizable compound and a polymerization initiator,
The colorant comprises a dye,
The resin is a structural unit derived from at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, structural units derived from monomers having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond; , The copolymer containing the structural unit derived from the monomer represented by Formula (i),

In formula (i), R <^a1> represents a hydrogen atom or a C1-C4 alkyl group.
X ^a1 represents a single bond ^{(單結合), -X a2 -} , * represents an -X ^a2 -O-, -S- or ^a2 * -X * -X ^a2 -NH-.
X ^a2 represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a coupling arm with O]
The coloring photosensitive resin composition whose content of the structural unit derived from the monomer represented by said Formula (i) is 0.1 mol% or more and 20 mol% or less with respect to the structural unit whole quantity which comprises the said copolymer. The method of claim 1,
The coloring photosensitive resin composition in which the said coloring agent contains a pigment further. The color filter formed by the coloring photosensitive resin composition of Claim 1 or 2. A display device provided with the color filter of claim 3.