JP2013080097A - Colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition capable of reducing foreign materials on a colored pattern.SOLUTION: There is provided a colored photosensitive resin composition including a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant contains a dye. The resin contains a copolymer comprising: a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride; a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond; and a structural unit derived from a monomer represented by the formula (x) and the content of the structural unit derived from the monomer represented by the formula (x) is 0.1 mol% or more and 20 mol% or less based on the total amount of the structural units constituting the copolymer. (In the formula (x), Rrepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Xrepresents a single bond, -X-, *-X-O-, *-X-S- or *-X-NH-. Xrepresents an alkanediyl group having 1 to 6 carbon atoms, and * represents a bonding hand that is bonded to O.]

Description

  The present invention relates to a colored photosensitive resin composition.

Colored photosensitive resin compositions are used in the production of color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. As such a colored photosensitive resin composition, a colored photosensitive resin containing a copolymer of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate as a resin. A composition is known (Patent Document 1).

JP 2010-211198 A

  In order to form a colored pattern using a colored photosensitive resin composition, a colored photosensitive resin composition is applied to a substrate to form a composition layer, and the composition layer is exposed through a photomask and developed. Then, a photolithography method for obtaining a pattern is used. However, in the conventionally proposed colored photosensitive resin composition, during development, a part of the unexposed portion of the composition layer formed from the colored photosensitive resin composition is peeled off, and the peeled piece is In some cases, the particles adhere to the colored pattern and become foreign matter.

［式（ｘ）中、Ｒ^ａ１は、水素原子又は炭素数１〜４のアルキル基を表す。
Ｘ^ａ１は、単結合、−Ｘ^ａ２−、＊−Ｘ^ａ２−Ｏ−、＊−Ｘ^ａ２−Ｓ−又は＊−Ｘ^ａ２−ＮＨ−を表す。
Ｘ^ａ２は、炭素数１〜６のアルカンジイル基を表す。
＊はＯとの結合手を表す。］
で表される単量体に由来する構造単位とを含む共重合体を含む樹脂であり、
式（ｘ）で表される単量体に由来する構造単位の含有量が、該共重合体を構成する構造単位全量に対して、０．１モル％以上２０モル％以下である着色感光性樹脂組成物。 The present invention includes the following inventions.
[1] including a colorant, a resin, a polymerizable compound, and a polymerization initiator,
The colorant is a colorant containing a dye,
A monomer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond A structural unit derived from the formula (x)

[In formula (x), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
X ^a1 represents a single ^{bond, -X a2 -, * - X} a2 -O -, * - X a2 -S- or ^* -X represents an a2 -NH-.
X ^a2 represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]
A resin including a copolymer containing a structural unit derived from a monomer represented by:
Colored photosensitivity wherein the content of the structural unit derived from the monomer represented by the formula (x) is 0.1 mol% or more and 20 mol% or less with respect to the total amount of the structural unit constituting the copolymer. Resin composition.

[2] The colored photosensitive resin composition according to [1], wherein the colorant further includes a pigment.
[3] A color filter formed from the colored photosensitive resin composition according to [1] or [2].
[4] A display device including the color filter according to [3].

  According to the colored photosensitive resin composition of the present invention, a part of the unexposed portion of the composition layer formed from the colored photosensitive resin composition is prevented from peeling during development, and foreign matter on the colored pattern is reduced. can do.

［式（ｘ）中、Ｒ^ａ１は、水素原子又は炭素数１〜４のアルキル基を表す。
Ｘ^ａ１は、単結合、−Ｘ^ａ２−、＊−Ｘ^ａ２−Ｏ−、＊−Ｘ^ａ２−Ｓ−又は＊−Ｘ^ａ２−ＮＨ−を表す。
Ｘ^ａ２は、炭素数１〜６のアルカンジイル基を表す。
＊はＯとの結合手を表す。］
で表される単量体に由来する構造単位との共重合体を含む樹脂である。
本発明の着色感光性樹脂組成物は、さらに、溶剤（Ｅ）を含むことが好ましい。
また、本発明の着色感光性樹脂組成物は、必要に応じて、重合開始剤（Ｄ１）及び界面活性剤（Ｆ）からなる群から選ばれる少なくとも１種を含んでもよい。
尚、前記各成分は、特に断りが無い限り、１種を単独で使用してもよく、２種以上を併用してもよい。 The colored photosensitive resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
The colorant (A) is a colorant containing a dye (A1),
The resin (B) has a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond. A structural unit derived from a monomer and the formula (x)

[In formula (x), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
X ^a1 represents a single ^{bond, -X a2 -, * - X} a2 -O -, * - X a2 -S- or ^* -X represents an a2 -NH-.
X ^a2 represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]
It is resin containing the copolymer with the structural unit derived from the monomer represented by these.
The colored photosensitive resin composition of the present invention preferably further contains a solvent (E).
Moreover, the colored photosensitive resin composition of this invention may contain at least 1 sort (s) chosen from the group which consists of a polymerization initiator (D1) and surfactant (F) as needed.
In addition, 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.

<Colorant (A)>
Examples of the colorant (A) include a dye (A1) and a pigment (A2).

The dye (A1) is not particularly limited, and a known dye can be used. Examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like, and dyes that are soluble in an organic solvent are preferable.
Examples of the dye (A1) include compounds classified as dyes by the Color Index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (Color Dyeing). Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 117, 162, 163, 167, 189;
C. I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent orange 2, 7, 11, 15, 26, 56, 77, 86;
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. I. Solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 41 , 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. Acid Green 1, 3, 5, 9, 16, 25, 27, 28, 41, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. I. Acid dyes,

C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 40, 41, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243 244,245,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse violet 26, 27;
C. I. Disperse Blue 1, 14, 56, 60;
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68;
C. I. C. such as Basic Green 1; I. Basic dyes C.I. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. Reactive Red 36; I. Reactive dyes C.I. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Modern dyes C.I. I. C. of Bat Green 1 etc. I. Examples include vat dyes.
These dyes may be appropriately selected according to the desired spectral spectrum of the color filter.

As the dye (A1), a xanthene dye (Aa) is preferable.
The xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (Aa) include C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted, and only the number is described), 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A, xanthene dyes described in Japanese Patent No. 4492760, and the like. Those that are soluble in organic solvents are preferred.

  Among these, as the xanthene dye (Aa), a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable. When using the compound (1a), the content of the compound (1a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye (Aa).

［式（１ａ）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子、−Ｒ⁸又は置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基を表す。Ｒ¹及びＲ^２は、一緒になって窒素原子を含む環を形成してもよく、Ｒ^３及びＲ^４は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ⁵は、−ＯＨ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜５の整数を表す。ｍが２以上の整数である場合、複数のＲ⁵は同一であるか相異なる。
ａは、０又は１の整数を表す。
Ｘは、ハロゲン原子を表す。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ⁹及びＲ¹⁰は、それぞれ独立に、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表し、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子を含んだ３〜１０員環の複素環を形成していてもよい。
Ｒ¹¹は、それぞれ独立に、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］

[In Formula (1a), R ^{1 to} R ⁴ each independently represents a hydrogen atom, —R ^8, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms that may have a substituent. . R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined to form a ring containing 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 represents NR ⁹ R ¹⁰
R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ are the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ 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 contain a nitrogen atom and a 3 to 10 member A heterocyclic ring may be formed.
R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms representing R ^{1 to} R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group.

In the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms representing R ^{1 to} R ⁴ , the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, —R ⁸ , —OH, —OR ⁸ , _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z +, -CO 2 H, -CO 2 R 8, -SR 8, be substituted by -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ Also good. Among these _{^{substituents, -SO 3 -, -SO 3 H}} , -SO 3 - is preferably at least one selected from Z ⁺ and the group consisting of _{^{-SO 2 NR 9 R 10, -SO}} 3 - Z + and More preferred is at least one selected from the group consisting of —SO ₂ NR ⁹ R ¹⁰ . In this case, —SO ₃ ^{− +} N (R ¹¹ ) ₄ is preferable as —SO ₃ ⁻ Z ⁺ . When R ^{1 to} R ⁴ are these groups, the colored photosensitive resin composition containing the compound (1a) can form a color filter with less generation of foreign matters and excellent heat resistance.
R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined to form a ring containing a nitrogen atom. Examples of the ring containing a nitrogen atom include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms representing R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, Linear alkyl groups such as decyl group, dodecyl group, hexadecyl group, icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, are mentioned.

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

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

Examples of —SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes, 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-butylsulfamoyl 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-hexylsulfamoyl N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2, , 2-tetramethylbutyl) sulfamoyl group and the like N-1 substituted sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2-substituted sulfamoyl groups such as a group.

In the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms representing R ⁹ and R ¹⁰ , a hydrogen atom contained in the saturated hydrocarbon group may be substituted with —OH or a halogen atom, and the saturated —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —CO—, —NH— or —NR ⁸ —.

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

The alkyl group having 1 to 6 carbon atoms that represents the R ⁶ and R ^7, of the linear alkyl groups and branched alkyl groups listed above, include those having 1 to 6 carbon atoms.

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

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .
As the ⁺ N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable. When R ¹¹ is these groups, the colored photosensitive resin composition containing the compound (1a) can form a color filter with few foreign matters.

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

  As the xanthene dye (Aa), a dye containing a compound represented by the formula (2a) (hereinafter sometimes referred to as “compound (2a)”) is more preferable. When the compound (2a) is used, the content of the compound (2a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more.

［式（２ａ）中、Ｒ²¹〜Ｒ²⁴は、それぞれ独立に、水素原子、−Ｒ²⁶又は炭素数６〜１０の１価の置換基を有していてもよい芳香族炭化水素基を表す。Ｒ²¹及びＲ²²は、一緒になって窒素原子を含む環を形成してもよく、Ｒ²³及びＲ²⁴は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ²⁵は、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ１⁺又は−ＳＯ₂ＮＨＲ²⁶を表す。
ｍ１は、０〜５の整数を表す。ｍ１が２以上の整数である場合、複数のＲ²⁵は同一であるか相異なる。
ａ１は、０又は１の整数を表す。
Ｘ１は、ハロゲン原子を表す。
Ｒ²⁶は、炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｚ１⁺は、⁺Ｎ（Ｒ²⁷）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ²⁷は、それぞれ独立に、炭素数１〜２０の１価の飽和炭化水素基又はベンジル基を表す。］

[In Formula (2a), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, —R ^26, or an aromatic hydrocarbon group that may have a monovalent substituent having 6 to 10 carbon atoms. . R ²¹ and R ²² may together form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may together form a ring containing a nitrogen atom.
R ²⁵ is, -SO ₃ ^- represents a Z1 ⁺ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.
m1 represents the integer of 0-5. When m1 is an integer of 2 or more, the plurality of R ²⁵ are the same or different.
a1 represents an 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 ⁺ .
R ²⁷ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms representing R ^{21 to} R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group in R ^{1 to} R ⁴ . Hydrogen atoms contained in the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, may be substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ^26.
As a combination of R ^{21 to} R ²⁴ , 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 aromatic hydrocarbons hydrogen atoms contained in the _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, those substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ preferred. A more preferred combination is that 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 hydrogen contained in the aromatic hydrocarbon group atom, -SO ₃ ^- in which are substituted with Z1 ⁺ or -SO ₂ NHR ^26.
R ²¹ and R ²² together form an aliphatic heterocyclic ring containing a nitrogen atom, and R ²³ and R ²⁴ together form an aliphatic heterocyclic ring containing a nitrogen atom. preferable.
When R ^{21 to} R ²⁴ are these groups, the colored photosensitive resin composition containing the compound (2a) can form a color filter having excellent heat resistance.

Examples of the aliphatic heterocycle include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms representing R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group in R ^{8 to} R ¹¹ .
-R ²⁶ in R ²¹ to R ²⁴ each independently represent a hydrogen atom, a methyl group or an ethyl group. As the R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ^26, preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, A 2-ethylhexyl group is more preferred. When R ²⁶ is these groups, the colored photosensitive resin composition containing the compound (2a) can form a color filter with less generation of foreign matters.

Z1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .
As the ⁺ N (R ²⁷ ) ₄ , at least two of the four R ²⁷ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ²⁷ is preferably 20 to 80, 20 to 60 is more preferable. The colored photosensitive resin composition containing the compound (2a) in which R ²⁷ is any of these groups can form a color filter with less generation of foreign matters.

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

Examples of the compound (2a) include compounds represented by the formula (1-1) to the formula (1-24). In the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. Among these, C.I. I. Acid red 289 sulfonamidation product, C.I. I. Quaternary ammonium salt of Acid Red 289, C.I. I. Acid violet 102 sulfonamidate or C.I. I. The quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12).

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

［式（３ａ）中、Ｒ³¹及びＲ³²は、互いに独立に、炭素数１〜４のアルキル基を表す。
Ｒ³³及びＲ³⁴は、互いに独立に、炭素数１〜４のアルキル基、炭素数１〜４のアルキルスルファニル基又は炭素数１〜４のアルキルスルホニル基を表す。
Ｒ³¹及びＲ³³は、一緒になって窒素原子を含む環を形成してもよく、Ｒ³²及びＲ³⁴は、一緒になって窒素原子を含む環を形成してもよい。
ｐ及びｑは、互いに独立に、０〜５の整数を表す。ｐが２以上である場合、複数のＲ³³は同一でも異なってもよく、ｑが２以上である場合、複数のＲ³⁴は同一でも異なってもよい。］

[In formula (3a), R ³¹ and R ³² each independently represent an alkyl group having 1 to 4 carbon atoms.
R ^<33> and R ^<34 > represent a C1-C4 alkyl group, a C1-C4 alkylsulfanyl group, or a C1-C4 alkylsulfonyl group mutually independently.
R ³¹ and R ³³ may be combined to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be combined to form a ring containing a nitrogen atom.
p and q represent the integer of 0-5 mutually independently. When p is 2 or more, the plurality of R ³³ may be the same or different, and when q is 2 or more, the plurality of R ³⁴ may be the same or different. ]

Examples of the alkyl group having 1 to 4 carbon atoms representing R ³¹ , R ³² , R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Groups and the like.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms representing R ³³ and R ³⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms representing R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
R ³¹ and R ³² are preferably, independently of each other, a methyl group 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.
m and n are preferably integers of 0 to 2, and are preferably 0 or 1.

  Examples of compound (3a) include compounds represented by formula (1-25) to formula (1-31), respectively. Especially, the compound represented by Formula (1-25) is preferable at the point which is excellent in the solubility to an organic solvent.

  As the xanthene dye (Aa), a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) may be used. it can. Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using the commercially available xanthene dye as a starting material.

Examples of the pigment (A2) include compounds classified as pigments according to the color index (published by The Society of Dyers and Colorists).
Examples of the pigment include C.I. 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. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
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. Pigments;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, 80; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

When the colored photosensitive resin composition of the present invention is prepared as a blue colored photosensitive resin composition, the pigment is C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and the like, and C.I. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38 are preferred. I. Pigment blue 15: 3, 15: 6 and C.I. I. Pigment Violet 23 is more preferable, and C.I. I. Pigment Blue 15: 6 is more preferable.
When the colored photosensitive resin composition of the present invention is prepared as a green colored photosensitive resin composition, the pigment is C.I. I. Green pigments such as CI Pigment Green 7, 36, and 58; I. Yellow pigments such as CI Pigment Yellow 138, 139 and 150 are preferred.
When the colored photosensitive resin composition of the present invention is prepared as a red colored photosensitive resin composition, the pigment is C.I. I. Red pigments such as C.I. Pigment Red 177, 209, 242, 254, 255; I. Orange pigments such as CI Pigment Orange 38, 43, 71, and C.I. I. Yellow pigments such as CI Pigment Yellow 138, 139 and 150 are preferred.
By including the pigment, it is easy to optimize the transmission spectrum, and the light resistance and chemical resistance of the color filter are improved.

Pigment (A2) is optionally treated with rosin, surface treatment using a pigment derivative having an acidic group or basic group introduced, grafting onto the pigment surface with a polymer compound, sulfuric acid atomization method, etc. May be subjected to the atomization treatment by, cleaning treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like.
The pigment (A2) preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), and Ajispur (Ajinomoto Fine). (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less with respect to the pigment (A2). When the amount of the pigment dispersant used is in the above range, a pigment dispersion with a uniform dispersion tends to be obtained.

  The colorant (A) preferably contains a dye (A1) and a pigment (A2). In this case, the content ratio of the dye (A1) and the pigment (A2) is preferably from 1:99 to 99: 1, more preferably from 3:97 to 90:10, based on mass. By setting such a ratio, the transmission spectrum can be easily optimized, and the resulting color filter tends to be excellent in contrast, brightness, heat resistance, and chemical resistance.

  In particular, the colorant (A) is preferably a colorant containing a xanthene dye (Aa) and a blue pigment. I. A coloring agent containing CI Pigment Blue 15: 6 is more preferable. The content ratio of the xanthene dye (Aa) and the blue pigment is, on a mass basis, preferably 1:99 to 90:10, more preferably 2:98 to 70:30, and further preferably 2:98 to 50:50.

The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 50% by mass, and further preferably 10 to 40% by mass with respect to the total amount of the solid content. When the content of the colorant (A) is within the above range, the color density when it is used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a necessary amount in the composition. Therefore, a color filter having sufficient mechanical strength can be formed.
Here, the “total amount of solids” in this specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored photosensitive resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

［式（ｘ）中、Ｒ^ａ１は、水素原子又は炭素数１〜４のアルキル基を表す。
Ｘ^ａ１は、単結合、−Ｘ^ａ２−、＊−Ｘ^ａ２−Ｏ−、＊−Ｘ^ａ２−Ｓ−又は＊−Ｘ^ａ２−ＮＨ−を表す。
Ｘ^ａ２は、炭素数１〜６のアルカンジイル基を表す。
＊はＯとの結合手を表す。］
で表される単量体（以下「（ｘ）」という場合がある）に由来する構造単位とを有する共重合体（以下「共重合体（Ｂ１）」という場合がある）を含み、（ｘ）に由来する構造単位の含有量は、該共重合体（Ｂ１）を構成する構造単位全量に対して、０．１モル％以上２０モル％以下であり、好ましくは０．５モル％以上１５モル％以下、より好ましくは１モル％以上１０モル％以下である。 <Resin (B)>
The resin (B) is a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and has 2 to 4 carbon atoms. A structural unit derived from a monomer having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”), and the formula (x)

[In formula (x), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
X ^a1 represents a single ^{bond, -X a2 -, * - X} a2 -O -, * - X a2 -S- or ^* -X represents an a2 -NH-.
X ^a2 represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]
And a copolymer having a structural unit derived from a monomer represented by (hereinafter sometimes referred to as “(x)”) (hereinafter sometimes referred to as “copolymer (B1)”), (x The content of the structural unit derived from) is from 0.1 mol% to 20 mol%, preferably from 0.5 mol% to 15 mol, with respect to the total amount of the structural unit constituting the copolymer (B1). The mol% or less, more preferably 1 mol% or more and 10 mol% 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.

The alkanediyl group having 1 to 6 carbon atoms representing the X ^a2, methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl, butane-1,4-diyl group, pentane -1,5-diyl group, hexane-1,6-diyl group, and the like. 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.

(X) is, for example, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in this technical field, the common name is “dicyclopentenyl (meth) acrylate”) 2- (tricyclo [5.2.1.0 ^2,6 ] decene-8-yloxy) ethyl (meth) acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] decene -8-ylsulfanyl) ethyl (meth) 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-ylsulfanyl) ethyl (meth) acrylate.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.
In the present specification, “(meth) acryloyl” represents at least one selected from the group consisting of acryloyl and methacryloyl. Notations such as “(meth) acrylic acid” and “(meth) acrylate” have the same meaning.

  (B) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.

  Examples of (b) include a monomer (a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

  (B1) is, for example, a monomer (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter may be referred to as “(b1-2)”).

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (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- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) Examples thereof include compounds and compounds represented by formula (II).

[In Formula (I) and Formula (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
X ^b1 and X ^b2 represents a single ^{bond, -R b3 -, * - R} b3 -O -, * - R b3 -S- or * -R ^b3 represents a -NH-.
R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
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, more preferably a hydrogen atom and a methyl group.

Examples of alkanediyl groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
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—, more preferably a single bond, * —CH _2. CH ₂ —O— (* represents a bond with O).

  Examples of the compound represented by the formula (I) include compounds represented by any one of the formulas (I-1) to (I-15). Among them, Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), and Formula (I-11) to Formula (I-15) A compound represented by any one of formula (I-1), formula (I-7), formula (I-9) and formula (I-15) is more preferred.

  Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) and formula (II-11) to formula (II-15) A compound represented by any one of formulas (II-1), (II-7), (II-9) and (II-15) is more preferred.

  The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or as a mixture in any ratio. When used as a mixture, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 5 on a molar basis. 90:10, more preferably 20:80 to 80:20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

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

  (B) is preferably (b1) in that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferable in that the storage stability of the colored photosensitive resin composition is excellent.

Further, the copolymer (B1) is different from (a), (b) and (x) and is derived from a monomer copolymerizable with these (hereinafter sometimes referred to as “(c)”). You may have a structural unit.
Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclopentyl (meth) acrylate, Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, “dicyclopenta Nyl (meth) acrylate "and sometimes" tricyclodecyl (meth) acrylate "), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) Acrylate, allyl (meth) a Relate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) (meth) acrylic acid esters such as acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;

  Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2. .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

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

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, and 2,3-dimethyl-1,3-butadiene.
Of these, styrene, vinyltoluene, benzyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept from the viewpoints of copolymerization reactivity and heat resistance. 2-ene and the like are preferable. Of these, vinyltoluene and N-cyclohexylmaleimide are more preferable because of excellent heat resistance.

When the copolymer (B1) is a copolymer comprising a structural unit derived from (x), a structural unit derived from (a), and a structural unit derived from (b), The content ratio is based on the total amount of structural units constituting the copolymer.
Structural unit derived from (x); 0.1 to 20 mol%
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 35-95 mol%
Is preferred,
Structural unit derived from (x); 1 to 10 mol%
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 50 to 80 mol%
Is more preferable.
When the ratio of each structural unit is within the above range, in the composition layer formed from the colored photosensitive resin composition, unexposed part peeling at the time of development is suppressed, and the generation of foreign matters tends to be reduced. There is.

The copolymer (B1) is a copolymer comprising a structural unit derived from (x), a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from (c). In this case, the content ratio of the structural units derived from each is based on the total amount of structural units constituting the copolymer,
Structural unit derived from (x); 0.1 to 20 mol%
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 2 to 80 mol%
Is preferred,
Structural unit derived from (x); 1 to 10 mol%
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5-65 mol%
Is more preferable.
When the ratio of each structural unit is within the above range, in the composition layer formed from the colored photosensitive resin composition, unexposed part peeling at the time of development is suppressed, and the generation of foreign matters tends to be reduced. There is.

  The copolymer (B1) can be prepared by, for example, the method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and It can manufacture with reference to the cited reference described in the said literature.

  Specifically, a predetermined amount of (x), (a), (b) and, if necessary, (c), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, nitrogen is substituted with oxygen. Thus, there is a method of heating and keeping warm while stirring in a deoxygenated atmosphere. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) As the solvent, any solvent that dissolves each monomer may be used, and examples of the solvent for the colored photosensitive resin composition include a solvent (E) described later.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using a solvent (E) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

The polystyrene equivalent weight average molecular weight of the copolymer (B1) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. It is. When the molecular weight is in the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer is good, and 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, and more preferably 1.2 to 4.

  The acid value of the copolymer (B1) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150, and still more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

  The content of the copolymer (B1) is preferably 2 to 65% by mass, more preferably 5 to 60% by mass, and further preferably 15 to 55% by mass with respect to the total amount of the solid content. . When the content of the copolymer (B1) is within the above range, in the composition layer formed from the colored photosensitive resin composition, unexposed part peeling at the time of development is suppressed. There is a tendency to decrease.

The resin (B) may include a resin different from the copolymer (B1) (hereinafter sometimes referred to as “resin (B2)”). The resin (B2) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B2) include the following resins [K1] to [K6].
Resin [K1]: Copolymer of (a) and (b);
Resin [K2]: Copolymer of (a), (b) and (c);
Resin [K3]: a copolymer of (a) and a monomer that is copolymerizable with (a) and that is different from (a) and (b) (hereinafter sometimes referred to as “(c ′)”) Polymer;
Resin [K4]: a resin obtained by reacting (b) with a copolymer of (a) and (c ′);
Resin [K5]: a resin obtained by reacting (a) with a copolymer of (b) and (c ′);
Resin [K6]: A resin obtained by reacting (a) with a copolymer of (b) and (c ′) and further reacting with a carboxylic acid anhydride.
Here, examples of (c ′) include the monomers exemplified in the above (x) and (c).

In the resin [K1], the ratio of the structural units derived from each is relative to all the structural units constituting the resin [K1].
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40-98 mol%
Is preferred,
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%
Is more preferable.
When the ratio of the structural unit of the resin [K1] is in the above range, the colored photosensitive resin composition is excellent in storage stability, developability when forming a colored pattern, and solvent resistance of the resulting colored pattern. Tend.

  Resin [K1] can be produced, for example, in the same manner as described for the production method of copolymer (B1).

In the resin [K2], the ratio of the structural units derived from each of the structural units in the resin [K2]
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored photosensitive resin composition, the developability when forming the colored pattern, and the solvent resistance of the resulting colored pattern, There is a tendency to be excellent in heat resistance and mechanical strength.

  Resin [K2] can be produced, for example, in the same manner as described for the production method of copolymer (B1).

In the resin [K3], the proportion of structural units derived from each of the structural units constituting the resin [K3]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (c ′); 40 to 98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (c ′); 50-90 mol%
It is more preferable that
Resin [K3] can be produced, for example, in the same manner as described in the method for producing copolymer (B1).

Resin [K4] obtains a copolymer of (a) and (c ′), and (b) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms. It can be manufactured by adding to a product.
First, a copolymer of (a) and (c ′) is produced in the same manner as the method described as the production method of the copolymer (B1). In this case, it is preferable that the ratio of the structural units derived from each is the same as that described for the resin [K3].

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c ′), the atmosphere in the flask is replaced with nitrogen to air, and (b) a reaction catalyst (for example, tris) of carboxylic acid or carboxylic anhydride and cyclic ether is used. (Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4]. Can do.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By making it in this range, the storage stability of the colored photosensitive resin composition, the developability when forming the colored pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting colored pattern are good. Tend to be. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c ′). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c ′).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5] obtains a copolymer of (b) and (c ′) as the first step, as in the method described as the method for producing copolymer (B1). Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c ′) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol%
Structural unit derived from (c ′); 5-95 mol%
It is preferable that
Structural unit derived from (b); 10-90 mol%
Structural unit derived from (c ′); 10 to 90 mol%
It is more preferable that

Furthermore, the carboxylic acid or carboxylic acid possessed by (a) is added to the cyclic ether derived from (b) possessed by the copolymer of (b) and (c ′) under the same conditions as in the resin [K4] production method. Resin [K5] can be obtained by reacting an anhydride.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (highmic acid anhydride) and the like. It is done. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specific examples of the resin (B2) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6] decyl acrylate / (meth) acrylic acid / styrene copolymer, 3-methyl-3- (meth) Akuriruro Resin such as ruoxymethyloxetane / (meth) acrylic acid / N-cyclohexylmaleimide copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer Resin [K3] such as benzyl (meth) acrylate / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resins such as a resin obtained by adding glycidyl (meth) acrylate to a coalescence, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer [ K4]; tricyclodecyl (meth) acrylate / glycidyl (meth) acryl Such as a resin obtained by reacting (meth) acrylic acid with a copolymer of silicate, a resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate, etc. Resin [K5]; Resin such as a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and further tetrahydrophthalic anhydride [K6] ] Etc. are mentioned.
These resins may be used alone or in combination of two or more.

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

The polystyrene equivalent weight average molecular weight of the resin (B2) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer is good, and the resolution tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B2) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value of the resin (B2) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150, and still more preferably 70 to 135 mg-KOH / g.

  The resin (B) may be only the copolymer (B1), but when the resin (B2) is included, the content thereof is preferably 1 to 95% by mass with respect to the total amount of the resin (B). Preferably it is 5-90 mass%.

  Content of resin (B) becomes like this. Preferably it 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 the content of the resin (B) is within the above range, the resolution of the coloring pattern and the remaining film rate tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by heat or an active radical and / or acid generated from the polymerization initiator (D). For example, a compound having a polymerizable ethylenically unsaturated bond is used. Preferably, it is a (meth) acrylic acid ester compound.

Among these, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. The photopolymerizable compound (C) may be used alone or in combination of two or more.
Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

  The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. is there. When the content of the polymerizable compound (C) is in the above range, the remaining film ratio and chemical resistance of the colored pattern tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as 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 initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acyl phosphine oxide compounds, O-acyl oxime compounds, biimidazole compounds, and the like, and polymerization initiators containing O-acyl oxime compounds are preferred. A polymerization initiator containing an acyloxime compound and an alkylphenone compound is more preferable.

Ｏ−アシルオキシム化合物としては、例えば、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュア（登録商標）ＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。 The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-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-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used.

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.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Etc. Commercial products such as Irgacure (registered trademark) 369, 907 and 379 (manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -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) Thenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-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 (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913).

  Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, Examples thereof include benzoin tosylate.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator (D) is in the above range, the sensitivity is increased and the exposure time tends to be shortened, so that productivity is improved.

In addition to the polymerization initiator (D), a polymerization initiation assistant (D1) may further be included. The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the photopolymerizable compound that has been polymerized by the polymerization initiator.
Examples of the polymerization initiation assistant (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds, with thioxanthone compounds being preferred.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone and the like, and 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

  Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

  When these polymerization initiation assistants (D1) are used, the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent, aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc. Is mentioned.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol 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, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, and the like phenetol and methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 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 monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. Etc.

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

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

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

  Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Such solvents include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and 4-hydroxy-4-methyl- 2-Pentanone is preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferred.

  Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of a coloring photosensitive resin composition, More preferably, it is 75-92 mass%. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

<Surfactant (F)>
Examples of the surfactant (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) Can be mentioned.

  Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass or more and 0.00% by mass or less with respect to the total amount of the colored photosensitive resin composition. It is 1 mass% or less, More preferably, it is 0.01 mass% or more and 0.05 mass% or less. This content does not include the content of the pigment dispersant. When the content of the surfactant (F) is in the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored photosensitive resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a polymerization initiation assistant used as necessary ( D1), the solvent (E), the surfactant (F) and other components can be mixed.
When the pigment (A2) is included, the pigment (A2) is preferably mixed with the solvent (E) in advance and dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. In the obtained pigment dispersion, the remainder of the resin (B) and the polymerizable compound (C), the polymerization initiator (D) used as necessary, the remainder of the solvent (E), the surfactant (F ) And other components and the like are mixed so as to have a predetermined concentration, whereby the desired colored photosensitive resin composition can be prepared.
When the dye (A1) is contained, the dye (A1) may be previously dissolved in the solvent (E). The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.
The colored photosensitive resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of a method for producing a color filter color pattern from the colored photosensitive resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored photosensitive resin composition is applied to a substrate and dried to form a composition layer, and the composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the composition layer can be formed by not using a photomask and / or not developing during exposure.
The film thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted according to the purpose and application. ~ 6 μm.

  As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored photosensitive resin composition is applied onto a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent and drying to obtain a smooth composition layer.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the composition layer is not particularly limited, and can be appropriately adjusted according to the material used, the desired film thickness of the color filter, and the like.

Next, the composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
It is preferable to use an exposure apparatus such as a mask aligner and a stepper because the entire exposure surface can be irradiated with parallel rays uniformly and accurate alignment between the photomask and the substrate can be performed.

By developing the exposed composition layer in contact with a developer, a colored pattern is formed on the substrate. By the development, the unexposed portion of the composition layer is dissolved and removed in the developer. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

  Furthermore, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 0.5 to 10 minutes, and more preferably 1 to 5 minutes.

The colored pattern and the colored coating film thus obtained are useful as a color filter.
According to the colored photosensitive resin composition of the present invention, a color filter with particularly few surface foreign matters can be produced. Therefore, the color filter can be used for display devices (for example, liquid crystal display devices, organic EL devices, etc.), electronic paper. It is useful as a color filter used for a solid-state imaging device or the like.

  Next, the present invention will be described more specifically with reference to examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

[Synthesis Example 1]
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 Chugai Kasei Co., Ltd.) 15 in a flask equipped with a condenser and a stirrer. Part, 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added dropwise and 10.9 parts of thionyl chloride was added dropwise while maintaining at 20 ° C. or lower with stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. Precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and represented by dye (A1-1) (formula (A1-1-1) to formula (A2-2-8). 11.3 parts of a mixture of compounds to be obtained.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０部を乳酸エチル２２５部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、重量平均分子量Ｍｗは、１．１２×１０^４、固形分３６．７％、固形分酸価１１９ｍｇ−ＫＯＨ／ｇの共重合体（Ｂ１−１）溶液を得た。共重合体（Ｂ１−１）は、下記の構造単位を有する。

[Synthesis Example 2]
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel to form a nitrogen atmosphere. Next, 55 parts of acrylic acid, 81 parts of N-cyclohexylmaleimide, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and formula ( II-1) is mixed at a molar ratio of 50:50.) 224 parts, as well as tricyclo [5.2.1.0 ^2.6 ] decen-8-yl acrylate (formula (c- The compound represented by 1) and the compound represented by formula (c-2) are mixed at a molar ratio of 50:50.) A solution is prepared by dissolving 7 parts in 140 parts of ethyl lactate, The solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel.

On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After completion of dropping of the polymerization initiator solution, the solution 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%, solid content. A copolymer (B1-1) solution having an acid value of 119 mg-KOH / g was obtained. The copolymer (B1-1) has the following structural units.

[Synthesis Example 3]
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel to form a nitrogen atmosphere. Heated. Next, 56 parts by mass of acrylic acid, 83 parts of vinyl toluene, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and formula (II) -1) is mixed at a molar ratio of 50:50.) 229 parts by mass and tricyclo [5.2.1.0 ^2.6 ] decen-8-yl acrylate (formula (c- The compound represented by 1) and the compound represented by formula (c-2) are mixed at a molar ratio of 50:50.) 8 parts by mass is dissolved in 140 parts by mass of propylene glycol monomethyl ether acetate And the solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel. On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of propylene glycol monomethyl ether acetate was added to a flask using another dropping funnel over 4 hours. It was dripped in. After the addition of the solution of the polymerization initiator is completed, 4 hours, kept at 70 ° C., then cooled to room temperature, and the weight average molecular weight Mw, 1.00 × 10 ^4, solid content 37.5 wt%, solid A copolymer (B1-2) solution having a partial acid value of 107 mg-KOH / g was obtained. The copolymer (B1-2) has the following structural units.

[Synthesis Example 4]
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel to form a nitrogen atmosphere, 263 parts by mass of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Subsequently, 67 parts by mass of methacrylic acid, 82 parts of N-cyclohexylmaleimide, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound and a formula represented by the formula (I-1)) The compound represented by (II-1) is mixed at a molar ratio of 50:50.) 216 parts by mass, and tricyclo [5.2.1.0 ^2.6 ] decen-8-yl acrylate (formula ( The compound represented by c-1) and the compound represented by formula (c-2) are mixed at a molar ratio of 50:50.) 7 parts by mass is dissolved in 140 parts by mass of ethyl lactate to obtain a solution. The solution was prepared and dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel. On the other hand, a solution prepared by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. did. After completion of dropping of the polymerization initiator solution, the temperature was kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw was 9.8 × 10 ³ , the solid content was 37.2% by mass, the solid content A copolymer (B1-3) solution having a partial acid value of 110 mg-KOH / g was obtained. The copolymer (B1-3) has the following structural units.

[Synthesis Example 5]
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel to form a nitrogen atmosphere, and 258 parts by mass of propylene glycol monomethyl ether acetate was added up to 70 ° C. with stirring. Heated. Subsequently, 57 parts by mass of acrylic acid, 79 parts of vinyltoluene, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and formula (II) -1) is mixed at a molar ratio of 50:50.) 222 parts by mass, and tricyclo [5.2.1.0 ^2.6 ] decen-8-yl acrylate (formula (c- The compound represented by 1) and the compound represented by formula (c-2) are mixed at a molar ratio of 50:50.) 19 parts by mass is dissolved in 140 parts by mass of propylene glycol monomethyl ether acetate. And the solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel. On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of propylene glycol monomethyl ether acetate was added to a flask using another dropping funnel over 4 hours. It was dripped in. After dropping of the solution of the polymerization initiator is completed, the temperature is kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 1.05 × 10 ⁴ , the solid content is 37.7% by mass, the solid content A copolymer (B1-4) solution having a partial acid value of 106 mg-KOH / g was obtained. The copolymer (B1-4) has the following structural units.

[Synthesis Example 6]
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel to form a nitrogen atmosphere, and 257 parts by mass of propylene glycol monomethyl ether acetate was added and stirred to 70 ° C. Heated. Subsequently, 57 parts by mass of acrylic acid, 79 parts of vinyltoluene, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and formula (II) The compound represented by -1) is mixed at a molar ratio of 50:50.) 204 parts by mass, and tricyclo [5.2.1.0 ^2.6 ] decen-8-yl acrylate (formula (c- The compound represented by 1) and the compound represented by formula (c-2) are mixed at a molar ratio of 50:50.) 38 parts by mass is dissolved in 140 parts by mass of propylene glycol monomethyl ether acetate to obtain a solution And the solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel. On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of propylene glycol monomethyl ether acetate was added to a flask using another dropping funnel over 4 hours. It was dripped in. After completion of dropping of the polymerization initiator solution, the solution 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 , the solid content was 37.8% by mass, the solid content A copolymer (B1-5) solution having a partial acid value of 106 mg-KOH / g was obtained. A copolymer (B1-5) has the following structural units.

[Synthesis Example 7]
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel to form a nitrogen atmosphere, and 265 parts by mass of propylene glycol monomethyl ether acetate was added up to 70 ° C. with stirring. Heated. Next, 52 parts by mass of acrylic acid, 159 parts of benzyl methacrylate, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and formula (II) The compound represented by -1) is mixed at a molar ratio of 50:50.) 152 parts by mass, and tricyclo [5.2.1.0 ^2.6 ] decen-8-yl acrylate (formula (c- The compound represented by 1) and the compound represented by formula (c-2) are mixed in a molar ratio of 50:50.) 7 parts by mass is dissolved in 140 parts by mass of propylene glycol monomethyl ether acetate. And the solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel. On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of propylene glycol monomethyl ether acetate was added to a flask using another dropping funnel over 4 hours. It was dripped in. After completion of dropping of the polymerization initiator solution, the temperature 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 , the solid content was 37.0% by mass, A copolymer (B1-6) solution having a partial acid value of 96 mg-KOH / g was obtained. A copolymer (B1-6) has the following structural units.

[Synthesis Example 8]
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, 220 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 84 parts of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by formula (I-1) and a formula (II-1) The solution is prepared by dissolving 336 parts of the compound to be mixed at a molar ratio of 50:50 in 140 parts of ethyl lactate, and the solution is kept at 70 ° C. for 4 hours using a dropping funnel. The solution was dropped into the flask. On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After dropping of the solution of the polymerization initiator is completed, it is kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 8.0 × 10 ³ , the molecular weight distribution is 2.5, the solid content is A resin (B2-1) solution having 48% and a solution acid value of 50 mg-KOH / g (acid value in terms of solid content is 104 mgKOH / g) was obtained. Resin (B2-1) has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Examples 1-6
(Preparation of pigment dispersion)
Colorant (A); C.I. I. Pigment Blue 15: 6 (pigment) 10.1 parts Acrylic pigment dispersant 6.5 parts Solvent (E); Propylene glycol monomethyl ether acetate 59 parts Solvent (E); Ethyl lactate 25 parts are mixed and bead mill is used. A pigment dispersion A was obtained by sufficiently dispersing the pigment.
[Preparation of colored photosensitive resin composition]
The components shown in Table 1 were mixed to obtain a colored photosensitive resin composition.

In Table 1, each component represents the following.
Colorant (A); (A1-1); Dye (A1-1)
Colorant (A); (A2-1); Pigment dispersion obtained above Resin (B); (B1-1); Copolymer (B1-1) solution Resin (B); (B1-2) Copolymer (B1-2) solution resin (B); (B1-3); copolymer (B1-3) solution resin (B); (B1-4); copolymer (B1-4) solution Resin (B); (B1-5); Copolymer (B1-5) Solution Resin (B); (B1-6); Copolymer (B1-6) Solution Polymerizable Compound (C); (C- 1); dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D); (D-1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF; -Acyl oxime compound)
Polymerization initiator (D); (D-2); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF Corp .; alkylphenone compound )
Polymerization initiation assistant (D1); (D1-1); 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd .; thioxanthone compound)
Solvent (E); (E-1); Propylene glycol monomethyl ether acetate Solvent (E); (E-2); Ethyl lactate Surfactant (F); (F-1); Polyether-modified silicone oil (Tore Silicone) SH8400; manufactured by Toray Dow Corning Co., Ltd.)

Comparative Example C.I. I. Pigment Blue 15: 6 20 parts Acrylic dispersant 5 parts Propylene glycol monomethyl ether acetate 142 parts are mixed, and the pigment is sufficiently dispersed using a bead mill.
Dye A1 3.5 parts Resin (B2-1) solution 65 parts Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 31 parts N-benzoyloxy-1- (4-phenol) Sulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 9.3 parts Ethyl lactate 136 parts Propylene glycol monomethyl ether 255 parts I got a thing.

[Solubility evaluation]
After a colored photosensitive resin composition is applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by a spin coating method, the pressure is reduced by 2 at 50 Pa using a vacuum dryer (VCD; manufactured by Microtech Co., Ltd.). It was dried under reduced pressure for 2 seconds. An aqueous developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate was immersed in the dried film for 20 seconds at 23 ° C. and washed with water. The substrate after washing was observed using a microscope (magnification 250 times; VF-7510; manufactured by Keyence Corporation). If no foreign matter was observed on the substrate after washing, ○, on the substrate after washing. Table 2 shows the case where foreign matter was recognized as x. If no foreign matter is found on the substrate by this test, it can be said that no foreign matter is found on the substrate and the colored pattern even when the colored pattern is formed on the substrate by the photolithographic method.

[Preparation of colored pattern]
A colored photosensitive resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a composition layer. After standing to cool, the distance between the substrate on which the composition layer is formed and the quartz glass photomask having a pattern is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corporation) is used in an air atmosphere at 150 mJ. Light was irradiated with an exposure amount of / cm ² (based on 365 nm). As a photomask, a mask on which a 100 μm line and space pattern was formed was used. The composition layer after light irradiation is immersed and developed 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 in an oven at 230 ° C. for 30 minutes. Post-baking was performed to obtain a colored pattern.

[Film thickness measurement]
About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 2.

[Chromaticity evaluation]
About the coloring pattern on the obtained glass substrate, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the CIE XYZ color system using the color matching function of the C light source. Xy chromaticity coordinates (x, y) and brightness Y were measured. The results are shown in Table 2.

[Preparation of colored coating]
A colored photosensitive resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a composition layer. After standing to cool, the whole surface was irradiated with light at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). The composition layer after light irradiation was post-baked in an oven at 230 ° C. for 30 minutes to obtain a colored coating film.

[Heat resistance evaluation]
The obtained colored coating film was heated in an oven at 230 ° C. for 2 hours. Xy chromaticity coordinates (x, y) and brightness Y are measured before and after heating, and a color difference ΔEab * is calculated from the measured values by a method described in JIS Z 8730: 2009 (7. Calculation method of color difference). The results are shown in Table 2. A smaller value of ΔEab * means that the color change is smaller.

  In the colored photosensitive resin compositions of the examples, it was confirmed that peeling due to development was suppressed during the formation of the colored pattern, and no foreign matter was observed on the substrate after the colored pattern was formed. From this, a display apparatus can be manufactured with a high yield by using the colored pattern obtained from the colored photosensitive resin composition of the present invention as a color filter.

  According to the colored photosensitive resin composition of the present invention, a part of the unexposed portion of the composition layer formed from the colored photosensitive resin composition is prevented from peeling during development, and foreign matter on the colored pattern is reduced. can do.

Claims (4)

Including a colorant, a resin, a polymerizable compound and a polymerization initiator,
The colorant is a colorant containing a dye,
A monomer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond A structural unit derived from the formula (x)

[In formula (x), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
X ^a1 represents a single ^{bond, -X a2 -, * - X} a2 -O -, * - X a2 -S- or ^* -X represents an a2 -NH-.
X ^a2 represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]
A resin including a copolymer containing a structural unit derived from a monomer represented by:
Colored photosensitivity wherein the content of the structural unit derived from the monomer represented by the formula (x) is 0.1 mol% or more and 20 mol% or less with respect to the total amount of the structural unit constituting the copolymer. Resin composition.   The colored photosensitive resin composition according to claim 1, wherein the colorant further comprises a pigment.   A color filter formed from the colored photosensitive resin composition according to claim 1.   A display device comprising the color filter according to claim 3.