JP2016176075A - Colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition which achieves the reduction in generation of stripped pieces in a developing solution after developing.SOLUTION: A colored photosensitive resin composition includes colorant, resin, a polymerizable compound, a polymerization initiator, and a thiol compound. The colorant includes a xanthene dye and pigment. The polymerization initiator includes an o-acyloxime compound. Preferably, the xanthene dye comprises a compound represented by formula (1a) [R1-R4 independently represent H, a substituted/unsubstituted C1-C20 alkyl group or the like; R5 is -OH, -SO3-, -SO3H or the like; R6-R7 independently represent H or a C1-C6 alkyl group; m is an integer of 0 to 5; a is 0 or 1; X is halogen].SELECTED DRAWING: None

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 devices, electroluminescence display devices, and plasma displays. As such a colored photosensitive resin composition, a colored photosensitive resin composition containing only N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine as a polymerization initiator is known. (Patent Document 1).

JP 2011-28236 A

  When forming a colored pattern by the photolithographic method, when the colored photosensitive resin composition layer on the substrate is removed to the developer so as to peel off, the peeled piece adheres as a foreign matter on the colored pattern. There is a risk that the piping for discharging the developer after development may be blocked. The above-mentioned colored photosensitive resin compositions known in the past sometimes did not always satisfy the developability as described above.

［式（１ａ）中、Ｒ^１〜Ｒ^４は、互いに独立に、水素原子、置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基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し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。Ｒ^１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。
Ｒ^５は、−ＯＨ、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ、−ＳＯ_３ ⁻Ｚ^＋、−ＣＯ_２Ｈ、−ＣＯ_２ ⁻Ｚ^＋、−ＣＯ_２Ｒ^８、−ＳＯ_３Ｒ^８又は−ＳＯ_２ＮＲ^９Ｒ^１０を表す。
Ｒ^６及びＲ^７は、互いに独立に、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以上のとき、複数のＲ^５は同一でも異なってもよい。
ａは、０又は１の整数を表す。
Ｘは、ハロゲン原子を表す。
Ｚ^＋は、^＋Ｎ（Ｒ^１１）_４、Ｎａ^＋又はＫ^＋を表し、４つのＲ^１１は同一でも異なってもよい。
Ｒ^８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。
Ｒ^９及びＲ^１０は、互いに独立に、水素原子又は置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和脂肪族炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ^８−で置き換っていてもよく、Ｒ^９及びＲ^１０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。
Ｒ^１１は、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。］
［３］ ［１］又は［２］記載の着色感光性樹脂組成物から形成されるカラーフィルタ。
［４］ ［３］記載のカラーフィルタを含む表示装置。 The present invention includes the following inventions.
[1] includes a colorant, a resin, a polymerizable compound, a polymerization initiator, and a thiol compound,
The colorant is a colorant containing a xanthene dye and a pigment,
A colored photosensitive resin composition, wherein the polymerization initiator is a polymerization initiator containing an O-acyloxime compound.
[2] The colored photosensitive resin composition according to [1], wherein the xanthene dye is a dye containing a compound represented by the formula (1a).

[In Formula (1a), R ^{1 to} R ⁴ each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O—, —CO— or —NR ¹¹ —. Also good. 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 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and the four R ¹¹ may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and is contained in the saturated aliphatic hydrocarbon group— CH ₂ — may be replaced by —O—, —CO—, —NH—, or —NR ⁸ —, and R ⁹ and R ¹⁰ are bonded to each other to contain a nitrogen atom. A heterocyclic ring may be formed.
R ¹¹ 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. ]
[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, there is little generation of peeling pieces derived from the colored photosensitive resin composition in the developer after development.

The colored photosensitive resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a thiol compound (T).
The colored photosensitive resin composition of the present invention preferably further contains a solvent (E) and / or a leveling agent (F).
The colored photosensitive resin composition of the present invention may contain a polymerization initiation assistant (D1).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
The colorant (A) contains a xanthene dye (A1) and a pigment (A2), and may further contain a dye other than the xanthene dye (A1).

  The xanthene dye (A1) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (A1) 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 (A1), a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable. Compound (1a) may be a tautomer thereof. When using a compound (1a), content of the compound (1a) in a xanthene dye (A1) becomes like this. Preferably it is 50 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye (A1).

［式（１ａ）中、Ｒ^１〜Ｒ^４は、互いに独立に、水素原子、置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基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し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。Ｒ^１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。
Ｒ^５は、−ＯＨ、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ、−ＳＯ_３ ⁻Ｚ^＋、−ＣＯ_２Ｈ、−ＣＯ_２ ⁻Ｚ^＋、−ＣＯ_２Ｒ^８、−ＳＯ_３Ｒ^８又は−ＳＯ_２ＮＲ^９Ｒ^１０を表す。
Ｒ^６及びＲ^７は、互いに独立に、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以上のとき、複数のＲ^５は同一でも異なってもよい。
ａは、０又は１の整数を表す。
Ｘは、ハロゲン原子を表す。
Ｚ^＋は、^＋Ｎ（Ｒ^１１）_４、Ｎａ^＋又はＫ^＋を表し、４つのＲ^１１は同一でも異なってもよい。
Ｒ^８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。
Ｒ^９及びＲ^１０は、互いに独立に、水素原子又は置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和脂肪族炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ^８−で置き換っていてもよく、Ｒ^９及びＲ^１０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。
Ｒ^１１は、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 have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O—, —CO— or —NR ¹¹ —. Also good. 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 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and the four R ¹¹ may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and is contained in the saturated aliphatic hydrocarbon group— CH ₂ — may be replaced by —O—, —CO—, —NH—, or —NR ⁸ —, and R ⁹ and R ¹⁰ are bonded to each other to contain a nitrogen atom. A heterocyclic ring may be formed.
R ¹¹ 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. ]

In the formula (1a), when —SO ₃ ^— is present, the number thereof is one.

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

The aromatic hydrocarbon group substituent which may have a halogen _{^{atom, -R 8, -OH, -OR 8}} , -SO 3 -, -SO 3 H, -SO 3 - Z +, - _{^{CO 2 H, -CO 2 - Z}} +, -CO 2 R 8, -SO 3 R 8 or _-SO 2 ^NR 9 ^{R 10} can be mentioned. Among them, as the _{^{substituent, SO 3 -, -SO 3 H}} , -SO 3 - Z + and _-SO 2 ^NR 9 ^{R 10} is preferably, _-SO ³ - ^{Z +} and _-SO 2 ^NR 9 ^{R 10} is More preferred. _-SO ³ in this case - ^{Z + _{The, -SO 3 - + N (R}} 11) 4 are preferred. When R ^{1 to} R ⁴ are these groups, the colored photosensitive resin composition of the present invention containing the compound (1a) can form a color filter with less generation of foreign matters and excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{1 to} R ⁴ and R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Linear alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, are mentioned.
The hydrogen atom contained in the saturated hydrocarbon group in R ^{1 to} R ⁴ may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.
The hydrogen atom contained in the saturated hydrocarbon group in R ⁹ and R ¹⁰ may be substituted with, for example, a hydroxy group or a halogen atom.

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

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

R ^{5 _{is, -CO 2 H, -CO 2 -}} Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H or _SO 2 NHR ⁹ are preferred, SO ₃ ^{-, _{-SO 3 - Z +, -SO 3}} H or _SO 2 NHR ⁹ is more preferable.
m is preferably 1 to 4, and more preferably 1 or 2.

The alkyl group having 1 to 6 carbon atoms in R ⁶ and R ^7, among the alkyl groups listed above, include those having 1 to 6 carbon atoms.

Examples of the aralkyl group having 7 to 10 carbon atoms in 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 , it is preferable that at least two of the four R ¹¹ are 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. In the case where ⁺ N (R ¹¹ ) ₄ is present in the compound (1a), when R ¹¹ is any of these groups, the color filter having less foreign matters from the colored photosensitive resin composition of the present invention containing the compound (1a) Can be formed.

  The compound (1a) is preferably a compound represented by the formula (2a) (hereinafter sometimes referred to as “compound (2a)”). Compound (2a) may be a tautomer thereof.

［式（２ａ）中、Ｒ^２１〜Ｒ^２４は、互いに独立に、水素原子、−Ｒ^２６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。Ｒ^２１及びＲ^２２は、一緒になって窒素原子を含む環を形成してもよく、Ｒ^２３及びＲ^２４は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ^２５は、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ、−ＳＯ_３ ⁻Ｚ１^＋又は−ＳＯ_２ＮＨＲ^２６を表す。
ｍ１は、０〜５の整数を表す。ｍ１が２以上のとき、複数のＲ^２５は同一でも異なってもよい。
ａ１は、０又は１の整数を表す。
Ｘ１は、ハロゲン原子を表す。
Ｒ^２６は、炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｚ１^＋は、^＋Ｎ（Ｒ^２７）_４、Ｎａ^＋又はＫ^＋を表し、４つのＲ^２７は同一でも異なってもよい。
Ｒ^２７は、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 represent a hydrogen atom, —R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. . 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 2 or more, the plurality of R ²⁵ may be 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 ^{+ _{is, + N (R 27) 4}} , Na + or an ^{K +,} 4 one ^{R 27} may be the same or different.
R ²⁷ represents a monovalent saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{21 to} R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group for 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.}
When R ^{21 to} R ²⁴ are these groups, a color filter having excellent heat resistance can be formed from the colored photosensitive resin composition of the present invention containing the compound (2a).

As the ring containing a nitrogen atom formed by R ²¹ and R ²² together and the ring containing a nitrogen atom formed by R ²³ and R ²⁴ together, R ¹ and R ² are taken together. The thing similar to the ring to form is mentioned. Among these, an aliphatic heterocyclic ring is preferable. Examples of the aliphatic heterocycle include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group in R ^{8 to} R ¹¹ .
When R ^{21 to} R ²⁴ are —R ^26, it is preferable that —R ²⁶ is independently 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, a color filter with less generation of foreign matters can be formed from the colored photosensitive resin composition of the present invention containing the compound (2a).

Z1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .
As the ⁺ N (R ²⁷ ) ₄ , it is preferable that at least two of the four R ²⁷ are 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. When ⁺ N (R ²⁷ ) ₄ is present in the compound (2a), when R ²⁷ is any of these groups, the occurrence of foreign matters is less from the colored photosensitive resin composition of the present invention containing the compound (2a). A color filter can be formed.

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

  As the compound (1a), a compound represented by the formula (3a) (hereinafter sometimes referred to as “compound (3a)”) is also preferable. Compound (3a) may be a tautomer thereof.

［式（３ａ）中、Ｒ^３１及びＲ^３２は、互いに独立に、炭素数１〜１０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、炭素数６〜１０の芳香族炭化水素基又はハロゲン原子で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜３のアルコキシ基で置換されていてもよく、前記飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。
Ｒ^３３及びＲ^３４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。
Ｒ^３１及びＲ^３３は、一緒になって窒素原子を含む環を形成してもよく、Ｒ^３２及びＲ^３４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以上のとき、複数のＲ^３３は同一でも異なってもよく、ｑが２以上のとき、複数のＲ^３４は同一でも異なってもよい。
Ｒ^１１は、上記と同じ意味を表す。］

[In Formula (3a), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group has 6 to 6 carbon atoms. May be substituted with 10 aromatic hydrocarbon groups or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, —CH ₂ — contained in the hydrogen group may be replaced by —O—, —CO— or —NR ¹¹ —.
R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R ³¹ and R ³³ may 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.
R ¹¹ represents the same meaning as described above. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ³² include those having 1 to 10 carbon atoms among those in R ⁸ .
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be present as a substituent include the same groups as those in R ¹ .
As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group etc. are mentioned, for example.
R ³¹ and R ³² are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in 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.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in 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 in R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

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

Examples of compound (1a) include compounds represented by formula (1-1) to formula (1-43). In the formula, R ⁴⁰ 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 the above compounds, the compounds represented by the formula (1-1) to the formula (1-23) or the formula (1-37) to the formula (1-43) correspond to the compound (2a), and the formula (1- The compound represented by any one of 24) to formula (1-36) corresponds to the compound (3a).
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), or formula (1-12).
In addition, a compound represented by any one of formulas (1-24) to (1-33) is also preferable in that it has excellent solubility in an organic solvent.

  As the xanthene dye (A1), 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.

  The content of the xanthene dye (A1) is preferably 0.5 to 50% by mass, more preferably 0.5 to 40% by mass, and still more preferably 0 with respect to the total amount of the colorant (A). 0.5 to 30% by mass.

The pigment (A2) is not particularly limited, and a known pigment can be used. Examples thereof include pigments classified as pigments according to a 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, 194, 214;
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. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; 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.

  Examples of the pigment include C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38 are preferable. 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. By including the pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

If necessary, the pigment can be atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.
The pigment preferably has a uniform particle size. 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, more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (A2). When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

  The content of the pigment (A2) is preferably 50 to 99.5% by mass, more preferably 60 to 99.5% by mass, and still more preferably 70 to 9%, based on the total amount of the colorant (A). It is 99.5 mass%.

  The dye other than the xanthene dye (A1) (hereinafter sometimes referred to as “dye (A3)”) is not particularly limited as long as it is different from the xanthene dye (A1), and a known dye can be used. Azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, etc. Is mentioned. Of these, organic solvent-soluble dyes are preferred.

［式（４）中、Ｇ^１は炭素数２〜１２のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、炭素数１〜４のアルキル基で置換されていてもよく、該アルカンジイル基に含まれる−ＣＨ_２−は、−Ｏ−で置き換わっていてもよい。
Ｊ^１は、水素原子、−ＮＲ^ａＲ^ｂ又は−ＮＲ^ａＲ^ｂＨ^＋Ｑ⁻を表す。
Ｒ^ａ及びＲ^ｂは、互いに独立に、水素原子又は炭素数１〜８のアルキル基を表す。
Ｑ⁻は、ハロゲン化物イオン、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＣｌＯ_４ ⁻、Ｘ−ＣＯ_２ ⁻又はＹ−ＳＯ_３ ⁻を表す。
Ｘ及びＹは、それぞれ独立に、１価の有機基を表す。
ｐは１〜４の整数を表す。］
式（４）は、式（４−０）で表される化合物に含まれるｐ個の水素原子が、−ＳＯ_２−ＮＨ−Ｇ^１−Ｊ^１で置換されていることを表す。ｐが２以上である場合、複数の−ＳＯ_２−ＮＨ−Ｇ^１−Ｊ^１は、互いに同一でも異なっていてもよい。

Among these, a phthalocyanine dye is preferable, and a compound represented by the formula (4) is more preferable.

[In Formula (4), G ¹ represents an alkanediyl group having 2 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, —CH ₂ — contained in the alkanediyl group may be replaced by —O—.
J ¹ is a hydrogen atom, ^-NR a ^{R b} or ^-NR a ^R b ^H + Q ^- represents a.
R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
Q ⁻ represents a halide ion, BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , X—CO ₂ ^— or Y—SO ₃ ^— .
X and Y each independently represent a monovalent organic group.
p represents an integer of 1 to 4. ]
Formula (4) represents that p hydrogen atoms contained in the compound represented by formula (4-0) are substituted with —SO ₂ —NH—G ¹ —J ¹ . When p is 2 or more, the plurality of —SO ₂ —NH—G ¹ —J ¹ may be the same as or different from each other.

［式（Ｇ−１）及び式（Ｇ−２）中、Ｇ^２〜Ｇ^５は、それぞれ独立に、炭素数１〜８のアルカンジイル基を表す。
ｎ^１は、１〜３の整数を表す。
ｎ^２は、０〜３の整数を表す。
ただし、式（Ｇ−１）で表される基に含まれる炭素原子及び酸素原子の合計数は、３〜１２であり、式（Ｇ−２）で表される基に含まれる炭素原子及び酸素原子の合計数は、ぞれぞれ２〜１２である。
＊は、−ＮＨ−との結合手を表す。］ Examples of the alkanediyl group having 2 to 12 carbon atoms include a methylene group, an ethylene group, a propanediyl group, and a butanediyl group.
Examples of the alkanediyl group having 2 to 12 carbon atoms in which —CH ₂ — is replaced by —O— include a group represented by the formula (G-1) and a group represented by the formula (G-2). .

[In Formula (G-1) and Formula (G-2), G ^{2 to} G ⁵ each independently represents an alkanediyl group having 1 to 8 carbon atoms.
n ¹ represents an integer of 1 to 3.
n ² represents an integer of 0 to 3.
However, the total number of carbon atoms and oxygen atoms contained in the group represented by formula (G-1) is 3 to 12, and carbon atoms and oxygen contained in the group represented by formula (G-2). The total number of atoms is 2 to 12, respectively.
* Represents a bond with -NH-. ]

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

Examples of —SO ₂ —NH—G ¹ —J ¹ include groups represented by the following formulas.

When G ¹ is a group represented by the formula (G-1), examples of —SO ₂ —NH—G ¹ -J ¹ include a group represented by the following formula.

When G ¹ is a group represented by the formula (G-2), examples of —SO ₂ —NH—G ¹ -J ¹ include a group represented by the following formula.

When J ¹ is —NR ^a R ^b , examples of —SO ₂ —NH—G ¹ —J ¹ include groups represented by the following formulae.

When J ¹ is —NR ^a R ^b H ⁺ Q ^— , examples of —SO ₂ —NH—G ¹ —NR ^a R ^b H ⁺ include groups represented by the following formulae.

［Ｒ^ｙは、炭素数１〜２０のアルキル基を表す。
ｍは、０〜５の整数を表す。］
Ｑ⁻としては、Ｘ−ＣＯ_２ ⁻及びＹ−ＳＯ_３ ⁻が好ましく、式（Ｑ−４）で表されるアニオンがより好ましい。これらのアニオンであると、式（２）で表される化合物の溶剤への溶解性が高くなる傾向がある。 Q ⁻ represents a halide ion, BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , X—CO ₂ ^— or Y—SO ₃ ^— .
X and Y represent a monovalent organic group. As a monovalent organic group, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, the group which combined these, etc. are mentioned.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group.
Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and an anthryl group.
X—CO ₂ ^— is an organic anion containing a CO ₂ ^— group, and Y—SO ₃ ^— is an organic anion containing an SO ₃ ^— group. For example, the formula (Q-1) to the formula (Q-4) The anion represented by these is mentioned.

[ ^Ry represents an alkyl group having 1 to 20 carbon atoms.
m represents an integer of 0 to 5. ]
Q ^- The, X-CO ₂ ^- and Y-SO ₃ ^- are preferable, and anions represented by the formula (Q-4) is more preferable. When these anions are used, the solubility of the compound represented by the formula (2) in the solvent tends to increase.

Examples of the compound represented by formula (4) include compounds represented by formula (2-1) to formula (2-92). Formula (2-1) Among the compounds represented by - formula (2-92), if ^{n a} is an integer of 2 or more, a plurality of _-SO 2 ^{-NH-G 1} -J 1 is different each benzene It is preferably bonded to a ring.

For example, specific examples of the compound represented by the formula (2-24) include compounds represented by the formula (2-24-1) and the formula (2-24-2).

  When the colorant (A) contains the dye (A3), the content of the dye (A3) is preferably 0.5% by mass or more and 40% by mass or less with respect to the total amount of the colorant (A). More preferably, it is at least 30% by mass.

When the colorant (A) is a colorant composed of the xanthene dye (A1) and the pigment (A2), these contents are respectively based on the total amount of the colorant (A).
Xanthene dye (A1); 0.5 mass% or more and 50 mass% or less Pigment (A2); 50 mass% or more and 99.5 mass% or less is preferable,
Xanthene dye (A1); 0.5 mass% or more and 40 mass% or less Pigment (A2); 60 mass% or more and 99.5 mass% or less is more preferable.

When the colorant (A) is a colorant composed of the xanthene dye (A1), the pigment (A2) and the dye (A3), the content of each of these is relative to the total amount of the colorant (A).
Xanthene dye (A1); 0.5% by mass or more and 50% by mass or less Pigment (A2); 49.5% by mass or more and 99% by mass or less Dye (A3); 0.5% by mass or more and 40% by mass or less are preferable,
Xanthene dye (A1): 0.5 mass% or more and 40 mass% or less Pigment (A2); 59.5 mass% or more and 99 mass% or less Dye (A3); 0.5 mass% or more and 30 mass% or less is more preferable.

  The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and further preferably 10 to 50% 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 pattern with 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.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include resins [K1] to [K6].
Resin [K1]; at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (a) (hereinafter sometimes referred to as “(a)”), and a cyclic ether structure having 2 to 4 carbon atoms And a copolymer of a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);
Resin [K2]; (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) In some cases)
Resin [K3]; Copolymer of (a) and (c);
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.

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, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of 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.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(B) refers to a polymerizable compound having, for example, 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. . (B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (b1) 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.

  As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes 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, 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 Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (I), and Formula (II) The compound etc. which are represented by these are mentioned.

[In Formula (I) and Formula (II), R ^a and R ^b 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 ^a and ^{X b} is a single ^{bond, -R c -, * - R} c -O -, * - represents the R c -S- or ^* -R c -NH-.
R ^c 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 ^a and R ^b 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 the alkanediyl group 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 ^a and X ^b 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), or formula (I-11) to formula (I-15) A compound represented by formula (I-1), formula (I-7), formula (I-9) or 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) or formula (II-11) to formula (II-15) A compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferred.

  The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio thereof [the compound represented by the formula (I): the compound represented by the formula (II)] is: On a molar basis, it is preferably 5:95 to 95: 5, more preferably 20:80 to 80:20.

  (B2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (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.

  (B3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (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.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is said to be “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) ) Rishikuro (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
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 [2.2 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, etc. Bicyclounsaturated 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, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance. preferable.

In the resin [K1], the ratio of the structural unit derived from each is the total structural unit constituting the resin [K1]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40-98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%
It is more preferable that
When the ratio of the structural units 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 color filter. Tend.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere, with stirring, The method of heating and heat retention is mentioned. 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.) Any solvent may be used as long as it dissolves each monomer. Examples of the solvent (E) for the colored photosensitive resin composition of the present invention include the solvents 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 the solvent contained in the colored photosensitive resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored photosensitive resin composition of the present invention. Therefore, the manufacturing process of the colored photosensitive resin composition of the present invention can be simplified.

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 a colored pattern, and the solvent resistance of the resulting color filter, 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 the method described as the production method of resin [K1].

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 for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (a) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms that (b) has It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as described in the method for producing resin [K1]. 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 from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( 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]. it can.
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 within this range, the storage stability of the colored photosensitive resin composition, the developability when forming the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the pattern obtained are improved. Tend. 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 a first step in the same manner as in the method for producing resin [K1] described above. 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 respectively based on the total number of moles of all the 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

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product.
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, and the like. 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 (B) 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-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / Glycidyl (meth) acrylate was added to resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer such as (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer Resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic Resins such as resins obtained by adding glycidyl (meth) acrylate to an acid copolymer [K4]; resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid , Tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin [K5] such as a resin obtained by reacting a copolymer with (meth) acrylic acid; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid Furthermore, resin [K6] such as a resin obtained by reacting tetrahydrophthalic anhydride may be used.

  Among them, the resin (B) includes 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 copolymer containing a structural unit derived from a monomer having a phenotype, that is, resin [K1] and resin [K2] is preferable.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. Particularly preferred is 5,000 to 12,000. If the molecular weight is within the above range, the hardness of the color filter is improved, the solubility of the unexposed part in the developer is good, and the strips derived from the colored photosensitive resin composition are generated in the developer after development. Tend to be less.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value of the resin (B) 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 (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

  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, a colored pattern can be formed, and the resolution of the colored 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 an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of 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.
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 within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
A polymerization initiator is a compound which can generate | occur | produce an active radical, an acid, etc. by the effect | action of light or a heat | fever, and can start superposition | polymerization, A polymerization initiator (D) contains an O-acyl oxime compound.

［式（ｄ１）中、＊は結合手を表す。］ The O-acyloxime compound is a compound having a partial structure represented by the formula (d1), preferably a compound represented by the formula (d2).

[In formula (d1), * represents a bond. ]

［式（ｄ２）中、Ｒ^ｄ１は、炭素数１〜１２の飽和炭化水素基を表す。
Ｒ^ｄ２は、メチル基、フェニル基又はベンジル基を表す。
Ｌ^ｄ１は、単結合又は−ＣＯ−を表す。
Ｒ^ｄ３は、置換基を有していてもよいフェニルスルファニルフェニル基、又は置換基を有していてもよいカルバゾリル基を表す。］

[In the formula (d2), R ^d1 represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
R ^d2 represents a methyl group, a phenyl group or a benzyl group.
L ^d1 represents a single bond or —CO—.
R ^d3 represents a phenylsulfanylphenyl group which may have a substituent, or a carbazolyl group which may have a substituent. ]

Examples of the saturated hydrocarbon group include an alkyl group, an alicyclic saturated hydrocarbon group, and a group obtained by combining these.
Examples of the alkyl group include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group; an isopropyl group, And branched chain alkyl groups such as isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group.
Examples of the alicyclic saturated hydrocarbon group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, an adamantyl group, and the like.
Examples of the group in which these are combined include a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a methylcyclohexyl group, and the like.

Examples of the substituent that the phenylsulfanylphenyl group and the carbazolyl group may have include an alkyl group having 1 to 6 carbon atoms and a benzoyl group that may have a saturated hydrocarbon group having 1 to 10 carbon atoms. A hydrogen atom contained in the alkyl group and the saturated hydrocarbon group may be substituted with a hydroxy group, and a methylene group contained in the alkyl group and the saturated hydrocarbon group is replaced with an oxygen atom. Also good.
Examples of the alkyl group and saturated hydrocarbon group are the same as described above.
Examples of such a substituent include the above alkyl groups; 2-hydroxyethyl group, 2-hydroxyethoxy group, ethoxyethyl group; benzoyl group, 2-methylbenzoyl group, (3,3-dimethyl-2,4-di- Oxacyclopentanylmethyloxy) benzoyl group and the like.

［式（ｄ３）及び式（ｄ４）中、Ｒ^ｄ１及びＲ^ｄ２は、上記と同じ意味を表す。
Ｒ^ｄ４は、水素原子又は炭素数１〜６のアルキル基を表し、該アルキル基に含まれる水素原子はヒドロキシ基で置換されていてもよく、該アルキル基に含まれるメチレン基は、酸素原子で置き換わっていてもよい。
Ｒ^ｄ５は、炭素数１〜１０の飽和炭化水素基を有していてもよいベンゾイル基、水素原子又は炭素数１〜６のアルキル基を表し、該アルキル基及び該飽和炭化水素基に含まれる水素原子はヒドロキシ基で置換されていてもよく、該アルキル基及び該飽和炭化水素基に含まれるメチレン基は、酸素原子で置き換わっていてもよい。
Ｒ^ｄ６は、炭素数１〜６のアルキル基を表す。］ The compound represented by the formula (d2) is preferably a compound represented by the formula (d3) or the formula (d4), and more preferably a compound represented by the formula (d3).

[In formula (d3) and formula (d4), R ^d1 and R ^d2 represent the same meaning as described above.
R ^d4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group, and the methylene group contained in the alkyl group is an oxygen atom. It may be replaced.
R ^d5 represents a benzoyl group which may have a saturated hydrocarbon group having 1 to 10 carbon atoms, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is included in the alkyl group and the saturated hydrocarbon group. The hydrogen atom may be substituted with a hydroxy group, and the methylene group contained in the alkyl group and the saturated hydrocarbon group may be replaced with an oxygen atom.
R ^d6 represents an alkyl group having 1 to 6 carbon atoms. ]

  Examples of the alkyl group and saturated hydrocarbon group are the same as described above.

  Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like; described in JP 2001-233842 A, JP 2004-534797 A or JP 2011-132215 A The O-acyl oxime compound of these is mentioned. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferred, and N-benzoyloxy- 1- (4-phenylsulfanylphenyl) octane-1-one-2-imine is more preferred.

  The polymerization initiator (D) may contain a polymerization initiator other than the O-acyloxime compound as necessary. Moreover, you may use a sensitizer with a polymerization initiator (D) as needed.

  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 within the above range, there is little generation of peeling pieces in the developer after forming the colored pattern.

<Thiol compound (T)>
The thiol compound (T) is a compound having —SH in the molecule.

  Examples of the compound having one —SH in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2 -Sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4- Amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamidine -6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6 -Propylpyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2- Sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5-sulfanyl-1,2,4-triazole, 2- Methyl-4H-1,2,4-triazo Lu-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1 , 3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl) methanethiol, 2- Sulfanyl-5-thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl-4 (3H) -quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2 -Sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2 Sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1,2,4-triazole, 4- Examples include amino-6-sulfanylpyrazolo [2,4-d] pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo [2,4-d] pyrimidine and the like.

  Compounds having two or more —SH in the molecule include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl). Acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), tri Methylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyl Echirutorisu (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl-butyloxy) include butane and the like.

As the thiol compound (T), a compound having one —SH in the molecule is preferable.
The content of the thiol compound (T) is preferably 1 to 150 parts by mass, more preferably 5 to 100 parts by mass, and still more preferably 8 to 70 parts by mass with respect to 100 parts by mass of the polymerization initiator (D). It is. When the content of the thiol compound (T) is within this range, sensitivity tends to be high and developability tends to be good.

<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 (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

  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, include phenetol and methyl anisole and the like.

  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, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate, and the like.

  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. 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, cyclohexanone, 4-hydroxy-4-methyl-2 -Pentanone and N, N-dimethylformamide are 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 the coloring photosensitive resin composition of this invention, More preferably, it is 75-92 mass%. In other words, the total amount of 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 within 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. .

<Leveling agent (F)>
Examples of the leveling agent (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), 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 leveling agent (F) is preferably from 0.001% by mass to 0.2% by mass, and preferably from 0.002% by mass to 0.1%, based on the total amount of the colored photosensitive resin composition. It is 0.01 mass% or less, More preferably, it is 0.01 mass% or less and 0.05 mass% or less. This content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within 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 solvent (E) used as necessary. It can be prepared by mixing the leveling agent (F), the polymerization initiation assistant (D1) and other components.
The xanthene dye (A1) and the dye (A3) may be dissolved in part or all of the solvent (E) in advance to prepare a solution. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The pigment (A2) is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter 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. The desired colored photosensitive resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
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 the method for producing a colored pattern from the colored photosensitive resin composition of the present invention include a photolithographic method, an ink jet 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, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited, and can be adjusted as appropriate according to the purpose and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5. ~ 6 μm.

  As a 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 Further, aluminum, silver, a silver / copper / palladium alloy thin film or the like 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 on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
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 coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the coloring 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.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed.
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 1 to 120 minutes, more preferably 10 to 60 minutes.

  According to the colored photosensitive resin composition of the present invention, since a color filter can be produced particularly at a high yield, the color filter is used for a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor. It is useful as a color filter used in

Hereinafter, the colored photosensitive resin composition of the present invention will be described in more detail with reference to examples.
Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.
In the following synthesis examples, the compounds were identified by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

式（１−２４）で表される化合物の同定；
（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝［Ｍ＋Ｈ］^＋６０３．４
Ｅｘａｃｔ Ｍａｓｓ： ６０２．２ [Synthesis Example 1]
20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under shading conditions, and the resulting solution was stirred at 110 ° C. for 6 hours. did. The obtained reaction solution was cooled to room temperature, then added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour, whereby crystals were precipitated. The precipitated crystals were obtained as a suction filtration residue and dried to obtain 24 parts of a compound represented by the formula (1-24). The yield was 80%.

Identification of the compound represented by formula (1-24);
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 603.4
Exact Mass: 602.2

式（１−３２）で表される化合物の同定；
（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝［Ｍ＋Ｈ］^＋６５９．９
Ｅｘａｃｔ Ｍａｓｓ： ６５８．９ [Synthesis Example 2]
A compound represented by the formula (1-32) was obtained in the same manner as in Synthesis Example 1 except that N-propyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of the compound represented by formula (1-32);
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 659.9
Exact Mass: 658.9

[Synthesis Example 3]
A mixture of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (trade name Chugai Aminol Fast Pink R; manufactured by Chugai Kasei Co., Ltd.) 15 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. The precipitated crystals are separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and xanthene dye 1 [compound represented by formula (Aa-1-1) to formula (Aa-1-8) Of the mixture] to obtain 11.3 parts.

[Synthesis Example 4]
A suitable amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. with stirring. Then 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] 225 parts of a mixture of decan-9-yl acrylate (content ratio is 50:50 in molar ratio) and 81 parts of vinyltoluene (isomer mixture) were dissolved in 80 parts of propylene glycol monomethyl ether acetate. The mixed solution was dropped into the flask over 4 hours.
On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of dropping of the polymerization initiator solution, the solution was kept at 85 ° C. for 4 hours, and then cooled to room temperature to obtain a resin B1 (copolymer) solution. The solid content of the resin B1 solution was 37.5%, and the viscosity measured with a B-type viscometer (23 ° C.) was 246 mPa · s. The weight average molecular weight of Resin B1 was 1.06 × 10 ⁴ , the molecular weight distribution was 2.01, and the acid value in terms of solid content was 115 mg-KOH / g. Resin B1 has the following structural units.

[Synthesis Example 5]
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, and 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added and stirred. While heating to 70 ° C. Then 60 parts methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane. 240 parts of a mixture of -8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate (content ratio 50:50 in molar ratio) A solution was prepared by dissolving in 140 parts of methoxybutyl 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 prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was placed in a flask over another 4 hours using another dropping funnel. It was dripped in. After the dropping of the polymerization initiator solution was completed, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a resin B2 (copolymer) solution having a solid content of 33% by mass. Resin B2 had a weight average molecular weight of 1.3 × 10 ⁴ , a molecular weight distribution of 2.5, and an acid value in terms of solid content of 103 mg-KOH / g. Resin B2 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 to 5 and Comparative Example 1
[Preparation of colored photosensitive resin composition]
Each component was mixed so that it might become a composition shown in Table 1, and the colored photosensitive resin composition was obtained.

In Table 1, "A2-1" are acrylic pigment dispersant and "E-1 ^2)" of the amount of column, wherein propylene glycol monomethyl ether acetate, and "E-2 ^2)" column the amount of propylene glycol monomethyl according What was mixed with ether and dispersed in advance was used.
The “E-1 ¹⁾ ” column represents the total propylene glycol monomethyl ether acetate content, and the “E-2 ¹⁾ ” column represents the total propylene glycol monomethyl ether content.

チオール化合物（Ｔ）；２−スルファニルベンゾチアゾール（サンセラー（登録商標）Ｍ；三新化学工業（株）製）

溶剤（Ｅ）：Ｅ−１：プロピレングリコールモノメチルエーテルアセテート
溶剤（Ｅ）：Ｅ−２：プロピレングリコールモノメチルエーテル
溶剤（Ｅ）：Ｅ−３：乳酸エチル
溶剤（Ｅ）：Ｅ−４：３−メトキシ−１−ブタノール
溶剤（Ｅ）：Ｅ−５：３−メトキシブチルアセテート
レベリング剤（Ｆ）：ポリエーテル変性シリコーンオイル（トーレシリコーンＳＨ８４００；東レ・ダウコーニング（株）製） In Table 1, each component represents the following. Resin (B) represents content (part) in conversion of solid content.
Colorant (A): A1-1: Compound represented by formula (1-32) Colorant (A): A1-2: Xanthene dye 1
Colorant (A): A2-1: C.I. I. Pigment Blue 15: 6 (Pigment)
Colorant (A): A3-1: C.I. I. Salt of direct blue 264 and dodecylbenzenesulfonic acid (manufactured by Orient Chemical Co., Ltd.) (phthalocyanine dye)
Resin (B): B-1: Resin B1
Resin (B): B-2: Resin B2
Polymerizable compound (C): Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .; KAYARAD (registered trademark) DPHA)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF)

Thiol compound (T); 2-sulfanylbenzothiazole (Sunseller (registered trademark) M; manufactured by Sanshin Chemical Industry Co., Ltd.)

Solvent (E): E-1: Propylene glycol monomethyl ether acetate Solvent (E): E-2: Propylene glycol monomethyl ether Solvent (E): E-3: Ethyl lactate Solvent (E): E-4: 3-Methoxy -1-butanol Solvent (E): E-5: 3-methoxybutyl acetate Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Preparation of colored pattern>
A colored photosensitive resin composition was applied by spin coating on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer is formed and the photomask made of quartz glass is 100 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), 60 mJ / cm in an air atmosphere. Light was irradiated with an exposure amount of ² (based on 365 nm). A photomask having a 100 μm line and space pattern was used. The colored composition layer after the light irradiation is developed by immersing in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 26 ° C. for 60 seconds. After baking at 20 ° C. for 20 minutes, a colored pattern was obtained.

<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).

<Chromaticity evaluation>
About the obtained coloring pattern, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinates in the XYZ color system of CIE using the characteristic function of C light source (X, y) and tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 2.

<Observation of peeled piece>
In the production of the colored pattern, the developer after development was visually observed. In the case where no peeled piece derived from the colored photosensitive resin composition was observed in the developing solution, the mark was “◯”. If a peeled piece derived from the colored photosensitive resin composition is observed in the developer, it is not preferable because it may adhere as a foreign matter on the pattern and cause a defect. The results are shown in Table 2.

Example 4
A colored photosensitive resin composition is obtained in the same manner as in Example 1 except that the compound represented by the formula (1-24) is used instead of the compound represented by the formula (1-32). The same operation as described above is performed to obtain a high-lightness coloring pattern without causing peeling pieces in the developer.

  From the above results, according to the colored photosensitive resin composition of the present invention, no peeled piece was observed in the developer after development. Moreover, it was confirmed that the coloring pattern manufactured from the colored photosensitive resin composition of this invention has high brightness. From this, it can be seen that according to the colored photosensitive resin composition of the present invention, a color filter having excellent brightness can be produced with a high yield.

  According to the colored photosensitive resin composition of the present invention, there is little generation of peeling pieces derived from the colored photosensitive resin composition in the developer after development.

［式（４）中、Ｇ^１は炭素数２〜１２のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、炭素数１〜４のアルキル基で置換されていてもよく、該アルカンジイル基に含まれる−ＣＨ_２−は、−Ｏ−で置き換わっていてもよい。
Ｊ^１は、水素原子、−ＮＲ^ａＲ^ｂ又は−ＮＲ^ａＲ^ｂＨ^＋Ｑ⁻を表す。
Ｒ^ａ及びＲ^ｂは、互いに独立に、水素原子又は炭素数１〜８のアルキル基を表す。
Ｑ⁻は、ハロゲン化物イオン、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＣｌＯ_４ ⁻、Ｘ−ＣＯ_２ ⁻又はＹ−ＳＯ_３ ⁻を表す。
Ｘ及びＹは、それぞれ独立に、１価の有機基を表す。
ｐ１は１〜４の整数を表す。］
式（４）は、式（４−０）で表される化合物に含まれるｐ１個の水素原子が、−ＳＯ_２−ＮＨ−Ｇ^１−Ｊ^１で置換されていることを表す。ｐ１が２以上である場合、複数の−ＳＯ_２−ＮＨ−Ｇ^１−Ｊ^１は、互いに同一でも異なっていてもよい。

Among these, a phthalocyanine dye is preferable, and a compound represented by the formula (4) is more preferable.

[In Formula (4), G ¹ represents an alkanediyl group having 2 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, —CH ₂ — contained in the alkanediyl group may be replaced by —O—.
J ¹ is a hydrogen atom, ^-NR a ^{R b} or ^-NR a ^R b ^H + Q ^- represents a.
R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
Q ⁻ represents a halide ion, BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , X—CO ₂ ^— or Y—SO ₃ ^— .
X and Y each independently represent a monovalent organic group.
p 1 represents an integer of 1 to 4. ]
Equation (4) indicates that p 1 of the hydrogen atoms contained in the compound represented by the formula (4-0) _is replaced with ^{-SO 2 -NH-G 1 -J 1} . When p 1 is 2 or more, the plurality of —SO ₂ —NH—G ¹ —J ¹ may be the same as or different from each other.

［式（Ｇ−１）及び式（Ｇ−２）中、Ｇ^２〜Ｇ^５は、それぞれ独立に、炭素数１〜８のアルカンジイル基を表す。
ｎ^１は、１〜３の整数を表す。
ｎ^２は、０〜３の整数を表す。
ただし、式（Ｇ−１）で表される基に含まれる炭素原子及び酸素原子の合計数は、３〜１２であり、式（Ｇ−２）で表される基に含まれる炭素原子及び酸素原子の合計数は、それぞれ２〜１２である。
＊は、−ＮＨ−との結合手を表す。］ Examples of the alkanediyl group having 2 to 12 carbon atoms include a methylene group, an ethylene group, a propanediyl group, and a butanediyl group.
Examples of the alkanediyl group having 2 to 12 carbon atoms in which —CH ₂ — is replaced by —O— include a group represented by the formula (G-1) and a group represented by the formula (G-2). .

[In Formula (G-1) and Formula (G-2), G ^{2 to} G ⁵ each independently represents an alkanediyl group having 1 to 8 carbon atoms.
n ¹ represents an integer of 1 to 3.
n ² represents an integer of 0 to 3.
However, the total number of carbon atoms and oxygen atoms contained in the group represented by formula (G-1) is 3 to 12, and carbon atoms and oxygen contained in the group represented by formula (G-2). the total number of atoms is their respective 2 to 12.
* Represents a bond with -NH-. ]

[In Formula (I) and Formula (II), R ^{a 1} and R ^{b 1} 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 ^a and ^{X b} is a single ^{bond, -R c -, * - R} c -O -, * - represents the R c -S- or ^* -R c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Claims (4)

Including a colorant, a resin, a polymerizable compound, a polymerization initiator and a thiol compound,
The colorant is a colorant containing a xanthene dye and a pigment,
A colored photosensitive resin composition, wherein the polymerization initiator is a polymerization initiator containing an O-acyloxime compound. The colored photosensitive resin composition according to claim 1, wherein the xanthene dye is a dye containing a compound represented by the formula (1a).

[In Formula (1a), R ^{1 to} R ⁴ each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O—, —CO— or —NR ¹¹ —. Also good. 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 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and the four R ¹¹ may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and is contained in the saturated aliphatic hydrocarbon group— CH ₂ — may be replaced by —O—, —CO—, —NH—, or —NR ⁸ —, and R ⁹ and R ¹⁰ are bonded to each other to contain a nitrogen atom. A heterocyclic ring may be formed.
R ¹¹ 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. ]   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.