JP6369159B2 - Compound and colored curable resin composition containing the compound - Google Patents

Description

  The present invention relates to a compound and a colored curable resin composition containing the compound.

Dyes are used for color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, ink jets, and the like. As such a dye, a compound represented by the following formula (d0) is known.

Japanese Patent Application Laid-Open No. 2004-2630 (Example 1)

  In the process of forming a color filter from a colored curable resin composition containing a compound represented by the formula (d0), the problem was that the colorant sublimated.

［式（Ｚ）中、Ｒ^１は、アクリロイル基を含む基、メタクリロイル基を含む基又はケイ素原子を含む基を表す。
Ｒ^２は、水素原子、シアノ基又はカルバモイル基を表す。
Ｒ^３は、ハロゲン原子を有していてもよい炭素数１〜４のアルキル基を表す。
Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ⁸は、それぞれ独立して、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数２〜８のアルコキシアルキル基、ヒドロキシ基、シアノ基、ニトロ基、カルボキシル基又は−ＳＯ_３Ｍを表し、Ｍは、水素原子又はアルカリ金属原子を表す。］
［２］ケイ素原子を含む基が、式（Ｚ１）で表される基である［１］に記載の化合物。

［式中、Ｒ^１１Ａは、炭素数１〜１０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−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＲ^１０−、−ＯＣＯ−、−ＣＯＯ−、−ＯＣＯＮＨ−、−ＣＯＮＨ−または−ＮＨＣＯ−で置換されていてもよい。
Ｒ^１０は、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｒ^１２Ａ、Ｒ^１３Ａ及びＲ^１４Ａは、それぞれ独立して、水素原子、ヒドロキシ基、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表す。
＊は窒素原子との結合手を表す。］
［３］アクリロイル基を含む基又はメタクリロイル基を含む基が、式（Ｚ２）で表される基である［１］に記載の化合物。

［式中、Ｒ^１５Ａは、炭素数１〜１０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−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＲ^１１−、−ＯＣＯ−、−ＣＯＯ−、−ＯＣＯＮＨ−、−ＣＯＮＨ−または−ＮＨＣＯ−で置換されていてもよい。
Ｒ^１１は、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｒ^１６Ａは、アクリロイル基又はメタクリロイル基を表す。
＊は窒素原子との結合手を表す。］
［４］［１］〜［３］のいずれかに記載の化合物を含む着色剤。
［５］さらに顔料を含む［４］に記載の着色剤。
［６］顔料が、ハロゲン化銅フタロシアニン顔料及びハロゲン化亜鉛フタロシアニン顔料からなる群から選ばれる少なくとも一種である［５］に記載の着色剤。
［７］顔料が、塩素化銅フタロシアニン顔料、臭素化銅フタロシアニン顔料及び臭素化亜鉛フタロシアニン顔料からなる群から選ばれる少なくとも一種である［５］又は［６］に記載の着色剤。
［８］顔料が、Ｃ．Ｉ．ピグメントグリーン３６およびＣ．Ｉ．ピグメントグリーン５８からなる群から選ばれる少なくとも一種である［５］〜［７］のいずれかに記載の着色剤。
［９］［４］〜［８］のいずれかに記載の着色剤、樹脂、重合性化合物及び重合開始剤を含む着色硬化性樹脂組成物。
［１０］［９］に記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［１１］［１０］に記載のカラーフィルタを含む液晶表示装置。 The present invention includes the following inventions.
[1] A compound represented by the formula (Z).

[In formula (Z), R ¹ represents a group containing an acryloyl group, a group containing a methacryloyl group, or a group containing a silicon atom.
R ² represents a hydrogen atom, a cyano group or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms which may have a halogen atom.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkoxyalkyl having 2 to 8 carbon atoms. Represents a group, a hydroxy group, a cyano group, a nitro group, a carboxyl group or —SO ₃ M, and M represents a hydrogen atom or an alkali metal atom. ]
[2] The compound according to [1], wherein the group containing a silicon atom is a group represented by the formula (Z1).

[Wherein, R ^11A represents an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group represents —O—, —CO—, —NR ¹⁰ —, —OCO—, It may be substituted with -COO-, -OCONH-, -CONH- or -NHCO-.
R ¹⁰ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^12A , R ^13A and R ^14A each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
* Represents a bond with a nitrogen atom. ]
[3] The compound according to [1], wherein the group containing an acryloyl group or the group containing a methacryloyl group is a group represented by the formula (Z2).

[Wherein, R ^15A represents an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group represents —O—, —CO—, —NR ¹¹ —, —OCO—, It may be substituted with -COO-, -OCONH-, -CONH- or -NHCO-.
R ¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^16A represents an acryloyl group or a methacryloyl group.
* Represents a bond with a nitrogen atom. ]
[4] A colorant comprising the compound according to any one of [1] to [3].
[5] The colorant according to [4], further comprising a pigment.
[6] The colorant according to [5], wherein the pigment is at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment.
[7] The colorant according to [5] or [6], wherein the pigment is at least one selected from the group consisting of a chlorinated copper phthalocyanine pigment, a brominated copper phthalocyanine pigment, and a brominated zinc phthalocyanine pigment.
[8] The pigment is C.I. I. Pigment green 36 and C.I. I. The colorant according to any one of [5] to [7], which is at least one selected from the group consisting of CI Pigment Green 58.
[9] A colored curable resin composition comprising the colorant, resin, polymerizable compound and polymerization initiator according to any one of [4] to [8].
[10] A color filter formed from the colored curable resin composition according to [9].
[11] A liquid crystal display device including the color filter according to [10].

  When forming a color filter from the colored curable resin composition containing the compound of the present invention, sublimation of the colorant can be suppressed.

［式（Ｚ）中、Ｒ^１は、アクリロイル基を含む基、メタクリロイル基を含む基又はケイ素原子を含む基を表す。
Ｒ^２は、水素原子、シアノ基、又はカルバモイル基を表す。
Ｒ^３は、ハロゲン原子を有していてもよい炭素数１〜４のアルキル基を表す。
Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ⁸は、それぞれ独立して、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数２〜８のアルコキシアルキル基、ヒドロキシ基、シアノ基、ニトロ基、カルボキシル基又は−ＳＯ_３Ｍを表し、Ｍは、水素原子又はアルカリ金属原子を表す。］ <Compound represented by formula (Z) (hereinafter sometimes referred to as compound (Z))>

[In formula (Z), R ¹ represents a group containing an acryloyl group, a group containing a methacryloyl group, or a group containing a silicon atom.
R ² represents a hydrogen atom, a cyano group, or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms which may have a halogen atom.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkoxyalkyl having 2 to 8 carbon atoms. Represents a group, a hydroxy group, a cyano group, a nitro group, a carboxyl group or —SO ₃ M, and M represents a hydrogen atom or an alkali metal atom. ]

R ² is preferably a cyano group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ³ 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 halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the alkyl group having 1 to 4 carbon atoms having a halogen atom include a trifluoromethyl group, a pentafluoroethyl group, a trichloromethyl group, a tribromomethyl group, a pentachloroethyl group, a pentabromoethyl group, and a dichlorofluoromethyl group. Is mentioned. Preferably it is a C1-C4 fluorinated alkyl group.
R ³ is preferably an alkyl group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, more preferably a methyl group or a trifluoromethyl group, and even more preferably a methyl group.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec- Examples include butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and methylcyclohexyl group.
Examples of the alkoxy group having 1 to 8 carbon atoms represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl An oxy group and an octyloxy group are mentioned.
Examples of the alkoxyalkyl group having 2 to 8 carbon atoms represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxypentyl group, 1-ethoxypropyl group, 2-ethoxypropyl group, 1-ethoxy-1-methylethyl group, 1-methyl-2-ethoxyethyl group, 1- (1-methylethoxy) propyl group, 2- (1-methylethoxy ) Propyl group, 1- (1-methylethoxy) -1-methylethyl group, 2- (1-methylethoxy) -1-methylethyl group, 3-ethoxypropyl group.

Examples of the alkali metal atom represented by M include a lithium atom, a sodium atom, and a potassium atom.
M is preferably a hydrogen atom and a sodium atom, and more preferably a hydrogen atom.
Examples of —SO ₃ M represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ include —SO ₃ H and —SO ₃ Na.

［式中、Ｒ^１５Ａは、炭素数１〜１０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−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＲ^１１−、−ＯＣＯ−、−ＣＯＯ−、−ＯＣＯＮＨ−、−ＣＯＮＨ−または−ＮＨＣＯ−で置換されていてもよい。
Ｒ^１１は、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｒ^１６Ａは、アクリロイル基又はメタクリロイル基を表す。
＊は窒素原子との結合手を表す。］ The group containing an acryloyl group or the group containing a methacryloyl group means a group having at least one acryloyl group or methacryloyl group as a structural unit of the group.
The number of carbon atoms of the group containing an acryloyl group represented by R ¹ is usually 4-20, preferably 4-15, more preferably 4-10.
The number of carbon atoms of the group containing a methacryloyl group represented by R ¹ is usually 5-20, preferably 5-15, more preferably 5-10.
The group containing an acryloyl group is preferably a group containing an acryloyloxy group.
The group containing a methacryloyl group is preferably a group containing a methacryloyloxy group.
The group containing an acryloyl group represented by R ¹ or the group containing a methacryloyl group is preferably a group represented by the formula (Z2).

[Wherein, R ^15A represents an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group represents —O—, —CO—, —NR ¹¹ —, —OCO—, It may be substituted with -COO-, -OCONH-, -CONH- or -NHCO-.
R ¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^16A represents an acryloyl group or a methacryloyl group.
* Represents a bond with a nitrogen atom. ]

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ^15A include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene group, isobutylene group, 2-methyltrimethyl group. Examples include a methylene group, an isopentylene group, an isohexylene group, an isooctylene group and a 2-ethylhexylene group, preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl. Alkyl groups having 1 to 20 carbon atoms such as a group, hexadecyl group, icosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group;
Examples thereof include alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group.
R ¹¹ is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a methyl group or a hydrogen atom.

Examples of the group containing an acryloyl group or a methacryloyl group include a group represented by (ii-1) to a group represented by (ii-14).

［式中、Ｒ^１１Ａは、炭素数１〜１０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−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＲ^１０−、−ＯＣＯ−、−ＣＯＯ−、−ＯＣＯＮＨ−、−ＣＯＮＨ−または−ＮＨＣＯ−で置換されていてもよい。
Ｒ^１０は、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｒ^１２Ａ、Ｒ^１３Ａ及びＲ^１４Ａは、それぞれ独立して、水素原子、ヒドロキシ基、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表す。
＊は窒素原子との結合手を表す。］ The group containing a silicon atom means a group containing a silicon atom as a constituent element of the group.
The number of carbon atoms of the group containing a silicon atom represented by R ¹ is usually 1-30, preferably 1-20.
The group containing a silicon atom represented by R ¹ is preferably a group represented by the formula (Z1).

[Wherein, R ^11A represents an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group represents —O—, —CO—, —NR ¹⁰ —, —OCO—, It may be substituted with -COO-, -OCONH-, -CONH- or -NHCO-.
R ¹⁰ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^12A , R ^13A and R ^14A each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
* Represents a bond with a nitrogen atom. ]

As a C1-C10 alkanediyl group represented by R ^<11A >, the same thing as the C1-C10 alkanediyl group represented by R ^<15A > is mentioned. R ^11A is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.
Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ include the same as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ .

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^12A , R ^13A and R ^14A 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. Group, cyclopropyl group and cyclobutyl group.
Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^12A , R ^13A and R ^14A include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and a tert-butoxy group. Is mentioned.
R ^12A , R ^13A and R ^14A are preferably all the same group.
R ^12A , R ^13A and R ^14A are each independently preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

Examples of the group containing a silicon atom include the groups described below.

^Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —O— include the following groups (* represents a bond to a nitrogen atom).

Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —CO— include the following groups (* represents a bond to a nitrogen atom).

^Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —NR ¹¹ — include groups represented by the following (* represents a bond to a nitrogen atom).

Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —OCO— include the following groups (* represents a bond with a nitrogen atom).

Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —COO— include the groups shown below (* represents a bond).

Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —OCONH— include the following groups (* represents a bond with a nitrogen atom).

Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —CONH— include groups represented by the following (* represents a bond to a nitrogen atom).

Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —NHCO— include the following groups (* represents a bond to a nitrogen atom).

As the group containing a silicon atom, the following groups are preferred.

Specific examples of the compound (Z) include a compound represented by the formula (Z-1) to a compound represented by the formula (Z-68).

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ⁸は、上記と同じ意味を表す。Ａ^１は、無機アニオン又は有機アニオンを表す。］ Compound (Z) can be produced by reacting the method described in JP-B-7-88633 or a diazonium salt represented by formula (z2) with a compound represented by formula (z3).
The diazonium salt represented by the formula (z2) can be obtained, for example, by diazotizing the compound represented by the formula (z1) with nitrous acid, nitrite or nitrite.

[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the same meaning as described above. A ¹ represents an inorganic anion or an organic anion. ]

Examples of inorganic anions include halide ions such as fluoride ions, chloride ions, bromide ions, iodide ions; perchlorate ions, hypochlorite ions, and the like.
Examples of the organic anion include carboxylate anions such as CH ₃ COO ⁻ and PhCOO ⁻ (wherein Ph represents a phenyl group).
Preferably, chloride ion, bromide ion and _CH 3 COO ^- is.

  The compound (Z) can be produced by reacting the diazonium salt represented by the formula (z2) with the compound represented by the formula (z3) in an aqueous solvent such as N-methylpyrrolidone. The reaction temperature is preferably −5 to 60 ° C., more preferably 0 ° C. to 30 ° C. The reaction time is preferably 1 to 12 hours, and more preferably 1 to 4 hours.

［式中、Ｒ^１１３は、２価の連結基を表す。
Ｒ^１１４及びＲ^１１５は、それぞれ独立して、親水性基を表す。
Ｒ^１１６は、ケイ素原子を含む基を表す。
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ⁸は、上記と同じ意味を表す。］ Further, for example, the compound (Z) in which R ¹ is a group containing a silicon atom can be obtained by reacting a compound represented by the formula (z5) with a compound represented by the formula (z6). The compound represented by the formula (z5) is represented by the formula (z5) by diazo coupling the diazonium salt represented by the formula (z2) and the compound represented by the formula (z4). Compounds can be produced.

[Wherein R ¹¹³ represents a divalent linking group.
R ¹¹⁴ and R ¹¹⁵ each independently represent a hydrophilic group.
R ¹¹⁶ represents a group containing a silicon atom.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the same meaning as described above. ]

^Examples of the divalent linking group represented by R113 include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene group, isobutylene group, 2-methyltrimethylene group, and isopentylene. Group, an isohexylene group, an isooctylene group and a 2-ethylhexylene group and the like, and alkanediyl groups having 1 to 10 carbon atoms. —CH ₂ — contained in the alkanediyl group is substituted with —O—, —CO—, —NR ¹¹ —, —OCO—, —COO—, —OCONH—, —CONH— or —NHCO—. Also good.
Examples of the hydrophilic group represented by R ¹¹⁴ and R ¹¹⁵ include a hydroxy group and a carboxy group. However, R ¹¹⁴ and R ¹¹⁵ do not represent the same group.
The group containing a silicon atom represented by R ¹¹⁶ represents a group containing a silicon atom as a constituent element of the group.
A group represented by * —R ¹¹³ —R ¹¹⁶ (* represents a bond to a nitrogen atom) corresponds to R ¹ in the compound (Z).

  The reaction between the compound represented by the formula (z5) and the compound represented by the formula (z6) is preferably performed in the presence of a halogenated solvent such as chloroform. The reaction temperature is preferably from -10 ° C to 100 ° C, more preferably from 0 ° C to 50 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.

The amount of the compound represented by the formula (z6) is usually 1 mol or more and 8 mol or less, preferably 1 mol or more and 4 mol or less, with respect to 1 mol of the azo compound represented by the formula (z5). .
In the reaction, it is more preferable to add an acidic catalyst so that the reaction proceeds smoothly. Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.
Although the usage-amount of these catalysts is arbitrary, Preferably it is 0.01-4 mol with respect to 1 mol of compounds represented by a formula (z6), More preferably, it is 0.8-2 mol.

  The method for obtaining the target compound of the present invention from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, it is preferable that the reaction mixture is mixed with an acid (for example, acetic acid and the like) and water, and the precipitated crystals are collected by filtration. The acid is preferably prepared by preparing an aqueous solution of the acid in advance, and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is usually 10 ° C. or higher and 50 ° C. or lower, preferably 20 ° C. or higher and 50 ° C. or lower, preferably 20 ° C. or higher and 30 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of an acid, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystal collected by filtration is preferably washed with water or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

［式中、Ｒ^１１１は、２価の連結基を表す。
Ｒ^１１０は、アクリロイル基を含む基又はメタクリロイル基を含む基を表す。
Ｒ^１１２は、ハロゲン原子を表す。
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ⁸は、上記と同じ意味を表す。］ For example, the compound (Z) in which R ¹ is a group containing an acryloyl group or a group containing a methacryloyl group is obtained by reacting the compound represented by the formula (z8) with the compound represented by the formula (z9). Can be obtained. A compound represented by formula (z8) is produced by reacting a diazonium salt represented by formula (z2) with a compound represented by formula (z7). can do.

[Wherein, R ¹¹¹ represents a divalent linking group.
R ¹¹⁰ represents a group containing an acryloyl group or a group containing a methacryloyl group.
R ¹¹² represents a halogen atom.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the same meaning as described above. ]

^Examples of the divalent linking group represented by R ¹¹¹ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an isopropylene group, an isobutylene group, a 2-methyltrimethylene group, and isopentylene. Group, an isohexylene group, an isooctylene group and a 2-ethylhexylene group and the like, and alkanediyl groups having 1 to 10 carbon atoms. —CH ₂ — contained in the alkanediyl group is substituted with —O—, —CO—, —NR ¹¹ —, —OCO—, —COO—, —OCONH—, —CONH— or —NHCO—. Also good.
Examples of the halogen atom represented by R ¹¹² include a chlorine atom and a bromine atom.
Examples of the group containing an acryloyl group or a group containing a methacryloyl group represented by R ¹¹⁰ include a group having at least one acryloyl group or methacryloyl group as a structural unit of the group.
A group represented by * —R ¹¹¹ —R ¹¹⁰ (* represents a bond with a nitrogen atom) corresponds to R ¹ in the compound (Z).

  The reaction between the compound represented by the formula (z8) and the compound represented by the formula (z9) is preferably performed in the presence of a halogenated solvent such as chloroform. The reaction temperature is preferably from -10 ° C to 100 ° C, more preferably from 0 ° C to 50 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.

The usage-amount of the compound represented by a formula (z9) is 1 mol or more and 8 mol or less normally with respect to 1 mol of compounds represented by a formula (z8), Preferably they are 1 mol or more and 4 mol or less.
In the reaction, it is more preferable to add an acidic catalyst so that the reaction proceeds smoothly. Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.
Although the usage-amount of these catalysts is arbitrary, Preferably it is 0.01-4 mol with respect to 1 mol of compounds represented by a formula (z6), More preferably, it is 0.8-2 mol.

  The method for obtaining the target compound of the present invention from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, it is preferable that the reaction mixture is mixed with an acid (for example, acetic acid and the like) and water, and the precipitated crystals are collected by filtration. The acid is preferably prepared by preparing an aqueous solution of the acid in advance, and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is usually 10 ° C. or higher and 50 ° C. or lower, preferably 20 ° C. or higher and 50 ° C. or lower, preferably 20 ° C. or higher and 30 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of an acid, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystal collected by filtration is preferably washed with water or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  The compound (Z) of the present invention can be used as a dye.

The colored curable resin composition of the present invention includes a colorant (A) containing the compound (Z), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
As the colorant (A), two or more compounds (Z) may be used. Further, as the colorant (A), a dye or pigment (P) other than the compound (Z) may be used.
The colored curable resin composition of the present invention preferably further contains at least one selected from the group consisting of a solvent (E) and a leveling agent (F).
The colored curable resin composition of the present invention may further 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.

  As the dye other than the compound (Z), a yellow dye or a red dye is preferable, and a yellow dye is particularly preferable. Examples of yellow dyes include dyes having a coumarin skeleton.

The pigment (P) is not particularly limited, and a known pigment can be used. For example, pigments classified as Pigment in the Color Index (published by The Society of Dyers and Colorists) can be used. Can be mentioned.
Examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 180, 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, 14, 19, 23, 29, 32, 33, 36, 37, 38;
C. I. Green pigments such as CI Pigment Green 7, 10, 15, 25, 36, 47, 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.

The pigment (P) is preferably a phthalocyanine pigment,
More preferably, halogenated copper phthalocyanine pigment such as fluorinated copper phthalocyanine pigment, chlorinated copper phthalocyanine pigment, brominated copper phthalocyanine pigment and halogenated copper phthalocyanine pigment, chlorinated zinc phthalocyanine pigment, brominated zinc phthalocyanine pigment, etc. At least one selected from the group consisting of zinc phthalocyanine pigments,
More preferably, it is at least one selected from the group consisting of chlorinated copper phthalocyanine pigments, brominated copper phthalocyanine pigments and brominated zinc phthalocyanine pigments,
Particularly preferably, C.I. I. At least one selected from the group consisting of CI Pigment Green 36 and 58. These pigments are suitably used for green pigments, and by including the above-mentioned pigments, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

If necessary, the pigment is atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment to the pigment surface with a polymer compound, etc., sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment by an ion exchange method of ionic impurities, or the like may be performed. The pigments preferably have a uniform particle size.
The pigment can be made into a pigment dispersion in a state of being uniformly dispersed in the pigment dispersant solution by carrying out a dispersion treatment by containing a pigment dispersant. The pigments may be subjected to a dispersion treatment alone, or a plurality of types may be mixed and dispersed.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. 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 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion having a more uniform dispersion state tends to be obtained.

The content of the compound (Z) is preferably 0.01% by mass or more and 90% by mass or less, more preferably 0.1% by mass or more and 80% by mass or less, with respect to the total amount of the colorant (A). More preferably, it is 1 mass% or more and 65 mass% or less, More preferably, it is 2 mass% or more and 60 mass% or less.
When the pigment (P) is contained, the content thereof is preferably 10% by mass or more and 99.99% by mass or less, more preferably 20% by mass or more and 99.9% by mass with respect to the total amount of the colorant (A). % Or less, more preferably 35% by mass or more and 99% by mass or less, and more preferably 40% by mass or more and 98% by mass or less.
The content of the colorant (A) is usually 1% by mass or more and 99% by mass or less, preferably 2% by mass or more and 90% by mass or less, and more preferably 3% by mass with respect to the total amount of the solid content. It is 80 mass% or less, More preferably, it is 5 mass% or more and 70 mass% or less, More preferably, it is 5 mass% or more and 60 mass% or less, Most preferably, it is 5 mass% or more and 50 mass% or less. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.

  In this specification, the “total amount of solids” refers to the total amount of components obtained by removing the solvent (E) from the colored curable resin composition of the present invention. 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, and an addition polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. More preferred. Examples of such resins include the following resins [K1] to [K6].
Resin [K1] At least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), a cyclic ether structure having 2 to 4 carbon atoms, A copolymer with 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) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.
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.

  (B1-2) includes vinyl cyclohexylene monooxide, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by formula (I), a compound represented by formula (II), and the like.

[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 formula (I) and the compound represented by formula (II) may be used alone or in combination with the compound represented by formula (I) and the compound represented by formula (II). May be. When these are used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 5 on a molar basis. 90:10, more preferably 20:80 to 80:20.

  (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 curable 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 called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (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, vinyl toluene, 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.
Of these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N from the viewpoint of copolymerization reactivity and heat resistance. -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are 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 unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter are excellent. 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.) As the solvent, any solvent that dissolves each monomer may be used. Examples of the solvent (E) for the colored curable resin composition of the present invention include a solvent 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 curable 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 curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable 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 curable 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 unit derived from each is the same as that of 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 curable resin composition, the developability when forming the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern 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 (meth) acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3 , 4-epoxytricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3- menu Resin such as ru-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) Acrylic acid copolymer, resin such as benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer A resin in which glycidyl (meth) acrylate is added to a resin, a resin in which glycidyl (meth) acrylate is added to a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / Benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) acrylate Resin [K4] such as a resin to which a relate is added; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / Resin such as a resin obtained by reacting a copolymer of styrene / glycidyl (meth) acrylate with (meth) acrylic acid [K5]; a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate (meth) Examples thereof include a resin [K6] such as a resin obtained by reacting acrylic acid with a resin further reacted with tetrahydrophthalic anhydride.

  The resin (B) is preferably a kind selected from the group consisting of a resin [K1], a resin [K2] and a resin [K3], and more preferably from a group consisting of a resin [K2] and a resin [K3]. It is the kind chosen. When these resins are used, the colored curable resin composition is excellent in developability. Resin [K2] is more preferable from the viewpoint of adhesion between the coloring pattern and the substrate.

The weight average molecular weight in terms of polystyrene of the resin (B) is usually from 3,000 to 100,000, preferably from 5,000 to 50,000, more preferably from 5,000 to 35,000, Preferably it is 5,000-30,000, Most preferably, it is 6,000-30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.
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 usually 20 mg-KOH / g to 170 mg-KOH / g, preferably 30 mg-KOH / g to 170 mg-KOH / g, more preferably 40 mg-KOH / g to 170 mg. -KOH / g, more preferably 50 mg-KOH / g to 170 mg-KOH / g. Among them, 50 mg-KOH / g to 150 mg-KOH / g are preferable, 60 mg-KOH / g to 150 mg-KOH / g are more preferable, 60 mg-KOH / g to 135 mg-KOH / g are further preferable, and 70 mg-KOH / g. -135 mg-KOH / g is particularly preferred. 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.

The content of the resin (B) is preferably 7% by mass to 65% by mass, more preferably 10% by mass to 60% by mass, and still more preferably 13% by mass to 60% by mass with respect to the total amount of the solid content. It is mass%, Most preferably, it is 17 mass%-55 mass%. When the content of the resin (B) is in the above range, a colored pattern can be easily formed, and the resolution and remaining film ratio of the colored pattern 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.

  Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. And the above-mentioned (a), (a) and (c).

  Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (Meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

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 1 to 70% by mass, more preferably 2 to 65% by mass, and more preferably 5 to 65% by mass, based on the total amount of the solid content. It is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. is there.
Further, the content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is based on mass, preferably 20:80 to 80:20, more preferably. Is 35: 65-80: 20.
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)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

前記Ｏ−アシルオキシム化合物としては、例えば、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュアＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。中でも、Ｏ−アシルオキシム化合物は、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン及びＮ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミンからなる群から選ばれる少なくとも１種が好ましく、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミンがより好ましい。 The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine 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. 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-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred.

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

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

［式（ｄ５）中、Ｒ^５１〜Ｒ^５６は、置換基を有していてもよい炭素数６〜１０のアリール基を表す。］ The biimidazole compound is, for example, a compound represented by the formula (d5).

[In formula (d5), R ^{51 to} R ⁵⁶ represent an aryl group having 6 to 10 carbon atoms which may have a substituent. ]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group and a naphthyl group, and a phenyl group is preferable.
Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example, Preferably it is a methoxy group.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis ( 2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxy) Phenyl) biimidazo (For example, see Japanese Patent Publication No. 48-38403, Japanese Patent Laid-Open Publication No. 62-174204, etc.) And JP-A-7-10913). Among these, compounds represented by the following formula and mixtures thereof are preferable.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheny ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

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

  The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and more preferably. Is a polymerization initiator containing an O-acyloxime compound.

  The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is 1-30 mass parts, More preferably, it is 1-30 mass parts.

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

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

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

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

  Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

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

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (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, γ-butyrolactone and the like.

  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, phenetole, 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, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl 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, glycerin and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

These solvents may be used alone or in combination of two or more.
Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3- Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, di Propylene glycol methyl ether acetate, ethyl lactate, 3-methoxy Chill acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone, N, N- dimethylformamide, N- methylpyrrolidone and the like are more preferable.

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

<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 Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

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

  The content of the leveling agent (F) is preferably 0.0005% by mass or more and 0.6% by mass or less, more preferably 0.001% by mass or more and 0.000% by mass or more based on the total amount of the colored curable resin composition. 5 mass%, preferably 0.001 mass% or more and 0.2 mass% or less, preferably 0.002 mass% or more and 0.1 mass% or less, more preferably 0.005 mass% or more and 0.07 mass% or less. It is below mass%. 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 curable 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 curable resin composition>
The colored curable 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 pigment in the case of containing the pigment (P) 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 curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
The compound (1) is preferably prepared in advance by dissolving it in part or all of the solvent solvent (E). The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The colored curable 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 curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored curable 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 the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable 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 0.02 to 5% by mass, and even 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.

Next, the present invention will be described more specifically with reference to examples.
In Examples and Comparative Examples, “%” and “part” representing content or use amount are based on mass unless otherwise specified.
The structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 model, MASS; Agilent LC / MSD6130 model).

Example 1
After adding 4.0 parts of sodium hydroxide to 398 parts of water, 18.2 parts of a compound represented by the following formula (d1) was added. Under ice-cooling, 7.1 parts of sodium nitrite and 208 parts of water were added to the resulting mixture, followed by 7.1 parts of 35% hydrochloric acid. Thereafter, the obtained mixture was stirred for 2 hours to obtain a suspension containing a diazonium salt.

式（ｄ３）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＝ ４０１．０[Ｍ＋１]⁺
Ｅｘａｃｔ Ｍａｓｓ： ４００．１ 20.8 parts of the compound represented by the formula (d2) was suspended in 404 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. To the obtained mixture, the suspension containing the diazonium salt obtained above was added dropwise over 15 minutes. After completion of dropping, a yellow suspension was obtained by stirring for 30 minutes and further stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 38.5 parts of a compound represented by the formula (d3).

Identification of compound represented by formula (d3) (mass spectrometry) ionization mode = ESI +: m / z = 401.0 [M + 1] ⁺
Exact Mass: 400.1

4.0 parts of the compound represented by the formula (d3) and 1.4 parts of 2- (trimethylsilyl) ethanol were added to 100 parts of dehydrated chloroform. To the obtained mixture, 2.3 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 1.5 parts of 4-dimethylaminopyridine were further added and stirred at 30 ° C. for 6 hours. Water was added to the obtained reaction mixture, the organic layer was extracted, chloroform was distilled off, and a yellow solid was obtained. It dried at 60 degreeC under pressure reduction for 24 hours, and 4.2 parts of compounds represented by Formula (1-1) were obtained.

Identification of compound represented by formula (1-1) (mass spectrometry) ionization mode = ESI +: m / z = 502.1 [M + 1] ⁺
Exact Mass: 501.1

式（１−２）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＝ ５３８．１[Ｍ＋１]⁺
Ｅｘａｃｔ Ｍａｓｓ： ５３７．１ Example 2
In Example 1, a compound represented by the formula (1-2) was obtained in the same manner except that the compound represented by the following formula (d4) was used instead of the compound represented by the formula (d1). It was.

Identification of compound represented by formula (1-2) (mass spectrometry) ionization mode = ESI +: m / z = 538.1 [M + 1] ⁺
Exact Mass: 537.1

Example 3
After adding 4.0 parts of sodium hydroxide to 398 parts of water, 18.2 parts of a compound represented by the following formula (d5) was added. Under ice cooling, 7.1 parts of sodium nitrite and 208 parts of water were added, and then 7.1 parts of 35% hydrochloric acid were added. Thereafter, the mixture was stirred for 2 hours to obtain a suspension containing a diazonium salt.

19.4 parts of the compound represented by the following formula (d6) was suspended in 404 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt obtained above was added dropwise with a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 34.8 parts of a compound represented by the formula (d7).

Identification of compound represented by formula (d7) (mass spectrometry) ionization mode = ESI +: m / z = 381.7 [M + 1] ⁺
Exact Mass: 380.7

Next, 3.8 parts of the compound represented by the formula (d7) and 2.0 parts of triethylamine were added to 300 parts of chloroform, then 3.1 parts of methacrylic anhydride were added, and the mixture was kept at 50 ° C. for 3 hours. After completion of the reaction, 300 parts of water was added to extract the organic layer, and chloroform was distilled off to obtain a yellow solid. It dried at 60 degreeC under pressure reduction for 24 hours, and obtained 3.8 parts of compounds represented by Formula (1-9).

Identification of compound represented by formula (1-9) (mass spectrometry) ionization mode = ESI +: m / z = 442.3 [M + 1] ⁺
Exact Mass: 441.3

Example 4
In Example 3, the compound represented by the formula (1-10) was replaced with the compound represented by the following formula (d8) instead of the compound represented by the formula (d5). Got.

Identification of compound represented by formula (1-10) (mass spectrometry) ionization mode = ESI +: m / z = 478.1 [M + 1] ⁺
Exact Mass: 477.1

Synthesis example 1
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] Decan-9-yl acrylate (content ratio is 50:50 in molar ratio) 171 parts dissolved in propylene glycol monomethyl ether acetate 40 parts using a dropping pump over about 5 hours And dripped. On the other hand, a solution obtained by dissolving 26 parts of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was placed in the flask over another 5 hours using another dropping pump. It was dripped. After completion of dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a copolymer (resin B1) solution having a solid content of 43.5%. The obtained resin B1 had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mgKOH / g.

(Preparation of colored curable resin composition)
Example 5
Colorant (A): C.I. I. Pigment Green 58 (pigment) 27 parts,
12 parts acrylic pigment dispersant,
Resin (B): Resin B1 (solid content conversion) 9.5 parts and Solvent (E): Propylene glycol monomethyl ether acetate 180 parts were mixed, and a pigment dispersion liquid (3 )

Colorant (A): 3.0 parts of a compound represented by formula (1-1);
Resin (B): Resin B1 (solid content conversion) 40 parts;
Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 9.8 parts;
Solvent (E): 670 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 part; Obtained.

Example 6
C. of the colorant (A) I. Pigment Green 58 (pigment) I. A colored curable resin composition (J2) was obtained in the same manner as in Example 5 except that the pigment green 36 (pigment) was used instead.

Example 7
A colored curable resin composition (J3) was prepared in the same manner as in Example 5 except that the compound represented by formula (1-1) of the colorant (A) was replaced with the compound represented by formula (1-2). )

Example 8
C. of the colorant (A) I. Pigment Green 58 (pigment) I. A colored curable resin composition (J4) was obtained in the same manner as in Example 7 except that the pigment green 36 (pigment) was used instead.

Example 9
Colorant (A): C.I. I. Pigment Green 58 (pigment) 20 parts,
12 parts acrylic pigment dispersant,
Resin (B): Resin B1 (solid content conversion) 9.5 parts, and solvent (E): propylene glycol monomethyl ether acetate 180 parts were mixed, and a pigment dispersion liquid (4 )

Colorant (A): 2.5 parts of the compound represented by formula (1-9);
Resin (B): Resin B1 (solid content conversion) 40 parts;
Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 9.8 parts;
Solvent (E): 670 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 part; and a pigment dispersion (4) are mixed to obtain a colored curable resin composition (J5). Obtained.

Example 10
C. of the colorant (A) I. Pigment Green 58 (pigment) I. A colored curable resin composition (J6) was obtained in the same manner as in Example 9 except that it was replaced with CI Pigment Green 36 (pigment).

Example 11
A colored curable resin composition (J7) was prepared in the same manner as in Example 9, except that the compound represented by formula (1-9) of the colorant (A) was replaced with the compound represented by formula (1-10). )

Example 12
C. of the colorant (A) I. Pigment Green 58 (pigment) I. A colored curable resin composition (J8) was obtained in the same manner as in Example 11 except that it was replaced with Pigment Green 36 (pigment).

Comparative Example 1
Colorant (A): C.I. I. Pigment Green 58 (pigment) 27 parts,
12 parts acrylic pigment dispersant,
Resin (B): resin B1 (solid content conversion) 9.5 parts, and solvent (E): propylene glycol monomethyl ether acetate 180 parts were mixed, and a pigment dispersion liquid (5 )

Colorant (A): 1.0 part of a compound represented by formula (d0);
Resin (B): Resin B1 (solid content conversion) 40 parts;
Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 9.8 parts;
Solvent (E): 670 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 part; Obtained.

[Film thickness measurement]
The film thickness was measured using DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.

[Preparation of resin composition for sublimation test (SJS)]
Resin: Methacrylic acid / benzyl methacrylate (molar ratio: 30/70) copolymer (manufactured by Taoka Chemical Co., Ltd., average molecular weight 10700, acid value 70 mg KOH / g) 33.8% propylene glycol monomethyl ether acetate solution 40.2 Part;
Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.8 parts;
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Japan Ltd.) 0.58 parts;
Leveling agent: polyether-modified silicone (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.01 part;
Solvent: 46.6 parts of propylene glycol monomethyl ether; Solvent: 6.8 parts of propylene glycol monomethyl ether acetate were mixed to obtain a resin composition for sublimation test (SJS).

[Formation of resin coating film for sublimation test (SJSM)]
On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), the resin composition for sublimation test (SJS) obtained above was applied by spin coating, and volatile components were volatilized at 100 ° C. for 3 minutes. . After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), light irradiation was performed with an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. A resin coating film for sublimation test (SJSM) (thickness: 2.2 μm) was formed by heating in an oven at 220 ° C. for 2 hours.

Example 13
[Preparation of colored pattern and evaluation of sublimation]
A colored curable resin composition obtained in Example 1 was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer Formed. After cooling, the distance between the substrate on which the colored composition layer is formed and the quartz glass photomask is set to 200 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used, and 80 mJ / cm ^{2 in} an air atmosphere. The exposure amount (standard on 365 nm) was used. A photomask having a 100 μm line and space pattern was used. The colored composition layer after the exposure was developed by being immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 70 seconds, and washed with water. The film thickness was measured. The results are shown in Table 1.
The colored coating film and the resin coating film for sublimation test (SJSM) obtained above were opposed to each other with an interval of 70 μm, and a post-baking was performed at 230 ° C. for 10 minutes to obtain a colored pattern. . The color difference (ΔEab *) before and after heating of the resin coating film for sublimation test (SJSM) was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The color difference (ΔEab *) was 3.0. A color difference (ΔEab *) of 5.0 or more indicates that the colorant has sublimability. The results are shown in Table 1. In Table 1, in each Example, ◯ indicates that the colorant does not have sublimability, and x indicates that the colorant has sublimability.

Examples 14 to 20 and Comparative Example 2
Example 1 except that the colored curable resin composition (J1) obtained in Example 1 is replaced with a colored curable resin composition (J2) to a colored curable resin composition (J9), respectively. Similarly, a colored pattern was obtained and evaluated for sublimation. The results are shown in Table 1.

  When forming a color filter from the colored curable resin composition containing the compound of the present invention, sublimation of the colorant can be suppressed. The color filter using the colored curable resin composition containing the compound of the present invention is suitably used for a display device such as a liquid crystal display device.

Claims (10)

A compound represented by formula (Z).

[In Formula (Z), R ¹ represents a group represented by Formula (Z1).
R ² represents a hydrogen atom, a cyano group or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms which may have a halogen atom.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkoxyalkyl having 2 to 8 carbon atoms. Represents a group, a hydroxy group, a cyano group, a nitro group, a carboxyl group or —SO ₃ M, and M represents a hydrogen atom or an alkali metal atom.

(In the formula, R ^11A represents an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group is —O—, —CO—, —NR ¹⁰ —, —OCO—, It may be substituted with -COO-, -OCONH-, -CONH- or -NHCO-.
R ¹⁰ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^12A , R ^13A and R ^14A each independently represents an alkyl group having 1 to 4 carbon atoms.
* Represents a bond with a nitrogen atom. ]] The compound according to claim 1, wherein any one of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a carboxyl group or —SO ₃ M.   The coloring agent containing the compound of Claim 1 or 2.   The colorant according to claim 3, further comprising a pigment.   The colorant according to claim 4, wherein the pigment is at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment.   The colorant according to claim 4 or 5, wherein the pigment is at least one selected from the group consisting of a chlorinated copper phthalocyanine pigment, a brominated copper phthalocyanine pigment, and a brominated zinc phthalocyanine pigment.   The pigment is C.I. I. Pigment green 36 and C.I. I. The colorant according to any one of claims 4 to 6, which is at least one selected from the group consisting of CI Pigment Green 58.   A colored curable resin composition comprising the colorant, resin, polymerizable compound and polymerization initiator according to any one of claims 3 to 7.   A color filter formed from the colored curable resin composition according to claim 8.   A liquid crystal display device comprising the color filter according to claim 9.