JP7237626B2 - Colored curable resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a colored curable resin composition, a color filter, and a display device.

Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are produced from colored resin compositions. Squarylium dyes are known as colorants used in such colored resin compositions (Patent Documents 1 and 2, etc.).

JP 2015-086379 A JP 2015-086380 A

However, conventionally known color filters formed from a colored curable resin composition using a squarylium dye may not have sufficient heat resistance (preferably heat resistance and absorbance retention, or heat resistance and brightness). there were. Accordingly, an object of the present invention is to provide a colored curable resin composition capable of forming a color filter having excellent heat resistance (preferably heat resistance and absorbance retention, or heat resistance and brightness).

［式（Ｉ）中、
Ｒ¹～Ｒ⁴は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基又は置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基を表す。該１価の飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されていてもよい。
Ｒ⁵～Ｒ⁸は、それぞれ独立に、水素原子又はヒドロキシ基を表す。
Ｒ⁹及びＲ¹⁰は、それぞれ独立に、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基又は式（ｉ）で表される基を表す。該１価の飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されていてもよい。
Ａｒ¹及びＡｒ²は、それぞれ独立に、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基又は下式（ｉ）で表される基を表す。

［式（ｉ）中、
Ｒ¹²は、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基又は置換基を有していてもよい炭素数２～２０の１価の不飽和炭化水素基を表し、ｍは０～５の整数を表す。該１価の飽和炭化水素基を構成する炭素原子間に、酸素原子又は硫黄原子が挿入されていてもよい。ｍが２以上のとき、複数のＲ¹²は、それぞれ同一であっても異なっていてもよい。＊は、窒素原子との結合手を表す。］
［３］ 重合開始剤が、Ｏ－アシルオキシム化合物である［１］または［２］に記載の着色硬化性樹脂組成物。
［４］ ［１］～［３］のいずれか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。
［５］ ［４］に記載のカラーフィルタを含む表示装置。 The gist of the present invention is as follows.
[1] including a coloring agent, a resin, a polymerizable compound, and a polymerization initiator,
the coloring agent is a coloring agent comprising a squarylium dye;
A colored curable resin composition, wherein the resin is a resin containing a structural unit having a carbazole ring which may have a substituent.
[2] The colored curable resin composition according to [1], wherein the squarylium dye is a compound represented by formula (I).

[in the formula (I),
R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the monovalent saturated hydrocarbon group.
R ⁵ to R ⁸ each independently represent a hydrogen atom or a hydroxy group.
R ⁹ and R ¹⁰ each independently represent an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by formula (i). An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the monovalent saturated hydrocarbon group.
Ar ¹ and Ar ² each independently represent an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by the following formula (i).

[in the formula (i),
R ¹² is an optionally substituted monovalent saturated hydrocarbon group of 1 to 20 carbon atoms or an optionally substituted monovalent unsaturated hydrocarbon group of 2 to 20 carbon atoms and m represents an integer of 0 to 5. An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the monovalent saturated hydrocarbon group. When m is 2 or more, a plurality of R ¹² may be the same or different. * represents a bond with a nitrogen atom. ]
[3] The colored curable resin composition according to [1] or [2], wherein the polymerization initiator is an O-acyloxime compound.
[4] A color filter formed from the colored curable resin composition according to any one of [1] to [3].
[5] A display device including the color filter described in [4].

According to the colored curable resin composition of the present invention, a color filter excellent in heat resistance (preferably heat resistance and absorbance retention, or heat resistance and brightness) can be provided.

The colored curable resin composition of the present invention includes a coloring agent (hereinafter sometimes referred to as a coloring agent (A)), a resin (hereinafter sometimes referred to as a resin (B)), a polymerizable compound (hereinafter, a polymerizable compound (C)), and a polymerization initiator (hereinafter sometimes referred to as polymerization initiator (D)).
Colorant (A) comprises a squarylium dye.
Resin (B) contains a structural unit having an optionally substituted carbazole ring.
The colored curable resin composition of the present invention preferably further contains a solvent (hereinafter sometimes referred to as solvent (E)).
The colored curable resin composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as leveling agent (F)).
In this specification, the compounds exemplified as each component can be used singly or in combination unless otherwise specified.

<Colorant (A)>
Examples of the squarylium dye contained in the coloring agent (A) include compounds described in JP-A-2013-76926.
The squarylium dye is preferably a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)).
Compound (I) will be described in detail below. Compound (I) includes the resonance structure of formula (I) and compounds obtained by rotating each group in formula (I) around the bond axis of a single bond. shall also be included.

[in the formula (I),
R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the monovalent saturated hydrocarbon group.
R ⁵ to R ⁸ each independently represent a hydrogen atom or a hydroxy group.
R ⁹ and R ¹⁰ each independently represent an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by formula (i). An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the monovalent saturated hydrocarbon group.
Ar ¹ and Ar ² each independently represent an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by formula (i), preferably represented by formula ( represents a group represented by i);

[in the formula (i),
R ¹² is an optionally substituted monovalent saturated hydrocarbon group of 1 to 20 carbon atoms or an optionally substituted monovalent unsaturated hydrocarbon group of 2 to 20 carbon atoms and m represents an integer of 0 to 5. An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the monovalent saturated hydrocarbon group. When m is 2 or more, a plurality of R ¹² may be the same or different. * represents a bond with a nitrogen atom. ]

In formula (I), halogen atoms in R ¹ to R ⁴ include fluorine, chlorine, bromine and iodine atoms.

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms in R ¹ to R ⁴ , R ⁹ , R ¹⁰ , R ¹² , Ar ¹ and Ar ² include methyl group, ethyl group, propyl group and butyl group. , pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group, linear alkyl groups having 1 to 20 carbon atoms; isopropyl group, isobutyl group, sec-butyl tert-butyl, isopentyl, neopentyl and 2-ethylhexyl branched-chain alkyl groups having 3 to 20 carbon atoms; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tri Alicyclic alkyl groups having 3 to 20 carbon atoms such as cyclodecyl group and adamantyl group can be mentioned.

Substituents for these saturated hydrocarbon groups include halogen atoms such as a fluorine atom, a chlorine atom and iodine ^{; a} hydroxy ^group ; a carboxy ^group ; an alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; Examples of the 20 monovalent saturated hydrocarbon group include groups represented by the following formulae. In the following formula, * represents a bond.

A hydrogen atom or a methyl group contained in these saturated hydrocarbon groups may be substituted with a halogen atom, a hydroxy group, or an amino group substituted with one or two alkyl groups having 1 to 8 carbon atoms, and Examples include groups represented by the following formulas. Here, the amino group substituted with one or two alkyl groups having 1 to 8 carbon atoms includes methylamino group, ethylamino group, n-propylamino group, n-butylamino group and n-pentylamino group. , dimethylamino group, diethylamino group, dibutylamino group, methylethylamino group and the like. In the following formula, * represents a bond.

Examples of groups in which an oxygen atom or a sulfur atom is inserted between carbon atoms constituting these saturated hydrocarbon groups include groups represented by the following formulae. In the following formula, * represents a bond.

The monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms for R ¹² includes, for example, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group and decenyl group. be done.

Substituents of ^the unsaturated hydrocarbon group include halogen atoms such as fluorine atom, chlorine atom and ^iodine ; ^hydroxy group; carboxy ^group ; an alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; etc.

R ¹ to R ⁴ are preferably a hydrogen atom, a hydroxy group and an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a hydroxy group and a methyl group, and still more preferably a hydrogen atom.

At least one of R ⁵ to R ⁸ is preferably a hydroxy group. More preferably, at least one of R ⁵ and R ⁶ is a hydroxy group, and at least one of R ⁷ and R ⁸ is a hydroxy group.

R ⁹ and R ¹⁰ are preferably an optionally substituted C 3-14 alkyl group and a group represented by formula (i), and an optionally substituted C 3 to 6 straight-chain alkyl groups, optionally substituted straight-chain or branched-chain alkyl groups having 7 to 14 carbon atoms (e.g., octyl, nonyl, decyl, dodecyl, 2 -ethylhexyl group) and groups represented by formula (i) are more preferred, and a 2-ethylhexyl group is even more preferred.

The saturated hydrocarbon group for R ¹² is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group.
The unsaturated hydrocarbon group for R ¹² is preferably an alkenyl group having 2 to 4 carbon atoms, more preferably a vinyl group or an allyl group.
When m is 2 or more, at least one R ¹² is preferably a saturated hydrocarbon group. When m is 2 or more, an aspect in which all R ¹² are saturated hydrocarbon groups, or an aspect in which some of R ¹² are saturated hydrocarbon groups and some of R ¹² are unsaturated hydrocarbon groups are preferred. preferable.

m is preferably 1-5, more preferably 1-3.
Examples of the group represented by formula (i) include the following groups. * represents a bond with a nitrogen atom.

In formula (I),

で表される基をＸ¹、

A group represented by X ¹ ,

で表される基をＸ²としたとき、Ｘ¹及びＸ²で表される基としては、例えば、式（Ａ２－１）～（Ａ２－９）で表される基が挙げられる。＊は、炭素原子との結合手を表す。

When the group represented by is X ² , the groups represented by X ¹ and X ² include, for example, groups represented by formulas (A2-1) to (A2-9). * represents a bond with a carbon atom.

Examples of compound (I) include compound (AII-1) to compound (AII-27) shown in Table 1.

Compounds (AII-10) to (AII-18) are more preferred from the viewpoint of raw material availability.

The compound represented by formula (I) can be produced by reacting a compound represented by formula (pt1), a compound represented by formula (pt2), and a compound represented by formula (pt3). . In this reaction, the amount of the compound represented by the formula (pt3) used is preferably 0.05 per 1 mol of the compound represented by the formula (pt1) and the compound represented by the formula (pt2). It is 0.8 mol or more and more preferably 0.1 mol or more and 0.6 mol or less.

In the formula, R ¹ to R ¹⁰ , Ar ¹ and Ar ² each have the same meaning as above.

The reaction temperature is preferably 30°C to 180°C, more preferably 80°C to 140°C. The reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.

From the viewpoint of yield, the reaction is preferably carried out in an organic solvent. Examples of organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; alcohol solvents such as methanol, ethanol, isopropanol and butanol; nitrohydrocarbon solvents such as nitrobenzene; ketone solvents such as ketones; amide solvents such as 1-methyl-2-pyrrolidone; and the like, and these may be mixed and used. Among them, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent used is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 1 part by mass in total of the compound represented by the formula (pt1) and the compound represented by the formula (pt2). is 30 parts by mass or more and 150 parts by mass or less.

There are no particular restrictions on the method for removing the target compound (I) from the reaction mixture, and various known methods can be used. For example, there is a method of cooling after the completion of the reaction and filtering the precipitated crystals. The filtered crystals are preferably washed with water or the like and then dried. Further, if necessary, it may be further purified by a known method such as recrystallization.

The compound represented by the formula (IV-2) and the compound represented by the formula (IV-3) are reacted to produce the compound represented by the formula (IV-4), and then the compound represented by the formula (IV-4 ) can be reacted with a compound represented by formula (IV-5) to produce a compound represented by formula (pt1).

In formulas (IV-2) to (IV-5), R ¹ , R ² , R ⁵ , R ⁶ , R ⁹ and Ar ¹ each have the same meaning as above.

As a method for producing the compound represented by formula (IV-4) from the compound represented by formula (IV-2) and the compound represented by formula (IV-3), various known methods, For example, Eur. J. Org. Chem. 2012, 3105-3111. The method described in.

As a method for producing the compound represented by the formula (pt1) from the compound represented by the formula (IV-4) and the compound represented by the formula (IV-5), various known methods such as J Polymer Science Science Part A: Polymer Chemistry 2012, 50, 3788-3796.

Compounds represented by formula (pt2) can be produced using methods similar to those described above.

In addition to the squarylium dye, the coloring agent (A) may contain a coloring agent different from the squarylium dye, and the coloring agent different from the squarylium dye is a dye (hereinafter sometimes referred to as dye (A1)). , and pigment (hereinafter sometimes referred to as pigment (A2)), and the coloring agent different from the squarylium dye may contain one or both of these dye (A1) and pigment (A2) .

Dyes (A1) are not particularly limited, and known dyes can be used as long as they do not include squarylium dyes, and include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. Dyes include, for example, compounds classified as having hues other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Staining Note (Shikisensha). be done. Also, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, acridine dyes, styryl dyes, coumarin dyes, quinolines dyes and nitro dyes; Among these, organic solvent-soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, the description of C.I. Solvent Yellow is omitted and only the number is described.), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 , 117, 162, 163, 167, 189;
C. I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;
C. I. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. solvent blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. C.I. I. solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C. I. acid blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
C. I. acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109 and the like. I. acid dye,
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. C.I. I. disperse dyes,
C. I. Basic Red 1, 10;
C. I. basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C. I. basic violet 2;
C. I. basic red 9;
C. I. Basic Green 1 and other C.I. I. basic dye,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. C.I. I. reactive dyes,
C. I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C. I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28 , 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;
C. I. Modant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. C.I. I. modant dye,
C. I. C.I. I. and vat dyes.
These dyes may be appropriately selected according to the spectral spectrum of the desired color filter.

The pigment (A2) is not particularly limited, and known pigments can be used. Examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

Examples of pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. red pigments such as 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 Pigment Blue 15:6, 60;
C. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as Pigment Green 7, 36, 58;
C. I. Brown pigments such as Pigment Brown 23, 25;
C. I. Black pigments such as Pigment Black 1 and 7 are included.

If necessary, the pigment is subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic group or basic group is introduced, graft treatment to the pigment surface with a polymer compound, etc., atomization by a sulfuric acid atomization method, etc. Treatment, washing treatment with an organic solvent, water, or the like for removing impurities, removal treatment by an ion exchange method or the like for ionic impurities, or the like may be performed.
The pigment preferably has a uniform particle size. A pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained by adding the pigment dispersant and performing the dispersion treatment.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. As pigment dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Ajisper (Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), and the like.

When a pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less, relative to the total amount of the pigment (A2). When the amount of the pigment dispersant used is within the above range, there is a tendency to obtain a uniformly dispersed pigment dispersion.

When the colorant (A) contains the dye (A1) and/or the pigment (A2) in addition to the compound (I), the content of the compound (I) is preferably 1 with respect to the total amount of the colorant (A). It is 90 mass % or less, more preferably 1 mass % or more and 60 mass % or less, and still more preferably 3 mass % or more and 40 mass % or less.

The content of the coloring agent (A) in the colored curable resin composition is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 60% by mass, based on the total amount of solids. % by mass or less, more preferably 1% by mass or more and 50% by mass or less. When the content of the coloring agent (A) is within the above range, the color density of the color filter is sufficient, and the composition contains the resin (B) and the polymerizable compound (C) in the required amounts. Therefore, a pattern with sufficient mechanical strength can be formed.

Here, the "total amount of solid content" in this specification refers to the amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
Resin (B) contains a resin containing a structural unit having a carbazole ring which may have a substituent.
In this 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.

When the colored curable resin composition of the present invention contains the resin, the heat resistance of the color filter is improved.

A structural unit having an optionally substituted carbazole ring may be derived from an unsaturated compound having an optionally substituted carbazole ring. A structural unit derived from the unsaturated compound may be contained in a copolymer obtained by using the unsaturated compound as a monomer. Alternatively, it can be obtained by reacting another structural unit with a compound having a carbazole ring which may have a substituent.

The unsaturated compound containing a structural unit having an optionally substituted carbazole ring is preferably a compound represented by formula (III).

In formula (III), R ^1a represents a hydrogen atom, a methyl group, or a hydroxymethyl group.
R ^2a to R ^9a each independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is , an alkoxy group or an aryl group.
X ^a represents a single bond, an alkanediyl group having 1 or more carbon atoms, or a linear or branched group represented by the following formula (V).

(In formula (V), la represents an integer of 0 or more. ma represents an integer of 1 or more.)

The saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R ^2a to R ^9a are methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. , dodecyl group, hexadecyl group and icosyl group having 1 to 20 carbon atoms; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group, etc. branched chain alkyl group having 3 to 20 carbon atoms; alicyclic alkyl having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecyl group and adamantyl group groups.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ^2a to R ^9a include phenyl group, tolyl group, xylyl group and naphthyl group.

The alkoxy groups represented by R ^2a to R ^9a have, for example, 1 to 10 carbon atoms, and include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and heptyloxy groups.

The alkanediyl group having 1 or more carbon atoms represented by X ^a includes methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, and the like. is mentioned.

Compounds represented by formula (III) include N-vinylcarbazole, N-allylcarbazole, N-(meth)acryloylcarbazole, 2-(9-carbazolyl)ethyl (meth)acrylate, 2-(9-carbazolyl) ethoxyethyl (meth)acrylate, 2-(9-carbazolyl)-2-methylethyl (meth)acrylate, 2-(9-carbazolyl)-1-methylethyl (meth)acrylate and the like. Among them, N-vinylcarbazole, N-allylcarbazole and 2-(9-carbazolyl)ethyl (meth)acrylate are preferred.

Resin (B) is preferably an alkali-soluble resin. Examples of the alkali-soluble resin (B) include the following resins [K1] to [K6].

Resin [K1]: a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as "(a)"); , a structural unit derived from a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"), and a substituent. a copolymer consisting of structural units derived from an unsaturated compound (z) having a carbazole ring (hereinafter sometimes referred to as "(z)");
Resin [K2]; a structural unit derived from (a), a structural unit derived from (b), a structural unit derived from (z), and a monomer copolymerizable with (a) (c) ( However, different from (a), (b) and (z)) (hereinafter sometimes referred to as "(c)").
Resin [K3]; a copolymer consisting of a structural unit derived from (a) and a structural unit derived from (z);
Resin [K4]; a copolymer consisting of a structural unit derived from (a), a structural unit derived from (z), and a structural unit derived from (c);
Resin [K5]; a copolymer containing a structural unit derived from (a), a structural unit obtained by adding (a) to a structural unit derived from (b), and a structural unit derived from (z);
Resin [K6]; a structural unit derived from (a), a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride, and a structural unit derived from (z) A copolymer containing a structural unit.

In the structural unit derived from (a), the carboxy group or carboxylic anhydride of (a) preferably remains unreacted. In the resins [K1] and [K2], it is preferable that the structural unit derived from (b) has a cyclic ether structure having 2 to 4 carbon atoms remaining unreacted.

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-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic 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 [2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds containing a carboxy group;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;
Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate kind;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(b) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (eg, 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 cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond, monomer (b2) (hereinafter sometimes referred to as "(b2)") and monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"); be done.

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)”).

(b1-1) includes 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-tris (glycidyloxymethyl)styrene and the like.

(b1-2) includes vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cychromer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cychromer M100; manufactured by Daicel Corporation), the compound represented by formula (BI) and formula (BII) Compounds represented by and the like.

[In formula (BI) and formula (BII), R ^e and R ^f 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
X ^e and X ^f represent a single bond, *-R ^g -, *-R ^g -O-, *-R ^g -S- or *-R ^g -NH-.
R ^g represents an alkanediyl group having 1 to 6 carbon atoms.
* represents a bond with O. ]

Examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
Alkyl groups in which hydrogen atoms are substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.
R ^e and R ^f are preferably hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group and 2-hydroxyethyl group, more preferably hydrogen atom and methyl group.

The alkanediyl group includes methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane- A 1,6-diyl group and the like can be mentioned.
X ^e and X ^f 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 and *--CH ₂ CH ₂ --O-- (* represents a bond with O).

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

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

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

(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-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane 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 (eg, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(b) is preferably (b1) in that the heat resistance, chemical resistance, and other reliability of the resulting color filter can be further enhanced. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

(c) includes methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^{2, 6} ] Decane-8-yl (meth)acrylate (in the technical field, it is commonly referred to as “dicyclopentanyl (meth)acrylate”. It may also be referred to as “tricyclodecyl (meth)acrylate” ), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (in the technical field, it is commonly called “dicyclopentenyl (meth)acrylate”), Dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate ) (meth) acrylic acid esters such as acrylates;
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, and 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(cyclohexyl oxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

In the resin [K1], the ratio of the structural units derived from each of the total structural units constituting the resin [K1] is
Structural unit derived from (a); 2 to 45 mol%
Structural unit derived from (b); 2 to 90 mol%
Structural unit derived from (z); 1 to 90 mol%
is preferably
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (z); 5 to 80 mol%
is more preferable.
When the ratio of the structural units of the resin [K1] is within the above range, the absorption retention of the color filter obtained from the colored curable resin composition can be further improved.

The resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin, 1st edition, 1st edition, published on March 1, 1972) and the literature It can be manufactured with reference to the cited document described in .

Specifically, predetermined amounts of (a), (b) and (z), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and oxygen is replaced with nitrogen to create a deoxygenated atmosphere, A method of heating and keeping warm while stirring can be used. The polymerization initiator, solvent, and the like used here are not particularly limited, and those commonly used in the relevant field can be used. For example, polymerization initiators include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). As the solvent, any solvent can be used as long as it dissolves each monomer, and examples thereof include the solvents described later as the solvent (E) for the colored curable resin composition of the present invention.

The obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. You can use things. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent in this polymerization, the solution after the reaction can be 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 total structural units constituting the resin [K2] is
Structural unit derived from (a); 2 to 45 mol%
Structural unit derived from (b); 2 to 90 mol%
Structural unit derived from (z); 1 to 90 mol%
Structural unit derived from (c); 1 to 65 mol%
is preferably
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (z); 5 to 80 mol%
Structural unit derived from (c); 5 to 50 mol%
is more preferable.
When the ratio of the structural units of the resin [K2] is within the above range, the absorption retention of the color filter obtained from the colored curable resin composition can be further improved.

Resin [K2] can be produced, for example, in the same manner as the method for producing resin [K1].

In the resin [K3], the ratio of the structural units derived from each of the total structural units constituting the resin [K3] is
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (z); 40 to 98 mol%
is preferably
Structural unit derived from (a); 10 to 50 mol%
Structural unit derived from (z); 50 to 90 mol%
is more preferable.
Resin [K3] can be produced, for example, in the same manner as the method for producing resin [K1].

In the resin [K4], the ratio of the structural units derived from each of the total structural units constituting the resin [K4] is
Structural unit derived from (a); 2 to 45 mol%
Structural unit derived from (z); 1 to 90 mol%
Structural unit derived from (c); 1 to 65 mol%
is preferably
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (z); 5 to 80 mol%
Structural unit derived from (c); 5 to 50 mol%
is more preferable.
Resin [K4] can be produced, for example, in the same manner as the method for producing resin [K1].

For resin [K5], as the first step, a copolymer of (a), (b) and (z) is obtained in the same manner as in the method for producing resin [K1] described above. In the same manner as described above, the obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be converted into a solid (powder) by a method such as reprecipitation. You may use what was taken out as.

The ratio of the structural units derived from (a), (b) and (z) to the total number of moles of all the structural units constituting the copolymer is, respectively,
Structural unit derived from (a); 2 to 45 mol%
Structural unit derived from (b); 2 to 90 mol%
Structural unit derived from (z); 1 to 90 mol%
is preferably
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (z); 5 to 80 mol%
is more preferable.

Next, the inside of the flask is made into an air atmosphere, and the copolymer of (a), (b) and (z), (a), a reaction catalyst (for example, tris (for example, tris ( dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (e.g., hydroquinone, etc.) are placed in a flask and reacted at, for example, 60 to 130° C. for 1 to 10 hours to obtain (a), (b) and (z). Resin [K5] can be obtained by reacting the cyclic ether derived from (b) possessed by the copolymer with the carboxylic acid or carboxylic acid anhydride possessed by (a).
The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol per 100 mol of (b). (b1) is preferable as the (b) used for the resin [K5] because the cyclic ether has high reactivity and the unreacted (b) hardly remains.

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (z). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by weight per 100 parts by weight of the total amount of (a), (b) and (z).
Reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. As with 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 [K6] is a resin obtained by reacting resin [K5] with a carboxylic acid anhydride. The hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride is reacted with the carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic 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. The amount of the carboxylic anhydride used is preferably 0.5 to 1 mol per 1 mol of the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid/N-vinylcarbazole copolymer, 3,4-epoxycyclohexylmethyl (meth)acrylate/( meth)acrylic acid/N-allylcarbazole copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-vinylcarbazole copolymer, 3 , 4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-allylcarbazole copolymer [K1];
Glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid/N-vinylcarbazole copolymer, glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid/N-allylcarbazole copolymer coalescence, glycidyl (meth)acrylate/styrene/(meth)acrylic acid/N-vinylcarbazole copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid/N-allylcarbazole copolymer, 3,4- Epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-vinylcarbazole/2-hydroxyethyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5 .2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-allylcarbazole/2-hydroxyethyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane Resins such as /(meth)acrylic acid/styrene/N-vinylcarbazole copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene/N-allylcarbazole copolymer [K2];
Resins such as N-vinylcarbazole/(meth)acrylic acid copolymer, N-allylcarbazole/(meth)acrylic acid copolymer [K3];
Benzyl (meth)acrylate/(meth)acrylic acid/N-vinylcarbazole copolymer, benzyl (meth)acrylate/(meth)acrylic acid/N-allylcarbazole copolymer, styrene/(meth)acrylic acid/N- Vinylcarbazole copolymer, styrene/(meth)acrylic acid/N-allylcarbazole copolymer, (meth)acrylic acid/N-vinylcarbazole/2-hydroxyethyl (meth)acrylate copolymer, (meth)acrylic acid / N-allylcarbazole / resin [K4] such as 2-hydroxyethyl (meth)acrylate copolymer;
N-vinylcarbazole/(meth)acrylic acid/glycidyl(meth)acrylate copolymer reacted with (meth)acrylic acid, N-allylcarbazole/(meth)acrylic acid/glycidyl(meth)acrylate copolymer Resin [K5] such as a resin obtained by reacting a polymer with (meth)acrylic acid;
A resin obtained by reacting a copolymer of N-vinylcarbazole/(meth)acrylic acid/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting tetrahydrophthalic anhydride, N-allylcarbazole/( Examples thereof include resin [K6] such as a resin obtained by reacting a copolymer of meth)acrylic acid/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting tetrahydrophthalic anhydride.
Among them, as the resin (B), the resins [K1] to [K4] are preferable, and the resins [K1] and [K2] are more preferable.
The content of one or more selected from the group consisting of resins [K1] to [K4] (preferably one or both of resin [K1] and resin [K2], more preferably resin [K1]) is It is preferably 80 to 100% by mass, more preferably 100% by mass, based on the total solid content of B).

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. . When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the colored pattern tends to be improved.

The dispersity [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

The acid value of the resin (B) is preferably 20 mg-KOH/g or more, more preferably 30 mg-KOH/g or more, still more preferably 40 mg-KOH/g or more, and preferably 200 mg-KOH in terms of solid content. /g or less, more preferably 180 mg-KOH/g or less, still more preferably 150 mg-KOH/g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution. .

The content of resin (B) is preferably 7 to 80% by mass, more preferably 13 to 75% by mass, still more preferably 17 to 65% by mass, relative to the total solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film rate tend to be improved.

The content of the resin (B) is preferably 10 parts by mass or more and 95 parts by mass or less, more preferably 20 parts by mass or more, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is 90 parts by mass or less, more preferably 30 parts by mass or more and 85 parts by mass or less. When the content of the resin (B) is within the above range, the absorbance retention of the obtained color filter is further improved.
In addition, the content of the resin (B) is 55 parts by mass or more and 95 parts by mass or less, preferably 60 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is also preferable that When the content of the resin (B) is within the above range, the absorbance retention of the resulting color filter is significantly improved.
The content of the resin (B) is, for example, 10 parts by mass or more and 60 parts by mass or less, preferably 20 parts by mass or more and 55 parts by mass or less with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). In the case of , the absorbance retention and brightness of the resulting color filter are 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). Examples thereof include compounds having a polymerizable ethylenically unsaturated bond, preferably It is a (meth)acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl ) isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate.
Among them, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

The content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 55% by mass, based on the total solid content. be. When the content of the polymerizable compound (C) is within the above range, there is a tendency that the residual film ratio at the time of forming the colored pattern and the chemical resistance of the color filter are improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, etc. by the action of light or heat, and known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds.

Examples of the O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane, -1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl )-O-acyloxime compounds having a diphenylsulfide skeleton such as 3-cyclohexylpropan-1-one-2-imine; N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) Benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane -1-imine, carbazole such as N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine O-acyloxime compounds having a skeleton; O-acyloximes having a fluorene skeleton such as 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime compounds; and the like. Commercially available products such as Irgacure (registered trademark) OXE01 and OXE02 (manufactured by BASF), N-1919 (manufactured by ADEKA), and DFI-091 (manufactured by Daito Chemix Co., Ltd.) may also be used. Among them, O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3- Cyclohexylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl}-9H-carbazol-3-yl]ethan-1-imine and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime At least one selected from the group is preferred. These O-acyl oxime compounds tend to give high-brightness color filters.

Examples of the alkylphenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane, -1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl -1-(4-isopropenylphenyl)propan-1-one oligomer, α,α-diethoxyacetophenone, benzyl dimethyl ketal and the like. Commercially available products such as Irgacure (registered trademark) 369, 907, 379 (manufactured by BASF) may also be used.

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-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. is mentioned.

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

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 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(tri alkoxyphenyl)biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), the phenyl groups at the 4,4′,5,5′-positions are substituted with carboalkoxy groups; and biimidazole compounds (see, for example, JP-A-7-10913).

Polymerization initiators that generate acids include, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxy Onium salts such as phenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylates, benzoin tosylates and the like.

Furthermore, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.

As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds is preferred, and O-acyloxy More preferred is a polymerization initiator containing a chromium compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). part by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, thereby improving the productivity of the color filter.

<Solvent (E)>
The solvent (E) is not particularly limited, and solvents commonly used in the field can be used. For example, ester solvent (solvent containing -COO- in the molecule but not containing -O-), ether solvent (solvent containing -O- in the molecule but not containing -COO-), ether ester solvent (solvent containing -COO- in the molecule 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-, - solvents containing no CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide.

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

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. , propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methylanisole and the like.

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 and the like.

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.

Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

Among the above solvents, organic solvents having a boiling point of 120° C. or higher and 180° C. or lower at 1 atm are preferable from the viewpoint of coating properties and drying properties. Solvents include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone. and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate.

The content of the solvent (E) is preferably 70-95% by mass, more preferably 75-92% by mass, relative to the total amount of the colored curable resin composition of the present invention. In other words, the total 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 within the above range, the flatness at the time of coating is improved, and when a color filter is formed, the color density is not insufficient, so the display characteristics tend to be improved. .

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.
Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray SH7PA, Toray DC11PA, Toray SH21PA, Toray SH28PA, Toray SH29PA, Toray SH30PA, Toray Toray SH8400 (manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) and the like.

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

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

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.2% by mass or less, relative to the total amount of the colored curable resin composition. It is 2 mass % or less, more preferably 0.005 mass % or more and 0.2 mass % or less. This content does not include the content of the dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored curable resin composition of the present invention may optionally contain additives known in the art such as polymerization initiation aids, fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, and the like. agent.
Adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane. Ethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane , 3-isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-( aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxy Silane etc. are mentioned.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a coloring agent (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) and other ingredients.

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

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass whose surface is coated with silica; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; A thin film of aluminum, silver, silver/copper/palladium alloy, etc. is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be carried out using a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable resin composition is applied onto a substrate, dried by heating (pre-baking) and/or dried under reduced pressure to remove volatile components such as solvents, and dried to obtain a smooth colored composition layer.
Examples of coating methods include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature for heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
When drying under reduced pressure, it is preferably carried out at a pressure of 50 to 150 Pa and a temperature of 20 to 25°C.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the desired film thickness of the color filter.

The colored composition layer is then exposed through a photomask to form the desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use is used.
The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You can Specifically, mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, and the like can be used.
It is possible to uniformly irradiate the entire exposure surface with parallel light rays and to perform accurate alignment between the photomask and 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 development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and tetramethylammonium hydroxide are preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant.
The developing method may be any of a puddle method, a dipping method, a spray method, and the like. Furthermore, the substrate may be tilted at any angle during development.
It is preferable to wash with water after development.

Furthermore, it is preferable to post-bake the obtained colored pattern. The post-baking temperature is preferably 150-250°C, more preferably 160-235°C. Post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In the examples, percentages and parts representing contents or usage amounts are based on mass unless otherwise specified.
In the synthesis examples below, compounds were identified by NMR (JNM-EX-270; manufactured by JEOL Ltd.).

(Colorant Synthesis Example 1)
2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 parts, 2-ethylhexane bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 17.0 parts, and tetrabutylammonium bromide (manufactured by Wako Chemical Industry Co., Ltd. ) was mixed with 44.0 parts. The resulting mixture was stirred at 90° C. for 8 hours. After completion of the reaction, 50 parts of 10% aqueous sodium bicarbonate solution was added, followed by 100 parts of ethyl acetate, and the aqueous layer was discarded. After repeating the operation of washing with water and 10% hydrochloric acid twice, the solvent was distilled off. The obtained oil was dried under reduced pressure at 60° C. for 24 hours to obtain 9.3 parts of a compound represented by the following formula (a-1).

¹ H-NMR of the compound represented by formula (a-1) (270 MHz, δ value (ppm, TMS standard), DMSO-d6)
δ 0.85 (m, 6H), 1.23-1.42 (br, 8H), 1.59 (br, 1H), 2.04 (s, 3H), 2.12 (s, 3H), 2.91 (d, 2H), 4.37 (br, 1H), 6.38 (d, 1H), 6.75 (s, 1H), 6.77 (d, 1H)

3.0 parts of the compound represented by the formula (a-1) obtained above, 2.2 parts of 3-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.015 parts of palladium acetate, sodium tert-butoxy (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.2 parts, tri-tert-butylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.055 parts, and toluene 25.6 parts were mixed and stirred at 100 ° C. for 15 hours. . 30 parts of ethyl acetate and 100 parts of water were added to the resulting mixture, and the aqueous layer was discarded. After repeating the operation of washing with water twice, the solvent was distilled off. The residue was purified by silica gel chromatography (chloroform/hexane=1/1), and the obtained oil was dried under reduced pressure at 60° C. for 24 hours to obtain 1.9 parts of a compound represented by the following formula (a-2). rice field.

¹ H-NMR of the compound represented by formula (a-2) (270 MHz, δ value (ppm, TMS standard), DMSO-d6)
δ 0.85 (m, 6H), 1.23-1.42 (br, 8H), 1.55 (br, 1H), 1.94 (s, 3H), 2.27 (s, 3H), 2.90 (d, 2H), 6.37 (d, 1H), 6.75 (s, 1H), 6.76 (d, 1H), 6.92-7.14 (m, 4H), 8 .93 (s, 1H)

4.4 parts of the compound represented by the formula (a-2) obtained above, 0.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.), 1 - 90.0 parts of butanol and 60.0 parts of toluene were mixed. The resulting mixture was stirred at 125° C. for 3 hours while removing generated water using a Dean-Stark tube. After completion of the reaction, the solvent was distilled off, 15 parts of acetic acid was added, and the residue was added dropwise to 100 parts of 18% saline solution, and the precipitated solid was collected by filtration. The filtered solid was washed with hexane. The obtained solid was dried under reduced pressure at 60° C. for 24 hours to obtain 4.9 parts of the compound represented by formula (AII-10).

¹ H-NMR of the compound represented by formula (AII-10) (270 MHz, δ value (ppm, TMS standard), DMSO-d6)
δ 0.87 (m, 12H), 1.21-1.57 (m, 16H), 1.72 (br, 2H), 2.05 (s, 6H), 2.36 (s, 6H), 3.37 (br, 2H), 3.78 (br, 2H), 6.00 (br, 4H), 6.97-7.12 (m, 6H), 7.77-7.95 (m, 2H), 11.35 (s, 1H), 12.06 (s, 1H)

(Resin synthesis example 1)
A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 324 parts of propylene glycol monomethyl ether acetate was added, and the flask was heated to 85°C while stirring. Then, 60 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 ]decane-9-yl acrylate (mixture ratio is 1:1), 210 parts of 9-vinylcarbazole, and 190 parts of propylene glycol monomethyl ether acetate. It dripped over time. On the other hand, a mixed solution of 31 parts of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 155 parts of propylene glycol monomethyl ether acetate was dropped into the flask over 5 hours using another dropping pump. bottom. After the dropping of the polymerization initiator was completed, the same temperature was maintained for 3 hours, and then cooled to room temperature to obtain a copolymer (resin (B-1 )) solution was obtained. The obtained resin (B-1) had a weight average molecular weight (Mw) of 7900, a dispersity (Mw/Mn) of 1.99, and an acid value converted to solid content of 107 mg-KOH/g. Resin (B-1) has the following structural units.

The polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Apparatus; HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature; 40°C
Solvent; THF
Flow rate; 1.0 mL/min
Test liquid solid content concentration; 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(manufactured by Tosoh Corporation)
The ratio (Mw/Mn) of the polystyrene-equivalent weight-average molecular weight and the number-average molecular weight obtained above was defined as the degree of dispersion.

(Resin synthesis example 2)
A suitable amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 100 parts of propylene glycol monomethyl ether acetate was added, and the flask was heated to 85°C while stirring. Then, 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 ]decane-9-yl acrylate mixture (mixing ratio is 1:1) 171 parts dissolved in 40 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours using a dropping pump. . On the other hand, a solution of 26 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) dissolved in 120 parts of propylene glycol monomethyl ether acetate was added to the flask over about 5 hours using another dropping pump. Dripped. After the dropping of the polymerization initiator was completed, the temperature was maintained for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-2)) having a solid content of 43.5%. . The obtained resin (B-2) had a weight average molecular weight of 8000, a dispersity of 1.98, and an acid value of 53 mg-KOH/g in terms of solid content. Resin (B-2) has the following structural units.

[Examples 1 to 3, Comparative Example 1]
[Preparation of colored curable resin composition]
Each component was mixed so as to have the composition shown in Table 2 to obtain a colored curable resin composition.

In Table 2, each component represents the following compounds.
Coloring agent (A-1): compound represented by formula (AII-10) Resin (B-1): Resin (B-1) (solid content conversion)
Resin (B-2): Resin (B-2) (solid content conversion)
Polymerizable compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D-1): N-1919 (manufactured by ADEKA; O-acyloxime compound)
Polymerization initiator (D-2): DFI-091 (manufactured by Daito Chemix; O-acyl oxime compound)
Polymerization initiator (D-3): N-benzoyloxy-1-(4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime Compound)
Solvent (E-1): 4-hydroxy-4-methyl-2-pentanone Solvent (E-2): Propylene glycol monomethyl ether acetate Leveling agent (F-1): Polyether-modified silicone oil (Dow Corning Toray Co., Ltd. ) manufactured by “Toray Silicone SH8400”)

<Preparation of colored coating>
On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), the colored curable resin composition was applied by spin coating so that the film thickness after post-baking was 2.0 μm, and then coated at 100° C. for 3 hours. A colored composition layer was formed by pre-baking for 1 minute. After cooling, the colored composition layer was irradiated with light at an exposure dose of 100 mJ/cm ² (365 nm standard) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). After that, post-baking was performed in an oven at 230° C. for 30 minutes to obtain a colored coating film.

1. Heat resistance (ΔEab*)
After pre-baking and post-baking, the chromaticity was measured, and from the measured values, the color difference ΔEab* was calculated by the method described in JIS Z 8730:2009 (7. Color difference calculation method), and the results are shown in Table 3. . A smaller ΔEab* means a smaller color change.

2. Maximum absorbance retention The maximum absorbance was obtained from spectroscopy measured after pre-baking and after post-baking, and the retention of maximum absorbance was calculated according to the following formula. Table 4 shows the results.
Absorbance retention rate (ΔAbs.Max)=maximum absorbance after post-baking/maximum absorbance after pre-baking A higher absorbance retention rate means a higher suitability for the film formation process.

3. Brightness The chromaticity of the colored coating films formed from the colored curable resin compositions of Examples 1, 3, and Comparative Example 1 was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). The xy chromaticity coordinates (x, y) and the stimulus value Y in the CIE XYZ color system were obtained from the obtained spectrum and the characteristic function of the C light source, and the results are shown in Table 5. A larger Y value indicates a higher brightness.

According to the colored curable resin composition of the present invention, a color filter having excellent heat resistance can be formed.

Claims (6)

including a colorant, a resin, a polymerizable compound, and a polymerization initiator,
the coloring agent is a coloring agent comprising a squarylium dye;
The resin is a resin containing a structural unit having a carbazole ring which may have a substituent, and is selected from the group consisting of the following resins [K1] and resins [K2],
Resin [K1] is a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a cyclic ether structure having 2 to 4 carbon atoms. A copolymer comprising structural units derived from a monomer (b) having an ethylenically unsaturated bond and structural units derived from an unsaturated compound (z) having a carbazole ring which may have a substituent. and
Resin [K2] is a structural unit derived from (a), a structural unit derived from (b), a structural unit derived from (z), and a monomer copolymerizable with (a). A copolymer consisting of structural units derived from the body (c),
A colored curable resin composition, wherein the structural unit derived from (z) is a structural unit derived from a compound represented by formula (III).

[In formula (III), R ^1a represents a hydrogen atom, a methyl group, or a hydroxymethyl group.
R ^2a to R ^9a each independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is , an alkoxy group or an aryl group.
X ^a represents a single bond, an alkanediyl group having 1 or more carbon atoms, or a linear or branched group represented by the following formula (V) .

(In formula (V), la represents an integer of 0 or more. ma represents an integer of 1 or more.)] 2. The colored curable resin composition according to claim 1, wherein the squarylium dye is a compound represented by formula (I).

[in the formula (I),
R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, or an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the monovalent saturated hydrocarbon group.
R ⁵ to R ⁸ each independently represent a hydrogen atom or a hydroxy group.
R ⁹ and R ¹⁰ each independently represent an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by formula (i). An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the monovalent saturated hydrocarbon group.
Ar ¹ and Ar ² each independently represent an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by the following formula (i).

[in the formula (i),
R ¹² is an optionally substituted monovalent saturated hydrocarbon group of 1 to 20 carbon atoms or an optionally substituted monovalent unsaturated hydrocarbon group of 2 to 20 carbon atoms and m represents an integer of 0 to 5. An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the monovalent saturated hydrocarbon group. When m is 2 or more, a plurality of R ¹² may be the same or different. * represents a bond with a nitrogen atom. ] A structural unit derived from 2-(2-vinyloxyethoxy)ethyl acrylate, a structural unit derived from 2-(2-vinyloxyethoxy)ethyl succinate, a structural unit derived from N-vinylcarbazole, and 3-ethyl- 3. The colored curable resin composition according to claim 1, which does not contain a polymer having a structural unit derived from 3-vinyloxymethyloxetane. The colored curable resin composition according to any one of claims 1 to 3, wherein the polymerization initiator is an O-acyloxime compound. A color filter formed from the colored curable resin composition according to any one of claims 1 to 4. A display device comprising the color filter according to claim 5 .