CN113286828A

CN113286828A - Colored curable resin composition

Info

Publication number: CN113286828A
Application number: CN201980088648.XA
Authority: CN
Inventors: 土谷崇夫
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2019-02-08
Filing date: 2019-12-03
Publication date: 2021-08-20
Anticipated expiration: 2039-12-03
Also published as: KR20210124315A; TW202039699A; TWI816003B; WO2020162009A1; JP2020128496A; JP7203626B2; CN113286828B

Abstract

The invention provides a colored curable resin composition capable of forming a color filter with excellent absorbance retention rate. The present invention relates to a colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant comprises a squaric acid represented by the formula (I)

Colorant of dye, onThe resin is a resin containing a structural unit derived from an N-substituted maleimide.

Description

Colored curable resin composition

Technical Field

The present invention relates to a colored curable resin composition.

Background

Color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are produced from colored resin compositions. As a colorant used in such a colored resin composition, a squaric acid is known

Dyes (patent documents 1,2, etc.).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2015-86379

Patent document 2: japanese patent laid-open publication No. 2015-86380

Disclosure of Invention

However, the use of squaric acid has been known

A color filter formed of the above colored curable resin composition containing a dye as a colorant may not sufficiently satisfy the absorbance retention ratio. Accordingly, an object of the present invention is to provide a colored curable resin composition capable of forming a color filter having an excellent absorbance retention rate.

The gist of the present invention is as follows.

[1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator,

the colorant is a compound containing a squaric acid represented by the formula (I)

The colorant of the dye is selected from the group consisting of,

the resin is a resin containing a structural unit derived from an N-substituted maleimide.

[ in the formula (I),

R¹～R⁴each independently represents a hydrogen atom, a halogen atom, a hydroxyl group or a substituted 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms. An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group.

R⁵～R⁸Each independently represents a hydrogen atom or a hydroxyl group.

Ar¹And Ar²Each independently represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a group represented by the formula (i).

[ in the formula (i),

R¹²represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, and m represents an integer of 0 to 5. An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group. When m is 2 or more, plural R¹²May be the same or different, respectively. Denotes a bonding site to a nitrogen atom.]

R⁹And R¹⁰Each independently represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a group represented by the formula (i). An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group.]

[2] A color filter comprising the colored curable resin composition according to [1 ].

[3] A display device comprising the color filter of [2 ].

According to the colored curable resin composition of the present invention, a color filter having an excellent absorbance retention rate can be provided.

Detailed Description

The colored curable resin composition of the present invention contains a colorant (hereinafter, sometimes referred to as a colorant (a)), a resin (hereinafter, sometimes referred to as a resin (B)), a polymerizable compound (hereinafter, sometimes referred to as a polymerizable compound (C)), and a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (D)).

The colorant comprises a squaric acid represented by the formula (I)

A dye (hereinafter, sometimes referred to as compound (I)).

The resin contains structural units derived from an N-substituted maleimide.

The colored curable resin composition of the present invention preferably further contains a solvent (hereinafter, may be referred to as solvent (E)).

The colored curable resin composition of the present invention may contain a leveling agent (hereinafter, sometimes referred to as a leveling agent (F)).

In the present specification, the compounds exemplified as the respective components may be used alone or in combination of a plurality of them unless otherwise specified.

< colorant (A) >)

The colorant (A) contains a compound (I). The present invention will be described in detail below using the formula (I), but the compound (I) also includes a compound having a resonance structure of the formula (I) and obtained by rotating each group of the formula (I) around a single bond axis.

[ in the formula (I),

R⁵～R⁸Each independently represents a hydrogen atom or a hydroxyl group.

Ar¹And Ar²Each independently represents a 1-valent radical having 1 to 20 carbon atoms which may have a substituentThe saturated hydrocarbon group or the group represented by the formula (i) preferably represents a group represented by the formula (i).

[ in the formula (i),

In the formula (I), as R¹～R⁴Examples of the halogen atom in (2) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As R¹～R⁴、R⁹、R¹⁰、R¹²、Ar¹And Ar²The 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms in (A) includes, for example, a linear alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, and an eicosyl group; a branched alkyl group having 3 to 20 carbon atoms such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, and adamantyl.

Examples of the substituent for the saturated hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, and iodine; a hydroxyl group; a carboxyl group; -NR^aR^b(R^aAnd R^bEach independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; first of allAlkoxycarbonyl groups having 1 to 10 carbon atoms such as oxycarbonyl group and ethoxycarbonyl group; examples of the substituted 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms include groups represented by the following formulae. Wherein, represents a bonding site.

Examples of the group having an oxygen atom or a sulfur atom inserted between carbon atoms constituting these saturated hydrocarbon groups include groups represented by the following formulae. Wherein, represents a bonding site.

As R¹²Examples of the 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms in the (a) include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group.

Examples of the substituent for the unsaturated hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, and iodine; a hydroxyl group; a carboxyl group; -NR^cR^d(R^cAnd R^dEach independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; and the like.

As R¹～R⁴The alkyl group having 1 to 4 carbon atoms is preferably a hydrogen atom, a hydroxyl group or a methyl group, more preferably a hydrogen atom, a hydroxyl group or a methyl group, and still more preferably a hydrogen atom.

Preferably R⁵～R⁸At least 1 of them is a hydroxyl group. More preferably R⁵And R⁶At least one of them is hydroxyl, R⁷And R⁸At least one of them is a hydroxyl group.

As R⁹And R¹⁰The alkyl group having 3 to 14 carbon atoms which may have a substituent and the group represented by the formula (i) are preferable, and the alkyl group may have a substituent more preferablyA linear alkyl group having 3 to 6 carbon atoms which may have a substituent, a linear or branched alkyl group having 7 to 14 carbon atoms which may have a substituent (for example, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, etc.), and a group represented by the formula (i), and further preferably a linear alkyl group having 3 to 5 carbon atoms which has a hydroxyl group at the terminal, a linear alkyl group having 3 to 5 carbon atoms which has a carboxyl group at the terminal, and 2-ethylhexyl.

As R¹²The saturated hydrocarbon group of (3) is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group, an ethyl group or an isopropyl group.

As R¹²The unsaturated hydrocarbon group of (3) is preferably an alkenyl group having 2 to 4 carbon atoms, and more preferably a vinyl group or an allyl group.

When m is 2 or more, at least 1R is preferable¹²Is a saturated hydrocarbon group. When m is 2 or more, all R are more preferable¹²In the form of saturated hydrocarbon radicals, or a part of R¹²Is a saturated hydrocarbon group and a part of R¹²In the form of unsaturated hydrocarbon groups.

m is preferably 1 to 5, more preferably 1 to 3.

Examples of the group represented by the formula (i) include the following groups. Denotes a bonding site to a nitrogen atom.

In the formula (I), the compound is shown in the specification,

will be provided with

The group represented is set to X¹And will be

The group represented is set to X²When is taken as X¹And X²Examples of the group represented by (A) include groups represented by formulae (A2-1) to (A2-9). Denotes a bonding site to a carbon atom.

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

[ Table 1]

Compound (I)

R¹

R²

R³

R⁴

R⁵

R⁶

R⁷

R⁸

X¹

X²

(AII-1)

H

A2-1

(AII-2)

H

A2-2

(AII-3)

H

A2-3

(AII-4)

H

A2-4

(AII-5)

H

A2-5

(AII-6)

H

A2-6

(AII-7)

H

A2-7

(AII-8)

H

A2-8

(AII-9)

H

A2-9

(AII-10)

H

OH

H

A2-1

(AII-11)

H

OH

H

A2-2

(AII-12)

H

OH

H

A2-3

(AII-13)

H

OH

H

A2-4

(AII-14)

H

OH

H

A2-5

(AII-15)

H

OH

H

A2-6

(AII-16)

H

OH

H

A2-7

(AII-17)

H

OH

H

A2-8

(AII-18)

H

OH

H

A2-9

(AII-19)

H

OH

A2-1

(AII-20)

H

OH

A2-2

(AII-21)

H

OH

A2-3

(AII-22)

H

OH

A2-4

(AII-23)

H

OH

A2-5

(AII-24)

H

OH

A2-6

(AII-25)

H

OH

A2-8

(AII-26)

H

OH

A2-9

(AII-27)

H

OH

A2-7

More preferred are compounds (AII-10) to (AII-18).

The compound represented by the formula (I) can be produced by reacting the compound represented by the formula (pt3) with the compound represented by the formula (pt1) and the compound represented by the formula (pt 2). In this reaction, the amount of the compound represented by formula (pt3) used is preferably 0.05 to 0.8 mol, and more preferably 0.1 to 0.6 mol, based on 1 mol of the total of the compound represented by formula (pt1) and the compound represented by formula (pt 2).

In the formula, R¹～R¹⁰、Ar¹And Ar²Each means the same as described above.

The reaction temperature is preferably from 30 ℃ to 180 ℃ and more preferably from 80 ℃ to 140 ℃. 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 the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, chloroform and the like; alcohol solvents such as methanol, ethanol, isopropanol, butanol, etc.; nitrohydrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone; and the like, and these may be used in combination. Among them, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent to be used is preferably 10 to 200 parts by mass, more preferably 30 to 150 parts by mass, based on 1 part by mass of the total of the compound represented by formula (pt1) and the compound represented by formula (pt 2).

The method for removing the compound (I) as the target compound from the reaction mixture is not particularly limited, and various known methods can be used. For example, a method of cooling after the completion of the reaction and filtering out precipitated crystals is mentioned. The filtered crystals are preferably washed with water or the like, followed by drying. Further, if necessary, the extract may be further purified by a known method such as recrystallization.

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

In the formulae (IV-2) to (IV-5), R¹、R²、R⁵、R⁶、R⁹And Ar¹Each means the same as described above.

Examples of the method for producing the compound represented by the formula (IV-4) from the compound represented by the formula (IV-2) and the compound represented by the formula (IV-3) include various known methods, for example, the method described in Eur.J.org.chem.2012,3105-3111.

Examples of the 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) include various known methods, for example, the method described in J.Polymer Science Part A: Polymer Chemistry 2012,50, 3788-3796.

The compound represented by the formula (pt2) can be produced by the same method as described above.

The colorant (a) may contain a colorant different from the compound (I) in addition to the compound (I), and the colorant different from the compound (I) may be either a dye (hereinafter, sometimes referred to as a dye (a1)) or a pigment (hereinafter, sometimes referred to as a pigment (a2)), or the colorant different from the compound (I) may contain either one or both of the dye (a1) and the pigment (a 2).

As the dye (a1), any known dye may be used without particular limitation as long as it does not contain the compound (I), and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of The dye include compounds classified as substances having a color tone other than pigments (pigments) in The color index (published by The Society of Dyers and Colourists), and known dyes described in dyeing guidelines (color dyeing companies). Further, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like can be cited. Among them, organic solvent-soluble dyes are preferable.

Specifically, c.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: 1. 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

c.i. solvent dyes such as c.i. solvent green 1,3, 4,5, 7, 28, 29, 32, 33, 34, 35;

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, 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: 1. 91, 92, 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: 1. 58, 63, 65, 80, 104, 105, 106, 109, and the like c.i. acid dyes;

c.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

c.i. direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

c.i. direct blue 1,2,3,6, 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, 244, 246, 247, 245, 250, 251, 252, 257, 275, 268, 293, 268, 248;

c.i. direct dyes such as c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

c.i. disperse yellow 51, 54, 76;

c.i. disperse violet 26, 27;

c.i. disperse dyes such as c.i. disperse blue 1, 14, 56, 60, etc.;

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 dyes such as c.i. basic green 1;

c.i. reactive yellow 2, 76, 116;

c.i. reactive orange 16;

c.i. reactive dyes such as c.i. reactive red 36;

c.i. media yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

c.i. medium red 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. intermediate 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. intermediate 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. medium 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. mediator dyes such as c.i. mediator green 1,3, 4,5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53;

c.i. vat dyes such as c.i. vat green 1, and the like.

These dyes may be appropriately selected so as to match the spectral spectrum of the desired color filter.

As The pigment (a2), known pigments can be used without particular limitation, and examples thereof include pigments classified as pigments (pigments) in The color index (published by The Society of Dyers and Colourists).

Examples of the pigment include yellow pigments such as c.i. pigment yellow 1,3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

red pigments such as c.i. 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. pigment blue 15: 6. 60, etc. blue pigments;

c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;

green pigments such as c.i. pigment green 7, 36, 58;

c.i. brown pigments such as pigment brown 23, 25;

and black pigments such as c.i. pigment black 1 and 7.

The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative or the like into which an acidic group or a basic group has been introduced, grafting treatment of the pigment surface with a polymer compound or the like, micronization treatment by a sulfuric acid micronization method or the like, cleaning treatment by an organic solvent, water or the like for removing impurities, removal treatment by an ion exchange method or the like for removing ionic impurities, or the like, as necessary.

The pigment is preferably uniform in particle size. The pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained by performing the dispersion treatment by containing the pigment dispersant.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone, or 2 or more kinds may be used in combination. Examples of the pigment dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (manufactured by ZENECA Co., Ltd.), EFKA (manufactured by CIBA Co., Ltd.), AJISPER (manufactured by Ajinsu Fine chemical Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like.

When a pigment dispersant is used, the amount thereof is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, based on the total amount of the pigment (a 2). When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The content of the colorant (a) in the colored curable resin composition is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and still more preferably 1 to 50% by mass, based on the total amount of solid components. When the content of the colorant (a) is within the above range, the color density in the formation of a color filter is sufficient, and the desired amounts of the resin (B) and the polymerizable compound (C) can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed.

Here, the "total amount of solid components" in the present specification means an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid components and the contents of the respective components relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

The content of the compound (I) is preferably 1% by mass or more, more preferably 3% by mass or more, and may be 100% by mass, or 90% by mass or less, or 60% by mass or less, or 40% by mass or less of the total amount of the colorant (a).

< resin (B) >

The resin comprises a resin comprising structural units derived from an N-substituted maleimide.

When the colored curable resin composition of the present invention contains the above resin, the absorbance retention of the color filter is improved.

The structural unit derived from an N-substituted maleimide is preferably a structural unit represented by the following formula (Bm).

[ in the formula (Bm), R¹³Represents a 1-valent saturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, a 1-valent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a 1-valent heterocyclic group having 3 to 20 carbon atoms which may have a substituent.]

Examples of the 1-valent saturated hydrocarbon group having 1 to 15 carbon atoms include linear alkyl groups having 1 to 15 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, and an eicosyl group; a branched alkyl group having 3 to 15 carbon atoms such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group; and alicyclic saturated hydrocarbon groups having 3 to 15 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, and adamantyl.

Examples of the substituent of the saturated hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, and iodine; a hydroxyl group; a carboxyl group; -NR^hRⁱ(R^hAnd RⁱEach independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; an aromatic hydrocarbon group having 6 to 15 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; a group represented by the following formula (m-1), and the like.

[ in the formula (m-1), "represents a bonding site". ]

Examples of the 1-valent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.

Examples of the substituent of the aromatic hydrocarbon group include a hydroxyl group; a carboxyl group; halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a sulfamoyl group; c1-6 alkylsulfonyl such as methylsulfonyl; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; a group represented by the formula (m-1), and the like.

R¹³When the substituted C1-6 saturated hydrocarbon group is an alkyl group and the substituted C6-15 aromatic hydrocarbon group, R is¹³Represents a C7-21 valent aralkyl group.

Examples of the C7-21 valent aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the substituent for the aralkyl group include the same ones as those described as the substituents for the aromatic hydrocarbon group.

Examples of the 1-valent heterocyclic group having 3 to 20 carbon atoms include thienyl and benzo [ b ]]Thienyl, naphtho [2, 3-b ]]Thienyl, thianthryl, furyl, pyranyl, isobenzofuryl, benzopyranyl (Chromenyl), xanthenyl, thiophenyl

Thienyl (Phenoxathiinyl), 2H-pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, 1H-indazolyl, Purinyl (Purinyl), 4H-quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, 4 aH-carbazolyl, beta-carbolinyl, phenanthridinyl, acridinyl, perimidine (Perimidinyl), phenanthrolinyl (phenonthrolinyl), phenazinyl, phenarsinyl (phenaarsazinyl), isothiazolyl, phenothiazinyl, isothiazinyl

Azolyl, furazanyl, and thiophenyl groups

Oxazinyl (Phenoxazinyl), isochroman (Is)ochromanyl), chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, isoindolinyl, quinuclidinyl, morpholinyl, thioxanthyl (thioxanthyl), and the like.

Examples of the substituent of the heterocyclic group include the same ones as those described as the substituents of the aromatic hydrocarbon group.

As R¹³Preferably, the aromatic hydrocarbon compound is an alicyclic saturated hydrocarbon group having 3 to 8 carbon atoms, a 1-valent aromatic hydrocarbon group having 6 to 10 carbon atoms, or a 1-valent aralkyl group having 7 to 11 carbon atoms.

Examples of the structural unit derived from an N-substituted maleimide include structural units derived from N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N- (9-acridinyl) maleimide, and among them, structural units derived from N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide are preferable.

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

Resin [ K1 ]: a copolymer comprising a structural unit derived from at least 1 monomer (a) (hereinafter sometimes referred to as "(a)") selected from an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, and a structural unit derived from an N-substituted maleimide (m) (hereinafter sometimes referred to as "(m)");

resin [ K2 ]: a copolymer composed of a structural unit derived from (a), a structural unit derived from (b), a structural unit derived from (m), and a structural unit derived from a monomer (c) copolymerizable with (a) (but different from (a), (b) and (m)) (hereinafter sometimes referred to as "(c)");

resin [ K3 ]: a copolymer composed of a structural unit derived from (a) and a structural unit derived from (m);

resin [ K4 ]: a copolymer composed of a structural unit derived from (a), a structural unit derived from (m), and a structural unit derived from (c);

resin [ K5 ]: a copolymer comprising a structural unit derived from (b) to which a structural unit derived from (a) and a structural unit derived from (m) are added;

resin [ K6 ]: a copolymer comprising a structural unit obtained by adding (a) to a structural unit obtained by adding (b) to a structural unit obtained by adding a carboxylic anhydride to a structural unit obtained by adding (a) to a structural unit obtained by adding (b) to a structural unit obtained by adding (m) to a structural unit obtained by adding a carboxylic anhydride to a structural unit obtained by adding (a) to a structural unit obtained by adding a carboxylic anhydride to a structural unit obtained by adding (b) to a structural unit obtained by adding (m) to a structural unit obtained by adding a carboxylic anhydride to a structural unit obtained by adding (b) to a structural unit obtained by adding a carboxylic anhydride to a structural unit obtained by adding (m) to a structural unit obtained by adding a carboxylic anhydride to a structural unit obtained by adding (b) to a carboxylic anhydride obtained by adding a carboxylic anhydride to a structural unit obtained by adding (m) obtained by adding a structural unit obtained by adding (b) to a structural unit obtained by adding a carboxylic anhydride obtained by adding (c).

The structural unit derived from (a) preferably has a carboxyl group or a carboxylic acid anhydride of (a) remaining unreacted. In the resins [ K1] and [ K2], the structural unit derived from (b) preferably remains unreacted in the cyclic ether structure having 2 to 4 carbon atoms contained in (b).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid;

unsaturated dicarboxylic acids such as 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, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexene dicarboxylic acid;

carboxyl group-containing bicyclic unsaturated compounds such as 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 and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

unsaturated dicarboxylic anhydrides such as 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, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

unsaturated mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester and phthalic acid mono [ 2- (meth) acryloyloxyethyl ] ester;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid.

Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

(b) The polymerizable compound has, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) The monomer preferably contains a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" means at least 1 selected from acrylic acid and methacrylic acid. The expressions "(meth) acryloyl group" and "(meth) acrylate" and the like also have the same meaning.

Examples of (b) include a monomer (b1) (hereinafter sometimes referred to as "(b 1)") having an oxetanyl group and an ethylenically unsaturated bond, a monomer (b2) (hereinafter sometimes referred to as "(b 2)") having an oxetanyl group and an ethylenically unsaturated bond, and a monomer (b3) (hereinafter sometimes referred to as "(b 3)") having a tetrahydrofuranyl group and an ethylenically unsaturated bond.

Examples of (b1) include a monomer (b 1-1) (hereinafter sometimes referred to as "(b 1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and a monomer (b 1-2) (hereinafter sometimes referred to as "(b 1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

Examples of (b 1-1) include glycidyl (meth) acrylate,. beta. -methylglycidyl (meth) acrylate,. beta. -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether,. alpha. -methyl-o-vinylbenzyl glycidyl ether,. alpha. -methyl-m-vinylbenzyl glycidyl ether,. alpha. -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene, 2,4, 6-tris (glycidoxymethyl) styrene and the like.

Examples of (b 1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000 (manufactured by Daicel Co., Ltd.), (3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400 (manufactured by Daicel Co., Ltd.), (3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100 (manufactured by Daicel Co., Ltd.)), compounds represented by the formula (BI), and compounds represented by the formula (BII).

[ formula (BI) and formula (BII) wherein R^eAnd R^fRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group.

X^eAnd X^fRepresents a single bond, or-R^g－、＊－R^g－O－、＊－R^g-S-or-R^g－NH－。

R^gRepresents an alkanediyl group having 1 to 6 carbon atoms.

Represents a bonding site 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 a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-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.

As R^eAnd R^fPreferred examples thereof include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferred examples thereof include a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1, 2-diyl group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, and a hexane-1, 6-diyl group.

As X^eAnd X^fPreferable examples thereof include a single bond, methylene, ethylene and perylene-CH₂-O-and-CH₂CH₂O-is more preferably a single bond or O-CH₂CH₂-O- (. ANGSTROM.) represents a bonding site to O).

Examples of the compound represented by formula (BI) include compounds represented by any one of formulae (BI-1) to (BI-15). Among them, preferred are compounds represented by formula (BI-1), formula (BI-3), formula (BII-5), formula (BI-7), formula (BI-9) or formula (BI-11) to formula (BI-15), and more preferred are compounds represented by formula (BI-1), formula (BI-7), formula (BI-9) or formula (BI-15).

Examples of the compound represented by formula (BII) include compounds represented by any one of formulae (BII-1) to (BII-15). Among them, preferred are compounds represented by formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formulae (BII-11) to (BII-15), and more preferred are compounds represented by formula (BII-1), formula (BII-7), formula (BII-9) or formula (BII-15).

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination of 2 or more. When the compound represented by the formula (BI) and the compound represented by the formula (BII) are used in combination, their content ratio [ the compound represented by the formula (BI): the compound represented by the formula (BII) is preferably 5: 95-95: 5, more preferably 20: 80-80: 20.

as (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, and 3-ethyl-3-acryloxyethyloxetane.

As (b3), monomers having a tetrahydrofuranyl group and a (meth) acryloyloxy group are more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V #150, manufactured by Osaka organic chemical industries, Ltd.), tetrahydrofurfuryl methacrylate, and the like.

The component (b) is preferably (b1) from the viewpoint of enabling the obtained color filter to have higher reliability such as heat resistance and chemical resistance. Further, (b 1-2) is more preferable from the viewpoint of excellent storage stability of the colored curable resin composition.

Examples of (c) include 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, cyclohexyl (meth) acrylate, and (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) acrylate, and (meth) acrylate(s) acrylate, and (meth) acrylate(s) acrylate (meth) acrylate(s) acrylate,(meth) acrylic acid tricyclo [5.2.1.0^2,6]Decan-8-yl ester (which is known as "dicyclopentyl (meth) acrylate" and may be referred to as "tricyclodecanyl (meth) acrylate" as a common name in the art), and tricyclo (meth) acrylate [5.2.1.0 ]^2,6]Decen-8-yl ester (commonly known in the art as "dicyclopentenyl (meth) acrylate"), (meth) acrylic acid esters such as dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;

hydroxyl group-containing (meth) acrylates 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-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [ 2.1] hept-2-ene, 5, 6-bis (2.1) hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxyhept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-2.1 ] hept-2-ene, 5-hydroxy-2-hydroxy-2-hydroxy-1-2-hydroxy-2-1-hydroxy-2-hydroxy-2-1-2-ethyl-2-ene, 5-hydroxy-2-hydroxy-2, 5, 6-2-hydroxy-2-one, 5-2-one, 5, 6-one, 2-one, 2-one, 5, Bicyclic unsaturated compounds such as 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [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 and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluenes, 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 proportion of the structural unit derived from each unit is preferably 2 to 55 mol% of the structural unit derived from (a), 2 to 85 mol% of the structural unit derived from (b), 1 to 65 mol% of the structural unit derived from (m), more preferably 5 to 50 mol% of the structural unit derived from (a), 5 to 70 mol% of the structural unit derived from (b), and 5 to 60 mol% of the structural unit derived from (m) among all the structural units constituting the resin [ K1 ].

When the ratio of the structural unit of the resin [ K1] is within the above range, the absorption retention rate of a color filter obtained from the colored curable resin composition can be further improved.

The resin [ K1] can be produced, for example, by referring to the method described in "Experimental method for Polymer Synthesis" (published by Otsuka institute of Engineers, 1 st edition, chemical Co., Ltd., 1972, 3 months and 1 days), and the cited documents described in the above documents.

Specifically, the following methods are mentioned: the predetermined amounts of (a), (b) and (m), a polymerization initiator, a solvent and the like are charged into a reaction vessel, and oxygen is replaced with nitrogen to form a deoxygenated atmosphere, and heating and heat preservation are performed while stirring. The polymerization initiator and the solvent used herein are not particularly limited, and polymerization initiators and solvents generally used in this field can be used. Examples of the polymerization initiator include azo compounds (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), and organic peroxides (e.g., benzoyl peroxide), and examples of the solvent include solvents that dissolve the monomers, and solvents described below as the solvent (E) of the colored curable resin composition of the present invention.

The copolymer obtained may be used as it is, as a solution after the reaction, as a solution after concentration or dilution, or as a substance taken out as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent in the polymerization, the solution after the reaction can be directly used for preparing the colored curable resin composition of the present invention, and therefore, the production process of the colored curable resin composition of the present invention can be simplified.

In the resin [ K2], the proportion of the structural unit derived from each unit is preferably 2 to 55 mol% of the structural unit derived from (a), 2 to 85 mol% of the structural unit derived from (b), 1 to 65 mol% of the structural unit derived from (m), 1 to 50 mol% of the structural unit derived from (c), more preferably 5 to 50 mol% of the structural unit derived from (a), 5 to 70 mol% of the structural unit derived from (b), 5 to 60 mol% of the structural unit derived from (m), and 2 to 40 mol% of the structural unit derived from (c) among all the structural units constituting the resin [ K2 ].

When the ratio of the structural unit of the resin [ K2] is within the above range, the absorption retention rate of a color filter obtained from the colored curable resin composition can be further improved.

The resin [ K2] can be produced, for example, in the same manner as described for the production method of the resin [ K1 ].

In the resin [ K3], the proportion of the structural unit derived from each unit is preferably 2 to 60 mol% of the structural unit derived from (a) and 40 to 98 mol% of the structural unit derived from (m) among all the structural units constituting the resin [ K3], and more preferably 10 to 55 mol% of the structural unit derived from (a) and 45 to 90 mol% of the structural unit derived from (m).

The resin [ K3] can be produced, for example, in the same manner as described for the production method of the resin [ K1 ].

In the resin [ K4], the proportion of the structural unit derived from each unit is preferably 2 to 55 mol% of the structural unit derived from (a), 1 to 65 mol% of the structural unit derived from (m), 1 to 50 mol% of the structural unit derived from (c), more preferably 5 to 50 mol% of the structural unit derived from (a), 5 to 60 mol% of the structural unit derived from (m), and 2 to 40 mol% of the structural unit derived from (c) among all the structural units constituting the resin [ K1 ].

The resin [ K4] can be produced, for example, in the same manner as described for the production method of the resin [ K1 ].

The resin [ K5] was subjected to the first stage in the same manner as in the above-described process for producing the resin [ K1], to obtain a copolymer of (b) and (m). As described above, the copolymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a substance taken out as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (m) is preferably 5 to 95 mol% of the structural unit derived from (b), 5 to 95 mol% of the structural unit derived from (m), more preferably 10 to 90 mol% of the structural unit derived from (b), and 10 to 90 mol% of the structural unit derived from (m), respectively, based on the total mole number of all the structural units constituting the copolymer.

Next, the copolymer of (b) and (m), (a), a reaction catalyst of a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, tris (dimethylaminomethyl) phenol), and a polymerization inhibitor (for example, hydroquinone) are placed in the flask in an air atmosphere, and reacted at 60 to 130 ℃ for 1 to 10 hours, for example, to react the carboxylic acid or the carboxylic anhydride of (a) with the cyclic ether derived from (b) of the copolymer of (b) and (m), thereby obtaining a resin [ K5 ].

The amount of (a) to be used in the reaction with the copolymer is preferably 5 to 80 mol based on 100 mol of (b). The cyclic ether is highly reactive and (b1) is preferable as (b) used in the resin [ K5] in that the unreacted (b) does not easily remain.

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (m). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (m).

The reaction conditions such as the charging method, the reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. Similarly to the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production facilities, the amount of heat generated by polymerization, and the like.

The resin [ K6] was obtained by further reacting the resin [ K5] with a carboxylic acid anhydride. Reacting a carboxylic anhydride with a hydroxyl group produced by the reaction of the cyclic ether and the carboxylic acid or carboxylic anhydride.

Examples of the carboxylic anhydride 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, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride. The amount of the carboxylic anhydride to be used is preferably 0.5 to 1 mol based on 1 mol of the amount of (a).

Specific examples of the resin (B) include a 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid/N-phenylmaleimide copolymer, a 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, a 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid/N-benzylmaleimide copolymer, and a 3, 4-epoxytricyclo [5.2.1.0 ] acrylate^2,6]Decyl ester/(meth) acrylic acid/N-phenylmaleimide copolymer, acrylic acid 3, 4-epoxy tricyclo [5.2.1.0^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, acrylic acid 3, 4-epoxy tricyclo [5.2.1.0^2,6]Decyl ester/(meth) acrylic acid/N-benzylmaleimide copolymer and the like [ K1]]；

Glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid/N-phenylmaleimide copolymer, glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid/N-benzylmaleimide copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid/N-phenylmaleimide copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid/N-benzylmaleimide copolymer, glycidyl (meth) acrylate/styrene, and glycidyl (meth) acrylate/styrene,Acrylic acid 3, 4-epoxy tricyclo [5.2.1.0^2,6]Decyl ester/(meth) acrylic acid/N-phenylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, acrylic acid 3, 4-epoxy tricyclo [ 5.2.1.0%^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, acrylic acid 3, 4-epoxy tricyclo [ 5.2.1.0%^2,6]Resins such as decyl ester/(meth) acrylic acid/N-benzylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene/N-phenylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene/N-cyclohexylmaleimide copolymer, and 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene/N-benzylmaleimide copolymer [ K2]]；

Resins [ K3] such as N-phenylmaleimide/(meth) acrylic acid copolymers, N-cyclohexylmaleimide/(meth) acrylic acid copolymers, and N-benzylmaleimide/(meth) acrylic acid copolymers;

benzyl (meth) acrylate/(meth) acrylic acid/N-phenylmaleimide copolymer, benzyl (meth) acrylate/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, benzyl (meth) acrylate/(meth) acrylic acid/N-benzylmaleimide copolymer, styrene/(meth) acrylic acid/N-phenylmaleimide copolymer, styrene/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, styrene/(meth) acrylic acid/N-benzylmaleimide copolymer, meth) acrylic acid/N-phenylmaleimide/(meth) acrylic acid 2-hydroxyethyl copolymer, meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl copolymer, styrene/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, styrene/(meth) acrylic acid/2-hydroxyethyl copolymer, styrene/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, styrene/(meth) acrylic acid 2-cyclohexylmaleimide copolymer, styrene/(meth) acrylic acid/2-hydroxyethyl copolymer, styrene/(meth) acrylic acid/benzyl maleimide copolymer, styrene/(meth) acrylic acid/styrene-benzyl maleimide copolymer, styrene/(meth) acrylic acid/benzyl maleimide copolymer, styrene/(meth) acrylic acid/styrene/(, Resins [ K4] such as (meth) acrylic acid/N-benzylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer;

resins obtained by reacting (meth) acrylic acid with an N-phenylmaleimide/glycidyl (meth) acrylate copolymer, resins obtained by reacting (meth) acrylic acid with an N-cyclohexylmaleimide/glycidyl (meth) acrylate copolymer, and resins obtained by reacting (meth) acrylic acid with an N-benzylmaleimide/glycidyl (meth) acrylate copolymer [ K5 ];

resins obtained by reacting a copolymer of (meth) acrylic acid and N-phenylmaleimide/(glycidyl (meth) acrylate) and further tetrahydrophthalic anhydride, resins obtained by reacting a copolymer of (meth) acrylic acid and N-cyclohexylmaleimide/(glycidyl (meth) acrylate) and further tetrahydrophthalic anhydride, and resins obtained by reacting a copolymer of (meth) acrylic acid and N-benzylmaleimide/(glycidyl (meth) acrylate) and further tetrahydrophthalic anhydride [ K6], and the like.

Among them, the resin (B) is preferably a resin [ K1] to [ K4], and more preferably a resin [ K1] and a resin [ K2 ].

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, and still more preferably 5000 to 30000. When the molecular weight is within the above range, the color filter tends to have high hardness, a high residual film ratio, good solubility of unexposed portions in a developer, and high resolution of a colored pattern.

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

The acid value of the resin (B) is preferably 70 mg-KOH/g or more, more preferably 90 mg-KOH/g or more, further preferably 110 mg-KOH/g or more, preferably 220 mg-KOH/g or less, more preferably 210 mg-KOH/g or less, further preferably 200 mg-KOH/g or less, in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (B), and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

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

The content of the resin (B) is preferably 10 to 95 parts by mass, more preferably 20 to 90 parts by mass, and still more preferably 30 to 85 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the resin (B) is within the above range, the absorbance retention ratio of the obtained color filter is further improved.

The content of the resin (B) is preferably 55 to 95 parts by mass, more preferably 60 to 90 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the resin (B) is within the above range, the absorbance retention ratio of the obtained color filter is significantly improved.

When the content of the resin (B) is 10 to 60 parts by mass, preferably 20 to 55 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C), the absorbance retention ratio and luminance of the obtained color filter are improved.

< polymerizable Compound (C) >)

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and preferably (meth) acrylate compounds.

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 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 the like, Caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like.

Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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 amount of the solid content. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a 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 under the action of light or heat to initiate polymerization, and a known polymerization initiator can be used.

As the polymerization initiator generating active radicals, for example, an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a bisimidazole compound can be cited.

Examples of the O-acyloxime compounds include O-acyloxime compounds having a diphenylsulfide skeleton such as N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, and N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine; o-acyloxime compounds having a carbazole skeleton such as 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-dioxopentylmethoxy) 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-cyclopentylpropane-1-one-2-imine; an O-acyloxime compound having a fluorene skeleton such as 1- [ 7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] ethanone-O-acetyloxime; and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (both of which are available from BASF corporation), N-1919 (available from ADEKA corporation), and DFI-091 (available from Daito Chemix Co., Ltd.) can be used. Among them, the O-acyloxime compound is preferably at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine and 1- [ 7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] ethanone-O-acetyloxime. In the case of these O-acyloxime compounds, color filters having high luminance tend to be obtained.

Examples of the above-mentioned alkylphenone compound 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-morpholino) 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, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzildimethyl ketal, and the like. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (both manufactured by BASF corporation) may 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-methoxystyryl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1, 3, 5-triazine and the like.

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

Examples of the biimidazole compound include 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5' -tetraphenylbiimidazole (see, for example, japanese unexamined patent publication No. 6-75372, japanese unexamined patent publication No. 6-75373, etc.), 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese patent application laid-open No. 48-38403 and Japanese patent application laid-open No. 62-174204), and biimidazole compounds in which the phenyl group at the 4,4 ', 5, 5' -position is substituted with a carboalkoxy group (カルボアルコキシ group) (see, for example, Japanese patent application laid-open No. 7-10913).

Examples of the polymerization initiator for generating an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl-methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, and the like,Diphenyl iodide

P-toluenesulfonate and diphenyliodine

Hexafluoroantimonate and the like

Salts, nitrobenzyl tosylates, benzoin tosylates, and the like.

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, titanocene compounds, and the like.

As the polymerization initiator (D), a polymerization initiator containing at least 1 selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a bisimidazole compound is preferable, and a polymerization initiator containing an O-acyloxime compound is more preferable.

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

< solvent (E) >

The solvent (E) is not particularly limited, and a solvent generally used in this field can be used. Examples thereof include an ester solvent (a solvent containing-COO-and not containing-O-in the molecule), an ether solvent (a solvent containing-O-and not containing-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and-O-in the molecule), a ketone solvent (a solvent containing-CO-and not containing-COO-in the molecule), an alcohol solvent (a solvent containing OH and not containing-O-, -CO-, and-COO-, an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ -butyrolactone.

Examples of the ether solvent 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-di-n

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 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 monoethylether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol monobutyl ether acetate, and the like.

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

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-dimethylacetamide, and N-methylpyrrolidone.

Among the above solvents, organic solvents having a boiling point of 120 to 180 ℃ at 1atm are preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate, and ethyl 3-ethoxypropionate are more preferable.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total content of the solid content in the colored curable resin composition is preferably 5 to 30% by mass, and 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 becomes good, and the color density does not become insufficient at the time of forming a color filter, so that the display characteristics tend to become good.

< leveling agent (F) >

Examples of the leveling agent (F) include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone 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 Moviive Performance Properties Japan contract Co., Ltd.), and the like can be cited.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC (Co., Ltd.), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi electro chemical Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Nitron (Co., Ltd.), and E5844 (manufactured by King Kogyo chemical Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there may be mentioned MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477 and MEGAFAC F443 (manufactured by DIC Co., Ltd.).

The content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to 0.2% by mass, and still more preferably 0.005 to 0.2% by mass, based on the total amount of the colored curable resin composition. The content of the dispersant is not included in the content. 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 contain additives known in the art, such as a polymerization initiation aid, a filler, another polymer compound, an adhesion promoter, a light stabilizer, and a chain transfer agent, as required.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-thioalkylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, 3-chloropropylmethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethane, 3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and the like, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and the like.

< method for producing colored curable resin composition >

The colored curable resin composition of the present invention can be prepared, for example, by mixing the colorant (a), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and, if necessary, the solvent (E), the leveling agent (F), and other components.

< method for manufacturing color filter >

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include photolithography, ink jet printing, and printing. Among them, photolithography is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask and developed. In the photolithography method, a colored coating film which is a cured product of the colored composition layer can be formed without using a photomask and/or without performing development at the time of exposure. The colored pattern and the colored coating film formed in this way 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 suitably adjusted according to the purpose, application, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass having a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, a substrate of silicon, a substrate having a thin film of aluminum, silver/copper/palladium alloy formed on the substrate, or the like can be used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by photolithography can be performed by using a known or conventional apparatus and conditions. For example, the following can be used.

First, a colored curable resin composition is applied onto a substrate, and is dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent and dry the composition, thereby obtaining a smooth colored composition layer.

Examples of the coating method include a spin coating method, a slit and spin coating method.

The temperature for heating and drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When the drying is carried out under reduced pressure, the drying is preferably carried out under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃.

The film thickness of the colored 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 corresponding to the intended use is used.

The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350nm may be cut off using a filter that cuts off the wavelength region, or light near 436nm, near 408nm, or near 365nm may be selectively extracted using a band-pass filter that extracts these wavelength regions. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like can be given.

In order to uniformly irradiate parallel light rays to the entire exposure surface and perform precise alignment of the photomask and the substrate on which the colored composition layer is formed, an exposure apparatus such as a mask aligner and a stepper is preferably used.

The exposed colored composition layer is brought into contact with a developer to develop the colored composition layer, thereby forming a colored pattern on the substrate. 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 bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may contain a surfactant.

The developing method may be any of a spin coating immersion method (Paddle method), a dipping method, a spraying method, and the like. Further, the substrate can be inclined at an arbitrary angle during development.

After development, washing with water is preferred.

Further, the obtained colored pattern is preferably subjected to post-baking. The post-drying temperature is preferably 150-250 ℃, and more preferably 160-235 ℃. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

Examples

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In the examples,% and parts indicating the content or amount used are by mass unless otherwise specified.

In the following synthesis examples, the compounds were identified by NMR (JNM-EX-270, manufactured by JEOL Ltd.).

(coloring agent Synthesis example 1)

10.0 parts of 2, 4-dimethylaniline (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 17.0 parts of 2-ethylhexane bromide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 44.0 parts of tetrabutylammonium bromide (manufactured by photochemical Kasei Kogyo Co., Ltd.) were mixed. The resulting mixture was stirred at 90 ℃ for 8 hours. After the reaction, 50 parts of a 10% aqueous sodium bicarbonate solution was added, 100 parts of ethyl acetate was added, and the aqueous layer was discarded. The washing with water and 10% hydrochloric acid was repeated 2 times, and the solvent was distilled off. The resulting oily substance was dried at 60 ℃ under reduced pressure for 24 hours to obtain 9.3 parts of a compound represented by the following formula (a-1).

Process for producing compound represented by the formula (a-1)¹H-NMR (270MHz, delta values (ppm, TMS basis), DMSO-d₆)

δ0.85(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 Kasei Kogyo Co., Ltd.), 0.015 part of palladium acetate, 3.2 parts of sodium tert-butoxide (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.055 part of tri-tert-butylphosphine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 25.6 parts of toluene were mixed and stirred at 100 ℃ for 15 hours. To the resulting mixture were added 30 parts of ethyl acetate and 100 parts of water, and the aqueous layer was discarded. After washing with water was repeated 2 times, the solvent was distilled off. The residue was purified by silica gel column chromatography (chloroform/hexane ═ 1/1), and the obtained oil was dried at 60 ℃ under reduced pressure for 24 hours to obtain 1.9 parts of a compound represented by the following formula (a-2).

Process for producing compound represented by the formula (a-2)¹H-NMR (270MHz, delta values (ppm, TMS basis), DMSO-d₆)

δ0.85(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 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 90.0 parts of 1-butanol and 60.0 parts of toluene were mixed. The resulting mixture was stirred at 125 ℃ for 3 hours while removing the generated water using a Dean-Stark tube. After completion of the reaction, the solvent was distilled off, 15 parts of acetic acid was added thereto, and the mixture was added dropwise to 100 parts of 18% saline solution, and the precipitated solid was filtered off. The filtered solid was washed with hexane. The resulting solid was dried under reduced pressure at 60 ℃ for 24 hours to give 4.9 parts of a compound represented by the formula (AII-10).

Process for producing compound represented by the formula (AII-10)¹H-NMR (270MHz, delta values (ppm, TMS basis), DMSO-d₆)

δ0.87(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)

The structure of the compound was confirmed by MASS spectrometry (LC; model 1200 by Agilent, MASS; LC/MSD by Agilent).

(coloring agent Synthesis example 2)

50 parts of m-bromophenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 30 parts of imidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in 500 parts of methylene chloride (manufactured by Kanto Kasei Kogyo Co., Ltd.), cooled to 0 ℃ and 48 parts of t-butyldimethylsilyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise thereto. After the completion of the dropwise addition, the temperature was raised to 23 ℃ and the mixture was stirred for 16 hours. After the reaction, the organic layer was extracted with water, the solvent was concentrated, and the extract was separated and purified by silica gel column chromatography to obtain 74 parts of a compound represented by the formula (a-3).

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]⁺287.0

Precise molecular weight: +286.0

15 parts of 2, 4-dimethylaniline (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 35 parts of the compound represented by the formula (a-3), 14 parts of potassium hydroxide (manufactured by Wako pure chemical industries Co., Ltd.), 2 parts of tetrabutylammonium bromide (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 0.6 part of bis (tri-tert-butylphosphine) palladium (0) (manufactured by Aldrich Co., Ltd.) were dissolved in 250 parts of toluene (manufactured by Kanto Kasei Kogyo Co., Ltd.) and 15 parts of water, and the mixture was heated to 90 ℃ and stirred for 30 minutes. After completion of the reaction, the organic layer was extracted and concentrated, followed by separation and purification by silica gel column chromatography to obtain 14 parts of a compound represented by the formula (a-4).

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]⁺328.3

Precise molecular weight: +327.2

14 parts of the compound represented by the formula (a-4) and 10 parts of methyl 4-chloro-4-oxobutanoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in 255 parts of toluene (manufactured by Kanto Kasei Co., Ltd.), and the mixture was stirred at 90 ℃ for 1 hour. After the reaction, the organic layer was extracted with water, the solvent was concentrated, and the mixture was separated and purified by silica gel column chromatography to obtain 15 parts of a compound represented by the formula (a-5).

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]⁺442.3

Precise molecular weight: +441.2

15 parts of the compound represented by the formula (a-5) was dissolved in 150 parts of tetrahydrofuran (manufactured by Kanto chemical Co., Ltd.), the solution was cooled to 0 ℃ and 15 parts of a 1M tetrahydrofuran solution of tetra-n-butylammonium fluoride (manufactured by Tokyo chemical Co., Ltd.) was added dropwise. After the end of the dropwise addition, the temperature was raised to 23 ℃ and the mixture was stirred for 2 hours. After completion of the reaction, the solvent was concentrated, and the mixture was separated and purified by silica gel column chromatography to obtain 12 parts of a compound represented by the formula (a-6).

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]⁺328.2

Precise molecular weight: +327.2

12 parts of the compound represented by the formula (a-6) was dissolved in 240 parts of tetrahydrofuran (manufactured by Kanto Kagaku Co., Ltd.), and after cooling to 0 ℃ 180 parts of a borane 1M tetrahydrofuran solution (manufactured by Kanto Kagaku Co., Ltd.) was added dropwise. After the completion of the dropwise addition, the mixture was stirred for 30 minutes, water was added thereto, the tetrahydrofuran was concentrated, and the organic layer was extracted with ethyl acetate. The solvent was concentrated, and the mixture was separated and purified by silica gel column chromatography to obtain 6 parts of a compound represented by the formula (a-7).

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]⁺314.2

Precise molecular weight: +313.2

6 parts of the compound represented by the formula (a-7) and 0.2 part of lithium hydroxide monohydrate (Wako pure chemical industries, Ltd.) were dissolved in 20 parts of methanol (manufactured by Kanto Kagaku Co., Ltd.), 20 parts of tetrahydrofuran (manufactured by Kanto Kagaku Co., Ltd.) and 10 parts of water, and the mixture was stirred at 23 ℃ for 1 hour. After completion of the reaction, the organic solvent was concentrated, the organic layer was extracted with ethyl acetate, and the extract was separated and purified by silica gel column chromatography to obtain 4 parts of a compound represented by the formula (a-8).

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M +H]⁺300.2

Precise molecular weight: +299.2

4 parts of the compound represented by the formula (a-8) and 0.8 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (Wako pure chemical industries, Ltd.) were dissolved in 40 parts of toluene (Kanto Kagaku Co., Ltd.) and 10 parts of n-butanol (Kanto Kagaku Co., Ltd.) and stirred at 140 ℃ for 2 hours. After the solvent was concentrated, the extract was separated and purified by silica gel column chromatography to obtain 1.6 parts of a compound represented by the formula (AII-17).

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]⁺677.3

Precise molecular weight: +676.3

(coloring agent Synthesis example 3)

50 parts of 3-bromoanisole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 36.1 parts of 2,4, 6-trimethylaniline (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 434 parts of toluene (manufactured by Kanto Kasei Kogyo Co., Ltd.), and 30 parts of potassium hydroxide (manufactured by Kanto Kasei Kogyo Co., Ltd.), 25 parts of water, 2 parts of tetrabutylammonium bromide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 1.4 parts of bis (tri-t-butylphosphine) palladium (0) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed in the solution. After the temperature was raised to 90 ℃ and the mixture was stirred for 5 hours, an organic layer was obtained by extraction, and the solvent was distilled off to obtain 52.1 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 50.2 parts of a compound represented by the formula (a-9).

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]⁺242.3

Precise molecular weight: +241.2

33 parts of the compound represented by the formula (a-9), 26.8 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 286 parts of toluene (manufactured by Kanto Kasei Co., Ltd.) were mixed and heated at 100 ℃ for 16 hours with stirring. After the reaction was completed, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 30.7 parts of a compound represented by the formula (a-10).

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]⁺356.2

Precise molecular weight: +355.2

10 parts of the compound represented by the formula (a-10) was dissolved in 95 parts of methylene chloride (manufactured by Kanto chemical Co., Ltd.), and the solution was cooled to 0 ℃ with stirring. 28.2 parts of boron tribromide (manufactured by Fuji film and Wako pure chemical industries, Ltd.) was added dropwise while stirring. After the completion of the dropwise addition, the temperature was gradually raised and the mixture was stirred at 10 ℃ for 4 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and a water-organic solvent extraction operation was carried out to distill off the solvent, whereby 9.1 parts of a crude product was obtained. Wherein the content of the compound represented by the formula (a-11) is 48% and the content of the compound represented by the formula (a-12) is 36%.

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]⁺342.2

Precise molecular weight: +341.2

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]⁺328.1

Precise molecular weight: +327.2

13.2 parts of thionyl chloride (manufactured by tokyo chemical industries, Ltd.) was dissolved in 72 parts of methanol (manufactured by Kanto chemical Co., Ltd.) to obtain a solution, and 9.1 parts of the crude product containing the compound represented by the formula (a-11) and the compound represented by the formula (a-12) was added thereto while stirring the solution at 0 ℃. The reaction mixture was warmed to room temperature and allowed to react for 16 hours. The solvent was distilled off under reduced pressure to obtain 8.3 parts of a crude product containing the compound represented by the formula (a-11). The obtained crude product was purified by silica gel column chromatography to obtain 7.4 parts of a compound represented by the formula (a-11).

Precise molecular weight: +341.2

2 parts of the compound represented by the formula (a-11), 26.3 parts of a borane-1M tetrahydrofuran solution (manufactured by Kanto Kagaku K.K.) and 18 parts of tetrahydrofuran (manufactured by Kanto Kagaku K.K.) were mixed at 0 ℃ and stirred at 10 ℃ for 5 hours. After the reaction is finished, water is added for quenching, and the mixture is extracted by an organic solvent. The solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 1.64 parts of a compound represented by the formula (a-13).

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]⁺300.2

Precise molecular weight: +299.2

2.5 parts of the compound represented by the formula (a-13) and 0.55 part of 3, 4-dihydroxy-3-cyclobutene-1, 2-dione (manufactured by Fuji film and Wako pure chemical industries, Ltd.) were dissolved in 50 parts of toluene (manufactured by Kanto Kagaku Co., Ltd.) and 50 parts of n-butanol (manufactured by Kanto Kagaku Co., Ltd.) and heated at 110 ℃ for 6 hours with stirring. After completion of the reaction, the solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 2.7 parts of a compound represented by the formula (AII-18).

And (3) identification: (Mass Spectrometry) ionization mode ESI +: m/z ═ M + H]⁺677.4

Precise molecular weight: +676.4

(resin Synthesis example 1)

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was changed to a nitrogen atmosphere, and 223 parts of 3-methoxybutanol and 110 parts of 3-methoxybutyl acetate were added thereto, and the mixture was heated to 70 ℃ with stirring. Then, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise to the flask over 5 hours using a dropping pump^2,6]Decane-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0^2,6]A mixed solution of 180 parts of a mixture of decane-9-yl acrylate (mixing ratio 1: 1), 54 parts of acrylic acid, 67 parts of N-cyclohexylmaleimide and 180 parts of 3-methoxybutanol.

On the other hand, a mixed solution of 6 parts of 2, 2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator dissolved in 150 parts of 3-methoxybutyl acetate was added dropwise to the flask over 5 hours using another dropping pump. After completion of the dropwise addition of the polymerization initiator, the mixture was held at the same temperature for 3 hours and then cooled to room temperature to obtain a B-type copolymer (resin (B-1)) solution having a viscosity of 130mPas (23 ℃ C.) and a solid content of 30.9%. The weight average molecular weight (Mw) of the resulting copolymer was 8800, the acid value in terms of solid content was 137 mg-KOH/g, and the degree of dispersion was 1.76. The resin (B-1) has the following structural unit.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene were measured by GPC under the following conditions.

The device comprises the following steps: HLC-8120GPC (manufactured by Tosoh corporation)

Column: TSK-GELG2000HXL

Column temperature: 40 deg.C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

Detecting the concentration of the solid component in the liquid: 0.001 to 0.01% by mass

Sample introduction amount: 50 μ L

A detector: RI (Ri)

Calibration standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight in terms of polystyrene obtained above was defined as the degree of dispersion.

(resin Synthesis example 2)

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was changed to a nitrogen atmosphere, and 185 parts of 3-methoxybutanol and 216 parts of propylene glycol monomethyl ether acetate were added thereto, and the mixture was heated to 70 ℃ with stirring. Then, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise to the flask over 5 hours using a dropping pump^2,6]Decane-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0^2,6]149 parts of a mixture of decane-9-yl acrylate (mixing ratio: 1), 45 parts of acrylic acid, 56 parts of N-cyclohexylmaleimide and 158 parts of 3-methoxybutanol.

On the other hand, a mixed solution of 8 parts of 2, 2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator dissolved in 183 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 5 hours using another dropping pump. After completion of the dropwise addition of the polymerization initiator, the mixture was held at the same temperature for 4 hours and then cooled to room temperature to obtain a B-type copolymer (resin (B-2)) solution having a viscosity of 22mPas (23 ℃ C.) and a solid content of 26.1%. The weight-average molecular weight (Mw) of the resulting copolymer was 8900, the acid value in terms of solid content was 143 mg-KOH/g, and the degree of dispersion was 1.92. The resin (B-2) has the same structural unit as the resin (B-1).

(resin Synthesis example 3)

A suitable amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was changed to a nitrogen atmosphere, and 248 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ℃ with stirring. Then, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise to the flask over 5 hours using a dropping pump^2,6]Decane-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0² ^,6]Mixture of decane-9-yl acrylateThe mixing ratio is 1: 1)52 parts, 42 parts of acrylic acid, 141 parts of N-cyclohexylmaleimide and 352 parts of propylene glycol monomethyl ether acetate.

On the other hand, a mixed solution of 20 parts of 2, 2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator dissolved in 145 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 5 hours using another dropping pump. After completion of the dropwise addition of the polymerization initiator, the mixture was held at the same temperature for 3 hours and then cooled to room temperature to obtain a B-type copolymer (resin (B-3)) solution having a viscosity of 18mPas (23 ℃ C.) and a solid content of 25.7%. The weight average molecular weight (Mw) of the resulting copolymer was 8000, the acid value in terms of solid content was 119 mg-KOH/g, and the degree of dispersion was 2.09. The resin (B-3) has the same structural unit as the resin (B-1).

(resin Synthesis example 4)

A suitable amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was changed to nitrogen, and 191 parts of propylene glycol monomethyl ether acetate and 79 parts of propylene glycol monomethyl ether were added thereto and the mixture was heated to 80 ℃ while stirring. Then, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise to the flask over 5 hours using a dropping pump^2,6]Decane-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0^2,6]A mixed solution of 112 parts of a mixture of decane-9-yl acrylate (mixing ratio 1: 1), 80 parts of acrylic acid, 128 parts of N-cyclohexylmaleimide and 258 parts of propylene glycol monomethyl ether.

On the other hand, a mixed solution of 7 parts of 2, 2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator dissolved in 145 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 5 hours using another dropping pump. After completion of the dropwise addition of the polymerization initiator, the mixture was held at the same temperature for 3 hours and then cooled to room temperature to obtain a B-type copolymer (resin (B-4)) solution having a viscosity of 75mPas (23 ℃ C.) and a solid content of 34.7%. The weight average molecular weight (Mw) of the resulting copolymer was 8800, the acid value in terms of solid content was 181 mg-KOH/g, and the degree of dispersion was 2.20. The resin (B-4) has the same structural unit as the resin (B-1).

(resin Synthesis example 5)

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and a nitrogen atmosphere was changed, and 149 parts of diethylene glycol ethyl methyl ether and 110 parts of propylene glycol monomethyl ether were added thereto, and the mixture was heated to 70 ℃ with stirring. Then, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise to the flask over 5 hours using a dropping pump^2,6]Decane-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0^2,6]A mixed solution of 45 parts of a mixture of decane-9-yl acrylate (mixing ratio 1: 1), 75 parts of acrylic acid, 180 parts of N-cyclohexylmaleimide and 309 parts of diethylene glycol methyl ether.

On the other hand, a mixed solution of 5 parts of 2, 2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator dissolved in 127 parts of propylene glycol monomethyl ether was added dropwise to the flask over 5 hours using another dropping pump. After completion of the dropwise addition of the polymerization initiator, the mixture was held at the same temperature for 4 hours and then cooled to room temperature to obtain a B-type copolymer (resin (B-5)) solution having a viscosity of 66mPas (23 ℃ C.) and a solid content of 34.5%. The weight average molecular weight (Mw) of the resulting copolymer was 9000, the acid value in terms of solid content was 183 mg-KOH/g, and the degree of dispersion was 2.06.

The resin (B-5) has the same structural unit as the resin (B-1).

(resin Synthesis example 6)

A suitable amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was changed to nitrogen, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ℃ while stirring. Then, 19 parts of methacrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] were added dropwise to the flask over about 5 hours using a dropping pump^2,6]Decane-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0^2,6]171 parts of a mixture of decane-9-yl acrylate (mixing ratio: 1) was dissolved in 40 parts of propylene glycol monomethyl ether acetate.

On the other hand, a solution obtained by dissolving 26 parts of 2, 2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator in 120 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over about 5 hours using another dropping pump. After the completion of the dropwise addition of the polymerization initiator, the mixture was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a copolymer (resin (B-6)) solution having a solid content of 43.5%. The weight-average molecular weight of the obtained resin (B-2) was 8000, the degree of dispersion was 1.98, and the acid value in terms of solid content was 53 mg-KOH/g. The resin (B-6) has the following structural unit.

Examples 1 to 9 and comparative example 1

[ preparation of colored curable resin composition ]

The respective components were mixed so as to have the compositions shown in table 2, thereby obtaining colored curable resin compositions.

In table 2, each component represents the following compound.

Colorant (A-1): a compound represented by the formula (AII-10)

Colorant (a-2): a compound represented by the formula (AII-17)

Colorant (a-3): a compound represented by the formula (AII-18)

Resin (B-1): resin (B-1) (conversion of solid content)

Resin (B-2): resin (B-2) (conversion of solid content)

Resin (B-3): resin (B-3) (conversion of solid content)

Resin (B-4): resin (B-4) (conversion of solid content)

Resin (B-5): resin (B-5) (conversion of solid content)

Resin (B-6): resin (B-6) (conversion of solid content)

Polymerizable compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemicals, Inc.)

Polymerization initiator (D-1): n-1919 (manufactured by ADEKA Co., Ltd.; O-acyloxime Compound)

Polymerization initiator (D-2): DFI-091 (manufactured by Daito Chemix; O-acyloxime compound)

Polymerization initiator (D-3): n-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01, manufactured by BASF Corp.; O-acyloxime compound)

Solvent (E-1): 4-hydroxy-4-methyl-2-pentanone

Solvent (E-2): propylene glycol monomethyl ether acetate

Solvent (E-3): 3-Methoxybutyl acetate

Solvent (E-4): 3-methoxy-1-butanol

Solvent (E-5): diethylene glycol methyl ethyl ether

Solvent (E-6): propylene glycol monomethyl ether

Leveling agent (F-1): polyether-modified Silicone oil ("Toray Silicone SH 8400" manufactured by Dow Corning Toray corporation)

[ preparation of colored coating film ]

The colored curable resin composition was applied onto a 5cm square glass substrate (EAGLE 2000; manufactured by CORNING) by a spin coating method so that the post-baking film thickness was 2.0 μm, and then pre-baked at 100 ℃ for 3 minutes to form a colored composition layer. After cooling, the resultant was exposed to 100mJ/cm in an air atmosphere using an exposure apparatus (TME-150 RSK; manufactured by TOPCON Ltd.)²The exposure amount (365nm basis) of (b) is irradiated with light to the colored composition layer. Thereafter, the resultant was postbaked in an oven at 230 ℃ for 30 minutes to obtain a colored coating film.

[ evaluation of workability ]

1. Absorbance retention ratio

The maximum absorbance was obtained from the spectral spectra measured after the prebaking and after the postbaking, and the retention of the maximum absorbance was calculated from the following equation. The results are shown in Table 3.

Max (absorbance retention ratio) of maximum absorbance after postbaking/maximum absorbance after prebaking

The higher the absorbance retention ratio, the higher the suitability in the film forming step.

2. Color intensity

The chromaticity of the colored coating films formed from the colored curable resin compositions of examples 1 and 3 and comparative example 1 was determined from the spectral spectrum measured using a colorimeter (OSP-SP-200; manufactured by Olympus corporation) and the characteristic function of the C light source to find xy chromaticity coordinates (x, Y) and Y in the CIE XYZ color system. The results are shown in Table 4. The larger the value of Y, the higher the luminance.

[ Table 4]

	Example 1	Example 3	Comparative example 1
				Y	93.6	94.4	90.7

Industrial applicability

According to the colored resin composition of the present invention, a color filter having an excellent absorbance retention rate can be formed.

Claims

1. A colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator,

the colorant isComprising a squaric acid represented by the formula (I)

The colorant of the dye is selected from the group consisting of,

the resin is a resin containing a structural unit derived from an N-substituted maleimide,

in the formula (I), the compound is shown in the specification,

R¹～R⁴each independently represents a hydrogen atom, a halogen atom, a hydroxyl group or a substituted 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the 1-valent saturated hydrocarbon group,

R⁵～R⁸each independently represents a hydrogen atom or a hydroxyl group,

Ar¹and Ar²Each independently represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a group represented by the formula (i),

in the formula (i), the reaction mixture is,

R¹²represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a 1-valent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, m represents an integer of 0 to 5, oxygen atom or sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group, and when m is 2 or more, a plurality of R' s¹²May be the same or different, represent a bonding site with a nitrogen atom,

R⁹and R¹⁰Each independently represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a group represented by formula (i), and an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the 1-valent saturated hydrocarbon group.

2. A color filter comprising the colored curable resin composition according to claim 1.

3. A display device comprising the color filter of claim 2.