TWI708772B - Compound, colored curable resin composition, color filter and display device - Google Patents

Abstract

The present invention provides a compound, a colored curable resin composition, a color filter, and a display device. The use of the colored curable resin composition containing the compound of the present invention can provide a color filter and a display device having good heat resistance. The compound of the present invention is represented by formula (I).

Description

Compound, colored curable resin composition, color filter and display device

Invention field

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

Background of the invention

For example, dyes are used in the fields of fiber materials, liquid crystal display devices, inkjets, etc. to use reflected light or transmitted light for color display. As such a dye, it is well known that, for example, rhodamine B represented by the following formula (Rb) as a compound having a xanthene skeleton (Non-Patent Document 1).

Prior art literature

Non-patent literature

Non-Patent Document 1: "New Dye Chemistry" by Hosoda Toyohiro, Gihodo Co., Ltd., 1st edition, May 1973, page 274

Summary of the invention

The coloring curable resin composition containing the above-mentioned compound known so far does not sufficiently satisfy the requirements in terms of heat resistance.

The present invention includes the following inventions.

[1] The compound represented by formula (I).

[In formula (I), R ¹ represents an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted alkyl group having 1 to 20 carbon atoms, and an optionally substituted carbon number 2 to 20 An unsaturated hydrocarbon group or an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, and -CH ₂ -contained in the alkyl group may be replaced by -O-, -CO- or -NR ¹¹ -. However, the adjacent -CH ₂ -will not be replaced by -O- at the same time, and the terminal -CH ₂ -will not be replaced by -O-, -CO- or -NR ¹¹ -.

R ³ and R ⁴ each independently represent a hydrogen atom, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may have a substituent, an alkyl group having 1 to 20 carbon atoms that may have a substituent, and a carbon number 2 to 20 that may have a substituent 20 unsaturated hydrocarbon groups, or optionally substituted alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, -CH ₂ -contained in the alkyl group may be replaced by -O-, -CO- or -NR ^11- . However, the adjacent -CH ₂ -will not be replaced by -O- at the same time, and the terminal -CH ₂ -will not be replaced by -O-, -CO- or -NR ¹¹ -.

R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ⁷ represents a hydrogen ^{_{atom, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO 2 R 10, - SO ₃ R ¹⁰ or -SO ₂ NR ¹¹ R ¹² .

R ⁸ represents _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO 2 R 10, -SO 3 R ¹⁰ or -SO ₂ NR ¹¹ R ¹² .

m represents an integer of 0-4, and when m is 2 or more, a plurality of R ⁸ may be the same as or different from each other.

Z ⁺ represents ⁺ N(R ¹³ ) ₄ , Na ⁺ or K ⁺ .

R ¹⁰ represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom.

R ¹¹ and R ¹² each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms.

R ¹³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ¹³ may be the same as or different from each other.

X represents a halogen atom.

a represents an integer of 0 or 1. ]

[2] A colored curable resin composition comprising the compound described in [1], the resin (B), the polymerizable compound (C), and the polymerization initiator (D).

[3] A color filter formed from the coloring curable resin composition described in [2].

[4] A display device including the color filter described in [3].

The color filter formed from the coloring curable resin composition containing the compound of the present invention has good heat resistance.

Detailed ways

The compound of the present invention is a compound represented by formula (I) (hereinafter may also be described as "compound (I)"). The compound of the present invention also includes its tautomers.

Each component and group exemplified below can be used individually or in combination.

<Compound (I)>

[In formula (I), R ¹ represents an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted alkyl group having 1 to 20 carbon atoms, and an optionally substituted carbon number 2 to 20 An unsaturated hydrocarbon group or an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, and -CH ₂ -contained in the alkyl group may be replaced by -O-, -CO- or -NR ¹¹ -. However, the adjacent -CH ₂ -will not be replaced with -O-, -CO- or -NR ¹¹ -at the same time, and the terminal -CH ₂ -will not be replaced with -O-, -CO- or -NR ^11- .

R ³ and R ⁴ each independently represent a hydrogen atom, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may have a substituent, an alkyl group having 1 to 20 carbon atoms that may have a substituent, and a carbon number 2 to 20 that may have a substituent The 20 unsaturated hydrocarbon group or the optionally substituted alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, -CH ₂ -contained in the alkyl group may be replaced by -O-, -CO- or -NR ¹¹ -. However, the adjacent -CH ₂ -will not be replaced by -O- at the same time, and the terminal -CH ₂ -will not be replaced by -O-, -CO- or -NR ¹¹ -.

R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ⁷ represents a hydrogen ^{_{atom, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO 2 R 10, - SO ₃ R ¹⁰ or -SO ₂ NR ¹¹ R ¹² .

R ⁸ represents _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO 2 R 10, -SO 3 R ¹⁰ or -SO ₂ NR ¹¹ R ¹² .

m represents an integer of 0-4, and when m is 2 or more, a plurality of R ⁸ may be the same as or different from each other.

Z ⁺ represents ⁺ N(R ¹³ ) ₄ , Na ⁺ or K ⁺ .

R ¹⁰ represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom.

R ¹¹ and R ¹² each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms.

R ¹³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ¹³ may be the same as or different from each other.

X represents a halogen atom.

a represents an integer of 0 or 1. ]

In formula (I), when -SO ₃ ^- is present, its number is one.

Examples of the aromatic hydrocarbon groups having 6 to 30 carbon atoms represented by R ¹ , R ³ and R ⁴ include phenyl, tolyl, xylyl, mesityl, propylphenyl, and isopropylphenyl. , Tert-butylphenyl, sec-butylphenyl, pentylphenyl, hexylphenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, benzopyrenyl, etc., preferably phenyl, tolyl, xylyl . The carbon number of the aromatic hydrocarbon group represented by R ³ and R ⁴ is preferably 6-20, and more preferably 6-10.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ , R ³ and R ⁴ include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n- Straight-chain alkyl such as octyl, n-nonyl, and n-decyl; branched chain such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl The alkyl group is preferably a linear alkyl group. The carbon number of the alkyl group represented by R ¹ , R ³ and R ⁴ is preferably 1-10, more preferably 1-8.

Examples of the unsaturated hydrocarbon groups having 2 to 20 carbons represented by R ¹ , R ³ and R ⁴ include vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, and 2-methyl- 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 1-hexenyl linear or branched chain alkenyl with 2 to 20 carbons ; Ethynyl, propargyl, 2-butynyl, 3-butynyl, 1-pentynyl, 1-hexynyl and other linear or branched alkynyl groups with 2 to 20 carbon atoms. The carbon number of the unsaturated hydrocarbon group represented by R ¹ , R ³ and R ⁴ is preferably 2-10, more preferably 2-8.

The -CH ₂ -contained in the alkyl group having 1 to 20 carbons represented by R ¹ , R ³ and R ⁴ may be replaced by -O-, -CO- or -NR ¹¹ -, preferably, it may be -O -replace. However, the adjacent -CH ₂ -will not be replaced by -O- at the same time, and the terminal -CH ₂ -will not be replaced by -O-, -CO- or -NR ¹¹ -. In addition, when -CH ₂ -contained in the alkyl group is replaced by -O-, -CO- or -NR ¹¹ -, the hydrogen atom contained in the alkyl group is preferably substituted with a hydroxyl group as a substituent . The preferable carbon number of the alkyl group in which the methylene group can be substituted with -O-, -CO-, or -NR ¹¹ -is 2-10, more preferably 2-8, and still more preferably 2-6. As the alkyl group in which the methylene group can be replaced with -O-, -CO-, or -NR ¹¹ -, a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable.

In addition, when the methylene group is replaced with -O-, -CO- or -NR ¹¹ -, the end is between -O-, -CO- or -NR ¹¹ -, or -O-, -CO- or -NR ¹¹ The number of carbons between-and the oxygen atom or -CO- is preferably 1 to 4, and more preferably 2 to 3.

Examples of the alkyl group in which -CH ₂ -may be replaced by -O-, -CO-, or -NR ¹¹ -include groups represented by the following formulas. In the formula, * represents the bonding end.

Examples of the alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms represented by R ¹ , R ³ and R ⁴ include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tricyclodecyl Wait.

Examples of the substituent that can be substituted with the aromatic hydrocarbon group having 6 to 30 carbon atoms represented by R ¹ include halogen atoms such as fluorine atom, chlorine atom, and bromine atom; fluoromethyl, difluoromethyl, trifluoromethyl, Chloromethyl, dichloromethyl, and other C1-C12 haloalkyl groups; mercapto groups: hydroxyl groups; cyano groups; nitro groups; groups containing silicon atoms, etc.

Examples of alkyl having 1 to 20 carbon atoms, unsaturated hydrocarbon group having 2 to 20 carbon atoms, or 3 to 20 aliphatic cyclic saturated hydrocarbon group may be substituted by the substituents represented by R ¹ include a fluorine atom , Chlorine atom, bromine atom and other halogen atoms; mercapto group: hydroxyl group; cyano group; nitro group; carbon 6-10 aromatic hydrocarbon group and the like and silicon atom-containing groups, preferably halogen atom, hydroxyl group, and carbon number 6-10 The aromatic hydrocarbon group is particularly preferably a hydroxyl group.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include groups having 6 to 10 carbon atoms among the groups exemplified as the aromatic hydrocarbon group represented by R ¹ .

The above-mentioned group containing a silicon atom means a group containing a silicon atom as a constituent element of the group. The carbon number of the group containing a silicon atom is usually 1-30, preferably 1-20. As the group containing a silicon atom, a group represented by formula (Z1) is preferable.

[In the formula, R ^21A represents a single bond or an alkylene group having 1 to 14 carbon atoms. The -CH ₂ -contained in the alkylene group may be -O-, -CO-, -NR ²² -, -OCO- , -COO-, -OCONH-, -CONH- or -NHCO~ replacement, the hydrogen atom contained in the alkylene group can be replaced by a hydroxyl group.

R ²² represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

R ^22A , R ^23A and R ^24A each independently represent a hydrogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 4 carbons, or an alkoxy group having 1 to 4 carbons.

* Indicates the bonding end. ]

Examples of the alkylene group having 1 to 14 carbon atoms represented by R ^21A include methylene, ethylidene, propane-1,3-diyl, butane-1,4-diyl, and pentane-1 ,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1 , 10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl and other linear alkylene groups; ethane-1,1-diyl, propane-1,1 -Diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane Branched chain alkylene groups such as 1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, etc., preferably linear alkylene groups.

The number of carbon atoms in the alkylene group represented by R ^21A is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4.

-CH ₂ -contained in the alkylene group represented by R ^21A may be -O-, -CO-, -NR ²² -, -OCO-, -COO-, -OCONH-, -CONH- or -NHCO- Replacement, preferably, can be replaced by -OCO-, -COO- or -OCONH-. However, the adjacent -CH ₂ -will not be replaced with -O- at the same time, and the terminal -CH ₂ -will not be replaced with -O-, -CO-, -NR ²² -, -OCO-, -COO- , -OCONH-, -CONH- or -NHCO-.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ²² include linear or branched alkyl groups exemplified as the alkyl group represented by R ¹ and examples of the alicyclic saturated hydrocarbon group represented by R ¹ The group is preferably a linear or branched alkyl group.

The carbon number of the saturated hydrocarbon group represented by R ²² is preferably 1-12, more preferably 1-8, and still more preferably 1-6.

Examples of saturated hydrocarbon groups having 1 to 4 carbon atoms represented by R ^22A , R ^23A and R ^24A include linear alkyl groups such as methyl, ethyl, n-propyl, and n-butyl; isopropyl and sec-butyl. Branched chain alkyl groups such as cyclopropyl and tert-butyl; alicyclic saturated hydrocarbon groups such as cyclopropyl and cyclobutyl.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^22A , R ^23A and R ^24A include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, and sec-butoxy And tert-butoxy.

R ^22A , R ^23A and R ^{24A are} preferably all the same group.

R ^22A , R ^23A and R ^{24A are} preferably each independently an alkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4 carbons.

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

Examples of groups in which -CH ₂ -contained in the alkylene group represented by R ^21A are replaced by -O- include the groups shown below (* represents a bonding terminal).

Examples of groups in which -CH ₂ -contained in the alkylene group represented by R ^21A are replaced by -CO- include the groups shown below (* represents a bonding terminal).

Examples of groups in which -CH ₂ -contained in the alkylene group represented by R ^21A are replaced by -NR ¹² -include the groups shown below (* represents a bonding terminal).

Examples of the group in which -CH ₂ -contained in the alkylene group represented by R ^21A is replaced by -OCO- include the groups shown below (* represents a bonding terminal).

Examples of the group in which -CH ₂ -contained in the alkylene group represented by R ^21A is replaced by -COO- include the groups shown below (* represents a bonding terminal).

Examples of groups in which -CH ₂ -contained in the alkylene group represented by R ^21A are replaced by -OCONH- include the groups shown below (* represents a bonding terminal).

Examples of the group in which -CH ₂ -contained in the alkylene group represented by R ^21A is replaced by -CONH- include the groups shown below (* represents a bonding terminal).

Examples of the group in which -CH ₂ -contained in the alkylene group represented by R ^21A is replaced by -NHCO- include the groups shown below (* represents a bonding terminal).

Examples of the group in which the alkylene group represented by R ^21A may be substituted with a hydroxy group include the groups shown below (* represents a bonding terminal).

As the group containing a silicon atom, a group represented by the following formula is preferable.

Among these, as R ¹ , an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms or an optionally substituted alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 20 carbon atoms is more preferred.

As an aromatic hydrocarbon group having a carbon number by R ³ and R ⁴ represents a substituent having 6 to 30 of the substituents include a halogen atom, a haloalkyl group having a carbon number 1 to _{^{12, -OH, -OR 10, -SO 3}} - , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ¹⁰ , -SH, -SR ¹⁰ , -SO ₂ R ¹⁰ , -SO ₃ R ¹⁰ , -SO ₂ NR ¹¹ R ¹² , -CN, -NO ₂ and groups containing silicon atoms, preferably halogen atoms, halogenated alkyl groups, -SH, -OH, -CN, -NO ₂ and groups containing silicon atoms.

Examples of substituents that can be substituted with alkyl groups having 1 to 20 carbons, unsaturated hydrocarbon groups having 2 to 20 carbons, or alicyclic saturated hydrocarbon groups having 3 to 20 carbons represented by R ³ and R ⁴ include halogen atoms _{^{, -OH, -OR 10, -SO 3}} -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 10, -SH, -SR 10, -SO 2 R 10, - SO ₃ R ¹⁰ , -SO ₂ NR ¹¹ R ¹² , -CN, -NO ₂ and groups containing silicon atoms, preferably halogen atoms, -SH, -OH, -CN, -NO ₂ and groups containing silicon atoms .

In addition, -SO ₂ NR ¹¹ R ¹² is preferably -SO ₂ NHR ¹⁰ .

Examples of the above halogen atoms include fluorine atoms and chlorine atoms Atoms, bromine atoms, etc.

Examples of the halogenated alkyl group having 1 to 12 carbon atoms include the same groups as those exemplified as the halogenated alkyl group that can be substituted with the aromatic hydrocarbon group represented by R ¹ . Examples of the silicon atom-containing group include the same groups as those exemplified as the silicon atom-containing group that can be substituted with the aromatic hydrocarbon group represented by R ¹ .

As R ³ and R ⁴ , a hydrogen atom, an optionally substituted aromatic hydrocarbon group with 6 to 30 carbons or an optionally substituted alkyl group with 1 to 20 carbons are preferred, and a hydrogen atom, an ethyl group, a propyl group or A group represented by the following formula,

More preferably, it is a methyl group, an ethyl group, a propyl group, or a group represented by the following formula.

Preferably, one of R ³ and R ⁴ is an optionally substituted aromatic hydrocarbon group with 6 to 30 carbons, and the other is a hydrogen atom or an optionally substituted alkyl group with 1 to 20 carbons, or R ³ and R Any one of ⁴ is a C 1-20 alkyl group which may have a substituent.

In the compound represented by formula (I), at least one of R ¹ , R ³ and R ⁴ may be a group containing a silicon atom. In addition, when any one of R ³ and R ⁴ is a silicon atom-containing group, the other is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁵ and R ⁶ include groups having 1 to 6 carbon atoms in the linear or branched alkyl group exemplified as the alkyl group represented by R ¹ . Among them, as R ⁵ and R ⁶ , a hydrogen atom is preferable.

R ⁷ represents a hydrogen ^{_{atom, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO 2 R 10, - SO ₃ R ¹⁰ or -SO ₂ NR ¹¹ R ¹² is preferably a hydrogen atom, -SO ₃ ^- or -SO ₃ H, and more preferably -SO ₃ ^- or -SO ₃ H.

R ⁸ represents _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO 2 R 10, -SO 3 R ¹⁰ or -SO ₂ NR ¹¹ R ¹² , preferably -SO ₃ ^- or -SO ₃ H.

Examples of the saturated hydrocarbon group represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ include linear or branched alkyl groups exemplified as the alkyl group represented by R ¹ and the saturated hydrocarbon group represented by R ¹ The same groups as those exemplified for the cyclic saturated hydrocarbon group are preferably linear or branched chain alkyl groups. In addition, the carbon number of the saturated hydrocarbon group represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ is preferably 1-12, more preferably 1-8, and still more preferably 1-6.

The hydrogen atom contained in the saturated hydrocarbon group in R ¹¹ and R ¹² may be substituted by, for example, a hydroxyl group or a halogen atom as a substituent.

Examples of -OR ¹⁰ include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and tetracosyloxy. Alkoxy groups such as alkoxy and the like.

Examples of -CO ₂ R ¹⁰ include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, and eicosyloxycarbonyl.

Examples of -SR ¹⁰ include alkylsulfanyl groups such as methylsulfanyl, ethylsulfanyl, butylsulfanyl, hexylsulfanyl, decylsulfanyl, and eicosylsulfanyl. Wait.

Examples of -SO ₂ R ¹⁰ include alkoxy groups such as methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and eicosylsulfonyl. Sulfonyl and so on.

Examples of -SO ₃ R ¹⁰ include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl, and eicosanyloxy Alkoxysulfonyl groups such as sulfonyl groups and the like. As R -SO ₃ R ^{10 10,} carbon atoms, branched chain alkyl group preferably having 3 to 20 carbon atoms, more preferably branched chain alkyl group having 6 to 12, more preferably 2-ethylhexyl.

Examples of -SO ₂ NR ¹¹ R ¹² include sulfasulfonyl; N-methylsulfasulfonyl, N-ethylsulfasulfonyl, N-propylsulfasulfonyl, and N-isopropylamine Sulfonyl, N-butylsulfasulfonyl, N-isobutylsulfasulfonyl, N-sec-butylsulfasulfonyl, N-tert-butylsulfasulfonyl, N-pentylsulfasulfonyl Group, N-(1-ethylpropyl)sulfasulfonyl, N-(1,1-dimethylpropyl)sulfasulfonyl, N-(1,2-dimethylpropyl)sulfonyl Amino group, N-(2,2-dimethylpropyl)sulfasulfonyl, N-(1-methylbutyl)sulfasulfonyl, N-(2-methylbutyl)sulfasulfonyl , N-(3-Methylbutyl)sulfasulfonyl, N-cyclopentylsulfasulfonyl, N-hexylsulfasulfonyl, N-(1,3-dimethylbutyl)sulfasulfonyl Group, N-(3,3-dimethylbutyl)sulfasulfonyl, N-heptylsulfasulfonyl, N-(1-methylhexyl)sulfasulfonyl, N-(1,4- Dimethylpentyl)sulfasulfonyl, N-octylsulfasulfonyl, N-(2-ethylhexyl)sulfasulfonyl, N-(1,5-dimethyl)hexylsulfasulfonyl , N-(1,1,2,2-tetramethylbutyl)sulfasulfonyl and other N-1 substituted sulfasulfonyl groups; N,N-dimethylsulfasulfonyl, N,N-ethyl Methanesulfonyl, N,N-diethylsulfamethonyl, N,N-propylmethylsulfonyl, N,N-isopropylmethylsulfonyl, N,N- Tert-Butylmethylsulfasulfonyl, N,N-butylethylsulfasulfonyl, N,N-bis(1-methylpropyl)sulfasulfonyl, N,N-heptylmethylsulfasulfonyl N, N-2 substituted sulfamoyl and other groups. In the N-1 substituted sulfamoyl group, R ⁸ is preferably a branched chain alkyl group having 3 to 20 carbon atoms, more preferably a branched chain alkyl group having 6 to 12 carbon atoms, and even more preferably a 2-ethylhexyl group.

Z ⁺ is ⁺ N(R ¹³ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹³ ) ₄ .

^{In +} N(R ¹³ ) ₄ , it is preferable that all four R ¹³ are the same. In addition, the total carbon number of the four R ¹³ is preferably 20 to 80, and more preferably 20 to 60.

-SO ₃ ^- Z ⁺ is preferably -SO ₃ ^-+ N(R ¹³ ) ₄ .

Examples of -CO ₂ ^- Z ⁺ include -CO ₂ Na and -CO ₂ K.

Examples of ⁺ N(R ¹³ ) ₄ include NH ₄ ⁺ and a cation represented by the following formula.

m is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

As specific examples of the compound represented by formula (I), The compound represented by the following formula is mentioned. Among them, the compound represented by the formula (I-1) ~ the compound represented by the formula (I-4), the compound represented by the formula (I-25) ~ the compound represented by the formula (I-30), the compound represented by the formula ( The compound represented by I-35) ~ the compound represented by formula (I-40), the compound represented by formula (I-75) ~ the compound represented by formula (I-114), more preferably the compound represented by formula (I-75) ~ A compound represented by formula (I-114).

Compound (I) can be made from formula (II) in the presence of alkali metal carbonate in an organic solvent, for example

[In the formula, X ¹¹¹ and X ¹¹² each independently represent a halogen atom. ]

The compound represented (hereinafter sometimes referred to as "compound (II)") and the formula (III)

[In the formula (III), R ³ and R ⁴ each have the same meaning as above. ]

The compound represented (hereinafter sometimes referred to as "compound (III)") is reacted to obtain the formula (IV)

[In the formula (IV), X ¹¹² , R ³ and R ⁴ each have the same meaning as above. ] Represented by the compound (hereinafter sometimes referred to as "compound (IV)".), the compound (IV) is combined with the formula (V) [chemical formula 52] R ¹ -in the presence of an alkali metal carbonate in an organic solvent SH (V)

[In the formula (V), R ¹ has the same meaning as described above. ]

The compound shown (hereinafter may be referred to as "compound (V)") is produced by reacting.

Examples of the organic solvent in the reaction between compound (II) and compound (III) include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohols such as methanol, ethanol, and butanol Solvents; nitrated hydrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone.

The reaction temperature in the reaction of the compound (II) and the compound (III) is preferably 0°C to 100°C, and more preferably 20°C to 80°C. Excellent response time Select 1 hour to 12 hours, more preferably 1 hour to 8 hours.

The amount of the compound (III) used is preferably 1 mol or more and 30 mol or less, and more preferably 1 mol or more and 20 mol or less with respect to 1 mol of the compound (II).

Examples of organic solvents in the reaction of compound (IV) and compound (V) include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; and alcohols such as methanol, ethanol, and butanol. Solvents; nitrated hydrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone.

The reaction temperature in the reaction of the compound (IV) and the compound (V) is preferably 0°C to 180°C, more preferably 10°C to 130°C. The reaction time is preferably 1 hour to 48 hours, more preferably 1 hour to 24 hours.

The amount of the compound (V) used is preferably 1 mol or more and 30 mol or less, and more preferably 1 mol or more and 20 mol or less, relative to 1 mol of the compound (III).

The method for obtaining the compound (I) as the target compound from the reaction mixture is not particularly limited, and various known methods can be adopted. For example, a method of filtering the deposited precipitate after the completion of the reaction can be cited. The crystals collected by filtration are preferably washed with water or the like, and then dried. In addition, if necessary, it can be further refined by a known technique such as recrystallization.

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

<Colored curable resin composition>

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), As the colorant (A), the compound (I) is included. Two or more of the above-mentioned compounds (I) may be included.

The colorant (A) may further include at least one selected from the group consisting of pigment (A1) and dye (A2) (however, different from compound (I)).

The colored photosensitive resin composition of the present invention may further contain a solvent (E), a leveling agent (F), and the like.

The content of the compound (I) contained in the colored photosensitive resin composition is preferably 0.025 mass% or more and 48 mass% or less in the total solid content, more preferably 0.08 mass% or more and 42 mass% or less, and still more preferably 0.1% by mass or more and 30% by mass or less.

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

In addition, in 100% by mass of the total amount of the colorant (A), the content of the compound (I) is preferably 10% by mass or more, more preferably 20% by mass or more, and it may be 100% by mass or 90% by mass. the following.

<Pigment (A1)>

It does not specifically limit as a pigment (A1), A well-known pigment can be used, For example, the compound classified as a pigment by a color index (published by The Society of Dyers and Colourists) is mentioned.

Examples of pigments include CI Pigment Yellow 1 (hereinafter the description of CI Pigment Yellow is omitted, and only the serial number is described.), 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 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, 80 and other cyan pigments; CI Pigment Violet 1, Violet pigments such as 19, 23, 29, 32, 36, 38; CI pigment green 7, 36, 58 and other green pigments.

As the pigments, yellow pigments such as CI Pigment Yellow 138, 139, and 150, red pigments such as CI Pigment Red 177, 242, and 254, and cyan pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, and 60 are preferred. CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments. Among them, yellow pigments and red pigments are particularly preferred.

The content of the pigment (A1) is usually 10 to 500 parts by mass relative to 100 parts by mass of the compound (I), preferably 30 to 500 parts by mass, and more preferably 30 to 400 parts by mass.

<Dye (A2)>

Examples of the dye (A2) include dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. Examples include color index ( Published by The Society of Dyers and Colourists) classified as dyes Compounds, well-known dyes described in Dyeing Notes (Sei Dyesha). In addition, according to the chemical structure, azo dyes, coumarin dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, and Azamethine dyes, squaraine dyes, acridine dyes, styryl dyes, quinoline dyes, merocyanine dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

Specifically, CI solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162 can be listed; CI solvent red 45, 49, 125, 130, 218; CI solvent orange 2, 7, 11, 15, 26, 56; CI solvent blue 4, 5, 37, 67, 70, 90; CI solvent green 1, 4, 5, 7, 34, 35 and other CI solvent dyes, CI 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; CI Acid Red 1 , 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94 , 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228 , 249, 252, 257,258,260,261,266,268,270,274,277,280,281,289,308,312,315,316,339,341,345,346,349,382,383,388,394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107 , 108, 169, 173; CI Acid Violet 6B, 7, 9, 17, 19, 30, 102; CI Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70 , 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161 , 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335; CI Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes, CI 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; CI 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; CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107 ； CI direct purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225,226,228,229,236,237,238,242,243,244,245,246,247,248,249,250,251,252,256,257,259,260,268,274,275, 293; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dyes, CI disperse yellow 54, 76 and other CI dispersion Dyes, CI Basic Red 1, 10; CI Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68; CI basic dyes such as CI basic green 1, CI reactive yellow 2, 76, 116; CI reactive orange 16; CI reactive red 36 and other CI reactive dyes; CI Mordant Yellow 5, 8, 10, 16 , 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI Mordant Red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32 , 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1, 2, 4, 5 , 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI mordant blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61, 74, 77, 83, 84; CI mordant green 1, 3, 4 ,5,10,15,26,29,33,34,35,41,43,53 and other CI mordant dyes; CI vat green 1 and other CI vat dyes.

The dye (A2) is preferably at least one selected from the group consisting of yellow dye (A3) and red dye (A4).

The yellow dye means a dye having a maximum absorption wavelength of 400 to 470 nm in chloroform, and a dye having a maximum absorption wavelength of 430 to 470 nm is preferable.

The red dye indicates a dye having a maximum absorption wavelength of 490 to 550 nm in chloroform, and a dye having a maximum absorption wavelength of 490 to 540 nm is preferable.

As the red dye (A4), it is preferable to have a compound (I) The dyes with different xanthene skeletons are more preferably dyes with xanthene skeletons in which the carbon atoms at the 3 and 6 positions of the xanthene are bonded to the nitrogen atom.

As the dye having a xanthene skeleton, a compound represented by formula (1b) (hereinafter, sometimes referred to as "compound (1b)") is preferred. Compound (1b) may be its tautomer.

[In formula (1b), R ^51a to R ^54a independently represent a hydrogen atom, an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbons, or an optionally substituted 1 with 6 to 10 carbon atoms A valence aromatic hydrocarbon group, the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR ^61a -. R ^51a and R ^52a may together form a ring containing a nitrogen atom, and R ^3a and R ^4a may together form a ring containing a nitrogen atom.

R ^55a represents _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 58a, -SO 3 R 58a or -SO ₂ NR ^59a R ^60a .

R ^56a and R ^57a independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ^55a may be the same or different.

a represents an integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N(R ^61a ) ₄ , Na ⁺ or K ⁺ , and the four R ^61a may be the same or different.

R ^58a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ^59a and R ^60a independently represent a hydrogen atom or an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbon atoms. The -CH ₂ -contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NH- or -NR ^58a -replacement, R ^59a and R ^60a can be combined with each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

R ^61a represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. ]

When -SO ₃ ^- is contained in the formula (1a), its number is one.

The saturated hydrocarbon groups represented by R ^51a to R ^54a include the same groups as the linear or branched alkyl groups exemplified as the alkyl groups represented by R ^{3 or} the groups exemplified as the alicyclic saturated hydrocarbon groups Examples of the aromatic hydrocarbon group represented by R ^51a to R ^54a include the same groups as those having 6 to 10 carbons among the groups exemplified as the aromatic hydrocarbon group represented by R ³ .

Among them, it is preferable that any one of R ^51a and R ^52a and any one of R ^53a and R ^54a is an aromatic hydrocarbon group that may have a substituent, and the other is a hydrogen atom or a saturated hydrocarbon group that may have a substituent, or R ^51a to R ^54a All are saturated hydrocarbon groups that may have substituents.

As the alkyl group represented by R ^56a and R ^57a , the same groups as the alkyl group exemplified as R ^{5 can} be mentioned. As R ^56a and R ^57a , a hydrogen atom is preferable.

As the saturated hydrocarbon group represented by R ^58a , R ^59a , R ^60a, and R ^61a , the same groups as those exemplified as the saturated hydrocarbon group represented by R ^{10 can be} cited.

Examples of the aralkyl group represented by R ^61a include the same groups as those having 7 to 10 carbon atoms in the groups exemplified as the aralkyl group represented by R ¹ .

Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

As a red dye (A4), the compound represented by the following formula is mentioned, for example. R ⁴⁰ in the following formula represents 2-ethylhexyl.

The content of the dye (A2) is preferably 1 to 30 parts by mass relative to 100 parts by mass of the compound (I), more preferably 1 to 20 parts by mass, and still more preferably 1 to 10 parts by mass.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one monomer (a) selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter sometimes referred to as "(a)) ") is a copolymer of structural units.

The copolymer having a structural unit derived from (a) preferably has a monomer derived from a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b) (hereinafter sometimes referred to as "(b)" A copolymer of at least one selected from the structural unit of) and the structural unit having an ethylenically unsaturated bond. The copolymer may further have other structural units.

Examples of other structural units include those derived from monomer (c) copolymerizable with (a) (However, it is different from (a) and (b).) (Hereinafter sometimes Referred to as "(c)") structural unit.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and p-vinyl benzoic acid; maleic acid, fumaric acid, citracin Acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6 -Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, dimethyltetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid Acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept -2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6 -Ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinyl Phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5 ,6-Dicarboxybicyclo[2.2.1]hept-2-ene anhydride and other unsaturated dicarboxylic acid anhydrides; succinic acid mono[2-(meth)propenoxyethyl] ester, phthalic acid mono[ Unsaturated mono [(meth)acryloyloxyalkyl] esters of polycarboxylic acids with two or more valences such as 2-(meth)acryloyloxyethyl] ester; such as α-(hydroxymeth)acrylic acid The unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule.

Among these, from the aspect of copolymerization reactivity, the obtained resin is soluble in alkali water From the viewpoint of solubility in the liquid, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable.

When the copolymer contains a structural unit derived from (a), in 100% by mass of the copolymer, the ratio thereof is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass.

(b) refers to, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond Polymeric compound.

(b) It is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

In addition, in this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

As (b), for example, a monomer having an oxirane group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuran group and an ethylenically unsaturated bond, Monomer etc.

Examples of (b) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, vinyl benzyl glycidyl ether, and 3,4-ring (meth)acrylate Oxycyclohexyl methyl ester, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane, ( Tetrahydrofurfuryl meth)acrylate.

As (b), since the reliability of the heat resistance, chemical resistance, etc. of the color filter obtained can be improved further, the monomer which has an oxirane group and an ethylenic unsaturated bond is preferable.

When the copolymer contains a structural unit derived from (b), the ratio of the structural unit derived from (b) in 100% by mass of the copolymer is preferably 50 to 99% by mass, more preferably 70 to 95% by mass.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate. Ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate , Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this technical field In, as a common name, it is called "dicyclopentyl (meth)acrylate". In addition, it is sometimes called "tricyclodecyl (meth)acrylate".), tricyclo (meth)acrylate [5.2.1.0 ^2,6 ] Decene-8-yl ester (in this technical field, it is called "dicyclopentenyl (meth)acrylate" as a common name), dicyclopentyloxyethyl (meth)acrylate, ( Isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate , (Meth)acrylates such as benzyl (meth)acrylate; (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]heptan -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[2.2.1]hept-2-ene, 5,6-diethyl Oxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept- Bicyclic unsaturated compounds such as 2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide Amine, N-benzylmaleimide, N-succinimidyl-3-maleimidin benzoate, N-succinimidyl-4-maleimidin butyrate , N-succinimidyl-6-maleimine caproate, N-succinimidyl-3-maleimine propionate, N-(9-acridinyl) maleate Dicarbonylimine derivatives such as imines; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene , Vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, Isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyl toluene, benzyl (meth)acrylate, and tricyclo[5.2.1.0 ^2,6 ]decane-8- (meth)acrylate are preferred. Base ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene.

When the copolymer contains a structural unit derived from (c), the ratio of the structural unit derived from (c) in 100% by mass of the copolymer is preferably 1 to 99% by mass.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group in the side chain. A resin having such a structural unit is obtained by making a polymer having a structural unit from (a) and (b) and a group having a group that can react with the group (a) and (b) and an ethylenically unsaturated bond It is obtained by monomer addition.

Examples of such a structural unit include a structural unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit, and addition of 2-hydroxyethyl (meth)acrylate to maleic anhydride. A structural unit formed by a unit, a structural unit formed by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit, and the like. Moreover, when these structural units have a hydroxyl group, as a structural unit which has an ethylenic unsaturated bond, the structural unit which added carboxylic anhydride further can also be mentioned.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, and 3,4-epoxy tricyclic (meth)acrylate [ 5.2.1.0 ^2.6 ] Decyl ester/(meth)acrylic acid copolymer and other copolymers having structural units derived from (a) and (b); glycidyl (meth)acrylate/benzyl (meth)acrylate/( (Meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decyl ester/( (Meth)acrylic acid/N-cyclohexylmaleimide copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decyl ester/(meth)acrylic acid/vinyl toluene copolymer , 3-Methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, etc. have structures derived from (a), (b) and (c) Copolymer of units; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/ (Meth)acrylic acid copolymer; a resin formed by adding glycidyl (meth)acrylate and benzyl (meth)acrylate/(meth)acrylic acid copolymer to make glycidyl (meth)acrylate and (Meth) tricyclodecyl acrylate/styrene/(meth)acrylic acid copolymer addition resin, combining glycidyl (meth)acrylate with tricyclodecyl (meth)acrylate/(methyl) ) Copolymers with structural units derived from (a) and (c) such as resins obtained by addition of benzyl acrylate/(meth)acrylic acid copolymers; making (meth)acrylic acid and (meth)acrylic acid tricyclodecane Ester/glycidyl (meth)acrylate copolymer reaction resin, (meth)acrylic acid and tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate copolymer The resulting resin has a copolymer of (a) a structural unit added to a structural unit derived from (b) and a structural unit derived from (c); making (meth)acrylic acid and (meth)acrylic tricyclic The resin obtained by reacting the copolymer of decyl ester/glycidyl (meth)acrylate and the resin obtained by further reacting with tetrahydrophthalic anhydride has the structural unit derived from (b) added to (a), Furthermore, the copolymer etc. of the structural unit which added carboxylic anhydride, and the structural unit derived from (c).

For the resin (B), for example, refer to the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd.) Chemical Doujin 1st Edition It is produced by printing the method described in (issued on March 1, 1972) and the cited documents in this document once.

The resin (B) is preferably selected from copolymers having structural units derived from (a) and (b), copolymers having structural units derived from (a), (b) and (c), and copolymers having structural units derived from (a) And one of the copolymers of structural units of (c), more preferably selected from copolymers having structural units derived from (a) and (b), and copolymers having structural units derived from (a), (b) and (c) One of the copolymers of structural units is particularly preferably a copolymer having structural units derived from (a) and (b).

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. If the molecular weight is within the above-mentioned range, the hardness of the coating film will increase, the residual film rate will also be high, the solubility of the unexposed part in the developing solution will be good, and the resolution of the colored pattern will tend to increase.

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

The acid value of the resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 30 to 150 mg-KOH/g, and still more preferably 40 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and it can be determined, for example, by titration using an aqueous potassium hydroxide solution.

In the total solid content, the content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. If the content of resin (B) is within the above range, it can It can form a colored pattern, and has a tendency to increase the resolution of the colored pattern and the residual film rate.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by living radicals and/or acid generated by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenic unsaturated bond, etc., preferably (former Base) Acrylate compound.

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

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

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

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2900 or less, and more preferably 250 to 1500 or less.

In the total solid content, the content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass.

In addition, the content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] on a mass basis is preferably 20:80 to 80:20, more preferably 35:65 ~80:20.

When the content of the polymerizable compound (C) is within the above-mentioned range, the residual film rate during the formation of the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc., to initiate polymerization by the action of light and heat, and a known polymerization initiator can be used.

As the polymerization initiator (D), O-acyl oxime compounds, alkane Phenyl ketone compounds, biimidazole compounds, triazine compounds, and phosphine oxide compounds.

As the O-acetoxime compound, for example, N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine Oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)- 3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-oxazole-3 -Base] ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxolanylmethoxy) benzyl}-9H-oxazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-( 2-methylbenzyl)-9H-oxazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6- (2-Methylbenzyl)-9H-azol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (the above are made by BASF), and N-1919 (made by ADEKA) can be used. Among them, the O- oxime compound is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyloxy 1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanylphenyl)-3 -At least one of cyclopentylpropane-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1-one- 2-imine.

As the alkyl phenyl ketone compound, for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino- 1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethyl Amino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy-2-methyl -1-Phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone , 2-Hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one oligomer, α,α-diethoxyacetophenone, benzil dimethyl condensation Ketones and so on. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (the above are made by BASF Corporation) can be used.

Examples of the biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403 and Japanese Patent Application Publication No. 62 -174204, etc.), an imidazole compound in which the phenyl group at the 4, 4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 7-10913 etc.).

Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-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, etc.

As an acylphosphine oxide compound, 2,4,6-trimethylbenzyl diphenyl phosphine oxide, etc. are mentioned.

Furthermore, as the polymerization initiator (D), benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. can be mentioned. Compounds; benzophenone, o-benzophenone methyl benzoate, 4-phenylbenzophenone, 4-benzophenone-4'-methyl diphenyl sulfide, 3,3', Benzophenone compounds such as 4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethyl Quinone compounds such as anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkyl phenyl ketone compound, a triazine compound, an phosphine oxide compound, an O-oxime compound, and a biimidazole compound, and is more preferably A polymerization initiator containing an O-oxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, and more preferably 1 to 30 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).

<Solvent (E)>

The solvent (E) is not particularly limited, and it can be used commonly in the field The solvent used. For example, ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecule), ether ester solvents (Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (containing OH in the molecule, no -O-, -CO -And -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, and isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclic Hexanol acetate, γ-butyrolactone, etc.

Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3- Methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether , Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenylethyl ether and methyl anisole, etc.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropionic acid Methyl ester, 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 monoethyl ether acetate, propylene glycol monopropyl ether acetate, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether ethyl Acid esters and so on.

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

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

As an aromatic hydrocarbon solvent, benzene, toluene, xylene, 1,3,5-trimethylbenzene, etc. are mentioned.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone (1-methyl-2-pyrrolidone), and the like.

These solvents may be used alone or in combination of two or more kinds.

Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether are preferred. Alcohol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxypropionic acid Ethyl, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethyl Formamide, N-methylpyrrolidone (1-methyl-2-pyrrolidone), etc., more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl Ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N-methylpyrrolidone (1-methyl- 2-pyrrolidone).

The content of the solvent (E) relative to the total amount of the colored curable resin composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. If the content of the solvent (E) is within the above-mentioned range, the flatness at the time of application becomes good, and the color density is not insufficient when the color filter is formed, so there is a tendency for the display characteristics to become good.

<Leveling agent (F)>

As the leveling agent (F), organosilicon surfactants, fluorine surfactants, organosilicon surfactants having fluorine atoms, and the like can be mentioned. These may have a polymerizable group in the side chain.

Examples of the organosilicon-based surfactant include surfactants having siloxane bonds in the molecule, and the like. Specifically, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: Toray-Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 ( Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, T SF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Advanced Materials Japan Contracting Corporation) Wait.

Examples of the above-mentioned fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule, and the like. Specifically, Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554 , R30, RS-718-K (manufactured by DIC Co., Ltd.), Eftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon ) (Registered trademarks) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Institute of Fine Chemicals Co., Ltd.), etc.

Examples of the above-mentioned organosilicon surfactants having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Co., Ltd.) and the like can be cited.

When the leveling agent (F) is contained, relative to the total amount of the colored curable resin composition, its content is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less , More preferably, it is 0.005 mass% or more and 0.07 mass% or less. If 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 Polymerization initiation aids, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and other additives known in the technical field.

<Production method of colored curable resin composition>

The colored curable resin composition of the present invention can be prepared by mixing the colorant (A), the resin (B), the polymerizable compound (C), and the polymerization initiator (D), as well as the solvent (E), and the solvent used as needed. The flat agent (F) and other ingredients are mixed and prepared.

When the pigment (A1) is contained, the pigment is preferably mixed with a part or all of the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, a part or all of a pigment dispersant and resin (B) can be blended as needed. By mixing the remaining components in the pigment dispersion liquid obtained in this way so as to have a predetermined concentration, the target colored curable resin composition can be prepared.

The compound (I) is preferably dissolved in part or all of the solvent (E) in advance to prepare a solution. It is preferable to filter the solution with a filter with a pore diameter of about 0.01 to 1 μm.

It is preferable to filter the mixed colored curable resin composition with a filter having a pore diameter of about 0.01 to 10 μm.

<Method of Manufacturing Color Filter>

As a method of producing a colored pattern from the colored curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. may be mentioned. Among them, photolithography is preferred. The photolithography method is to apply the above-mentioned colored curable resin composition to a substrate, dry to form a colored composition layer, and then color it through a photomask. The composition layer is exposed and developed. In the photolithography method, by not using a photomask and/or not developing during exposure, it is possible to form a colored coating film that is a cured product of the colored composition layer. The colored pattern and colored coating film formed in this way are used as the color filter of the present invention.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the purpose, use, etc., 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, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass whose surface is coated with silicon dioxide, polycarbonate, polymethyl methacrylate, polymer Resin plates such as ethylene phthalate, silicon, aluminum, silver, and silver/copper/palladium alloy thin films formed on the above-mentioned substrates. Additional color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates.

The formation of pixels of each color by photolithography can be performed under known or customary equipment and conditions. For example, it can be produced as follows.

First, the colored curable resin composition is applied on a substrate, and dried by heating (pre-baking) and/or under reduced pressure to remove volatile components such as the solvent and dry to obtain a smooth colored composition layer. As the coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. can be cited.

The temperature at the time of heat drying is preferably 30 to 120°C, and more preferably 50 to 110°C. In addition, as the heating time, 10 seconds to 60 minutes are preferable, and 30 seconds to 30 minutes are more preferable. In the case of drying under reduced pressure, it is preferably carried out in a temperature range of 20 to 25°C under a pressure of 50 to 150 Pa.

The film thickness of the coloring composition layer is not particularly limited, and it can be The film thickness of the color filter is appropriately selected.

Next, the coloring composition layer is exposed to light via a photomask for forming the target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use is used.

As a light source used for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferable. For example, a filter that shields light of less than 350 nm may be used to shield this wavelength region, or a band pass filter that passes light near 436 nm, 408 nm, or 365 nm may be used to selectively extract these wavelength regions. Specifically, as the light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, and the like can be cited.

Since it is possible to uniformly irradiate the entire exposure surface with parallel light and perform accurate alignment of the photomask and the substrate on which the coloring composition layer is formed, it is preferable to use exposure devices such as a mask aligner and a stepper.

The coloring composition layer after exposure is brought into contact with a developing solution for development, thereby forming a coloring pattern on the substrate. By development, the unexposed part of the coloring composition layer is dissolved and removed in the developer. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant.

The development method may be any of the rotary immersion method, dipping method, and spray method. Furthermore, the substrate can be inclined at an arbitrary angle during development. It is preferable to wash with water after development.

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

The coloring curable resin composition containing the compound of the present invention can provide a color filter having good heat resistance. This color filter can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

Example

The following examples are given to illustrate the present invention more specifically, but the present invention is not substantially limited by the following examples. Of course, it can also be implemented with appropriate changes within the scope of the main content described above and below. They are all included in In the technical scope of the present invention. In the examples, as long as there is no special description, the% and parts indicating the content and the amount used are the mass basis.

In the following examples, the structure of the compound was confirmed by mass analysis (LC; Agilent 1200 type, MASS; Agilent LC/MSD type).

Example 1

40.6 parts of a compound represented by the following formula (VIH-1) as compound (II), 8.0 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as compound (III), and 14 parts of potassium carbonate were mixed, and The resulting solution was stirred at 30°C for 3 hours in the presence of 50 parts of 1-methyl-2-pyrrolidone. After the obtained reaction liquid was cooled to room temperature, it was added to a mixed liquid of 400 parts of water and 20 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. As a result, crystals precipitated. The precipitated crystal was obtained as a residue of suction filtration and then dried to obtain 44.0 parts of the compound represented by the formula (I-4-A).

Next, 44.2 parts of the compound represented by formula (I-4-A), 22.5 parts of 3-mercapto-1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 14 parts of potassium carbonate in the presence of 500 parts of methanol, Heated under reflux for 5 hours. After the obtained reaction liquid was cooled to room temperature, methanol was distilled off under reduced pressure, 100 parts of water was added to the residue, filtered, and washed with 100 parts of water. The obtained crystals were dried under reduced pressure at 60°C for 24 hours to obtain 39 parts of a compound represented by formula (I-76).

Identification of the compound represented by formula (I-76)

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 498.1

Accurate quality: 497.1

Example 2

In Example 1, 2-(2-mercaptoethoxy)ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 3-mercapto-1-propanol. 1 It was synthesized in the same manner to obtain 51 parts of a compound represented by formula (I-77).

Identification of the compound represented by formula (I-77)

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 528.1

Accurate quality: 527.1

[Synthesis of resin]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was introduced to form a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 85°C while stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylic acid and acrylic acid were dropped into the flask using a dropping pump for about 5 hours. A mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl ester (content ratio is 50:50 in molar ratio) (trade name "E-DCPA", Daicel Corporation Manufacturing) A solution prepared by dissolving 171 parts in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, a separate drip pump was used to drip into the flask over about 5 hours to dissolve 26 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in propylene glycol monomethyl A solution of 120 parts of ether acetate. After the dropping of the polymerization initiator was completed, the temperature was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-1)) with a solid content of 43.5%. The weight average molecular weight of the obtained resin (B-1) was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mg-KOH/g.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene of the resin was performed under the following conditions by the GPC method.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: Tetrahydrofuran (THF)

Flow rate: 1.0mL/min

The concentration of the solid content of the tested liquid: 0.001~0.01% by mass

Injection volume: 50μL

Detector: RI

Standard materials for calibration: 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 in terms of polystyrene obtained above and the number average molecular weight (Mw/Mn) was taken as the molecular weight distribution.

[Preparation of colored curable resin composition]

Each component was mixed so that it might become a composition shown in Table 1, and the colored curable resin composition was obtained.

In Table 1, each component is as follows.

Coloring agent (A-1): compound represented by formula (I-76)

Coloring agent (A-2): compound represented by formula (I-77)

Coloring agent (A-3): Rhodamine B

Resin (B): Resin B1 (calculated as solid content)

Polymerizable compound (C): Dipentaerythritol hexaacrylate

Polymerization initiator (D): N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Manufactured by the company; O-acetoxime compound)

Solvent (E-1): 1-methyl-2-pyrrolidone

Solvent (E-2): ethyl lactate

Solvent (E-3): Dimethylformamide

Leveling agent (F): Polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

Mixed to obtain a colored curable resin composition.

[Formation of Coloring Pattern]

After coating the colored photosensitive composition on a 2-inch square glass substrate (Eagle XG; manufactured by Corning Corporation) by a spin coating method, it was pre-baked at 100°C for 3 minutes to obtain a composition layer. After cooling, the distance between the glass substrate on which the composition layer was formed and the photomask made of quartz glass was 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an air atmosphere at a temperature of 150 mJ. Light irradiation is performed at an exposure amount of /cm ² (365nm standard). As the photomask, a photomask formed with a pattern of 100 μm lines and gaps was used. After light irradiation, the above-mentioned coating film was immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23°C for 80 seconds. After washing with water, it was carried out in an oven at 220°C for 20 seconds. Bake in minutes to get a colored pattern.

[Evaluation of heat resistance]

In the formation of the above-mentioned colored pattern, a coating film was obtained in the same manner as described above, except that the photomask was not passed through during light irradiation. The chromaticity of the obtained coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). Next, after heating the same coating film at 230°C for 20 minutes, the chromaticity was measured again using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS), and the color difference (△Eab *). The color difference (ΔEab*) of the coating films formed from the colored curable resin compositions of Examples 3 and 4 were 9.4 and 10.2, respectively. In addition, the coloring of Comparative Example 1 The color difference (ΔEab*) of the coating film formed from the curable resin composition was 50.3. This shows that the colored coating film and the colored pattern formed from the colored curable resin composition containing the compound of the present invention have excellent heat resistance.

Industrial availability

According to the coloring curable resin composition containing the compound of the present invention, a color filter having good heat resistance can be provided. This color filter can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

(no)

Claims (4)

A compound represented by formula (I):

In formula (I), R ¹ represents an optionally substituted alkyl group with 1 to 20 carbon atoms or an optionally substituted alicyclic saturated hydrocarbon group with 3 to 20 carbon atoms, and the aforementioned substituents represent halogen atoms, mercapto groups, and hydroxyl groups. , Cyano, nitro, or a group containing a silicon atom, the -CH ₂ -contained in the alkyl group may be replaced by -O-, -CO- or -NR ¹¹ -, but the adjacent -CH _2- It will not be replaced with -O- at the same time, and the terminal -CH ₂ -will not be replaced with -O-, -CO- or -NR ¹¹ -. R ³ and R ⁴ each independently represent a hydrogen atom and may have a substituent the alkyl group having 1 to 20 carbon atoms or saturated alicyclic hydrocarbon group may have a substituent group of carbon number of 3 to 20, the substituent group represents a halogen _{^{atom, -OH, -OR 10, -SO 3}} -, -SO 3 H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ¹⁰ , -SH, -SR ¹⁰ , -SO ₂ R ¹⁰ , -SO ₃ R ¹⁰ , -SO ₂ NR ¹¹ R ¹² , -CN, -NO ₂ , or a group containing a silicon atom, the -CH ₂ -contained in the alkyl group can be replaced by -O-, -CO- or -NR ¹¹ -, but adjacent -CH ₂ -will not be at the same time Is replaced by -O-, the terminal -CH ₂ -will not be replaced by -O-, -CO- or -NR ¹¹ -, R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkane with 1 to 6 carbon atoms group, R ⁷ represents a hydrogen ^{_{atom, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO 2 R 10 , -SO ₃ R ¹⁰ or _{^{-SO 2 NR 11 R 12, R}} 8 represents _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO ₂ ^- Z ⁺ , -CO ₂ R ¹⁰ , -SO ₃ R ¹⁰ or -SO ₂ NR ¹¹ R ¹² , m represents an integer from 0 to 4, and when m is 2 or more, multiple R ⁸ may be the same or different, Z ⁺ represents ⁺ N(R ¹³ ) ₄ , Na ⁺ or K ⁺ , R ¹⁰ represents a saturated hydrocarbon group with 1 to 20 carbon atoms that may have a halogen atom, and R ¹¹ and R ¹² each independently represent a hydrogen atom or a carbon number of 1~ A saturated hydrocarbon group of 20, R ¹³ represents a hydrogen atom or a saturated hydrocarbon group of 1 to 20 carbon atoms, a plurality of R ¹³ may be the same or different from each other, X represents a halogen atom, and a represents an integer of 0 or 1. A coloring curable resin composition comprising the compound of claim 1, resin (B), polymerizable compound (C) and polymerization initiator (D). A color filter formed of the coloring curable resin composition of claim 2. A display device including the color filter as claimed in claim 3.