TW201734008A - Compound, colored curable resin composition, color filter and display device having relatively good heat resistance - Google Patents

Abstract

This invention provides a compound, a colored curable resin composition, a color filter and a display device. By using the colored curable resin composition comprising the compound provided by this invention, the color filter and the display device which have relatively good heat resistance can be provided. The compound provided by this invention is shown as formula (I).

Description

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

FIELD OF THE INVENTION The present invention relates to a compound and a colored curable resin composition.

BACKGROUND OF THE INVENTION Dyes are used, for example, in the fields of fiber materials, liquid crystal display devices, inkjet, and the like to perform color display using reflected light or transmitted light. As such a dye, for example, Rhodamine B represented by the following formula (Rb), which is a compound having a xanthene skeleton, is known (Non-Patent Document 1).

[Chemical Formula 1] Prior art document non-patent literature

Non-Patent Document 1: Hiroshi Hiroshi, "New Dye Chemistry", Co., Ltd., First Edition, May 1973, p. 274

Disclosure of the Invention Problems to be Solved by the Invention The colored curable resin composition containing the above-mentioned compound which has been known so far does not sufficiently satisfy the heat resistance. Means for solving problems

The invention includes the following invention. [1] A compound represented by the formula (I). [Chemical Formula 2] In the formula (I), R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon number of 2 to 20 which may have a substituent. The unsaturated hydrocarbon group or the 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 which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon number which may have a substituent 2 2 An unsaturated hydrocarbon group of 20, or a condensed 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 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 to 4, and when m is 2 or more, a plurality of R ^{8 's} 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 according to [1], a resin (B), a polymerizable compound (C), and a polymerization initiator (D). [3] A color filter formed from the colored curable resin composition according to [2]. [4] A display device comprising the color filter according to [3]. Effect of the invention

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

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention is a compound represented by the formula (I) (hereinafter sometimes referred to as "compound (I)"). The tautomers are also included in the compounds of the invention. The respective components and groups exemplified below may be used singly or in combination. <Compound (I)>

[Chemical Formula 3]

In the formula (I), R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon number of 2 to 20 which may have a substituent. The unsaturated hydrocarbon group or the 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-, -CO- or -NR ¹¹ - 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 which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon number which may have a substituent 2 2 An unsaturated hydrocarbon group of 20 or a condensed 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 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 to 4, and when m is 2 or more, a plurality of R ^{8 's} may be the same or different. 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 the formula (I), in the case where -SO ₃ ^- is present, the number thereof is one.

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

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ , R ³ and R ⁴ include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, and a positive alkyl group. a linear alkyl group such as octyl, n-decyl or n-decyl; a branched chain such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or 2-ethylhexyl An alkyl group is preferably a linear alkyl group. The alkyl group represented by R ¹ , R ³ and R ⁴ preferably has 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms. Examples of the unsaturated hydrocarbon group having 2 to 20 carbon atoms represented by R ¹ , R ³ and R ⁴ include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-methylvinyl group, and a 2-methyl group. a linear or branched alkenyl group having 2 to 20 carbon atoms, which is 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl or 1-hexenyl a linear or branched alkynyl group having 2 to 20 carbon atoms such as an ethynyl group, a propargyl group, a 2-butynyl group, a 3-butynyl group, a 1-pentynyl group or a 1-hexynyl group. The number of carbon atoms of the unsaturated hydrocarbon group represented by R ¹ , R ³ and R ⁴ is preferably 2 to 10, and more preferably 2 to 8.

-CH ₂ - contained in the alkyl group having 1 to 20 carbon atoms represented by R ¹ , R ³ and R ⁴ may be replaced by -O-, -CO- or -NR ¹¹ -, preferably, 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 -. Further, in the case where -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 by a hydroxyl group as a substituent. . A preferred carbon number of the alkyl group in which the methylene group may be replaced by -O-, -CO- or -NR ¹¹ - is 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6. As the alkyl group in which the methylene group may be replaced by -O-, -CO- or -NR ¹¹ -, a linear or branched alkyl group is preferred, and a linear alkyl group is more preferred. In addition, when the methylene group is replaced by -O-, -CO- or -NR ¹¹ -, the terminal is between -O-, -CO- or -NR ¹¹ - or -O-, -CO- or -NR ¹¹ The number of carbon atoms with the oxygen atom or -CO- is preferably from 1 to 4, more preferably from 2 to 3.

The alkyl group which may be replaced by -O-, -CO- or -NR ¹¹ - as -CH ₂ - may, for example, be a group represented by the following formula. Where * represents the bond end.

[Chemical Formula 4]

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

Examples of the substituent which may be substituted with an aromatic hydrocarbon group having 6 to 30 carbon atoms represented by R ¹ include a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group; a halogenated alkyl group having 1 to 12 carbon atoms such as chloromethyl or dichloromethyl; an anthracenyl group; a hydroxyl group; a cyano group; a nitro group; a group containing a halogen atom. In addition, examples of the substituent which may be substituted with an alkyl group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group having 2 to 20 carbon atoms, or an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms represented by R ¹ include a fluorine atom. a halogen atom such as a chlorine atom or a bromine atom; a mercapto group: a hydroxyl group; a cyano group; a nitro group; an aromatic hydrocarbon group having 6 to 10 carbon atoms; and a group containing a halogen atom, preferably a halogen atom, a hydroxyl group, and a carbon number of 6 to 10. The aromatic hydrocarbon group is particularly preferably a hydroxyl group. The aromatic hydrocarbon group having 6 to 10 carbon atoms is a group having 6 to 10 carbon atoms in the group exemplified as the aromatic hydrocarbon group represented by R ¹ .

The group containing a ruthenium atom represents a group containing a ruthenium atom as a constituent element of the group. The carbon group-containing group has a carbon number of usually 1 to 30, preferably 1 to 20. As the group containing a ruthenium atom, a group represented by the formula (Z1) is preferred.

[Chemical Formula 5]

^Wherein R ^21A represents a single bond or an alkylene group having 1 to 14 carbon atoms, and -CH ₂ - contained in the alkylene group may be -O-, -CO-, -NR ²² -, -OCO- Substituting -COO-, -OCONH-, -CONH- or -NHCO-, the hydrogen atom contained in the alkylene group may be substituted 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 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. * indicates the bonding end. ]

Examples of the alkylene group having 1 to 14 carbon atoms represented by R ^21A include a methylene group, an ethyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1. , 5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,9-diyl, decane-1 a linear alkyl group such as 10-diyl, undecane-1,11-diyl or dodecane-1,12-diyl; 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 A branched alkyl group such as a 1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group or the like is preferably a linear alkyl group. The number of carbon atoms of the alkylene group represented by R ^21A is preferably from 1 to 8, more preferably from 1 to 6, still more preferably from 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- Alternatively, it may preferably be replaced by -OCO-, -COO- or -OCONH-. 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-, -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 a linear or branched chain alkyl group shown by the embodiment represented by R ¹ and an alicyclic saturated hydrocarbon group represented by R ¹ embodiment shown by the The group is preferably a linear or branched alkyl group. The number of carbon atoms of the saturated hydrocarbon group represented by R ²² is preferably from 1 to 12, more preferably from 1 to 8, still more preferably from 1 to 6.

Examples of the saturated hydrocarbon group having 1 to 4 carbon atoms represented by R ^22A , R ^23A and R ^24A include a linear alkyl group such as a methyl group, an ethyl group, a n-propyl group or a n-butyl group; and an isopropyl group or a sec-butyl group; a branched chain alkyl group such as a benzyl group or a tert-butyl group; an alicyclic saturated hydrocarbon group such as a cyclopropyl group and a cyclobutyl group; and the like. Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^22A , R ^23A and R ^24A include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, and a sec-butoxy group. Base and tert-butoxy. R ^22A , R ^23A and R ^{24A are} preferably all the same groups. R ^22A , R ^23A and R ^24A are each preferably independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

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

[Chemical Formula 6]

[Chemical Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

The group in which -CH ₂ - contained in the alkylene group represented by R ^21A is replaced by -O- includes a group shown below (* represents a bonding end).

[Chemical Formula 11]

The group in which -CH ₂ - contained in the alkylene group represented by R ^21A is replaced by -CO- includes a group shown below (* represents a bonding end).

[Chemical Formula 12]

[Chemical Formula 13]

The group in which -CH ₂ - contained in the alkylene group represented by R ^21A is replaced by -NR ¹² - may, for example, be a group shown below (* represents a bonding end).

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

The group in which -CH ₂ - contained in the alkylene group represented by R ^21A is replaced by -OCO- includes a group shown below (* represents a bonding end).

[Chemical Formula 18]

[Chemical Formula 19]

The group in which -CH ₂ - contained in the alkylene group represented by R ^21A is replaced by -COO- includes a group shown below (* represents a bonding end).

[Chemical Formula 20]

[Chemical Formula 21]

The group in which -CH ₂ - contained in the alkylene group represented by R ^21A is replaced by -OCONH- includes a group shown below (* represents a bonding end).

[Chemical Formula 22]

[Chemical Formula 23]

The group in which -CH ₂ - contained in the alkylene group represented by R ^21A is replaced by -CONH- includes a group shown below (* represents a bonding end).

[Chemical Formula 24]

[Chemical Formula 25]

The group in which -CH ₂ - contained in the alkylene group represented by R ^21A is replaced by -NHCO- includes a group shown below (* represents a bonding end).

[Chemical Formula 26]

[Chemical Formula 27]

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

[Chemical Formula 28]

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

[Chemical Formula 29]

[Chemical Formula 30]

[Chemical Formula 31]

[Chemical Formula 32]

[Chemical Formula 33]

In particular, R ¹ is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and more preferably an alkyl group having 1 to 20 carbon atoms.

Examples of the substituent which may be substituted with an aromatic hydrocarbon group having 6 to 30 carbon atoms represented by R ³ and R ⁴ include a halogen atom, a halogenated alkyl group having 1 to 12 carbon atoms, -OH, -OR ¹⁰ and -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 And -CN, -NO ₂ and a group containing a halogen atom, preferably a halogen atom, a halogenated alkyl group, -SH, -OH, -CN, -NO ₂ and a group containing a halogen atom. Examples of the substituent which may be substituted by an alkyl group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group having 2 to 20 carbon atoms or an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms represented by R ³ and R ⁴ include 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 and a group containing a halogen atom, preferably a halogen atom, -SH, -OH, -CN, -NO ₂ and a group containing a halogen atom . Further, as -SO ₂ NR ¹¹ R ¹² , -SO ₂ NHR ¹⁰ is preferable.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. The halogenated alkyl group having 1 to 12 carbon atoms is the same as the group exemplified as the halogenated alkyl group which may be substituted with the aromatic hydrocarbon group represented by R ¹ . The group containing the ruthenium atom is the same as the group exemplified as the group containing a ruthenium atom which may be substituted with the aromatic hydrocarbon group represented by R ¹ .

R ³ and R ^{4 are} preferably a hydrogen atom, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and preferably a hydrogen atom, an ethyl group, a propyl group or a group represented by the following formula,

[Chemical Formula 34]

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

[Chemical Formula 35]

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

In the compound represented by the formula (I), at least one of R ¹ , R ³ and R ⁴ may be a group containing a ruthenium atom. Further, in the case where any of R ³ and R ⁴ is a group containing a halogen atom, 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 a group having 1 to 6 carbon atoms in the linear or branched chain alkyl group exemplified as the alkyl group represented by R ¹ . Among them, as R ⁵ and R ⁶ , a hydrogen atom is preferred.

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, 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.

The saturated hydrocarbon group represented by R ^10, R ^11, R ¹² and R ¹³ represent, and include a straight or branched chain alkyl group shown by the group represented by R in Example ^1, and a lipid ^represented by R The same group as exemplified as the cyclic saturated hydrocarbon group is preferably a linear or branched alkyl group. Further, the number of carbon atoms of the saturated hydrocarbon group represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ is preferably from 1 to 12, more preferably from 1 to 8, still more preferably from 1 to 6. The hydrogen atom contained in the saturated hydrocarbon group in R ¹¹ and R ¹² may be substituted, for example, by a hydroxyl group or a halogen atom as a substituent.

Examples of -OR ¹⁰ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and a An alkoxy group such as an alkoxy group.

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

Examples of -SR ¹⁰ include alkylsulfonyl groups such as methylsulfanyl, ethylsulfanyl, butylsulfanyl, hexylsulfanyl, mercaptosulfanyl and eicosylsulfanyl groups. Wait. Examples of -SO ₂ R ¹⁰ include alkoxy groups such as methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and eicosylsulfonyl. Sulfonyl and the like. Examples of -SO ₃ R ¹⁰ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an eicosyloxy group. An alkoxysulfonyl group such as a sulfonyl group. 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.

As -SO ₂ NR ¹¹ R ¹² , an amine sulfonyl group; N-methylamine sulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, N-isopropylamine Sulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-sec-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine sulfonate Base, N-(1-ethylpropyl)amine sulfonyl, N-(1,1-dimethylpropyl)amine sulfonyl, N-(1,2-dimethylpropyl)amine sulfonate Indenyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonyl , N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine sulfonate , N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonyl, N-(1,4- Dimethylpentyl)aminesulfonyl, N-octylaminesulfonyl, N-(2-ethylhexyl)aminesulfonyl, N-(1,5-dimethyl)hexylaminesulfonyl N-substituted sulfonyl group such as N-(1,1,2,2-tetramethylbutyl)amine sulfonyl;

N,N-dimethylaminesulfonyl, N,N-ethylmethylaminesulfonyl, N,N-diethylaminesulfonyl, N,N-propylmethylaminesulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tert-butylmethylamine sulfonyl, N,N-butylethylamine sulfonyl, N,N-bis(1-methylpropane N, N-2 substituted amine sulfonyl group, etc., such as an aminesulfonyl group or an N,N-heptylmethylamine sulfonyl group. In the N-1 substituted amine sulfonyl 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 still more preferably 2-ethylhexyl group. Z ⁺ is ⁺ N(R ¹³ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹³ ) ₄ . ^{In the case of +} N(R ¹³ ) ₄ , it is preferred that all four R ¹³ are the same. Further, the total carbon number of the four R ¹³ is preferably from 20 to 80, and more preferably from 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.

[Chemical Formula 36]

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

Specific examples of the compound represented by the formula (I) include compounds represented by the following formulas. Among them, a compound represented by the formula (I-1), a compound represented by the formula (I-4), a compound represented by the formula (I-25), a compound represented by the formula (I-30), and a formula ( The compound represented by the formula I-35), the compound represented by the formula (I-40), the compound represented by the formula (I-75), the compound represented by the formula (I-114), more preferably the formula (I-75) a compound represented by the formula (I-114).

[Chemical Formula 37]

[Chemical Formula 38]

[Chemical Formula 39]

[Chemical Formula 40]

[Chemical Formula 41]

[Chemical Formula 42]

[Chemical Formula 43]

[Chemical Formula 44]

[Chemical Formula 45]

[Chemical Formula 46]

[Chemical Formula 47]

[Chemical Formula 48]

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

[Chemical Formula 49]

[wherein, X ¹¹¹ and X ¹¹² each independently represent a halogen atom. a compound (hereinafter sometimes referred to as "compound (II)")) and by formula (III)

[Chemical Formula 50]

In the formula (III), R ³ and R ⁴ each have the same meanings as described above. The compound represented by the formula (hereinafter sometimes referred to as "compound (III)")) is obtained by the formula (IV)

[Chemical Formula 51]

In the formula (IV), X ¹¹² , R ³ and R ⁴ each have the same meanings as described above. After the compound (hereinafter sometimes referred to as "compound (IV)")), the compound (IV) and the formula (V) are allowed to be present in an organic solvent in the presence of an alkali metal carbonate.

[Chemical Formula 52]

[In the formula (V), R ¹ represents the same meaning as described above. The compound (hereinafter sometimes referred to as "compound (V)")) is produced by a reaction.

Examples of the organic solvent in the reaction between the compound (II) and the compound (III) include a hydrocarbon solvent such as toluene or xylene; a halogenated hydrocarbon solvent such as chlorobenzene, dichlorobenzene or chloroform; and an alcohol such as methanol, ethanol or butanol. Solvent; nitrohydrocarbon solvent such as nitrobenzene; ketone solvent such as methyl isobutyl ketone; guanamine solvent such as 1-methyl-2-pyrrolidone.

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

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

Examples of the organic solvent in the reaction between the compound (IV) and the compound (V) include a hydrocarbon solvent such as toluene or xylene; a halogenated hydrocarbon solvent such as chlorobenzene, dichlorobenzene or chloroform; and an alcohol such as methanol, ethanol or butanol. Solvent; nitrohydrocarbon solvent such as nitrobenzene; ketone solvent such as methyl isobutyl ketone; guanamine solvent such as 1-methyl-2-pyrrolidone.

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

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

The method of obtaining the compound (I) as a target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, a method of filtering out the precipitated precipitate after completion of the reaction can be mentioned. For the crystallized by filtration, it is preferably washed with water or the like, followed by drying. Further, if necessary, it can be further purified by a known method such as recrystallization.

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

<Coloring Curable Resin Composition> The coloring curable resin composition of the present invention contains a coloring agent (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D) as a coloring agent (A). Containing Compound (I). Two or more kinds of the above compounds (I) may be contained. The colorant (A) may further contain at least one selected from the group consisting of the pigment (A1) and the dye (A2) (however, different from the 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) in the coloring photosensitive resin composition is preferably 0.025% by mass or more and 48% by mass or less, more preferably 0.08% by mass or more and 42% by mass or less, more preferably the total amount of the solid content. 0.1% by mass or more and 30% by mass or less. In addition, the "total amount of solid content" in this specification is the quantity after removing the content of the solvent from the total amount of the coloring curable resin composition. The total amount of the solid components and the content of each component with respect to the total amount of the solid components can be measured, for example, by a known analytical means such as liquid chromatography or gas chromatography.

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

<Pigment (A1)> The pigment (A1) is not particularly limited, and a known pigment can be used. For example, a compound classified as a pigment in a color index (published by The Society of Dyers and Colourists) can be cited. Examples of the pigment 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, Yellow pigments such as 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; 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, Red pigments such as 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; CI Pigment Blue 15, 15:3, 15:4, 15:6, 60, 80 cyan pigments; CI pigment purple 1,19,23,29,32,36,38 and other purple pigments; CI pigment green 7,36,58 and other green pigments.

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

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

<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. For example, a compound classified as a dye in the color index (published by The Society of Dyers and Colourists) and a known dye described in the dyeing note (color dyeing company) are listed. Further, examples of the chemical structure include azo dyes, coumarin dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, and even Nitromethine dyes, squaric acid dyes, acridine dyes, styryl dyes, quinoline dyes, merocyanine dyes, and nitro dyes. Among these, an organic solvent-soluble dye is preferred.

Specifically, CI solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; 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, 1, 5, 7, 34, 35, etc. CI Solvent Dye, 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 Acidic 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, 8 4, 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 ,2 74, 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 dispersion yellow 54, 76 and other CI disperse dyes, CI basic red 1, 10; CI alkaline blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68; CI alkaline green 1 and other CI basic dyes, CI active yellow 2, 76, 116; CI active orange 16; CI active 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, 25, 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 purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; 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 mord green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53 and other CI mordant dyes; CI reduction green 1 and other CI vat dyes.

The dye (A2) is preferably at least one selected from the group consisting of a yellow dye (A3) and a red dye (A4). The yellow dye indicates a dye having a maximum absorption wavelength of 400 to 470 nm in chloroform, and preferably a dye having a maximum absorption wavelength of 430 to 470 nm. 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), a dye having a xanthene skeleton different from the compound (I) is preferable, and a dye having a xanthene skeleton having a carbon atom bonded to the nitrogen atom at the 3 and 6 positions of xanthene is more preferable.

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

[Chemical Formula 53]

In the formula (1b), R ^51a to R ^54a independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon number of 6 to 10 which may have a substituent. The valent aromatic hydrocarbon group in which 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 of each other 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 a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom. R ^59a and R ^60a independently of each other represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NH- or -NR ^58a - substitution, R ^59a and R ^60a may be bonded to each other to form a 3- to 10-membered ring heterocyclic ring containing a nitrogen atom. R ^61a represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

When -SO ₃ ^- is contained in the formula (1a), the number thereof is one. Examples of the saturated hydrocarbon group represented by R ^51a to R ^54a include the same groups as those exemplified as the linear or branched alkyl group exemplified as the alkyl group represented by R ³ or the alicyclic saturated hydrocarbon group. The aromatic hydrocarbon group represented by R ^51a to R ^54a is the same as the group having 6 to 10 carbon atoms in the group exemplified as the aromatic hydrocarbon group represented by R ³ . Among them, preferred one of R ^51a and R ^52a and any one of R ^53a and R ^54a is an aromatic hydrocarbon group which may have a substituent, and the other is a hydrogen atom or a saturated hydrocarbon group which may have a substituent, or R ^51a to R ^54a All of them are saturated hydrocarbon groups which may have a substituent. Examples of the alkyl group represented by R ^56a and R ^57a include the same groups as the alkyl group exemplified as R ⁵ . As R ^56a and R ^57a , a hydrogen atom is preferred. Examples of the saturated hydrocarbon group represented by R ^58a , R ^59a , R ^60a and R ^61a include the same groups as those exemplified as the saturated hydrocarbon group represented by R ¹⁰ . The aralkyl group represented by R ^61a is the same as the group having a carbon number of 7 to 10 in the group exemplified as the aralkyl group represented by R ¹ . The halogen atom represented by X may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom. The red dye (A4) is, for example, a compound represented by the following formula. R ⁴⁰ in the following formula represents 2-ethylhexyl.

[Chemical Formula 54]

[Chemical Formula 55]

[Chemical Formula 56]

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

<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 the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes A copolymer of structural units referred to as "(a)"). The copolymer having the structural unit derived from (a) preferably has a monomer (b) derived from a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)" a copolymer of at least one selected from the group consisting of structural units and structural units having ethylenically unsaturated bonds. The copolymer may further have other structural units. Examples of the other structural unit include a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)"). .

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, and citrine 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-dicarboxylate 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]g 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 a carboxyl group-containing bicyclic unsaturated compound such as ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinyl group 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, etc. And dicarboxylic anhydrides; succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester, etc. An unsaturated mono[(meth)acryloxyalkylalkyl]ester of a polyvalent carboxylic acid; an unsaturated acrylate which has a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid. Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

In the case where the copolymer contains the structural unit derived from (a), the proportion thereof is preferably from 1 to 50% by mass, and more preferably from 5 to 30% by mass, based on 100% by mass of the copolymer. (b) means, for example, a cyclic ether structure having a carbon number of 2 to 4 (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) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group. In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acrylinyl" and "(meth)acrylate" have the same meaning.

Examples of (b) include a monomer having an epoxyethyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, and a tetrahydrofuranyl group and an ethylenically unsaturated bond. Monomers, etc. Examples of (b) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, and 3,4-cyclo(meth)acrylate. oxygen cyclohexyl methacrylate, 3,4-epoxy-tricyclo [5.2.1.0 ^2,6] decyl, 3-ethyl-3- (meth) oxymethyl Bing Xixi oxetane, ( Tetrahydrofurfuryl methacrylate.

(b) is preferably a monomer having an epoxy group and an ethylenically unsaturated bond, in that reliability of heat resistance and chemical resistance of the obtained color filter can be further improved.

In the case where the copolymer contains the structural unit derived from (b), the proportion of the structural unit derived from (b) in 100% by mass of the copolymer is preferably from 50 to 99% by mass, and more preferably from 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 the technical field) In the conventional name, it is called "dicyclopentanyl (meth)acrylate". In addition, it may be called "tricyclodecyl (meth)acrylate".), tricyclo(meth)acrylate [5.2.1.0 ^2,6 ]nonene-8-yl ester (in the technical field, as a conventional name, it is called "dicyclopentenyl (meth) acrylate).), dicyclopentyloxyethyl (meth) acrylate, ( Isobornyl methyl methacrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, (Meth) acrylate such as phenyl methacrylate, naphthyl (meth) acrylate or benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate a hydroxy group-containing (meth) acrylate such as propyl ester; a dicarboxylic acid diester such as diethyl maleate, diethyl fumarate or diethyl itaconate; bicyclo [2.2.1] g-2 - alkene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1] Hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl) Bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2. 1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5- a bicyclic unsaturated compound such as hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene or 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene; N-benzene Maleidin, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-amber Imino-4-maleimine butyrate, N-succinimide-6-maleimide caprate, N-succinimide-3-maleimide a dicarbonylimine derivative such as an acid salt or N-(9-acridinyl)maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, Vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, different Pentadiene, 2,3-dimethyl-1,3-butadiene, and the like. Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyl toluene, benzyl (meth)acrylate, and tricyclo(methyl)acrylate [5.2.1.0 ^2,6 ]decane-8- are preferable. Base ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene.

In the case where the copolymer contains the structural unit derived from (c), the proportion of the structural unit derived from (c) is preferably from 1 to 99% by mass in 100% by mass of the copolymer.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acrylonitrile group in a side chain. The resin having such a structural unit is obtained by reacting a polymer having structural units derived from (a), (b) with a group having a group reactive with (a), (b), and an ethylenically unsaturated bond. 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 adding 2-hydroxyethyl (meth)acrylate to maleic anhydride. A structural unit composed of a unit, a structural unit obtained by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit, and the like. Further, when these structural units have a hydroxyl group, as a structural unit having an ethylenically unsaturated bond, a structural unit in which a carboxylic anhydride is further added may be mentioned.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and (meth)acrylic acid 3,4-epoxytricyclo[ 5.2.1.0 ^2.6 ] oxime ester / (meth)acrylic acid copolymer and the like having a copolymer derived from structural units (a) and (b); glycidyl (meth) acrylate / benzyl (meth) acrylate / ( Methyl)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate/( Methyl)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl methacrylate/(meth)acrylic acid/vinyltoluene copolymer , 3-methyl-3-(meth)acryloxymethyloxybutane/(meth)acrylic acid/styrene copolymer, etc. having structures from (a), (b) and (c) Copolymer of unit; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(methyl)propene a tricyclodecyl ester/(meth)acrylic acid copolymer; a resin obtained by adding a glycidyl (meth)acrylate to a copolymer of benzyl (meth)acrylate/(meth)acrylic acid to make (methyl a resin obtained by adding a glycidyl acrylate to a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer, a glycidyl (meth)acrylate and a tricyclo(meth)acrylate a resin obtained by adding an oxime ester/benzyl (meth) acrylate/(meth)acrylic acid copolymer, etc., having a structural unit derived from (a) and (c); (meth)acrylic acid and (a) Resin for the copolymerization of tricyclodecyl acrylate/glycidyl (meth) acrylate, (meth)acrylic acid and tricyclodecyl (meth) acrylate/styrene/glycidyl (meth)acrylate A resin obtained by reacting an ester copolymer or the like has a copolymer obtained by adding (a) to a structural unit derived from the structural unit of (b) and a structural unit derived from (c); and (meth)acrylic acid ( Trimethyl decyl methacrylate / (meth) propylene The resin obtained by reacting the copolymer of the acid glycidyl ester with tetrahydrophthalic anhydride further has (a) added to the structural unit derived from (b), and further added with a carboxylic anhydride. a copolymer of the structural unit and the structural unit derived from (c).

For example, the resin (B) can be referred to the method described in the "Experimental Method for Polymer Synthesis" (Otsuno Ryokan Publishing Co., Ltd., First Edition, First Printing, March 1, 1972). The cited references are manufactured.

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

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the coating film hardness is increased, the residual film ratio is also high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 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, 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 can be obtained, for example, by titration using a potassium hydroxide aqueous solution.

The content of the resin (B) in the total amount of the solid components is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film ratio tend to be 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 a polymerizable ethylenically unsaturated bond. The compound or the like is preferably a (meth) acrylate compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylic acid. Ester, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like, and (a), (b), and (c) above.

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di( Methyl) 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 a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylic acid. Ester, dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol nin (meth) acrylate Ester, tris(2-(meth)acryloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate Ester, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol tetra(meth) acrylate, caprolactone modified dipentaerythritol hexa Methyl) acrylate or the like, among which dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 to 1,500 or less.

The content of the polymerizable compound (C) in the total amount of the solid content is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass. Further, the content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20, more preferably 35:65 by mass. ~80:20. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of 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 a living radical, an acid, or the like by the action of light or heat, and a known polymerization initiator can be used. . Examples of the polymerization initiator (D) include an O-indenylhydrazine compound, an alkylphenylketone compound, a biimidazole compound, a triazine compound, and a mercaptophosphine oxide compound.

Examples of the O-indenyl ruthenium compound include N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzamide. Oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)- 3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3 -yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxearylmethoxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-( 2-methylbenzimidyl)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl-6- (2-Methylbenzylidene)-9H-oxazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can be used. Wherein the O-indenyl hydrazine compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzylformamide 1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylsulfanylphenyl)-3 At least one of cyclopentylpropan-1-one-2-imine, more preferably N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one- 2-imine.

Examples of the alkyl phenyl ketone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino group- 1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1- [4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4-(2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane An oligomer of 1-ketone, α,α-diethoxyacetophenone, benzoin dimethyl ketal, and the like. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation) can be used.

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

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloro). Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-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 Wait.

The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

Further, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. a compound; benzophenone, methyl o-benzhydrylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3', a benzophenone compound such as 4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethyl Anthraquinone compounds such as sulfonium and camphorquinone; 10-butyl-2-chloroacridone, benzoin, methyl phenylglyoxylate, titanium titanate, and the like.

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, a fluorenyl phosphine oxide compound, an O-mercapto fluorene compound, and a biimidazole compound, and more preferably A polymerization initiator comprising an O-indenyl ruthenium 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, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C).

<Solvent (E)> The solvent (E) is not particularly limited, and a solvent which is generally used in the field can be used. For example, an ester solvent (a solvent containing -COO- or a solvent containing no -O- in a molecule), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether ester solvent (in the molecule) a solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule, a solvent not containing -COO-), an alcohol solvent (containing OH in the molecule, and containing no -O-, -CO) - and -COO-solvent), aromatic hydrocarbon solvent, guanamine solvent, dimethyl hydrazine, and the like.

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

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, 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, phenethyl ether and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl 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 Butyl ether acetate, dipropylene glycol methyl 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-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene. Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone (1-methyl-2-pyrrolidone).

These solvents may be used singly or in combination of two or more. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and digan 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 ester, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone (1-methyl-2-pyrrolidone), etc., more preferably propylene glycol monomethyl Ethyl 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) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, 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 when the color filter is formed, the color density is not insufficient, and thus the display characteristics tend to be good.

<Leveling agent (F)> Examples of the leveling agent (F) include an organic lanthanoid surfactant, a fluorine-based surfactant, and an organic lanthanoid surfactant having a fluorine atom. They may have a polymerizable group in the side chain. Examples of the organic oxime-based surfactant include a surfactant having a decane bond in the molecule. 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, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (made by Momentive Advanced Materials Japan Contract Co., Ltd.).

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, フロラード (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), メガファック (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), エフトップ (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Corporation, Ltd.), サーフロン (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) Manufactured) and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.).

The organic ruthenium-based surfactant having a fluorine atom as described above includes a surfactant having a siloxane chain and a fluorocarbon chain in the molecule. Specifically, メガファック (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation) and the like are exemplified.

When the leveling agent (F) is contained, the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, and more preferably 0.002% by mass or more and 0.1% by mass or less based on the total amount of the colored curable resin composition. Further, it is more preferably 0.005% by mass or more and 0.07% by mass or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other components> The colored curable resin composition of the present invention may contain a polymerization initiation aid, a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, a chain transfer agent, etc., as needed. Additives well known in the art.

<Method for Producing Colored Curable Resin Composition> The colored curable resin composition of the present invention can be, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). And preparing according to the solvent (E), the leveling agent (F) and other components used as needed. The pigment in the case of containing the pigment (A1) is preferably mixed with a part or all of the solvent (E) in advance, and is dispersed by using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, a part or all of the pigment dispersant and the resin (B) may be blended as needed. By mixing the remaining components in the pigment dispersion liquid thus obtained so as to have a predetermined concentration, the intended colored curable resin composition can be prepared. In the case of the compound (I), it is preferred to prepare a solution by dissolving a part or all of the solvent (E) in advance. It is preferred to filter the solution with a filter having a pore diameter of about 0.01 to 1 μm. The mixed colored curable resin composition is preferably filtered by a filter having a pore diameter of about 0.01 to 10 μm.

<Method for Producing Color Filter> A method of producing a colored pattern by the colored curable resin composition of the present invention includes a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. In the photolithography method, the colored curable resin composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a coloring coating film which is a cured product of the coloring composition layer can be formed by using a photomask and/or no development at the time of exposure. The colored pattern and the colored coating film thus formed 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 depending on the purpose, use, 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, quartz glass, borosilicate glass, aluminosilicate glass, a glass plate such as soda lime glass coated with cerium oxide on the surface, polycarbonate, polymethyl methacrylate, and poly-pair can be used. A resin plate or the like such as ethylene phthalate or the like, and a product such as an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Additional color filter layers, resin layers, transistors, circuits, and the like can be formed on these substrates.

The formation of each color pixel by photolithography can be carried out under known or conventional devices and conditions. For example, it can be produced as follows. First, the colored curable resin composition is applied onto a substrate, and dried by heating (prebaking) and/or drying under reduced pressure to remove a volatile component such as a solvent and dry it to obtain a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit, and a spin coating method. The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Further, the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. In the case of performing vacuum drying, it is preferably carried out at a pressure of 50 to 150 Pa and a temperature of 20 to 25 °C. The film thickness of the coloring composition layer is not particularly limited, and can be appropriately selected depending on the film thickness of the target color filter.

Next, the colored composition layer is exposed through a photomask for forming a colored pattern of the target. The pattern on the photomask is not particularly limited, and a pattern conforming to the intended use is used. As the light source for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, the wavelength region may be shielded using a filter that shields light of less than 350 nm, or these wavelength regions may be selectively taken out using a band pass filter that passes light in the vicinity of 436 nm, near 408 nm, and around 365 nm. Specifically, examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, and the like. Since the parallel light rays can be uniformly irradiated to the entire exposed surface, the correct alignment of the photomask and the substrate on which the colored composition layer is formed is performed. Therefore, an exposure apparatus such as a mask aligner and a stepper is preferably used.

The colored composition layer after exposure is developed in contact with the developer to form a colored pattern on the substrate. By development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed. As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferable. 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. Further, the developer may contain a surfactant. The developing method may be any one of a spin coating immersion method, a dipping method, and a spray method. Further, the substrate can be inclined at an arbitrary angle during development. It is preferred to carry out water washing after development.

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

A color filter having excellent heat resistance can be provided by the colored curable resin composition containing the compound of the present invention. This color filter can be used as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, or the like) and a solid-state image pickup element. Example

The present invention will be more specifically described by the following examples, but the present invention is not limited to the following examples, and may be appropriately modified within the scope of the main contents that can be adapted before and after, and they are all included in Within the technical scope of the present invention. In the examples, unless otherwise indicated, the % and the parts of the content and the amount used are based on the mass basis.

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

Example 1 40.6 parts of the compound represented by the following formula (VIH-1), 8.0 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 14 parts of potassium carbonate as the compound (III). 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 the mixture was stirred at room temperature for 1 hour, and crystals were precipitated. The precipitated crystal was obtained as a residue by suction filtration and then dried to obtain 44.0 parts of a compound represented by formula (I-4-A).

[Chemical Formula 57]

Next, 44.2 parts of the compound represented by the 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 cooling the obtained reaction liquid to room temperature, methanol was distilled off under reduced pressure, and 100 parts of water was added to the residue, and the mixture was filtered and washed with 100 parts of water. The obtained crystal was dried under reduced pressure at 60 ° C for 24 hours to obtain 39 parts of the compound represented by the formula (I-76).

[Chemical Formula 58]

Identification (mass analysis) of the compound represented by formula (I-76) Ionization mode = ESI+: m/z = [M+H] ⁺ 498.1 Accurate mass: 497.1

Example 2 The same procedure as in Example 1 was carried out except that 2-(2-mercaptoethoxy)ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 3-mercapto-1-propanol in Example 1. 51 parts of the compound represented by the formula (I-77).

[Chemical Formula 59]

Identification (mass analysis) of the compound represented by formula (I-77) Ionization mode = ESI+: m/z = [M+H] ⁺ 528.1 Accurate mass: 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 allowed to flow into a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 85 with stirring. °C. Next, a drop pump was used in the flask for about 5 hours to make 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and acrylic acid. a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl ester (content ratio is 50:50 by molar ratio) (trade name "E-DCPA", Daicel 株式会社) Manufactured 171 parts of a solution obtained by dissolving 40 parts of propylene glycol monomethyl ether acetate. On the other hand, an additional drip pump was used to drip into the flask over a period of 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 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 solution of a copolymer (resin (B-1)) having a solid content of 43.5%. The obtained resin (B-1) had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value of 53 mg-KOH/g in terms of solid content.

[Chemical Formula 60]

The measurement of the polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin was carried out under the following conditions by the GPC method. Device: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40 ° C Solvent: Tetrahydrofuran (THF) Flow rate: 1.0 mL/min Solid content of the test solution: 0.001 to 0.01% by mass Injection amount: 50 μL Detector: Standard for RI calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation) The ratio of the average molecular weight to the number average molecular weight (Mw/Mn) is taken as the molecular weight distribution.

[Preparation of Colored Curable Resin Composition] Each component was mixed so as to have the composition shown in Table 1, and a colored curable resin composition was obtained.

【Table 1】

In Table 1, each component is as follows. Coloring agent (A-1): Compound coloring agent (A-2) represented by formula (I-76): Compound coloring agent (A-3) represented by formula (I-77): Rhodamine B resin (B): Resin B1 (in terms of solid content) Polymerizable compound (C): Dipentaerythritol hexaacrylate polymerization initiator (D): N-benzylideneoxy-1-(4-phenylsulfanylphenyl) Octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) Solvent (E-1): 1-methyl-2-pyrrolidone solvent ( E-2): ethyl lactate solvent (E-3): dimethylformamide leveling agent (F): polyether modified eucalyptus oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) A curable resin composition is colored.

[Formation of Colored Pattern] The colored photosensitive composition was applied onto a 2 inch square glass substrate (Eagle XG; manufactured by Corning Incorporated) by spin coating, and then prebaked 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 exposure was performed at 150 mJ/cm ² in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Konica Minolta Co., Ltd.). The amount (365 nm reference) was irradiated with light. As the photomask, a photomask in which a line pattern of 100 μm line and gap was formed was used. After the light irradiation, the coating film was immersed and developed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 80 seconds, washed with water, and then subjected to an oven at 220 ° C. After a minute of baking, a colored pattern was obtained.

[Evaluation of heat resistance] In the formation of the above-described 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 color of the obtained coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS Co., Ltd.). Then, the same coating film was heated at 230 ° C for 20 minutes, and then the chromaticity was measured again using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS Co., Ltd.), and the color difference of the coating film before and after heating (ΔEab*) was determined. ). The color difference (ΔEab*) of the coating film formed from the colored curable resin compositions of Examples 3 and 4 was 9.4 and 10.2, respectively. In addition, the color difference (ΔEab*) of the coating film formed from the colored curable resin composition of Comparative Example 1 was 50.3. From this, it is understood that the colored coating film and the colored pattern formed of the colored curable resin composition containing the compound of the present invention are excellent in heat resistance. Industrial availability

According to the colored curable resin composition containing the compound of the present invention, a color filter having excellent heat resistance can be provided. This color filter can be used as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, or the like) and a solid-state image pickup element.

(no)

Claims (4)

A compound represented by formula (I): In the formula (I), R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon number of 2 to 20 which may have a substituent. a saturated hydrocarbon group or a 3 to 20 alicyclic saturated hydrocarbon group which may have a substituent, and -CH ₂ - contained in the alkyl group may be replaced by -O-, -CO- or -NR ¹¹ -, however, adjacent -CH ₂ - will not be replaced by -O- at the same time, the terminal -CH ₂ - will not be replaced by -O-, -CO- or -NR ¹¹ -, and R ³ and R ⁴ each independently represent a hydrogen atom. An aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, or may have a substituent An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and -CH ₂ - contained in the alkyl group may be replaced by -O-, -CO- or -NR ¹¹ -, however, the adjacent -CH ₂ - will not At the same time, it is replaced by -O-, and the terminal -CH ₂ - is not replaced by -O-, -CO- or -NR ¹¹ -, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a carbon number of 1 to 6. Alkyl, 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 to 4, and when m is 2 or more, a plurality of R ⁸ may The same or different from each other, Z ⁺ represents ⁺ N(R ¹³ ) ₄ , Na ⁺ or K ⁺ , and R ¹⁰ represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom, and R ¹¹ and R ¹² each independently represent hydrogen. The atomic or saturated hydrocarbon group, the carbon number of 1 to 20 R ¹³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R ^{13 's} may be the same or different, and X represents a halogen atom, and a represents an integer of 0 or 1. A colored curable resin composition comprising the compound of claim 1, a resin (B), a polymerizable compound (C), and a polymerization initiator (D). A color filter formed of the colored curable resin composition of claim 2. A display device comprising the color filter of claim 3.