TW201823377A - Colored curable resin composition, color filter formed from the colored curable resin composition and display device including the color filter - Google Patents

Abstract

Known color filter formed by colored curable resin composition sometimes cannot sufficiently satisfy light durability. This invention relates to a colored curable resin composition, a color filter formed from the colored curable resin composition and a display device including the color filter. The colored curable resin composition including a coloring agent, a resin, a polymerizable compound and a polymerizable initiator, wherein, the coloring agent includes a compound represented by the following formula (I) and an anthraquinone dye.

Description

   Colored curable resin composition, a color filter formed from the colored curable resin composition, and a display device including the color filter   

The present invention relates to a coloring curable resin composition, a color filter formed from the coloring curable resin composition, and a display device including the color filter.

A color filter used in a liquid crystal display device, a display device such as an electroluminescence display device and a plasma display, and a solid-state imaging element such as a CCD or CMOS sensor is made of a coloring curable resin composition. As such a coloring curable resin composition, a composition containing two kinds of compounds represented by the following formulas as a colorant is known (Patent Document 1).

    [Prior Art Literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Laid-Open No. 2015-38201

In some cases, a color filter formed of a conventionally-known colored curable resin composition may not sufficiently satisfy light resistance.

The present inventors have found that a color filter having excellent light resistance can be formed by including a specific triarylmethane dye and an anthraquinone dye in a colored curable resin composition, and the present invention has been completed.

The present invention includes the following inventions.

[1] A coloring curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant includes a compound represented by the formula (I) and an anthraquinone dye.

[In formula (I), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon group which may have a substituent. An aralkyl group of 7 to 30, the aromatic hydrocarbon group and the substituent that the aralkyl group may have are -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , and the saturated hydrocarbon group contains The hydrogen atom may be substituted by a substituted or unsubstituted amine group or a halogen atom. When the carbon number of the saturated hydrocarbon group is 2 to 20, -CH ₂ -contained in the saturated hydrocarbon group may be replaced by- At least one of O- and -CO-. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH ₂ -is not replaced with -O- at the same time, and -CH ₂ -at the terminal is not replaced with -O- or -CO-. R ⁴¹ and R ⁴² may be bonded and form a ring together with the nitrogen atom to which R ⁴¹ and R ⁴² are bonded, and R ⁴³ and R ⁴⁴ may be bonded and form together with the nitrogen atom to which R ⁴³ and R ⁴⁴ are bonded ring.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl _{^{group, -SO 3 -, -SO 2 -N}} - -SO ₂ -R ^f, or alkyl having a carbon number of 1 to 8, constituting the -CH ₂ -of an alkyl group may be replaced with at least one of -O- and -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S-, or -SO _2- . However, in this alkyl group, adjacent -CH ₂ -will not be replaced with -O- at the same time, and terminal -CH ₂ -will not be replaced with -O- or -CO-.

Ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group, or a carbon number 6 which may have a substituent. To 20 aromatic hydrocarbon groups. The substituent which the aromatic hydrocarbon group may have is -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f .

M ^{r +} represents a hydrogen ion, an r-valent metal ion, or a substituted or unsubstituted ammonium ion.

k represents the sum of the number of -SO ₃ ^-and the number of -SO ₂ -N ^-- SO ₂ -R ^f that R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have.

r represents an integer of 1 or more.

R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms.

However, R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have at least one -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . ]

[2] A color filter formed of the colored hardening resin composition according to [1].

[3] A display device including the color filter according to [2].

According to the coloring curable resin composition of the present invention, a color filter excellent in light resistance can be formed.

The colored curable resin composition of the present invention contains a colorant, a resin, a polymerizable compound, and a polymerization initiator.

    <Colorant>    

The colorant contains a compound represented by formula (I) (hereinafter sometimes referred to as "compound (I)") and an anthraquinone dye.

Compound (I) also includes tautomers and their salts. The components and functional groups exemplified below can be used individually or in combination.

[In formula (I), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon group which may have a substituent. An aralkyl group of 7 to 30, the aromatic hydrocarbon group and the substituent that the aralkyl group may have are -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , and the saturated hydrocarbon group contains The hydrogen atom may be substituted by a substituted or unsubstituted amine group or a halogen atom. When the carbon number of the saturated hydrocarbon group is 2 to 20, -CH ₂ -contained in the saturated hydrocarbon group may be replaced by- At least one of O- and -CO-. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ -is not replaced with -O- at the same time, and the terminal -CH ₂ -is not replaced with -O- or -CO-. R ⁴¹ and R ⁴² may be bonded and form a ring together with the nitrogen atom to which R ⁴¹ and R ⁴² are bonded, and R ⁴³ and R ⁴⁴ may be bonded and form together with the nitrogen atom to which R ⁴³ and R ⁴⁴ are bonded ring.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl _{^{group, -SO 3 -, -SO 2 -N}} - -SO ₂ -R ^f, or alkyl having a carbon number of 1 to 8, constituting the -CH ₂ -of an alkyl group may be replaced with at least one of -O- and -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S-, or -SO _2- . However, in this alkyl group, adjacent -CH ₂ -will not be replaced with -O- at the same time, and terminal -CH ₂ -will not be replaced with -O- or -CO-.

Ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group, or a carbon number 6 which may have a substituent. To 20 aromatic hydrocarbon groups. The substituent which the aromatic hydrocarbon group may have is -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f .

M ^{r +} represents a hydrogen ion, an r-valent metal ion, or a substituted or unsubstituted ammonium ion.

k represents the sum of the number of -SO ₃ ^-and the number of -SO ₂ -N ^-- SO ₂ -R ^f that R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have.

r represents an integer of 1 or more.

R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms.

However, R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have at least one -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . ]

The aromatic heterocyclic ring represented by ring T ¹ may be a single ring or a condensed ring. The carbon number of the aromatic heterocyclic ring represented by the ring T ¹ is 3 to 10, and preferably 3 to 8. The aromatic heterocyclic ring is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring. Examples of the monocyclic aromatic heterocyclic ring include a pyrrole ring, 5-membered rings containing nitrogen atoms, such as azole, pyrazole, imidazole, and thiazole rings; 5-membered rings containing no nitrogen atoms, such as furan and thiophene rings; pyridine, pyrimidine, and pyridine rings Ring, pyridine 6-membered rings containing a nitrogen atom such as a ring, etc. Examples of the aromatic heterocyclic ring having a fused ring include an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring; Furan rings and the like do not contain fused rings such as nitrogen atoms.

Examples of the substituent which the aromatic heterocyclic ring of ring T ¹ may have include a halogen atom, a cyano group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a substituted or unsubstituted amine group, or Aromatic hydrocarbon groups having 6 to 20 carbon atoms having a substituent, etc., preferably, saturated hydrocarbon groups having 1 to 20 carbon atoms, substituted or unsubstituted amine groups, or 6 to 20 carbon atoms which may have a substituent. Aromatic hydrocarbon group. The ring T ¹ preferably has an amine group which may have a substituent. The substituent which the amine group may have is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and may have Aryl groups having 7 to 30 carbon atoms of the substituent and the like.

Among these, as the aromatic heterocyclic ring of the ring T ^1, an aromatic heterocyclic ring containing a nitrogen atom is preferable, and a 5-membered ring aromatic heterocyclic ring containing a nitrogen atom is more preferable.

The ring T ¹ is preferably a ring represented by formula (t1).

[In the formula (t1), R ⁵⁶ represents a saturated hydrocarbon group a hydrogen atom, a carbon number of 1 to 20 carbon atoms, or may have a substituent, an aromatic hydrocarbon group having 6 to 20.

X2 represents -O-, -N (R ⁵⁷ )-or -S-.

R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent, or 7 carbon atoms which may have a substituent When the aralkyl group of 30 to 30 and the carbon number of the saturated hydrocarbon group is 2 to 20, -CH ₂ -contained in the saturated hydrocarbon group may be replaced with at least one of -O- and -CO-. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH ₂ -is not replaced with -O- at the same time, and -CH ₂ -at the terminal is not replaced with -O- or -CO-. R ⁴⁵ and R ⁴⁶ may be bonded and form a ring together with the nitrogen atom to which R ⁴⁵ and R ⁴⁶ are bonded.

* Indicates a bonding end with a carbocation. ]

The ring T ^{1 is} also preferably a ring represented by formula (t2).

[In formula (t2), ring T ³ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms having a nitrogen atom.

R ⁵⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f .

R ⁵⁹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent, or an aralkyl group having 7 to 30 carbons which may have a substituent .

k2 means 0 or 1.

* Indicates a bonding end with a carbocation. ]

The ring T ^{1 is} also more preferably a ring represented by the formula (t2-1).

[In formula (t2-1), R ⁶⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

R ⁶¹ represents a hydrogen atom, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f .

R ⁵⁹ is synonymous with the above.

* Indicates a bonding end with a carbocation. ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ and the saturated hydrocarbon group having 1 to 20 carbon atoms which the amine group which may be substituted by ring T ¹ may have a straight chain Either shape, branched chain, or cyclic. Examples of the linear or branched saturated hydrocarbon group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, Linear alkyl groups such as hexadecyl and eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The carbon number of the saturated hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6.

The cyclic saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ^{60 and} the cyclic saturated hydrocarbon group which the amine group which the ring T ¹ may have may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The carbon number of the cyclic saturated hydrocarbon group is preferably 3 to 10, and more preferably 6 to 10.

Examples of the saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ^{60 and} the saturated hydrocarbon group which the amine group which ring T ¹ may have include methyl, ethyl, isopropyl, and propyl. , Butyl, pentyl, hexyl, isobutyl, 2-ethylhexyl, cyclohexyl, adamantyl and the like.

The saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ and the amine group which ring T ¹ may have The saturated hydrocarbon group which may have a substituted or unsubstituted amine group or a halogen atom as a substitution base. Examples of the substituted amino group include an alkylamino group such as a dimethylamino group and a diethylamino group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. When the halogen atom is a fluorine atom, the saturated hydrocarbon group having a fluorine atom as a substituent is preferably a perfluoroalkyl group such as a trifluoromethyl group, a perfluoroethyl group, or a perfluoropropyl group.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ include a straight chain or branched chain saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ⁴¹ . group.

In addition, examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ include a group having 1 to 10 carbon atoms in the linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ⁴¹ . .

When the carbon number of the saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ is 2 to 20, -CH ₂ -contained in the saturated hydrocarbon group may be substituted with at least one of -O- and -CO-. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ -is not replaced with -O- at the same time, and the terminal -CH ₂ -is not replaced with -O- or -CO-. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (that is, a linear or branched alkyl group), and more preferably a linear saturated hydrocarbon group (that is, a linear chain) alkyl). The preferable carbon number of the saturated hydrocarbon group in which -CH ₂ -can be replaced with at least one of -O- and -CO- is 2 to 10, and more preferably 2 to 8. In addition, when -CH ₂ -is replaced with at least one of -O- and -CO-, between the terminal and -O- or -CO-, or between -O- or -CO- and -O- or- The number of carbons before CO- is 1 or more, preferably 1 to 5, more preferably 2 to 3, and even more preferably 2.

In addition, the aromatic hydrocarbon group which may have a substituent represented by R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ^{60 and} the aromatic hydrocarbon group which the amine group which ring T ¹ may have (wherein the aromatic hydrocarbon group may have The number of carbons having a substituent) is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, and a phenyl group, a naphthyl group, a tolyl group, and a xylene group are preferred. The group is particularly preferably a phenyl group. The aromatic hydrocarbon group may have one or two or more substituents. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; a halogenated alkyl group having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; and a carbon group such as a methoxy group and an ethoxy group. Alkoxy groups of 1 to 6; hydroxyl groups; aminesulfonyl groups; alkylsulfonyl groups of 1 to 6 carbon numbers such as methylsulfonyl; methoxycarbonyl, ethoxycarbonyl groups such as 1 to 6 carbon atoms alkoxycarbonyl _{^{group; -SO 3 -; -SO 2 -N}} - -SO 2 -R f , etc., may be -SO ₃ ^- or _{^{-SO 2 -N - -SO 2 -R f}} . However, it is preferable that -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^{f are} directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, to replace a hydrogen atom bonded to the aromatic hydrocarbon ring.

Specific examples of the aromatic hydrocarbon group which may have a substituent include a group represented by the following formula. In the following formula, * represents a bonding end with a nitrogen atom.

Examples of the aralkyl group which may have a substituent represented by R ⁴¹ to R ⁴⁶ and R ^{59 and} the aralkyl group which the amine group which ring T ¹ may have (wherein the aralkyl group may have a substituent) are listed. An alkylene group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as a methylene group, an ethylene group, or a propyl group is bonded to a group such as the group described as the aromatic hydrocarbon group. The carbon number of the aralkyl group is preferably 7 to 30, more preferably 7 to 20, and even more preferably 7 to 17 carbons.

As R ⁴¹ and R ⁴² lines bonded to form together with the nitrogen atom of the R ⁴¹ and R ⁴² are bonded a ring, R ⁴³ and R ⁴⁴ based bond and the atom to which the R ⁴³ and R ⁴⁴ are bonded nitrogen ring, and R ⁴⁵ and R ⁴⁶ together form a ring system and is bonded to the R ⁴⁵ form together with the nitrogen atom R ⁴⁶ are bonded, include a pyrrolidine ring, a morpholine ring, a piperidine ring, quack A nitrogen-containing non-aromatic 4- to 7-membered ring such as a ring, preferably a 4- to 7-membered ring having only one nitrogen atom as a hetero atom such as a pyrrolidine ring and a pyridine ring.

R ⁵⁸ is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

Among them, as R ⁴¹ to R ⁴⁴ , R ⁵⁶ , and R ⁵⁸ to R ⁶⁰ , a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent is preferable, and each independently having 1 to 8 carbon atoms is more preferable. The saturated hydrocarbon group is a group represented by the following formula. R ⁵⁶ and R ⁵⁸ to R ^{60 are} more preferably a group represented by the following formula. In the following formula, * represents a bonding end with a nitrogen atom.

R ⁴⁵ to R ⁴⁶ are each preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ -constituting an alkyl group having 2 to 20 carbon atoms is substituted with at least one of -O- and -CO- The group is either an aromatic hydrocarbon group which may have a substituent, or R ⁴⁵ and R ⁴⁶ are bonded and form a ring together with the nitrogen atom to which R ⁴⁵ and R ⁴⁶ are bonded. R ⁴⁵ to R ^{46 are} more preferably each independently a saturated hydrocarbon group, alkoxyalkyl group having 1 to 8 carbon atoms, or a group represented by the following formula, or R ⁴⁵ and R ^{46 are} bonded to form only one A 4- to 7-membered ring having a nitrogen atom as a hetero atom is more preferably a saturated hydrocarbon group, an alkoxyalkyl group, or a group represented by the following formula each independently having 1 to 8 carbon atoms. In the following formula, * represents a bonding end with a nitrogen atom.

Further, the saturated hydrocarbon group represented by R ⁴⁷ to R ⁵⁴ represents a C 1-8 alkyl group include a saturated hydrocarbon group as the embodiment shown represented by R ⁴¹ is a linear or branched chain of 1 to 8 carbon atoms, Group. In addition, a group in which -CH ₂ -constituting a 2 to 8 carbon alkyl group represented by R ⁴⁷ to R ⁵⁴ is substituted with at least one of -O- and -CO- (however, the alkane groups, adjacent -CH ₂ - are not simultaneously substituted with -O-, -CH ends ₂ - can not be replaced with -O- or -CO-), constituting the above mentioned R ⁴¹ to R A group having a carbon number of 8 or less in a group in which -CH ₂ -of the alkyl group having 2 to 20 carbon atoms represented by ⁴⁶ is replaced with at least one of -O- and -CO-.

R ⁴⁷ to R ^{54 are} preferably each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and more preferably each independently a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

In addition, as R ⁵⁷ , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable.

R ⁶¹ is preferably a hydrogen atom.

Examples of the r-valent metal ion represented by M ^{r +} include alkali metal ions such as lithium ion, sodium ion, and potassium ion; beryllium ion, magnesium ion, calcium ion, strontium ion, and barium ion; Transition metal ions such as zirconium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions; zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, bismuth ions and other typical metal ions Wait. r is 1 or more, preferably 2 or more, preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. Examples of the substituted or unsubstituted ammonium ion represented by M ^{r +} include a quaternary ammonium ion such as a tetraalkylammonium ion.

M ^{r +} is preferably a hydrogen ion or a metal ion having an valence of r, more preferably an alkaline earth metal ion, a typical metal ion, and the like, more preferably an alkaline earth metal ion and a zinc ion, and even more preferably an alkaline earth metal ion.

Of formula (I), the number ratio becomes M ^{r +} R ⁴¹ to R ^44, R ⁴⁷ to R ⁵⁴ and T ¹ ring having -SO ₃ ^- and the number of -SO ₂ -N ^- -SO ₂ -R ^f The sum of the number of (k) is one less. Therefore, the valence of the compound (I) is 0, that is, it becomes an electrically neutral compound.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by R ^f include monofluoromethyl, difluoromethyl, perfluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, and tetrafluoromethane. Fluoroethyl, perfluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, perfluoropropyl, monofluorobutyl, di Fluorobutyl, trifluorobutyl, tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl, perfluorobutyl and the like. Among them, the fluoroalkyl group represented by R ^f is preferably a perfluoroalkyl group. The carbon number of the fluoroalkyl group represented by R ^f is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

In formula (I), R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have at least one -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . The sum (k) of the numbers of -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f that R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have is 1 or more, and preferably 1 to 7, more preferably 2 to 7, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.

-SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f preferably satisfies at least one or more conditions selected from the following (Ia) to (Id), and more preferably satisfies the conditions selected from (Ia) and (Ib) ) At least one of the conditions.

(Ia) contains as any one of the above R ⁴⁷ to R ⁵⁴

(Ib) is bonded to any one of the aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent represented by R ⁴¹ to R ⁴⁴

(Ic) is bonded to any of aralkyl groups having 7 to 30 carbon atoms which may have a substituent represented by R ⁴¹ to R ⁴⁴

(Id) is bonded to an aromatic hydrocarbon group having 6 to 20 carbon atoms in which a hydrogen atom of the aromatic heterocyclic ring represented by T ^{1 is} substituted

However, when -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f is bonded to an aromatic hydrocarbon group or an aralkyl group, -SO ₃ ^- or -SO ₂ -N ^-- SO is preferred. ₂ -R ^f is directly bonded to an aromatic hydrocarbon group or an aromatic hydrocarbon ring of an aralkyl group. That is, it is preferable that -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f replace a hydrogen atom bonded to an aromatic hydrocarbon ring.

Preferably -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f representing R ⁴¹ to R ⁴⁴ may be a substituent having a carbon number of 6 to 20 aromatic hydrocarbon group, or is R ⁴¹ to R ⁴⁴ is The aromatic hydrocarbon ring (for example, a benzene ring) in the aralkyl group having 7 to 30 carbon atoms which may have a substituent is bonded to the para position with respect to the bonding position with the nitrogen atom.

When compound (I) contains plural -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , plural -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f may be bonded to the same aromatic hydrocarbon ring, but is preferably bonded to different aromatic hydrocarbon rings.

The compound (I) preferably does not have an ethylenically unsaturated bond.

The compound (I) is preferably a compound represented by the following formula (I-1) (hereinafter sometimes referred to as "compound (I-1)").

[In the formula (I-1), R ⁸¹ to R ⁹⁰ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f .

k1 represents the sum of the number of -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f in R ⁴¹ , R ⁴³ , R ⁴⁷ to R ⁵⁴ , R ⁸¹ to R ⁹⁰ and ring T ¹ .

R ⁴¹ , R ⁴³ , R ⁴⁷ to R ⁵⁴ , T ¹ , Mr ⁺ , r, R ^f have the same meanings as described above.

However, R ⁴¹ , R ⁴³ , R ⁴⁷ to R ⁵⁴ , R ⁸¹ to R ⁹⁰ and ring T ¹ have at least one -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . ]

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁸¹ to R ⁹⁰ include the same groups as those exemplified as the saturated hydrocarbon group represented by R ⁴¹ . R ⁸¹ to R ^{90 are} preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , and more preferably a hydrogen atom, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f .

-SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f preferably satisfies at least one or more conditions selected from (Ie) to (Ig), and more preferably satisfies a condition selected from (If) and (Ig) At least one of the conditions is more preferably the condition of (If).

(Ie) contains as any one of R ⁴⁷ to R ⁵⁴

(If contains) as any one of R ⁸¹ to R ⁹⁰

(Ig) Bonded to an aromatic hydrocarbon group having 6 to 20 carbon atoms in which a hydrogen atom of the aromatic heterocyclic ring represented by T ^{1 is} substituted

-SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^{f still} more preferably satisfies the condition of (If ').

(If ') contains as either of R ⁸⁶ and R ⁸⁹

In formula (I-1), each of R ⁴¹ , R ⁴³ , R ⁴⁷ to R ⁵⁴ , R ⁸¹ to R ^90, and -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f possessed by ring T ¹ The sum (k1) of numbers is preferably 1 to 7, more preferably 1 to 4, and even more preferably 1 or 2.

As the compound (I), as shown in Tables 1 to 16, compounds represented by the formula (I-I-1) to the formula (I-I-1080) and the like can be cited.

In Tables 1 to 16, Me represents a methyl group, Et represents an ethyl group, Pr represents an n-propyl group, Bt represents an n-butyl group, and Ph1 to Ph19 each represent a group represented by the formula (Ph1) to (Ph19). In the formula, * represents a bonding end.

As the compound (I), as shown in Tables 17 to 24, compounds represented by the formula (I-II-1) to the formula (I-II-540) and the like can also be cited. However, in the formulae (I-II-1) to (I-II-540), the hydrogen atom represented by ^Rh may be substituted with -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -CF ₃ , -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -CF ₃ may be bonded to R ⁴¹ to R ⁴⁶ represents or R ⁵⁶ is Ph8 'to Ph12', Ph20 Ph22 to an aromatic hydrocarbon ring (benzene Ring), the sum of the number of -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -CF ₃ possessed by ^Rh , R ⁴¹ to R ⁴⁶ and R ⁵⁶ is two.

In Tables 17 to 24, Me represents a methyl group, Et represents an ethyl group, Pr represents an n-propyl group, and Bt represents an n-butyl group. Ph8 'to Ph12' and Ph20 to 22 respectively represent formulas (Ph8 ') to (Ph12) '), A group represented by formula (Ph20) to formula (Ph22). In the formula, * represents a bonding end.

As the compound (I), formulae (II-136) to (II-270), (II-676), (II-810), and (I-II-136) to (I-II- 270), more preferably a compound represented by formula (II-136) to formula (II-156), formula (II-175) to formula (II-177), formula (II-190) to formula (II-192) Formula (II-205) to Formula (II-207), Formula (II-220) to Formula (II-222), Formula (II-235) to Formula (II-237), Formula (II-250) to Formula (II-252), Formula (I-II-175) to Formula (I-II-177), Formula (I-II-190) to Formula (I-II-192), Formula (I-II-205 ) To a compound represented by formula (I-II-207), formula (I-II-220) to formula (I-II-222), formula (I-II-235) to formula (I-II-252), Particularly preferred are compounds represented by formulae (II-136) to (II-156) and formulae (I-II-238) to (I-II-252).

The compound (I) can be produced, for example, by sulfonating a compound represented by the formula (IC) (hereinafter sometimes referred to as a compound (IC)). The compound (IC) is preferably a hydrochloride, a phosphate, a perchlorate, a BF ₄ salt, or a PF ₆ salt.

[In the formula (IC), R ¹ to R ⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon group which may have a substituent. An aralkyl group of 7 to 30. In the saturated hydrocarbon group of 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amine group or a halogen atom. The saturated hydrocarbon group -CH ₂ -contained in may be substituted with at least one of -O- and -CO-. R ¹ and R ² may be bonded to form a ring together with the R ¹ and R nitrogen atom ² are bonded, R ³ and R ⁴ may be bonded and ³ and R ⁴ bond the nitrogen atom to form a ring together with the R.

R ⁷ to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and -CH ₂ -constituting the alkyl group may be replaced with -O- and -CO- At least one of. R ⁸ and R ¹² may be bonded to each other to form -NH-, -S-, or -SO _2- .

The ring T ¹⁰ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

M ¹ represents Cl ⁻ , phosphate ion, perchlorate ion, BF ₄ ⁻ or PF ₆ ⁻ . ]

When the compound (I) is a compound having a -SO ₃ ^- group and no -SO ₂ -N ^-- SO ₂ -R ^f (hereinafter sometimes referred to as "compound (IA-1)"), The compound (IA-1) is reacted with a compound represented by the formula (IB).

[In formula (IB), R ^f has the same meaning as described above. ]

When compound (I) is a compound in which M ^{r +} is a hydrogen ion in formula (I) (hereinafter sometimes referred to as compound (IA-2)), compound (IA-2) and The halide (preferably chloride), acetate, phosphate, sulfate, silicate or cyanide of the metal ion is reacted.

Examples of the sulfonation method include various known methods, for example, the methods described in Journal of Organic Chemistry, (1994), Vol. 59, No. 11, pp. 3232-3236.

The content of the compound (I) is preferably 1 to 99% by mass, more preferably 20 to 99% by mass, and still more preferably 50 to 99% by mass in the total amount of the colorant (A).

As the anthraquinone dye, a known substance can be used. Examples of the anthraquinone dye include CI Solvent Yellow 117 (hereinafter, the description of CI Solvent Yellow is omitted, and only the serial number is described), 163, 167, 189, CI Solvent Orange 77, 86, CI Solvent Red 111, 143, 145, and 146. , 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, CI Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100 , 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, CI Solvent Green 3, 28, 29, 32, 33, CI Acid Red 80, CI Acid Green 25, 27, 28, 41, CI Acid Violet 34, CI Acid Blue 25, 27, 40, 45, 78, 80, 112 CI Disperse Yellow 51, CI Disperse Violet 26, 27, CI Disperse Blue 1, 14, 56, 60, CI Direct Blue 40 , CI Mordant Red 3, 11, CI Mordant Blue 8, etc. The anthraquinone dye is preferably an anthraquinone dye dissolved in an organic solvent, and more preferably a cyan or green anthraquinone dye.

Among these, as the anthraquinone dye, a compound represented by formula (II) (hereinafter sometimes referred to as "compound (II)") is preferable.

[In formula (II), R ⁹¹ and R ⁹² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent, or Is a group represented by formula (p1).

(In formula (p1), R ⁹³ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, -SO ₃ H, -SO ₃ Z, -CO ₂ H, -CO ₂ Z, -CO ₂ R ⁹⁴ , -NHCOR ⁹⁴ , -SO ₃ R ⁹⁴ or -SO ₂ NR ⁹⁴ R ⁹⁵ .

R ⁹⁴ represents an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms which may have a halogen atom, a hydroxyl group, or an amine group as a substituent, or an aliphatic saturated hydrocarbon group which may have a halogen atom, a hydroxyl group, or an amine group as a substituent. Alicyclic hydrocarbon group.

R ⁹⁵ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.

r represents an integer from 0 to 5. When r is 2 or more, plural R ⁹³ may be the same or different.

X ⁹¹ represents a single bond or an alkylene group having 1 to 6 carbon atoms.

Z represents Na ⁺ or K ⁺ .

(* Indicates bonding end)]

Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ⁹¹ and R ⁹² , R ⁹⁴ and R ⁹⁵ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Base, nonyl, decyl, isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl, 2-ethylhexyl, and the like.

As a substituent which these aliphatic hydrocarbon groups may have, a hydroxyl group, a halogen atom, etc. are mentioned.

Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ⁹¹ , R ⁹² and R ⁹⁴ include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and the like .

As a substituent which these alicyclic hydrocarbon groups may have, a hydroxyl group, a halogen atom, etc. are mentioned.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁹³ include a group having 1 to 6 carbon atoms among the groups exemplified as the aliphatic hydrocarbon group represented by R ⁹¹ .

Examples of -CO ₂ R ⁹⁴ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group.

Examples of -NHCOR ⁹⁴ include N-ethylamidoamino, N-propylamidoamino, N-butylamidoamino, N-isobutylamidoamino, and N-neopentamidoamino.

Examples of -SO ₃ R ⁹⁴ include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexylsulfonyl and eicosane Oxysulfonyl and the like.

Examples of -SO ₂ NR ⁹⁴ R ⁹⁵ include N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-isopropylaminesulfonyl, N -Butylaminesulfonyl, N-isobutylaminesulfonyl, N-second butylaminesulfonyl, N-third butylaminesulfonyl, N-pentylaminesulfonyl, N -(1-ethylpropyl) aminosulfonyl, N- (1,1-dimethylpropyl) aminosulfonyl, N- (1,2-dimethylpropyl) aminosulfonyl, N- (2,2-dimethylpropyl) sulfamomidino, N- (1-methylbutyl) sulfamomidino, N- (2-methylbutyl) sulfamomidino, N- (3-methylbutyl) aminosulfonyl, N-cyclopentylaminesulfonyl, N-cyclohexylaminesulfonyl, N-hexylaminesulfonyl, N- (1,3-dimethyl Butyl) sulfamidino, N- (3,3-dimethylbutyl) sulfamidino, N-heptylaminesulfonyl, N- (1-methylhexyl) sulfamidino, N -(1,4-dimethylpentyl) aminosulfonyl, N-octylaminesulfonyl, N- (2-ethylhexyl) aminesulfonyl, N- (1,5-dimethyl ) N-1 substituted amine sulfonates such as hexylaminesulfonyl, N- (1,1,2,2-tetramethylbutyl) aminesulfonyl, N- (5-aminopentyl) aminesulfonyl Fluorenyl; N, N-dimethylaminosulfonyl, N, N-ethylmethylsulfanyl N, N-diethylaminesulfonyl, N, N-propylmethylaminesulfonyl, N, N-isopropylmethylaminesulfonyl, N, N-tert-butylmethylamine Sulfonyl, N, N-butylethylaminesulfonyl, N, N-bis (1-methylpropyl) aminesulfonyl, N, N-heptylmethylaminesulfonyl, etc.N, N-2 substituted sulfamoyl and the like.

Examples of the alkylene group having 1 to 6 carbon atoms represented by X ⁹¹ include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, and butane-1, 4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, butane-1,3-diyl, 2-methylpropane -1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, and the like.

R ⁹³ is preferably an alkyl group having 1 to 5 carbon atoms which may have a hydroxyl group, -SO ₃ R ⁹⁴ , -SO ₂ NR ⁹⁴ R ⁹⁵ , more preferably -SO ₂ NR ⁹⁴ R ⁹⁵ , and even more preferably -SO ₂ NHR ⁹⁴ .

Examples of the compound (II) include compounds represented by the formula (II-1) to the formula (II-19).

As the anthraquinone dye, a compound represented by the formula (1I) and R ⁹¹ and R ⁹² are a hydrogen atom, an alkyl group having 1 to 5 carbons, and a group represented by the formula (p1), and more preferably a compound represented by the formula ( II-8), (II-15), (II-17), (II-18) and (II-19).

The content of the anthraquinone dye is preferably 1 part by mass or more and 99 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less, and even more preferably 1 part by mass with respect to 100 parts by mass of the compound (I). Above 30 parts by mass.

The total content of the compound (I) and the anthraquinone dye is preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass or more in the total amount of the colorant (A). The total content may be substantially 100% by mass.

The colorant (A) may contain a dye (A1) and / or a pigment (A2) in addition to the compound (1) and an anthraquinone dye.

The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dye include a compound classified in the color index (published by The Society of Dyers and Colourists) as a substance having a hue other than a pigment, and a well-known dye described in Dyeing Notes (Seiransha). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, Acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

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

These dyes can be appropriately selected according to the required spectral spectrum of the color filter.

The dye (A1) preferably contains a xanthene dye.

The xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (Aa) include CI Acid Red 51 (hereinafter, the description of CI Acid Red is omitted, and only the serial number is described. The same is true for others), 52, 87, 92, 94, 289, 388, and CI Acid Red 9 , 30, 102, CI Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, CI Basic Red 10, 11, CI Basic Violet 10 (Rhodamine B), 11, CI Solvent Red 218, CI mordant red 27, CI reactive red 36 (rose red B), sulforhodamine G, xanthene dye described in Japanese Patent Application Laid-Open No. 2010-32999, and xanthene dye described in Japanese Patent No. 4492760. Xanthene dyes dissolved in organic solvents are preferred.

Among these, as the xanthene dye (Aa), a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferred. Compound (1a) may be its tautomer. When using the compound (1a), the content of the compound (1a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. In particular, as the xanthene dye (Aa), it is preferable to use only the compound (1a).

[In the formula (1a), R ^a1 to R ^a4 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent saturated hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. -CH ₂ -contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, or -NR ^a11- . R ^a1 and R ^a2 may form a ring containing a nitrogen atom together, and R ^a3 and R ^a4 may form a ring containing a nitrogen atom together.

R ^a5 represents _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R a8, -SO 3 R a8 or -SO ₂ NR ^a9 R ^a10 .

R ^a6 and R ^a7 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 ^a5 may be the same or different.

a represents an integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N (R ^a11 ) ₄ , Na ⁺ or K ⁺ . The four R ^a11 may be the same or different.

R ^a8 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 with a halogen atom.

R ^a9 and R ^a10 independently 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 aliphatic hydrocarbon group may be -O-,- CO-, -NH- or -NR ^a8 -substitution, R ^a9 and R ^a10 may be bonded to each other to form a 3 to 10 membered heterocyclic ring containing a nitrogen atom.

R ^a11 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. ]

In formula (Ia), when -SO ₃ ^- is present, the number is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^a1 to R ^a4 include phenyl, tolyl, xylyl, mesyl, propylphenyl, and butylphenyl. .

Examples of the aromatic hydrocarbon group may have a substituent group include a halogen ^{atom, -R a8, -OH, -OR a8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO ₂ R ^a8 , -SR ^a8 , -SO ₂ R ^a8 , -SO ₃ R ^a8 or -SO ₂ NR ^a9 R ^a10 . Among these, as a substituent group, preferably _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO ₂ NR ^a9 R ^a10, and more preferably -SO ₃ ^- Z ⁺ and -SO ₂ NR ^a9 R ^a10. As in this case -SO ₃ ^- Z ^+, preferably _{^{-SO 3 - + N (R a11}} ) 4. When R ^a1 to R ^a4 are these groups, a color filter with little generation of foreign matter and excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (1a).

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^a1 to R ^a4 and R ^a8 to R ^a11 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the like. Linear alkyl groups such as octyl, nonyl, decyl, dodecyl, cetyl, eicosyl; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethyl Hexyl and other branched chain alkyl groups; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms.

The hydrogen atom contained in the saturated hydrocarbon group in R ^a1 to R ^a4 may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.

The hydrogen atom contained in the saturated hydrocarbon group in R ^a9 and R ^a10 may be substituted with, for example, a hydroxyl group or a halogen atom.

Examples of the ring formed by R ^a1 and R ^a2 together and the ring formed by R ^a3 and R ^a4 include, for example, the following rings. In the formula, * represents a bonding end.

Examples of -OR ^a8 include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and dioxy Decadecyl and the like.

Examples of -CO ₂ R ^a8 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group.

Examples of -SR ^a8 include methylsulfanyl, ethylsulfanyl, butylsulfanyl, ^{hexylsulfanyl} , ^{decylsulfanyl} , and ^{eicosylsulfanyl} .

Examples of -SO ₂ R ^a8 include methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, and eicosylsulfonyl.

Examples of -SO ₃ R ^a8 include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a third butoxysulfonyl group, a hexyloxysulfonyl group, and icosyl Alkoxysulfonyl and the like.

Examples of -SO ₂ NR ^a9 R ^a10 include aminesulfonyl; N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, and N-isopropyl Aminosulfonyl, N-butylaminesulfonyl, N-isobutylaminesulfonyl, N-second butylaminesulfonyl, N-thirdbutylaminesulfonyl, N-pentyl Aminosulfonyl, N- (1-ethylpropyl) aminosulfonyl, N- (1,1-dimethylpropyl) aminosulfonyl, N- (1,2-dimethylpropyl ) Aminosulfonyl, N- (2,2-dimethylpropyl) aminosulfonyl, N- (1-methylbutyl) aminesulfonyl, N- (2-methylbutyl) amine Sulfonyl, N- (3-methylbutyl) aminesulfonyl, N-cyclopentylaminesulfonyl, N-hexylaminesulfonyl, N- (1,3-dimethylbutyl) Aminosulfonyl, N- (3,3-dimethylbutyl) sulfanilino, N-heptylaminesulfonyl, N- (1-methylhexyl) sulfamoyl, N- (1 , 4-dimethylpentyl) aminosulfonyl, N-octylaminesulfonyl, N- (2-ethylhexyl) aminesulfonyl, N- (1,5-dimethyl) hexylamine N-1 substituted aminesulfonyl groups such as sulfonyl, N- (1,1,2,2-tetramethylbutyl) aminesulfonyl; N, N-dimethylaminesulfonyl, N, N -Ethylmethylaminesulfonyl, N, N-diethylaminesulfonyl, N, N -Propylmethylaminesulfonyl, N, N-isopropylmethylaminesulfonyl, N, N-third butylmethylaminesulfonyl, N, N-butylethylaminesulfonyl, N, N-bis (1-methylpropyl) aminosulfonyl, N, N-heptylmethylaminesulfonyl and the like, N, N-2 substituted aminesulfonyl and the like.

R ^a5 is preferably ^{_{-CO 2 H, -CO 2 - Z}} +, -CO 2 R a8, -SO 3 -, -SO 3 - Z +, -SO 3 H or SO ₂ NHR ^a9, more preferably SO ₃ ^-, -SO ₃ ^- Z ⁺ , -SO ₃ H, or SO ₂ NHR ^a9 .

m is preferably 1 to 4, and more preferably 1 or 2.

Examples of the alkyl group having 1 to 6 carbon atoms in R ^a6 and R ^a7 include alkyl groups having 1 to 6 carbon atoms in the alkyl groups listed above.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^a11 include benzyl, phenylethyl, and phenylbutyl.

Z ⁺ is ⁺ N (R ^a11 ) ₄ , Na ⁺ or K ⁺ , and is preferably ⁺ N (R ^a11 ) ₄ .

As the ⁺ N (R ^a11 ) ₄ , at least two of the four R ^a11 are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. The total carbon number of the four R ^a11 is preferably 20 to 80, and more preferably 20 to 60. When ⁺ N (R ^a11 ) ₄ is present in the compound (1a), if R ^a11 is these groups, the color hardening resin composition of the present invention containing the compound (1a) can form a color filter with few foreign matters. Device.

The compound (1a) is preferably a compound represented by the formula (3a) (hereinafter sometimes referred to as "compound (3a)"). Compound (3a) may be its tautomer.

[In formula (3a), R ^a31 and R ^a32 independently of each other represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be an aromatic hydrocarbon group having 6 to 10 carbon atoms or A halogen atom is substituted. A hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbon atoms. The -CH ₂ -contained in the saturated hydrocarbon group may be -O-, -CO-, or- NR ^a11 -replacement.

R ^a33 and R ^a34 independently of each other represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.

R ^a31 and R ^a33 may form a ring containing a nitrogen atom together, and R ^a32 and R ^a34 may form a ring containing a nitrogen atom together.

p and q represent an integer of 0 to 5 independently of each other. When p is 2 or more, the plural R ^a33 may be the same or different, and when q is 2 or more, the plural R ^a34 may be the same or different.

R ^a11 has the same meaning as described above. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ^a31 and R ^a32 include a group having 1 to 10 carbon atoms in the saturated hydrocarbon group in R ^a8 .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be used as the substituent include the same groups as the aromatic hydrocarbon group in R ^a1 .

Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

R ^a31 and R ^a32 are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in R ^a33 and R ^a34 include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, second butyl, and third butyl. .

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ^a33 and R ^a34 include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, butylsulfanyl group, and isopropyl group. Sulfanyl and the like.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ^a33 and R ^a34 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropyl Sulfonyl and others.

R ^a33 and R ^{a34 are} preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

p and q are preferably integers of 0 to 2, preferably 0 or 1.

Examples of the compound (1a) include compounds represented by the formula (1-1) to the formula (1-13).

In addition, a compound represented by any one of formulas (1-1) to (1-10) is also preferred in terms of excellent solubility in an organic solvent.

As the xanthene dye (Aa), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink R-H / C" manufactured by Sinochem Chemical Co., Ltd., and "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.) can be used. In addition, a commercially available xanthene dye may be used as an initial raw material, and synthesized by referring to Japanese Patent Application Laid-Open No. 2010-32999.

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

Examples of the pigment include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 16, 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, 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 and other cyan pigments; CI Pigment Violet 1, 19, 23, 29, 32 , 36, 38 purple pigments; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other brown pigments; CI pigment black 1, 7 and other black pigments.

As the pigment, cyan pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60 are preferred; purple pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 are more preferred, and CI pigments are more preferred. Blue 15: 3, 15: 6 and CI Pigment Violet 23, more preferably CI Pigment Blue 15: 6. By including the pigment described above, it is easy to optimize the transmission spectrum, and the light resistance and chemical resistance of the color filter become good.

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

The pigment preferably has a uniform particle size. By performing a dispersion treatment by containing a pigment dispersant, a pigment dispersion liquid in a state where the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more kinds. As the pigment dispersant, it is represented by a trade name, and examples include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOREN (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by zeneca Co., Ltd.), and EFKA (manufactured by CIBA) , Adisper (manufactured by Ajinomoto fine-techno Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), and the like.

When a pigment dispersant is used, the use amount thereof is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less with respect to the total amount of the pigment (A2). When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state is obtained.

The content ratio of the dye (A1) and the pigment (A2) (dye (A1) / pigment (A2)) is on a quality basis, preferably 1/99 to 99/1, more preferably 5/95 to 50/50, and further It is preferably 10/90 to 20/80.

The content of the colorant (A) is preferably 1 to 60% by mass, more preferably 3 to 55% by mass, and still more preferably 5 to 50% by mass with respect to the total amount of the solid content. When the content of the colorant (A) is within the above range, the color density at the time of forming a color filter is sufficient, and a necessary amount of resin and polymerizable compound can be contained in the composition, so that a pattern with sufficient mechanical strength can be formed. . Here, the "total amount of solid content" in the present specification means an amount after removing the content of the solvent from the total amount of the coloring curable resin composition. The total amount of the solid component and the content of each component relative to the solid component can be measured by a known analysis means such as liquid chromatography or gas chromatography.

    <Resin (B)>    

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6] and the like.

Resin [K1]: having a structural unit derived from at least one (a) (hereinafter sometimes referred to as "(a)") selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a ring derived from a ring having 2 to 4 carbon atoms Copolymer of a monomeric ether structure and the structural unit of an ethylenically unsaturated monomer (b) (hereinafter sometimes referred to as "(b)"); resin [K2]: having a structural unit derived from (a) and derived from ( Copolymerization of a structural unit of b) and a structural unit derived from a monomer (c) copolymerizable with (a) (however, it is different from (a) and (b)) (hereinafter sometimes referred to as "(c)") Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c); resin [K4]: a structural unit having a structural unit derived from (a) added to (b) Copolymer with a structural unit derived from (c); Resin [K5]: a copolymer having a structural unit derived from (b) added to (a) and a structural unit derived from (c); resin [K6] ]: A copolymer having a structural unit derived from (b) by adding (a) to a structural unit derived from carboxylic anhydride and a structural unit derived from (c).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid, fumaric acid, and citraconic acid , Mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6- Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid , 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] heptane- 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-vinyl phthalic anhydride, 4-vinyl ophthalic anhydride Phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5, 6-Dicarboxybicyclo [2.2.1] heptan-2-enoic anhydride Acid anhydrides; poly [2- (meth) acryloxyethyl] succinate, poly [2- (meth) acryloxyethyl] phthalate, and more than 2 polyvalent carboxylic acids Unsaturated mono [(meth) acryloxyalkyl] esters; unsaturated acrylic esters such as α- (hydroxymethyl) acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule.

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

(b) means, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond Polymerizable compound. (b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloxy group is preferred.

In addition, in this specification, "(meth) acrylic acid" means at least 1 sort (s) chosen from acrylic acid and methacrylic acid. The expressions "(meth) acrylfluorenyl" and "(meth) acrylate" have the same meaning.

Examples of (b) include, for example, a monomer (b1) having an epoxyethyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), an oxetanyl group, and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as "(b2)"), monomer (b3) (hereinafter sometimes referred to as "(b3)") having a tetrahydrofuryl group and an ethylenically unsaturated bond, and the like.

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

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl vinyl ether. , O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2, 4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3, 4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, etc.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel, Inc.), and (methyl) 3,4-epoxycyclohexyl methyl acrylate (for example, CYCLOMER A400; manufactured by Daicel); 3,4-epoxycyclohexyl methyl (meth) acrylate (for example, CYCLOMER M100; limited company competition) Made by Lu), a compound represented by formula (I), a compound represented by formula (II), and the like.

[In formulae (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^a and X ^b represents a single ^{bond, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-.

R ^c represents an alkylene group having 1 to 6 carbon atoms.

* Indicates a bonding end with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, and third butyl.

Examples of the alkyl group having a hydrogen atom substituted with a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, and 1-hydroxyl. 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

As R ^a and R ^b, preferably, a hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, and more preferably include a hydrogen atom, a methyl group.

Examples of the alkylene group include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5. -Diyl, hexane-1,6-diyl and the like.

As X ^a and X ^b , a single bond, methylene, ethylidene, * -CH ₂ -O-, and * -CH ₂ CH ₂ -O- are preferably exemplified, and more preferably, a single bond, *- CH ₂ CH ₂ -O- (* indicates a bonding end with O).

Examples of the compound represented by the formula (I) include compounds represented by any one of the formulae (I-1) to (I-15). Among them, it is preferably from formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I The compound represented by -15) is more preferably a compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by any one of the formula (II-1) to the formula (II-15). Among them, it is preferably from formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), or formula (II-11) to formula (II) The compound represented by -15) is more preferably a compound represented by formula (II-1), formula (II-7), formula (II-9), or formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used individually, or two or more kinds may be used in combination. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, their content ratio [compound represented by the formula (I): compound represented by the formula (II)] is measured on a Mohr basis. , Preferably 5:95 to 95: 5, and more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3- Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-propenemethyloxetane, 3-methyl-3-methacryloxy Ethylethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, 3 -Ethyl-3-propenyloxyethyloxetane and the like.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth) acrylfluorenyl group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, VISCOAT V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), it is preferable that (b1) is the point which can further improve the reliability, such as heat resistance and chemical resistance, of the obtained color filter. Furthermore, (b1-2) is more preferable at the point which is excellent in the storage stability of a coloring curable resin composition.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and third (meth) acrylate Butyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate Ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester (in this technology In the field, as a common name, it is called "dicyclopentyl (meth) acrylate." It is also sometimes called "tricyclodecyl (meth) acrylate"), and tricyclo (meth) acrylate [5.2.1.0 ^2,6 ] decene-8-yl ester (known in the technical field as "bicyclopentenyl (meth) acrylate"), dicyclopentyloxyethyl (meth) acrylate, (formyl Base) isobornyl acrylate, adamantane (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, 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, itaconic acid Dicarboxylic acid diesters such as diethyl ester; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] heptane- 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-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy -5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2 .1] hept-2-ene, 5-third-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5 -Phenoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5,6-bis (third butoxycarbonyl) bicyclo [2.2.1] Bicyclic unsaturated compounds such as -2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene; N-phenylmaleimide, N-cyclohexyl horse Lyme imine, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide Butyrate, N-succinimide-6-maleimide hexanoate, N-succinimide-3-maleimide propionate, N- (9-acridinyl ) Dicarbonylimine derivatives such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene , Acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl -1,3-butadiene and the like.

Among these, styrene, vinyltoluene, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, and N-cyclohexylmaleimide are preferred from the viewpoint of copolymerization reactivity and heat resistance. Imine, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene, etc.

The ratio of the structural unit derived from each monomer in the resin [K1] is preferably the structural unit derived from (a) among all the structural units constituting the resin [K1]: 2 to 60 mol%

Structural unit from (b): 40 to 98 mol%, more preferably structural unit from (a): 10 to 50 mol%

Structural unit from (b): 50 to 90 mole%.

When the ratio of the structural unit of the resin [K1] is within the above-mentioned range, there is a tendency that the storage stability of the colored curable resin composition, the developability when a colored pattern is formed, and the solvent resistance of the obtained color filter tend to be excellent.

Resin [K1] can be referred to, for example, the method described in the document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Doujin, First Edition, First Printing, March 1, 1972) and the document Documented citations.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel. For example, oxygen is replaced with nitrogen to form a deoxidizing atmosphere, and heating and stirring are performed. Method of insulation. In addition, there are no particular restrictions on the polymerization initiator, solvent, and the like used here, and those generally used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.), organic compounds As a solvent, an oxide (such as benzamidine peroxide) may be used as long as each monomer is dissolved. Examples of the solvent (E) of the colored curable resin composition of the present invention include solvents described below.

The obtained copolymer may be used as it is after the reaction, as a concentrated or diluted solution, or as a solid (powder) taken out by a method such as reprecipitation. In particular, during the polymerization, by using the solvent contained in the colored curable resin composition of the present invention as a solvent, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of this invention can be simplified.

The ratio of the structural unit derived from each monomer in the resin [K2] is preferably the structural unit derived from (a) among all the structural units constituting the resin [K2]: 2 to 45 mol%

Structural unit from (b): 2 to 95 mole%

Structural unit from (c): 1 to 65 mol%, more preferably structural unit from (a): 5 to 40 mol%

Structural unit from (b): 5 to 80 mole%

Structural unit from (c): 5 to 60 mole%.

If the ratio of the structural unit of the resin [K2] is within the above range, there are storage stability of the colored curable resin composition, developability when a colored pattern is formed, and solvent resistance, heat resistance, and mechanical properties of the obtained color filter The strength tends to be excellent.

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

In the resin [K3], in terms of the ratio of the structural unit derived from each monomer, among all the structural units constituting the resin [K3], the structural unit derived from (a) is preferred: 2 to 60 mol%

Structural unit from (c): 40 to 98 mole%, more preferably structural unit from (a): 10 to 50 mole%

Structural unit from (c): 50 to 90 mole%.

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

The resin [K4] can be produced by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms in (b) to a carboxylic acid and / or carboxylic acid anhydride in (a). .

First, the copolymers (a) and (c) can be produced in the same manner as described in the method for producing the resin [K1], and the ratio of the structural unit derived from each monomer is preferably the same as the ratio listed in the resin [K3]. The ratio.

Next, (b) the cyclic ether having 2 to 4 carbon atoms is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.

Next, the copolymer of (a.) And (c) is manufactured, the atmosphere in the flask is replaced with nitrogen, and the reaction catalyst (e.g., tris (dimethylamine), (b), a carboxylic acid or a carboxylic acid anhydride, and a cyclic ether is replaced with nitrogen. (Methylmethyl) phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) are put into a flask, and for example, a reaction can be performed at 60 to 130 ° C for 1 to 10 hours, thereby making it possible to produce a resin [K4].

The amount of (b) used is preferably 5 to 80 moles, and more preferably 10 to 75 moles, with respect to (a) 100 moles. By setting it as this range, there exists a tendency for the balance of the storage stability of a coloring curable resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern to become favorable. Since cyclic ether has high reactivity and unreacted (b) does not easily remain, (b) for resin [K4] is preferably (b1), and more preferably (b1-1).

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

The reaction conditions such as the feeding method, the reaction temperature, and the time can be appropriately adjusted in consideration of production equipment, the amount of heat generated by polymerization, and the like. In addition, similarly to the polymerization conditions, it is possible to appropriately adjust the feeding method and the reaction temperature in consideration of production equipment, heat generation from polymerization, and the like.

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

As for the ratio of the structural unit derived from (b) and (c), it is preferable that each is the structural unit derived from (b) with respect to the total number of moles of all the structural units constituting the above-mentioned copolymer: 5 to 95 mole%

Structural unit from (c): 5 to 95 mol%, more preferably structural unit from (b): 10 to 90 mol%

Structural unit from (c): 10 to 90 mole%.

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) which is obtained by copolymerizing the carboxylic acid or carboxylic acid anhydride (a) and (b) and (c) with (a) By reacting, a resin [K5] can be obtained.

The usage-amount of (a) which reacts with the said copolymer is 5-80 mol with respect to 100 mol of (b). Since the cyclic ether has high reactivity and unreacted (b) does not easily remain, (b) used for the resin [K5] is preferably (b1), and more preferably (b1-1).

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

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, etc. . The use amount of the carboxylic anhydride is preferably 0.5 to 1 mole relative to the use amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxy tricycloacrylic acid [5.2.1.0 ^2.6 ] Decyl ester / (meth) acrylic copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / Styrene / (meth) acrylic acid copolymer, acrylic acid 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl ester / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3- Methyl-3- (meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymer, acrylic acid / (meth) acrylic 3,4-epoxy tricyclic [5.2. 1.0 ^2.6 ] Decyl ester / cyclohexyl maleimide / 2-hydroxyethyl methacrylate copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic copolymer, styrene / ( Resins such as (meth) acrylic copolymers [K3]; resins obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic copolymer, and (meth) acrylic acid Glycidyl ester and tricyclodecyl (meth) acrylate / styrene / (formaldehyde ) Addition of acrylic copolymer resin, addition of glycidyl (meth) acrylate and tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin [K4]; resin that reacts (meth) acrylic acid with tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer, and (meth) acrylic acid with (meth) acrylic acid ) Resin and other resins [K5], which are copolymers of copolymers of tricyclodecyl acrylate / styrene / glycidyl (meth) acrylate; (meth) acrylic acid and tricyclodecyl (meth) acrylate / ( Resin [K6] and the like obtained by reacting a copolymer of glycidyl (meth) acrylate copolymer with tetrahydrophthalic anhydride.

Among them, as the resin (B), resin [K1] and resin [K2] are preferred.

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

The degree of dispersion [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) in terms of solid content is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and still more preferably 70 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 by, for example, titration using an aqueous potassium hydroxide solution.

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 with respect to the total amount of the solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and the residual film rate of the colored pattern tend to be improved.

    <Polymerizable compound (C)>    

The polymerizable compound (C) is a compound that can be polymerized by living radicals and / or acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (A ) Acrylate compounds.

Among these, 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) acrylate. , Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nine (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 pentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (methyl) Group) acrylate and the like.

Among these, 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 or more and 1500 or less.

The content rate 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 with respect to the total amount of the solid content. When the content of the polymerizable compound (C) is within the above-mentioned range, the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

    <Polymerization initiator (D)>    

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, and the like by the action of light and heat, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates living radicals include alkyl phenyl ketone compounds, Compounds, fluorenyl phosphine oxide compounds, O-fluorenyl oxime compounds, and biimidazole compounds.

The O-fluorenyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * indicates a bonding end.

Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzidine Oxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylsulfanylphenyl)- 3-cyclopentylpropane-1-one-2-imine, N-ethoxyl-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 Oxetanylmethoxy) benzylidene} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- ( 2-methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercially available products such as IRGACURE OXE01, OXE02 (the above are manufactured by BASF), and N-1919 (made by ADEKA Corporation) can be used. Among these, the O-fluorenyl oxime compound is preferably selected from the group consisting of N-benzyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, and 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) octan-1-one- 2-imine. If these O-fluorenyl oxime compounds are used, they tend to obtain color filters with high brightness.

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

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1-one, and 2-di Methylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl Group] -1- [4- (4-morpholinyl) phenyl] butane-1-one and the like. Commercially available products such as IRGACURE 369, 907, and 379 (above manufactured by BASF) can be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1- Oligomers of ketones, α, α-diethoxyacetophenone, benzophenone dimethyl ketal, etc.

In terms of sensitivity, as the alkylphenyl ketone compound, a compound having a partial structure represented by formula (d2) is preferred.

As above three Examples of the compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.

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

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 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'-tetrakis (dialkoxyphenyl) biimidazole, 2,2' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62- 174204 and the like), imidazole compounds in which the 4,4 ', 5,5'-phenyl group is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 7-10913).

Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone and ortho-benzophenone Methyl benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (third-butyl Peroxycarbonyl) benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10 -Butyl-2-chloroacridone, benzodiazone, methyl phenylglyoxylate, titanocene compound and the like. These are preferably used in combination with a polymerization initiator (D1) (particularly, amines) described later.

Examples of the acid generator include 4-hydroxyphenyldimethylfluorene-p-toluenesulfonate, 4-hydroxyphenyldimethylfluorene hexafluoroantimonate, and 4-ethoxyfluorenyldiphenyl Methylfluorene-p-toluenesulfonate, 4-Ethyloxyphenylmethylbenzylfluorene hexafluoroantimonate, triphenylfluorene-p-toluenesulfonate, triphenylfluorene hexafluoroantimonate Salts, onium salts such as diphenyliodonium-p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltosylate, benzoin tosylate, and the like.

As the polymerization initiator (D), it is preferred that A polymerization initiator for at least one of a compound, a fluorenylphosphine oxide compound, an O-fluorenyl oxime compound, and a biimidazole compound, and a polymerization initiator containing an O-fluorenyl oxime compound is more preferable.

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

    <Polymerization starter (D1)>    

The polymerization initiation aid (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound that is polymerized with the polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine. Isoamylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine; 4, 4'-bis (dimethylamino) benzophenone (commonly known as Michler ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis ( Ethylmethylamino) benzophenone and the like, among them, 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

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

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

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, and dimethylphenylsulfanyl. Alkylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycolic acid, naphthyloxyacetic acid, and the like.

When using these polymerization initiators (D1), the content is preferably 0.1 to 30 parts by mass, more preferably 100 to 30 parts by mass, and more preferably 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be further formed with high sensitivity, and the productivity of the color filter tends to increase.

    <Solvent (E)>    

The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. Examples include ester solvents (solvents containing -COO- and -O-free in the molecule), ether solvents (solvents containing -O- and -COO-free in the molecule), and ether ester solvents (in the molecule Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO-, -COO-free in the molecule), alcohol solvents (containing OH in the molecule, -O-,- CO- and -COO- solvents), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene, 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 formate, and isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclamate Hexanol acetate and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, 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-di Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether, and methyl ether Anisole and so on.

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, 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropanoate, 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, and Diethylene glycol monobutyl ether acetate and the like.

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

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.

Examples of the amine solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among the solvents described above, organic solvents having a boiling point of 1 ° C or higher and 180 ° C or lower at 1 atm are preferred in terms of coating properties and drying properties. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol are preferred. Glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone, and N, N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate , Propylene glycol monomethyl ether, N-methylpyrrolidone, ethyl lactate, and ethyl 3-ethoxypropionate.

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 of the present invention. In other words, the total content of 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-mentioned range, the flatness at the time of coating is good, and the color density is not insufficient when a color filter is formed, so that the display characteristics tend to be good.

    <Leveling agent (F)>    

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

Examples of the silicone-based surfactant include a surfactant having a siloxane 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 Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd. (LLC)).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specifically, FLUORAD (registered trademark) FC430, FC431 (made by Sumitomo 3M Co., Ltd.), MEGAFACE (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (DIC Co., Ltd.), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), SURFLON (registered trademark) S381, S382, SC101, SC105 (made by Asahi Glass Co., Ltd. ) And E5844 (manufactured by Daikin Fine Chemical Institute).

Examples of the above-mentioned organosilicon surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include MEGAFACE (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less with respect to the total amount of the colored curable resin composition, and Preferably it is 0.005 mass% or more and 0.05 mass% or less. It should be noted that the content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be made good.

    <Other ingredients>    

The colored curable resin composition of the present invention may contain additives known in the technical field such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, as necessary.

    <Manufacturing method of colored curable resin composition>    

The colored resin composition of the present invention can be obtained by combining a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and a solvent (E) and a leveling agent ( F) and other ingredients.

    <Manufacturing Method of Color Filter>    

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among them, photolithography is preferred. The photolithography method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a light mask to develop. In the photolithography method, a colored coating film that is a cured product of the coloring composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and colored coating film thus formed can be 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, application, and the like, and is, for example, 0.1 to 30 m, preferably 0.1 to 20 m, and more preferably 0.5 to 6 m.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silicon dioxide, etc., polycarbonate, polymethyl methacrylate, polyparaphenylene can be used. Resin plates such as ethylene dicarboxylate, silicon, and products of aluminum, silver, silver / copper / palladium alloy films, and the like are formed on the substrate. Additional color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates.

The formation of each color element using the photolithography method can be performed under a known or conventional apparatus and conditions. For example, it can be produced as follows.

First, a colored curable resin composition is coated on a substrate, and dried by heating (pre-baking) and / or drying under reduced pressure to remove and dry volatile components such as solvents 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, and the like.

The temperature during the heat drying is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferably performed under a pressure of 50 to 150 Pa and a temperature range of 20 to 25 ° C.

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

Next, the coloring composition layer is exposed through a light mask for forming a target coloring pattern. The pattern on the light mask is not particularly limited, and a pattern suitable for the intended use can be used.

As a light source for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferred. For example, the wavelength range may be cut using a filter that cuts light of less than 350 nm, or these wavelength ranges may be selectively removed using a band-pass filter that extracts light near 436 nm, 408 nm, and 365 nm. Specific examples include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

Since the entire exposure surface can be uniformly irradiated with parallel light rays, and accurate alignment of the light mask and the substrate on which the coloring composition layer is formed, an exposure device such as a mask aligner and a stepper is preferably used.

The coloring composition layer after exposure is developed by contacting with the developing solution, thereby forming a coloring pattern on the substrate. By the development, the unexposed part of the coloring composition layer is dissolved in the developing solution and removed. As the developing solution, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, 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. Furthermore, the developing solution may contain a surfactant.

The development method may be any of a spin-on immersion method, a dipping method, and a spray method. Furthermore, the substrate can be tilted at an arbitrary angle during development.

After development, washing with water is preferred.

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

By including the compound of the present invention as a colorant, a color filter having particularly excellent light resistance can be produced. This color filter can be used as a color filter for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

    [Example]    

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited by these examples. In the examples,% and parts indicating content or usage amount are quality standards unless otherwise specified.

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

    [Synthesis example 1]    

The following reactions were performed under a nitrogen atmosphere. After putting 32.2 parts of potassium thiocyanate and 160 parts of acetone into a flask having a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Next, 50 parts of 2-fluorobenzidine chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After the dropwise addition was completed, the mixture was further stirred at room temperature for 2 hours. Next, after the reaction mixture was ice-cooled, 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the dropwise addition was completed, the mixture was further stirred at room temperature for 30 minutes. Next, after the reaction mixture was ice-cooled, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise. After the dropwise addition was completed, the reaction mixture was further stirred at room temperature for 30 minutes. Next, 31.3 parts of chloroacetic acid was dropped into the reaction mixture at room temperature. After completion of the dropwise addition, the reaction mixture was stirred for 7 hours under heating and refluxing. Next, after the reaction mixture was allowed to cool to room temperature, the reaction mixture was poured into 120 parts of tap water, 200 parts of toluene was added, and stirred for 30 minutes. Next, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, and separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then washed with 200 parts of tap water, and finally washed with 200 parts of saturated brine. An appropriate amount of thenardite was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer. The obtained organic layer was subjected to solvent distillation with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C to obtain 49.9 parts of a compound represented by the formula (B-I-2). The yield was 51%.

The following reactions were performed under a nitrogen atmosphere. After putting 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide in a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, and then stirred for 1 hour while warming to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction mixture little by little, and stirred at room temperature for 24 hours. The reaction mixture was added to 200 parts of ice water little by little, and then allowed to stand at room temperature for 15 hours. The water was removed by decantation to obtain a thick solid as a residue. After 60 parts of methanol was added to this viscous solid, it was stirred at room temperature for 15 hours. The precipitated solid was separated by filtration and then purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ° C to obtain 9.8 parts of a compound represented by the formula (C-I-2). The yield was 53%.

The following reactions were performed under a nitrogen atmosphere. 8.2 parts of a compound represented by formula (BI-2), 10 parts of a compound represented by formula (CI-2), and 20 parts of toluene were put into a flask equipped with a cooling tube and a stirring device, and 12.2 parts of phosphorus oxychloride was added. Stir at 95 to 100 ° C for 3 hours. Next, the reaction mixture was cooled to room temperature, and then diluted with 170 parts of isopropanol. Next, the diluted reaction mixture was poured into 300 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, and separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain an organic layer. The obtained organic layer was subjected to solvent distillation with an evaporator to obtain a blue-violet solid. Furthermore, the blue-violet solid was dried under reduced pressure at 60 ° C to obtain 18.4 parts of a compound represented by the formula (X-II-2). The yield was 100%.

Identification of compound represented by formula (X-II-2)

(Quality analysis) Ionization mode = ESI +: m / z = 687.3 [M-Cl] ⁺

Exact mass: 722.3

The following reactions were performed under a nitrogen atmosphere. After putting 2.0 parts of a compound represented by formula (X-II-2) and 7.3 parts of dichloromethane into a flask provided with a cooling tube and a stirring device, the reaction solution was ice-cooled. Next, 1.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred overnight while warming to room temperature. Next, the reaction solution was diluted with 34 parts of N, N-dimethylformamide while cooling on ice. Next, the diluted reaction solution was poured into 140 parts of toluene, followed by stirring for 30 minutes. Next, the stirring was stopped and decantation was performed to obtain a blue-purple viscous solid. Furthermore, the blue-violet viscous solid was dried under reduced pressure at 60 ° C to obtain 2.3 parts of a compound represented by the formula (X-I-2). The yield was 100%.

Identification of compound represented by formula (X-I-2)

(Quality analysis) Ionization mode = ESI +: m / z = 847.3 [M + H] ⁺

ESI-: m / z = 845.5 [MH] ^-

Exact mass: 846.2

The following reactions were performed under a nitrogen atmosphere. A flask equipped with a cooling tube and a stirring device was charged with 2.0 parts of a compound represented by the formula (X-I-2) and 167 parts of ion-exchanged water, and stirred at 40 ° C for 30 minutes. 5.8 parts of barium chloride dihydrate and 35 parts of ion-exchanged water were added to the beaker, and stirred for 30 minutes. In the aqueous solution of the compound represented by the formula (X-I-2) prepared previously, a barium chloride aqueous solution was dropped into the aqueous solution while maintaining the liquid temperature of the aqueous solution at 40 ° C, and stirred for 1 hour and 20 minutes. The obtained reaction suspension was filtered, and the filtered solid was washed with 67 parts of ion-exchanged water and then washed with 20 parts of ion-exchanged water. The obtained solid was dried under reduced pressure at 60 ° C to obtain 1.9 parts of a compound represented by the formula (A-I-3). The yield was 89%.

    [Synthesis example 2]    

A compound represented by the formula (XI-4) was obtained in the same manner as in Example 1 except that the compound represented by the formula (CI-2) was changed to a compound represented by the formula (BP-2). In addition, in the formula, -SO ₃ ^- means that any one of the hydrogen atoms contained in the partial structure in the parentheses is substituted.

Identification of compound represented by formula (X-I-4)

(Quality analysis) Ionization mode = ESI +: m / z = 931.5 [M + H] ⁺

Exact mass: 930.3

A compound represented by the formula (A-I-4) was obtained in the same manner as in Example 1 except that the compound represented by the formula (X-I-2) was changed to a compound represented by the formula (X-I-4).

    [Synthesis example 3]    

A compound represented by the formula (A-X-1) (hereinafter also referred to as a compound (A-X-1)) was synthesized by a method described in Japanese Patent Application Laid-Open No. 2015-38201.

    [Synthesis example 4]    

20 parts of a compound represented by formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was obtained at 110 ° C. Stir for 6 hours. The obtained reaction solution was cooled to room temperature, and then added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. As a result, crystals were precipitated. The precipitated crystal was obtained as a residue of suction filtration and then dried to obtain a compound represented by the formula (A-IV).

Identification of the compound represented by formula (A-IV)

(Quality analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 659.9

Exact mass: 658.9

    [Synthesis example 5]    

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, a suitable amount of nitrogen was introduced into the flask, replaced with a nitrogen atmosphere, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were placed. To 85 ° C. Next, 38 parts of acrylic acid, acrylic acid 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester, and acrylic acid 3,4-epoxytricyclo [5.2.1.0] were added dropwise over 5 hours. ^2,6 ] A mixed solution of 25 parts of decane-9-yl ester, 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate . On the other hand, a mixed solution prepared by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was dropped over 6 hours. After the dropwise addition was completed, the solution was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having a solid content of 25.6%. The weight average molecular weight Mw of the produced copolymer was 8000, the degree of dispersion was 2.1, and the acid value in terms of solid content was 111 mg-KOH / g.

    [Synthesis example 6]    

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was allowed to flow in, replaced with a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was placed, and heated to 80 ° C while stirring. Next, 38 parts of acrylic acid, acrylic acid 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester, and acrylic acid 3 were dripped into the flask using a dropping pump over about 5 hours. A solution of 289 parts of 4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-yl ester dissolved in 125 parts of propylene glycol monomethyl ether acetate. On the other hand, 33 parts of a polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in propylene glycol monomethyl by dripping into the flask using another dropping pump over about 6 hours. A solution of 235 parts of ether acetate. After the dropwise addition was completed, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) having a solid content of 35.1%. The weight average molecular weight Mw of the produced copolymer was 9,200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by gel chromatography (GPC method) under the following conditions.

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

Column: TSK-GELG2000HXL

Column temperature: 40 ℃

Solvent: THF

Flow rate: 1.0mL / min

Solid content concentration of test liquid: 0.001 to 0.01% by mass

Injection volume: 50 μL

Detector: RI

Calibration reference materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The polystyrene-equivalent weight average molecular weight and number average molecular weight ratio (Mw / Mn) is defined as the degree of dispersion.

    [Method for making dispersion]    

16.2 parts of compound (AI-4), 12.1 parts of dispersant BYKLPN-6919 (solid content conversion), 4.0 parts of resin (B-2) (solid content conversion) as resin, and 174 parts of propylene glycol monomethyl ether acetate After weighing, 600 parts of 0.4 μm zirconia beads were placed, and shaken for 1 hour using a paint conditioner (manufactured by LAU), and then the zirconia beads were removed by filtration to prepare a dispersion liquid 1.

CI Pigment Blue 15: 6 (pigment) 2.4 parts, acrylic pigment dispersant (solid content conversion) 2.8 parts, propylene glycol monomethyl ether acetate 18 parts, and ethyl lactate 1.8 parts were mixed, and the pigment was made using a pearl mill Disperse sufficiently to prepare dispersion liquid 2.

    [Examples 1 to 6, Comparative Example 1]         [Preparation of colored curable resin composition]    

Each component was mixed with the number of parts shown in Table 25, and the colored curable resin composition was obtained.

In Table 25, each component shows the following compounds.

    ‧Colorant (A)    

(A-I-3): Compound (A-I-3) obtained in Synthesis Example 1

(A-I-4): Compound (A-I-4) obtained in Synthesis Example 2

(A-X-1): Compound (A-X-1) obtained in Synthesis Example 3

(A-II-1): C.I. Solvent Blue 45

(A-II-2): C.I. Acid Green 28

(A-II-3): C.I. Solvent Blue 132

(A-II-4): C.I. Solvent Green 3

(A-III): C.I. Pigment Blue 15: 6

(A-IV): Compound (A-IV) obtained in Synthesis Example 4

    ‧Resin (B)    

(B-1): Resin (B-1) obtained in Synthesis Example 5 (solid content conversion)

(B-2): Resin (B-2) obtained in Synthesis Example 6 (solid content conversion)

    ‧Polymerizable compound (C)    

(C-1): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

    ‧Polymerization initiator (D)    

(D-1): N-benzyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (IRGACURE (registered trademark) OXE-01; BASF Corporation Manufacturing; oxime compounds)

    ‧Solvent (E):    

(E-1): N-methylpyrrolidone

(E-2): Propylene glycol monomethyl ether acetate

(E-3): ethyl lactate

    ‧Leveling agent (F)    

(F-1): Polyether modified silicone oil (solid content conversion)

(TORAY SILICONE SH8400; manufactured by Toray Dow Corning Corporation)

    <Preparation of colored coating film>    

A 5 cm square glass substrate (EAGLE 2000; manufactured by Corning Corporation) was applied with a color-hardening resin composition by spin coating so that the post-baking film thickness was 2.0 μm, and then pre-baked at 100 ° C for 3 minutes to obtain Coloring composition layer. After being allowed to cool, the coloring composition layer was irradiated with light using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) at an exposure amount of 60 mJ / cm ² (based on 365 nm) in an atmospheric atmosphere. After light irradiation, it was baked in an oven at 230 ° C. for 20 minutes to obtain a colored coating film.

The film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.).

    <Chroma Evaluation>    

With respect to the obtained coloring pattern, a spectrometer (OSP-SP-200; manufactured by Olympus Co., Ltd.) was used to measure the spectrometry, and a characteristic function of the C light source was used to measure the xy chromaticity coordinates in the XYZ color system of CIE. (x, y) and stimulus value Y.

    <Evaluation of light resistance>    

An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by HOYA Corporation; cut-off light below 380 nm) was arranged on the obtained colored coating film, and a light resistance tester (SUNTEST CPS +: manufactured by Toyo Seiki Co., Ltd.) was irradiated for 48 hours. light.

The xy chromaticity coordinates (x, y) and Y were measured before and after irradiation, and the color difference ΔEab * was calculated from the measured values using the method described in JIS Z 8730: 2009 (7. Calculation method of color difference). in. The smaller ΔEab *, the smaller the color change. In addition, if the light resistance of the colored coating film is good, it can be said that the light resistance of a coloring pattern produced from the same coloring curable resin composition is also good.

    <Evaluation of heat resistance>    

The obtained colored coating film was heated in an oven at 230 ° C for 2 hours. The xy chromaticity coordinates (x, y) and Y were measured before and after heating. From the measured values, the color difference ΔEab * was calculated using the method described in JIS Z 8730: 2009 (7. Calculation method of color difference). The results are shown in Table 26. in. The smaller ΔEab *, the smaller the color change. In addition, if the heat resistance of the colored coating film is good, it can be said that the heat resistance of a colored pattern produced from the same colored curable resin composition is also good.

    [Industrial availability]    

By using the coloring curable resin composition of the present invention, a color filter excellent in light resistance can be produced.

Claims (3)

A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant includes a compound represented by formula (I) and an anthraquinone dye, In formula (I), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have substituents. An aralkyl group of 7 to 30, the aromatic hydrocarbon group and the substituent which the aralkyl group may have are -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , and the saturated hydrocarbon group contains The hydrogen atom may be substituted by a substituted or unsubstituted amine group or a halogen atom. When the carbon number of the saturated hydrocarbon group is 2 to 20, -CH ₂ -contained in the saturated hydrocarbon group may be replaced with -O. At least one of-and -CO-, but in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH ₂ -will not be replaced with -O- at the same time, and -CH ₂ -at the terminal will not be replaced with -O- or -CO-, R ⁴¹ and R ⁴² may be bonded and form a ring with the nitrogen atom to which R ⁴¹ and R ⁴² are bonded, and R ⁴³ and R ⁴⁴ may be bonded and bonded to R ⁴³ and R ring ⁴⁴ is formed are bonded together with the nitrogen atom, R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl _{^{group, -SO 3 -, -SO 2 -N}} - -SO 2 -R f , or C1-C8 alkyl group, -CH ₂ -constituting the alkyl group May be substituted with at least one of -O- and -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S-, or -SO _2- , but in this alkyl group, Adjacent -CH ₂ -will not be replaced with -O- at the same time, and -CH ₂ -at the end will not be replaced with -O- or -CO-. Ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms. The aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The aromatic hydrocarbon group may have The substituent may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , M ^{r +} represents a hydrogen ion, an r-valent metal ion, or a substituted or unsubstituted ammonium ion, and k represents R ⁴¹ The sum of the number of -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ , r represents an integer of 1 or more, R ^f Represents a fluoroalkyl group having 1 to 12 carbon atoms, but R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have at least one -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f .     A color filter is formed by the colored hardening resin composition described in the first patent application scope.         A display device includes the color filter described in item 2 of the scope of patent application.