TW201823367A - Colored composition, colored curable resin composition, color filter and display device - Google Patents

Abstract

The present invention provides a colored composition which is capable of forming a high-brightness color filter, a colored curable resin composition, a color filter and a display device. The colored composition according to the present invention comprises a triarylmethane compound having a heterocyclic ring, a dispersing agent and a solvent, and the amine value of the dispersing agent is 70 mg KOH/ g or less. As the triarylmethane compound having a heterocyclic ring, it is preferable that at least one compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) is included.

Description

 Coloring composition, coloring curable resin composition, color filter, and display device  

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

A color filter used in a solid-state imaging device such as a display device such as a liquid crystal display device, an electroluminescence display device, or a plasma display, or a CCD or a CMOS sensor is manufactured from a color-curable resin composition. A composition containing a triarylmethane dye and a dispersant having an amine value of 72 mgKOH/g is known as a coloring composition contained in the colored curable resin composition (Patent Document 1).

 [Prior Art Literature]    [Patent Literature]  

Patent Document 1: Japanese Laid-Open Patent Publication No. 2016-164247

The color filter formed of the above-described colored curing resin composition known in the related art may not sufficiently satisfy the brightness. The present invention provides a colored composition capable of forming a high-intensity color filter.

[1] A colored composition comprising a triarylmethane compound having a hetero ring, a dispersing agent, and a solvent, wherein the dispersing agent has an amine value of 70 mgKOH/g or less.

[2] The colored composition according to [1], which contains at least one compound selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II) as a triaryl group having a heterocyclic ring Methane compound.

[In the 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 a substituent 7 to 30 aralkyl groups, the aromatic hydrocarbon group and the aralkyl group may have a substituent -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , hydrogen contained in the saturated hydrocarbon group The atom may be substituted by a substituted or unsubstituted amino group or a halogen atom, and 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 -O- and -CO- At least one. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not simultaneously substituted with -O-, and the terminal -CH ₂ - is not replaced with -O- or -CO-. R ⁴¹ and R ⁴² may be bonded to 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 formed 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 an alkyl group having 1 to 8 carbon atoms, constituting the alkane The group -CH ₂ - may be replaced by 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 the alkyl group, the adjacent -CH ₂ - will not be replaced by -O- at the same time, and the terminal -CH ₂ - will not be replaced by -O- 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 of 1 to 20 carbon atoms, a substituted or unsubstituted amine group or a carbon number of 6 to 20 which may have a substituent Aromatic hydrocarbon group. The substituent which the aromatic hydrocarbon group may have 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.

k represents the sum of the number of -SO ₃ ^{- and} the number of -SO ₂ -N ^- -SO ₂ -R ^f of R ⁴¹ 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.

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 . ]

[In the formula (II), [Y ² ] ^n- represents an arbitrary n-valent anion.

R ^b41 to R ^b44 each independently represent a hydrogen atom, saturated hydrocarbon group may have a substituent group having a carbon number 1 to 20, an oxygen atom is inserted between carbon atoms constituting the alkyl group having 2 to 20 carbon groups, may have An aromatic hydrocarbon group of a substituent or an aralkyl group which may have a substituent. Forming R ^b41 and R ^b42 may be bonded with the R ^b41 and R ^b42 are bonded to the nitrogen atom together form a ring, R ^b43 and R ^b44 may be bonded to form together with the R ^b43 and R ^b44 are bonded to the nitrogen atom ring.

R ^b45 to R ^b52 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a group having an oxygen atom interposed between carbon atoms constituting an alkyl group having 2 to 8 carbon atoms. Or R ^b46 and R ^b50 may be bonded to each other to form -O-, -NH-, -S- or -SO ₂ -.

Y ¹ represents an aromatic heterocyclic group which may have a substituent.

When the compound represented by the formula (II) contains a plurality of cations, the plurality of cations may have the same structure or different structures.

n represents an arbitrary natural number. ]

[3] A colored curable resin composition comprising the colored composition according to [1] or [2], the resin (B), the polymerizable compound (C), and a polymerization initiator (D).

[4] A color filter comprising the color-curable resin composition according to [3].

[5] A display device comprising the color filter according to [4].

According to the present invention, there is provided a colored composition which can form a high brightness color filter.

The coloring composition of the present invention comprises a triarylmethane compound having a heterocyclic ring, a dispersing agent, and a solvent.

The colored curable resin composition of the present invention contains the colored composition of the present invention, the resin (B), the polymerizable compound (C), and a polymerization initiator (D). The colored curable resin composition of the present invention may contain other coloring agents in addition to a coloring agent such as a triarylmethane compound having a hetero ring contained in the coloring composition of the present invention. These colorants are collectively referred to as colorants (A).

 <Coloring composition>    <Triarylmethane compound having a heterocyclic ring>  

The triarylmethane compound having a heterocyclic ring has a structure in which three aromatic rings are bonded to one carbon atom, and one or more of them are aromatic heterocyclic rings, preferably two aromatic hydrocarbon rings and one aromatic group. A compound in which a heterocyclic ring is bonded to a structure of one carbon atom.

The triarylmethane compound having a heterocyclic ring is preferably a compound represented by the formula (I) (hereinafter sometimes referred to as "compound (I)").

A tautomer or a salt of the tautomer is also included in the compound (I). Further, each component and functional group exemplified below can be used singly or in combination.

[In the 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 a substituent 7 to 30 aralkyl groups, the aromatic hydrocarbon group and the aralkyl group may have a substituent -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , hydrogen contained in the saturated hydrocarbon group The atom may be substituted by a substituted or unsubstituted amino group or a halogen atom, and 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 -O- and -CO- At least one of them. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not simultaneously substituted with -O-, and the terminal -CH ₂ - is not replaced with -O- or -CO-. R ⁴¹ and R ⁴² may be bonded to 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 formed 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 an alkyl group having 1 to 8 carbon atoms, constituting the alkane The group -CH ₂ - 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 the alkyl group, the adjacent -CH ₂ - will not be replaced by -O- at the same time, and the terminal -CH ₂ - will not be replaced by -O- 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 of 1 to 20 carbon atoms, a substituted or unsubstituted amine group or a carbon number of 6 to 20 which may have a substituent Aromatic hydrocarbon group. The substituent which the aromatic hydrocarbon group may have 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.

k represents the sum of the number of -SO ₃ ^{- and} the number of -SO ₂ -N ^- -SO ₂ -R ^f of R ⁴¹ 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.

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 the ring T ¹ may be a single ring or a condensed ring. The aromatic heterocyclic ring represented by the ring T ¹ has a carbon number of from 3 to 10, preferably from 3 to 8. Further, the aromatic heterocyclic ring is preferably a 5- to 10-membered ring, more preferably a 5- to 9-membered ring. Examples of the monocyclic aromatic heterocyclic ring include a 5-membered ring containing a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring, and a 5-membered member containing no nitrogen atom such as a furan ring or a thiophene ring. a ring; a 6-membered ring containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring; and an aromatic heterocyclic ring of a condensed ring; an anthracene ring, a benzimidazole ring, a benzothiazole ring, and a quin A condensed ring containing a nitrogen atom such as a porphyrin ring; a condensed ring containing no nitrogen atom such as a benzofuran ring or the like.

The substituent which the aromatic heterocyclic ring of the ring T ¹ may have may, for example, be 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 may have a substituent. The aromatic hydrocarbon group having 6 to 20 carbon atoms or the like is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group or a carbon group having 6 to 20 carbon atoms which may have a substituent. The ring T ¹ preferably has an amine group which may have a substituent, and the substituent which the amine group may have, preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent An aralkyl group having 7 to 30 carbon atoms which may have a substituent.

Among them, the aromatic heterocyclic ring of the ring T ¹ is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably a 5-membered aromatic heterocyclic ring containing a nitrogen atom.

The ring T ^{1 is} preferably a ring represented by the formula (t1).

[In the formula (t1), R ⁵⁶ 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.

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 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number 7 which may have a substituent When the carbon number of the saturated hydrocarbon group is from 2 to 20, the -CH ₂ - contained in the saturated hydrocarbon group may be replaced with at least one of -O- and -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not simultaneously substituted with -O-, and the terminal -CH ₂ - is not replaced with -O- or -CO-. R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which R ⁴⁵ and R ⁴⁶ are bonded.

* indicates the bonding end with a carbocation. ]

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

[In the formula (t2), the 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 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent.

K2 represents 0 or 1.

* indicates the bonding end with a carbocation. ]

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

[In the 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 the 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 the ring T ¹ may have a linear chain Any of a shape, a branched chain, and a ring shape. The linear or branched chain saturated hydrocarbon group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a dodecyl group or a hexadecyl group. a linear alkyl group such as an alkyl group or an eicosyl group; or a branched chain alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group or a 2-ethylhexyl group. The saturated hydrocarbon group preferably has a carbon number of from 1 to 10, more preferably from 1 to 8, still more preferably from 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 have a single ring or a polycyclic ring. Examples of the cyclic saturated hydrocarbon group include an alicyclic saturated hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or an adamantyl group. The cyclic saturated hydrocarbon group preferably has a carbon number of from 3 to 10, more preferably from 6 to 10.

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 the ring T ¹ may have may, for example, be a methyl group, an ethyl group, an isopropyl group or a propyl group. 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 saturated hydrocarbon group which the amine group which the ring T ¹ may have may have a substituted or unsubstituted amino group or a halogen atom as a substituent. Examples of the substituted amino group include an alkylamino group such as a dimethylamino group or a diethylamino group. Further, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Further, 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.

The alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ is a group having 1 to 8 carbon atoms among the linear or branched chain saturated hydrocarbon groups exemplified as the saturated hydrocarbon group represented by R ⁴¹ . .

In addition, as the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ , a group having 1 to 10 carbon atoms among the linear or branched chain saturated hydrocarbon groups exemplified as the saturated hydrocarbon group represented by R ⁴¹ is exemplified. .

When the carbon number of the saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ is from 2 to 20, -CH ₂ - contained in the saturated hydrocarbon group may be replaced with at least one of -O- and -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not simultaneously substituted with -O-, 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 chain saturated hydrocarbon group (i.e., a linear or branched chain alkyl group), more preferably a linear saturated hydrocarbon group (i.e., a linear alkane). base). The preferred carbon number of the -CH ₂ -saturated hydrocarbon group which may be replaced by at least one of -O- and -CO- is from 2 to 10, more preferably from 2 to 8. Further, when -CH ₂ - is replaced with at least one of -O- and -CO-, the terminal is between -O- or -CO-, or -O- or -CO- and -O- or -CO The carbon number between - is 1 or more, preferably 1 to 5, more preferably 2 to 3, still more preferably 2.

Further, 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 ring T ¹ may have may have an aromatic hydrocarbon group (wherein the aromatic hydrocarbon group may be The carbon number having a substituent.) is preferably from 6 to 20, more preferably from 6 to 15, still more preferably from 6 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthranyl 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 xylyl group are preferred. Particularly preferred is phenyl. Further, 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 or a bromine atom; a halogenated alkyl group having 1 to 6 carbon atoms such as a chloromethyl group or a trifluoromethyl group; and a carbon number such as a methoxy group or an ethoxy group; Alkoxy group to 6; hydroxy group; amsulfoxonyl group; alkylsulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl group; alkoxy group having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group Alkylcarbonyl; -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 preferred 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, preferably substituted for hydrogen bonded to the aromatic hydrocarbon ring atom.

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

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 the ring T ¹ may have (wherein the aralkyl group may have a substituent), An alkylene group having a carbon number of 1 to 10 (preferably having 1 to 5 carbon atoms) such as a methylene group, an ethylene group or a propylene group bonded to a group described as the above aromatic hydrocarbon group, or the like. The aralkyl group preferably has a carbon number of 7 to 30, more preferably 7 to 20, still more preferably 7 to 17 carbon atoms.

R ⁴¹ and R ⁴² are bonded to form together with the nitrogen atom of the R ⁴¹ and R ⁴² are bonded a ring, R ⁴³ and formed with R ⁴⁴ bonded together with the R nitrogen atom R ⁴⁴ are bonded ⁴³ ring, and R ⁴⁵ and R ⁴⁶ are bonded and the ring formed by R ⁴⁵ R ⁴⁶ together with the nitrogen atom are bonded, include a pyrrolidine ring, a morpholine ring, a nitrogen-containing non piperidine ring, a piperazine ring or the like The aromatic 4 to 7 membered ring is preferably a 4- to 7-membered ring having only one nitrogen atom as a hetero atom such as a pyrrolidine ring or an acridine 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.

Wherein R ⁴¹ to R ⁴⁴ , R ⁵⁶ and R ⁵⁸ to R ^{60 are} preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent, more preferably each independently having a carbon number of 1 to 8. A saturated hydrocarbon group or a group represented by the following formula. Further, R ⁵⁶ and R ⁵⁸ to R ^{60 are} more preferably a group represented by the following formula. In the following formula, * represents a bond terminal with a nitrogen atom.

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

In addition, the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ may be a linear or branched chain saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ^{41 and} having 1 to 8 carbon atoms. Group. Further, a group in which -CH ₂ - of the alkyl group having 2 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ is substituted with at least one of -O- and -CO- (only, the alkane In the base, the adjacent -CH ₂ - will not be replaced by -O- at the same time, and the -CH ₂ - at the end will not be replaced by -O- or -CO-), and the composition may be exemplified by R ⁴¹ to R ⁴⁶ described above. The group in which the -CH ₂ - of the alkyl group having 2 to 20 carbon atoms is replaced by at least one of -O- and -CO- has a carbon number of 8 or less.

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

Further, R ^{57 is} preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

R ^{61 is} preferably a hydrogen atom.

Examples of the metal ion of the r-valent metal ion represented by Mr ⁺ include alkali metal ions such as lithium ions, sodium ions, and potassium ions; alkaline earth metal ions such as barium ions, magnesium ions, calcium ions, barium ions, and barium ions; titanium ions, Transition metal ions such as zirconium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, and copper ions; typical metal ions such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, and cesium ions . r is 1 or more, preferably 2 or more, preferably 5 or less, more preferably 4 or less, still more preferably 3 or less. Further, examples of the substituted or unsubstituted ammonium ion represented by Mr ⁺ include a quaternary ammonium ion such as a tetraalkylammonium ion.

M ^{r+ is} preferably a hydrogen ion or a r-valent metal ion, more preferably an alkaline earth metal ion, a typical metal ion, etc., and further preferably an alkaline earth metal ion, a zinc ion, and further preferably an alkaline earth metal ion.

In the formula (I), the number of Mr ⁺ becomes the number of -SO ₃ ^- which is derived from R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and the ring T ¹ and -SO ₂ -N ^- -SO ₂ -R ^f The sum of the numbers (k) is one less. Therefore, the valence of the compound (I) is 0, that is, it becomes an electrically neutral compound.

The fluoroalkyl group having 1 to 12 carbon atoms represented by R ^f may, for example, be a monofluoromethyl group, a difluoromethyl group, a perfluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group or a tetrafluoro group. Ethyl, perfluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, perfluoropropyl, monofluorobutyl, difluoro Butyl, trifluorobutyl, tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl, perfluorobutyl and the like. Among them, a fluoroalkyl group represented by R ^f is preferably a perfluoroalkyl group. Further, the fluoroalkyl group represented by R ^f preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms.

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

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

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

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

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

(Id) with an aromatic hydrocarbon group substituted with a hydrogen atom of the aromatic heterocyclic ring represented by ¹ T 6 to 20 carbon atoms bonded either

Wherein -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f is bonded to an aromatic hydrocarbon group or an aralkyl group, preferably -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^{f is} directly bonded to an aromatic hydrocarbon ring of an aromatic hydrocarbon group or an aralkyl group. That is, it is preferred that -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f be substituted with a hydrogen atom bonded to an aromatic hydrocarbon ring.

Preferably Department -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f in R ⁴¹ to R ⁴⁴ represents a substituent group may have a carbon number of 6 to 20 aromatic hydrocarbon group, or R ⁴¹ to R ⁴⁴ represents a 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 bonding position to the nitrogen atom in the para position.

In the case where the compound (I) contains a plurality of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , a plurality of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f may be used. Bonded to the same aromatic hydrocarbon ring, but preferably bonded to a different aromatic hydrocarbon ring.

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} the number of -SO ₂ -N ^- -SO ₂ -R ^f of 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 , M ^r+ , r, R ^{f are} synonymous with the 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 . ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁸¹ to R ⁹⁰ is the same as the group 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 , 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 satisfy at least one or more conditions selected from the group consisting of (Ie) to (Ig), and more preferably satisfy the selection from (If) and ( The condition of at least one or more of Ig) is more preferably the condition of (If).

(Ie) contains either R ⁴⁷ to R ⁵⁴

(If) contains either R ⁸¹ to R ⁹⁰

(Ig) bonded to an aromatic hydrocarbon group having 6 to 20 carbon atoms substituted with a hydrogen atom of an aromatic heterocyclic ring represented by T ¹

-SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^{f is} further more preferably a condition satisfying (If').

(If') contains either R ⁸⁶ and R ⁸⁹

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

The compound (I-I) is as shown in Tables 1 to 16, and examples thereof include a compound represented by the formula (I-I-1) to the formula (I-I-1080).

In Tables 1 to 16, Me represents a methyl group, Et represents an ethyl group, Pr represents a n-propyl group, Bt represents an n-butyl group, and Ph1 to Ph19 means a group represented by the following formula. Where * is the bond end.

The compound (I) is preferably a compound represented by the formula (II-136) to the formula (II-270) and the formula (II-676) to the formula (II-810), more preferably from the formula (II-136). 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 a compound represented by the formula (II-222), the formula (II-235) to the formula (II-237), and the formula (II-250) to the formula (II-252), particularly preferably a formula (II) II-136) to a compound represented by the formula (II-156).

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 or the like.

[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 number which may have a substituent The aralkyl group of 7 to 30, in the saturated hydrocarbon group having 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, and the saturated hydrocarbon group is contained -CH ₂ - may be replaced with at least one of -O- and -CO-. R ¹ and R ² may be bonded and form a ring together with the nitrogen atom to which R ¹ and R ² are bonded, and R ³ and R ⁴ may be bonded and formed together with the nitrogen atom to which R ³ and R ⁴ are bonded. ring.

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 them. 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 ^- , a phosphate ion, a perchlorate ion, BF ₄ ^- , 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 the formula (IB), R ^f is synonymous with the above. ]

Further, when the compound (I) is a compound of the formula (I) in which M ^r+ is a hydrogen ion (hereinafter sometimes referred to as a compound (IA-2)), the compound (IA-2) and the metal ion having an r-valent value can be obtained. The reaction of a halide (preferably chloride), acetate, phosphate, sulfate, citrate or cyanide.

The method of sulfonation can be exemplified by various known methods, for example, the method described in Journal of Organic Chemistry, (1994), Vol. 59, No. 11, pp. 3232-3236.

Further, the triarylmethane compound having a hetero ring is preferably a compound represented by the formula (II) (hereinafter sometimes referred to as "compound (II)").

[In the formula (II), [Y ² ] ^n- represents an arbitrary n-valent anion.

R ^b41 to R ^b44 each independently represent a hydrogen atom, saturated hydrocarbon group may have a substituent group having a carbon number 1 to 20, an oxygen atom inserted between carbon constituting the alkyl group having a carbon number of 2 to 20 group atoms, may have An aromatic hydrocarbon group of a substituent or an aralkyl group which may have a substituent. Forming R ^b41 and R ^b42 may be bonded with the R ^b41 and R ^b42 are bonded to the nitrogen atom together form a ring, R ^b43 and R ^b44 may be bonded to form together with the R ^b43 and R ^b44 are bonded to the nitrogen atom ring.

R ^b45 to R ^b52 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a group having an oxygen atom interposed between carbon atoms constituting an alkyl group having 2 to 8 carbon atoms. Or R ^b46 and R ^b50 may be bonded to each other to form -O-, -NH-, -S- or -SO ₂ -.

Y ¹ represents an aromatic heterocyclic group which may have a substituent.

When the compound represented by the formula (II) contains a plurality of cations, the plurality of cations may have the same structure or different structures.

n represents an arbitrary natural number. ]

[Y ² ] ^n- represents an arbitrary n-valent anion. The anion represented by Y ² is not particularly limited as long as it is an anion capable of forming a counter ion with a cation, and is preferably a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, a halogen atom having a chlorine atom, and a tungsten atom. At least one element of molybdenum, rhenium and phosphorus and an anion of an oxygen atom.

Examples of the boron-containing anion and the aluminum-containing anion include an anion represented by the formula (4).

In the formula (4), W ¹ and W ² each independently represent a group having two monovalent proton-donating substituents. M represents boron or aluminum. ]

The group having two monovalent proton-donating substituents may be a group obtained by releasing a proton from a compound having at least two monovalent proton-donating substituents (for example, a hydroxyl group or a carboxyl group). The compound is preferably a catechol which may have a substituent, a 2,3-dihydroxynaphthalene which may have a substituent, a 2,2'-biphenol which may have a substituent, a 3-hydroxy-2 which may have a substituent -naphthoic acid, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, a binaphthol which may have a substituent, a salicylic acid which may have a substituent, Diphenyl glycolic acid which may have a substituent or mandelic acid which may have a substituent.

In each of the compounds exemplified as the compound having at least two monovalent proton-donating substituents, the substituent may, for example, be a saturated hydrocarbon group (for example, an alkyl group or a cycloalkyl group), a halogen atom, a hydroxyl group, an amine group or a nitrate. Base, alkoxy group, and the like.

Examples of the salicylic acid which may have a substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, and 4 -trifluoromethylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-amino group Monoamine salicylic acid such as salicylic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5-hydroxysalicylide Monohydroxysalicylic acid such as acid (2,5-dihydroxybenzoic acid) or 6-hydroxysalicylic acid (2,6-dihydroxybenzoic acid); 4,5-dihydroxysalicylic acid, 4,6-di Dihydroxysalicylic acid such as hydroxysalicylic acid; 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromine water Monohalogenated salicylic acid such as salicylic acid, 5-bromoslic acid, 6-bromosalicylic acid; 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, 3,5-diiodide Dihaloperylic acid such as salicylic acid; trihaloperic acid such as 3,5,6-trichlorosalicylic acid or the like.

Diphenyl glycolic acid which may have a substituent can be exemplified

The mandelic acid which may have a substituent can be exemplified by:

Wait.

Examples of the fluorine-containing anion include groups represented by the formulae (6), (7), (8), and (9).

[In the formula (6), W ³ and W ⁴ each independently represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms, or W ³ together with W ⁴ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms. ]

In the formula (7), W ⁵ to W ⁷ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. ]

[In the formula (8), Y ^a represents a fluorinated alkanediyl group having 1 to 4 carbon atoms. ]

[In the formula (9), Y ^b represents a fluorinated alkyl group having 1 to 4 carbon atoms. ]

In the formulae (6), (7) and (9), a fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , and -CF ₂ CF (CF). ₃ ) ₂ , -C(CF ₃ ) ₃ and the like.

In the formulae (6) and (8), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, and examples thereof include -CF ₂ -, -CF ₂ CF ₂ -, and -CF _{2 .} CF ₂ CF ₂ -, -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, and the like.

An anion represented by the formula (6) (hereinafter sometimes referred to as "anion (6)")) may be an anion represented by the formula (6-1) to the formula (6-6) (hereinafter sometimes referred to as "" Anion (6-1) "to" anion (6-6)").

Examples of the anion having at least one element selected from the group consisting of tungsten, molybdenum, niobium and phosphorus and an oxygen atom include a polypolyacid anion having the element, and a polyacid such as an allopolyacid anion having the element. Anion.

Examples of the anion of isopoly acid or homopoly acid containing tungsten as an essential element include, for example, Keggin-type phosphotungstic acid ion α-[PW ₁₂ O ₄₀ ] ^3- , Dawson-type phosphotungstic acid ion α-[P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin-type lanthanum tungstate ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- Further, as another example, [P ₂ W ₁₇ O ₆₁ ] ¹⁰ , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and mixtures of these examples. The anion of the isopoly acid or the homopoly acid containing tungsten as an essential element is preferably an anion of phosphotungstic acid, lanthanum tungstic acid, and tungsten-based homopoly acid.

Further, it is preferable to further contain at least one element selected from the group consisting of ruthenium and phosphorus and an anion of oxygen, and examples of the anion include SiO ₃ ^2- and PO ₄ ^3- .

[Y ² ] ^{n- is} preferably a fluorine-containing anion or a polyacid anion, more preferably an anion represented by the formula (6), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [ SiW ₁₂ O ₄₀ ] ^4- or [W ₁₀ O ₃₂ ] ^4- , further more preferably an anion represented by the formula (6-1) to the formula (6-5), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^{6- is} particularly preferably an anion represented by the formula (6-2), [PW ₁₂ O ₄₀ ] ^3- .

n represents an arbitrary natural number equal to the negative charge of the anion [Y ² ] ^n- . The n-system on the cation side is determined in such a manner that the anion [Y ² ] ^n- is equal to the charge of the cation. n is preferably a natural number of 1 to 10.

Carbon atoms represented by R ^b41 to R ^b44 is a saturated hydrocarbon group of 1 to 20 may be either a linear, branched, or cyclic. Further, the saturated hydrocarbon group is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, still more preferably a carbon number of 1 to 6, particularly preferably a carbon number of 1 to 4.

Examples of the linear or branched saturated hydrocarbon group include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group or a fluorenyl group; A branched chain alkyl group such as a benzyl group, an isobutyl group or a 2-ethylhexyl group. The carbon number of the linear or branched chain saturated hydrocarbon is preferably from 1 to 8, more preferably from 1 to 6, still more preferably from 1 to 4.

Further, the above cyclic saturated hydrocarbon group may be a single ring or a polycyclic ring. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like. The carbon number of the cyclic saturated hydrocarbon group is preferably from 3 to 10, more preferably from 6 to 10.

A hydrogen atom saturated hydrocarbon group R ^b41 to R ^b44 may be substituted. The substituent may, for example, be a substituted or unsubstituted amino group or a halogen atom. The substituted amino group may, for example, be a dialkylamino group such as a dimethylamino group, and the halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

A group represented by R ^b41 to R ^b44, the group interrupted by oxygen atoms between alkylene group formed of 2 to 20 carbon atoms constituting methyl group (carbon atoms) includes, for example by the following formula Group. In the following formula, * represents a bond terminal with a nitrogen atom. Among them, a group in which an oxygen atom is interposed between methylene groups constituting the alkyl group is preferably a group having 2 to 10 carbon atoms, more preferably a group having 2 to 6 carbon atoms. The alkyl group to which the oxygen atom is inserted is preferably a linear alkyl group. Further, the number of carbon atoms between oxygen atoms is preferably from 1 to 4, more preferably from 2 to 3.

R ^b41 to R ^b44, the aromatic hydrocarbon group is preferably a carbon number of 6 to 20, more preferably 6 to 10, aralkyl group having a carbon number is preferably 7-20, more preferably 7-10 carbon atoms.

Further, R ^b41 to R ^b44 aromatic hydrocarbon group include a phenyl, naphthyl, tolyl and the like.

Aromatic hydrocarbon aralkyl R ^b41 to R ^b44 in include a phenyl group, a naphthyl group, an aralkyl group include a group bonded to the end of the alkylene aromatic hydrocarbon group formed by bonding . The above alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is preferably a linear alkylene group. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, and a naphthyl group. Ethyl and the like.

A group represented by R ^b41 to R ^b44, the aromatic hydrocarbon group and aralkyl, the substituent include a halogen atom such as fluorine atom, chlorine atom, an iodine atom; a methoxy group, an ethoxy carbon atoms An alkoxy group of 6 to 6; a hydroxy group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; an alkoxycarbonyl group having 2 to 6 carbon atoms such as a methoxycarbonyl group or an ethoxycarbonyl group; and the like.

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

The aralkyl group which may have a substituent may, for example, be a group in which an alkylene group such as a methylene group or an ethylene group is bonded to a bond terminal of the above aromatic hydrocarbon group.

R ^b41 and R ^b42 are bonded and the nitrogen atom R ^b42 are bonded form together with the R ^b41 ring, and R ^b43 and R ^b44 bond and the R ^b43 formed together with the nitrogen atom R ^b44 are bonded Examples of the ring include a 5-membered ring such as a pyrrolidine ring; a 6-membered ring such as a morpholine ring, an acridine ring or a pyridazine ring.

A saturated hydrocarbon group having 1 to R ^b41 each R ^b44 independently is preferred system may have a substituent group to 20, an aromatic hydrocarbon group may have a substituent group or aralkyl group may have a substituent group, more preferably independently based It is a saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group which may have a substituent represented by the following formula. In the following formula, * represents a bond terminal with a nitrogen atom.

The saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ^b45 to R ^b52 may be any of a linear chain, a branched chain and a cyclic group, and is preferably a linear chain or a branched chain. R ^b45 to R ^b52 saturated hydrocarbon group having a carbon number of 1 to 8, a saturated hydrocarbon group include R ^b41 to R ^b44 Examples of saturated hydrocarbon radicals shown in 1 to 8 carbon atoms. A group in which an oxygen atom is interposed between methylene groups (carbon atoms) constituting the alkyl group is more preferably an alkyl group having 2 to 8 carbon atoms. The alkyl group to which the oxygen atom is inserted is preferably a linear alkyl group, and the number of carbon atoms between the oxygen atoms is preferably from 1 to 4, more preferably from 2 to 3.

R ^b45 to R ^b52 are each independently a hydrogen atom, a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably each independently a hydrogen atom, a methyl group or a fluorine atom, in terms of ease of synthesis. Or chlorine atoms.

R ^b46 and R ^b50 may be bonded to each other to form -O-, -NH-, -S- or -SO ₂ -.

Y ¹ represents an aromatic heterocyclic group which may have a substituent.

The above aromatic heterocyclic ring may be any of a monocyclic ring and a condensed ring, preferably a 5- to 10-membered ring, more preferably a 5- to 9-membered ring.

Examples of the monocyclic aromatic heterocyclic ring include a 5-membered ring having a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; and a 5-membered member having an oxygen atom or a sulfur atom such as a furan ring or a thiophene ring. Ring; a 6-membered ring having a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring. The aromatic heterocyclic ring of the condensed ring may, for example, be a condensed ring having a nitrogen atom such as an anthracene ring, a benzimidazole ring, a benzothiazole ring or a quinoline ring, or a ring having an oxygen atom or a sulfur atom such as a benzofuran ring.

The compound (II) is more preferably a compound represented by the formula (II-1).

[In the formula (II-1), [Y ² ] ^n- , R ^b41 to R ^b52 and n are the same as described above.

R ^b53 and R ^b54 each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a group having an oxygen atom interposed between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms, and may have An aromatic hydrocarbon group of a substituent or an aralkyl group which may have a substituent.

R ^b55 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent.

X1 represents an oxygen atom, -NR ^b57 - or a sulfur atom.

R ^b57 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

When the compound represented by the formula (II-1) contains a plurality of cations, the plurality of cations may have the same structure or may have a different structure. ]

R ^b53, R ^b54 and R ^b57 include a group similar to the group R ^b44 and R ^b41 exemplified.

Carbon atoms, saturated hydrocarbon group represented by R ^b55 1 to 20, include the same groups and a saturated hydrocarbon group examples of R ^b41 to R ^b44 illustrated. Among them, preferred is an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms. .

Interrupted by oxygen atoms between carbon atoms constituting the alkyl group represented by R ^b55, include a group similar to the group R ^b44 and R ^b41 exemplified. The alkyl group to which the oxygen atom is inserted is preferably a linear alkyl group. Further, the number of carbon atoms between oxygen atoms is preferably from 1 to 4, more preferably from 2 to 3.

In R ^b55 , the aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.

Further, R ^b55 aromatic hydrocarbon group include the same groups as R ^b44 and R ^b41 to exemplified, preferably a phenyl group.

Examples of the substituent of the aromatic hydrocarbon group of R ^b55 include a halogen atom such as a fluorine atom, a chlorine atom or an iodine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a hydroxyl group; and an amsulfoxon group; An alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; an alkoxycarbonyl group having 2 to 6 carbon atoms such as a methoxycarbonyl group or an ethoxycarbonyl group; and the like.

R ^{b55 is} preferably a saturated hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group which may have a substituent, more preferably an alkyl group having 1 to 8 carbon atoms, or an alkoxy group which may be a halogen atom or a carbon number of 1 to 4. The aromatic hydrocarbon group substituted with a hydroxy group or a methylsulfonyl group is more preferably a group represented by the following formula. In the following formula, * represents a bond terminal with a carbon atom.

X1 represents an oxygen atom, -NR ^b57 - or a sulfur atom. The cyclic structure containing X1 may, for example, be a group represented by the following formula. ^Wherein R ^b53 to R ^b55 are each synonymous with the above, and * represents a bonding end with a carbocation. Among them, X1 is preferably an oxygen atom or a sulfur atom, and particularly preferably a sulfur atom.

Examples of the cationic moiety of the formula (II) include the cation 1 to the cation 27 represented by the formula (II-I-1) shown in the following table.

Among them, preferred are cation 1 to cation 6, cation 11 or cation 12, and particularly preferably cation 1, cation 2 or cation 12.

In Table 17, Ph1 to Ph12 refer to a group represented by the following formula.

The coloring composition may contain only one type of compound (II) or two or more types. The compound (II) is preferably a dye which is soluble in an organic solvent.

In the coloring composition of the present invention, the content of the triarylmethane compound having a hetero ring is preferably from 1 to 100% by mass, more preferably from 20% by weight based on the total amount of the coloring agent contained in the coloring composition. 100% by mass, still more preferably 50 to 100% by mass.

The coloring composition of the present invention may contain a dye (A1) and a pigment (A2) in addition to a heterocyclic triarylmethane compound.

The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mord dyes. Examples of the dye include a compound classified as a substance having a color tone other than a pigment in a color index (published by The Society of Dyers and Colourists), and a known dye described in a dyeing note (color dyeing company). Further, according to the chemical structure, examples thereof include an azo dye, a cyanine dye, a triphenylmethane dye, a xanthene dye, a phthalocyanine dye, an anthraquinone dye, a naphthoquinone dye, a quinone imine dye, a methine dye, and an azo group. Anthraquinone dyes, squaric acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, an organic solvent-soluble dye is preferred.

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

These dyes can be appropriately selected depending on the spectroscopic spectrum of the desired 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. Others are the same), 52, 87, 92, 94, 289, 388, CI acid violet 9, 30, 102, CI alkaline red 1 (Rhodamine 6G), 2, 3, 4, 8, CI alkaline red 10, 11, CI alkaline purple 10 (Rhodamine B), 11, CI solvent red 218 , X-ray dyed red 27, CI active red 36 (Rose red B), sulfo-Rhodamine G, and the xanthene dyes described in Japanese Patent Laid-Open Publication No. 2010-32999, and the xanthene dyes described in Japanese Patent No. 4492760 Wait. A xanthene dye dissolved in an organic solvent is preferred.

Among these, the xanthene dye (Aa) is preferably a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as "compound (1a)"). Compound (1a) may be a tautomer thereof. When the compound (1a) is used, 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 still more preferably 90% by mass or more. In particular, it is preferred to use only the compound (1a) for the xanthene dye (Aa).

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

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 ⁺ , and 4 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 by a halogen atom.

R ^a9 and R ^a10 independently of each other represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated aliphatic hydrocarbon group may be -O-, -CO -, -NH- or -NR ^a8 - is substituted, and R ^a9 and R ^a10 may be bonded to each other to form a heterocyclic ring of a 3 to 10 membered 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 the case of -SO ₃ ^- in the formula (1a), the number thereof is one.

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

Examples of the substituent which the aromatic hydrocarbon group may have 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, the substituent is preferably -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ^a9 R ^a10 , more preferably -SO ₃ ^- Z ⁺ and -SO ₂ NR ^a9 R ^a10 . The -SO ₃ ^- Z ^{+ in} this case is preferably -SO ₃ ^-+ N(R ^a11 ) ₄ . When R ^a1 to R ^a4 are these groups, the colored curable resin composition of the present invention containing the compound (1a) can form a color filter which is less likely to generate foreign matter and is excellent in heat resistance.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^a1 to R ^a4 and R ^a8 to R ^a11 may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or a octyl group. a linear alkyl group such as a thiol group, a decyl group, a decyl group, a dodecyl group, a hexadecyl group or an eicosyl group; an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group; A branched chain alkyl group; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

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 with the ring formed by R ^a3 and R ^a4 include the following rings. Where * is the bond end.

Examples of -OR ^a8 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an eicosane. Oxyl and the like.

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

Examples of the -SR ^a8 include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a mercaptosulfanyl group, and an eicosylsulfanyl group.

Examples of the -SO ₂ R ^a8 include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a nonylsulfonyl group, and an eicosylsulfonyl group.

Examples of the -SO ₃ R ^a8 include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an eicosyloxy group. Sulfonyl and the like.

Examples of -SO ₂ NR ^a9 R ^a10 include asulfonyl group; N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfonate Sulfhydryl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfonyl, N-tert-butylsulfonyl, N-pentylsulfonamide , N-(1-ethylpropyl) amisulphol, N-(1,1-dimethylpropyl)sulfamoyl, N-(1,2-dimethylpropyl)sulfazone Base, N-(2,2-dimethylpropyl)sulfamoyl, N-(1-methylbutyl)sulfamoyl, N-(2-methylbutyl)sulfamoyl, N-(3-methylbutyl)ammonsulfonyl, N-cyclopentylsulfamoyl, N-hexylsulfonyl, N-(1,3-dimethylbutyl)sulfamoyl , N-(3,3-dimethylbutyl)sulfamoyl, N-heptylsulfamoyl, N-(1-methylhexyl)sulfamoyl, N-(1,4-di Methyl amyl) sulfonamide, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(1,5-dimethyl)hexylsulfamoyl, N-substituted sulfonamide such as N-(1,1,2,2-tetramethylbutyl)sulfamoyl; N,N-dimethylsulfamoyl, N,N-ethyl A Sulfasulfonyl, N,N-diethylammoniumsulfonyl, N,N-propylmethylammonium Sulfhydryl, N,N-isopropylmethylsulfamoyl, N,N-tert-butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-double (1 N,N-2, such as a methylpropyl)sulfamidyl group or an N,N-heptylmethylsulfamoyl group, is substituted with an amsulfoxyl group.

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 from 1 to 4, more preferably 1 or 2.

The alkyl group having 1 to 6 carbon atoms in R ^a6 and R ^a7 may, for example, be an alkyl group having 1 to 6 carbon atoms in the above-exemplified alkyl group.

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

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

The above ⁺ N(R ^a11 ) _{4 is} preferably such that at least two of the four R ^a11 are a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ^a11 is preferably from 20 to 80, more preferably from 20 to 60. When ⁺ N(R ^a11 ) ₄ is present in the compound (1a), if R ^a11 is such a group, the color-developing resin composition of the present invention containing the compound (1a) can form a color filter having less foreign matter. Device.

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

[In the 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. By atom substitution, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ - contained in the above 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 together form a ring containing a nitrogen atom, and R ^a32 and R ^a34 may together form a ring containing a nitrogen atom.

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

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

The monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ^a31 and R ^a32 may, for example, be a group having 1 to 10 carbon atoms in the saturated hydrocarbon group in R ^a8 .

The aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent may be the same 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, a propoxy group and the like.

R ^a31 and R ^{a32 are} preferably 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 a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

The alkylsulfanyl group having 1 to 4 carbon atoms in R ^a33 and R ^a34 may, for example, be a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group or an isopropyl sulfide. Alkyl and the like.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ^a33 and R ^a34 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.醯基等.

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

p and q are preferably an integer of 0 to 2, more preferably 0 or 1.

The compound (1a) is, for example, a compound represented by the formula (1-1) to the formula (1-43). Further, in the formula, R ^a40 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, more preferably 2-ethylhexyl group.

The compound (1a) is preferably a compound represented by the formula (1-24) to the formula (1-36), more preferably a compound represented by the formula (1-29) to the formula (1-32).

For the xanthene dye (Aa), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Sino-foreign Chemical Co., Ltd., "Rhodamin 6G" manufactured by Tajika Chemical Industry Co., Ltd.) can be used. In addition, the commercially available xanthene dye can be used as a starting material, and the synthesis can be carried out by referring to JP-A-2010-32999.

The pigment (A2) is not particularly limited, and a known pigment can be used. For example, a pigment classified as a pigment in the excellent index (published by The Society of Dyers and Colourists) can be cited.

Examples of the pigment include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128. Yellow pigments such as 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, Orange pigments such as 61, 64, 65, 71, 73; 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 purple 1, 19, 23, 29, 32, 36 , purple pigment such as 38; green pigment such as CI pigment green 7, 36, 58; brown pigment such as CI pigment brown 23, 25; black pigment such as CI pigment black 1, 7.

The pigments are preferably cyan pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments, more preferably CI Pigment blue 15:3, 15:6 and CI Pigment Violet 23, further preferably CI Pigment Blue 15:6. By including the above-described pigment, it is easy to optimize the penetration spectrum, and the light resistance and chemical resistance of the color filter are improved.

The pigment may be subjected to a rosin treatment, a surface treatment such as a pigment derivative in which an acidic group or a basic group is introduced, a graft treatment on a surface of a pigment such as a polymer compound, or a particle using a sulfuric acid micronization method. The treatment or the washing treatment of an organic solvent for removing impurities, water, or the like, and the removal treatment of an ionic impurity by an ion exchange method or the like are used.

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 in which the pigment is uniformly dispersed in a solution can be obtained.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used singly or in combination of two or more. For the trade name of the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoei Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA), and Adisper ( Ajinomoto Fine Techno (manufactured by Fine Chemicals Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), and the like.

When the pigment dispersant is used, the 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 based on 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 can be obtained.

The content ratio of the dye (A1) to the pigment (A2) (dye (A1) / pigment (A2)) is preferably from 1/99 to 99/1, more preferably from 5/95 to 50/50, on a mass basis. Further preferably, it is from 10/90 to 20/80.

In the colored composition of the present invention, the content of the colorant is preferably from 9 to 99% by mass, more preferably from 20 to 90% by mass, still more preferably from 40 to 80% by mass based on the total amount of the solid content of the coloring composition. %. When the content of the coloring agent (A) is within the above range, the color density when the color filter is formed is sufficient, and the necessary amount of the resin or the polymerizable compound can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed. .

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

 <dispersant>  

The coloring composition contains a dispersing agent having an amine value of 70 mgKOH/g or less. By providing a dispersing agent having an amine value of 70 mgKOH/g or less, a coloring composition capable of forming a high-intensity color filter is provided. The amine value of the dispersing agent is preferably 65 mgKOH/g or less, more preferably 60 mgKOH/g or less, further preferably 55 mgKOH/g or less, preferably 0 mgKOH/g or more, more preferably 5 mgKOH/g or more, further Preferably it is 10 mgKOH/g or more.

The amine value [mgKOH/g] represents the total amount of the primary amine (RNH ₂ ), the secondary amine (R ₂ NH), the tertiary amine (RN(CH ₃ ) ₂ , R ₂ NCH ₃ , R ₃ N), "The number of mg of potassium hydroxide of the hydrochloric acid equivalent required to neutralize all the amines in 1 g of fats and oils" is defined. The amine value was measured by dissolving the sample in neutral ethanol (tetrahydrofuran, acetone, etc.), using bromophenol blue and crystal violet as an indicator, neutralizing titration with an ethanolic hydrochloric acid solution (or perchloric acid), or measuring the potential difference.

The dispersing agent having an amine value of 70 mgKOH/g or less may, for example, be DISPERBYK-161 (amine value: 11 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-162 (amine value: 13 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-163 (amine value: 10 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-164 (amine value: 18 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-166 (amine value: 20 mgKOH/g, BYK Chemical Made by the company), DISPERBYK-167 (amine value: 13 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-182 (amine value: 13 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-184 (amine value: 15 mgKOH/g) , manufactured by BYK Chemical Co., Ltd., DISPERBYK-185 (amine value: 17 mg KOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-2000 (amine value: 4 mg KOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-2001 (amine value) : 29 mg KOH / g, manufactured by BYK Chemical Co., Ltd., DISPERBYK-2008 (amine value: 66 mg KOH / g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-2009 (amine value: 4 mg KOH / g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK- 2022 (amine value: 61 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-2050 (amine value: 30 mgKOH/g, manufactured by BYK Chemical Co., Ltd.) DISPERBYK-2055 (amine value: 40 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-2061 (amine value: 3 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-2150 (amine value: 57 mg KOH/g, BYK Chemical Made by the company), DISPERBYK-2155 (amine value: 48 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-2163 (amine value: 10 mgKOH/g, manufactured by BYK Chemical Co., Ltd.), DISPERBYK-2164 (amine value: 14 mgKOH/g) , manufactured by BYK Chemical Co., Ltd., BYK-9077 (amine value: 48 mg KOH/g, manufactured by BYK Chemical Co., Ltd.), BYKLPN-21116 (amine value: 29 mg KOH/g, manufactured by BYK Chemical Co., Ltd.), BYKLPN-21324 (amine value) : 0 mg KOH / g, manufactured by BYK Chemical Co., Ltd., and the like.

The amount of the dispersant is from 1 to 1000 parts by mass, preferably from 3 to 100 parts by mass, more preferably from 5 to 50 parts by mass, particularly preferably from 10 to 30 parts by mass per 100 parts by mass of the triarylmethane compound having a heterocyclic ring. Parts by mass.

 <solvent>  

The solvent can be used as long as it can use a solvent (E) which is a coloring curable resin composition. In order to disperse the triarylmethane compound having a hetero ring, a particularly preferred solvent is, for example, an ether ester solvent, more preferably an ether of an alkylene glycol or a polyalkylene glycol, and esterification of the remaining hydroxyl group. Examples of the solvent to be formed include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol. Monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like. These solvents may be contained alone or in combination.

The amount of the solvent is, for example, 1 to 50 parts by mass, preferably 2 to 30 parts by mass, more preferably 3 to 10 parts by mass, per part by mass of the triarylmethane compound having a hetero ring.

In addition, when the dye (A1) is contained in the colored curable resin composition to be described later, the colored composition may contain a part or all of the dye (A1) in advance, and it is preferred to contain all of the dye (A1) in advance. Further, the coloring composition may contain a part or all of the pigment (B2) in advance, and it is preferable to contain all of them in advance.

The coloring composition may contain a part or all of the resin (B) used in the coloring curable resin composition in advance, and it is preferable to contain a part in advance. By containing a resin in advance, the dispersibility in the case of forming a colored curable resin composition can be further improved. The content of the resin in the coloring composition is, for example, 1 to 300 parts by mass, preferably 10 to 100 parts by mass, more preferably 20 to 70 parts by mass, per 100 parts by mass of the triarylmethane compound having a hetero ring.

In the preparation of the dispersion, it is preferred to carry out fine dispersion using a dispersing device after appropriately adding the necessary components. The dispersing device can use a bead mill device. The beads to be used are generally hard beads such as zirconia beads, and the particle diameter thereof is, for example, selected from the range of 0.05 mm or more and 20 mm or less, preferably 0.1 to 10 mm, more preferably 0.1 to 0.5 mm.

Further, the coloring composition is preferably basically composed of a triarylmethane compound having a hetero ring, a dispersing agent having an amine value of 70 mgKOH/g or less, and a solvent, and a triaryl group having a heterocyclic ring in 100% by mass of the coloring composition. The content of the dispersant and the solvent of the methane compound and the amine value of 70 mgKOH/g or less is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and still more preferably 90% by mass. More than % by mass. After the coloring composition is prepared, by mixing with the resin (B), the polymerizable compound (C), the polymerization initiator (D), or the like, it is possible to improve the heat resistance when the color filter is formed.

From the above viewpoints, the content of the resin (B) is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, more preferably 100% by mass of the coloring composition. It is preferably 1% by mass or less, and particularly preferably 0% by mass.

In addition, the content of the polymerizable compound (C) and the polymerization initiator (D) is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass in 100% by weight of the coloring composition. % or less is more preferably 0.1% by mass or less, and particularly preferably 0% by mass.

 <Coloring curable resin composition>    <Resin (B)>  

The resin (B) is not particularly limited, and is preferably an alkali-soluble resin. The resin (B) may, for example, be the following resins [K1] to [K6].

Resin [K1]: having a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (a) (hereinafter sometimes referred to as "(a)"), and having a carbon number of 2 a copolymer of a cyclic ether structure of 4 and a monomer (b) of an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"); a resin [K2]: having: derived from (a) The structural unit and the structural unit derived from (b), and the monomer (c) derived from (a) copolymerizable (unless, different from (a) and (b)) (hereinafter sometimes referred to as "( a copolymer of structural units of c)"); a resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c); a resin [K4] having a (b) addition a copolymer of a structural unit derived from the structural unit derived from (a) and a structural unit derived from (c); a resin [K5] having a structural unit which adds (a) to the structural unit derived from (b) a copolymer derived from the structural unit of (c); a resin [K6]: a structural unit having (a) added to the structural unit derived from (b), further added to the carboxylic anhydride, and derived from (c) Copolymer of structural unit.

(a) specifically, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, and zhongkang Acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydroortene Unsaturated dicarboxylic acid such as phthalic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5- Carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene , 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] Bicyclic unsaturated compounds containing a carboxyl group such as hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic acid Anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-di Unsaturated dicarboxylic anhydrides such as carboxybicyclo[2.2.1]hept-2-ene anhydride Unsaturated polyvalent carboxylic acid of two or more succinic acid mono [2-(methyl) propylene methoxyethyl] phthalate or phthalic acid mono [2-(methyl) propylene methoxyethyl] ester A mono[(meth)acryloxyalkylene]ester; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

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

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

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

(b) Examples thereof include a monomer (b1) having an epoxyethyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), having an oxetanyl group and an ethylenically unsaturated bond. The monomer (b2) (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)")).

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

(b1-1) Examples 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(glycidoxymethyl)styrene, 2,4 - bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4 - tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3 4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

(b1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel), (meth)acrylic acid 3 , 4-epoxycyclohexyl methyl ester (for example, CYCLOMER A400; manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMER M100; manufactured by Daicel), A compound represented by the formula (I), a compound represented by the formula (II), and the like.

[In the formulae (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a 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 the bond end with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, and a t-butyl group.

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

R ^a and R ^{b are} preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

The alkylene group may, for example, be a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group or a pentane-1,5-di group. Base, hexane-1,6-diyl, and the like.

X ^a and X ^{b are} preferably a single bond, a methylene group, an ethylene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, more preferably a single bond, *- CH ₂ CH ₂ -O- (* indicates the bonding end with O).

The compound represented by the formula (I) may, for example, be a compound represented by any one of the formula (I-1) to the formula (I-15). Wherein, it is preferably from the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9) or the formula (I-11) to the formula (I) The compound represented by I-15) is more preferably a compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15).

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

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

(b2) More preferably, it is a monomer having an oxetanyl group and a (meth) propylene fluorenyloxy group. (b2) may, for example, be 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane or 3-ethyl- 3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropenyloxyethyl Oxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3-ethyl 3-propenyloxyethyloxetane and the like.

(b3) More preferably, it is a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group. (b3) Specific examples thereof include tetrahydrofurfuryl acrylate (for example, VISCOAT V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(b) It is preferably (b1) in terms of further improving the reliability of heat resistance, chemical resistance, and the like of the obtained color filter. Furthermore, it is more preferable (b1-2) that the storage stability of the colored curable resin composition is excellent.

(c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, ( 2-ethylhexyl methacrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, (a) Cyclohexyl acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl (meth) acrylate (in the art, conventional entitled "(meth) acrylate, dicyclopentadiene acrylate." In addition, sometimes referred to as "(meth) acrylate, tricyclodecane acrylate."), (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decene 8-amino ester (commonly known in the art as "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, Adamantyl methyl methacrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (meth) acrylates; 2-hydroxyethyl (meth) acrylate, (a) a hydroxyl group-containing (meth) acrylate such as 2-hydroxypropyl acrylate; a dicarboxylic acid diester such as diethyl maleate, diethyl fumarate or diethyl itaconate; bicyclo [2.2. 1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]g 2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo [2.2.1] Hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6- Di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy Bicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2 - alkene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butyl Oxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2- Alkene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2 .1] bicyclic unsaturated compounds such as hept-2-ene; N-phenyl maleimine, N-cyclohexylmaleimine, N-benzyl maleimide, N-amber Amino-3-maleimide benzoate, N-amber succinimide-4-maleimide butyrate, N-succinimide-6-maleimide Dicarbonylimine derivatives such as acid salt, N-succinimide-3-maleimide propionate, N-(9-acridinyl)maleimide; styrene, α- Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methyl acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyl toluene, 2-hydroxyethyl (meth)acrylate, N-phenyl maleimide, N- are preferable. Cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, and the like.

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

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

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

When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored curable resin composition, the developability in forming a colored pattern, and the solvent resistance of the obtained color filter tend to be excellent.

The resin [K1] can be referred to, for example, in the method described in the "Experimental Method for Polymer Synthesis" (Dajin Takashi Publishing Co., Ltd., Chemicals, 1st Edition, 1st Printing, March 1, 1972). The cited references are manufactured.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction container, for example, oxygen is substituted for nitrogen to form an oxygen-removing environment, and heating and heat are maintained while stirring. method. The polymerization initiator, the solvent, and the like used herein are not particularly limited, and those generally used in the field can be used. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), and an organic peroxide ( The solvent (E) which is a composition of the colored curable resin composition of the present invention may be a solvent to be described later, and the solvent may be used as the solvent.

The obtained copolymer may be used as it is as a solid (powder) by directly using the solution after the reaction, or by using a concentrated or diluted solution, or by reprecipitation or the like. In particular, in 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 directly used in the preparation of the colored curable resin composition of the present invention. The production steps of the colored curable resin composition of the present invention can be simplified.

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

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

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

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

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

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

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

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

The structural unit derived from (c): 40 to 98 mol%, more preferably the structural unit derived from (a): 10 to 50 mol%

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

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

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

First, the copolymers (a) and (c) can be produced in the same manner as the method described in the production method of the resin [K1]. At this time, the ratio of the structural unit derived from each monomer is preferably the same ratio as that enumerated in the resin [K3].

Then, (b) a 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 above copolymer.

Next, the copolymer of (a) and (c) is prepared by substituting the environment inside the flask with nitrogen for air, and reacting the catalyst of (b), a carboxylic acid or a carboxylic anhydride with a cyclic ether (for example, dimethylamino group) A resin such as methyl phenol or the like and a polymerization inhibitor (for example, hydroquinone) are charged into the flask, for example, at 60 to 130 ° C for 1 to 10 hours to produce a resin [K4].

The amount of use of (b) is relative to (a) 100 moles, preferably 5 to 80 moles, more preferably 10 to 75 moles. When it is in this range, the storage stability of the colored curable resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity balance of the obtained pattern tend to be good. . Since the reactivity of the cyclic ether is high and the unreacted (b) is not easily retained, (b) used in the resin [K4] is preferably (b1), more preferably (b1-1).

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

The reaction conditions such as the feed method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like. Further, similarly to the polymerization conditions, the feeding method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generation generated by the polymerization, and the like.

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

The ratio of the structural units derived from (b) and (c) is preferably from the structural unit of (b): 5 to 95 mol% with respect to the total number of moles of all the structural units constituting the above copolymer.

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

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

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) having the carboxylic acid or carboxylic anhydride having (a) and the copolymer of (b) and (c) The reaction can obtain the resin [K5].

The amount of (a) used in the reaction with the above copolymer is preferably from 5 to 80 moles per 100 moles of (b). Since the reactivity of the cyclic ether is high, the unreacted (b) is less likely to remain, and (b), preferably (b1), more preferably (b1-1), which is used for the resin [K5].

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

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydrophthalic acid. Anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, and the like. The amount of the carboxylic anhydride to be used is 1 mole based on the amount of use of (a), preferably 0.5 to 1 mole.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate. Resin such as /(meth)acrylic copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene /(Meth)acrylic acid copolymer, 3,4-epoxytricyclo[?.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl- 3-(Meth)acryloxymethyloxybutane/(meth)acrylic acid/styrene copolymer, acrylic acid/(meth)acrylic acid 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] Resin such as oxime ester/cyclohexylmaleimide/2-hydroxyethyl methacrylate copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(methyl) Resin such as acrylic copolymer [K3]; a resin obtained by adding a glycidyl (meth)acrylate to a copolymer of benzyl (meth)acrylate/(meth)acrylic acid, and glycidyl (meth)acrylate Addition to tricyclodecyl (meth) acrylate / styrene / (methyl) propyl a resin obtained from an olefinic acid copolymer and a resin obtained by adding a glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer Resin [K4]; a resin which reacts a copolymer of (meth)acrylic acid with tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, and (meth)acrylic acid and (meth)acrylic acid a resin such as a resin obtained by reacting a copolymer of tricyclononyl ester/styrene/glycidyl (meth)acrylate [K5]; (meth)acrylic acid and tricyclodecyl (meth)acrylate/(methyl) A resin such as a resin obtained by reacting a copolymer of glycidyl acrylate with a resin which is further reacted with tetrahydrophthalic anhydride, such as a resin [K6].

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

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 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 to the developer 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 from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the resin (B) is preferably from 50 to 170 mg-KOH/g, more preferably from 60 to 150 mg-KOH/g, still more preferably from 70 to 135 mg-KOH/g, in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained, for example, by titration using a potassium hydroxide aqueous solution.

The content of the resin (B) is preferably from 20 to 70% by mass, more preferably from 30 to 65% by mass, still more preferably from 40 to 60% by mass, based on the total amount of the solid content of the colored curable resin composition. . When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film ratio tend to increase.

 <Polymerizable compound (C)>  

The polymerizable compound (C) is a living radical and/or acid-polymerizable compound which can be produced by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, etc., preferably (A) Base) acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. , dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol 九 (meth) acrylate , tris(2-(meth)acryloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate , propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa Base) acrylate and the like.

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

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

The content of the polymerizable compound (C) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid components. When the content of the polymerizable compound (C) is within the above range, there is a tendency that the residual film ratio at the time of formation of the colored pattern and the chemical resistance of the color filter are improved.

 <Polymerization initiator (D)>  

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating a living radical, an acid or the like by the action of light or heat, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates the living radicals include an alkyl phenyl ketone compound, a triazine compound, a decyl phosphine oxide compound, an O-mercapto fluorene compound, and a biimidazole compound.

The above O-indenyl ruthenium compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * indicates the key end.

The above O-indenyl hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzylformyloxy 1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)-3- Cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl Ethyl-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxa) Cyclopentylmethoxy)benzylidene}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-(2- Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylidene-1-(9-ethyl-6-(2) -Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercial products such as IRGACURE OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can be used. Wherein, the O-indenyl hydrazine compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoic acid醯oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylsulfanylphenyl) At least one of 3-cyclopentylpropan-1-one-2-imine, more preferably N-benzylidene-1-(4-phenylsulfanylphenyl)octane-1 - keto-2-imine. If an O-fluorenyl compound is used for this purpose, a color filter of high brightness tends to be obtained.

The above 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.

The compound having a partial structure represented by the formula (d2) may, for example, be 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one or 2-dimethyl Amino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercial products such as IRGACURE 369, 907, and 379 (above, manufactured by BASF Corporation) can be used.

The compound having a partial structure represented by the formula (d3) may, for example, be 2-hydroxy-2-methyl-1-phenylpropan-1-one or 2-hydroxy-2-methyl-1-[4-( 2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Oligomer, α,α-diethoxyacetophenone, benzoin dimethyl ketal, and the like.

In terms of sensitivity, the alkyl phenyl ketone compound is preferably a compound having a partial structure represented by the formula (d2).

The above triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloromethane). 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2 -(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene 1,1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1 , 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc. .

The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. A commercially available product such as IRGACURE (registered trademark) 819 (manufactured by BASF Corporation) can be used.

The biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di) (Chlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole (for example, see JP-A-6-75372, JP-A-6-75373, etc.), 2, 2'- Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-four (alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2' - bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403, JP-A-62-- Japanese Patent Publication No. 174204, etc., an imidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, see JP-A-7-10913, etc.).

Further, 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, methyl o-benzhydrylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4, a benzophenone compound such as 4'-tetrakis(tert-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylhydrazine Anthraquinone compounds such as ruthenium, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzophenone, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) to be described later.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine-p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenoxyphenyldimethylene.鋶-p-toluenesulfonate, 4-ethenyloxyphenylmethylbenzylphosphonium hexafluoroantimonate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, An anthracene salt such as diphenyliodonium-p-toluenesulfonate or diphenyliodonium hexafluoroantimonate, a nitrobenzyl tosylate or a benzoin tosylate.

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

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

 <Polymerization Initiator (D1)>  

The polymerization initiation aid (D1) is a compound or a sensitizer used to promote polymerization of a polymerizable compound after polymerization by a polymerization initiator. When the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include an amine compound, an alkoxyfluorene compound, a thioxanthone compound, and a carboxylic acid compound.

The above amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethylamine. Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine; 4,4' - bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamine) The benzophenone or the like is preferably 4,4'-bis(diethylamino)benzophenone. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

The above alkoxy ruthenium compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl-9. , 10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

The above thioxanthone compound may, for example, be 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone or 1-chloro -4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, and dimethylphenylsulfane. Acetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxy Acetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

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

 <Colorant (A)>  

The coloring agent (A) is not particularly limited, and is preferably a triarylmethane compound having a hetero ring, a dye (A1), a pigment (A2), or the like. The colorant (A) is preferably a dye (A1), more preferably a xanthene dye, and still more preferably a compound represented by the formula (1a).

In addition, in the colored curable resin composition of the present invention, the content of the colorant (A) is preferably from 1 to 60% by mass, more preferably from 1 to 60% by mass based on the total amount of the solid content of the colored curable resin composition. 3 to 55 mass%, further preferably 5 to 50 mass%. When the content of the coloring agent (A) is in the above range, the color density when the color filter is formed is sufficient, and a necessary amount of the resin or the polymerizable compound can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed.

 <Solvent (E)>  

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

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl bromide. Ethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy 3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, two Glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. , ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy Ethyl -2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ethyl acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and digan Alcohol 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 glycerin.

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

Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

Among the above-mentioned solvents, from the viewpoint of coatability and drying property, an organic solvent having a boiling point of 1 atm of 120 ° C or more and 180 ° C or less is preferable. The solvent is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, two 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 from 70 to 95% by mass, more preferably from 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 from 5 to 30% by mass, more preferably from 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be good.

 <Leveling agent (F)>  

The leveling agent (F) may, for example, be a polyfluorene-based surfactant, a fluorine-based surfactant, or a polyfluorene-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

The organic ruthenium-based surfactant may, for example, be a surfactant having a decane bond in the molecule. Specific examples thereof include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 ( Shin-Etsu Chemical Co., Ltd., TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

The fluorine-based surfactant described above may be a surfactant having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M), Megfac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K ( DIC (manufactured by Asahi Glass Co., Ltd.), EFTOP (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Integrated 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 Research Institute).

The organic ruthenium-based surfactant having a fluorine atom may, for example, be a surfactant having a siloxane chain and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC) can be cited.

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, more preferably further, based on the total amount of the colored curable resin composition. It is 0.005 mass% or more and 0.05 mass% or less. Further, the content of the above pigment dispersant is not included in the content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

 <Other ingredients>  

The colored curable resin composition of the present invention may contain additives known in the art such as a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, as needed.

 <Method for Producing Colored Composition and Colored Curable Resin Composition>  

In the present invention, a triarylmethane compound having a heterocyclic ring is mixed with a dispersing agent and a solvent to prepare a colored composition.

The colored curable resin composition of the present invention can be contained in the coloring composition of the present invention, the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the coloring composition used as needed. The coloring agent (A), the solvent (E), the leveling agent (F), and other components other than the coloring agent are mixed and prepared. When the colored composition is mixed with the resin (B), the polymerizable compound (C), the polymerization initiator (D), or the like to form a colored curable resin composition, the color filter can be further improved. Heat resistance.

 <Method of Manufacturing Color Filter>  

The method of producing a colored pattern by the colored curable resin composition of the present invention includes a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. The photolithography method is a method in which the colored curable resin composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to be developed. In the photolithography method, the coloring coating film of the cured product of the colored composition layer can be formed by using a photomask and/or no development at the time of exposure. The colored pattern and the colored coating film thus formed 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 depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, quartz glass, borosilicate glass, aluminosilicate glass, a glass plate such as a soda lime glass coated with cerium oxide on the surface, polycarbonate, polymethyl methacrylate, or polyethylene terephthalate can be used. A resin plate or the like of a glycol ester or the like, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Additional color filter layers, resin layers, transistors, circuits, and the like can be formed on these substrates.

The formation of each color pixel by photolithography can be performed under known or conventional devices and conditions. For example, it can be produced as follows.

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

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

The temperature at the time of heat drying is preferably from 30 to 120 ° C, more preferably from 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferably carried out at a temperature of from 20 to 25 ° C under a pressure of from 50 to 150 Pa.

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

The colored composition layer is then exposed through a photomask used to form the desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern matching the intended use can be used.

The light source used for the exposure is preferably a light source that generates light of a wavelength of 250 to 450 nm. For example, light of less than 350 nm can be cut off using a filter that cuts off the wavelength range, or light of around 436 nm, around 408 nm, and around 365 nm can be selectively taken out using a band pass filter that takes out these wavelength ranges. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

Since the parallel light rays can be uniformly irradiated to the entire exposed surface, and the correctness of the photomask and the substrate on which the colored composition layer is formed is aligned, an exposure apparatus such as a mask aligner and a stepper is preferably used.

The developed coloring composition layer is brought into contact with the developing solution to develop, and a colored pattern is formed on the substrate. By development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed. The developer is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide. The concentration in the aqueous solution of these basic compounds is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The developing method may be any one of a spin coating immersion method, a dipping method, and a spray method. Further, the substrate can be inclined at an arbitrary angle during development.

It is preferred to carry out water washing after development.

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

By preparing a colored curable resin composition from the colored composition of the present invention, a color filter having particularly excellent brightness can be produced from the colored curable resin composition. This color filter can be used as a color filter used for a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state imaging device.

 [Examples]  

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. In the examples, the % and the parts indicating the content or the amount used are based on mass unless otherwise specified.

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

The amine number is determined in accordance with ASTM D 2074.

 [Synthesis Example 1]  

The following reaction was carried out under a nitrogen atmosphere. After adding 32.2 parts of potassium thiocyanate and 160 parts of acetone to a flask having a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Then, 50 parts of 2-fluorobenzhydryl chloride (manufactured by Tosoh Kasei Co., Ltd.) was added dropwise over 10 minutes. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Then, 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 completion of the dropwise addition, 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% aqueous sodium hydroxide solution was added dropwise. After the end of the dropwise addition, the reaction mixture was further stirred at room temperature for 30 minutes. Next, 31.3 parts of chloroacetic acid was added dropwise to the reaction mixture at room temperature. After the end of the dropwise addition, the reaction mixture was stirred under heating and reflux for 7 hours. Next, after cooling the reaction mixture to room temperature, the reaction mixture was poured into 120 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Stirring was then stopped and allowed to stand for 30 minutes to separate the organic layer and the 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 Glauber's salt was added to the organic layer, stirred for 30 minutes, and filtered to obtain a dried 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 formula (B-I-2). The yield was 51%.

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

The following reaction was carried out under a nitrogen atmosphere. 8.2 parts of the compound represented by the formula (BI-2), 10 parts of the compound represented by the formula (CI-2), and 20 parts of toluene were placed in a flask equipped with a cooling tube and a stirring device, and then 12.2 parts of phosphorus oxychloride was added. Stir at 95 to 100 ° C for 3 hours. Then, after cooling the reaction mixture to room temperature, it was diluted with 170 parts of isopropyl alcohol. Then, the diluted reaction mixture was poured into 300 parts of saturated brine, and then 100 parts of toluene was added, followed by stirring 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 water layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of thenardite was added to the organic layer, stirred for 30 minutes, and filtered to give an organic layer. The obtained organic layer was subjected to solvent distillation with an evaporator to give a blue-violet solid. Further, the blue-violet solid was dried under reduced pressure at 60 ° C to obtain 18.4 parts of the compound represented by formula (X-II-2). The yield was 100%.

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

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

Exact quality: 722.3

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

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

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

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

Exact quality: 846.2

The following reaction was carried out under a nitrogen atmosphere. Into a flask equipped with a cooling tube and a stirring device, 2.0 parts of a compound represented by the formula (X-I-2) and 167 parts of ion-exchanged water were placed, and the mixture was stirred at 40 ° C for 30 minutes. 5.8 parts of cerium chloride dihydrate and 35 parts of ion-exchanged water were placed in a beaker, and stirred for 30 minutes. In the aqueous solution of the compound represented by the formula (X-I-2) prepared above, the liquid temperature was directly maintained at 40 ° C, and an aqueous solution of ruthenium chloride was added dropwise thereto, followed by stirring for 1 hour and 20 minutes. The obtained reaction suspension was filtered, and the filtered solid was suspended in 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 formula (A-I-3). The yield was 89%.

 [Synthesis Example 2]  

20 parts of the compound represented by the formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under a light-shielding condition, and the obtained solution was at 110 ° C. Stir for 6 hours. After the obtained reaction liquid was cooled to room temperature, it was added to a mixed liquid of 800 parts of water and 50 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour, and crystals were precipitated. The precipitated crystal was obtained as a residue by suction filtration, and dried to obtain a compound represented by the formula (1-32).

Identification of compounds represented by formula (1-32)

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

Exact quality: 658.9

 [Synthesis Example 3]  

The compound represented by the formula (A-X-2) (hereinafter sometimes referred to as the compound (A-X-2)) is synthesized by the method described in JP-A-2015-38201.

 [Synthesis Example 4]  

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was introduced and replaced with a nitrogen atmosphere, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were placed and stirred. Heat to 85 ° C. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and/or 3,4-epoxytricyclobutyl acrylate were added dropwise over 5 hours [5.2. Mixture of 1.0 ^2,6 ]decane-9-yl ester mixture, 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, 338 parts of propylene glycol monomethyl ether acetate Solution. On the other hand, a mixed solution obtained by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (B-1) solution having a solid content of 25.6%. The resulting copolymer had a weight average molecular weight Mw of 8,000, a degree of dispersion of 2.1, and an acid value of 111 mg-KOH/g in terms of solid content.

 [Synthesis Example 5]  

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was introduced, and the mixture was replaced with a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 80 ° C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and acrylic acid 3,4 were dropped into the flask over a period of about 5 hours using a drip pump. A solution of a mixture of epoxide tricyclo[5.2.1.0 ^2,6 ]decane-9-yl ester in 289 parts dissolved in propylene glycol monomethyl ether acetate (125 parts). On the other hand, an additional drip pump was used to dissolve the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) 33 parts in propylene glycol monomethyl ether over a period of about 6 hours. A solution of 235 parts of acetate. After completion of the dropwise addition, 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 resulting copolymer had a weight average molecular weight Mw of 9,200, a degree of dispersion of 2.08, and an acid value of 77 mg-KOH/g in terms of solid content.

The measurement of the polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin was carried out by gel permeation chromatography (GPC method) under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF

Flow rate: 1.0mL/min

Solid concentration of the tested liquid: 0.001 to 0.01% by mass

Injection volume: 50μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh)

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

 [Method for Producing Dispersion (Coloring Compositions 1-1 to 1-5)]  

10 parts of the compound represented by the formula (AI-3), 2 parts of the solid component of the dispersant P-1, 4 parts of a solid component of a resin (resin B-2) solution (solid content: 35.1%), propylene glycol monomethyl group After weighing 186 parts of ether acetate, 600 parts of 0.4 μm zirconia beads were placed, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Co., Ltd.), and zirconia beads were removed by filtration to prepare a dispersion (coloring). Composition 1-1).

In the same manner as the coloring agent 1-1 except that the dispersing agent P-1 was used as the dispersing agent P-2, the dispersing agent P-3, and the dispersing agent P-4, respectively, a dispersion liquid (coloring composition 1-2, Coloring composition 1-3, coloring composition 1-4).

The same formula as the coloring composition 1-1 except that the compound represented by the formula (AI-3) is a compound represented by the formula (AX-2) and the dispersant P-1 is used as the dispersant P-5. A dispersion (coloring composition 1-5) was prepared.

¹⁾ DISPERBYK-161 (amine value 11 mgKOH/g. Solid content 30% propylene glycol monomethyl ether acetate solution)

²⁾ DISPERBYK-2050 (amine value 30 mgKOH/g. solid content 52% propylene glycol monomethyl ether acetate solution)

³⁾ DISPERBYK-2150 (amine value 57 mgKOH/g. Solid content 52% propylene glycol monomethyl ether acetate solution)

⁴⁾ BYKLPN-21324 (amine value 0 mgKOH/g. 40% solids propylene glycol monomethyl ether acetate solution)

⁵⁾ BYKLPN-6919 (amine value 72 mgKOH/g. Solid content 60% propylene glycol monomethyl ether acetate solution)

⁶⁾ represents the total content of propylene glycol monomethyl ether acetate.

 Examples 1 to 8 and Comparative Examples 1 to 2  

Each component was mixed so as to have the composition shown in Table 19, and the colored curable resin composition was obtained.

¹⁾ shows the amount of the resin contained in the colored composition.

²⁾ shows the amount of propylene glycol monomethyl ether acetate contained in the colored composition.

In addition, in Table 19, each component shows the following. Further, the resin (B) represents a part by mass in terms of solid content.

Colorant (A) 1-1: Colored composition 1-1 (amine value of dispersant: 11 mgKOH/g)

Colorant (A) 1-2: Coloring composition 1-2 (amine value of dispersing agent: 30 mgKOH/g)

Colorant (A) 1-3: Coloring composition 1-3 (amine value of dispersing agent: 57 mgKOH/g)

Colorant (A) 1-4: Coloring composition 1-4 (amine value of dispersing agent: 0 mgKOH/g)

Colorant (A) 1-5: Colored composition 1-5 (amine value of dispersant: 72 mgKOH/g)

Colorant (A) A-1: a compound represented by formula (1-32)

Resin (B) B-1: Resin (B-1)

Resin (B) B-2: Resin (B-2)

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

Polymerization initiator (D) D-1: N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE 01 ;Manufactured by BASF; 肟 compound)

Solvent (E)E-1: Propylene glycol monomethyl ether acetate

Leveling agent (F) F-1: polyether modified polyoxygenated oil (TORAY SILICONE SH8400; manufactured by Toray Dow Corning)

 <Production of coloring pattern>  

The colored curable resin composition was applied by spin coating on a 5 cm square glass substrate (EAGLE 2000; manufactured by Corning), and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. After cooling, the interval between the substrate on which the colored composition layer was formed and the photomask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon) was used in an air atmosphere at 60 mJ/cm. The exposure amount of ² (365 nm reference) was irradiated with light. The photomask used a photomask formed with a line pattern of 100 μm lines and spaces. The colored composition layer after light irradiation was immersed and developed at 24 ° C for 60 seconds in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, washed with water, and then dried in an oven at 230 ° C. After 20 minutes of baking, a colored pattern was obtained.

 <Measurement of film thickness>  

The film thickness (μm) of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

 <Color Evaluation>  

For the obtained coloring pattern, the color separation was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus), and the xy chromaticity coordinate in the XYZ color system of CIE was measured using the characteristic function of the C light source ( x, y) and stimulus value Y. The larger the value of Y, the higher the brightness. The results are shown in Table 20.

 [Industrial availability]  

According to the colored curable resin composition containing the colored composition of the present invention, a color filter having high brightness and excellent color can be produced.

Claims (5)

 A colored composition comprising a triarylmethane compound having a heterocyclic ring, a dispersing agent, and a solvent, wherein the dispersing agent has an amine value of 70 mgKOH/g or less.   The colored composition according to claim 1, wherein the triarylmethane compound having a heterocyclic ring contains a group selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II). At least one compound: In the 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 a substituent of 7 The aralkyl group to 30, the aromatic hydrocarbon group and the substituent which the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , and the hydrogen atom contained in the saturated hydrocarbon group It may be substituted by a substituted or unsubstituted amino group or a halogen atom, and 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 at least -O- and -CO- In addition, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - will not be replaced by -O- at the same time, and the terminal -CH ₂ - will not be replaced by -O- or -CO. -, R ⁴¹ and R ⁴² may be bonded to 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 to each other and to the nitrogen atom to which R ⁴³ and R ⁴⁴ are bonded. Forming a ring together, 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 an alkyl group having 1 to 8 carbon atoms -CH ₂ - constituting the alkyl group may be replaced with at least one of -O- and -CO-, R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or -SO ₂ -, but in the alkyl group, the adjacent -CH ₂ - is not simultaneously substituted with -O-, the terminal -CH ₂ - It is not substituted with -O- or -CO-, and 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. a group or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the aromatic hydrocarbon group may have a substituent -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , and M ^r+ represents hydrogen Ionic, r-valent metal ion or substituted or unsubstituted ammonium ion, k represents the number of -SO ₃ ^- and -SO ₂ -N ^- - which R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have The sum of the numbers of SO ₂ -R ^f , r represents an integer of 1 or more, and 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 a -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , (II) In the formula, [Y ^{2] n-} represents an arbitrary n-valent anion of, R ^b41 to R ^b44 each independently represent a hydrogen atom, a saturated hydrocarbon group may have a substituent group having 1 to 20 carbon atoms constituting a group in which an oxygen atom is interposed between carbon atoms of 2 to 20 alkyl groups, an aromatic hydrocarbon group which may have a substituent or an aralkyl group which may have a substituent, and R ^b41 and R ^b42 may be bonded to and bonded to R ^b41 The nitrogen atoms bonded to R ^b42 together form a ring, and R ^b43 and R ^b44 may be bonded to form a ring together with the nitrogen atom to which R ^b43 and R ^b44 are bonded, and R ^b45 to R ^b52 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a group in which an oxygen atom is interposed between carbon atoms constituting an alkyl group having 2 to 8 carbon atoms, or R ^b46 and R ^b50 may be bonded to each other. Forming -O-, -NH-, -S- or -SO ₂ -, Y ¹ represents an aromatic heterocyclic group which may have a substituent, and when the compound represented by the formula (II) contains a plurality of cations, a plurality of cations may be used. For the same structure as each other, it can also be a different structure, and n represents an arbitrary natural number.  A colored curable resin composition comprising the colored composition according to claim 1 or 2, a resin (B), a polymerizable compound (C), and a polymerization initiator (D).    A color filter formed by the color hardening resin composition described in claim 3 of the patent application.    A display device comprising the color filter of claim 4 of the patent application.