TWI745479B - 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 colored composition, a colored curable resin composition, a color filter, and a display device.

Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, plasma displays, and solid-state imaging elements such as CCD and CMOS sensors are made of a coloring curable resin composition. As the coloring composition contained in such a coloring curable resin composition, a composition containing a triarylmethane dye and a dispersant having an amine value of 72 mgKOH/g is known (Patent Document 1).

[Prior Art Literature] [Patent Literature]

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

The color filter formed from the above-mentioned coloring curable resin composition known in the past may not have sufficient brightness. The present invention provides a coloring composition capable of forming a high-brightness color filter.

[1] A coloring composition comprising: a triarylmethane compound having a heterocyclic ring, a dispersant, and a solvent, and the amine value of the dispersant is 70 mgKOH/g or less.

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

[式(I)中，R⁴¹至R⁴⁴各自獨立地表示氫原子、碳數1至20的飽和烴基、可具有取代基的碳數6至20的芳香族烴基或可具有取代基的碳數7至30的芳烷基，該芳香族烴基和該芳烷基可具有的取代基可為-SO₃ ^-或者-SO₂-N^--SO₂-R^f，該飽和烴基中所含的氫原子可被取代或未取代的胺基或鹵素原子取代，該飽和烴基的碳數為2至20時，該飽和烴基中所含的-CH₂-可被替換為-O-和-CO-的至少一者。惟，在該碳數2至20的飽和烴基中，鄰接的-CH₂-不會同時被替換為-O-，末端的-CH₂-不會被替換為-O-或-CO-。R⁴¹與R⁴²可 鍵結並與該R⁴¹與R⁴²所鍵結的氮原子一起形成環，R⁴³與R⁴⁴可鍵結並與該R⁴³與R⁴⁴所鍵結的氮原子一起形成環。R⁴⁷至R⁵⁴各自獨立地表示氫原子、鹵素原子、硝基、羥基、-SO₃ ^-、-SO₂-N^--SO₂-R^f或碳數1至8的烷基，構成該烷基的-CH₂-可被替換為-O-和-CO-的至少一者，R⁴⁸和R⁵²可相互鍵結而形成-NH-、-S-或-SO₂-。惟，該烷基中，鄰接的-CH₂-不會同時被替換為-O-，末端的-CH₂-不會被替換為-O-或-CO-。

[In formula (I), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons, or a substituted carbon number The aralkyl group of 7 to 30, the aromatic hydrocarbon group and the substituent that the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , the hydrogen contained in the saturated hydrocarbon group The atom may be substituted by a substituted or unsubstituted amine group or a halogen atom. When the carbon number of the saturated hydrocarbon group is 2 to 20, the -CH ₂ -contained in the saturated hydrocarbon group can be replaced with -O- and -CO- At least one. However, in the saturated hydrocarbon group with 2 to 20 carbon atoms, the adjacent -CH ₂ -will not be replaced with -O- at the same time, and the terminal -CH ₂ -will not be replaced with -O- or -CO-. R ⁴¹ and R ⁴² may be bonded to form a ring together with the nitrogen atom of the R ⁴¹ and R ⁴² are bonded, R ⁴³ and R ⁴⁴ may be bonded and the R ⁴³ forming together with the nitrogen atom 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 alkyl The -CH ₂ -of the group may be replaced with at least one of -O- and -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or -SO ₂ -. However, in this alkyl group, the adjacent -CH ₂ -will not be replaced with -O- at the same time, and the terminal -CH ₂ -will not be replaced with -O- or -CO-.

Ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group, or a substituted or unsubstituted amine group having 6 to 20 carbon atoms. Aromatic hydrocarbon group. The substituent that 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 ^{- of R 41} to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and the ring T ¹ and the number of -SO ₂ -N ^-- SO ₂ -R ^f .

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 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 A substituted aromatic hydrocarbon group 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 carbons, or a group in which an oxygen atom is inserted between the carbon atoms constituting an alkyl group having 2 to 8 carbons , Or R ^b46 and R ^b50 can 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 plural cations, the plural cations may have the same structure or different structures.

n represents any natural number. ]

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

[4] A color filter formed of the coloring curable resin composition described in [3].

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

According to the present invention, there is provided a coloring composition capable of forming a high-brightness color filter.

The coloring composition of the present invention includes a triarylmethane compound having a heterocyclic ring, a dispersant, and a solvent.

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

<Coloring composition> <Triarylmethane compound with heterocycle>

Triarylmethane compounds with heterocycles have three aromatic rings bonded to one carbon atom, and one or more of them are aromatic heterocycles. Preferably they have two aromatic hydrocarbon rings and one aromatic ring. A compound with a structure in which a heterocyclic ring is bonded to 1 carbon atom.

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

Compound (I) also includes its tautomers or salts of the tautomers. In addition, each component and functional group exemplified below can be used individually or in combination.

[式(I)中，R⁴¹至R⁴⁴各自獨立地表示氫原子、碳數1至20的飽和烴基、可具有取代基的碳數6至20的芳香族烴基或可具有取代基的碳數7至30的芳烷基，該芳香族烴基和該芳烷基可具有的取代基可為-SO₃ ^-或者-SO₂-N^--SO₂-R^f，該飽和烴基中所含的氫原子可被取代或未取代的胺基或鹵素原子取代，該飽和烴基的碳數為2至20時，該飽和烴基中所含的-CH₂-可被替換為-O-和-CO-中的至少一者。惟，在該碳數2至20的飽和烴基中，鄰接的-CH₂-不會同時替換為-O-，末端的-CH₂-不會被替換為-O-或-CO-。R⁴¹與R⁴²可鍵結並與該R⁴¹與R⁴²所鍵結的氮原子一起形成環，R⁴³與R⁴⁴可鍵結並與該R⁴³與R⁴⁴所鍵結的氮原子一起形成環。

[In formula (I), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons, or a substituted carbon number The aralkyl group of 7 to 30, the aromatic hydrocarbon group and the substituent that the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , the hydrogen contained in the saturated hydrocarbon group Atoms may be substituted by substituted or unsubstituted amine groups or halogen atoms. When the saturated hydrocarbon group has 2 to 20 carbon atoms, the -CH ₂ -contained in the saturated hydrocarbon group can be replaced with -O- and -CO- At least one of. However, 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 of the R ⁴¹ and R ⁴² are bonded, R ⁴³ and R ⁴⁴ may be bonded and the R ⁴³ forming together with the nitrogen atom 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 alkyl The -CH ₂ -of the group may be replaced with at least one of -O- and -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or -SO ₂ -. However, in this alkyl group, the adjacent -CH ₂ -will not be replaced with -O- at the same time, and the terminal -CH ₂ -will not be replaced with -O- or -CO-.

Ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group, or a substituted or unsubstituted amine group having 6 to 20 carbon atoms. Aromatic hydrocarbon group. The substituent that 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 ^{- of R 41} to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and the ring T ¹ and the number of -SO ₂ -N ^-- SO ₂ -R ^f .

r represents an integer of 1 or more.

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

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

The aromatic heterocyclic ring represented by ring T ¹ may be a monocyclic ring or a condensed ring. The carbon number of the aromatic heterocyclic ring represented by ring T ^{1 is 3-10, preferably 3-8.} In addition, the aromatic heterocyclic ring is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring. Examples of monocyclic aromatic heterocyclic rings include 5-membered rings containing nitrogen atoms such as pyrrole ring, oxazole ring, pyrazole ring, imidazole ring, and thiazole ring; 5-membered ring containing no nitrogen atoms such as furan ring and thiophene ring Ring; pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring and other 6-membered rings containing nitrogen atoms, etc. The aromatic heterocyclic ring of the condensed ring includes indole ring, benzimidazole ring, benzothiazole ring, quine Condensed rings containing nitrogen atoms such as morpholine rings; condensed rings containing no nitrogen atoms such as benzofuran rings.

The substituent that the aromatic heterocyclic ring of ring T ¹ may have includes a halogen atom, a cyano group, an optionally substituted saturated hydrocarbon group having 1 to 20 carbons, a substituted or unsubstituted amine group, or an optionally substituted group The aromatic hydrocarbon group having 6 to 20 carbons, etc., preferably include saturated hydrocarbon groups having 1 to 20 carbons, substituted or unsubstituted amine groups, or optionally substituted aromatic hydrocarbon groups having 6 to 20 carbons. The ring T ¹ preferably has an amine group that may have a substituent. The substituent that the amine group may have is preferably a saturated hydrocarbon group having 1 to 20 carbons, and an aromatic hydrocarbon group having 6 to 10 carbons that may have a substituent. , Optionally substituted aralkyl groups having 7 to 30 carbon atoms, etc.

Wherein, as the aromatic heterocyclic ring T ¹ is preferably an aromatic heterocyclic system containing a nitrogen atom, more preferably an aromatic heterocyclic ring system containing five ring nitrogen atom.

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

[式(t1)中，R⁵⁶表示氫原子、碳數1至20的飽和烴基或可具有取代基的碳數6至20的芳香族烴基。

[In 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 that 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 carbons which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent, or a carbon 7 to 20 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 with 2 to 20 carbon atoms, the adjacent -CH ₂ -will not be replaced with -O- at the same time, and the terminal -CH ₂ -will not be replaced with -O- 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 the carbocation. ]

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

[式(t2)中，環T³表示具有氮原子的碳數3至10的芳香族雜環。

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

R ⁵⁸ represents a saturated hydrocarbon group having 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f .

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

k2 represents 0 or 1.

* Indicates the bonding end to the carbocation. ]

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

[式(t2-1)中，R⁶⁰表示氫原子、碳數1至20的飽和烴基或者可具有取代基的碳數6至20的芳香族烴基。

[In formula (t2-1), R ⁶⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an aromatic hydrocarbon group having 6 to 20 carbons that 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 the carbocation. ]

The saturated hydrocarbon group having 1 to 20 carbons represented by R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ and the saturated hydrocarbon group of 1 to 20 carbons that may have the amine group which may be substituted with ^{the ring T 1 may be straight chain} Any one of shape, branched chain and cyclic. Linear or branched saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and hexadecyl groups. Linear alkyl groups such as alkyl and eicosyl; branched chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc. The carbon number of the saturated hydrocarbon group is preferably from 1 to 10, more preferably from 1 to 8, and 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 that the amine group that ring T 1} may have may have a single ring or a polycyclic ring. Examples of the cyclic saturated hydrocarbon group include alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The carbon number of the cyclic saturated hydrocarbon group is preferably 3-10, more preferably 6-10.

The saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ^{60 and the saturated hydrocarbon group that the amine group that ring T 1} may have may have, for example, methyl, ethyl, isopropyl, propyl, Butyl, pentyl, hexyl, isobutyl, 2-ethylhexyl, cyclohexyl, adamantyl, etc.

The saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ^56, and R ⁵⁸ to R ^{60 and the saturated hydrocarbon group that the amine group that the ring T 1} may have may have a substituted or unsubstituted amine group or a halogen atom as a substituent. Examples of the substituted amino group include alkylamino groups such as dimethylamino and diethylamino. In addition, the halogen atom includes fluorine, chlorine, bromine, and iodine. In addition, 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, and a perfluoropropyl group.

The alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ includes groups having 1 to 8 carbon atoms among the linear or branched saturated hydrocarbon groups ^{exemplified as the saturated hydrocarbon group represented by R 41} .

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

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

In addition, the aromatic hydrocarbon group that may have a substituent represented ^{by R 41} to R ⁴⁶ , R ^56, and R ⁵⁸ to R ^{60 and the aromatic hydrocarbon group that the amine group that ring T 1} may have may have (wherein, the aromatic hydrocarbon group may It has a substituent.) The carbon number is preferably 6-20, more preferably 6-15, and still more preferably 6-12. Examples of the aromatic hydrocarbon group include phenyl, tolyl, xylyl, naphthyl, anthryl, phenanthryl, biphenyl, terphenyl, etc., preferably phenyl, naphthyl, tolyl, and xylyl , Phenyl is particularly preferred. In addition, the aromatic hydrocarbon group may have 1 or 2 or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; halogenated alkyl groups having 1 to 6 carbon atoms such as chloromethyl and trifluoromethyl; and methoxy and ethoxy groups having 1 to 6 carbon atoms. Alkoxy group to 6; hydroxyl group; sulfamoyl group; alkyl sulfonyl group with carbon number 1 to 6 such as methylsulfonyl group; alkoxycarbonyl group with carbon number 1 to 6 such as methoxycarbonyl group and ethoxycarbonyl group carbonyl _{^{group; -SO 3 -; -SO 2 -N}} - -SO 2 -R f , etc., may be -SO ₃ ^- or _{^{-SO 2 -N - -SO 2 -R f}} . However, it is preferable that -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^{f are} directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, it is preferable to substitute the 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 bonding terminal to a nitrogen atom.

The aralkyl group that may have a substituent represented by R ⁴¹ to R ⁴⁶ and R ^{59 and the aralkyl group that the amino group that the ring T 1} may have may have (wherein, the aralkyl group may have a substituent), and examples thereof include Examples include groups in which an alkylene group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as a methylene group, an ethylene group, and a propylene group are bonded to the groups described as the above-mentioned aromatic hydrocarbon groups. The carbon number of the aralkyl group is preferably from 7 to 30, more preferably from 7 to 20, and still more preferably from 7 to 17.

R ⁴¹ and R ⁴² are bonded to form a ring together with the nitrogen atom to which R ⁴¹ and R ^{42 are bonded, R 43} and R ^{44 are} bonded to form a ring with the nitrogen atom to which R ⁴³ and R ⁴⁴ are bonded 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 preferably includes a 4- to 7-membered ring having only one nitrogen atom as a hetero atom, such as a pyrrolidine ring and a piperidine ring.

R ^{58 is} preferably a saturated hydrocarbon group having 1 to 20 carbons or an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent.

Among them, R ⁴¹ to R ⁴⁴ , R ⁵⁶ , R ⁵⁸ to R ^{60 are} preferably saturated hydrocarbon groups having 1 to 20 carbons or aromatic hydrocarbon groups that may have substituents, and more preferably are each independently having 1 to 8 carbons. A saturated hydrocarbon group or a group represented by the following formula. R ⁵⁶ and R ⁵⁸ to R ^{60 are} more preferably a group represented by the following formula. In the following formula, * represents a bonding terminal to a nitrogen atom.

Preferably, R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ -constituting an alkyl group having 2 to 20 carbon atoms is replaced with 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 carbons, an alkoxyalkyl group, or a group represented by the following formula, or R ⁴⁵ and R ^{46 are} bonded to form only one nitrogen The 4- to 7-membered ring in which the atom is a hetero atom is 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 bonding terminal to a nitrogen atom.

In addition, the alkyl group having 1 to 8 carbon atoms represented ^{by R 47} to R ⁵⁴ includes those having 1 to 8 carbon atoms among the linear or branched saturated hydrocarbon groups ^{exemplified as the saturated hydrocarbon group represented by R 41.} Group. In addition, a _{group in which -CH 2} -constituting an alkyl group having 2 to 8 carbon atoms represented ^{by R 47} to R ⁵⁴ is replaced with at least one of -O- and -CO- (except that the alkane In the group, the adjacent -CH ₂ -will not be replaced with -O- at the same time, and the terminal -CH ₂ -will not be replaced with -O- or -CO-). The composition can be listed as the above R ⁴¹ to R ⁴⁶ Among the groups represented by the alkyl group having 2 to 20 carbon atoms, -CH ₂ -is replaced with at least one of -O- and -CO-, a group having 8 or less carbon atoms.

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

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

R ^{61 is} preferably a hydrogen atom.

^{Metal ions with r valence represented by Mr+} include alkali metal ions such as lithium ion, sodium ion, and potassium ion; alkaline earth metal ions such as beryllium ion, magnesium ion, calcium ion, strontium ion, and barium ion; titanium ion, Zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion and other transition metal ions; zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion, bismuth ion and other typical metal ions, etc. . r is 1 or more, preferably 2 or more, preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less. In addition, the substituted or unsubstituted ammonium ions represented by Mr ^{+ include quaternary ammonium ions such as tetraalkylammonium ions.}

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

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

The fluoroalkyl group having 1 to 12 carbon atoms represented by R ^f includes monofluoromethyl, difluoromethyl, perfluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoro Ethyl, perfluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, perfluoropropyl, monofluorobutyl, difluoro Butyl, trifluorobutyl, tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl, perfluorobutyl, etc. Among them, ^{the fluoroalkyl group represented by R f} is preferably a perfluoroalkyl group. In addition, ^{the carbon number of the fluoroalkyl group represented by R f} is preferably from 1 to 10, more preferably from 1 to 5, and still more preferably from 1 to 3.

In formula (I), R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have at least one -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . The sum (k) of the numbers of -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f of R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ^{1 is 1 or more, preferably 1} 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 condition selected from the following (Ia) to (Id), more preferably satisfies selected from (Ia) And at least one or more of the conditions in (Ib).

(Ia) Contains any one of ^{R 47} to R ^{54 above}

(Ib) Bonding to any one of the aromatic hydrocarbon groups having 6 to 20 carbons and which may have substituents represented ^{by R 41} to R ⁴⁴

(Ic) Bonding to any one of the aralkyl groups having 7 to 30 carbons and which may have substituents represented ^{by R 41} to R ⁴⁴

(Id) is bonded to any one of the aromatic hydrocarbon groups with 6 to 20 carbon atoms substituted by the hydrogen atom of the aromatic heterocyclic ring represented by ^{T 1}

Among them, when -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f is bonded to an aromatic hydrocarbon group or aralkyl group, it is preferably -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^{f is} directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group or aralkyl group. That is, it is preferable that -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f replace the hydrogen atom bonded to the 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 para position with respect to the bonding position with the nitrogen atom.

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

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

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

[式(I-1)中，R⁸¹至R⁹⁰各自獨立地表示氫原子、碳數1至20的飽和烴基、鹵素原子、-SO₃ ^-或-SO₂-N^--SO₂-R^f。

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

k1 represents the sum of the number of -SO ₃ ^- _{and -SO 2} -N ^-- SO ₂ -R ^f 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 , Mr ⁺ , r, and R ^f have the same meaning as above.

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

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

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

(Ie) Contains any one of ^{R 47} to R ⁵⁴

(If) contains any one of ^{R 81} to R ⁹⁰

(Ig) Bonding to an aromatic hydrocarbon group having 6 to 20 carbons substituted by the hydrogen atom of the aromatic heterocyclic ring represented by ^{T 1}

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

(If') contains any one of ^{R 86} and R ⁸⁹

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

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

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

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

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

[式(IC)中，R¹至R⁴各自獨立地表示氫原子、碳數1至20的飽和烴基、可具有取代基的碳數6至20之芳香族烴基或可具有取代基的碳數7至30的芳烷基，在該碳數1至20的飽和烴基中，該飽和烴基中所含的氫原子可被取代或未取代的胺基或鹵素原子取代，該飽和烴基中所含的-CH₂-可被替換為-O-和-CO-中的至少一者。R¹與R²可鍵結並與該R¹與R²所鍵結的氮原子一起形成環，R³與R⁴可鍵結並與該R³與R⁴所鍵結的氮原子一起形成環。

[In formula (IC), R ¹ to R ⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons, or a substituted carbon number An aralkyl group of 7 to 30. In the saturated hydrocarbon group of 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amine group or halogen atom. The saturated hydrocarbon group contains -CH ₂ -may be replaced with at least one of -O- and -CO-. R ¹ and R ² may be bonded to form a ring together with the R ¹ and the nitrogen atom R ² are bonded, R ³ and R ⁴ may be bonded and the R ³ forming together with the nitrogen atom 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 carbons, and -CH ₂ -constituting the alkyl group may be replaced with -O- and -CO- At least one of. R ⁸ and R ¹² may be bonded to each other to form -NH-, -S- or -SO ₂ -.

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

M ¹ represents Cl ^-, phosphate ion, perchlorate _{^{ion, BF 4 -, PF 6 -}} . ]

When the compound (I) is a compound having -SO ₃ ^- group but not having -SO ₂ -N ^-- SO ₂ -R ^f (hereinafter sometimes referred to as "compound (IA-1)"), compound ( IA-1) reacts with the compound represented by formula (IB).

[式(IB)中，R^f與上述同義。]

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

In addition, when compound (I) is a compound in formula (I) in which Mr ⁺ is a hydrogen ion (hereinafter sometimes referred to as compound (IA-2).), compound (IA-2) can be combined with a metal ion containing r valence. The halide (preferably chloride), acetate, phosphate, sulfate, silicate or cyanide reaction.

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

In addition, the triarylmethane compound having a heterocyclic ring is preferably a compound also represented by formula (II) (hereinafter sometimes referred to as "compound (II)").

[式(II)中，[Y²]^n-表示任意的n價之陰離子。

[In 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 A substituted aromatic hydrocarbon group 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 carbons, or a group in which an oxygen atom is inserted between the carbon atoms constituting an alkyl group having 2 to 8 carbons , 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 formula (II) contains a plurality of cations, the plurality of cations may have the same structure or different structures.

n represents any 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 that can form a counter ion with the cation, but is preferably a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, a halogen atom such as a chlorine atom, and a group selected from tungsten, An anion of at least one element of molybdenum, silicon, and phosphorus and an oxygen atom.

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

[式(4)中，W¹、W²各自獨立地表示具有2個1價的質子給予性取代基的基團。M表示硼或鋁。]

[In 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 includes groups in which protons are respectively released from a compound having at least two monovalent proton-donating substituents (for example, a hydroxyl group, a carboxyl group, etc.). The compound is preferably catechol which may have substituents, 2,3-dihydroxynaphthalene which may have substituents, 2,2'-biphenol which may have substituents, and 3-hydroxy-2 which may have substituents. -Naphthoic acid, optionally substituted 2-hydroxy-1-naphthoic acid, optionally substituted 1-hydroxy-2-naphthoic acid, optionally substituted binaphthol, optionally substituted salicylic acid, Diphenyl glycolic acid which may have a substituent or mandelic acid which may have a substituent.

In each compound exemplified as the compound having at least two monovalent proton-donating substituents, the substituents include saturated hydrocarbon groups (for example, alkyl groups, cycloalkyl groups, etc.), halogen atoms, hydroxyl groups, amino groups, and nitro groups. Group, alkoxy, etc.

The salicylic acid that may have a substituent includes salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4 -Trifluoromethylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-amino Monoaminosalicylic acid such as salicylic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid Acid (2,5-dihydroxybenzoic acid), 6-hydroxysalicylic acid (2,6-dihydroxybenzoic acid) and other monohydroxysalicylic 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-bromosalicylic acid Salicylic acid, 5-bromosalicylic acid, 6-bromosalicylic acid and other monohalogenated salicylic acids; 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, 3,5-diiodide Salicylic acid and other dihalogenated salicylic acid; 3,5,6-trichlorosalicylic acid and other trihalogenated salicylic acid, etc.

The diphenyl glycolic acid that may have substituents can be listed

The mandelic acid that may have substituents can be listed as follows:

Wait.

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

[式(6)中，W³和W⁴各自獨立地表示氟原子或碳數1至4的氟代烷基，或W³與W⁴一起表示碳數1至4的氟化烷二基。]

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

[式(7)中，W⁵至W⁷各自獨立地表示氟原子或碳數1至4的氟化烷基。]

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

[式(8)中，Y^a表示碳數1至4的氟化烷二基。]

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

[式(9)中，Y^b表示碳數1至4的氟化烷基。]

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

In the formulas (6), (7) and (9), the fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. The perfluoroalkyl group includes -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ and so on.

In formulas (6) and (8), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, and examples include -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, etc.

The anion represented by the formula (6) (hereinafter sometimes referred to as "anion (6)"), respectively, can be exemplified by the anions represented by the formula (6-1) to (6-6) (hereinafter sometimes referred to as " Anion (6-1)" to "Anion (6-6)").

An anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and an oxygen atom, including polyacid anions such as isopolyacid anions having the element, and allopolyacid anions having the element Anion.

Anions of isopolyacid or allopolyacid containing tungsten as an essential element, 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 silicotungstate α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , and as other examples, [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. As the anion of the isopoly acid or allopoly acid containing tungsten as an essential element, anions of phosphotungstic acid, silicotungstic acid, and tungsten-based allopoly acid are preferred.

In addition, it is preferable to also contain at least one element selected from silicon 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 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- , more preferably an anion represented by formula (6-1) to formula (6-5), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , particularly preferably an anion represented by formula (6-2), [PW ₁₂ O ₄₀ ] ^3- .

n represents an arbitrary natural number and is equal to the negative charge possessed by the ^{anion [Y 2} ] ^n-. The n on the cation side is determined so that the charges of the ^{anion [Y 2} ] ^{n- and the cation are equal.} n is preferably a natural number from 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. In addition, the saturated hydrocarbon group preferably has 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, and particularly preferably a carbon number of 1 to 4.

The linear or branched saturated hydrocarbon group includes linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, and decyl; Branched chain alkyl groups such as butyl group, isobutyl group and 2-ethylhexyl group. The carbon number of the linear or branched saturated hydrocarbon is preferably from 1 to 8, more preferably from 1 to 6, and still more preferably from 1 to 4.

In addition, the above-mentioned cyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The carbon number of the cyclic saturated hydrocarbon group is preferably 3-10, more preferably 6-10.

A hydrogen atom saturated hydrocarbon group R ^b41 to R ^b44 may be substituted. Examples of the substituent include substituted or unsubstituted amine groups and halogen atoms. Examples of the substituted amino group include a dialkylamino group such as a dimethylamino group, and the like, and a halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and 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的组。 The group. In the following formula, * represents a bonding terminal to a nitrogen atom. Among them, the group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group is preferably a group having 2 to 10 carbon atoms, and more preferably a group having 2 to 6 carbon atoms. The alkyl group into which the oxygen atom is inserted is preferably a straight-chain alkyl group. In addition, the number of carbons between oxygen atoms is preferably 1 to 4, more preferably 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 carbon number of the above-mentioned alkylene group is preferably 1 to 10, more preferably 1 to 5, and is preferably a linear alkylene group. Specific examples of the above-mentioned alkylene group include methylene, ethylene, propylene, butylene, pentylene and the like, and the aralkyl group includes benzyl, phenylethyl, naphthylmethyl, and naphthyl. Ethyl and so on.

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 Alkoxy to 6; hydroxy; alkylsulfonyl having 1 to 6 carbons such as methylsulfonyl; alkoxycarbonyl having 2 to 6 carbons such as methoxycarbonyl and ethoxycarbonyl, etc.

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 bonding terminal to a nitrogen atom.

Examples of the aralkyl group which may have a substituent include groups in which an alkylene group such as a methylene group or an ethylene group is bonded to the bonding terminal of the above-mentioned 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 5-membered rings such as a pyrrolidine ring; 6-membered rings such as a morpholine ring, a piperidine ring, and a piperazine 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 bonding terminal to a nitrogen atom.

The saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ^b45 to R ^b52 may be linear, branched, and cyclic, and is preferably linear or branched. 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 inserted between the 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 1 to 4, more preferably 2 to 3.

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

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

Monocyclic aromatic heterocycles include 5-membered rings with nitrogen atoms such as pyrrole ring, oxazole ring, pyrazole ring, imidazole ring, and thiazole ring; 5-membered rings with oxygen atom and sulfur atom such as furan ring and thiophene ring Ring; 6-membered ring with nitrogen atom such as pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc. Examples of the aromatic heterocyclic ring of the condensed ring include condensed rings having a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring; and a ring having an oxygen atom and a sulfur atom such as a benzofuran ring.

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

[式(II-1)中，[Y²]^n-、R^b41至R^b52和n與上述相同。

[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 in which an oxygen atom is inserted between the carbon atoms constituting an alkyl group having 2 to 20 carbon atoms, and may have A substituted aromatic hydrocarbon group 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 that 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 different structures. ]

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, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, an alkyl group having 1 to 6 carbon atoms is still more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred. .

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 inserted with an oxygen atom is preferably a straight chain alkyl group. In addition, the number of carbons between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

In R ^b55 , the carbon number of the aromatic hydrocarbon group is preferably 6-20, more preferably 6-10.

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

^In the aromatic hydrocarbon group of R b55, the substituent includes halogen atoms such as a fluorine atom, a chlorine atom, and an iodine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a sulfonamide group; Alkylsulfonyl groups having 1 to 6 carbon atoms, such as methylsulfonyl; alkoxycarbonyl groups having 2 to 6 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl.

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

X1 represents an oxygen atom, -NR ^b57 -or a sulfur atom. The cyclic structure containing X1 includes, for example, a group represented by the following formula. In the formula, R ^b53 to R ^b55 have the same meanings as above, and * represents the bonding end to the carbocation. Among them, X1 is preferably an oxygen atom or a sulfur atom, and particularly preferably a sulfur atom.

The cation part of the formula (II) includes cation 1 to cation 27 represented by the formula (II-I-1) shown in the following table, and the like.

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

In Table 17, Ph1 to Ph12 refer to groups represented by the following formulas.

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

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

The dye (A1) is not particularly limited, and well-known dyes can be used. For example, solvent dyes, acid dyes, direct dyes, and mordant dyes can be cited. Examples of the dye include compounds classified as substances having a hue other than pigments in the color index (published by The Society of Dyers and Colourists), and well-known dyes described in the dyeing notes (Sei Dyers Co., Ltd.). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, etc. Squara dyes, squaraine dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes, etc. Among these, organic solvent-soluble dyes are preferred.

Specifically, CI Solvent Yellow 4 (hereinafter the description of CI Solvent Yellow is omitted, and only the serial number is described.), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 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, CI solvent dyes such as 32, 33, 34, 35, 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 Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56 , 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 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, CI acid dyes such as 109, CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102 , 108, 109, 129, 136, 138, 141; CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI direct orange 26, 34, 39, 41, 46 , 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct purple 47, 52, 5 4, 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; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct Dyes, CI Disperse Yellow 51, 54, 76; CI Disperse Violet 26, 27; CI Disperse Blue 1, 14, 56, 60 and other CI Disperse Dyes, CI Basic Red 1, 10; CI Basic Blue 1, 3, 5 , 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83 , 88, 89; CI Basic Violet 2; CI Basic Red 9; CI Basic Green 1 and other CI basic dyes, CI Reactive Yellow 2, 76, 116; CI Reactive Orange 16; CI Reactive Red 36 and other CI reactive dyes CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 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, 2 1, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1, 1: 1, 2, 3, 4, 5, 6, 7, 8 , 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45 , 47, 48, 49, 53, 58; 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 mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21 , 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other CI mordant dyes, CI vat green 1 and other CI vat dyes.

These dyes can be appropriately selected according to the spectroscopic spectrum of the desired color filter.

The dye (A1) preferably contains xanthene dye.

The xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of xanthene dyes (Aa) include CI Acid Red 51 (hereinafter the description of CI Acid Red is omitted, and only the serial number is described. The same applies to the others.), 52, 87, 92, 94, 289, 388, CI Acid Violet 9, 30, 102, CI Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, CI Basic Red 10, 11, CI Basic Violet 10 (Rhodamine B), 11, CI Solvent Red 218 , CI Mordant Red 27, CI Reactive Red 36 (Rose Red B), Sulorhodamine G, Xanthene Dyes described in Japanese Patent Laid-Open No. 2010-32999 and Xanthene dyes described in Japanese Patent No. 4492760 Wait. Preferably, it is a xanthene dye dissolved in an organic solvent.

Among these, the xanthene dye (Aa) is preferably a dye containing a compound represented by formula (1a) (hereinafter sometimes referred to as "compound (1a)"). Compound (1a) may be its tautomer. 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 preferable to use only the compound (1a) as the xanthene dye (Aa).

[式(1a)中，R^a1至R^a4相互獨立地表示氫原子、可具有取代基的碳數1至20的1價之飽和烴基或可具有取代基的碳數6至10的1價之芳香族烴基，該飽和烴基中所含的-CH₂-可被-O-、-CO-或-NR^a11-替換。R^a1和R^a2可一起形成含有氮原子的環，R^a3和R^a4可一起形成含有氮原子的環。

[In formula (1a), R ^a1 to R ^a4 independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbons which may have a substituent, or a monovalent saturated hydrocarbon group with 6 to 10 carbons 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 -. ^Ra1 and ^Ra2 can form a ring containing a nitrogen atom together, and ^Ra3 and ^Ra4 can form a ring containing a nitrogen atom together.

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

R ^a6 and R ^a7 independently 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 ^Ra5 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 the four ^Ra11 may be the same or different.

R ^a8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ^a9 and R ^a10 independently represent a hydrogen atom or a monovalent saturated hydrocarbon group with a carbon number of 1 to 20 that may have a substituent, and the -CH ₂ -contained in the saturated aliphatic hydrocarbon group may be -O-, -CO -, -NH- or -NR ^a8 -replacement, ^Ra9 and ^Ra10 may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

R ^a11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. ]

In the formula (1a), when -SO ₃ ^- is present, its number is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in ^Ra1 to ^{Ra4 include phenyl, tolyl, xylyl, mesityl, propylphenyl, and butylphenyl.}

The aromatic hydrocarbon group may have a substituent group include a halogen ^{atom, -R a8, -OH, -OR a8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, - CO ₂ R ^a8 , -SR ^a8 , -SO ₂ R ^a8 , -SO ₃ R ^a8 or -SO ₂ NR ^a9 R ^a10 . Among these, preferred substituents are based _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO ₂ NR ^a9 R ^a10, more preferably based -SO ₃ ^- Z ⁺ and -SO ₂ NR ^a9 R ^a10 . In this case, -SO ₃ ^- Z ^{+ is} preferably -SO ₃ ^-+ N(R ^a11 ) ₄ . If ^Ra1 to ^Ra4 are these groups, the coloring and curable resin composition of the present invention containing the compound (1a) can form a color filter with little foreign matter generation and excellent heat resistance.

The ^{monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms in Ra1} to ^Ra4 and ^Ra8 to ^Ra11 include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Alkyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl and other linear alkyl groups; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl And other branched chain alkyl groups; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other alicyclic saturated hydrocarbon groups with 3 to 20 carbons.

^{The hydrogen atom contained in the saturated hydrocarbon group in Ra1} to ^Ra4 may be substituted by, 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 by, for example, a hydroxyl group or a halogen atom.

^{Examples of the ring formed by Ra1} and ^Ra2 together and the ring formed by ^Ra3 and ^Ra4 together include the following rings. In the formula, * represents the bonding end.

-OR ^a8 includes, for example, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and eicosane Oxy etc.

-CO ₂ R ^a8 includes, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group.

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

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

-SO ₃ R ^a8 includes, for example, methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl and eicosanyloxy Sulfonyl and so on.

-SO ₂ NR ^a9 R ^a10 includes, for example, sulfamoyl; N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, and N-isopropylsulfamoyl Aceyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-pentylsulfamoyl , N-(1-ethylpropyl)sulfamoyl, N-(1,1-dimethylpropyl)sulfamoyl, N-(1,2-dimethylpropyl)sulfamoyl Group, N-(2,2-dimethylpropyl)sulfamoyl, N-(1-methylbutyl)sulfamoyl, N-(2-methylbutyl)sulfamoyl, N-(3-methylbutyl)sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl, N-(1,3-dimethylbutyl)sulfamoyl , N-(3,3-dimethylbutyl)sulfamoyl, N-heptylsulfamoyl, N-(1-methylhexyl)sulfamoyl, N-(1,4-bis Methylpentyl)sulfamoyl, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(1,5-dimethyl)hexylsulfamoyl, N-(1,1,2,2-tetramethylbutyl)sulfamoyl and other N-1 substituted sulfamoyl; N,N-dimethylsulfamoyl, N,N-ethyl methyl N,N-diethylsulfamoyl, N,N-propylmethylsulfamoyl, N,N-isopropylmethylsulfamoyl, N,N-tert Butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1-methylpropyl)sulfamoyl, N,N-heptylmethylsulfamoyl Etc. N, N-2 substituted sulfamoyl and so on.

R ^a5 is preferably based ^{_{-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 based SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or SO ₂ NHR ^a9 .

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

The alkyl groups having 1 to 6 carbon atoms in R ^a6 and R ^a7 include alkyl groups having 1 to 6 carbon atoms among the alkyl groups exemplified above.

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

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

The above-mentioned ⁺ N(R ^a11 ) _{4 is} preferably a monovalent saturated hydrocarbon group with 5 to 20 carbon atoms in at least 2 of the 4 ^Ra11. In addition, ^{the total carbon number of the four Ra11} is preferably 20 to 80, and more preferably 20 to 60. In the case where ⁺ N(R ^a11 ) ₄ is present in the compound (1a) ^{, if R a11} is these groups, the colored curable resin composition of the present invention containing the compound (1a) can form a color filter with less foreign matter Device.

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

[式(3a)中，R^a31和R^a32相互獨立地表示碳數1至10的1價的飽和烴基，該飽和烴基中所含的氫原子可被碳數6至10的芳香族烴基或鹵素原子取代，該芳香族烴基中所含的氫原子可被碳數1至3的烷氧基取代，上述飽和烴基中所含的-CH₂-可被-O-、-CO-或-NR^a11-替代。

[In formula (3a), R ^a31 and R ^a32 independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbons, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted by an aromatic hydrocarbon group having 6 to 10 carbons or halogen Atom substitution, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbons, and the -CH ₂ -contained in the above saturated hydrocarbon group may be -O-, -CO- or -NR ^a11 -Alternative.

R ^a33 and R ^a34 independently represent an alkyl group having 1 to 4 carbons, an alkylsulfanyl group having 1 to 4 carbons, or an alkylsulfonyl group having 1 to 4 carbons.

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

p and q represent an integer from 0 to 5 independently of each other. When p is 2 or more, the plurality of ^Ra33 may be the same or different, and when q is 2 or more, the plurality of ^Ra34 may be the same or different.

R ^a11 has the same meaning as above. ]

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

It may have an aromatic hydrocarbon group having 6 to 10 carbon atoms as a substituent, and examples thereof include the same groups as the aromatic hydrocarbon group in ^Ra1.

The alkoxy group having 1 to 3 carbon atoms includes, for example, a methoxy group, an ethoxy group, and a propoxy group.

R ^a31 and R ^{a32 are} preferably a monovalent saturated hydrocarbon group having 1 to 3 carbons independently of each other.

The alkyl groups having 1 to 4 carbon atoms in R ^a33 and R ^a34 include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and the like.

The alkylsulfanyl groups having 1 to 4 carbon atoms in R ^a33 and R ^a34 include methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl, and isopropylsulfide. Alkyl and so on.

The alkylsulfonyl groups having 1 to 4 carbon atoms in R ^a33 and R ^a34 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropylsulfonyl. Li Ji et al.

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 integers from 0 to 2, more preferably 0 or 1.

Examples of the compound (1a) include compounds represented by formula (1-1) to formula (1-43). ^Furthermore , 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.

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

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

The pigment (A2) is not particularly limited, and well-known pigments can be used. For example, pigments classified as pigments in the Excellent Index (published by The Society of Dyers and Colourists) can be used.

Examples of pigments 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, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 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 Violet 1, 19, 23, 29, 32, 36 , 38 and other purple pigments; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Brown 23, 25 and other brown pigments; CI Pigment Black 1, 7 and other black pigments.

The pigment is preferably CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other cyan pigments; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments, more preferably CI Pigment Blue 15:3, 15:6 and CI Pigment Violet 23, and more preferably CI Pigment Blue 15:6. By including the above-mentioned pigments, it is easy to optimize the transmission spectrum, and the light resistance and chemical resistance of the color filter become better.

The pigment system can be subjected to rosin treatment, surface treatment using pigment derivatives introduced with acidic or basic groups, etc., grafting treatment to the surface of the pigment using polymer compounds, etc., fine particles using sulfuric acid micronization method, etc. Chemical treatment, or cleaning treatment using organic solvents, water, etc. to remove impurities, removal treatment of ionic impurities using ion exchange methods, etc.

The pigment preferably has a uniform particle size. By containing the pigment dispersant and performing the dispersion treatment, it is possible to obtain a pigment dispersion in a state where the pigment is uniformly dispersed in the solution.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and other surfactants. These pigment dispersants may be used alone or in combination of two or more kinds. Regarding the trade name of the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Adisper (manufactured by Kyoeisha Chemical Co., Ltd.), Ajinomoto Fine Techno (manufactured by Fine Techno Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), etc.

When a pigment dispersant is used, the amount used 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 relative to the total amount of the pigment (A2). If the amount of the pigment dispersant used is in the above-mentioned range, there is a tendency that a pigment dispersion in a uniformly dispersed state can be obtained.

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

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

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

<Dispersant>

The coloring composition contains a dispersant having an amine value of 70 mgKOH/g or less. By including a dispersant having an amine value of 70 mgKOH/g or less, a coloring composition capable of forming a high-brightness color filter can be provided. The amine value of the dispersant 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, and more preferably Preferably, it is 10 mgKOH/g or more.

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

Dispersants having an amine value of 70 mgKOH/g or less include 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: 10mgKOH/g, manufactured by BYK Chemical Company), DISPERBYK-164 (amine value: 18mgKOH/g, manufactured by BYK Chemical Company), DISPERBYK-166 (amine value: 20mgKOH/g, BYK Chemical Company) Manufactured by the company), DISPERBYK-167 (amine value: 13mgKOH/g, manufactured by BYK Chemie), DISPERBYK-182 (amine value: 13mgKOH/g, manufactured by BYK Chemie), DISPERBYK-184 (amine value: 15mgKOH/g) , BYK Chemical Company), DISPERBYK-185 (Amine Value: 17mgKOH/g, BYK Chemical Company), DISPERBYK-2000 (Amine Value: 4mgKOH/g, BYK Chemical Company), DISPERBYK-2001 (Amine Value: 4mgKOH/g, BYK Chemical Company) : 29mgKOH/g, manufactured by BYK Chemie), DISPERBYK-2008 (amine value: 66mgKOH/g, manufactured by BYK Chemie), DISPERBYK-2009 (amine value: 4mgKOH/g, manufactured by BYK Chemie), DISPERBYK- 2022 (amine value: 61mgKOH/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: 3mgKOH/g, manufactured by BYK Chemical Company), DISPERBYK-2150 (amine value: 57mgKOH/g, manufactured by BYK Chemical Company), DISPERBYK-2155 (amine value: 48mgKOH/g, complete Manufactured by Kechem), DISPERBYK-2163 (amine value: 10mgKOH/g, manufactured by BYK Chemical Company), DISPERBYK-2164 (amine value: 14mgKOH/g, manufactured by BYK Chemical Company), BYK-9077 (amine value: 48mgKOH) /g, BYK Chemie), BYKLPN-21116 (amine value: 29 mgKOH/g, BYK Chemie), BYKLPN-21324 (amine value: 0 mgKOH/g, BYK Chemie), etc.

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

<Solvent>

The solvent can be used as long as it can be used as the solvent (E) of the colored curable resin composition. In order to disperse the triarylmethane compound having a heterocyclic ring, a particularly preferred solvent is, for example, an ether ester solvent, more preferably one hydroxyl group of alkylene glycol or polyalkylene glycol is etherified, and the remaining hydroxyl group is esterified. The resulting solvent includes, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, etc. These solvents may be contained singly or in multiples.

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

Moreover, when the dye (A1) is contained in the coloring curable resin composition mentioned later, if necessary, the colored composition may contain a part or all of the dye (A1) in advance, and it is preferable to contain all of it in advance. In addition, the coloring composition may contain a part or all of the pigment (B2) in advance, and it is preferable to contain all of the pigment (B2) in advance.

The colored composition may contain a part or all of the resin (B) used in the colored curable resin composition as necessary, and it is preferable to contain a part in advance. By containing the resin in advance, the dispersibility when the coloring curable resin composition is made 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, and more preferably 20 to 70 parts by mass relative to 100 parts by mass of the triarylmethane compound having a heterocyclic ring.

When preparing a dispersion, it is preferable to use a dispersing device to perform fine dispersion after appropriately adding necessary ingredients. The dispersion device can use a bead mill device. The beads used are generally hard beads such as zirconia beads, and the particle size is selected from the range of 0.05 mm or more and 20 mm or less, preferably 0.1 to 10 mm, and more preferably 0.1 to 0.5 mm.

Furthermore, the coloring composition is preferably basically composed of a triarylmethane compound having a heterocyclic ring, a dispersant having an amine value of 70 mgKOH/g or less, and a solvent. In 100% by mass of the coloring composition, the triaryl group having a heterocyclic ring The content of the methane compound, the dispersant having an amine value of 70 mgKOH/g or less, and the solvent is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90 Above mass%. After the colored composition is first prepared, it is mixed with the resin (B), the polymerizable compound (C), the polymerization initiator (D), etc., so that the improvement in heat resistance when the color filter is produced can be expected.

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

In addition, in 100% by weight of the coloring composition, 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 still more preferably 1% by mass % Or less, more preferably 0.1% by mass or less, and particularly preferably 0% by mass.

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

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

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

(a) Specific examples include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and p-vinyl benzoic acid; maleic acid, fumaric acid, citraconic acid, Zhongkang Acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid Unsaturated dicarboxylic acids such as phthalic acid, dimethyltetrahydrophthalic acid, 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 carboxyl groups such as hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride Acid anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-di Carboxybicyclo[2.2.1]hept-2-ene anhydride and other unsaturated dicarboxylic acid anhydrides; succinic acid mono[2-(meth)propenoxyethyl] ester, phthalic acid mono[2-(form) Unsaturated mono [(meth)acryloyloxyalkyl] esters of polycarboxylic acids with two or more valences, such as acryloxyethyl] ester; α-(hydroxymeth)acrylic acid is in the same molecule Unsaturated acrylates containing hydroxyl and carboxyl groups.

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

(b) refers to, 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) Preferably, it is a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

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

(b) The system includes, for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), an oxetanyl group and an ethylenically unsaturated bond The monomer (b2) (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc.

(b1) Examples include monomers (b1-1) having a structure in which linear or branched aliphatic unsaturated hydrocarbons are epoxidized (hereinafter sometimes referred to as "(b1-1)"), Monomer (b1-2) of the structure in which the alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

(b1-1) Examples include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α -Methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4 -Bis(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, etc.

(b1-2) Examples include vinylcyclohexene monoxide, 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-epoxycyclohexyl methyl (meth)acrylate (for example, CYCLOMER M100; manufactured by Daicel), The compound represented by the formula (I), the compound represented by the formula (II), and the like.

[式(I)和式(II)中，R^a和R^b表示氫原子或碳數1至4的烷基，該烷基中所含的氫原子可被羥基取代。

[In the formula (I) and Formula (II), R ^a and R ^b represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, the hydrogen atoms contained in the alkyl group may be substituted with hydroxy.

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 bonding end with O. ]

The alkyl group having 1 to 4 carbon atoms includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl.

Alkyl groups in which a hydrogen atom is substituted by a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy- 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

R ^a and R ^b are preferred series include a hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably based include hydrogen atom, methyl.

The alkylene group includes methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl Base, hexane-1,6-diyl, etc.

X ^a and X ^b preferably include single bonds, methylene, ethylene, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, more preferably single bonds, *- CH ₂ CH ₂ -O- (* indicates the bonding end with O).

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

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

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

(b2) More preferably, it is a monomer having an oxetanyl group and a (meth)acryloxy group. (b2) Examples include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-methacryloyloxymethyloxetane, 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 tetrahydrofuran group and a (meth)acryloxy group. (b3) Specifically, tetrahydrofurfuryl acrylate (for example, VISCOAT V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like can be specifically mentioned.

(b) In terms of being able to further improve the reliability of the resulting color filter such as heat resistance and chemical resistance, (b1) is preferred. Furthermore, the system (b1-2) is more preferable in terms of excellent storage stability of the colored curable resin composition.

(c) Examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, ( 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, (meth)acrylate Yl)cyclohexyl acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this technical field, customary The name is "dicyclopentyl (meth)acrylate". In addition, it is sometimes called "tricyclodecyl (meth)acrylate".), (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decene -8-yl ester (in this technical field, the common name is "dicyclopentenyl (meth)acrylate".), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, ( Adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, etc. (Meth)acrylates; (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; diethyl maleate, fumarate Diethyl phosphate, diethyl itaconate and other dicarboxylic acid diesters; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'- Hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-Dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyl Ethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept -2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl -5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexoxycarbonylbicyclo[2.2.1] Hept-2-ene, 5-phenoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5, Bicyclic unsaturated compounds such as 6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N- Benzylmaleimide, N-succinimidyl-3-maleimide benzyl Acid salt, N-succinimidyl-4-maleimidin butyrate, N-succinimidyl-6-maleimidin caproate, N-succinimidyl-3 -Dicarbonylimine derivatives such as maleimide propionate and N-(9-acridinyl)maleimide; styrene, α-methylstyrene, m-methylstyrene, P-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyl toluene, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N- Cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc.

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

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

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

If the ratio of the structural units of the resin [K1] is within the above-mentioned range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter tend to be excellent.

The resin [K1] can, for example, refer to the method described in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd., the first edition of the chemical doujin first edition issued on March 1, 1972) and the method described in the document Manufactured by the cited literature.

Specifically, it can be exemplified by filling the predetermined amount of (a) and (b), polymerization initiator, solvent, etc. into the reaction vessel, for example, replacing oxygen with nitrogen to form a deoxygenated environment, and heating and insulating while stirring method. The polymerization initiator, solvent, etc. used here are not particularly limited, and those generally used in this field can be used. For example, the polymerization initiator includes azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic peroxides ( Benzoyl peroxide, etc.), the solvent may be any solvent as long as it can dissolve each monomer, and as the solvent (E) of the coloring curable resin composition of the present invention, the solvents described below may be mentioned.

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

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

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

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

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

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

If the ratio of the structural units of the resin [K2] is within the above range, there are the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance and heat resistance of the resulting color filter Tendency to have excellent mechanical strength.

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

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 the structural unit derived from (a): 2 to 60 mol%

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

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

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

Resin [K4] can be obtained by obtaining a copolymer of (a) and (c), and adding the cyclic ether with a carbon number of 2 to 4 in (b) to the carboxylic acid and/or carboxylic anhydride of (a) manufacture.

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

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

Following the manufacture of the copolymer of (a) and (c), the atmosphere in the flask is replaced by nitrogen to air, and the reaction catalyst of (b), carboxylic acid or carboxylic acid anhydride and cyclic ether (for example, reference (dimethylamino group) (Methyl)phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) are charged into a flask, and reacted at 60 to 130°C for 1 to 10 hours, for example, to produce resin [K4].

The amount of (b) used is relative to (a) 100 mol, preferably 5 to 80 mol, more preferably 10 to 75 mol. By making it into this range, there is a tendency that the storage stability of the colored curable resin composition, the developability when forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern become good. . Since the cyclic ether has high reactivity, unreacted (b) is unlikely to remain, so (b) used in the resin [K4] is preferably (b1), more preferably (b1-1).

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

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

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

The ratio of the structural units derived from (b) and (c), relative to the total number of moles of all the structural units constituting the above-mentioned copolymer, preferably each is a structural unit derived from (b): 5 to 95 mole%

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

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

Furthermore, under the same conditions as the production method of resin [K4], the copolymer of (a) carboxylic acid or carboxylic anhydride and (b) and (c) has a cyclic ether derived from (b) By reaction, resin [K5] can be obtained.

The amount of (a) used to react with the above-mentioned copolymer is preferably 5 to 80 mol relative to (b) 100 mol. Since the reactivity of the cyclic ether is high, the unreacted (b) is unlikely to remain. As (b) used for the resin [K5], (b1) is preferred, and (b1-1) is more preferred.

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

Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride Acid anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. The amount of carboxylic anhydride used is 1 mol relative to the amount of (a) used, preferably 0.5 to 1 mol.

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 /(Meth)acrylic acid copolymer and other resins [K1]; (meth)acrylic acid glycidyl ester/(meth)acrylic acid benzyl ester/(meth)acrylic acid copolymer, (meth)acrylic acid glycidyl ester/styrene /(Meth)acrylic acid copolymer, 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl- 3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, acrylic acid/(meth)acrylic acid 3,4-epoxy tricyclic ring [5.2.1.0 ^2.6 ] Resins such as decyl ester/cyclohexyl maleimide/2-hydroxyethyl methacrylate copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth) Resins such as acrylic copolymers [K3]; Resins made by adding glycidyl (meth)acrylate and benzyl (meth)acrylate/(meth)acrylic acid copolymers to glycidyl (meth)acrylate Addition to tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer resin, adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/ Resins such as benzyl (meth)acrylate/(meth)acrylic acid copolymer [K4]; make (meth)acrylic acid and tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate Resins such as copolymers reacted with (meth)acrylic acid and tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate copolymers [K5]; (K6 ]Wait.

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

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. If the molecular weight is within the above-mentioned range, the hardness of the color filter increases, the residual film rate is high, the solubility of the unexposed part to the developer is good, and the resolution of the colored pattern tends to increase.

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

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

The content of the resin (B) relative to the total solid content of the colored curable resin composition is preferably 20 to 70% by mass, more preferably 30 to 65% by mass, and still more preferably 40 to 60% by mass . If 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 rate tend to increase.

<Polymerizable compound (C)>

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

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Such polymerizable compounds include, for example, 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 nine (meth) acrylate , Tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate , Propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) Base) acrylate and the like.

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

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass in the total solid content, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. If the content of the polymerizable compound (C) is within the above-mentioned range, the residual film rate during the formation of the colored pattern and the chemical resistance of the color filter tend to increase.

<Polymerization initiator (D)>

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

The above-mentioned O-acetoxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * indicates the bonding end.

The above-mentioned O- oxime compound can enumerate, for example, N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyloxy -1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)-3- Cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-azol-3-yl ] Ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxa Cyclopentylmethoxy)benzyl}-9H-azol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2- Methylbenzyl)-9H-oxazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-(2 -Methylbenzyl)-9H-Zolazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as IRGACURE OXE01, OXE02 (the above are manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Co., Ltd.) can be used. Among them, the O-acyl oxime compound is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyl Acetyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanylphenyl) At least one of -3-cyclopentylpropan-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1 -Keto-2-imine. If such an O-acetoxime compound is used, a high-brightness color filter tends to be obtained.

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

The compound having a partial structure represented by the formula (d2) includes, for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethyl Amino-1-(4-morpholinophenyl)-2-benzylbutane-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 (the above are made by BASF Corporation) can be used.

The compound having a partial structure represented by formula (d3) includes, for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-( 2-hydroxyethoxy)phenyl)propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Oligomers, α,α-diethoxy acetophenone, benzyl dimethyl ketal, etc.

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

The triazine compound can be exemplified by 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Yl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2 -(5-Methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene Group]-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. .

Examples of the above-mentioned phosphine oxide compound include 2,4,6-trimethylbenzyl diphenyl phosphine oxide. Commercial products such as IRGACURE (registered trademark) 819 (manufactured by BASF Corporation) can be used.

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

Furthermore, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-Benzoyl methyl benzoate, 4-phenylbenzophenone, 4-Benzoyl-4'-methyl diphenyl sulfide, 3,3',4, Benzophenone compounds such as 4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylanthracene Quinone, camphorquinone and other quinone compounds; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with the polymerization initiator (D1) (especially amines) described later.

Examples of acid generators include 4-hydroxyphenyl dimethyl sulfonium-p-toluenesulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethyl Alumium-p-toluenesulfonate, 4-acetoxyphenylmethylbenzyl alumium hexafluoroantimonate, triphenyl alumium-p-toluenesulfonate, triphenyl alumium hexafluoroantimonate, Onium salts such as diphenyliodonium-p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, etc.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkyl phenyl ketone compound, a triazine compound, an oxyphosphine oxide compound, an O-oxy oxime compound, and a biimidazole compound, and more preferably It is a polymerization initiator containing an O-acetoxime 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 with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiator (D) is within the above-mentioned range, there is a tendency to increase sensitivity and shorten the exposure time, so the productivity of the color filter improves.

<Polymerization initiator (D1)>

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

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

The above-mentioned amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 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) Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can be used.

The above-mentioned alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9 ,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

The above-mentioned thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro -4-Propoxythioxanthone and so on.

The above-mentioned carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, and dimethylphenylsulfane. Acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy Acetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.

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

<Colorant (A)>

The colorant (A) is not particularly limited, but a triarylmethane compound having a heterocyclic ring, dye (A1), pigment (A2), etc. are preferred. The coloring agent (A) is preferably a dye (A1), more preferably a xanthene dye, and still more preferably a compound represented by formula (1a).

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

<Solvent (E)>

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

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, propylene Butyl Butyrate, Isopropyl Butyrate, Ethyl Butyrate, Butyl Butyrate, Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Methyl Acetate, Ethyl Acetate, Cyclohexanol Acetate and γ-butyrolactone, etc.

The ether solvent can include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. Base ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy 3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol Glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-Methoxy Propionate, 2-Ethoxy Methyl Propionate, 2-Ethoxy Ethyl Propionate, 2-Methoxy-2-Methyl Propionate, 2-Ethoxy Ethyl-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Base ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol Alcohol monobutyl ether acetate, etc.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone , Cyclopentanone, cyclohexanone and isophorone, etc.

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, 1,3,5-trimethylbenzene, and the like.

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

Among the above-mentioned solvents, an organic solvent having a boiling point of 120° C. or more and 180° C. or less of 1 atm is preferable in terms of coating properties and drying properties. 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 70 to 95% by mass, and more preferably 75 to 92% by mass relative to the total amount of the colored curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. If the content of the solvent (E) is within the above-mentioned range, the flatness at the time of application becomes good, and the color density is not insufficient when the color filter is formed, so the display characteristics tend to become good.

<Leveling agent (F)>

The leveling agent (F) includes silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.

Examples of the organosilicon-based surfactant include surfactants having siloxane bonds in the molecule, and the like. Specifically, TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 ( Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan contract joint stock company system), etc.

The above-mentioned fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule, and the like. Specifically, Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megfac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K ( DIC (Stock) Manufacturing), EFTOP (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Materials Electronics Corporation), SURFLON (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) And E5844 (made by DAIKIN FINE CHEMICAL Research Institute) and so on.

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

The content of the leveling agent (F) relative to the total amount of the colored curable resin composition 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, and still more preferably It is 0.005 mass% or more and 0.05 mass% or less. In addition, the content of the above-mentioned pigment dispersant is not included in this content. If the content of the leveling agent (F) is within the above-mentioned range, the flatness of the color filter can be improved.

<Other ingredients>

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

<Production method of colored composition and colored curable resin composition>

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

The colored curable resin composition of the present invention can be used by combining the colored composition of the present invention, resin (B), polymerizable compound (C) and polymerization initiator (D), and the above-mentioned colored composition used as needed. The coloring agent (A), solvent (E), leveling agent (F) and other ingredients other than the coloring agent are mixed to prepare. If the colored composition is mixed with resin (B), polymerizable compound (C), polymerization initiator (D), etc. to form a colored curable resin composition, the performance of the color filter can be further improved. Heat resistance.

<Method of Manufacturing Color Filter>

As a method of producing a colored pattern from the colored curable resin composition of the present invention, a photolithography etching method, an inkjet method, a printing method, etc. can be mentioned. Among them, the photolithography etching method is preferred. The photolithographic etching method is a method of applying the colored curable resin composition to a substrate, drying it to form a colored composition layer, and exposing the colored composition layer through a photomask to develop the colored composition layer. In the photolithographic etching method, by not using a photomask and/or not developing during exposure, a colored coating film of the cured product of the colored composition layer can be formed. The colored pattern and colored coating film formed in this way can be used as the color filter of the present invention.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the purpose, application, etc., for example, it is 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 6 μm.

The substrate can use quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silica on the surface, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. Resin plates such as glycol esters, silicon, aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed on the above-mentioned substrates. Additional color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates.

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

First, a colored curable resin composition is coated on a substrate, and volatile components such as a solvent are removed and dried by heat drying (pre-baking) and/or reduced pressure drying to obtain a smooth colored composition layer.

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

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

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

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

Then, the colored composition layer is exposed to light through a photomask used to form the intended colored pattern. The pattern on the photomask is not particularly limited, and it can be used as a pattern suitable for the intended use.

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

Since parallel light can be uniformly irradiated to the entire exposure surface to accurately align the photomask and the substrate on which the colored composition layer is formed, it is preferable to use an exposure device such as a mask aligner and a stepper.

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

The development method may be any of the rotary immersion method, the dipping method, and the spray method. Furthermore, the substrate can be tilted to an arbitrary angle during development.

It is preferable to wash with water after development.

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

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. The color filter can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

[Example]

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

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

The amine value is measured in accordance with ASTM D 2074.

[Synthesis Example 1]

The following reactions are carried out in a nitrogen environment. After putting 32.2 parts of potassium thiocyanate and 160 parts of acetone into a flask equipped with a cooling tube and a stirring device, it was stirred at room temperature for 30 minutes. Then, 50 parts of 2-fluorobenzyl chloride (manufactured by Tokyo Kasei Co., Ltd.) were dropped over 10 minutes. After completion of the dropping, it was further stirred at room temperature for 2 hours. Then, after cooling the reaction mixture on ice, 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped. After completion of the dropping, it was further stirred at room temperature for 30 minutes. Next, after the reaction mixture was ice-cooled, 34.2 parts of a 30% sodium hydroxide aqueous solution was dropped. After completion of the dropping, the reaction mixture was further stirred at room temperature for 30 minutes. Next, 31.3 parts of chloroacetic acid was dropped into the reaction mixture at room temperature. After the dropping, the reaction mixture was stirred for 7 hours under heating and refluxing. Next, after the reaction mixture was allowed to cool to room temperature, the reaction mixture was poured into 120 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, and the organic layer and the water layer were separated. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of Glauber's salt was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dried organic layer. The solvent of the obtained organic layer was distilled off with an evaporator to obtain a pale yellow liquid. The obtained light 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 reactions are carried out in a nitrogen environment. After putting 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide into 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 Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, the mixture was stirred for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the reaction mixture, and stirred at room temperature for 24 hours. After adding the reaction mixture to 200 parts of ice water little by little, it was allowed to stand at room temperature for 15 hours, and the water was removed by decantation to obtain a viscous solid as a residue. After adding 60 parts of methanol to this viscous solid, it was stirred at room temperature for 15 hours. The precipitated solid is separated by filtration and refined by column chromatography. The purified pale yellow solid was dried at 60°C under reduced pressure to obtain 9.8 parts of a compound represented by formula (C-I-2). The yield was 53%.

The following reactions are carried out in a nitrogen environment. After putting 8.2 parts of the compound represented by formula (BI-2), 10 parts of the compound represented by formula (CI-2), and 20 parts of toluene into a flask equipped with a cooling tube and a stirring device, 12.2 parts of phosphorus oxychloride was added, Stir at 95 to 100°C for 3 hours. Then, after the reaction mixture was cooled to room temperature, it was diluted with 170 parts of isopropanol. Then, after pouring the diluted reaction mixture into 300 parts of saturated brine, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes to separate 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 Glauber's salt was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain an organic layer. The solvent was distilled off the obtained organic layer with an evaporator to obtain a blue-violet solid. Furthermore, the blue-violet solid was dried at 60°C under reduced pressure to obtain 18.4 parts of the compound represented by formula (X-II-2). The yield was 100%.

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

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

Accurate quality: 722.3

The following reactions are carried out in a nitrogen environment. After putting 2.0 parts of the compound represented by the formula (X-II-2) and 7.3 parts of dichloromethane into 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, the reaction solution was diluted with 34 parts of N,N-dimethylformamide while being ice-cooled. Next, after pouring the diluted reaction solution into 140 parts of toluene, it stirred for 30 minutes. Then, the stirring was stopped and decantation was performed to obtain a blue-violet viscous solid. Furthermore, the blue-violet viscous solid was dried under reduced pressure at 60°C to obtain 2.3 parts of the compound represented by formula (X-I-2). The yield was 100%.

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

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

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

Accurate quality: 846.2

The following reactions are carried out in a nitrogen environment. 2.0 parts of the compound represented by the formula (X-I-2) and 167 parts of ion-exchanged water were added to a flask equipped with a cooling tube and a stirring device, and the mixture was stirred at 40°C for 30 minutes. Add 5.8 parts of barium chloride dihydrate and 35 parts of ion-exchange water to the beaker, and stir for 30 minutes. In the previously prepared aqueous solution of the compound represented by formula (X-I-2), while keeping the liquid temperature at 40°C, the barium chloride aqueous solution was dropped and stirred for 1 hour and 20 minutes. The obtained reaction suspension was filtered, and the filtered solid was suspended and washed with 67 parts of ion exchange water, and then washed with 20 parts of ion exchange 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 formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was heated 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 stirred at room temperature for 1 hour. As a result, crystals precipitated. The precipitated crystal was obtained as a residue of suction filtration and then dried to obtain a compound represented by formula (1-32).

Identification of the compound represented by formula (1-32)

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

Accurate quality: 658.9

[Synthesis Example 3]

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

[Synthesis Example 4]

In a flask equipped with a reflux cooler, a dropping funnel and a stirrer, an appropriate amount of nitrogen is introduced, replaced with a nitrogen environment, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate are put in and stirred while stirring. Heat to 85°C. Then, 38 parts of acrylic acid, acrylic acid 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester and/or acrylic acid 3,4-epoxy tricyclo [5.2. 1.0 ^2,6 ] A mixture of 25 parts of a mixture of decane-9-yl ester, 137 parts of cyclohexyl maleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate Solution. On the other hand, it was dripped in the mixed solution which melt|dissolved 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate over 6 hours. After the dripping was completed, it was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (B-1) solution with a solid content of 25.6%. The weight average molecular weight Mw of the resulting copolymer was 8000, the degree of dispersion was 2.1, and the acid value in terms of solid content was 111 mg-KOH/g.

[Synthesis Example 5]

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was introduced to replace it with a nitrogen atmosphere, 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 acrylic acid and 3,4 acrylic acid were dropped into the flask for about 5 hours using a dropping pump -A solution obtained by dissolving 289 parts of a mixture of epoxy tricyclo[5.2.1.0 ^2,6 ] decane-9-yl ester in 125 parts of propylene glycol monomethyl ether acetate. On the other hand, 33 parts of polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) were dissolved in propylene glycol monomethyl ether by dripping into the flask for about 6 hours using another drip pump. A solution of 235 parts of acetate. After completion of the dripping, it was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) with a solid content of 35.1%. The weight average molecular weight Mw of the produced copolymer was 9,200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g.

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

Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: THF

Flow rate: 1.0mL/min

Solid content concentration of the liquid to be tested: 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 Co., Ltd.)

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

[Method of Making Dispersion Liquid (Coloring Compositions 1-1 to 1-5)]

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

Except that the dispersant P-1 is set as the dispersant P-2, the dispersant P-3, and the dispersant P-4, the rest of the system is the same as the coloring agent 1-1 to prepare a dispersion (coloring composition 1-2, Coloring composition 1-3, coloring composition 1-4).

Except that the compound represented by the formula (AI-3) is the compound represented by the formula (AX-2), and the dispersant P-1 is the dispersant P-5, the rest is the same as the coloring composition 1-1 A dispersion liquid (coloring composition 1-5) was prepared.

¹⁾ DISPERBYK-161 (Amine value 11mgKOH/g. Propylene glycol monomethyl ether acetate solution with 30% solid content)

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

³⁾ DISPERBYK-2150 (Amine value 57mgKOH/g. Propylene glycol monomethyl ether acetate solution with 52% solid content)

⁴⁾ BYKLPN-21324 (Amine value 0mgKOH/g. Propylene glycol monomethyl ether acetate solution with 40% solid content)

⁵⁾ BYKLPN-6919 (Amine value 72mgKOH/g. Propylene glycol monomethyl ether acetate solution with 60% solid content)

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

Examples 1 to 8, Comparative Examples 1 to 2

Each component was mixed so that it might become the composition shown in Table 19, and the colored curable resin composition was obtained.

^{1) It} shows the amount of resin contained in the coloring composition.

^{2) It} shows the amount of propylene glycol monomethyl ether acetate contained in the coloring composition.

In addition, in Table 19, each component shows the following. Moreover, resin (B) shows the mass part in solid content conversion.

Coloring agent (A) 1-1: Coloring composition 1-1 (amine value of dispersant: 11 mgKOH/g)

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

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

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

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

Coloring agent (A) A-1: 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-benzyloxy-1-(4-phenylsulfanylphenyl) octane-1-one-2-imine (IRGACURE (registered trademark) OXE 01 ; Manufactured by BASF; oxime compound)

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

Leveling agent (F) F-1: Polyether modified polysiloxane oil (TORAY SILICONE SH8400; manufactured by Toray Dow Corning (Stock))

<Creation of Colored Patterns>

After coating the colored curable resin composition on a 5 cm square glass substrate (EAGLE 2000; manufactured by Corning Corporation) by spin coating, it was pre-baked at 100° C. for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which the coloring 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 Co., Ltd.) was used under an atmospheric atmosphere at 60 mJ/cm Light irradiation is performed at an exposure amount of ^{2 (365nm standard).} The photomask used a photomask formed with a pattern of 100 μm lines and gaps. The light-irradiated coloring composition layer is immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds. After washing with water, it is carried out in an oven at 230°C. Bake after 20 minutes to obtain a colored pattern.

<Film Thickness Measurement>

With respect to the obtained colored pattern, the film thickness (μm) was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Chromaticity Evaluation>

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

[Industrial availability]

According to the coloring curable resin composition containing the coloring composition of the present invention, a color filter with high brightness and excellent can be manufactured.

Claims (4)

A coloring composition comprising: a triarylmethane compound with a heterocycle, a dispersant and a solvent, the dispersant has an amine value of 70mgKOH/g or less, wherein the triarylmethane compound with a heterocycle includes a compound selected from formula (I At least one compound in the group consisting of the compound represented by) and the compound represented by formula (II):

In formula (I), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons, or a substituted carbon number 7 The aralkyl group to 30, the aromatic hydrocarbon group and the substituent that the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , the hydrogen atom contained in the saturated hydrocarbon group It may be substituted by a substituted or unsubstituted amine group or a halogen atom. When the carbon number of the saturated hydrocarbon group is 2 to 20, the -CH ₂ -contained in the saturated hydrocarbon group may be replaced with at least -O- and -CO- One, but, in the saturated hydrocarbon group with 2 to 20 carbons, the adjacent -CH ₂ -will not be replaced with -O- at the same time, and the terminal -CH ₂ -will not be replaced with -O- or -CO -, R ⁴¹ and R ⁴² can bond and form a ring together with the nitrogen atom bonded by ^{R 41} and R ^{42 , and R 43} and R ⁴⁴ can bond with the nitrogen atom bonded by ^{R 43} and R ⁴⁴ form a ring, R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ together ^-, -SO ₂ -N ^- -SO ₂ -R ^f or alkyl having 1 to 8 carbon _{, -CH 2} -constituting the alkyl group can be replaced with at least one of -O- and -CO-, R ⁴⁸ and R ⁵² can be bonded to each other to form -NH-, -S- or -SO ₂ -, However, in this alkyl group, the adjacent -CH ₂ -will not be replaced with -O- at the same time, and the terminal -CH ₂ -will not be replaced with -O- or -CO-. Ring T ¹ represents carbon number 3. The aromatic heterocyclic ring having a carbon number of 1 to 10, the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbons, a substituted or unsubstituted amine group, or an aromatic hydrocarbon group having 6 to 20 carbons that may have a substituent, the aromatic The substituent that the hydrocarbon group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , where Mr ⁺ represents a hydrogen ion, an r-valent metal ion or a substituted or unsubstituted ammonium ion, and k represents R ⁴¹ To the sum of the number of -SO ₃ ^-and the number of -SO ₂ -N ^-- SO ₂ -R ^{f that R 44} , R ⁴⁷ to R ⁵⁴ and ring T ¹ have, r represents an integer greater than 1, R ^f It represents a fluoroalkyl group having 1 to 12 carbon atoms, but R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have at least one -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f ,

(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 inserted between the carbon atoms of an alkyl group of 2 to 20, an aromatic hydrocarbon group which may have a substituent, or an aralkyl group which may have a substituent, R ^b41 and R ^b42 may be bonded to each other and the R ^b41 and The nitrogen atom bonded by R ^b42 forms a ring together, R ^b43 and R ^b44 can bond and form a ring together with the nitrogen atom bonded by ^{R b43} and R ^{b44 , 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 carbons, or a group in which an oxygen atom is inserted between the carbon atoms constituting an alkyl group having 2 to 8 carbons, or R ^b46 and R ^b50 may be bonded to each other. Form -O-, -NH-, -S- or -SO ₂ -, Y ¹ represents an aromatic heterocyclic group which may have a substituent, and when the compound represented by formula (II) contains plural cations, plural cations may be They have the same structure or different structures, and n represents an arbitrary natural number. A coloring and curable resin composition comprising the coloring composition described in item 1 of the scope of patent application, resin (B), polymerizable compound (C) and polymerization initiator (D). A color filter is formed by the colored curable resin composition described in item 2 of the scope of patent application. A display device includes the color filter described in item 3 of the scope of patent application.