TWI733945B - Colored curable resin composition, color filter formed from the colored curable resin composition and display device including the color filter - Google Patents

Abstract

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

Description

Colored curable resin composition, color filter formed of the foregoing colored curable resin composition, and display device including the foregoing color filter

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

The color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are made of a coloring curable resin composition. As such a colored curable resin composition, a composition containing two kinds of compounds represented by the following formula as a colorant is known (Patent Document 1).

[Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. 2015-38201

The color filter formed from the above-mentioned colored curable resin composition known in the related art may not have sufficient light resistance.

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

The present invention includes the following inventions.

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

[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的芳香族烴基或者是 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以是-SO₃ ^-或者是-SO₂-N^--SO₂-R^f，該飽和烴基中所含的氫原子可以被經取代或未經取代的胺基或者是鹵素原子取代，該飽和烴基的碳數為2至20的情況下，該飽和烴基中所含的-CH₂-可以被置換為-O-和-CO-中的至少一者。不過，在該碳數2至20的飽和烴基中，鄰接的-CH₂-不會同時被置換為-O-，末端的-CH₂-不會被置換為-O-或者是-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 an optionally substituted carbon An aralkyl group having a number 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 , and the saturated hydrocarbon group contains The hydrogen atom of 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 one of O- and -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted 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 alkyl having a carbon number of 1 to 8, constituting the The -CH ₂ -of the alkyl group may be substituted with at least one of -O- and -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or -SO ₂ -. However, in this alkyl group, the adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted 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 carbon atoms. To 20 aromatic hydrocarbon groups. 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 . ]

[2] A color filter formed from the coloring curable resin composition described in [1].

[3] A display device including the color filter described in [2].

The coloring curable resin composition of the present invention can form a color filter excellent in light resistance.

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

<Colorant>

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

Compound (I) also includes its tautomers and their salts. 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的芳香族烴基或者是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以為-SO₃ ^-或者是-SO₂-N^--SO₂-R^f，該飽和烴基中所含的氫原子可以被經取代或未經取代的胺基或者是鹵素原子取代，該飽和烴基的碳數為2至20的情況下，該飽和烴基中所含的-CH₂-可以被置換為-O-和-CO-中的至少一者。不過，該碳數2至20的飽和烴基中，鄰接的-CH₂-不會同時被置換為-O-，末端的-CH₂-不會被置換為-O-或者是-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 an optionally substituted carbon An aralkyl group having a number 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 , and the saturated hydrocarbon group contains The hydrogen atom of 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 one of O- and -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted 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 alkyl having a carbon number of 1 to 8, constituting the The -CH ₂ -of the alkyl group may be substituted with at least one of -O- and -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or -SO ₂ -. 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 carbon atoms. To 20 aromatic hydrocarbon groups. 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 . ]

唑環、吡唑環、咪唑環、噻唑環等含有氮原子的5員環；呋喃環、噻吩環等不含氮原子的5員環；吡啶環、嘧啶環、噠

環、吡

環等含有氮原子的6員環等，作為稠環的芳香族雜環，可列舉出吲哚環、苯並咪唑環、苯並噻唑環、喹啉環等含有氮原子的稠環；苯並呋喃環等不含氮原子的稠環等。 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 to 10, preferably 3 to 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 heterocycles include pyrrole ring,

5-membered ring containing nitrogen atom such as azole ring, pyrazole ring, imidazole ring, thiazole ring; 5-membered ring containing no nitrogen atom such as furan ring, thiophene ring; pyridine ring, pyrimidine ring, pyridine ring

Ring, pyridine

6-membered rings containing nitrogen atoms such as rings. Examples of condensed aromatic heterocycles include indole rings, benzimidazole rings, benzothiazole rings, quinoline rings, and other condensed rings containing nitrogen atoms; benzo Condensed rings that do not contain nitrogen atoms, such as furan rings.

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

Wherein, as the aromatic heterocyclic ring T ¹ is preferably an aromatic heterocyclic ring containing a nitrogen atom, more preferably an aromatic heterocyclic 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的飽和烴基或者是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 carbons, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons.

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 substituted carbon 7 When the carbon number of the saturated hydrocarbon group is from 2 to 20, the -CH ₂ -contained in the saturated hydrocarbon group may be replaced with at least one of -O- and -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted 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 to the carbocation. ]

In addition, the ring T ^{1 is} also preferably 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 with 1 to 20 carbons which may have a substituent, an aromatic hydrocarbon group with 6 to 20 carbons which may have a substituent, or an aralkyl group with 7 to 30 carbons which may have a substituent .

k2 means 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的飽和烴基或者是可具有取代基的碳數6至20的芳香族烴基。

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

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 to the carbocation. ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ , R ^56, and R ⁵⁸ to R ⁶⁰ and the saturated hydrocarbon group having 1 to 20 carbon atoms that can be substituted with ^{the ring T 1 may be linear.} Any one of shape, branched chain and cyclic. Examples of linear or branched saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, Straight-chain alkyl such as hexadecyl and eicosyl; branched alkyl 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 even 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 the ring T 1} may have may have a monocyclic 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 amine group that the ring T 1} may have may include a methyl group, an ethyl group, an isopropyl group, and a propyl group. , 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 amine group that ring T 1} may have may have a saturated hydrocarbon group that may have a substituted or unsubstituted amine group or a halogen atom as a substitution base. Examples of substituted amino groups include alkylamino groups such as dimethylamino and diethylamino. In addition, examples of the halogen atom include 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.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ include straight-chain or branched saturated hydrocarbon groups ^{exemplified as the saturated hydrocarbon group represented by R 41 and those having 1 to 8 carbon atoms.} group.

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 in the linear or branched saturated hydrocarbon group ^{exemplified as the saturated hydrocarbon group represented by R 41} .

When the carbon number of the saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ _{is 2 to 20, -CH 2} -contained in the saturated hydrocarbon group may be replaced with at least one of -O- and -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted with -O- or -CO-. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (that is, a linear or branched alkyl group), and a linear saturated hydrocarbon group (that is, a linear alkyl). The preferred carbon number of the saturated hydrocarbon group in which -CH ₂ -can be substituted with at least one of -O- and -CO- is 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 between -O- or -CO- and -O- or- The carbon number before CO- 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 The carbon number of the substituent) 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, anthracenyl, phenanthryl, biphenyl, terphenyl, etc., preferably phenyl, naphthyl, tolyl, and xylene The group is particularly preferably a phenyl group. 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 group and trifluoromethyl group; carbon atoms such as methoxy group and ethoxy group. Alkoxy groups of 1 to 6; hydroxy; sulfamsulfonyl; alkylsulfonyl with 1 to 6 carbons such as methylsulfonyl; methoxycarbonyl, ethoxycarbonyl and other carbons 1 to 6 alkoxycarbonyl _{^{group; -SO 3 -; -SO 2 -N}} - -SO 2 -R f , etc., may be -SO ₃ ^- or _{^{-SO 2 -N - -SO 2 -R f}} . However, it is preferable that -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^{f are} directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, to replace the hydrogen atom bonded to the aromatic hydrocarbon ring.

As a specific example of the aromatic hydrocarbon group which may have a substituent, the group represented by the following formula is mentioned, for example. In the following formula, * represents the bonding terminal to the nitrogen atom.

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

環等含氮非芳香族4至7員環，優選地可列舉出吡咯啶環、呱啶環等只具有1個氮原子作為雜原子的4至7員環。 As R ⁴¹ and R ⁴² lines bonded to form together with the nitrogen atom of the R ⁴¹ and R ⁴² are bonded a ring, R ⁴³ and R ⁴⁴ based bond and the atom to which the R ⁴³ and R ⁴⁴ are bonded nitrogen ring, and R ⁴⁵ and R ⁴⁶ together form a ring system and is bonded to the R ⁴⁵ form together with the nitrogen atom R ⁴⁶ are bonded, include a pyrrolidine ring, a morpholine ring, a piperidine ring, quack

Nitrogen-containing non-aromatic 4- to 7-membered rings such as rings, preferably pyrrolidine rings, piperidine rings, and the like, 4- to 7-membered rings having only one nitrogen atom as a heteroatom.

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

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

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

In addition, examples of the alkyl group having 1 to 8 carbon atoms represented ^{by R 47} to R ⁵⁴ include linear or branched saturated hydrocarbon groups having 1 to 8 carbon atoms ^{exemplified as the saturated hydrocarbon group represented by R 41.}的组。 The group. In addition, as a _{group in which -CH 2} -constituting an alkyl group having 2 to 8 carbons represented ^{by R 47} to R ⁵⁴ is substituted with at least one of -O- and -CO- (however, 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-). Examples include the composition consisting of the above R ⁴¹ to R ^Among _{the groups in which the -CH 2} -of the alkyl group having 2 to 20 carbon atoms represented by 46 is substituted with at least one of -O- and -CO-, a group having 8 or less carbon atoms.

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

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

As R ⁶¹ , a hydrogen atom is preferable.

^{Examples of the r-valent metal ion 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; and 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 Wait. 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, examples of the substituted or unsubstituted ammonium ion represented by Mr ^{+ include quaternary ammonium ions such as tetraalkylammonium ions.}

As Mr ⁺ , a hydrogen ion or an r-valent metal ion is preferable, an alkaline earth metal ion, a typical metal ion, etc. are more preferable, an alkaline earth metal ion and a zinc ion are still more preferable, and an alkaline earth metal ion is still more preferable.

In the formula (I), ^{the number of Mr+} is greater than the number of -SO ₃ ^{- possessed by 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.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by R ^f include monofluoromethyl, difluoromethyl, perfluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, and tetrafluoromethyl. Fluoroethyl, perfluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, perfluoropropyl, monofluorobutyl, difluoropropyl Fluorobutyl, 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 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.

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

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

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

(Ib) Bonding with 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 having 6 to 20 carbon atoms in which the hydrogen atom of the aromatic heterocyclic ring represented by ^{T 1 is substituted}

However, when -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f is bonded to an aromatic hydrocarbon group or an aralkyl group, it is preferably -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f is directly bonded to an aromatic hydrocarbon group or an aromatic hydrocarbon ring which is an aralkyl group. That is, it is preferable that -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f replaces the hydrogen atom bonded to the aromatic hydrocarbon ring.

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

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

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

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

[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 ^-或者是-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 ^{- of R 41} , R ⁴³ , R ⁴⁷ to R ⁵⁴ , R ⁸¹ to R ⁹⁰ and ring T ¹ and the number of -SO ₂ -N ^-- SO ₂ -R ^f .

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.} As R ⁸¹ to R ⁹⁰ , a hydrogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f are preferable, and a hydrogen atom, -SO ₃ ^-, or -SO ₂ -N ^-- SO ₂ -R ^f .

-SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f preferably satisfies at least one or more conditions selected from (Ie) to (Ig), more preferably satisfies selected from (If) and (Ig) It is more preferable that at least one or more of the conditions among them satisfy the condition (If).

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

(If contained) as any 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 more preferably satisfies the condition (If').

(If') contains as any 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.

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

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

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

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

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

Compound (I) can be produced, for example, by sulfonating a compound represented by formula (IC) (hereinafter sometimes referred to as compound (IC)). 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的芳香族烴基或者是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以被經取代或未經取代的胺基或者是鹵素原子取代，該飽和烴基中所含的-CH₂-可以被置換為-O-和-CO-中的至少一者。R¹與R²可鍵結並與該R¹與R²鍵結的氮原子一起形成環，R³與R⁴可鍵結並與該R³與R⁴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 group An aralkyl group having a number of 7 to 30. In the saturated hydrocarbon group having a carbon number of 1 to 20, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amine group or a halogen atom. The saturated hydrocarbon group _{-CH 2} -contained in can 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 R nitrogen atom ² are bonded, R ³ and R ⁴ may be bonded and ³ and R ⁴ bond the nitrogen atom to form a ring together with the R.

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

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

M ¹ represents Cl ^-, phosphate ion, perchlorate ion, BF ₄ ^- or 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)"), it may be The compound (IA-1) reacts with the compound represented by the 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 of formula (I) in which Mr ⁺ is a hydrogen ion (hereinafter sometimes referred to as compound (IA-2)), compound (IA-2) can be combined with an r-valent The metal ion reacts with halide (preferably chloride), acetate, phosphate, sulfate, silicate, or cyanide.

As the method of sulfonation, various well-known methods can be cited, for example, the method described in Journal of Organic Chemistry, (1994), Vol. 59, No. 11, pages 3232-3236.

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

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

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

[式(II)中，R⁹¹和R⁹²各自獨立地表示氫原子、可具有取代基的碳數1至10的脂肪族烴基、可具有取代基的碳數3至10的脂環式烴基或者是由式(p1)表示的基團。

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

(式(p1)中，R⁹³表示碳數1至6的烷基、鹵素原子、-SO₃H、-SO₃Z、-CO₂H、-CO₂Z、-CO₂R⁹⁴、-NHCOR⁹⁴、-SO₃R⁹⁴或者是-SO₂NR⁹⁴R⁹⁵。

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

R ⁹⁴ represents an aliphatic saturated hydrocarbon group with 1 to 10 carbon atoms which may have a halogen atom, a hydroxyl group or an amino group as a substituent, or a carbon number 3 to 10 which may have a halogen atom, a hydroxyl group or an amino group as a substituent Alicyclic hydrocarbon group.

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

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

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

Z stands for Na ⁺ or K ⁺ .

＊Indicating the bonding end)]

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

Examples of the substituent that these aliphatic hydrocarbon groups may have include a hydroxyl group, a halogen atom, and the like.

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

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

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

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

Examples of -NHCOR ⁹⁴ include N-acetylamino, N-propanylamino, N-butyrylamino, N-isobutyrylamino, N-neopentylamino, and the like.

Examples of -SO ₃ R ⁹⁴ include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl and eicosanyl Oxysulfonyl and so on.

Examples of -SO ₂ NR ⁹⁴ R ⁹⁵ include N-methylsulfasulfonyl, N-ethylsulfasulfonyl, N-propylsulfasulfonyl, N-isopropylsulfasulfonyl, N -Butyl sulfasulfonyl, N-isobutyl sulfasulfonyl, N-second butyl sulfasulfonyl, N-tertiary butyl sulfasulfonyl, N-pentyl sulfasulfonyl, N -(1-Ethylpropyl)sulfasulfonyl, N-(1,1-dimethylpropyl)sulfasulfonyl, N-(1,2-dimethylpropyl)sulfasulfonyl, N-(2,2-Dimethylpropyl)sulfasulfonyl, N-(1-methylbutyl)sulfasulfonyl, N-(2-methylbutyl)sulfasulfonyl, N- (3-Methylbutyl)sulfasulfonyl, N-cyclopentylsulfasulfonyl, N-cyclohexylsulfasulfonyl, N-hexylsulfasulfonyl, N-(1,3-dimethyl Butyl)sulfasulfonyl, N-(3,3-dimethylbutyl)sulfasulfonyl, N-heptylsulfasulfonyl, N-(1-methylhexyl)sulfasulfonyl, N -(1,4-Dimethylpentyl)sulfasulfonyl, N-octylsulfasulfonyl, N-(2-ethylhexyl)sulfasulfonyl, N-(1,5-dimethyl )Hexylsulfasulfonyl, N-(1,1,2,2-tetramethylbutyl)sulfasulfonyl, N-(5-aminopentyl)sulfasulfonyl and other N-1 substituted sulfonamides Aceyl; N,N-Dimethylsulfasulfonyl, N,N-Ethylmethylsulfasulfonyl, N,N-Diethylsulfasulfonyl, N,N-propylmethylsulfonyl N,N-isopropyl methylsulfamate, N,N-tertiary butyl methylsulfamate, N,N-butylethylsulfasulfame, N,N-bis(1 -Methylpropyl)sulfasulfonyl, N,N-heptylmethylsulfasulfonyl, etc., N,N-2 substituted sulfasulfonyl and the like.

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

As R ⁹³ , an alkyl group having 1 to 5 carbon atoms which may have a hydroxyl group, -SO ₃ R ⁹⁴ , and -SO ₂ NR ⁹⁴ R ⁹⁵ are preferred, -SO ₂ NR ⁹⁴ R ^{95 is} more preferred, and -SO ₂ NHR ^{94 is} further preferred.

As the compound (II), for example, compounds represented by formula (II-1) to formula (II-19) can be cited.

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

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

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

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

The dye (A1) is not particularly limited, and well-known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes 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, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, square Acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

Specifically, CI Solvent Yellow 4 (hereinafter the description of CI Solvent Yellow is omitted, and only the serial number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162 can be cited; CI solvent red 45, 49, 125, 130, 218; CI solvent orange 2, 7, 11, 15, 26, 56; CI solvent blue 4, 5, 37, 67, 70, 90; CI solvent green 1, 4, 5, 7, 34, 35 and other CI solvent dyes, CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73 , 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168 , 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238 , 240, 242, 243, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 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, 38, 49, 72, 102; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18 , 22, 23, 24, 26, 29, 34, 38, 41, 42, 43, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 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, 50, 50: 1, 58 , 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes, CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105 , 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250 ; CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct purple 47, 52, 54, 59 , 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI direct green 25, 27, 31, 32, 34, 37 , 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dyes, CI disperse yellow 54, 76 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, etc. CI reactive dye CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 4, 9, 12 , 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52 , 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; CI Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant 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, 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料 etc.

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

The dye (A1) preferably contains a xanthene dye.

The xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of 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 others), 52, 87, 92, 94, 289, 388, and 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), sulforhodamine G, xanthene dye described in Japanese Patent Laid-Open No. 2010-32999, xanthene dye described in Japanese Patent No. 4492760, and the like. Xanthene dyes dissolved in organic solvents are preferred.

Among these, as the xanthene dye (Aa), a dye containing a compound represented by formula (1a) (hereinafter sometimes referred to as "compound (1a)") is preferable. 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 even more preferably 90% by mass or more. In particular, as the xanthene dye (Aa), it is preferable to use only the compound (1a).

[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價的飽和烴基或者是可具有取代基的碳數6至10的1價的芳香族烴基，該飽和烴基中所含的-CH₂-可以被-O-、-CO-或者是-NR^a11-置換。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 _{The -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 0 or an integer of 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 having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -contained in the saturated aliphatic hydrocarbon group may be -O-,- With CO-, -NH- or -NR ^a8 -substitution, R ^a9 and R ^a10 may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

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

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

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

Examples of the aromatic hydrocarbon group may have a substituent group include a halogen ^{atom, -R a8, -OH, -OR a8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO ₂ R ^a8 , -SR ^a8 , -SO ₂ R ^a8 , -SO ₃ R ^a8 or -SO ₂ NR ^a9 R ^a10 . Among these, as a substituent group, preferably _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO ₂ NR ^a9 R ^a10, and more preferably -SO ₃ ^- Z ⁺ and -SO ₂ NR ^a9 R ^a10. As -SO ₃ ^- Z ^{+ in} this case, -SO ₃ ^-+ N(R ^a11 ) ₄ is preferable. If ^Ra1 to ^Ra4 are these groups, the coloring 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.

^{Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms in Ra1} to ^Ra4 and ^Ra8 to ^Ra11 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, Octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl and other linear alkyl groups; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethyl Branched chain alkyl groups such as hexyl; 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.

Examples of -OR ^a8 include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and diethylhexyloxy. Decaalkoxy and so on.

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

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

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

Examples of -SO ₃ R ^a8 include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tertiary butoxysulfonyl, hexyloxysulfonyl, and oxacin Alkoxysulfonyl and the like.

Examples of -SO ₂ NR ^a9 R ^a10 include sulfasulfonyl; N-methylsulfasulfonyl, N-ethylsulfasulfonyl, N-propylsulfasulfonyl, and N-isopropyl Sulfamoyl, N-Butyl Sulfamoyl, N-Isobutyl Sulfamoyl, N-Second Butyl Sulfamoyl, N-Third Butyl Sulfamoyl, N-Pentyl Sulfamyl, N-(1-ethylpropyl)sulfamethonyl, N-(1,1-dimethylpropyl)sulfamethonyl, N-(1,2-dimethylpropyl) )Sulfasulfonyl, N-(2,2-dimethylpropyl)sulfasulfonyl, N-(1-methylbutyl)sulfasulfonyl, N-(2-methylbutyl)amine Sulfonyl, N-(3-methylbutyl)sulfasulfonyl, N-cyclopentylsulfasulfonyl, N-hexylsulfasulfonyl, N-(1,3-dimethylbutyl) Sulfamoyl, N-(3,3-dimethylbutyl)sulfasulfonyl, N-heptylsulfasulfonyl, N-(1-methylhexyl)sulfasulfonyl, N-(1 ,4-Dimethylpentyl)sulfasulfonyl, N-octylsulfasulfonyl, N-(2-ethylhexyl)sulfasulfonyl, N-(1,5-dimethyl)hexylamine Sulfonyl, N-(1,1,2,2-tetramethylbutyl)sulfasulfonyl and other N-1 substituted sulfasulfonyl groups; N,N-dimethylsulfasulfonyl, N,N -Ethyl methylsulfamate, N,N-diethylsulfamate, N,N-propyl methylsulfamate, N,N-isopropyl methylsulfamate, N A N, N-2 substituted sulfasulfonyl groups such as sulfasulfonyl groups and the like.

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

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

^{Examples of the alkyl group having 1 to 6 carbon atoms in Ra6} and ^Ra7 include alkyl groups having 1 to 6 carbon atoms among the alkyl groups exemplified above.

As the number of carbon atoms in R ^a11 7-10 aralkyl group include a benzyl group, phenylethyl, phenylbutyl and the like.

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

As the above-mentioned ⁺ N(R ^a11 ) ₄ , it is preferable ^{that at least two of the four Ra11} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. 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 coloring and curable resin composition of the present invention containing the compound (1a) can form a color filter with less foreign matter Device.

In addition, as the compound (1a), a compound represented by formula (3a) (hereinafter may be referred to as "compound (3a)") is preferred. 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以被碳數6至10的芳香族烴基或者是鹵素原子取代，該芳香族烴基中所含的氫原子可以被碳數1至3的烷氧基取代，上述飽和烴基中所含的-CH₂-可以被-O-、-CO-或者是-NR^a11-置換。

[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 A halogen atom is substituted, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbon atoms, and the -CH ₂ -contained in the above-mentioned saturated hydrocarbon group may be -O-, -CO- or- NR ^a11 -replacement.

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. ]

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

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms that can be possessed as a substituent include the same groups as the aromatic hydrocarbon group in ^Ra1.

As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example.

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

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

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ^a33 and R ^{a34 include methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl, and isopropyl.} Sulfuryl and so on.

Examples of the alkylsulfonyl groups having 1 to 4 carbon atoms in R ^a33 and R ^{a34 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropyl.} Sulfonyl and so on.

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

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

As the compound (1a), for example, compounds represented by formula (1-1) to formula (1-13) can be cited.

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

As the xanthene dye (Aa), commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Zhongwai 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 known pigments can be used. For example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists) can be cited.

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, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216 , 224, 242, 254, 255, 264, 265 and other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other cyan pigments; CI Pigment Violet 1, 19, 23, 29, 32 , 36, 38 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.

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

If necessary, the pigment can be treated with rosin, surface treatment with pigment derivatives introduced with acidic or basic groups, etc., grafting treatment with polymer compounds, etc. to the surface of the pigment, and sulfuric acid micronization method Micronization treatment such as, or cleaning treatment using organic solvents, water, etc. for removing impurities, removal treatment of ionic impurities using ion exchange methods, or the like.

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. As a pigment dispersant, it is represented by a trade name, and includes KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOREN (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), and EFKA (manufactured by CIBA) , Adisper (manufactured by Ajinomoto fine-techno Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), 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 and 50% by mass 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 to obtain a pigment dispersion in a uniformly dispersed state.

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

The content of the coloring agent (A) is preferably 1 to 60% by mass, more preferably 3 to 55% by mass, and still more preferably 5 to 50% by mass relative to the total amount of solid content. If the content of the colorant (A) is within the above-mentioned 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 that a pattern with sufficient mechanical strength can be formed . Here, the "total amount of solid content" in this specification refers to the amount excluding the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid content and the content of each component with respect to it can be measured by well-known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. As the resin (B), the following resins [K1] to [K6] and the like can be cited.

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 structure derived from a ring having 2 to 4 carbon atoms A copolymer of structural units of monomer (b) (hereinafter sometimes referred to as "(b)") having a crystalline ether structure and ethylenic unsaturated bond; resin [K2]: having structural units derived from (a) and derived from ( Copolymerization of the structural unit of b) and the structural unit derived from the monomer (c) copolymerizable with (a) (but different from (a) and (b)) (hereinafter sometimes referred to as "(c)") Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c); resin [K4]: a structural unit having a structural unit derived from (a) added to (b) Copolymer with the structural unit from (c); resin [K5]: a copolymer with the structural unit from (b) added to the structural unit from (a) and the structural unit from (c); resin [K6 ]: A copolymer having a structural unit derived from (a) added to a structural unit derived from (b), and a structural unit derived from carboxylic anhydride, and a structural unit derived from (c).

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

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 aqueous alkali solution.

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

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

Examples of (b) include monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), and 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)") and the like.

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

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

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Co., Ltd.), (methyl) 3,4-epoxycyclohexyl methyl acrylate (e.g., CYCLOMER A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexyl methyl (meth)acrylate (e.g., CYCLOMER M100; Co., Ltd. competition Made by Lu), 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表示氫原子或者是碳數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. ]

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

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

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

Examples of alkylene include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5. -Diyl, 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).

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

As the compound represented by formula (II), a compound represented by any one of formula (II-1) to formula (II-15), and the like can be cited. Among them, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) or the formula (II-11) to the formula (II The compound represented by -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 formula (I) and the compound represented by formula (II) are used in combination, their content ratio [compound represented by formula (I): compound represented by formula (II)] is calculated on a molar basis , Preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth)acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-methacryloyloxymethyloxetane, 3- Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-methacryloxy Ethyl oxetane, 3-methyl-3-propenyloxyethyl oxetane, 3-ethyl-3-methylpropenyloxyethyl oxetane, 3 -Ethyl-3-propenyloxyethyloxetane and the like.

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

As (b), (b1) is preferable from the point which can further improve the reliability of the heat resistance, chemical resistance, etc. of the color filter obtained. Furthermore, (b1-2) is more preferable in terms of excellent storage stability of the colored curable resin composition.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and third (meth)acrylate Butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate Ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this technology In the field, as a common name, it is called "dicyclopentyl (meth)acrylate." In addition, it is sometimes called "tricyclodecyl (meth)acrylate") and tricyclo (meth)acrylate [5.2.1.0 ^2,6 ] decene-8-yl ester (in this technical field, as a common name, called "(meth)acrylate dicyclopentenyl ester"), (meth)acrylate dicyclopentyloxyethyl, (meth) Base) isobornyl acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (Meth)acrylates such as benzyl (meth)acrylate; (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; horses Diethyl acrylate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept- 2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene Ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2. 1]Hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5, 6-Bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxy Bicyclo[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-tertiary-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyl Oxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tertiary butoxycarbonyl)bicyclo[2.2. 1]Hept-2-ene, 5,6-bis(cyclohexoxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N- Cyclohexylmaleimide, N-benzylmaleimide, N-succinimide 3-maleimidinyl benzoate, N-succinimidyl-4-maleimidin butyrate, N-succinimidyl-6-maleimidin caproic acid Salt, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl)maleimide and other dicarbonylimine derivatives; styrene, α-methyl Methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methyl Base propenyl amide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyl toluene, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, and N-cyclohexylmaleimide are preferred. Imines, N-benzylmaleimines, bicyclo[2.2.1]hept-2-ene, etc.

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

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

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

If the ratio of the structural units of the resin [K1] is within the above-mentioned range, there is a tendency that the storage stability of the colored curable resin composition, the developability when a colored pattern is formed, and the solvent resistance of the resulting color filter are 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. Chemical Doujin 1st Edition First Printing Issued on March 1, 1972) and the method described in this document Manufactured by the cited literature.

Specifically, it can be exemplified by filling the predetermined amounts of (a) and (b), polymerization initiator, solvent, etc. in a reaction vessel, for example, replacing oxygen with nitrogen to form a deoxygenated atmosphere, heating and stirring while stirring. Methods of heat preservation. It should be noted that the polymerization initiator, solvent, etc. used here are not particularly limited, and substances commonly used in this field can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic The oxide (benzyl peroxide, etc.) can be used as a solvent as long as each monomer is dissolved, and as the solvent (E) of the coloring curable resin composition of the present invention, the solvents described below can be cited.

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

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

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

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

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

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

If the ratio of the structural unit of the resin [K2] is within the above-mentioned 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 mechanical properties of the resulting color filter. Tendency to be excellent in 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], in terms of the ratio of the structural unit derived from each monomer, among all the structural units constituting the resin [K3], the structural unit derived from (a) is preferably: 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 produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether with 2 to 4 carbon atoms in (b) to the carboxylic acid and/or carboxylic anhydride of (a) .

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

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.

Next to the production 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 anhydride and cyclic ether (for example, tris(dimethylamine) (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 preferably 5 to 80 mol, and more preferably 10 to 75 mol relative to (a) 100 mol. By setting it within this range, the storage stability of the colored curable resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern tend to become good. Since the reactivity of the cyclic ether is high, and the unreacted (b) is unlikely to remain, as (b) used for the resin [K4], (b1) is preferable, and (b1-1) is more preferable.

Regarding the amount of the reaction catalyst used, it 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, reaction temperature, and time can be appropriately adjusted in consideration of manufacturing equipment, the amount of heat generated by 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 manufacturing equipment, the 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.

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

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

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

Furthermore, under the same conditions as the production method of the resin [K4], the cyclic ether derived from (b) which the copolymer of (a) has carboxylic acid or carboxylic anhydride and (b) and (c) has 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, and the unreacted (b) is unlikely to remain, the (b) used for the resin [K5] is preferably (b1), and more preferably (b1-1).

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

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxy tricyclic acrylic acid [5.2.1.0 ^2.6 ] Resins such as decyl ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate /Styrene/(meth)acrylic acid copolymer, acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ] decyl ester/(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 [5.2. 1.0 ^2.6 ] Resins such as decyl ester/cyclohexylmaleimide/2-hydroxyethyl methacrylate copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/( Resins such as meth)acrylic acid copolymer [K3]; a resin formed by adding glycidyl (meth)acrylate and benzyl (meth)acrylate/(meth)acrylic acid copolymer to make (meth)acrylic acid Resin made by addition of glycidyl ester and tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, making glycidyl (meth)acrylate and tricyclodecyl (meth)acrylate /(Meth)acrylic acid benzyl ester/(meth)acrylic acid copolymer resin and other resins [K4]; make (meth)acrylic acid and (meth)acrylic acid tricyclodecyl ester/(meth)acrylic acid Resins made by the reaction of glycidyl ester copolymers, resins made by reacting (meth)acrylic acid and tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate copolymers, such as resins [K5 ]; Resins obtained by reacting (meth)acrylic acid and (meth)acrylic acid tricyclodecyl ester/(meth)acrylic acid glycidyl ester copolymer and further reacting with tetrahydrophthalic anhydride, etc. Resin [K6] and so on.

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

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 range, the hardness of the color filter will increase, the residual film rate will be high, the solubility of the unexposed part in the developer will be good, and the resolution of the colored pattern will tend 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) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass relative to the total solid content. 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 using living radicals and/or acid generated by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenic unsaturated bond, etc., preferably (former Base) Acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. , 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, and more preferably 250 or more and 1500 or less.

The content rate of the polymerizable compound (C) is preferably 7 to 65% by mass relative to 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)>

化合物、醯 基氧化膦化合物、O-醯基肟化合物和聯咪唑化合物。 The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids, etc. by the action of light and heat, and a known polymerization initiator can be used. As a polymerization initiator that generates living radicals, for example, alkyl phenyl ketone compounds, three

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, * represents the bonding end.

Examples of the above-mentioned O-acetoxime compound include N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine Oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)- 3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3 -Yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxolanylmethoxy) benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-( 2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6- (2-Methylbenzyl)-9H-carbazol-3-yl]-3-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- oxime compound is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyloxy 1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanylphenyl)-3 -At least one of cyclopentylpropane-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1-one- 2-imine. In the case of these O-acyl oxime compounds, there is a tendency to obtain a color filter with high brightness.

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

As a compound having a partial structure represented by formula (d2), for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-di Methylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methan Group]-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.

As the compound having a partial structure represented by the formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4- (2-Hydroxyethoxy)phenyl)propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1- Oligomers of ketones, 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).

化合物，可列舉例如2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯 基)-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三

、2，4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三

等。 As the above three

The compound includes, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri

Wait.

As said acylphosphine oxide compound, 2,4,6-trimethylbenzyl diphenyl phosphine oxide etc. are mentioned. Commercial products such as IRGACURE (registered trademark) 819 (manufactured by BASF Corporation) can be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra (Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403 and Japanese Patent Application Publication No. 62- 174204, etc.), 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.).

Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; benzophenone, o-benzoic acid Methyl benzoate, 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butyl Peroxycarbonyl) benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10 -Butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with the polymerization initiation aid (D1) (particularly amines) described later.

As the acid generator, for example, 4-hydroxyphenyl dimethyl sulfonium-p-toluenesulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoroantimonate, 4-acetoxy phenyl two Methyl sulfonium-p-toluene sulfonate, 4-acetoxyphenyl methyl benzyl sulfonate hexafluoroantimonate, triphenyl sulfonium-p-toluenesulfonate, triphenyl sulfonium hexafluoroantimonate Onium salts such as diphenyliodonium-p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, etc.

化合物、醯基氧化膦化合物、O-醯基肟化合物和聯咪唑化合物中的至少一種的聚合起始劑，更優選包含O-醯基肟化合物的聚合起始劑。 As the polymerization initiator (D), it is preferable to contain a compound selected from alkyl phenyl ketone compounds, three

A polymerization initiator of at least one of a compound, an oxime compound, an O-oxime compound, and a biimidazole compound, and a polymerization initiator containing an O-oxime compound is more preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass relative 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 initiation aid (D1)>

The polymerization initiator (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound whose polymerization is initiated with a polymerization initiator. When the polymerization initiator (D1) is included, 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, carboxylic acid compounds, and the like.

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

Examples of the above-mentioned alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

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

Examples of the above-mentioned carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, and dimethylphenylsulfide. Alkyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

In the case of using these polymerization initiation aids (D1), the content thereof is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C), and more preferably It is 1 to 20 parts by mass. If the amount of the polymerization initiation assistant (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.

<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) Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (containing OH in the molecule, no -O-,- CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc.

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

烷、二甘醇二甲基醚、二甘醇二乙基醚、二甘醇甲基乙基醚、二甘醇二丙基醚、二甘醇二丁基醚、茴香醚、苯乙醚和甲基茴香醚等。 Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3- Methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-di

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenylethyl ether and methyl alcohol Ganisole and so on.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2-methyl propionate, 2- Ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and Diethylene glycol monobutyl ether acetate, etc.

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

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

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

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

Among the above-mentioned solvents, organic solvents having a boiling point at 1 atm of 120° C. or more and 180° C. or less are preferable in terms of coatability and drying properties. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether are preferred. Glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate , Propylene glycol monomethyl ether, N-methylpyrrolidone, ethyl lactate and ethyl 3-ethoxypropionate.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass 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 there is a tendency for the display characteristics to become good.

<Leveling agent (F)>

As the leveling agent (F), organosilicon surfactants, fluorine surfactants, organosilicon surfactants having fluorine atoms, and the like can be cited. 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 Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd. (LLC)), etc.

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

Examples of the above-mentioned organosilicon surfactants having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, MEGAFACE (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Co., Ltd.) 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 further Preferably it is 0.005 mass% or more and 0.05 mass% or less. It should be noted that this content does not include the content of the above-mentioned pigment dispersant. 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.

<Manufacturing method of colored curable resin composition>

The coloring resin composition of the present invention can be prepared by combining the colorant (A), the resin (B), the polymerizable compound (C) and the polymerization initiator (D), as well as the solvent (E) and leveling agent ( F) It is prepared by mixing with other ingredients.

<Method of Manufacturing Color Filter>

As a method of producing a colored pattern from the colored curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, and the like can be cited. Among them, the photolithography method is preferred. The photolithography method is a method of applying the above-mentioned colored curable resin composition to a substrate, drying to form a colored composition layer, and exposing the colored composition layer through a light mask to develop it. In the photolithography method, by not using a photomask and/or not developing at the time of exposure, it is possible to form a colored coating film as a cured product of the colored composition layer. 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 color filter to be produced is not particularly limited, and can be appropriately adjusted according to the purpose, application, etc., and is, for example, 0.1 to 30 m, preferably 0.1 to 20 m, and more preferably 0.5 to 6 m.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silica on the surface, polycarbonate, polymethyl methacrylate, and poly-p-phenylene can be used. Resin plates such as ethylene dicarboxylate, 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 image elements of each color using the photolithography method can be performed under known or customary devices and conditions. For example, it can be produced as follows.

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

As the coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. can be cited.

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

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

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

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

As a light source for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferable. For example, a filter that cuts light of less than 350 nm may be used to cut off the wavelength range, or a band pass filter that cuts light near 436 nm, 408 nm, and 365 nm may be used to selectively extract these wavelength ranges. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, etc. can be cited.

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

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

The development method may be any of the rotary immersion method, the dipping method, and the spray method. Furthermore, the substrate can be inclined at 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 including the compound of the present invention as a colorant, a color filter having particularly excellent light resistance can be produced. This color filter can be used as a color filter for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

[Example]

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

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

[Synthesis Example 1]

The following reactions are carried out in a nitrogen atmosphere. 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. Next, 50 parts of 2-fluorobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped over 10 minutes. After completion of the dropping, it was further stirred at room temperature for 2 hours. Next, after the reaction mixture was ice-cooled, 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was 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. Next, 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 the liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then washed with 200 parts of tap water, and finally washed with 200 parts of saturated saline. An appropriate amount of Glauber's salt was added to the organic layer, stirred for 30 minutes, and filtered to obtain a dry 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 at 60°C under reduced pressure to obtain 49.9 parts of a compound represented by formula (B-I-2). The yield was 51%.

The following reactions are carried out under a nitrogen atmosphere. After putting 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide 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. After the precipitated solid was separated by filtration, it was purified 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 under a nitrogen atmosphere. 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. Next, after the reaction mixture was cooled to room temperature, it was diluted with 170 parts of isopropanol. Next, after pouring the diluted reaction mixture into 300 parts of saturated brine, 100 parts of toluene was added and stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes to separate into an organic layer and an aqueous layer. After the water layer was discarded by the liquid separation operation, the organic layer was washed with 300 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 an organic layer. The solvent was distilled off the obtained organic layer with an evaporator to obtain a blue-purple solid. Furthermore, the purple 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] ⁺

Exact quality: 722.3

The following reactions are carried out under a nitrogen atmosphere. 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. Next, 1.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred overnight while raising the temperature to room temperature. Next, 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. Next, the stirring was stopped and decantation was performed to obtain a blue-purple viscous solid. Furthermore, the blue-violet viscous solid was dried at 60°C under reduced pressure to obtain 2.3 parts of a 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] ^-

Exact mass: 846.2

The following reaction was carried out in a nitrogen atmosphere. 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 the formula (X-I-2), while maintaining the liquid temperature of the aqueous solution 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]

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

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

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

Exact quality: 930.3

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

[Synthesis Example 3]

The compound represented by formula (A-X-1) (hereinafter also referred to as compound (A-X-1)) was synthesized according to the method described in JP 2015-38201 A.

[Synthesis Example 4]

20 parts of the compound represented by the formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries Co., 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 were precipitated. The precipitated crystal was obtained as a residue of suction filtration and then dried to obtain a compound represented by formula (A-IV).

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

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

Exact quality: 658.9

[Synthesis Example 5]

In a flask with reflux condenser, dropping funnel and stirrer, let an appropriate amount of nitrogen flow in, replace it with a nitrogen atmosphere, put in 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate, and heat while stirring To 85°C. Next, 38 parts of acrylic acid, acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester and acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ] A mixed solution 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 . 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 25.6% solid content copolymer (resin (B-1)) solution. The weight average molecular weight Mw of the produced copolymer was 8000, the degree of dispersion was 2.1, and the acid value in terms of solid content was 111 mg-KOH/g.

[Synthesis Example 6]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was introduced, replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was put in, and heated to 80°C while stirring. ^{Next, 38 parts of acrylic acid, 3,4-epoxy tricyclo [5.2.1.0 2,6} ] decane-8-yl acrylic acid and 3,4-epoxy tricyclo [5.2.1.0 2,6] decane-8-yl acrylic acid were dropped into the flask for about 5 hours using a drip pump. A solution obtained by dissolving 289 parts of a mixture of 4-epoxytricyclo[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) was dissolved in propylene glycol monomethyl by dripping into the flask for about 6 hours using another drip pump. A solution of 235 parts of ether acetate. 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 (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 by gel chromatography (GPC method) under the following conditions.

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

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: THF

Flow rate: 1.0mL/min

Solid content concentration of 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 defined as the degree of dispersion.

[Method of Making Dispersion]

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

Mix 2.4 parts of CI Pigment Blue 15:6 (pigment), 2.8 parts of acrylic pigment dispersant (in terms of solid content), 18 parts of propylene glycol monomethyl ether acetate, and 1.8 parts of ethyl lactate. Use a bead mill to make the pigment Disperse sufficiently to prepare Dispersion Liquid 2.

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

The components were mixed in the parts shown in Table 25 to obtain a colored curable resin composition.

In Table 25, each component represents the following compound.

‧Colorant (A)

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

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

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

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

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

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

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

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

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

‧Resin (B)

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

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

‧Polymerizable compound (C)

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

‧Polymerization initiator (D)

(D-1): N-Benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (IRGACURE (registered trademark) OXE-01; BASF Corporation Manufacturing; oxime compound)

‧Solvent (E):

(E-1): N-methylpyrrolidone

(E-2): Propylene glycol monomethyl ether acetate

(E-3): Ethyl lactate

‧Leveling agent (F)

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

(TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Production of Colored Coating Film>

A 5 cm square glass substrate (EAGLE 2000; manufactured by Corning Incorporated) was coated with a colored curable resin composition by spin coating so that the film thickness after post-baking became 2.0 μm, and then pre-baked at 100°C for 3 minutes to obtain Coloring composition layer. After being allowed to cool, an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used to irradiate the colored composition layer with light at an exposure amount of ^{60 mJ/cm 2 (365 nm standard) in an atmosphere.} After light irradiation, post-baking was performed in an oven at 230°C for 20 minutes to obtain a colored coating film.

In addition, the film thickness 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.

<Light resistance evaluation>

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

The xy chromaticity coordinates (x, y) and Y were measured before and after irradiation, and the color difference △Eab* was calculated from the measured values using the method described in JIS Z 8730:2009 (7. Color difference calculation method). The results are shown in Table 26 middle. The smaller the △Eab*, the smaller the color change. In addition, if the light resistance of the colored coating film is good, it can be said that the coloring pattern produced from the same coloring curable resin composition also has good light resistance.

<Evaluation of heat resistance>

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

[Industrial availability]

With the coloring curable resin composition of the present invention, a color filter having excellent light resistance can be manufactured.

Claims (3)

A coloring and curable resin composition comprising a coloring agent, a resin, a polymerizable compound, and a polymerization initiator. The coloring agent includes a compound represented by formula (I) and an anthraquinone dye,

In formula (I), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent, or a carbon number which may have a substituent. 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 saturated hydrocarbon group contains The hydrogen atom may be substituted by a substituted or unsubstituted amine group or a halogen atom. When the carbon number of the saturated hydrocarbon group is 2 to 20, the -CH ₂ -contained in the saturated hydrocarbon group may be replaced with -O At least one of-and -CO-, but in the saturated hydrocarbon group 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 can be bonded to form a ring together with the nitrogen atom to ^{which R 41} and R ^{42 are bonded, R 43} and R ⁴⁴ can be bonded ^{to form a ring with R 43} and R ring ⁴⁴ is formed are bonded together with the nitrogen atom, R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl _{^{group, -SO 3 -, -SO 2 -N}} - -SO 2 -R f , or An alkyl group having 1 to 8 carbon atoms, the -CH ₂ -constituting the alkyl group may be substituted with at least one of -O- and -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S- or -SO ₂ -, but in this alkyl group, 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 may have a substituent The aromatic hydrocarbon group having 6 to 20 carbon atoms is used as a substituent, and the substituent that the aromatic hydrocarbon group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , and M ^r+ represents a hydrogen ion, r-valent metal ion or substituted or unsubstituted ammonium ion, k represents the number of -SO ₃ ^- _{and -SO 2} -N ^{- possessed by R 41} to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ The _{sum of the number of -SO 2} -R ^f , r represents an integer of 1 or more, R ^f represents a fluoroalkyl group having 1 to 12 carbons, but R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have At least 2 -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f . A color filter is formed from the coloring curable resin composition described in item 1 of the scope of patent application. A display device includes the color filter described in item 2 of the scope of patent application.