CN102914943B

CN102914943B - Colored curable resin composition

Info

Publication number: CN102914943B
Application number: CN201210283622.0A
Authority: CN
Inventors: 秋山裕次; 铃木智也
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2011-08-04
Filing date: 2012-08-01
Publication date: 2018-01-12
Anticipated expiration: 2032-08-01
Also published as: CN102914943A

Abstract

A kind of colored curable resin composition containing colouring agent, resin, polymerizable compound and polymerization initiator, colouring agent contain the compound shown in formula (1).[in formula (1), R¹And R²Represent there can be the phenyl of substituent independently of one another.R³And R⁴1 valency saturated hydrocarbyl of carbon number 1~10 is represented independently of one another.R⁵Represent OH, SO₃H、‑8O₂NR⁹R¹⁰Deng.R⁶And R⁷The alkyl of hydrogen atom or carbon number 1~6 is represented independently of one another.M represents 0~4 integer.R⁹And R¹⁰1 valency saturated hydrocarbyl of hydrogen atom or carbon number 1~20 is represented independently of one another.].

Description

Colored curable resin composition

Technical field

The present invention relates to colored curable resin composition.

Background technology

Known colored curable resin composition be used to manufacture liquid crystal display panel, electroluminescence panel and plasma The colour filter used in the display devices such as display pannel.As such colored curable resin composition, it is known to a kind of Colored curable resin composition (JP2010-211198-A), it contains the compound and formula (A2-1b) shown in formula (A2-1a) Dyestuff and C.I. alizarol saphirol of the shown compound after 2 ethyl hexylamine carries out sulfuryl amine are as colouring agent.

For conventionally known above-mentioned colored curable resin composition, obtained by the colored curable resin composition Colour filter brightness, can not be fully satisfactory.

The content of the invention

The present invention contains following invention.

[1] colored curable resin composition containing colouring agent, resin, polymerizable compound and polymerization initiator, Toner contains the compound shown in formula (1).

[in formula (1), R¹And R²Represent there can be the phenyl of substituent independently of one another.

R³And R⁴1 valency saturated hydrocarbyl of carbon number 1~10 is represented independently of one another, the hydrogen original contained in the saturated hydrocarbyl Son can be substituted by the aromatic hydrocarbyl of carbon number 6~10 or halogen atom, and the hydrogen atom contained in the aromatic hydrocarbyl can be by carbon The alkyl of atomicity 1~3 or the alkoxy of carbon number 1~3 substitute ,-the CH contained in above-mentioned saturated hydrocarbyl₂- can by-O- ,- CO- or-NR¹¹- replace.

R¹And R³The ring of nitrogen atom, R can be formed together with nitrogen-atoms²And R⁴Nitrogen atom can be formed together with nitrogen-atoms Ring.

R⁵Expression-OH ,-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃R⁸Or-SO₂NR⁹R¹⁰。

R⁶And R⁷The alkyl of hydrogen atom or carbon number 1~6 is represented independently of one another.

M represents 0~4 integer.When m is more than 2 integer, multiple R⁵It is identical or different between each other.

R⁸1 valency saturated hydrocarbyl of carbon number 1~20 is represented, the hydrogen atom contained in the saturated hydrocarbyl can be taken by halogen atom Generation.

Z⁺Represent⁺N(R¹¹)₄、Na⁺Or K⁺。

R⁹And R¹⁰1 valency saturated hydrocarbyl of hydrogen atom or carbon number 1~20, R are represented independently of one another⁹And R¹⁰It can be in Key forms the heterocycle of 3~10 yuan of nitrogen atom together with nitrogen-atoms.

R¹¹Hydrogen atom, 1 valency saturated hydrocarbyl of carbon number 1~20 or the virtue of carbon number 7~10 are represented independently of one another Alkyl.]

[2] colored curable resin composition as described in [1], colouring agent further contain pigment.

[3] colored curable resin composition as described in [1], colouring agent contain the compound shown in formula (1 ').

[in formula (1 '), R¹、R²、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹, m and Z⁺Meaning it is same as described above.

R⁴³And R⁴⁴1 valency saturated hydrocarbyl of carbon number 1~10, the hydrogen contained in the saturated hydrocarbyl are represented independently of one another Atom can be substituted by halogen atom ,-the CH contained in the saturated hydrocarbyl₂- can be by-O- ,-CO- or-NR¹¹- replace.

R¹And R⁴³The ring of nitrogen atom, R can be formed together with nitrogen-atoms²And R⁴⁴Nitrogen atom can be formed together with nitrogen-atoms Ring.]

[4] colored curable resin composition as described in [1], colouring agent contain the compound shown in formula (2).

[in formula (2), R²¹、R²²、R²³And R²⁴The alkyl of carbon number 1~4 is represented independently of one another.R and s are independently of one another Represent 0~5 integer.When r is more than 2, multiple R²³It is identical or different, when s is more than 2, multiple R²⁴It is identical between each other It is or different.]

[5] colored curable resin composition as described in [1], colouring agent contain the compound shown in formula (3).

[in formula (3), R³¹And R³²The alkyl of carbon number 1~4 is represented independently of one another.

R³³、R³⁴、R³⁵And R³⁶The alkyl of hydrogen atom or carbon number 1~4 is represented independently of one another.]

[6] colour filter formed as the colored curable resin composition described in any one of [1]~[5].

[7] display device of [6] described colour filter is contained.

According to the colored curable resin composition of the present invention, the colour filter of high brightness can be formed.

Embodiment

The colored curable resin composition of the present invention contains colouring agent (A), resin (B), polymerizable compound (C) and gathered Initiator (D) is closed, colouring agent (A) contains the compound (below also referred to as " compound (1) ") shown in formula (1).

It is preferred that colouring agent (A) further contains pigment (A1).

It is preferred that the colored curable resin composition of the present invention further contains solvent (E).

In addition, the colored curable resin composition of the present invention can be as needed, containing selected from different from compound (1) It is at least one kind of in the group that dyestuff (following to be also referred to as " dyestuff (A2) "), polymerization initiator (D1) and surfactant (F) are formed.

The colored curable resin composition of the present invention, by being used as colouring agent containing compound (1), can manufacture high brightness Colour filter.Can be its dynamic isomer as compound (1).

[in formula (1), R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹, m and Z⁺Meaning it is same as described above.]

Represent R⁸、R⁹、R¹⁰And R¹¹1 valency saturated hydrocarbyl of carbon number 1~20 can enumerate, such as methyl, ethyl, third The carbon numbers such as base, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl and eicosyl 1 ~20 straight-chain alkyl；The carbon such as isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, neopentyl and 2- ethylhexyls are former The branched-chain alkyl of subnumber 3~20；The carbon numbers such as cyclopropyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl and tricyclodecyl 3 ~20 ester ring type saturated hydrocarbyl.

-OR⁸It can enumerate, such as methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, epoxide in heptan, pungent oxygen Base, 2- ethyl hexyl oxies and eicosane epoxide.

-CO₂R⁸It can enumerate, such as methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxy Carbonyl and eicosane epoxide carbonyl.

-SR⁸It can enumerate, such as methylsulfanyl, Ethylsulfanyl, butyl sulfanyl, hexyl sulfanyl, decyl sulfanyl And eicosyl sulfanyl.

-SO₂R⁸It can enumerate, such as methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, decyl sulphonyl Base and eicosyl sulfonyl.

-SO₃R⁸It can enumerate, such as methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxy sulphonyl Base, hexyloxy sulfonyl and eicosane epoxide sulfonyl.

-SO₂NR⁹R¹⁰It can enumerate, such as sulfamoyl；

N- Methylsulfamoyls, N- ethylsulfamovls, N- propylsulfamovs, N- isopropylsulfamoyls base, N- butyl Sulfamoyl, N- isobutyl groups sulfamoyl, N- sec-butyls sulfamoyl, N- tert-butyl groups sulfamoyl, N- amyl groups sulfamoyl, N- (1- ethyl propyls) sulfamoyl, N- (1,1- dimethyl propyl) sulfamoyl, N- (1,2- dimethyl propyl) sulfamoyl, N- (2,2- dimethyl propyl) sulfamoyl, N- (1- methyl butyls) sulfamoyl, N- (2- methyl butyls) sulfamoyl, N- (3- Methyl butyl) sulfamoyl, N- Cyclopentylsulfamoyls base, N- hexyls sulfamoyl, N- (1,3- dimethylbutyl) sulfamoyl, N- (3,3- dimethylbutyl) sulfamoyl, N- heptyl sulfamoyl, N- (1- methylhexyls) sulfamoyl, N- (Isosorbide-5-Nitraes-diformazan Base amyl group) sulfamoyl, N- octyl groups sulfamoyl, N- (2- ethylhexyls) sulfamoyl, N- (1,5- dimethyl) hexyl ammonia sulphur The N-1 such as acyl group, N- (1,1,2,2- tetramethyl butyl) sulfamoyl substitute sulfamoyl；

N, N- DimethylsuIfamoyl, N, N- ethyl-methyls sulfamoyl, N, N- diethyl aminos sulfonyl, N, N- propyl group first Base sulfamoyl, N, N- isopropyl methyls sulfamoyl, N, N- tertbutyl methyls sulfamoyl, N, N- butyl ethyl sulfonamides Base, N, N- bis- (1- methyl-propyls) sulfamoyl, N, N-2 the substitution sulfamoyl such as N, N- hept-ylmethyl sulfamoyls etc..

R⁹And R¹⁰Mutually bonding 3~10 yuan of nitrogen heterocyclic ring can be formed together with nitrogen-atoms (containing more than 1 nitrogen original in ring The heterocycle of son).The heterocycle can enumerate for example following heterocycle.

Represent R³And R⁴1 valency saturated hydrocarbyl of carbon number 1~10 can enumerate, as R⁸Saturated hydrocarbyl cited by The alkyl of carbon number 1~10 among alkyl.

The aromatic hydrocarbyl of carbon number 6~10 can be enumerated, phenyl, naphthyl etc..It may replace these carbon numbers 6~10 Among the group of the hydrogen atom contained in aromatic hydrocarbyl, as the alkyl of carbon number 1~3, methyl, ethyl, just there are Propyl group, isopropyl etc., as the alkoxy of carbon number 1~3, it there are methoxyl group, ethyoxyl, positive propoxy, isopropoxy Deng.

Saturated hydrocarbyl after being substituted by the aromatic hydrocarbyl of carbon number 6~10 can be enumerated, for example, benzyl, phenylethyl, Phenyl propyl, phenyl butyl, tolylmethyl, tolylethyl, tolylpropyl, tolyl butyl, methoxyphenyl methyl, Methoxyphenyl ethyl, methoxyphenyl propyl group and methoxyphenyl butyl.

Halogen atom can be enumerated, such as fluorine atom, chlorine atom, bromine atoms and iodine atom.

Saturated hydrocarbyl after being substituted by halogen atom can be enumerated, such as methyl fluoride, difluoromethyl, trifluoromethyl, perfluoro-ethyl And chlorobutyl.

R³And R⁴It is preferred that 1 valency saturated hydrocarbyl of unsubstituted carbon number 1~10,1 valency of more preferably carbon number 1~4 are satisfied And alkyl, 1 valency saturated hydrocarbyl of further preferred carbon number 1~3, particularly preferred methyl and ethyl.

Represent R⁶And R⁷The alkyl of carbon number 1~6 can enumerate, such as methyl, ethyl, propyl group, butyl, amyl group, oneself Base, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl and neopentyl.

Represent R¹¹The aralkyl of carbon number 7~10 can enumerate, such as benzyl, phenylethyl and phenyl butyl.

Z⁺For⁺N(R¹¹)₄、Na⁺Or K⁺, preferably⁺N(R¹¹)₄。

As above-mentioned⁺N(R¹¹)₄, preferably 4 R¹¹Among, at least 21 valency saturated hydrocarbyls for carbon number 5~20. Furthermore it is preferred that 4 R¹¹Total carbon atom number be 20~80, more preferably 20~60.

Represent R¹And R²Phenyl can have substituent.The substituent can be enumerated, such as halogen atom ,-R⁸、-OH、-OR⁸、- SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂R⁸、-SR⁸、-SO₂R⁸、-SO₃R⁸And-SO₂NR⁹R¹⁰.Among these substituents, preferably-R⁸, more It is preferred that 1 valency saturated hydrocarbyl of carbon number 1~10.- SO now₃ ^-Z⁺It is preferred that-SO₃ ^-+N(R¹¹)₄。

Phenyl with substituent, tolyl, 3,5-dimethylphenyl, ethylbenzene, propyl phenyl, isopropyl phenyl, first can be enumerated Base methyldisulfanylphenyl, methylsulfonyl phenyl etc..Wherein, preferably there is the benzene of substituent at the ortho position of the bonding position with nitrogen Base.

R¹And R²It is preferably the phenyl of the 1 valency saturated hydrocarbyl with carbon number 1~4, more preferably toluene independently of one another Base or 3,5-dimethylphenyl, further preferred o-tolyl or 2,6- 3,5-dimethylphenyl.

R¹And R³The ring of nitrogen atom, R can be formed together with nitrogen-atoms²And R⁴Nitrogen atom can be formed together with nitrogen-atoms Ring.Ring containing the nitrogen-atoms can be enumerated for example as follows.

R⁵It is preferred that-SO₃H、-SO₃ ^-Z⁺And-SO₂NR⁹R¹⁰。

R⁶And R⁷It is preferred that hydrogen atom, methyl and ethyl, more preferably hydrogen atom.

M preferably 0~2 integer, more preferably 1 or 2.

Compound (1) is preferably the compound shown in formula (1 ').

[in formula (1 '), R¹、R²、R⁴³、R⁴⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹, m and Z⁺Meaning it is same as described above.]

As 1 valency saturated hydrocarbyl of carbon number 1~10, R can be enumerated³And R⁴Middle identical group, preferable group also phase Together.

As R¹And R⁴³With the ring of the nitrogen atom formed together with nitrogen-atoms, and R²And R⁴⁴Contain with what is formed together with nitrogen-atoms The ring of nitrogen-atoms, can be enumerated and R¹And R³With the ring identical ring of the nitrogen atom formed together with nitrogen-atoms.

Compound shown in compound (1) preferred formula (2).

[in formula (2), R²¹、R²²、R²³、R²⁴, r and s meaning it is same as described above.]

Represent R²¹、R²²、R²³And R²⁴The alkyl of carbon number 1~4 can enumerate, methyl, ethyl, propyl group, butyl, isopropyl Base, isobutyl group, sec-butyl, tert-butyl group etc..

R²¹And R²²1 valency saturated hydrocarbyl of preferred carbon number 1~3, more preferably methyl and ethyl independently of one another.R²³And R²⁴It is preferred that methyl.

R and s preferably 0~2 integer, preferably 1 or 2.

Compound shown in compound (1) preferred formula (3).

[in formula (3), R³¹、R³²、R³³、R³⁴、R³⁵And R³⁶Meaning it is same as described above.]

Represent R³¹~R³⁶Carbon number 1~4 alkyl it is same as described above.

R³¹And R³²1 valency saturated hydrocarbyl of preferred carbon number 1~3, more preferably methyl and ethyl independently of one another.R³³~ R³⁶It is preferably hydrogen atom or methyl independently of one another.

Compound (1) can be enumerated, such as the compound shown in any one in formula (1-1)~formula (1-15).Wherein, base In the point that dissolubility in organic solvent is excellent, the chemical combination shown in preferred formula (1-1), formula (1-2) or formula (1-5)~formula (1-12) Thing.

The manufacture method of compound (1) can be enumerated, make compound shown in formula (1a) and the compound shown in formula (1b) and Compound shown in formula (1c), in presence of organic solvent or the solvent-free lower method reacted.Point based on yield, it is excellent Select it is solvent-free under be allowed to react.Preferably 30 DEG C~180 DEG C, more preferably 80 DEG C~130 DEG C of reaction temperature.Reaction time preferably 1 is small When~12 hours, more preferably 3 hours~8 hours.

[in formula (1b) and formula (1c), R¹~R⁴Meaning difference it is same as described above.]

Above-mentioned organic solvent can be enumerated, the hydrocarbon solvent such as toluene, dimethylbenzene；The halogenated hydrocarbon solvents such as chlorobenzene, dichloro-benzenes, chloroform； The alcoholic solvents such as methanol, ethanol, butanol；The nitro hydrocarbon solvent such as nitrobenzene；The ketone solvents such as methyl iso-butyl ketone (MIBK)；1- methyl -2- pyrroles Amide solvents such as alkanone etc..

The usage amount of the compound shown in compound and formula (1c) shown in formula (1b), relative to 1 mole of formula (1a) Suo Shi Compound, respectively preferably less than more than 1 mole 8 moles, more preferably less than more than 1 mole 5 moles.It can be allowed to interim respectively Reaction, or simultaneous reactions.

Based on the point of easy to manufacture compound (1), the compound shown in preferred formula (1b) and the compound shown in formula (1c) For identical structure.

Obtain from reactant mixture and be not particularly limited as the method for the compound (1) of target compound, can be taken known Various methods.Such as, reactant mixture and acid (such as, acetic acid etc.) be mixed together, may filter that the crystal for obtaining and separating out.It is excellent The aqueous solution of the choosing by above-mentioned sour pre-coordination for acid, then reactant mixture is added into the above-mentioned aqueous solution.Addition reaction mixing Preferably less than more than 10 DEG C 50 DEG C of temperature during thing.Furthermore it is preferred that stir 0.5~2 hour or so at that same temperature afterwards. The crystal of leaching is preferably cleaned with water etc., then is dried.In addition, also can be as needed, pass through method known to recrystallization etc. Further purification.

The content of compound (1) relative to solid constituent total amount, preferably more than 0.025 mass % below 48 mass %, More preferably more than 0.08 mass % below 42 mass %, further preferred below the mass % of more than 0.1 mass % 30.Herein, originally " total amount of solid constituent " in specification refers to, after removing solvent from the total amount of colored curable resin composition Amount.The total amount of solid constituent and each composition, can be for example, by liquid chromatography or gas relative to the content of the solid constituent total amount Analysis method known to phase chromatography etc. is measured.

In addition, when also containing pigment (A1) and/or dyestuff (A2) while colouring agent (A) contains compound (1), compound (1) content relative to colouring agent (A) total amount, preferably more than 0.5 mass % below 80 mass %, more preferably 1 mass % with Upper below 70 mass %, further preferred below the mass % of more than 1 mass % 50.

Pigment (A1) is not particularly limited, and known pigment can be used, can enumerate such as color index (the イ Application デッ Network of ヵラ mono- The compound of pigment ス) is categorized as in (The Society of Dyers and Colourists publication).

Pigment can be enumerated, for example, C.I. pigment yellows 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93, 94th, the yellow such as 109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214 Pigment；

C.I. the orange pigment such as pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71,73；

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,175,176,177,180,192,209, 215th, the red pigment such as 216,224,242,254,255,264,265；

C.I. pigment blue 15,15:3、15:4、15:6th, the blue pigment such as 60,80；C.I. pigment violet 1,19,23,29,32, 36th, the violet pigment such as 38；

C.I. the viridine green such as pigment Green 7,36,58；

C.I. the brown pigments such as bistre 23,25；

C.I. black pigment such as pigment black 1,7 etc..

These pigment can be used alone, or two or more is mixed.

The preferred C.I. pigment blue 15s of pigment, 15:3、15:4、15:6th, the blue pigments such as 60 and C.I. pigment violet 1s, 19,23, 29th, the violet pigment such as 32,36,38, more preferably C.I. pigment blue 15s:3、15:6 and C.I. pigment Violet 23s, further preferred C.I. Pigment blue 15:6.By the way that containing above-mentioned pigment, the colored curable resin composition of the present invention especially is being modulated into au bleu During colored curable resin composition, easily transmitted spectrum is optimized, the light resistance and chemical proofing of colour filter Improve.

Pigment (A1) can be as needed, implements rosin processing, the pigment derivative by having imported acidic groups or basic group Etc. being surface-treated, grafting processing is carried out to surface of pigments by high-molecular compound etc., entered by sulfuric acid particles method etc. The processing of row micronized, or implement the cleaning treatment by organic solvent or water etc., the ion-exchange of ionic impurity etc. Removing processing etc. is to remove impurity.

Pigment (A1) preferable particle size is homogeneous.By be allowed to containing pigment dispersing agent carry out decentralized processing, can obtain pigment with Uniform state is scattered in the dispersible pigment dispersion in solution.

Above-mentioned pigment dispersing agent can be enumerated, such as cation system, anion system, nonionic system, both sexes, Polyester, poly- Pigment dispersing agents such as amine system, acrylic acid series etc..These pigment dispersing agents can be used singly or two or more kinds in combination.Pigment dispersing agent It can be enumerated with trade name, KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), the レ Application of Off ロ mono- (common prosperity society chemistry (strain) system), ソ Le スパ mono- ス (ゼネヵ (strain) systems), EFKA (CIBA societies system), ァジスパ mono- (monosodium glutamate Off ァイ Application テ Network ノ (strain) systems), Disperbyk (the society's systems of PVC ッ Network ケミ mono-) etc..

When using pigment dispersing agent, its usage amount relative to pigment (A1), preferably more than 1 mass % 100 mass % with Under, more preferably more than 5 mass % below 50 mass %.When pigment dispersing agent usage amount within the above range when, have obtain The tendency of the dispersible pigment dispersion of homogeneous dispersity.

When colouring agent (A) contains pigment (A1), the content of pigment (A1) relative to colouring agent (A) total amount, preferably 20 Below the mass % of more than quality % 99.5, more preferably more than 30 mass % below 99 mass %.

Dyestuff (A2) can be enumerated, oil-soluble dyes, acid dyes, basic-dyeable fibre, direct dyes, mordant dye, acid dye The dyestuff such as the amine salt of material or the sulfamide derivative of acid dyes, such as color index (The Society of can be used Dyers and Colourists are published) in be categorized as the compound of dyestuff, or the public affairs described in dyeing handbook (Se Ran societies) Know dyestuff.In addition, it can be enumerated according to chemical constitution, azo dyes, cyanine dye, triphenhlmethane dye, xanthene dye, phthalocyanine Dyestuff, naphthoquinone dyestuff, quinoneimine dye, methine type dye, azo methine type dye, squaraine dye, acridine dye, styryl Dyestuff, coumarine dye, quinoline dye and nitro dye etc..Wherein, preferable organic solvent soluble dye.

Specifically, can enumerate C.I. solvent yellows 4 (record of C.I. solvent yellows omitted below, only describe its numbering), 14, 15、23、24、38、62、63、68、82、94、98、99、162；

C.I. solvent red 45,49,125,130,218；

C.I. solvent orange 2,7,11,15,26,56；

C.I. solvent blue 4,5,37,67,70,90；

C.I. the green C.I. solvent dyes such as 1,4,5,7,34,35 of solvent,

C.I. Indian 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；

C.I. azogeramine, 4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66, 73、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、182、 183、195、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、 274、277、280、281、289、308、312、315、316、339、341、345、346、349、382、383、388、394、401、 412、417、418、422、426；

C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108, 169、173；

C.I. acid violet 6B, 7,9,17,19,30,102；

C.I. Blue VRS, 7,9,15,18,22,29,42,59,60,62,70,72,74,82,83,86,87,90,92, 93、100、102、103、104、113、117、120、126、130、131、142、147、151、154、158、161、166、167、 168、170、171、184、187、192、199、210、229、234、236、242、243、256、259、267、285、296、315、 335；

C.I. the C.I. acid dyes such as acid green 1,3,5,9,16,50,58,63,65,80,104,105,106,109,

C.I. directly Huang 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；

C.I. direct 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；

C.I. direct orange 26,34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107；

C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104；

C.I. directly indigo plant 1,2,6,8,15,22,25,41,57,71,76,78,80,81,84,85,86,90,93,94,95, 97、98、99、100、101、106、107、108、109、113、114、115、117、119、120、137、149、150、153、155、 156、158、159、160、161、162、163、164、165、166、167、168、170、171、172、173、188、189、190、 192、193、194、195、196、198、199、200、201、202、203、207、209、210、212、213、214、222、225、 226、228、229、236、237、238、242、243、244、245、246、247、248、249、250、251、252、256、257、 259、260、268、274、275、293；

C.I. the C.I. such as direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82 directly contaminates Material,

C.I. disperse yellow 54,76 grade C.I. disperse dyes,

C.I. alkali red 1:1,10；

C.I. alkali blue 1,3,5,7,9,19,24,25,26,28,29,40,41,54,58,59,64,65,66,67,68；

C.I. Viride Nitens 1；Deng C.I. basic-dyeable fibres,

C.I. active yellow 2,76,116；

C.I. reactive orange 16；

C.I. active red 36；Deng C.I. reactive dye,

C.I. mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65；

C.I. mordant rouge 1,2,4,9,12,14,17,18,19,22,23,24,25,26,27,30,32,33,36,37,38, 39、41、43、45、46、48、53、56、63、71、74、85、86、88、90、94、95；

C.I. mordant dyeing orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47, 48；

C.I. mordant dyeing purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53,58；

C.I. mordant dyeing indigo plant 1,2,3,7,9,12,13,15,16,19,20,21,22,26,30,31,39,40,41,43,44, 49、53、61、74、77、83、84；

C.I. the C.I. mordant dyes such as viridon 1,3,4,5,10,15,26,29,33,34,35,41,43,53,

C.I. the grade of vat green 1 C.I. reducing dyes etc..

Wherein, preferably blue dyes, cudbear and orchil.

These dyestuffs spectrophotometric spectra of colour filter according to expected from is suitably selected.These dyestuffs can individually make With or two or more be used in combination.

In addition, when being classified according to chemical constitution, preferably phthalocyanine dye, the more preferably compound shown in formula (4).

[in formula (4), G¹The alkylidene of carbon number 2~12 is represented, the hydrogen atom contained in the alkylidene can be by carbon atom The alkyl of number 1~4 substitutes ,-the CH contained in the alkylidene₂- can be replaced by-O-.

J¹Represent hydrogen atom ,-NR^aR^bOr-NR^aR^bH⁺Q^-。

R^aAnd R^bThe alkyl of hydrogen atom or carbon number 1~8 is represented independently of one another.

Q^-Represent halide ion, BF₄ ^-、PF₆ ^-、ClO₄ ^-、X-CO₂ ^-Or Y-SO₃ ^-。

X and Y represents 1 valency organic group independently of one another.

P represents 1~4 integer.]

The p hydrogen atom contained in compound shown in formula (4) expression (4-0) is by-SO₂-NH-G¹-J¹Substitution.When p is When more than 2, multiple-SO₂-NH-G¹-J¹It may be the same or different each other.

The alkylidene of carbon number 2~12 can be enumerated, methylene, ethylidene, propylidene, butylidene etc..

-CH₂The alkylidene of-the carbon number 2~12 that substituted for Bei-O- can be enumerated, group and formula shown in formula (G-1) (G-2) group shown in.

[in formula (G-1) and formula (G-2), G²~G⁵The alkylidene of carbon number 1~8 is represented independently of one another.

n¹Represent 1~3 integer.

n²Represent 0~3 integer.

Wherein, the carbon atom and the sum of oxygen atom contained in group shown in formula (G-1) is 3~12, base shown in formula (G-2) The carbon atom and the sum of oxygen atom contained in group is 2~12.

* the bonding position with-NH- is represented.]

The alkyl of carbon number 1~4 can be enumerated, methyl, ethyl, propyl group, butyl etc..

-SO₂-NH-G¹-J¹It can enumerate, such as the group shown in following formula.

Work as G¹For shown in formula (G-1) during group ,-SO₂-NH-G¹-J¹It can enumerate, such as the group shown in following formula.

Work as G¹For shown in formula (G-2) during group ,-SO₂-NH-G¹-J¹It can enumerate, such as the group shown in following formula.

Work as J¹For-NR^a R^bWhen ,-SO₂-NH-G¹-J¹It can enumerate, such as the group shown in following formula.

Work as J¹For-NR^a R^bH⁺Q^-When ,-SO₂-NH-G¹-NR^aR^bH⁺It can enumerate, such as the group shown in following formula.

X and Y represents 1 valency organic group.1 valency organic group can be enumerated, and the alkyl of carbon number 1~20, carbon number 3~ 20 cycloalkyl, the aryl of carbon number 6~20 and combinations thereof group etc..

The alkyl of carbon number 1~20 can be enumerated, methyl, ethyl, propyl group, butyl, hexyl, decyl etc..

The cycloalkyl of carbon number 3~20 can be enumerated, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclodecyl etc..

The aryl of carbon number 6~20 can be enumerated, and phenyl, naphthyl, fear base etc..

X-CO₂ ^-To contain CO₂ ^-The organic matter anion of base, Y-SO₃ ^-To contain SO₃ ^-The organic matter anion of base, can be enumerated Such as the anion shown in formula (Q-1)~formula (Q-4).

[R^yRepresent the alkyl of carbon number 1~20.

M represents 0~5 integer.]

The preferred X-CO of Q-₂ ^-And Y-SO₃ ^-, the anion more preferably shown in formula (Q-4).When for these anion when, there is formula (2) tendency that the dissolubility of compound in a solvent shown in uprises.

Compound shown in formula (4) can be enumerated, such as the compound shown in formula (2-1)~formula (2-92).Formula (2-

1) among the compound shown in~formula (2-92), n is worked as^aFor more than 2 integer when, preferably multiple-SO₂-NH-G¹-J¹ It is bonded respectively from different phenyl ring.

For example, the further concrete example of the compound shown in formula (2-24) can be enumerated, formula (2-24-1) and formula (2-24- 2) compound shown in.

When colouring agent (A) contains dyestuff (A2), the content of dyestuff (A2) relative to colouring agent (A) total amount, preferably 0.5 Below the mass % of more than quality % 35, more preferably more than 1 mass % below 30 mass %.

Colouring agent (A) preferably, the colouring agent being made up of compound (1) and pigment (A1), and by compound (1), pigment (A1) and dyestuff (A2) form colouring agent.

When colouring agent (A) is the colouring agent being made up of compound (1) and pigment (A1), they are relative to colouring agent (A) The content of total amount, is respectively preferably

Compound (1)：Below the mass % of more than 0.5 mass % 80

Pigment (A1)：Below the mass % of more than 20 mass % 99.5, more preferably

Compound (1)：Below the mass % of more than 1 mass % 50

Pigment (A1)：Below the mass % of more than 50 mass % 99.

When colouring agent (A) is the colouring agent being made up of compound (1), pigment (A1) and dyestuff (A2), they relative to The content of colouring agent (A) total amount, is respectively preferably

Compound (1)：Below the mass % of more than 0.5 mass % 79.5

Pigment (A1)：Below the mass % of more than 20 mass % 99

Dyestuff (A2)：Below the mass % of more than 0.5 mass % 35 are more preferably

Compound (1)：Below the mass % of more than 1 mass % 50

Pigment (A1)：Below the mass % of more than 49 mass % 98

Dyestuff (A2)：Below the mass % of more than 1 mass % 30.

Colouring agent (A) more preferably 8~55 mass %, enters relative to content preferably 5~60 mass % of solid constituent total amount One step preferably 10~50 mass %.When colouring agent (A) content within the above range when, when being made colour filter, have enough Colour saturation, and resin (B) and polymerizable compound (C) in composition containing necessary amount can be made, therefore mechanical strength can be formed and filled The pattern divided.

Resin (B) though be not particularly limited, preferably alkali soluble resin.As resin (B), following resin can be enumerated [K1]~[K6] etc..

At least one kind of (a) in the group that resin [K1] is formed selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides is (following to be also referred to as " (a) "), with the monomer (b) of the ring-type ether structure with carbon number 2~4 and ethene unsaturated bond (below also referred to as " (b) ") Copolymer；

Resin [K2] (a) is with (b) with that (can be also referred to as below with the monomer (c) (but not identical with (a) and (b)) of (a) copolymerization " (c) ") copolymer；

The copolymer of resin [K3] (a) and (c)；

Resin [K4] (a) and (c) copolymer again with (b) reaction obtained by resin；

Resin [K5] (b) and (c) copolymer again with (a) reaction obtained by resin；

Resin [K6] (b) and (c) copolymer react with (a) again, further again with carboxylic acid anhydride reactant obtained by resin.

(a) can specifically enumerate, for example, acrylic acid, methacrylic acid, butenoic acid, it is o-, m-, to vinyl benzoic acid etc. no Saturated monocarboxylic acid class；

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- ethene phthalandione, 4- ethene phthalandione, 3,4,5,6- The unsaturated dicarboxylic acid class such as tetrahydrochysene phthalandione, 1,2,3,6- tetrahydrochysene phthalandiones, dimethyl tetrahydro phthalandione, Isosorbide-5-Nitrae-cyclohexene dicarboxylic acid；

Methyl -5- ENBs -2,3- dicarboxylic acids, bicyclic [the 2.2.1] -2- heptene of 5- carboxyls, 5,6- dicarboxyls are bicyclic [2.2.1] -2- heptene, 5- carboxyl -5- methyl bicycle [2.2.1] -2- heptene, 5- carboxyl -5- ethyls bicyclic [2.2.1] -2- heptan Alkene, 5- carboxyl -6- methyl bicycle [2.2.1] -2- heptene, bicyclic [the 2.2.1] -2- heptene of 5- carboxyl -6- ethyls etc. contain carboxyl Bicyclic unsaturated compound class；

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3- ethene anhydride phthalic acid, 4- ethene anhydride phthalic acid, 3,4,5,6- tetrahydrochysene phthalandiones The insatiable hunger such as acid anhydride, 1, bicyclic [the 2.2.1] -2- heptene acid anhydrides of 2,3,6- tetrahydrochysene anhydride phthalic acids, dimethyl tetrahydro anhydride phthalic acid, 5,6- dicarboxyls With dicarboxylic acids class acid anhydrides；

The divalents such as mono succinate (2- (methyl) acrylyl oxy-ethyl) ester, phthalandione list (2- (methyl) acrylyl oxy-ethyl) ester Single ((methyl) acryloyloxyalkyl) esters of unsaturation of above polybasic carboxylic acid；

The such unsaturated esters of acrylic acid containing hydroxyl and carboxyl in same molecule of α-(hydroxymethyl) acrylic acid Deng.

Wherein, the point based on copolyreaction or the deliquescent point in the resin aqueous alkali of gained, preferably propylene Acid, methacrylic acid, maleic anhydride etc..

(b) refer to, such as, have carbon number 2~4 ring-type ether structure (be selected from oxirane ring, oxa- ring fourth It is at least one kind of in the group that alkane ring and tetrahydrofuran ring are formed) and ethene unsaturated bond polymerizable compound.(b) preferred tool There are the cyclic ether of carbon number 2~4 and the monomer of (methyl) acryloxy.

In addition, in this manual, " (methyl) acrylic acid " represents, in the group being made up of acrylic acid and methacrylic acid It is at least one kind of.The statement such as " (methyl) acryloyl " and " (methyl) acrylate " also has the identical meaning.

(b) can enumerate, such as, there is the monomer (b1) of epoxy ethyl and ethene unsaturated bond (following also referred to as " (b1) "), monomer (b2) with oxetanylmethoxy and ethene unsaturated bond (below also referred to as " (b2) "), with tetrahydrofuran Monomer of base and ethene unsaturated bond (b3) (below also referred to as " (b3) ") etc..

(b1) can enumerate, such as, there is the lists of resulting structures after straight-chain or branched unsaturated fatty hydrocarbons epoxidation Body (b1-1) (also referred to as following " (b1-1) "), have resulting structures after the oxidation of unsaturated lipid ring type hydrocarbon ring monomer (b1-2) (with Down also referred to as " (b1-2) ").

(b1-1) can enumerate, (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (first Base) acrylic acid B- ethyl glycidyls ester, glycidyl vinyl ether, adjacent vinylbenzyl glycidyl base ether, an ethene Base benzyl glycidyl ether, to vinylbenzyl glycidyl base ether, Alpha-Methyl neighbour's vinylbenzyl glycidyl base ether, α- Vinylbenzyl glycidyl base ether, Alpha-Methyl are to vinylbenzyl glycidyl base the ether, (glycidyls of 2,3- bis- between methyl Epoxide methyl) styrene, 2,4- bis- (glycidyl oxy methyl) styrene, 2,5- bis- (glycidyl oxy methyl) benzene Ethene, 2,6- bis- (glycidyl oxy methyl) styrene, 2,3,4- tri- (glycidyl oxy methyl) styrene, 2,3, 5- tri- (glycidyl oxy methyl) styrene, 2,3,6- tri- (glycidyl oxy methyl) styrene, 3,4,5- tri- (contractings Water glyceryl epoxide methyl) styrene, 2,4,6- tri- (glycidyl oxy methyl) styrene etc..

(b1-2) can enumerate, a vinylcyclohexene oxide, 1,2- epoxy -4- vinyl cyclohexanes (such as, ャロキサイド2000；ダイセ Le chemical industry (strain) make), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates (such as, サイ Network ロ The A400 of マ mono-；ダイセ Le chemical industry (strain) make), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates (such as, サイ Network ロ The M100 of マ mono-；ダイセ Le chemical industry (strain) is made), compound shown in compound and formula (II) shown in formula (I) etc..

[in formula (I) and formula (II), R⁵¹And R⁵²The alkyl of hydrogen atom or carbon number 1~4 is represented, contained by the alkyl Hydrogen atom can be optionally substituted by a hydroxyl group.

X⁵¹And X⁵²Represent singly-bound ,-R⁵³-、*-R⁵³-O-、*-R⁵³- S- or *-R⁵³-NH-。

R⁵³Represent the alkylidene of carbon number 1~6.

* the bonding position with O is represented.]

The alkyl of carbon number 1~4 can be enumerated, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group Deng.

Alkyl after hydrogen atom is optionally substituted by a hydroxyl group can be enumerated, hydroxymethyl, 1- hydroxyethyls, 2- hydroxyethyls, 1- hydroxyls Propyl group, 2- hydroxypropyls, 3- hydroxypropyls, 1- hydroxyl -1- Methylethyls, 2- hydroxyl -1- Methylethyls, 1- hydroxybutyls, 2- Hydroxybutyl, 3- hydroxybutyls, 4- hydroxybutyls etc..

R⁵¹And R⁵²It is preferred that hydrogen atom, methyl, hydroxymethyl, 1- hydroxyethyls, more preferably 2- hydroxyethyls, hydrogen can be enumerated Atom, methyl.

Alkylidene can be enumerated, methylene, ethylidene, 1,2- propylidene, 1,3- propylidene, Isosorbide-5-Nitrae-butylidene, 1,5- Asias penta Base, 1,6- hexylidenes etc..

X⁵¹And X⁵²It is preferred that singly-bound, methylene, ethylidene, *-CH can be enumerated₂- O- and *-CH₂CH₂- O-, more preferably singly Key, *-CH₂CH₂- O- (* represents the bonding position with O).

Compound shown in formula (I) can be enumerated, compound shown in any one of formula (I-1)~formula (I-15) etc..It is excellent Select the compound shown in formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11)~formula (I-15).More Compound shown in preferred formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

Compound shown in formula (II) can be enumerated, compound shown in any one of formula (II-1)~formula (II-15) etc.. Shown in preferred formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)~formula (II-15) Compound.Compound more preferably shown in formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

The compound shown in compound and formula (II) shown in formula (I) can be used individually.In addition, they can also appoint Meaning ratio is mixed.During mixing, its blending ratio is with molar ratio computing, preferably formula (I): formula (II) be 5: 95~95: 5, it is more excellent Select 10: 90~90: 10, further preferred 20: 80~80: 20.

As the monomer (b2) with oxetanylmethoxy and ethene unsaturated bond, more preferably with oxetanylmethoxy and The monomer of (methyl) acryloxy.(b2) can enumerate, 3- methyl -3- methacryloxymethyls oxetanes, 3- first Base -3- acryloyloxymethyls oxetanes, 3- ethyl -3- methacryloxymethyls oxetanes, 3- ethyls -3- Acryloyloxymethyl oxetanes, 3- methyl -3- methacryloxyethyls oxetanes, 3- methyl -3- propylene Trimethylammonium oxetanes, 3- ethyl -3- methacryloxyethyls oxetanes, 3- ethyl -3- acryloyl-oxies Base Ethyloxetane etc..

Monomer (b3) with tetrahydrofuran base and ethene unsaturated bond is more preferably with tetrahydrofuran base and (methyl) The monomer of acryloxy.

(b3) can specifically enumerate acrylic acid tetrahydro furfuryl ester (such as, ト V#150 of PVC ス Us one, Osaka Organic Chemical Industry (strain) makes), methacrylic acid tetrahydro furfuryl ester etc..

(b) point of the reliability of heat resistance, chemical proofing based on the colour filter that can further improve acquisition etc., it is excellent Elect as (b1).Further, the point of the excellent storage stability based on colored curable resin composition, more preferably (b1-2).

(c) can enumerate, for example, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) acrylic acid ten Dialkyl ester, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) acrylic acid cyclopentyl ester, (first Base) cyclohexyl acrylate, (methyl) acrylic acid 2- methyl cyclohexanes base ester, the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] decane- (in the art, popular name is also referred to as " the bicyclic pentyl ester of (methyl) acrylic acid " to 8- base esters.In addition, it is also referred to as " (methyl) acrylic acid Tricyclodecyl ester ".), the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] (in the art, popular name is also referred to as decene -8- base esters " (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate ".), (methyl) acrylic acid Bicvclopentyl epoxide ethyl ester, (methyl) isobomyl acrylate Base ester, (methyl) acrylic acid adamantane esters, (methyl) allyl acrylate, (methyl) acrylic acid propargyl ester, (methyl) (methyl) esters of acrylic acids such as phenyl acrylate, (methyl) acrylic acid naphthyl ester, (methyl) benzyl acrylate；

Hydroxyl (methyl) acrylic acid such as (methyl) acrylic acid 2- hydroxyethyls ester, (methyl) acrylic acid 2- hydroxy-propyl esters Esters；

The dicarboxylic diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate；

Bicyclic [2.2.1] -2- heptene, 5- methyl bicycles [2.2.1] -2- heptene, bicyclic [the 2.2.1] -2- heptene of 5- ethyls, Bicyclic [the 2.2.1] -2- heptene of 5- hydroxyls, bicyclic [the 2.2.1] -2- heptene of 5- hydroxymethyls, 5- (2 '-hydroxyethyl) are bicyclic Bicyclic [the 2.2.1] -2- heptene of [2.2.1] -2- heptene, 5- methoxyl groups, bicyclic [the 2.2.1] -2- heptene of 5- ethyoxyls, 5,6- dihydroxies Bicyclic [the 2.2.1] -2- heptene of base, bicyclic [the 2.2.1] -2- heptene of 5,6- bis- (hydroxymethyl), 5,6- bis- (2 '-hydroxyethyl) are double Ring [2.2.1] -2- heptene, bicyclic [the 2.2.1] -2- heptene of 5,6- dimethoxys, 5,6- diethoxies bicyclic [2.2.1] -2- heptan Bicyclic [the 2.2.1] -2- heptene of alkene, 5- hydroxy-5-methyl bases, bicyclic [the 2.2.1] -2- heptene of 5- hydroxyl -5- ethyls, 5- hydroxyl first Base -5- methyl bicycle [2.2.1] -2- heptene, bicyclic [the 2.2.1] -2- heptene of 5- tert-butoxycarbonyls, 5- cyclohexyl Epoxide carbonyls Bicyclic [2.2.1] -2- heptene, bicyclic [the 2.2.1] -2- heptene of 5- phenyloxycarbonyls, 5,6- bis- (tert-butoxycarbonyl) are bicyclic The bicyclic unsaturated compound classes such as [2.2.1] -2- heptene, bicyclic [the 2.2.1] -2- heptene of 5,6- bis- (cyclohexyl Epoxide carbonyl)；

N-phenylmaleimide, N- N-cyclohexylmaleimides, N- benzyl maleimides, N- succinimidos- 3- maleimidobenzoyls ester, N- succinimido -4- malimidobutanoates, N- succinimido -6- Malaysias The dicarbapentaborane such as acid imide capronate, N- succinimido -3- maleimidopropionic acids ester, N- (9- acridinyls) maleimide Imide derivative class；

Styrene, α-methylstyrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene second Alkene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3- Butadiene, isoprene, 2,3- dimethyl -1,3-butadiene etc..

Wherein, the point based on copolyreaction and heat resistance, optimization styrene, N-phenylmaleimide, N- cyclohexyl Maleimide, N- benzyl maleimides, bicyclic [2.2.1] -2- heptene etc..

In resin [K1], ratio of each construction unit in the general construction unit for forming resin [K1] is preferred respectively

Come from the construction unit of (a)：2~60 moles of %

Come from the construction unit of (b)：40~98 moles of %

More preferably

Come from the construction unit of (a)：10~50 moles of %

Come from the construction unit of (b)：50~90 moles of %.

When resin [K1] construction unit ratio within the above range when, have colored curable resin composition guarantor Deposit stability, formed pattern when developability and acquisition pattern excellent solvent resistance tendency.

Resin [K1] refers to such as document《The experimental method of Polymer Synthesizing》(big Jin Longhangzhu publishing houses (strain) chemistry is same The brush of people the 1st edition the 1st distribution on March 1st, 1972) described in method and the document described in citation manufactured.

Specifically, method can be listed below, the loadings such as (a) and (b), polymerization initiator and solvent of ormal weight are reacted and held In device, such as by replacing oxygen by nitrogen, deoxidation atmosphere is made, is heated and be incubated while stirring.It is in addition, used herein Polymerization initiator and solvent etc. be not particularly limited, chemical agent usually used in the field can be used.For example, polymerization initiator It can enumerate, azo-compound (2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2,4- methyl pentane nitrile) etc.) or organic peroxy Compound (benzoyl peroxide etc.), as solvent, as long as each monomer can be dissolved, it can enumerate as colored curable resin Aftermentioned solvent of solvent (E) of composition etc..

In addition, the copolymer obtained can directly use reacted solution, it is possible to use the solution after concentration or dilution, The solid (powder) that the methods of passing through reprecipitation can be used to take out.Solvent during particularly as the polymerization, by using this hair The solvent contained in bright colored curable resin composition, directly reacted solution can be used to modulate coloring of the invention Hardening resin composition, thus manufacturing process can be simplified.

In resin [K2], ratio of each construction unit in the general construction unit for forming resin [K2] is preferred respectively

Come from the construction unit of (a)：2~45 moles of %

Come from the construction unit of (b)：2~95 moles of %

Come from the construction unit of (c)：1~65 mole of %

More preferably

Come from the construction unit of (a)：5~40 moles of %

Come from the construction unit of (b)：5~80 moles of %

Come from the construction unit of (c)：5~60 moles of %.

When resin [K2] construction unit ratio within the above range when, have colored curable resin composition guarantor The solvent resistance of pattern of developability and acquisition when depositing stability, forming pattern, heat resistance and mechanical strength are inclined To.

Resin [K2] can be taken with entering for example as the method identical method described in resin [K1] manufacture method Row manufacture.

In resin [K3], ratio of each construction unit in the general construction unit for forming resin [K3] is preferred respectively

Come from the construction unit of (a)；2~60 moles of %

Come from the construction unit of (c)；40~98 moles of %

More preferably

Come from the construction unit of (a)；10~50 moles of %

Come from the construction unit of (c)；50~90 moles of %.

Resin [K3] can be taken with entering for example as the method identical method described in resin [K1] manufacture method Row manufacture.

Manufacture can be performed as follows in resin [K4]：(a) and (c) copolymer are obtained, makes carbon number 2 possessed by (b) ~4 cyclic ether carries out addition with carboxylic acid possessed by (a) and/or carboxylic acid anhydrides.

First, according to the copolymerization for manufacturing (a) and (c) in the same manner with the method described in the manufacture method as resin [K1] Thing, now, the ratio cited by the ratio and resin [K3] of preferably each construction unit are identical.

Then, the cyclic ether of carbon number 2~4 possessed by (b) and the carboxylic acid for coming from (a) in above-mentioned copolymer are made And/or the part reaction of carboxylic acid anhydrides.

After copolymer of the manufacture (a) with (c), the atmosphere gas in flask is and then replaced as air by nitrogen, will (b), the catalysts of carboxylic acid or carboxylic acid anhydrides and cyclic ether (such as three (dimethylaminomethyl) phenol etc.) and polymerization inhibitor (example Such as hydroquinones) etc. be added in flask, by being reacted 1~10 hour at such as 60~130 DEG C, resin can be obtained [K4]。

(b) usage amount is relative to 100 moles of (a), preferably 5~80 moles, more preferably 10~75 moles.By in this model The pattern of developability and acquisition when in enclosing, there is the storage stability of colored curable resin composition, forming pattern The tendency that solvent resistance, heat resistance, mechanical strength and the balance of sensitivity improve.Reactivity based on cyclic ether is high, unreacted (b) be not easy the point of remaining, (b) used in resin [K4], preferably (b1), further preferred (b1-1).

The usage amount of above-mentioned catalysts, relative to the mass parts of total amount 100 of (a), (b) and (c), preferably 0.001~5 Mass parts.The usage amount of above-mentioned polymerization inhibitor is relative to the mass parts of total amount 100 of (a), (b) and (c), preferably 0.001~5 mass Part.

The reaction conditions such as loading method, reaction temperature and time are contemplated that caloric value caused by manufacturing equipment or polymerization Deng being suitably adjusted.In addition, same polymerizing condition, it is contemplated that to caloric value etc. caused by manufacturing equipment or polymerization, suitably adjust Whole loading method or reaction temperature.

As resin [K5] first stage, the manufacture method identical method with above-mentioned resin [K1] can be taken, is obtained (b) with the copolymer of (c).Ibid, the copolymer of acquisition can directly use reacted solution, it is possible to use concentration or dilution Solution afterwards, it is possible to use the solid (powder) that the methods of passing through reprecipitation is taken out.

Come from the ratio of the construction unit of (b) and (c), relative to the total of all construction units for forming above-mentioned copolymer Molal quantity, preferably in following scope：

Come from the construction unit of (b)：5~95 moles of %

Come from the construction unit of (c)：5~95 moles of %

More preferably

Come from the construction unit of (b)；10~90 moles of %

Come from the construction unit of (c)；10~90 moles of %.

Further, with the manufacture method of resin [K4] under the same conditions, by making carboxylic acid possessed by (a) or carboxylic acid Acid anhydride, with the copolymer of (b) and (c) possessed by come from (b) cyclic ether react, resin [K5] can be obtained.

With the usage amount of (a) of above-mentioned copolymer reaction, relative to 100 moles of (b), preferably 5~80 moles.Based on ring-type Reactive high, unreacted (b) of ether is not easy remaining, and (b) is preferred (b1) used in resin [K5], further preferred (b1- 1)。

Resin [K6] be resin [K5] further with carboxylic acid anhydride reactant obtained by resin.

The hydroxyl for being generated the reaction of cyclic ether and carboxylic acid or carboxylic acid anhydrides, with carboxylic acid anhydride reactant.

Carboxylic acid anhydrides can be enumerated, maleic anhydride, citraconic anhydride, itaconic anhydride, 3- ethene anhydride phthalic acid, 4- ethene anhydride phthalic acid, 3, Bicyclic [the 2.2.1] -2- of 4,5,6- tetrahydrochysene anhydride phthalic acids, 1,2,3,6- tetrahydrochysene anhydride phthalic acids, dimethyl tetrahydro anhydride phthalic acid, 5,6- dicarboxyls Heptene acid anhydrides (carbic anhydride) etc..The usage amount of carboxylic acid anhydrides relative to (a) 1 mole of usage amount, preferably 0.5~1 mole.

Resin (B) can specifically be enumerated, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates/(methyl) acrylic acid copolymer Thing, acrylic acid 3, the ring [5.2.1.0 of 4- epoxies three^2.6] resin [K1] such as decyl ester/(methyl) acrylic copolymer；(methyl) third Olefin(e) acid ethylene oxidic ester/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/ Styrene/(methyl) acrylic copolymer, acrylic acid 3, the ring [5.2.1.0 of 4- epoxies three^2.6] decyl ester/(methyl) acrylic acid/N- N-cyclohexylmaleimide copolymer, 3- methyl -3- (methyl) acryloyloxymethyls oxetanes/(methyl) acrylic acid/ The resins such as styrol copolymer [K2]；(methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) third The resins such as olefin(e) acid copolymer [K3]；(methyl) benzyl acrylate/(methyl) acrylic copolymer shrinks with (methyl) acrylic acid Resin, (methyl) acrylic acid tricyclodecyl ester/styrene/(methyl) acrylic copolymer and (methyl) obtained by glyceride addition Resin, (methyl) acrylic acid tricyclodecyl ester/(methyl) benzyl acrylate/(first obtained by glycidyl acrylate addition Base) resin [K4] such as resin obtained by acrylic copolymer and (methyl) glycidyl acrylate addition；(methyl) acrylic acid The copolymer of tricyclodecyl ester/(methyl) glycidyl acrylate and resin, (methyl) obtained by (methyl) propylene acid reaction The copolymer of acrylic acid tricyclodecyl ester/styrene/(methyl) glycidyl acrylate and (methyl) propylene acid reaction and obtain The resin [K5] such as resin；The copolymer of (methyl) acrylic acid tricyclodecyl ester/(methyl) glycidyl acrylate and (first Base) resin obtained by propylene acid reaction further with tetrahydrochysene phthalandione anhydride reactant obtained by the resin [K6] such as resin etc..

These resins can be used alone or two or more is used in combination.

Wherein, resin (B) preferred resin [K1], resin [K2] and resin [K4].

The polystyrene conversion weight average molecular weight preferably 3 of resin (B), 000~100,000, more preferably 5,000~50, 000, further preferred 5,000~30,000.When molecular weight within the above range when, have improve hardness of film, residual film ratio is also Height, the tendency that favorable solubility of the unexposed portion in developer solution, resolution are improved.

The molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] preferably 1.1~6 of resin (B), more preferably 1.2~4.

The acid number preferably 50~170mg-KOH/g, more preferably 60~150mg-KOH/g, further preferred 70 of resin (B)~ 135mg-KOH/g.Acid number herein is the value determined as the amount (mg) for neutralizing the potassium hydroxide needed for 1g resins, can be passed through Such as titrated using potassium hydroxide aqueous solution to try to achieve.

The content of resin (B) is relative to the total amount of solid constituent, preferably 7~65 mass %, more preferably 13~60 mass %, Further preferred 17~55 mass %.When resin (B) content within the above range when, pattern can be formed by having, exploring in addition The tendency that the residual film ratio of degree and pattern is improved.

Polymerizable compound (C) is that one kind can be by living radical and/or acid as caused by heat or polymerization initiator (D) And the compound being polymerize, it can enumerate for example, with compound for polymerizeing sex ethylene unsaturated bond etc., preferably (methyl) third Enoic acid ester compounds.

Wherein, preferred polymeric compound (C) is the polymerizable compound with more than 3 ethene unsaturated bonds.This The polymerizable compound of sample can be enumerated, such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) propylene Acid esters, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) third Olefin(e) acid ester, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, (first of tetrapentaerythritol ten Base) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2- (methyl) acrylyl oxy-ethyl) isocyanuric acid esters, second Glycol modification pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylate, propane diols Modified pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, caprolactone modification Pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc..Polymerizable compound It can be used alone or two or more is applied in combination.

Wherein, preferably (methyl) acrylate of dipentaerythritol five and dipentaerythritol six (methyl) acrylate.

The weight average molecular weight of polymerizable compound (C) preferably less than more than 150 2,900, more preferably less than 250~1,500.

The content of polymerizable compound (C) is relative to the total amount of solid constituent, preferably 7~65 mass %, more preferably 13~ 60 mass %, further preferred 17~55 mass %.When polymerizable compound (C) content within the above range when, have figure The tendency that the chemical proofing of residual film ratio and pattern during case formation is improved.

Polymerization initiator (D) starts the chemical combination of polymerization as long as living radical, acid etc. can be produced by light or heat effect Thing is not particularly limited, and known polymerization initiator can be used.

Polymerization initiator (D) preferably comprise selected from benzene alkyl assimilation compound, triaizine compounds, acylphosphine oxide compound, At least one kind of polymerization initiator in the group that O- acyl groups oxime compound and double imidazole compound are formed, further preferably O- acyl groups The polymerization initiator of oxime compound.

O- acyl group oxime compounds are the compounds for having part-structure shown in formula (d1).

Hereinafter, * represents bonding position.

O- acyl groups oxime compound can be enumerated, such as, N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) -1- butanone-2s - Imines, N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) -1- octanone -2- imines, N- benzoyloxys -1- (4- phenyl sulphur Alkyl phenyl) -3- cyclopenta propane -1- ketone -2- imines, N- acetoxyl groups -1- [9- ethyls -6- (2- methyl benzoyls) - 9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- { 2- methyl -4- (3,3- dimethyl -2,4- bis- Oxocyclopentyl methyl epoxide) benzoyl -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -3- cyclopenta propane -1- imines, N- benzoyloxys -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -3- cyclopenta propane -1- ketone -2- imines etc..イ Le ガキュ can also be used The commercially available products such as ァ (registration mark) OXE01, OXE02 (above BASF societies system), N-1919 (ADEKA societies system).

Benzene alkyl assimilation compound is the compound for having part-structure shown in part-structure shown in formula (d2) or formula (d3).This In a little part-structures, phenyl ring can have substituent.

Compound with part-structure shown in formula (d2) can be enumerated, such as, 2- methyl -2- morpholinoes -1- (4- methyl mercaptos Phenyl) -1- acetone, 2- dimethylaminos -1- (4- morpholinyl phenyls) -2- benzyl -1- butanone, 2- (dimethylamino) -2- [(4- Aminomethyl phenyl) methyl] -1- [4- (4- morpholinyls) phenyl] -1- butanone etc..イ Le ガキュァ (registration mark) can also be used 369th, the commercially available product such as 907 and 379 (above BASF societies systems).

Compound with part-structure shown in formula (d3) can be enumerated, such as, 2- hydroxy-2-methyl -1- phenyl-propanes -1- Ketone, 2- hydroxy-2-methyls -1- (4- (2- hydroxyl-oxethyls) phenyl) -1- acetone, 1- hydroxycyclohexylphenylketones, 2- hydroxyls -2- Methyl isophthalic acid-(4- isopropenyls phenyl) -1- acetone oligomer, α, α-diethoxy acetophenone, benzyl dimethyl ketal etc..

Point based on sensitivity, preferably benzene alkyl assimilation compound, the compound with part-structure shown in formula (d2).

Triaizine compounds can be enumerated, such as, 2,4- bis- (trichloromethyl) -6- (4- methoxyphenyls) -1,3,5-triazines, 2, 4- bis- (trichloromethyl) -6- (4- methoxyl groups naphthyl) -1,3,5-triazines, 2,4- bis- (trichloromethyl) -6- piperonyls -1,3,5- tri- Piperazine, 2,4- bis- (trichloromethyl) -6- (4- methoxyl-styrenes) -1,3,5-triazines, 2,4- bis- (trichloromethyl) -6- (2- (5- Methylfuran -2- bases) vinyl) -1,3,5-triazines, 2,4- bis- (trichloromethyl) -6- (2- (furans -2- bases) vinyl) -1, 3,5- triazines, 2,4- bis- (trichloromethyl) -6- (2- (4- diethylamino -2- aminomethyl phenyls) vinyl) -1,3,5-triazines, 2, 4- bis- (trichloromethyl) -6- (2- (3,4- Dimethoxyphenyl) vinyl) -1,3,5-triazines etc..

Acylphosphine oxide compound can enumerate TMDPO etc..イ Le can also be used The commercially available products such as ガキュァ (registration mark) 819 (BASF societies system).

Double imidazole compound can be enumerated, such as, 2,2 '-two (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl double imidazole, 2, 2 '-two (2,3- dichlorophenyl) -4,4 ', 5,5 '-tetraphenyl double imidazole is (for example, referring to Japanese Patent Laid-Open 6-75372 public affairs Report, Japanese Patent Laid-Open 6-75373 publications etc..), 2,2 '-two (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl double imidazole, The double imidazoles of 2,2 '-two (2- chlorphenyls) -4,4 ', 5,5 '-four (alkoxyl phenyls), 2,2 '-two (2- chlorphenyls) -4,4 ', 5,5 ' - The double imidazoles of four (dialkoxy phenyl), 2,2 '-two (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) double imidazoles (examples Such as, with reference to Japan Patent examined patent publication 48-38403 publications, Japanese Patent Laid-Open No. Sho 62-174204 publications etc..), 4,4 ' 5, The imidazolium compounds that the phenyl of 5 '-position is substituted by alkoxy carbonyl base is (for example, referring to Japanese Patent Laid-Open 7-10913 public affairs Report etc.) etc..

Further, polymerization initiator (D) can be enumerated, and benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin are different The benzoin compound such as propyl ether, benzoin isobutyl ether；Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- phenyl hexichol Ketone, 4- benzoyls -4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6- The benzophenone cpds such as tri-methyl benzophenone；The naphtoquinone compounds such as 9,10- phenanthrenequione, 2- EAQs, camphorquinone；10- butyl- 2- chloro-acridines ketone, benzil, phenylglyoxalates methyl esters, titanocenes compound etc..These compounds preferably with it is described later polymerize draw Hair auxiliary agent (D1) (especially amine) is applied in combination.

Acid agent can be enumerated, such as, 4- hydroxy phenyl dimethyl sulfoniums tosilate, 4- hydroxy phenyls dimethyl sulfonium six Fluorine antimonate, dimethyl (4- acetoxyl groups phenyl) sulfonium tosilate, benzyl (4- acetoxyl groups phenyl) methyl sulfonium hexafluoro Stibate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl The Jia salts such as iodine Jia hexafluoro antimonates, or nitrobenzyl tosylate class, benzoin toluenesulfonic acid salt etc..

The content of polymerization initiator (D), it is excellent relative to the mass parts of total amount 100 of resin (B) and polymerizable compound (C) Select 0.1~30 mass parts, more preferably 1~20 mass parts.When polymerization initiator (D) content within the above range when, due to tool Having the tendency of high-sensitivity shortens the time for exposure, therefore productivity ratio is improved.

While containing polymerization initiator (D), further it can trigger auxiliary agent (D1) containing polymerization.Polymerization triggers auxiliary agent (D1) it is compound for promoting the polymerization for the photopolymerizable compound for triggering polymerization by polymerization initiator, or sensitizer.

Polymerization triggers auxiliary agent (D1) to enumerate, and amines, alkoxy fear compound, thioxanthone compounds and carboxylic acid chemical combination Thing etc..

Amines can be enumerated, triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylaminobenzoic acid first Ester, EDMAB, 4- dimethylaminobenzoic acids isopentyl ester, benzoic acid 2- dimethylamino ethyl esters, 4- Dimethylaminobenzoic acid 2- ethylhexyls, N, N- dimethyl-p-toluidines, 4,4 '-two (dimethylamino) benzophenone are (logical Claim Michler's keton), 4,4 '-two (diethylamino) benzophenone, 4,4 '-two (ethylmethylamino) benzophenone etc., wherein excellent Select 4,4 '-two (diethylamino) benzophenone.The commercially available products such as EAB-F (hodogaya chemical industry (strain) system) can also be used.

Alkoxy anthracene compound can be enumerated, and 9,10- dimethoxys are feared, EDMO, 9,10- diethyls Epoxide is feared, 2- ethyl -9,10- diethoxies anthracene, 9,10- dibutoxies are feared, 2- ethyl -9,10- dibutoxy anthracenes etc..

Thioxanthone compounds can be enumerated, ITX, ITX, 2,4- diethyl thioxanthones, 2, Chloro- 4- propoxythioxanthones of the clopenthixal ketones of 4- bis-, 1- etc..

Carboxylic acid compound can be enumerated, thiophenyl acetic acid, methylphenyl-sulfanyl acetic acid, ethylthiophenyl acetic acid, ethyl methyl benzene Ethyl thioglycollic acid, dimethyl benzene ethyl thioglycollic acid, Methoxv-phenylsulfanvl acetic acid, dimethoxyphenylthio acetic acid, chlorophenylsulfanyl acetic acid, two Chlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio acetic acid, N- naphthyls glycine, naphthoxy acetic acid etc..

Polymerization triggers auxiliary agent (D1) to be used singly or two or more kinds in combination.

In the case where triggering auxiliary agent (D1) using these polymerizations, its usage amount is relative to resin (B) and polymerism chemical combination The mass parts of total amount 100 of thing (C), more preferably preferably 0.1~30 mass parts, 1~20 mass parts.When polymerization triggers auxiliary agent (D1) When measuring within the range, have and pattern is further formed with high sensitivity, improve the tendency of pattern productivity ratio.

Solvent (E) is not particularly limited, and solvent usually used in the field can be used.Such as can be from ester solvent (intramolecular Containing-COO-, the solvent without-O-), ether solvents (intramolecular contains-O-, the solvent without-COO-), ether-ether solvent (molecule The interior solvent containing-COO- He-O-), ketone solvent (intramolecular contains-CO-, the solvent without-COO-), alcoholic solvent, aromatic series Select to use in hydrocarbon solvent, amide solvent, dimethyl sulfoxide etc..

Ester solvent can be enumerated, methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-isobutyric alkanoic acids methyl esters, ethyl acetate, N-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyric acid fourth Ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate and Gamma-butyrolacton etc..

Ether solvents can be enumerated, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol only son Base ether, diethylene glycol monomethyl ether, TC, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propane diols Single ethylether, propylene glycol monopropyl ether, glycol monobutyl ether, 3- methoxyl groups-n-butyl alcohol, 3- methoxyl group -3- methyl butanols, four Hydrogen furans, oxinane, Isosorbide-5-Nitrae-dioxanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methylethyl Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methyl anisole etc..

Ether-ether solvent can be enumerated, methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethyoxyl second Sour methyl esters, ethoxy ethyl acetate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- second Epoxide ethyl propionate, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- ethoxy-propionic acids Methyl esters, 2- ethoxyl ethyl propionates, 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, 3- methoxies Base butylacetic acid ester, 3- methyl -3- methoxybutyls acetic acid esters, propylene glycol monomethyl ether, propylene glycol monoethyl second Acid esters, propylene glycol monopropyl ether acetic acid esters, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, diethylene glycol Single monoethyl ether acetate and diethylene glycol monobutyl ether acetic acid esters etc..

Ketone solvent can be enumerated, 4- hydroxy-4-methyl-2-pentanones, acetone, 2- butanone, 2-HEPTANONE, 3- heptanone, 4- heptanone, 4- Methyl -2 pentanone, cyclopentanone, cyclohexanone and isophorone etc..

Alcohols solvent can be enumerated, methanol, ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propane diols and glycerine Deng.

Aromatic hydrocarbon solvents can be enumerated, benzene,toluene,xylene and mesitylene etc..

Amide solvent can be enumerated, DMF, DMA and 1-METHYLPYRROLIDONE etc..

These solvents can be used singly or two or more kinds in combination.

Among above-mentioned solvent, the point based on coating, drying property, boiling point in preferably 1atm more than 120 DEG C 180 DEG C with Under organic solvent.Solvent (E) preferably propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, 3- ethyoxyls Ethyl propionate, ethylene glycol single methyl ether, diethylene glycol monomethyl ether, TC, 4- hydroxy-4-methyls -2- penta Ketone and DMF, more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl lactate and 3- second Epoxide ethyl propionate.

The content of solvent (E) is relative to the total amount of colored curable resin composition, preferably 70~95 mass %, more preferably 75~92 mass %.In other words, the solid constituent of colored curable resin composition preferably 5~30 mass %, more preferably 8~25 Quality %.

When solvent (E) content within the above range when, have coating when flatness improve, in addition, formed colour filter When the colour saturation fully tendency that makes display characteristic improve.

Surfactant (F) can be enumerated, silicone-based surfactant, fluorine system surfactant and the silicone with fluorine atom It is surfactant etc..They can have polymerizable group in side chain.

Silicone-based surfactant can be enumerated, and intramolecular has surfactant of siloxanes key etc..It can specifically enumerate, TORAY silicone DC3PA, same to SH7PA, same to DC11PA, same to SH21PA, same to SH28PA, same to SH29PA, same to SH30PA, same to SH8400 (trade name：The eastern ニ Application グ (strain) of レダウ Us one system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (the マ Application スマテリァ Le ズジャパ Application contracts commercial firms of モメ Application ティ Block パ Off ォ mono- System) etc..

Above-mentioned fluorine system surfactant can be enumerated, and intramolecular has surfactant of fluoro carbochain etc..It can specifically arrange Lift De (registration mark) FC430 of Off ロラ mono-, same to FC431 (the ェ system (strain) of Sumitomo スリ mono- system), メガ Off ァッ Network (registrars Mark) F142D, same to F171, same to F172, same to F173, same to F177, same to F183, same to F554, same to R30, same to RS-718-K (DIC (strain) System), ェ Off トップ (registration mark) EF301, same to EF303, same to EF351, same to EF352 (Mitsubishi マテリァ Le electronics be melted into (strain) System), サ mono- Off ロ Application (registration mark) S381, same to S382, same to SC101, same to SC105 (Asahi Glass (strain) system) and E5844 ((strain) The research of ダイキ Application Off ァイ Application ケミヵ Le is made) etc..

The above-mentioned silicone-based surfactant with fluorine atom can be enumerated, and intramolecular has siloxanes key and fluoro carbochain Surfactant etc..Can specifically enumerate メガ Off ァッ Network (registration mark) R08, same to BL20, same to F475, with F477 and same F443 (DIC (strain) systems) etc..

These surfactants can be used singly or two or more kinds in combination.

The content of surfactant (F) relative to colored curable resin composition total amount, preferably 0.001 mass % with Upper below 0.2 mass %, more preferably more than 0.002 mass % below 0.1 mass %, further preferred more than 0.01 mass % Below 0.05 mass %.In addition, do not include the content of above-mentioned pigment dispersing agent in the content.When the content of surfactant (F) exists When in above range, the flatness of film can be made to improve.

The colored curable resin composition of the present invention, filler, other high-molecular compounds can be contained as needed, glued Close the various additives such as accelerator, antioxidant, light stabilizer, chain-transferring agent.

The colored curable resin composition of the present invention can be by mixing such as compound (1), resin (B), polymerism Compound (C) and polymerization initiator (D) and as needed used in pigment (A1), dyestuff (A2), polymerization trigger auxiliary agent (D1), Surfactant (F), solvent (E) and other compositions are prepared.

When containing pigment (A1), preferably pigment (A1) is mixed with some or all of solvent (E) in advance, uses pearl Grinding machine etc. is allowed to scattered, until the average grain diameter of pigment is changed into less than 0.2 μm of degree.Now, also can compound tree as needed Fat (B) part or all, above-mentioned pigment dispersing agent.The mixed compound (1), surplus in the dispersible pigment dispersion of acquisition can be passed through Remaining resin (B), polymerizable compound (C) and polymerization initiator (D) and remaining solvent (E), the table used as needed Face activating agent (F) and other compositions etc., make defined concentration, are thus combined to prepare target coloration curable resin Thing.

Compound (1) and the dyestuff (A2) during containing dyestuff (A2), can be dissolved separately in some or all of in advance Solvent (E) is configured to solution.It is preferred that the solution is filtered with the filter of 0.01~1 μm of degree in aperture.

It is preferred that mixed colored curable resin composition was carried out with the filter of 0.01~10 μm of degree in aperture Filter.

As by the present invention colored curable resin composition manufacture color filter pattern method, can enumerate photoetching process, Ink-jet method, print process etc..Wherein preferred photoetching process.Photoetching process is that above-mentioned colored curable resin composition is coated on into substrate, Composition layer is formed by drying, the method be exposed via photomask to said composition layer, developed.In photoetching process, pass through In exposure without using photomask, and/or without developing, the film of combinations thereof nitride layer solidfied material can be formed.

The pattern thickness of making is not particularly limited, and can be suitably adjusted according to purpose or purposes etc., such as 0.1~30 μm, preferably 0.1~20 μm, further preferred 0.5~6 μm.

The soda lime glass of quartz glass, borosilicate glass, aluminosilicate glass, face coat silica can be used in substrate Deng glass plate, or the resin plate such as makrolon, polymethyl methacrylate, polyethylene terephthalate, silicon, above-mentioned base Aluminium, silver, silver/copper/palldium alloy film etc. are formd on plate.Other color-filter layer, resin bed, crystal can be formed on these substrates Pipe, circuit etc..

Each color pixel is formed by photoetching process to carry out with the conditions of in known or usual device.Such as it can be performed as follows Make.

First, colored curable resin composition is coated on substrate, it is dry by heat drying (preliminary drying) and/or decompression The volatile ingredients such as dry removing solvent are allowed to drying, obtain smooth composition layer.

Coating method can be enumerated, spin-coating method, slot coated method, slit ＆ method of spin coating etc..

Preferably 30~120 DEG C, more preferably 50~110 DEG C of temperature when being thermally dried.In addition, heat time preferred 1O Second~60 minutes, more preferably 30 seconds~30 minutes.

When being dried under reduced pressure, carried out preferably under 50~150Pa pressure, under 20~25 DEG C of temperature range.

The thickness of composition layer is not particularly limited, and can suitably be adjusted according to the material that uses, purposes etc..

Then, composition layer is exposed to form it into target pattern via photomask.Pattern on the photomask It is not particularly limited, pattern can be used according to intended applications.

Exposure light source used, preferably produce the light source of the light of 250~450nm wavelength.Such as it can be used by the end of the ripple The filter in long region is ended to the light less than 350nm, is attached to 436nm using the bandpass filter for selecting the wavelength region Closely, light of the 408nm nearby, near 365nm carries out selective taking-up.It can specifically enumerate, mercury lamp, light emitting diode, halogenation gold Belong to lamp, Halogen lamp LED etc..

Due to integrally can equably irradiate parallel rays to plane of exposure, or photomask is set correctly to be aligned with composition layer, Therefore it is preferred that use the exposure devices such as mask aligner, step-by-step exposure machine.

Developed by making the composition layer after exposure be contacted with developer solution, pattern can be formed on substrate.By aobvious Shadow, the unexposed portion of composition layer can be made to be dissolved in developer solution to remove.Developer solution preferably such as potassium hydroxide, bicarbonate The aqueous solution of the alkali compounds such as sodium, sodium carbonate, TMAH.Concentration in the aqueous solution of these alkali compounds, It is preferred that 0.01~10 mass %, more preferably 0.03~5 mass %.Further, developer solution can also contain surfactant.

Developing method can use any of paddling process, infusion process and spray-on process etc..Further, during development, substrate It can be tilted with any angle.

Preferably washed after development.

Further, the pattern that preferred pair obtains dries after carrying out.Temperature preferably 150~250 DEG C, more preferably 160~235 are dried afterwards ℃.Preferably 1~120 minute, more preferably 10~60 minutes time is dried afterwards.

The pattern and film being obtained as described above can be used as colour filter.

According to the colored curable resin composition of the present invention, the excellent colour filter of especially brightness can be made.The colour filter Device is as the filter in display device (such as liquid crystal display device, organic el device etc.), Electronic Paper, solid-state imager etc. Color device is useful.

Embodiment

Then, embodiment is enumerated, the present invention is described in further detail.In example, content or usage amount are represented If % and part unless otherwise instructed, as quality criteria.

(synthesis example 1)

20 parts of compound shown in formula (1a) is being hidden for 200 parts with N- ethyl-ortho-toluidines (and Wako Pure Chemical Industries (strain) are made) Mixed under optical condition, the solution of stirring to obtain 6 hours at 110 DEG C.After the reaction solution of acquisition is cooled into room temperature, addition Enter and stirred at room temperature 1 hour in the mixed liquor of 800 parts of water, 50 parts of 35% hydrochloric acid, separate out crystal.Suction strainer is obtained as residue Separate out crystal to be dried, obtain the compound shown in 24 parts of formulas (1-1).Yield is 80%.

The structure of compound passes through mass spectral analysis (LC shown in formula (1-1)；The type of Agilent systems 1200, MASS；Agilent systems LC/MSD types) confirmed.

(mass spectral analysis) ionization mode=ESI+：M/z=[M+H]⁺603.4

Exact Mass：602.2

(synthesis example 2)

N- ethyl-ortho-toluidines are substituted using N- isopropyls ortho-aminotoluene, in addition, with synthesis example 1, obtain formula (1-5) Shown compound.

The identification of compound shown in formula (1-5)

(mass spectral analysis) ionization mode=ESI+：M/z=[M+H]⁺632.3

Exact Mass：631.3

(synthesis example 3)

N- ethyl-ortho-toluidines are substituted using N- propyl group -2,6- dimethylaniline, in addition, with synthesis example 1, obtain formula Compound shown in (1-8).

The identification of compound shown in formula (1-8)

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

Exact Mass：658.9

(synthesis example 4)

N- ethyl-ortho-toluidines are substituted using N- benzyls -2,6- dimethylaniline, in addition, with synthesis example 1, obtain formula Compound shown in (1-12).

The identification of compound shown in formula (1-12)

(mass spectral analysis) ionization mode=ESI+：M/z=[M+H]⁺755.3

Exact Mass：754.2

(synthesis example 5)

Into the flask for possessing condenser pipe and agitating device, compound and formula (A2- shown in 15 parts of formulas (A2-1a) are put into Mixture (the trade name Chugai Aminol Fast Pink R of compound shown in 1b)；Middle tank formation system), 150 parts of chloroforms And 8.9 parts of DMFs, while less than 20 DEG C are maintained under stirring, 10.9 parts of thionyl chloride is added dropwise.It is added dropwise After end, 50 DEG C are warming up to, maintains be allowed to react within synthermal lower 5 hours, is cooled to 20 DEG C thereafter.By the reaction solution after cooling While maintaining less than 20 DEG C with stirring, the mixed liquor of 12.5 parts of 2 ethyl hexylamines and 22.1 parts of triethylamines is added dropwise.Thereafter, Synthermal lower stirring is allowed to react for 5 hours.Then after the reactant mixture of acquisition being distilled off into solvent with rotary evaporator, add Enter a small amount of methanol to be stirred vigorously.In the ion exchange water mixed liquid for stirring the mixture for 375 parts of addition, crystal is separated out.Filter to take The crystal that must be separated out, is cleaned up with ion exchange water, is dried under reduced pressure at 60 DEG C, obtains 11.3 parts of dyestuffs (A2-2) (mixture of formula (A2-2-1)~compound shown in formula (A2-2-8)).

(synthesis example 6)

Nitrogen is passed through with 0.02L/ points into the flask for possessing mixer, thermometer, reflux condenser and dropping funel, is made Nitrogen atmosphere gas, adds 305 parts of propylene glycol monomethyl ethers, is heated to 70 DEG C while stirring.Then, methyl-prop is dissolved 60 parts of olefin(e) acid, acrylic acid 3, the ring [5.2.1.0 of 4- epoxies three^2.6] decyl ester (compound and formula (II-1) institute shown in formula (I-1) The compound shown is mixed with mol ratio 50: 50) 240 parts and 140 parts of propylene glycol monomethyl ether be configured to solution, and will The lysate lasts 4 hours with dropping funel and is added dropwise to insulation in 70 DEG C of flask.

On the other hand, polymerization initiator 2,30 parts of 2 '-azo two (2,4- methyl pentane nitrile) are dissolved in propane diols list first 225 parts of obtained solution of base ether acetic acid ester, last 4 hours with another dropping funel and be added dropwise in flask.Polymerization initiator solution Drip after end, be maintained at 70 DEG C 4 hours, be cooled to room temperature thereafter, it is 1.3 × 10 to obtain weight average molecular weight (Mw)⁴, molecular weight It is distributed as 2.5, solid constituent 33%, solution acid number is 34mgKOH/g (acid number of solid constituent conversion is 103mgKOH/g) The solution of resin B 1.Resin B 1 has construction unit shown below.

(synthesis example 7)

Into the flask for possessing mixer, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe, propane diols is imported Monomethyl ether acetate 182g, after the atmosphere gas in flask is transformed into nitrogen by air, after being warming up to 100 DEG C, to by methyl Benzyl acrylate 70.5g (0.40 mole), methacrylic acid 43.0g (0.5 mole), the monomethacrylate of tricyclodecane skeleton Acid esters (ring [the 5.2.1.0 of methacrylic acid three^2,6] decane -8- base esters；Hitachi is melted into (strain) FA-513M processed) (0.10 rubs 22.0g You) and propylene glycol monomethyl ether 136g form mixture in be added dropwise with the addition of 2,2 '-azodiisobutyronitrile 3.6g's Solution, further continue to stir at 100 DEG C.Then, the atmosphere gas in flask is transformed to air by nitrogen, thrown into flask Enter GMA 35.5g [0.25 mole, (carboxyl relative to methacrylic acid used in this reaction is 50 moles of %)], three (dimethylamino methyl) phenol 0.9g and hydroquinones 0.145g, continue to react at 110 DEG C, weighed Average molecular weight (Mw) is 3.0 × 10⁴, the mass % of solid constituent 37, solid constituent acid number be 79mgKOH/g the solution of resin B 2. Resin B 2 has construction unit shown below.

(synthesis example 8)

Into the flask for possessing reflux condenser, dropping funel and mixer, nitrogen is passed through with 0.02L/ points, is made nitrogen atmosphere Gas, adds 270 parts of propylene glycol monomethyl ethers, is heated to 70 DEG C while stirring.Then, by 38 parts of acrylic acid, with And acrylic acid 3, the ring [5.2.1.0 of 4- epoxies three^2.6] decyl ester (chemical combination shown in compound and formula (II-1) shown in formula (I-1) Thing is mixed with mol ratio 50: 50) 282 parts be dissolved in 150 parts of propylene glycol monomethyl ether and be configured to solution, by this Solution is lasted with dropping funel is added dropwise to insulation for 4 hours as in 70 DEG C of flask.On the other hand, by polymerization initiator 2,2 '-idol 30 parts of nitrogen two (2,4- methyl pentane nitrile) is dissolved in the solution obtained in 230 parts of propylene glycol monomethyl ether, with another drop Liquid funnel lasts 4 hours and is added dropwise in flask.After polymerization initiator solution completion of dropwise addition, it is maintained at 70 DEG C 4 hours, it is cold thereafter But to room temperature, it is 8.6 × 10 to obtain weight average molecular weight (Mw)³, molecular weight distribution 2.2, solid constituent 35%, solid constituent The acid number of conversion is the 81mgKOH/g solution of resin B 3.Resin B 3 has construction unit shown below.

(synthesis example 9)

Nitrogen is passed through with 0.02L/ points into the flask for the 1L for possessing reflux condenser, dropping funel and mixer, is made nitrogen Atmosphere gas, 220 parts of ethyl lactate is added, while stirring, be heated to 70 DEG C.Then, by 84 parts of methacrylic acid, Yi Jibing Olefin(e) acid 3, the ring [5.2.1.0 of 4- epoxies three^2.6] decyl ester (and the compound shown in compound and formula (II-1) shown in formula (I-1) with Mol ratio 50: 50 is mixed) 336 parts be dissolved in 140 parts of ethyl lactate and be configured to solution, the solution is gone through with dropping funel When 4 hours, be added dropwise to and be incubated in 70 DEG C of flask.On the other hand, by polymerization initiator 2, (2, the 4- dimethyl of 2 '-azo two Valeronitrile) 30 parts be dissolved in 95 parts of obtained solution of ethyl lactate, lasting 4 hours with another dropping funel is added dropwise in flask.It is poly- After closing initiator solution completion of dropwise addition, it is maintained at 70 DEG C 4 hours, is cooled to room temperature thereafter, obtaining weight average molecular weight (Mw) is 8.0×10³, molecular weight distribution 2.5, solid constituent 48%, solution acid number be the 50mg-KOH/g (acid of solid constituent conversion Be worth for 104mgKOH/g) the solution of resin B 4.Resin B 4 has construction unit shown below.

The weight average molecular weight (Mw) of resin obtained by synthesis example and the measure GPC method of number-average molecular weight (Mn), by following Condition is carried out.

Device：K2479 ((strain) Shimadzu Seisakusho Ltd. system)

Chromatographic column：SHIMADZU Shim-pack GPC-80M

Chromatogram column temperature：40℃

Solvent：THF (tetrahydrofuran)

Flow velocity：1.0mL/min

Detector：RI

Correction standard substance：TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500 (eastern ソ mono- (strain) system)

Using polystyrene conversion the ratio between weight average molecular weight and number-average molecular weight (Mw/Mn) obtained as above as molecular weight point Cloth.

Embodiment and comparative example

Composition as shown in table 1 and table 2 mixes each composition, obtains colored curable resin composition.

【Table 1】

【Table 2】

In addition, in table 1 and table 2, " A1-1¹) " and acrylic acid series pigment dispersing agent and " E-1³) " the propane diols list measured described in column Methylether acetate mixes, and is allowed to pre-dispersed.

“E-1²) " column represent propylene glycol monomethyl ether content summation.

In table 1 and table 2, each composition represents as follows.In addition, resin (B) represents the mass parts of solid constituent conversion.

(A) colouring agent：1-1：Compound shown in formula (1-1)

(A) colouring agent：1-5：Compound shown in formula (1-5)

(A) colouring agent：1-8：Compound shown in formula (1-8)

(A) colouring agent：1-12：Compound shown in formula (1-12)

(A) colouring agent：A1-1：C.I. pigment blue 15:6 (pigment)

(A) colouring agent：A2-1：C.I. direct indigo plant 264 and salt (the オリヱ Application ト chemical industry (strain) of DBSA System) (dyestuff)

(A) colouring agent：A2-2：Dyestuff (A2-2)

(B) resin：B-1：Resin B 1

(B) resin：B-2：Resin B 2

(B) resin：B-3：Resin B 3

(B) resin：B-4：Resin B 4

(C) polymerizable compound：C-1：Dipentaerythritol acrylate (Japanese chemical drug (strain) system；KAYARAD (registrations Trade mark) DPHA)

(D) polymerization initiator：D-1：N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) -1- octanone -2- imines (イ Le ガキュァ (registration mark) OXE 01；BASF societies system)

(E) solvent：E-1：Propylene glycol monomethyl ether

(E) solvent：E-2：Propylene glycol monomethyl ether

(E) solvent：E-3：Ethyl lactate

(F) surfactant：F-1：メガ Off ァッ Network (registration mark) F554 (DIC (strain) systems)

(F) surfactant：F-2：Polyether modified silicone oil (TORAY silicone SH8400；The eastern ニ Application グ of レダウ Us one (strain) makes)

(formation of pattern)

In glass substrate (the グ Le XG of イ mono- of 2 inch squares；The ニ Application グ societies system of U one) on, it is coated with and is coloured by spin-coating method After photosensitive composite, preliminary drying 3 minutes, obtain composition layer at 100 DEG C.After cooling, make the glass formed with composition layer Between substrate and quartz glass photomask at intervals of 100 μm, use exposure machine (TME-150RSK；トプ Us Application (strain) is made), in Under atmospheric atmosphere gas, with 150mJ/cm²Light exposure (365nm benchmark) carry out light irradiation.As photomask, using foring The photomask of 100 μm of line width and line intermittent pattern (Line and Space Pattern).After light irradiation, by above-mentioned film in It is immersed in 80 seconds in the water system developer solution containing nonionic surfactants 0.12% and potassium hydroxide 0.04% to enter at 23 DEG C Row development, after washing, the rear baking of 20 minutes is carried out in baking oven, at 220 DEG C, obtains pattern.

(film thickness measuring)

For the pattern of acquisition, film thickness measuring device (DEKTAK3 is used；Japanese vacuum technique (strain) system)) determine its film It is thick.It the results are shown in Table 3.

(chromaticity evaluation)

For the pattern on the glass substrate of acquisition, color measurement instrument (OSP-SP-200 is used；オリ Application パス (strain) make) survey Fixed light splitting (spectrum), xy chromaticity coordinates (x, y) and three thorns in CIE XYZ colour systems are determined by the color matching function of illuminant-C Swash value Y.Y value is bigger to represent that brightness is higher.It the results are shown in Table 3.

(contrast evaluation)

When exposure without using photomask in addition to, operate with the making identical of pattern, in shape on glass substrate Into film.For the film of acquisition, contrast color measurement instrument (CT-1 is used：Pot Ban electricity Ji She systems, detector：BM-5A, light source： F-10), it is that blank value determines contrast with 30000.Glass substrate light polarizing film (the POLAX-38S of film will be formd；ルケオ societies system) clamping after as measure sample.It the results are shown in Table 3.

【Table 3】

Confirmed from the result of embodiment, the pattern obtained by the colored curable resin composition of the present invention is highlighted The blueness of degree.It follows that the pattern obtained by the colored curable resin composition of the present invention, the colour filter as high brightness Useful, further, the display device containing the colour filter has excellent display characteristic.

Claims

1. colored curable resin composition, containing colouring agent, resin, polymerizable compound and polymerization initiator,

Colouring agent contains the compound shown in compound and formula (4) shown in formula (1)；

In formula (1), R¹And R²Tolyl or 3,5-dimethylphenyl are represented independently of one another,

R³And R⁴1 valency saturated hydrocarbyl of carbon number 1~10, the hydrogen atom quilt contained by the saturated hydrocarbyl are represented independently of one another Whether aromatic hydrocarbyl or the halogen atom substitution of carbon number 6~10 or not, and the hydrogen atom contained by the aromatic hydrocarbyl is by carbon The alkoxy substitution of the alkyl or carbon number 1~3 of atomicity 1~3 or not ,-the CH that the saturated hydrocarbyl contains₂- by- O- ,-CO- or-NR¹¹- replace or do not replace,

R¹And R³With forming the ring of nitrogen atom together with nitrogen-atoms or not forming ring, R²And R⁴With forming nitrogen atom together with nitrogen-atoms Ring or do not form ring,

R⁵Expression-OH ,-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃R⁸Or-SO₂NR⁹R¹⁰,

R⁶And R⁷The alkyl of hydrogen atom or carbon number 1~6 is represented independently of one another,

M represents 0~4 integer, when m is more than 2 integer, multiple R⁵It is identical or different between each other,

R⁸1 valency saturated hydrocarbyl of carbon number 1~20 is represented, the hydrogen atom contained by the saturated hydrocarbyl is substituted or not by halogen atom Substitution,

Z⁺Represent⁺N(R¹¹)₄、Na⁺Or K⁺,

R⁹And R¹⁰1 valency saturated hydrocarbyl of hydrogen atom or carbon number 1~20, R are represented independently of one another⁹And R¹⁰Mutual bonding and nitrogen Atom forms 3~10 member heterocyclic ring containing nitrogens or does not form ring together,

R¹¹Hydrogen atom, 1 valency saturated hydrocarbyl of carbon number 1~20 or the aralkyl of carbon number 7~10 are represented independently of one another；

In formula (4), G¹The alkylidene of carbon number 2~12 is represented, the hydrogen atom contained in the alkylidene is by carbon number 1~4 Alkyl substitutes or not substituted ,-the CH contained in the alkylidene₂- replaced or do not replaced by-O-,

J¹Represent hydrogen atom ,-NR^aR^bOr-NR^aR^bH⁺Q^-,

R^aAnd R^bThe alkyl of hydrogen atom or carbon number 1~8 is represented independently of one another,

Q^-Represent halide ion, BF₄ ^-、PF₆ ^-、ClO₄ ^-、X-CO₂ ^-Or Y-SO₃ ^-,

X and Y represents 1 valency organic group independently of one another,

P represents 1~4 integer.

2. colored curable resin composition according to claim 1, colouring agent further contain pigment.

3. colored curable resin composition according to claim 1, the compound shown in formula (1) is shown in formula (1 ') Compound；

In formula (1 '),

R¹And R²Tolyl or 3,5-dimethylphenyl are represented independently of one another,

R⁴³And R⁴⁴1 valency saturated hydrocarbyl of carbon number 1~10 is represented independently of one another, and the hydrogen atom that the saturated hydrocarbyl contains is by halogen Atom substitutes or not substituted ,-the CH that the saturated hydrocarbyl contains₂- by-O- ,-CO- or-NR¹¹- replace or do not replace,

R¹And R⁴³With forming the ring of nitrogen atom together with nitrogen-atoms or not forming ring, R²And R⁴⁴With forming nitrogenous original together with nitrogen-atoms The ring of son does not form ring,

Z⁺Represent⁺N(R¹¹)₄、Na⁺Or K⁺,

R¹¹Hydrogen atom, 1 valency saturated hydrocarbyl of carbon number 1~20 or the aralkyl of carbon number 7~10 are represented independently of one another.

4. colored curable resin composition according to claim 1, the compound shown in formula (1) is shown in formula (2) Compound；

In formula (2), R²¹、R²²、R²³And R²⁴The alkyl of carbon number 1~4 is represented independently of one another,

R and s represents 0~5 integer independently of one another, when r is more than 2, multiple R²³It is identical or different, when s is more than 2, Multiple R²⁴It is identical or different between each other.

5. colored curable resin composition according to claim 1, the compound shown in formula (1) is shown in formula (3) Compound；

In formula (3), R³¹And R³²The alkyl of carbon number 1~4 is represented independently of one another,

R³³、R³⁴、R³⁵And R³⁶The alkyl of hydrogen atom or carbon number 1~4 is represented independently of one another.

6. colour filter, formed as the colored curable resin composition described in any one of Claims 1 to 5.

7. display device, contain the colour filter described in claim 6.