CN107861336A

CN107861336A - Red hardening resin composition, the colour filter formed by red hardening resin composition, the display device comprising colour filter

Info

Publication number: CN107861336A
Application number: CN201710859378.0A
Authority: CN
Inventors: 辻内翔; 嘉村亮平; 井上胜治
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2016-09-21
Filing date: 2017-09-21
Publication date: 2018-03-30
Anticipated expiration: 2037-09-21
Also published as: CN107861336B

Abstract

The colour filter that is formed the present invention relates to red hardening resin composition, by above-mentioned red hardening resin composition and the display device for including above-mentioned colour filter.The red hardening resin composition of the present invention includes colouring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D) and solvent (E), it can be included with the dyestuff (A1) and red pigment (P) that the maximum absorption wavelength in silicon atom and chloroform is 500nm~600nm as colouring agent (A), propylene glycol monomethyl ether can be included as solvent (E), and the containing ratio of propylene glycol monomethyl ether is more than 10 mass % and below 78 mass % in solvent (E) total amount.

Description

Red hardening resin composition, the filter formed by red hardening resin composition Color device, the display device comprising colour filter

Technical field

The present invention relates to red hardening resin composition.

Background technology

Colored curable resin composition can be used for manufacture in liquid crystal display device, el display device, plasma Colour filter used in the display devices such as body display.As such colored curable resin composition, it is known that comprising by Colored curable resin composition (such as patent document 1) of the compound that following formula represents as colouring agent.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2016-027075 publications

The content of the invention

The invention problem to be solved

Known colored curable resin composition is deposited in terms of having foreign on the surface of gained colour filter so far In room for improvement.

Means for solving the problems

The present invention includes following invention.

[1] red hardening resin composition, which contain toner (A), resin (B), polymerizable compound (C), polymerization Initiator (D) and solvent (E), there is the dyestuff (A1) that the maximum absorption wavelength in silicon atom and chloroform is 500nm~600nm Colouring agent (A) is included as with red pigment (P), propylene glycol monomethyl ether is included as solvent (E), and The containing ratio of propylene glycol monomethyl ether is more than 10 mass % and below 78 mass % in solvent (E) total amount.

[2] the red hardening resin composition described in above-mentioned [1], wherein, in solvent (E) total amount, contain 22 matter Measure more than the % SP values solvent higher than propylene glycol monomethyl ether.

[3] the red hardening resin composition described in above-mentioned [1] or [2], wherein, in solvent (E) total amount, contain 22 More than quality %'s is selected from propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diacetone alcohol, ethyl lactate, 3- methoxyl group -1- fourths Solvent in alcohol, 3- ethoxyl ethyl propionates, cyclohexanone, gamma-butyrolacton, 1-METHYLPYRROLIDONE.

[4] the red hardening resin composition described in any one of above-mentioned [1]~[3], wherein, dyestuff (A1) be with The compound of xanthene skeleton.

[5] the red hardening resin composition described in any one of above-mentioned [1]~[4], wherein, also comprising metallic complex salt Azo dyes is as colouring agent (A).

[6] colour filter formed as the red hardening resin composition described in any one of above-mentioned [1]~[5].

[7] display device, it includes the colour filter described in above-mentioned [6].

The effect of invention

In the colour filter formed by the red hardening resin composition of the present invention, the generation of the foreign matter at surface obtains Suppress.

Embodiment

The red hardening resin composition of the present invention includes colouring agent (A), resin (B), polymerizable compound (C) and gathered Close initiator (D).

In addition, the compound illustrated in this specification and functional group are as long as no special instructions, it can be used alone or incite somebody to action Multiple combinations use.

The red hardening resin composition of the present invention include maximum absorption wavelength in chloroform as 500nm~600nm and Dyestuff (A1) (below also sometimes referred to as " dyestuff (A1) ") and red pigment (P) with silicon atom are used as colouring agent (A).Make For dyestuff (A1), dyestuff that the maximum absorption wavelength preferably in chloroform is 500nm~580nm is very big in particularly preferred chloroform Absorbing wavelength is 500nm~560nm dyestuff.

As above-mentioned dyestuff (A1), preferably with silicon atom and with imidazole skeleton, triarylmethane skeleton, cyanines skeleton Or the dyestuff of xanthene skeleton.As the dyestuff with silicon atom and with imidazole skeleton, such as include Japanese Unexamined Patent Application Publication 2010- The compound represented by formula (IA) disclosed in No. 526897 publications.

[in formula (IA), R¹For the group represented by formula (ia), X is halogen atom.

[n represents 1~8 integer, R²The alkyl of hydrogen atom or carbon number 1~4 is represented, * expressions are bonded with nitrogen-atoms End.]]

As the compound represented by formula (IA), the compound represented by following formula can be preferably included.

In dyestuff (A1), preferably with silicon atom and with being selected from triarylmethane skeleton, cyanines skeleton and xanthene skeleton In at least one skeleton dyestuff, more preferably with silicon atom and with the dyestuff of xanthene skeleton.As with silicon atom simultaneously And the dyestuff with xanthene skeleton, the preferably dyestuff with the xanthene skeleton with organic silicon substrate in substituent.Wherein, it is organic Silicon substrate represents the group with carbon-silicon key.In with the dyestuff of the xanthene skeleton with organic silicon substrate in substituent, preferably With in substituent with trimethyl silyl alkyl, triethylsilyl alkyl, trimethoxysilyl alkyl, The dyestuff of the xanthene skeleton of the silyl alkyls such as triethoxysilyl alkyl, the compound more preferably represented by formula (IB) (below also sometimes referred to as " compound (IB) ").Its dynamic isomer is also included in compound (IB).

[in formula (IB), R²¹~R²⁴Independently of one another represent hydrogen atom, carbon number 1~10 1 valency saturated hydrocarbyl, can have The phenyl of substituent or the group represented by formula (ib).But, R²¹~R²⁴In at least one be by formula (ib) represent base Group.

*-R⁵⁰-Si(R²⁹)₃(ib)

[R²⁹The alkoxy of hydrogen atom, hydroxyl, the alkyl of carbon number 1~4 or carbon number 1~4 is represented, * is represented and nitrogen-atoms Bonding end.Multiple R²⁹Can be with mutually the same also different.

R⁵⁰The alkylidene of carbon number 1~10 is represented, forms-the CH of the alkylidene₂- can be by-O- ,-CO- ,-NR¹¹-、- OCO- ,-COO- ,-OCONH- ,-CONH- or-NHCO- are replaced.But, in the alkylidene, adjacent-CH₂- will not simultaneously by for Change ,-the CH of end₂- will not also be replaced.]

R²¹~R²⁴In, contained hydrogen atom can be substituted with halogen atoms in the saturated hydrocarbyl of 1 valency of carbon number 1~10, should Contained-CH in saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR¹¹- ,-OCO- ,-COO- ,-OCONH- ,-CONH- or-NHCO- Replace.But, in the saturated hydrocarbyl, adjacent-CH₂- will not be replaced simultaneously ,-the CH of end₂- will not also be replaced.

R²⁵And R²⁶The alkyl of hydrogen atom or carbon number 1~6 is represented independently of one another.

R²⁷And R²⁸Expression-OH ,-SO independently of one another₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂ ^-、-CO₂H、-CO₂ ^-Z⁺、-CO₂R¹⁰、- SO₃R¹⁰Or-SO₂NR¹¹R¹²。

R¹⁰The saturated hydrocarbyl of 1 valency of carbon number 1~20 is represented, contained hydrogen atom can be by halogen atom in the saturated hydrocarbyl Substitution.

Z⁺Represent⁺N(R¹³)₄、Na⁺Or K⁺。

R¹¹And R¹²The saturated hydrocarbyl of 1 valency of hydrogen atom or carbon number 1~20 is represented independently of one another.

R¹³Independently of one another represent hydrogen atom, carbon number 1~20 1 valency saturated hydrocarbyl.

P represents 0~4 integer.]

In the compound represented by formula (IB) also include by formula (IC) represent compound (below also sometimes referred to as " compound (IC) ") and its dynamic isomer.

[in formula (IC), R³¹~R³⁴Independently of one another represent hydrogen atom, carbon number 1~10 1 valency saturated hydrocarbyl, can have The phenyl of substituent or the group represented by formula (ic).But, R³¹~R³⁴Middle at least one is the group represented by formula (ic).

[n represents 1~8 integer, R³⁹The alkyl of hydrogen atom or carbon number 1~4 is represented, * expressions are bonded with nitrogen-atoms End.]

R³¹~R³⁴In, contained hydrogen atom can be substituted with halogen atoms in the saturated hydrocarbyl of 1 valency of carbon number 1~10, should Contained-CH in saturated hydrocarbyl₂- can be by-O- ,-CO- or-NR¹¹- replace.But, in the saturated hydrocarbyl, adjacent- CH₂- will not be replaced simultaneously ,-the CH of end₂- will not also be replaced.

R³⁵And R³⁶The alkyl of hydrogen atom or carbon number 1~6 is represented independently of one another.

R³⁷And R³⁸Expression-OH ,-SO independently of one another₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂ ^-、-CO₂H、-CO₂ ^-Z⁺、-CO₂R¹⁰、- SO₃R¹⁰Or-SO₂NR¹¹R¹²。

Z⁺Represent⁺N(R¹³)₄、Na⁺Or K⁺。

M represents 0~4 integer.]

In formula (IB) and formula (IC), as by R²¹~R²⁴And R³¹~R³⁴The saturated hydrocarbyl of 1 valency of the carbon number 1~10 of expression, Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, just can be included Octyl group, decyl, 1- methyl butyls, 1,1,3,3- tetramethyl butyls, 1,5- dimethylhexanyls, 1,6- dimethyl heptyl, 2- ethyls Hexyl and 1,1,5,5- tetramethylhexyls etc..

As by R²¹~R²⁴And R³¹~R³⁴The saturated hydrocarbyl of 1 valency of the carbon number 1~10 of expression, preferably methyl, ethyl, third Base, butyl.

By R²¹~R²⁴And R³¹~R³⁴Contained hydrogen atom can be by halogen in the saturated hydrocarbyl of 1 valency of the carbon number 1~10 of expression Plain atom substitution.As the halogen atom, such as fluorine atom, chlorine atom, bromine atoms and iodine atom can be included.

As the saturated hydrocarbyl of 1 valency of the carbon number 1~10 being substituted with halogen atoms, such as methyl fluoride, difluoro can be included Methyl, trifluoromethyl, perfluoro-ethyl and chlorobutyl.

By R²¹~R²⁴And R³¹~R³⁴Contained-CH in the saturated hydrocarbyl of 1 valency of the carbon number 1~10 of expression₂- can by- O- ,-CO- or-NR¹¹- replace.But, in the saturated hydrocarbyl, adjacent-CH₂- will not be replaced simultaneously ,-the CH of end₂- It will not be replaced.

As by R¹¹The saturated hydrocarbyl of 1 valency of the carbon number 1~10 of expression, methyl, ethyl, n-propyl, positive fourth can be included Base, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-hexadecyl and n-eicosane The straight-chain alkyl of the carbon numbers such as base 1~20；Isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, neopentyl and 2- ethyl hexyls The branch's chain state alkyl of the carbon numbers such as base 3~20；The carbon such as cyclopropyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl and tricyclodecyl The ester ring type saturated hydrocarbyl of number 3~20.

As-CH contained in the saturated hydrocarbyl of 1 valency of the carbon number 1~10₂- the group that substituted for Bei-O-, such as can arrange Enumerate the group represented by following formula (* represents bonding end).

As-CH contained in the saturated hydrocarbyl of 1 valency of the carbon number 1~10₂- the group that substituted for Bei-CO-, such as can Include the group represented by following formula (* represents bonding end).

As-CH contained in the saturated hydrocarbyl of 1 valency of the carbon number 1~10₂- by-NR¹¹- the group that substituted for, such as can Include the group represented by following formula (* represents bonding end).

By R²¹~R²⁴And R³¹~R³⁴Contained-CH in the saturated hydrocarbyl of 1 valency of the carbon number 1~10 of expression₂- can be chosen Replaced from least one group in-OCO- ,-COO- ,-OCONH- ,-CONH- and-NHCO-.But, it is adjacent in the saturated hydrocarbyl - the CH connect₂- will not be replaced simultaneously ,-the CH of end₂- will not also be replaced.

As-CH contained in the saturated hydrocarbyl of 1 valency of the carbon number 1~10₂- the group that substituted for Bei-OCO-, such as can Include the group represented by following formula (* represents bonding end).

As-CH contained in the saturated hydrocarbyl of 1 valency of the carbon number 1~10₂- the group that substituted for Bei-COO-, such as can Include the group represented by following formula (* represents bonding end).

As-CH contained in the saturated hydrocarbyl of 1 valency of the carbon number 1~10₂- the group that substituted for Bei-OCONH-, such as The group represented by following formula can be included (* represents bonding end).

As-CH contained in the saturated hydrocarbyl of 1 valency of the carbon number 1~10₂- the group that substituted for Bei-CONH-, such as The group represented by following formula can be included (* represents bonding end).

As-CH contained in the saturated hydrocarbyl of 1 valency of the carbon number 1~10₂- the group that substituted for Bei-NHCO-, such as The group represented by following formula can be included (* represents bonding end).

By R²¹~R²⁴And R³¹~R³⁴The phenyl of expression can have substituent.As the substituent, halogen original can be included Son ,-R¹⁰、-OH、-OR¹⁰、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂R¹⁰、-SR¹⁰、-SO₂R¹⁰、-SO₃R¹⁰With-SO₂NR¹¹R¹²。

As by R¹⁰~R¹³The saturated hydrocarbyl of 1 valency of the carbon number 1~20 of expression, can include methyl, ethyl, n-propyl, Normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-hexadecyl and positive two The straight-chain alkyl of the carbon numbers such as ten alkyl 1~20；Isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, neopentyl and 2- second The branch's chain state alkyl of the carbon numbers such as base hexyl 3~20；Cyclopropyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl and tricyclodecyl Deng the ester ring type saturated hydrocarbyl of carbon number 3~20.

It is used as-OR¹⁰, such as methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygen in heptan can be included Base, octyloxy, 2- ethyl hexyl oxies and eicosane epoxide.

It is used as-SO₃ ^-Z⁺, preferably-SO₃ ^-N⁺(R¹³)₄。

It is used as-CO₂R¹⁰, such as can include methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, Hexyloxy carbonyl and eicosane epoxide carbonyl.

It is used as-SR¹⁰, such as methylsulfanyl, Ethylsulfanyl, butyl sulfanyl, hexyl sulfanyl, decyl can be included Sulfanyl and eicosyl sulfanyl.

It is used as-SO₂R¹⁰, such as methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, the last of the ten Heavenly stems can be included Base sulfonyl and eicosyl sulfonyl.

It is used as-SO₃R¹⁰, such as methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tertiary fourth oxygen can be included Base sulfonyl, hexyloxy sulfonyl and eicosane epoxide sulfonyl.

It is used as-SO₂NR¹¹R¹², such as N- Methylsulfamoyls, N- ethylsulfamovls, N- propyl group sulfonamides can be included Base, N- isopropylsulfamoyls base, N- Butylsulfamoyls base, N- isobutyl groups sulfamoyl, N- sec-butyls sulfamoyl, the N- tert-butyl groups Sulfamoyl, N- amyl groups sulfamoyl, N- (1- ethyl propyls) sulfamoyl, N- (1,1- dimethyl propyls) sulfamoyl, N- (1,2- dimethyl propyls) sulfamoyl, N- (2,2- dimethyl propyls) sulfamoyl, N- (1- methyl butyls) sulfamoyl, N- (2- methyl butyls) sulfamoyl, N- (3- methyl butyls) sulfamoyl, N- Cyclopentylsulfamoyls base, N- hexyls sulfamoyl, N- (1,3- dimethylbutyls) sulfamoyl, N- (3,3- dimethylbutyls) sulfamoyl, N- heptyl sulfamoyl, N- (1- first Base hexyl) sulfamoyl, N- (1,4- dimethyl amyl groups) sulfamoyl, N- octyl groups sulfamoyl, N- (2- ethylhexyls) ammonia sulphur The N-1 such as acyl group, N- (1,5- dimethyl) hexyl sulfamoyl, N- (1,1,2,2- tetramethyl butyls) sulfamoyl substitute sulfonamides Base；

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, double (1- methyl-propyls) sulfamoyls of N-, N, N-2 the substitution sulfamoyl such as N, N- hept-ylmethyl sulfamoyls.

As by R²¹~R²⁴And R³¹~R³⁴The substituent that the phenyl of expression has, preferably-R¹⁰, more preferably carbon number 1~10 1 valency saturated hydrocarbyl.

R²¹~R²⁴In at least one be by formula (ib) represent group.

In the group represented by formula (ib), R²⁹Represent the alkane of hydrogen atom, hydroxyl, the alkyl of carbon number 1~4 or carbon number 1~4 Epoxide.

As by R²⁹The alkyl of the carbon number 1~4 of expression, can include methyl, ethyl, propyl group, butyl.

As by R²⁹The alkoxy of the carbon number 1~4 of expression, can include methoxyl group, ethyoxyl, propoxyl group, tert-butoxy Deng.

As the R in the group represented by formula (ib)²⁹, preferably methyl, ethyl, methoxyl group, ethyoxyl, more preferably methoxyl group Or ethyoxyl.

As by R⁵⁰The alkylidene of the carbon number 1~10 of expression, methylene, ethylidene, trimethylene, four methylenes can be included Base, pentamethylene, hexa-methylene, isopropylidene, isobutylidene, 2- methyl trimethylenes, isoamylidene, sub- isohesyl, Asia are different Octyl group, 2- ethyl hexylens etc., wherein it is preferred that the alkylidene of the alkylidene of carbon number 1~6, more preferably carbon number 1~4.

As the group represented by formula (ib), such as the group represented by following formula can be included.

In formula (ib), as composition R⁵⁰- CH₂- the group that substituted for Bei-O-, such as following shown bases can be included Group (* represents bonding end).

In formula (ib), as composition R⁵⁰- CH₂- the group that substituted for Bei-CO-, such as following shown bases can be included Group (* represents bonding end).

In formula (ib), as composition R⁵⁰- CH₂- by-NR¹¹- the group that substituted for, for example, can include it is following shown in Group (* represents bonding end).

In formula (ib), as composition R⁵⁰- CH₂- the group that substituted for Bei-OCO-, for example, can include it is following shown in Group (* represents bonding end).

In formula (ib), as composition R⁵⁰- CH₂- the group that substituted for Bei-COO-, for example, can include it is following shown in Group (* represents bonding end).

In formula (ib), as composition R⁵⁰- CH₂- the group that substituted for Bei-OCONH-, such as can include following shown Group (* represent bonding end).

In formula (ib), as composition R⁵⁰- CH₂- the group that substituted for Bei-CONH-, for example, can include it is following shown in Group (* represents bonding end).

In formula (ib), as composition R⁵⁰- CH₂- the group that substituted for Bei-NHCO-, for example, can include it is following shown in Group (* represents bonding end).

As formula (ib), the group preferably represented by following formula.

It is preferred that R³¹~R³⁴Middle at least one is the group represented by formula (ic).

In formula (ic), as by R³⁹The alkyl of the carbon number 1~4 of expression, can include methyl, ethyl, propyl group, butyl.

As R³⁹, preferably hydrogen atom, methyl, ethyl, propyl group, more preferably hydrogen atom, methyl, ethyl.

As the group represented by formula (ic), such as the group represented by following formula (i-1)~formula (i-12) can be included. As the group represented by formula (ic), the group preferably represented by formula (i-2), formula (i-3), formula (i-5), formula (i-6).

As by R²⁵、R²⁶、R³⁵And R³⁶The alkyl of the carbon number 1~6 of expression, can include methyl, ethyl, propyl group, butyl, Amyl group, hexyl, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl and neopentyl.

As by R²⁷、R²⁸、R³⁷And R³⁸- the SO represented₃ ^-Z⁺, preferably-SO₃Na or-SO₃K。

As by R²⁷、R²⁸、R³⁷And R³⁸- the CO represented₂ ^-Z⁺, preferably-CO₂Na or-CO₂K。

As by R²⁷、R²⁸、R³⁷And R³⁸- the CO represented₂R¹⁰, such as methoxycarbonyl, ethoxy carbonyl, third can be included Epoxide carbonyl, tert-butoxycarbonyl, hexyloxy carbonyl and eicosane epoxide carbonyl.

As by R²⁷、R²⁸、R³⁷And R³⁸- the SO represented₃R¹⁰, such as methoxysulfonyl, ethyoxyl sulphonyl can be included Base, propoxysulfonyl, tert-butoxy sulfonyl, hexyloxy sulfonyl and eicosane epoxide sulfonyl.

As by R²⁷、R²⁸、R³⁷And R³⁸- the SO represented₂NR¹¹R¹², such as N- Methylsulfamoyls, N- ethyls can be included Sulfamoyl, N- propylsulfamovs, N- isopropylsulfamoyls base, N- Butylsulfamoyls base, N- isobutyl groups sulfamoyl, N- are secondary Butylsulfamoyl base, N- tert-butyl groups sulfamoyl, N- amyl groups sulfamoyl, N- (1- ethyl propyls) sulfamoyl, N- (1,1- bis- Methyl-propyl) sulfamoyl, N- (1,2- dimethyl propyls) sulfamoyl, N- (2,2- dimethyl propyls) sulfamoyl, N- (1- Methyl butyl) sulfamoyl, N- (2- methyl butyls) sulfamoyl, N- (3- methyl butyls) sulfamoyl, N- cyclopenta ammonia sulphurs Acyl group, N- hexyls sulfamoyl, N- (1,3- dimethylbutyls) sulfamoyl, N- (3,3- dimethylbutyls) sulfamoyl, N- Heptyl sulfamoyl, N- (1- methylhexyls) sulfamoyl, N- (1,4- dimethyl amyl groups) sulfamoyl, N- octyl group sulfonamides Base, N- (2- ethylhexyls) sulfamoyl, N- (1,5- dimethyl) hexyl sulfamoyl, N- (1,1,2,2- tetramethyl butyls) ammonia The N-1 such as sulfonyl substitute sulfamoyl；

As by R¹⁰The saturated hydrocarbyl of 1 valency of the carbon number 1~20 of expression, preferably methyl, ethyl, propyl group, butyl.

By R¹⁰Contained hydrogen atom can be substituted with halogen atoms in the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of expression.

As the halogen atom, such as fluorine atom, chlorine atom, bromine atoms and iodine atom can be included.

As the saturated hydrocarbyl of 1 valency of the carbon number 1~20 being substituted with halogen atoms, such as methyl fluoride, two can be included Methyl fluoride, trifluoromethyl, perfluoro-ethyl and chlorobutyl.

As Z⁺, preferably⁺N(R¹³)₄。

⁺N(R¹³)₄In 4 R¹³It is it is preferred that all identical.In addition, 4 R¹³Total carbon number preferably 20~80, more preferably 20 ~60.

As by R¹¹And R¹²The saturated hydrocarbyl of 1 valency of the carbon number 1~20 of expression, preferably methyl, ethyl, propyl group, butyl or 2- ethylhexyls.

As by R¹³The saturated hydrocarbyl of 1 valency of the carbon number 1~20 of expression, preferably methyl, ethyl, propyl group, butyl, more preferably Methyl, ethyl, propyl group.

R²¹~R²⁴In, at least one is the group represented by formula (ib), as other R²¹~R²⁴, preferably methyl, ethyl, Propyl group and following group (* represents the bonding end with nitrogen-atoms).

More preferably methyl, ethyl, propyl group and following group (* represents the bonding end with nitrogen-atoms).

R³¹~R³⁴In, at least one is the group represented by formula (ic), as other R³¹~R³⁴, preferably methyl, ethyl, Propyl group and following group.

R²⁵、R²⁶、R³⁵And R³⁶Preferably hydrogen atom, methyl, ethyl, more preferably hydrogen atom.

R²⁷、R²⁸、R³⁷And R³⁸Preferably-CO₂ ^-、-CO₂H、-SO₃H、-SO₃ ^-, more preferably-SO₃H、-SO₃ ^-。

R¹⁰Preferably methyl, ethyl, propyl group, butyl.

R¹¹Preferably hydrogen atom, methyl, ethyl, propyl group, butyl, 2- ethylhexyls.

R¹²Preferably hydrogen atom, methyl, ethyl, propyl group, butyl, 2- ethylhexyls.

R¹³Preferably hydrogen atom, methyl, ethyl, propyl group, butyl.

P and m preferably 0~2 integer, more preferably 0 or 1, more preferably 0.

As compound (IB) concrete example, such as following shown compounds can be included.It is excellent as compound (IB) Select (I-1)~(I-4), (I-13)~(I-16), (I-25)~(I-28), (I-37)~(I-40), (I-49)~(I-54), (I-55)~(I-62), (I-87)~(I-94), (I-117)~(I-123), more preferably (I-1)~(I-4), (I-13)~(I- 16), (I-25)~(I-28), (I-55)~(I-62), (I-87)~(I-94), (I-117), (I-119)~(I-123).

As compound (IC) concrete example, for example, can include by above-mentioned formula (I-1)~(I-54) represent compound, By the compound of formula (I-117)~formula (I-119) expression, the compound represented by formula (I-121), by formula (I-123) expression Compound.As compound (IC), preferably by the compound of formula (I-1)~formula (I-4) expression, by formula (I-13)~formula (I-16) The compound of expression, the compound represented by formula (I-25)~formula (I-28), the chemical combination represented by formula (I-37)~formula (I-40) Thing, the compound represented by formula (I-49)~formula (I-54), the compound represented by formula (I-117)~formula (I-119), more preferably The compound that is represented by formula (I-1)~formula (I-4), the compound represented by formula (I-13)~formula (I-16), by formula (I-25)~ The compound of formula (I-28) expression, the compound represented by formula (I-117), the compound represented by formula (I-119).

Compound (IB) can be by will be by formula (IV)

[in formula, R²¹、R²²、R²⁵、R²⁶、R²⁸、R²⁷Represent implication same as described above respectively with p.X²Represent halogen atom or Trimethyl fluoride sulfonyl epoxide] represent compound (hereinafter sometimes referred to as " compound (IV) ") with by formula (V)

[in formula, R²³And R²⁴Represent implication same as described above respectively] represent compound (hereinafter sometimes referred to as " change Compound (V) ") mix in organic solvent and it is reacted and is manufactured.

As by X²The halogen atom of expression, fluorine atom, chlorine atom, bromine atoms and iodine atom, preferably chlorine can be included Atom.

X²Preferably halogen atom, more preferably chlorine atom.

R²⁷Preferably-SO₃ ^-。

For compound (V) usage amount, relative to 1 mole of compound (IV), usually more than 1 mole and 10 moles Hereinafter, preferably more than 1 mole and less than 3 moles, more preferably more than 1 mole and less than 2 moles.

R²⁷For-SO₃ ^-Or-CO₂ ^-Compound (IB) (hereinafter sometimes referred to compound (II-1)) can be by will be by formula (VI)

[in formula, R²⁵、R²⁶、R²⁸Implication same as described above is represented with p.

X¹And X²Halogen atom or trimethyl fluoride sulfonyl epoxide are represented independently of one another.

R⁴⁰Expression-SO₂- or-CO-.]

The compound (hereinafter sometimes referred to as " compound (VI) ") of expression with by formula (III)

[in formula, R²¹And R²²Represent implication same as described above.]

The compound (hereinafter sometimes referred to as " compound (III) ") of expression mixes and makes its reaction in organic solvent, Next, will be by formula (V)

[in formula, R²³And R²⁴Implication same as described above is represented respectively.]

The compound of expression mixes and it is reacted and is manufactured in organic solvent.

As by X¹The halogen atom of expression, fluorine atom, chlorine atom, bromine atoms and iodine atom, preferably chlorine can be included Atom.

It is preferred that X¹With X²It is identical.

X¹And X²It is preferably halogen atom, more preferably chlorine atom independently of one another.

R⁴⁰Preferably-SO₂-。

For compound (III) usage amount, relative to 1 mole of compound (VI), usually more than 1 mole and 30 rub You are following, preferably more than 1 mole and less than 20 moles, more preferably more than 1 mole and less than 10 moles, more preferably More than 1 mole and less than 3 moles, particularly preferably more than 1 mole and less than 2 moles.

For compound (V) usage amount, relative to 1 mole of compound (VI), usually more than 1 mole and 30 moles Hereinafter, preferably more than 1 mole and less than 20 moles, more preferably more than 1 mole and less than 10 moles, more preferably 1 More than mole and less than 3 moles, particularly preferably more than 1 mole and less than 2 moles.

For compound (V) usage amount, relative to 1 mole of compound (III), usually more than 1 mole and 50 rub You are following, preferably more than 1 mole and less than 30 moles, more preferably more than 1 mole and less than 20 moles.

Compound (IB) can be used as dyestuff.Because dissolubility in organic solvent is high, liquid crystal display especially can be used as Deng display device colour filter in the colouring agent of colored curable resin composition that uses.

For dyestuff (A1) containing ratio, in the matter of total amount 100 of the solid constituent of red hardening resin composition Measure in %, preferably more than 0.1 mass %, more preferably more than 0.2 mass %, preferably below 30 mass %, more preferably 20 matter Measure below %.

Wherein, " total amount of solid constituent " in this specification refers to incite somebody to action from the total amount of red hardening resin composition Amount after the content removing of solvent.The total amount of solid constituent and it can for example pass through liquid phase color relative to the content of its each composition Analysis means measure known to spectrum or gas-chromatography etc..

For dyestuff (A1) containing ratio, in the mass % of total amount 100 of colouring agent (A), preferably 0.01 mass % with Upper and below 80 mass %, more preferably more than 0.1 mass % and below 60 mass %, further preferred more than 1 mass % and 40 Below quality %.

And then for compound (IB) containing ratio, in the mass % of dyestuff (A1) 100, preferably 80 mass % with On, more preferably more than 90 mass %, more preferably more than 95 mass %.

In addition, for dyestuff (A1) containing ratio, in total 100 mass % of dyestuff, preferably 10 mass % with On, preferably also 100 mass %, more preferably can be below 80 mass % more preferably more than 20 mass %.

＜ red pigments (P) ＞

The red hardening resin composition of the present invention is also made in addition to above-mentioned dyestuff (A1) comprising red pigment (P) For colouring agent (A).

As red pigment (P), can including colour index, (The Society of Dyers and Colourists go out Version) in be categorized as red compound in the compound of pigment.

Specifically, can include C.I. Pigment Red 9s (record of C.I. paratoneres omitted below, only record sequence number), 97, 105、122、123、144、149、166、168、175、176、177、180、192、209、215、216、224、242、254、255、 264th, 265 etc., preferably C.I. paratoneres 254,255.

The containing ratio of red pigment (P) is preferably more than 0.1 mass % in the mass % of colouring agent (A) 100, more preferably More than 10 mass %, more preferably more than 30 mass %, preferably below 99 mass %, more preferably 95 mass % with Under.

And then above-mentioned dyestuff (A1) contains with the total of red pigment (P) in the mass % of total amount 100 of colouring agent (A) It is preferably more than 80 mass %, more preferably more than 90 mass % to have rate.

In addition, the content ratio (dyestuff (A1)/red pigment (P)) of above-mentioned dyestuff (A1) and red pigment (P) is with quality base Quasi- meter, preferably 1/99~99/1, more preferably 2/98~95/5.

＜ pigment (Q) ＞

The red hardening resin composition of the present invention can include red in the degree of performance for not damaging gained colour filter Pigment (Q) beyond color pigment (P) is used as colouring agent (A)., can be without particular limitation using known face as pigment (Q) Material, such as can include in colour index (The Society of Dyers and Colourists publication) and be categorized as pigment Compound.

, can be without particular limitation using known face as above-mentioned pigment (Q) (but different from red pigment (P)) Material, such as the change that pigment is categorized as in colour index (The Society of Dyers andColourists publication) can be included Compound.

As pigment (Q), such as can include：C.I. pigment yellow 1 (record of C.I. pigment yellows omitted below, is only recorded Sequence number), 3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137, 138th, the yellow uitramarine such as 139,147,148,150,153,154,166,173,194,214；

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 blue 15,15：3、15：4、15：6th, the green pigment such as 60,80；

C.I. the violet pigment such as pigment violet 1,19,23,29,32,36,38；

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

C.I. the brown such as pigment brown 23,25；

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

These pigment can be used alone, and can also be used in mixed way two or more.

As pigment (Q), preferably yellow uitramarine or orange pigment.

Total containing ratio of pigment is preferably more than 0.1 mass % in the mass % of total amount 100 of colouring agent (A), more It is still more preferably more than 50 mass % more preferably more than 30 mass % preferably more than 10 mass %, is preferably Below 99 mass %, more preferably below 95 mass %.

＜ dyestuffs (A2) ＞

The red hardening resin composition of the present invention can include in the degree of the performance for the colour filter for not damaging to obtain Dyestuff (A2) beyond dyestuff (A1) is used as colouring agent (A).As dyestuff (A2) (but different from dyestuff (A1)), can include Oil-soluble dyes, acid dyes, basic-dyeable fibre, direct dyes, mordant dye, the amine salt of acid dyes, the sulphonyl of acid dyes The dyestuffs such as amine derivative, metallic complex salt dyestuff, such as colour index (The Society of Dyers and can be included Colourists publish) in be categorized as dyestuff compound, dyeing notes (Se Ran societies) described in known dyestuff.In addition, According to chemical constitution, xanthene dye, the phthalein beyond azo dyes, cyanine dyes, triphenhlmethane dye, dyestuff (A1) can be included Cyanine dyes, naphthoquinone dyestuff, quinoneimine dye, methine dyes, azomethine dyes, squaraine dye, acridine dye, styryl Dyestuff, coumarine dye, quinoline dye and nitro dye etc..In these, preferable organic solvent soluble dye.

Specifically, C.I. solvent yellows 4,14,15,23,24,38,62,63,68,82,94,98,99,162 can be included；

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. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177, 179、181、182、184、204、207、211、213、218、220、221、222、232、233、234、241、243、246、250；

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. the grade C.I. of Viride Nitens 1 basic-dyeable fibres,

C.I. active yellow 2,76,116；

C.I. reactive orange 16；

C.I. the grade C.I. of active red 36 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 orchil, orange and weld.

These dyestuffs can properly select according to the spectrophotometric spectra of desired colour filter.These dyestuffs can be used alone, Also two or more may be used.

As dyestuff (A2), preferably metallic complex salt dyestuff.Metallic complex salt dyestuff be with molecule containing can be with metallic atom The dyestuff that the dye molecule of the group of complex salt forms as part, by metallic atom complex salt.As the dye as part Material, can include azo dyes, methine dyes etc., preferably azo dyes.In other words, as metallic complex salt dyestuff, can enumerate Go out metallic complex salt azo dyes, metallic complex salt methine dyes etc., preferably metallic complex salt azo dyes.As above-mentioned metal raw Son, chromium, cobalt, nickel etc., preferred chromium, cobalt can be included.

As above-mentioned metallic complex salt dyestuff, such as can include：C.I. solvent yellow 13,19,21,25,25：1、62、79、 81、82、83、83：1、88、89、90、151、161；C.I. solvent orange 5,11,20,40：1、41、45、54、56、58、62、70、 81、99；C.I. solvent red 8,35,83：1、84：1、90、90：1、91、92、118、119、122、124、125、127、130、132、 160、208、212、214、225、233、234、243；C.I. solvent violet 2,21,21：1、46、49、58、61；C.I. solvent blue 137；C.I. solvent brown 28,42,43,44,53,62,63, C.I. acid yellow 59s, 121；C.I. acid orange 74,162；C.I. it is acid Red 211, the metallic complex salt dyestuff described in Japanese Unexamined Patent Publication 2010-170117 publications.These metallic complex salt dyestuffs can individually make With also two or more may be used.

In these, metallic complex salt dyestuff has maximum absorption ripple preferably in more than 410nm and below 580nm scope It is long, there is maximum absorption wavelength more preferably in more than 490nm and below 580nm scope.

The content ratio (dyestuff (A1)/metallic complex salt dyestuff) of dyestuff (A1) and metallic complex salt dyestuff is excellent in terms of quality criteria Elect more than 0.1, more preferably more than 0.2, preferably less than 10, more preferably less than 4 as.

Total containing ratio of dyestuff is preferably more than 0.1 mass % in the mass % of total amount 100 of colouring agent (A), more Preferably more than 1 mass %, more preferably more than 5 mass %, preferably below 50 mass %, more preferably 40 mass % Hereinafter, more preferably below 30 mass %.

Relative to the total amount of solid constituent, the containing ratio of colouring agent (A) be preferably more than 1 mass % and 70 mass % with Under, more preferably more than 1 mass % and below 60 mass %, more preferably more than 1 mass % and below 50 mass %.Such as The containing ratio of fruit colouring agent (A) is in above-mentioned scope, then can obtain desired light splitting, colour saturation.

＜ resins (B) ＞

Resin (B) is not particularly limited, preferably alkali soluble resin, more preferably have come from from unsaturated carboxylic acid and The copolymer of the construction unit of at least one monomer (a) (hereinafter sometimes referred to " (a) ") selected in unsaturated carboxylic acid anhydrides.

Copolymer with the construction unit from (a) is preferably with from from the ring-type ether structure with carbon number 2~4 With the construction unit of the monomer (b) (hereinafter sometimes referred to " (b) ") of ethylenic unsaturated bond and the structure with ethylenic unsaturated bond At least one copolymer selected in unit.The copolymer can further have other construction units.

As other construction units, can include from the monomer (c) that can be copolymerized with (a) (but with (a) and (b) not The construction unit of (hereinafter sometimes referred to " (c) ") together).

As (a), specifically, such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p- vinyl benzene can be enumerated The unsaturated monocarboxylic class such as formic acid；

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- vinylphthalic acids, 4- vinyl neighbours benzene two Formic acid, 3,4,5,6- tetrahydrophthalic acids, 1,2,3,6- tetrahydrophthalic acids, dimethyl tetrahydro phthalic acid, 1,4- The unsaturated dicarboxylic class such as cyclohexene dicarboxylic acid；

Methyl -5- ENB -2,3- dicarboxylic acids, bicyclic [2.2.1] hept-2-ene" of 5- carboxyls, 5,6- dicarboxyls are bicyclic [2.2.1] hept-2-ene", 5- carboxyl -5- methyl bicycles [2.2.1] hept-2-ene", bicyclic [2.2.1] the hept- 2- of 5- carboxyl -5- ethyls Alkene, 5- carboxyl -6- methyl bicycles [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene" of 5- carboxyl -6- ethyls etc. contain carboxyl Bicyclic unsaturated compound class；

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acids acid anhydride, 4- vinylphthalic acids acid anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl tetrahydro phthalic anhydride, 5,6- The unsaturated dicarboxylic anhydrides such as bicyclic [2.2.1] the hept-2-ene" acid anhydride of dicarboxyl；

Mono succinate [2- (methyl) acryloyl-oxyethyl] ester, phthalic acid list [2- (methyl) acryloxy second Base] more than 2 yuan of the polybasic carboxylic acid such as ester single [(methyl) acryloxyalkyl] esters of unsaturation；

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

It is excellent in terms of copolyreaction, the deliquescent aspect of obtained resin in aqueous alkali in these Select acrylic acid, methacrylic acid, maleic anhydride etc..

(b) refer to the ring-type ether structure for example with carbon number 2~4 (for example, selected from oxirane ring, oxetanes ring With it is at least one kind of in tetrahydrofuran ring) and ethylenic unsaturated bond polymerizable compound.

(b) monomer of the cyclic ether preferably with carbon number 2~4 and (methyl) acryloxy.

It should illustrate, in this specification, " (methyl) acrylic acid " represents at least 1 in acrylic acid and methacrylic acid Kind.The statement such as " (methyl) acryloyl group " and " (methyl) acrylate " also has the same meaning.

As (b), monomer for example with epoxy ethyl and ethylenic unsaturated bond can be included, with oxetanylmethoxy and The monomer of ethylenic unsaturated bond, the monomer with tetrahydrofuran base and ethylenic unsaturated bond etc..

As (b), such as (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methyl glycidyl can be included Ester, vinylbenzyl glycidyl base ether, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates, the ring of acrylic acid 3,4- epoxies three [5.2.1.0^2,6] last of the ten Heavenly stems ester, 3- ethyls -3- (methyl) acryloyloxymethyls oxetanes, (methyl) tetrahydrofurfuryl acrylate.

As (b), the side of the reliability of heat resistance, chemical-resistant in the colour filter that can further improve to obtain etc. Face, it is however preferred to have the monomer of epoxy ethyl and ethylenic unsaturated bond.

As (c), such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid can be included just Butyl ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) propylene Sour dodecyl ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid ring pentyl ester, (methyl) Cyclohexyl acrylate, (methyl) acrylic acid 2- methyl cyclohexyls, the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] decane -8- base esters (in the technical field, as trivial name, it is referred to as " the bicyclic pentyl ester of (methyl) acrylic acid ".In addition, it is sometimes referred to as " (methyl) third Olefin(e) acid tricyclodecyl "), the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] decene -8- base esters are (in the technical field, as usual Name, be referred to as " (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate "), the bicyclic amoxy ethyl ester of (methyl) acrylic acid, the different ice of (methyl) acrylic acid Piece ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) allyl acrylate, (methyl) propargylacrylate, (methyl) acrylic acid (methyl) esters of acrylic acids such as phenyl ester, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate；

(methyl) acrylic acid containing hydroxyl such as (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters Esters；

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

Bicyclic [2.2.1] hept-2-ene", 5- methyl bicycles [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene" of 5- ethyls, Bicyclic [2.2.1] hept-2-ene" of 5- hydroxyls, bicyclic [2.2.1] hept-2-ene" of 5- hydroxymethyls, 5- (2 '-hydroxyethyl) are bicyclic Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5- methoxyl groups, bicyclic [2.2.1] hept-2-ene" of 5- ethyoxyls, 5,6- dihydroxies Bicyclic [2.2.1] hept-2-ene" of base, bicyclic [2.2.1] hept-2-ene"s of 5,6- bis- (hydroxymethyl), 5,6- bis- (2 '-hydroxyethyl) are double Bicyclic [2.2.1] hept-2-ene" of ring [2.2.1] hept-2-ene", 5,6- dimethoxys, bicyclic [2.2.1] the hept- 2- of 5,6- diethoxies Bicyclic [2.2.1] hept-2-ene" of alkene, 5- hydroxy-5-methyl bases, bicyclic [2.2.1] hept-2-ene" of 5- hydroxyl -5- ethyls, 5- hydroxyl first The bicyclic unsaturated compound classes such as base -5- methyl bicycles [2.2.1] hept-2-ene"；

N-phenylmaleimide, N- N-cyclohexylmaleimides, N- benzyl maleimides, N- succinimides base- 3- maleimidobenzoyls salt, N- succinimide base -4- maleimidobutyrates salt, N- succinimide base -6- Malaysias The dicarbapentaborane such as acid imide caproate, N- succinimide base -3- maleimidopropionic acids salt, N- (9- acridinyls) maleimide Imine derivative class；

Styrene, α-methylstyrene, m- methyl styrene, p-methylstyrene, vinyltoluene, p- methoxyl group Styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinylacetate, 1, 3- butadiene, isoprene, 2,3- dimethyl -1,3- butadiene etc..

In these, from copolyreaction and heat resistance aspect, optimization styrene, vinyltoluene, (methyl) third Olefin(e) acid benzyl ester, the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] decane -8- base esters, N-phenylmaleimide, N- cyclohexyl Malaysia Acid imide, N- benzyl maleimides, bicyclic [2.2.1] hept-2-ene".

Construction unit with ethylenic unsaturated bond is preferably in construction unit of the side chain with (methyl) acryloyl group.Tool Have the resin of such construction unit by make with from (a), the construction unit of (b) polymer with can with (a), (b) the monomer addition of the group and ethylenic unsaturated bond of the radical reaction having and obtain.

As such construction unit, the addition of (methyl) acrylic acid units (methyl) glycidyl of sening as an envoy to can be enumerated Construction unit that ester forms, make construction unit that maleic anhydride units addition (methyl) acrylic acid 2- hydroxy methacrylates form, make (first Base) construction unit that forms of the addition of glycidyl acrylate unit (methyl) acrylic acid etc..In addition, have in these construction units In the case of having hydroxyl, the construction unit for further forming carboxylic acid anhydrides addition also can be as the structure with ethylenic unsaturated bond Unit is enumerated.

As resin (B), specifically, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates/(methyl) acrylic acid can be enumerated Copolymer, the ring [5.2.1.0 of (methyl) acrylic acid 3,4- epoxies three^2.6] last of the ten Heavenly stems ester/(methyl) acrylic copolymer etc. has and come from (a) and (b) construction unit copolymer；(methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) propylene Acid copolymer, (methyl) glycidyl acrylate/styrene/(methyl) acrylic copolymer, (methyl) acrylic acid 3,4- rings Ring [the 5.2.1.0 of oxygen three^2.6] last of the ten Heavenly stems ester/(methyl) acrylic acid/N- N-cyclohexylmaleimides copolymer, (methyl) acrylic acid 3,4- Ring [the 5.2.1.0 of epoxy three^2.6] last of the ten Heavenly stems ester/(methyl) acrylic acid/vinyl toluene copolymer, 3- methyl -3- (methyl) acryloyl-oxy Ylmethyl oxetanes/(methyl) acrylic/styrene copolymer etc. has the construction unit from (a), (b) and (c) Copolymer；(methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) acrylic copolymer, (methyl) third Olefin(e) acid benzyl ester/(methyl) acrylic acid tricyclodecyl/(methyl) acrylic copolymer；Make (methyl) glycidyl acrylate with Resin that (methyl) benzyl acrylate/(methyl) acrylic copolymer addition forms, make (methyl) glycidyl acrylate with Resin that (methyl) acrylic acid tricyclodecyl/styrene/(methyl) acrylic copolymer addition forms, (methyl) acrylic acid is set to contract Water glyceride forms with (methyl) acrylic acid tricyclodecyl/(methyl) benzyl acrylate/(methyl) acrylic copolymer addition Resin etc. has the copolymer of the construction unit from (a) and (c)；Make (methyl) acrylic acid and the ring last of the ten Heavenly stems of (methyl) acrylic acid three Resin that the copolymer reaction of ester/(methyl) glycidyl acrylate forms, make (methyl) acrylic acid and (methyl) acrylic acid Resin that the copolymer reaction of tricyclodecyl/styrene/(methyl) glycidyl acrylate forms etc. has and made from (b) The copolymer of the construction unit that construction unit addition (a) forms and the construction unit from (c)；Make (methyl) acrylic acid and (first Base) acrylic acid tricyclodecyl/(methyl) glycidyl acrylate the resin that forms of copolymer reaction it is further adjacent with tetrahydrochysene Resin that phthalic acid anhydride reactant forms etc., which has, forms the construction unit addition (a) from (b), further addition carboxylic acid anhydrides Construction unit and the copolymer of construction unit from (c) etc..

Above-mentioned resin for example being capable of bibliography《The experimental method of Polymer Synthesizing》(big Jin Longhangzhu publishing houses (strain) chemistry With the printing of people the 1st edition the 1st time distribution on March 1st, 1972) described in method and the document described in citation and make Make.

Resin (B) is preferably selected from the copolymer with the construction unit from (a) and (b)；With from (a), (b) and (c) copolymer of construction unit；And one kind in the copolymer with the construction unit from (a) and (c).

The weight average molecular weight of the polystyrene conversion of resin (B) is preferably 3000~100000, more preferably 5000~ 50000.If molecular weight is in above-mentioned scope, when forming colored pattern, the front and rear residual film ratio that develops is high, unexposed portion pair In the favorable solubility of developer solution, there is the tendency that the resolution ratio of colored pattern improves.

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

The acid number (solid constituent conversion) of resin (B) is preferably 10~200mg-KOH/g, more preferably 20~180mg- KOH/g.Wherein, acid number is the value that the amount (mg) high as the potassium hydroxide neutralized needed for resin (B) 1g is determined, such as can Titrated and obtained using potassium hydroxide aqueous solution.

For resin (B) content, relative to the total amount of solid constituent, preferably 7~75 mass %, more preferably 10 ~70 mass %, more preferably 13~70 mass %.If the content of resin (B), being capable of shape in above-mentioned scope Into colored pattern, the tendency that the resolution ratio with colored pattern and residual film ratio improve in addition.

＜ polymerizable compounds (C) ＞

Polymerizable compound (C) can utilize living radical and/or acid polymerization as caused by polymerization initiator (D) It compound, can include such as the compound of the ethylenic unsaturated bond with polymerism, be preferably (methyl) acroleic acid esterification Compound.

As the polymerizable compound with 1 ethylenic unsaturated bond, such as nonyl phenyl carbitol propylene can be included Acid esters, acrylic acid 2- hydroxyl -3- phenoxy-propyls, 2- ethylhexyl carbitols acrylate, acrylic acid 2- hydroxy methacrylates, N- second Vinyl pyrrolidone etc. and above-mentioned (a), (b) and (c).

As the polymerizable compound with 2 ethylenic unsaturated bonds, such as 1,6- hexylene glycols two (methyl) can be included Acrylate, ethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylic acid Double (acryloyl-oxyethyl) ether, 3- methyl pentanediols two (methyl) acrylate etc. of ester, bisphenol-A.

Wherein, polymerizable compound is preferably the polymerizable compound with the ethylenic unsaturated bond of more than 3.It is used as this The polymerizable compound of sample, such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) third can be included Olefin(e) acid ester, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) Acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, tetrapentaerythritol ten (methyl) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2- (methyl) acryloyl-oxyethyl) isocyanuric acids Ester, glycol-modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylate, third Glycol modification pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, caprolactone Modified pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc., wherein, preferably (methyl) acrylate of dipentaerythritol five and dipentaerythritol six (methyl) acrylate.

The weight average molecular weight of polymerizable compound (C) be preferably more than 150 and less than 2900, more preferably more than 250 and Less than 1500.

Relative to the total amount of solid constituent, the content of polymerizable compound (C) is preferably 4~65 mass %, and more preferably 7 ~60 mass %.

In addition, the content ratio [resin (B) of resin (B) and polymerizable compound (C)：Polymerizable compound (C)] with quality Benchmark meter, preferably 20：80~80：20, more preferably 35：65~80：20.

Residual film ratio when if the content of polymerizable compound (C) in above-mentioned scope, has colored pattern formation and The tendency that the chemical-resistant of colour filter improves.

＜ polymerization initiators (D) ＞

Polymerization initiator (D) triggers polymerization as long as living radical, acid etc. can be produced using light, hot effect Compound, then be not particularly limited, known polymerization initiator can be used.

As polymerization initiator (D), O- acyl groups oxime compound, alkyl phenyl assimilation compound, bisglyoxaline chemical combination can be included Thing, triaizine compounds and acylphosphine oxide compound etc..

As O- acyl group oxime compounds, can include such as N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) butane - 1- ketone -2- imines, N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) octane -1- ketone -2- imines, N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) -3- cyclopenta propane -1- ketone -2- imines, N- benzoyloxys -1- [9- ethyls -6- (2- methyl Benzoyl) -9H- carbazole -3- bases] -3- cyclopenta propane -1- ketone -2- imines etc. has the O- acyl group oximes of N- benzoyloxys Compound；N- acetoxyl groups -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] ethane -1- imines, N- second Acyloxy -1- [9- ethyls -6- { 2- methyl -4- (3,3- dimethyl -2,4- dioxolyls methoxyl group) 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- acetoxyl groups -1- (4- Phenylsulfanyls phenyl) -3- cyclohexyl propane -1- ketone -2- imines, [11- (2- ethylhexyls) -5- (2,4,6- trimethylbenzoyls) -11H- benzos [a] carbazole -8- bases]-[2- (2,2,3,3- Tetrafluoro propoxyl group) phenyl] ketoxime O- acetic acid esters etc. has O- acyl group oxime compounds of N- acetoxyl groups etc..It can be used Irgacure (registration mark) OXE01, OXE02 (being manufactured above for BASF AG), N-1919 (ADEKA Corp.'s manufacture) etc. Commercially available product.

Wherein, O- acyl groups oxime compound is preferably selected from N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) butane -1- Ketone -2- imines, N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) octane -1- ketone -2- imines, N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) -3- cyclopenta propane -1- ketone -2- imines, N- acetoxyl groups -1- [9- ethyls -6- (2- methylbenzenes Formoxyl) -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- (4- Phenylsulfanyls phenyl) -3- cyclohexyl third Alkane -1- ketone -2- imines and [11- (2- ethylhexyls) -5- (2,4,6- trimethylbenzoyls) -11H- benzos [a] carbazole -8- Base] it is at least one kind of in-[2- (2,2,3,3- tetrafluoro propoxyl group) phenyl] ketoxime O- acetic acid esters, it is more preferably selected from N- acetyl oxygen Base -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] ethane -1- imines and N- acetoxyl groups -1- (4- benzene Base methyldisulfanylphenyl) it is at least one kind of in -3- cyclohexyl propane -1- ketone -2- imines.

As alkyl phenyl assimilation compound, such as 2- methyl -2- morpholinoes -1- (4- methylsulfanyls phenyl) can be included Propane -1- ketone, 2- dimethylaminos -1- (4- morphlinophenyls) -2- benzyl butane -1- ketone, 2- (dimethylamino) -2- [(4- Aminomethyl phenyl) methyl] -1- [4- (4- morpholinyls) phenyl] butane -1- ketone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 2- Hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyls) phenyl] propane -1- ketone, 1- hydroxycyclohexylphenylketones, 2- hydroxyl -2- first The oligomer, α, α-diethoxy acetophenone, benzil dimethyl ketal etc. of base -1- (4- isopropenyls phenyl) propane -1- ketone. The commercially available products such as Irgacure (registration mark) 369,907,379 (being manufactured above for BASF AG) can be used.

As united imidazole, such as 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5 can be included, 5 '-tetraphenyl connection miaow Azoles, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (for example, referring to Japanese Unexamined Patent Publication 6-75372 Publication, Japanese Unexamined Patent Publication 6-75373 publications etc.), 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxalines (for example, With reference to Japanese Patent Publication 48-38403 publications, Japanese Unexamined Patent Application 62-174204 publications etc.), the phenyl of 4,4 ', 5,5 '-position Imidazolium compounds (for example, referring to Japanese Unexamined Patent Publication 7-10913 publications etc.) substituted by alkoxy carbonyl group etc..

As triaizine compounds, such as double (the trichloromethyl) -6- (4- methoxyphenyls) -1,3,5- tri- of 2,4- can be included Double (trichloromethyl) -6- (4- methoxyl groups the naphthyl) -1,3,5- triazines of piperazine, 2,4-, double (trichloromethyl) -6- piperonyl -1 of 2,4-, Double (trichloromethyl) -6- (4- the methoxyl-styrenes) -1,3,5- triazines of 3,5- triazines, 2,4-, double (the trichloromethyl) -6- of 2,4- Double (trichloromethyl) -6- [2- (furans -2- bases) ethene of [2- (5- methylfuran -2- bases) vinyl] -1,3,5- triazines, 2,4- Base] -1,3,5- triazines, double (trichloromethyl) -6- [2- (4- diethylamino -2- aminomethyl phenyls) the vinyl] -1,3,5- of 2,4- Double (trichloromethyl) -6- [2- (3,4- Dimethoxyphenyls) vinyl] -1,3,5- triazines of triazine, 2,4- etc..

As acylphosphine oxide compound, TMDPO etc. can be included.

And then as polymerization initiator (D), it is even that benzoin, benzoin methyl ether, benzoin ethyl ether, benzene can be included The benzoin compound such as relation by marriage isopropyl ether, benzoin isobutyl ether；Benzophenone, o- benzoyl methyl benzoate, 4- phenyl Benzophenone, 4- benzoyls -4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (tert-butyl crosses oxygen carbonyl) benzophenone, The benzophenone cpds such as 2,4,6- tri-methyl benzophenones；The naphtoquinone compounds such as 9,10- phenanthrenequione, 2- EAQs, camphorquinone； 10- butyl -2- chloro-acridines ketone, benzil, phenylglyoxalates methyl esters, titanocenes compound etc..

Polymerization initiator (D) is preferably to include selected from alkyl phenyl assimilation compound, triaizine compounds, acylphosphine oxide chemical combination The polymerization initiator of at least one of thing, O- acyl groups oxime compound and united imidazole, more preferably comprising O- acyl group oximes The polymerization initiator of compound.

In polymerization initiator (D), the containing ratio of O- acyl compounds is preferably more than 80 mass % more preferably 90 matter More than % is measured, more preferably more than 95 mass %.

It is excellent relative to the mass parts of total amount 100 of resin (B) and polymerizable compound (C), the content of polymerization initiator (D) Elect 0.1~40 mass parts, more preferably 1~30 mass parts as.

＜ polymerizations trigger auxiliary agent (D1) ＞

The red hardening resin composition of the present invention can further include polymerization and trigger auxiliary agent (D1).Polymerization triggers auxiliary agent (D1) be for promotion polymerization initiator triggered polymerization polymerizable compound polymerization compound or sensitizer.Comprising In the case that polymerization triggers auxiliary agent (D1), generally it is applied in combination with polymerization initiator (D).

Trigger auxiliary agent (D1) as polymerization, amines, alkoxy anthracene compound, thioxanthone compounds and carboxylic can be included Acid compound etc..

As above-mentioned amines, triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylaminos can be included Yl benzoic acid methyl esters, EDMAB, 4- dimethylaminobenzoic acids isopentyl ester, benzoic acid 2- dimethylaminos Base ethyl ester, 4- dimethylaminobenzoic acid 2- ethylhexyls, N, N- dimethyl-p-toluidines, 4,4 '-bis- (dimethylaminos) two Benzophenone (common name Michler's keton), 4,4 '-bis- (diethylamino) benzophenone, 4,4 '-bis- (ethylmethylamino) benzophenone Deng, wherein, preferably 4,4 '-bis- (diethylamino) benzophenone.EAB-F (hodogaya chemical industry (strain) manufacture) etc. can be used Commercially available product.

As above-mentioned alkoxy anthracene compound, 9,10- dimethoxys anthracene, 2- ethyl -9,10- dimethoxys can be included Anthracene, 9,10- diethoxies anthracene, 2- ethyl -9,10- diethoxies anthracene, 9,10- dibutoxies anthracene, the fourth oxygen of 2- ethyls -9,10- two Base anthracene etc..

As above-mentioned thioxanthone compounds, ITX, ITX, 2,4- diethyl can be included Thioxanthones, the clopenthixal ketones of 2,4- bis-, the chloro- 4- propoxythioxanthones of 1- etc..

As above-mentioned carboxylic acid compound, Phenylsulfanyl acetic acid, methyl phefzylsulfanyl acetic acid, ethylphenyl can be included Sulfanyl acetic acid, Methylethyl phenyl sulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenyl sulfanyl acetic acid, Dimethoxyphenyl sulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, benzene oxygen Base acetic acid, naphthalene sulfenyl acetic acid, N- naphthyls glycine, naphthoxy acetic acid etc..

Wherein, auxiliary agent (D1), preferably thioxanthone compounds are triggered as polymerization.

In the case of triggering auxiliary agent (D1) using these polymerizations, relative to adding up to for resin (B) and polymerizable compound (C) 100 mass parts are measured, its content is preferably 0.01~30 mass parts, more preferably 0.1~20 mass parts.If polymerization triggers auxiliary agent (D1) amount within the range, then further can form colored pattern, the productivity ratio of colour filter is tended to improve with high sensitivity.

In addition, polymerization triggers auxiliary agent (D1) and the ratio between the content of polymerization initiator (D) (polymerize initiation auxiliary agent (D1)/polymerize Initiator (D)) in terms of quality criteria, preferably more than 0.1, more preferably more than 0.3, more preferably more than 0.5, preferably For less than 2, more preferably less than 1.2, more preferably less than 0.8.

＜ antioxidants (J) ＞

The red hardening resin composition of the present invention preferably also includes antioxidant (J).Antioxidant (J) can include Phenol antioxidant, amine system antioxidant, phosphorous antioxidant and sulphur system antioxidant, preferably phenol antioxidant and phosphorus system resist Oxidant.

Phenol antioxidant is the antioxidant for having phenolic hydroxyl group in intramolecular, is preferably had at the ortho position of its phenolic hydroxyl group There is the alkyl of branch.In this specification, while there is phenolic hydroxyl group and phosphate ester structure or the antioxidant of phosphite ester structure It is categorized as phosphorous antioxidant.

As phenol antioxidant, such as 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) fourth can be included Alkane, 4,4 '-butylidene-bis- (3 methy 6 tert butyl phenols), (the 3,5- di-t-butyl -s 4- of 1,3,5- trimethyls -2,4,6- three Hydroxybenzyl) benzene, the 2- tert-butyl groups -6- (the 3- tert-butyl group -2- hydroxy-5-methyl bases benzyl) -4- aminomethyl phenyls acrylate, (four is [sub- Methyl -3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester] methane, [3- (the 3,5- di-t-butyl -4- hydroxyls of pentaerythrite four Base phenyl) propionic ester], octadecyl -3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester, 3,3 ', 3 ", 5,5 ', 5 " - Six-tert-butyl group-a, a ', a "-(bases of 1,3,5- trimethylbenzenes -2,4,6- three) three-p-Cresol, (the 3,5- di-t-butyl -s of 1,3,5- tri- 4- hydroxybenzyls) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone, the ((the 4- tert-butyl group -3- hydroxyls -2,6- two of 1,3,5- tri- Tolyl) methyl) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone, double [3- (the 3,5- di-t-butyl -s of thiodiethylene 4- hydroxy phenyls) propionic ester], benzenpropanoic acid, 3,5- double (1,1- dimethyl ethyls) -4- hydroxyls, C7-C9 pendant alkyl groups ester, 4,6- Double (pungent butylthiomethyl)-o-cresols, Irganox (registration mark) 3125 (BASF AG's manufacture), 2,4- double (n- pungent sulfenyls)- Double (2- (3- (3- tertiary butyl-4-hydroxy -5- the first of 6- (4- 3 ', 5 '-di-t-butyls of hydroxyl anilino-) -1,3,5- triazines, 3,9- Base phenyl) propionyloxy) -1,1- dimethyl ethyls) -2,4,8,10- four oxaspiro (5,5) hendecane, Sumilizer (registration Trade mark) BHT (Sumitomo Chemical (strain) manufacture), Sumilizer (registration mark) GA-80 (Sumitomo Chemical (strain) manufacture), Sumilizer (registration mark) GS (Sumitomo Chemical (strain) manufacture), ((strain) サイテッ of シアノッ Network ス (registration mark) 1790 Network manufactures) and vitamin E (エーザイ (strain) manufactures) etc..

In the case of comprising phenol antioxidant, its containing ratio preferably 1 in the mass % of total amount 100 of antioxidant (J) More than quality % and below 99 mass %.

Amine system antioxidant is the antioxidant for having amino in intramolecular.

As amine system antioxidant, for example, can include naphthalidine, phenyl-1-naphthylamine, p- octyl phenyl-naphthalidine, The naphthylamines system antioxidants such as p- nonyl phenyl-1-naphthylamine, p- dodecylphenyl-naphthalidine, phenyl-2-naphthylamine；N, N '-two Isopropyl-p-phenylenediamine, N, N '-diisobutyl-p-phenylenediamine, N, N '-diphenyl-p-phenylenediamine, the N ,-β of N '-two-naphthalene Base-p-phenylenediamine, N- phenyl-N '-isopropyl-p-phenylenediamine, N- cyclohexyl-N '-Phenyl-p-phenylenediamine, N-1,3- diformazans Base butyl-N '-Phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine, Phenylhexyl-p-phenylenediamine, phenyl octyl group-p- benzene two The phenylenediamine such as amine system antioxidant；It is bipyridyl amine, diphenylamines, right, to '-two-n-butyl diphenylamines, right, to '-two-tertiary fourth It is base diphenylamines, right, to '-di-tert-amyl group diphenylamines, right, to '-dioctyl diphenylamine, right, to '-dinonyldiphenylamine, right, It is right ' it is-didecyl diphenylamines, right, to '-two (dodecyl) diphenylamines, right, to '-two (styryl) diphenylamines, right, to '- Dimethoxy diphenylamines, 4,4 '-bis- (4- alpha, alpha-dimethyls benzoyl) diphenylamines, p- isopropoxydiphenylamine, bipyridyl The hexichol amine system antioxidant such as amine；Phenthazine, N- Methylphenothiazines, N- ethyl-phenothiazines, 3,7- dioctyls phenthazine, phenthazine The phenthazine such as carboxylate, phenoselenazine system antioxidant.

In the case of comprising amine system antioxidant, its containing ratio is preferably in the mass % of total amount 100 of antioxidant (J) More than 1 mass % and below 99 mass %.

Phosphorous antioxidant is the antioxidant with phosphate ester structure or phosphite ester structure.

As phosphorous antioxidant, such as 6- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) third oxygen can be included Base] -2,4,8,10- tetra--tert-butyl group dibenzo [d, f] [1,3,2] dioxaphosphepin cycloheptenes, three (2,4- di-t-butyl benzene Base) phosphite ester, diphenyl iso-octyl phosphite ester, 2,2 '-di-2-ethylhexylphosphine oxide (4,6- di-t-butyls phenyl) octyl group phosphorous acid Ester, diphenyl isodecyl phosphite, diphenyl isodecyl phosphite, triphenyl, Tributyl phosphate ester, distearyl Base pentaerythritol diphosphites, the base of ring-type neopentane four double (2,6- di-t-butyl -4- aminomethyl phenyls) phosphite ester, 6- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propoxyl group] four-tert-butyl groups of -2,4,8,10- benzo [d, f] [1,3,2] dioxa Phospha cycloheptene, three (nonyl phenyl) phosphite esters, three (single-to be mixed with dinonylphenyl) phosphite esters, diphenyl list (13 Alkyl) phosphite ester, 2,2 '-ethylenebis (4,6- di-t-butyls phenol) fluorophosphites, phenyl diiso decyl phosphorous acid Ester, three (2- ethylhexyls) phosphite esters, three (isodecyl) phosphite esters, three (tridecyl) phosphite esters, four (2,4- bis-- Tert-butyl-phenyl) -4,4 '-biphenylene-two-phosphonate ester, the phosphorous of 4,4 '-isopropylidene diphenyl tetraalkyl (C12-C15) two Acid esters, 4,4 '-butylidene double (3- methyl-6-tert butyl phenyl)-two (tridecyl) phosphite esters, double (nonyl phenyl) seasons penta Tetrol diphosphites, double (2,4- di-tert -s butyl phenyl) pentaerythrites-two-phosphite ester, ring-type neopentane four base it is double (2, 6- di-t-butyl -s 4- aminomethyl phenyls-phosphite ester), (2- methyl -4- two (tridecyl) phosphite ester -5- uncles of 1,1,3- tri- Butyl phenyl) butane, four (2,4- di-t-butyl -5- aminomethyl phenyls) -4,4 '-biphenylene diphosphonites, three -2- ethyl hexyls Base phosphite ester, three isodecyl phosphites, three stearyl phosphite esters, phenyl diiso decyl phosphite ester, three lauryls three Thiophosphite, distearyl pentaerythrityl diphosphite, three (nonyl phenyl) phosphite ester three [2- [[2,4,8,10- Four-tert-butyl group dibenzo [d, f] [1,3,2] dioxa phosphine -6- bases] oxygen] ethyl] amine, double (double (1,1- dimethyl second of 2,4- Base) -6- aminomethyl phenyls) ethyl ester phosphorous acid, Adekastab (registration mark) 329K ((strain) ADEKA manufactures), Adekastab (registration mark) PEP36 ((strain) ADEKA manufactures), Adekastab (registration mark) PEP-8 ((strain) ADEKA manufactures), Sandstab (registration mark) P-EPQ (manufacture of Network ラリア Application ト companies), ウェスト Application (registration mark) 618 (GE company systems Make), ウェスト Application (registration mark) 619G (manufacture of GE companies), ウ Le トラノッ Network ス (registration mark) 626 (GE company systems Make), 6- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propoxyl group] four-tert-butyl groups of -2,4,8,10- dibenzo [d, f] [1, 3,2] dioxaphosphepin cycloheptene) etc..

In the case of comprising phosphorous antioxidant, in the mass % of total amount 100 of antioxidant (J), its containing ratio is preferred For more than 1 mass % and below 99 mass %.

Sulphur system antioxidant is the antioxidant for having sulphur atom in intramolecular.

As sulphur system antioxidant, such as dilauryl thiodipropionate, two myristins or distearyl ester can be included Etc. β-alkane of the polyalcohol such as dialkyl thiodipropionate compound and four [methylene (3- dodecylthios) propionic ester] methane Base mercaptopropionic acid ester compounds etc..

In the case of comprising sulphur system antioxidant, in the mass % of total amount 100 of antioxidant (J), its containing ratio is preferred For more than 1 mass % and below 99 mass %.

As antioxidant (J), GPA-5001 ((strain) ADEKA manufactures) etc. can be used.

Wherein, it is preferably at least one kind of in phenol antioxidant and phosphorous antioxidant as antioxidant (J), preferably wrap Containing both phenol antioxidant and phosphorous antioxidant.

In the case that the red hardening resin composition of the present invention includes antioxidant (J), relative to solid constituent Total amount, its containing ratio are preferably 0.01~20 mass %, more preferably 0.05~10 mass %.Antioxidant if (J's) contains There is rate in above-mentioned scope, then the tendency with the excellent heat resistance of obtained colour filter.

The red hardening resin composition of the present invention also includes solvent (E), can include levelling agent (F) etc..

＜ solvents (E) ＞

For the solvent (E) in the present invention, with more than 10 mass % and below 78 mass % in solvent (E) total amount Containing ratio contain propylene glycol monomethyl ether.Propylene glycol monomethyl ether contains in solvent (E) total amount Rate is preferably more than 20 mass % and below 78 mass %, more preferably more than 30 mass % and below 78 mass %.

Solvent beyond propylene glycol monomethyl ether is not particularly limited, can use generally is made in the field Solvent.Such as ester solvent (including-COO-, the solvent without-O- in intramolecular), ether solvents can be included (in intramolecular Solvent comprising-O-, without-COO-), ether-ether solvent (including-COO- and-O- solvent in intramolecular), ketone solvent is (in molecule It is interior comprising-CO-, the solvent without-COO-), alcoholic solvent (intramolecular include OH, the solvent without-O- ,-CO- and-COO-), Aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide (DMSO) etc..

As ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-methyl isobutyl acids, acetic acid second can be included Ester, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, fourth Acid butyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Hexacyclonic Acid Ester, gamma-butyrolacton etc..

As ether solvents, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, second two can be included Alcohol single-butyl ether, diethylene glycol monomethyl ether, carbiphene, diethylene glycol monobutyl ehter, 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, 1,4- dioxanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol (DEG) methyl ethyl ether, two Glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole etc..

As ether-ether solvent, Methoxy Methyl Acetate, Methoxy acetic acid ethyl ester, Methoxy acetic acid butyl ester, second can be included Epoxide methyl acetate, ethyoxyl ethyl acetate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxy-propionic acid first Ester, 3- ethoxyl ethyl propionates, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- ethoxies Base methyl propionate, 2- ethoxyl ethyl propionates, 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, 3- methoxybutyls acetic acid esters, 3- methyl -3- methoxybutyls acetic acid esters, propylene glycol monomethyl ether, propane diols list second Base ether acetic acid ester, propylene glycol monopropyl ether acetic acid esters, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, two Glycol list monoethyl ether acetate, diethylene glycol monobutyl ehter acetic acid esters, dipropylene glycol methyl ether acetic acid esters etc..

As ketone solvent, 4- hydroxy-4-methyl-2-pentanones, acetone, 2- butanone, 2-HEPTANONE, 3- heptanone, 4- can be included Heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc..

As alcoholic solvent, methanol, ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propane diols, glycerine can be included Deng.

As aromatic hydrocarbon solvents, benzene,toluene,xylene, 1,3,5- trimethylbenzenes etc. can be included.

As amide solvent, DMF, DMA, 1-METHYLPYRROLIDONE can be included Deng.

These solvents can be used alone, and also two or more may be used.

Wherein, preferably propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, 3- ethoxy-propionic acid second Ester, ethylene glycol single methyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, carbiphene, dipropylene glycol methyl ether Acetic acid esters, acetic acid 3- methoxybutyls, 3- methoxyl groups-n-butyl alcohol, 4- hydroxy-4-methyl-2-pentanones, N, N- dimethyl formyls Amine, 3- ethoxyl ethyl propionates, 1-METHYLPYRROLIDONE etc., more preferably propylene glycol monomethyl ether, propylene glycol monomethyl Ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetic acid esters, ethyl lactate, acetic acid 3- methoxybutyls, 3- methoxyl groups -1- Butanol, 3- ethoxyl ethyl propionates, 4- hydroxy-4-methyl-2-pentanones, 1-METHYLPYRROLIDONE.

Solvent beyond propylene glycol monomethyl ether can be independent a kind, and also two or more may be used.Wherein, it is excellent Choosing big solvent of SP values (solubility parameter) compared with propylene glycol monomethyl ether.As propylene glycol monomethyl ether with Outer solvent, can be only using the big solvent of SP values compared with propylene glycol monomethyl ether.

SP values can for example apply J.Brandrup, E.H.Immergut, POLYMER HANDBOOK the 3rd edition, John The Hansen parameter of liquid described in Wiley＆Sons Solubility Parameter Value items, at 25 DEG C.As With (SP values (=9.0 (cal/cm for the propylene glycol monomethyl ether obtained by Hansen parameter using Hildebrand methods³ )^1/2) compare the high solvent of SP values, such as preferred the propylene glycol monomethyl ether ((cal/cm of SP values 10.7³)^1/2), ethylene glycol monobutyl The ether ((cal/cm of SP values 10.2³)^1/2), the diacetone alcohol ((cal/cm of SP values 10.2³)^1/2), the ethyl lactate ((cal/ of SP values 10.0 cm³)^1/2), 3- methoxyl groups-the n-butyl alcohol ((cal/cm of SP values 10.9³)^1/2), 3- the ethoxyl ethyl propionates ((cal/cm of SP values 9.1³ )^1/2), the cyclohexanone ((cal/cm of SP values 9.3³)^1/2), the gamma-butyrolacton ((cal/cm of SP values 12.8³)^1/2), 1-METHYLPYRROLIDONE ((the cal/cm of SP values 11.2³)^1/2).One kind can be used in these SP values solvent higher than propylene glycol monomethyl ether, can also incite somebody to action Two kinds of combination of the above.

The difference of the SP values of solvent beyond propylene glycol monomethyl ether and above-mentioned propylene glycol monomethyl ether is excellent Elect 0.1 (cal/cm as³)^1/2More than, more preferably 0.3 (cal/cm³)^1/2More than, more preferably 0.5 (cal/cm³)^1/2With On, it is still more preferably 0.7 (cal/cm³)^1/2More than, preferably 4 (cal/cm³)^1/2Hereinafter, more preferably 3 (cal/cm³ )^1/2Hereinafter, more preferably 2 (cal/cm³)^1/2Below.

In the case of using the SP values solvent bigger than propylene glycol monomethyl ether, it contains in solvent (E) total amount It is, for example, more than 22 mass %, preferably more than 28 mass %, for example, being below 60 mass %, preferably 52 mass % to have rate Below.

Relative to the total amount of red hardening resin composition, the content of solvent (E) is preferably 50~95 mass %, more excellent Elect 55~92 mass % as.In other words, the solid constituent of red hardening resin composition is preferably 5~50 mass %, more excellent Elect 8~45 mass % as.If the content of solvent (E), in above-mentioned scope, flatness when being coated with becomes good, in addition Colour saturation will not be insufficient when foring colour filter, therefore the tendency that display characteristic becomes good be present.

＜ levelling agents (F) ＞

The red hardening resin composition of the present invention can include levelling agent (F).As levelling agent (F), can include Machine silicon systems surfactant, fluorine system surfactant and silicone based surfactants with fluorine atom etc..These can be in side Chain has polymerizable group.

As silicone based surfactants, surfactant that there is siloxanes key in intramolecular etc. can be included.Tool Body, can enumerate Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names：Dong Li-DOW CORNING (strain) manufacture), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (モメ Application ティ Block パフォーマ Application スマテリア Le ズジャパ Application contracts commercial firm systems Make) etc..

As fluorine system surfactant, surfactant that there is fluorocarbon chain in intramolecular etc. can be included.Specifically, may be used Include Off ロラー De (registration mark) FC430, FC431 (Sumitomo 3M (strain) manufactures), メガ Off ァッ Network (registration mark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (DIC (strain) manufactures), エ Off トップ (registrars Mark) EF301, EF303, EF351, EF352 (Mitsubishi General Materials electronics chemical conversion (strain) manufacture), サー Off ロ Application (registration mark) ((strain) ダイキ Application Off ァイ Application ケミカ Le is studied by S381, S382, SC101, SC105 (Asahi Glass (strain) manufacture) and E5844 It is manufactured) etc..

As the above-mentioned silicone based surfactants with fluorine atom, can include has siloxanes key in intramolecular With the surfactant of fluorocarbon chain etc..Specifically, メガ Off ァッ Network (registration mark) R08, BL20, F475, F477 can be included With F443 (DIC (strain) manufactures) etc..

In the case of containing levelling agent (F), relative to the total amount of red hardening resin composition, its content is preferably More than 0.001 mass % and below 3 mass %, more preferably more than 0.002 mass % and below 2 mass %, further preferably For more than 0.005 mass % and below 1 mass %.If the content of levelling agent (F) can make colour filter in above-mentioned scope The flatness of device becomes good.

＜ other compositions ＞

The present invention red hardening resin composition, as needed, can include polymerization trigger auxiliary agent, filler, other High-molecular compound, closely sealed accelerator, antioxidant, light stabilizer, known addition in the technical field such as chain-transferring agent Agent.

The manufacture method ＞ of ＜ red hardening resin compositions

The red hardening resin composition of the present invention for example can be by by colouring agent (A), resin (B), polymerism Compound (C) and polymerization initiator (D), solvent (E) and the levelling agent (F) and the other compositions mixing that use as needed and make It is standby.

Red pigment (P) and the pigment (Q) used as needed are preferably mixed with part or all of solvent (E) in advance Close, make it scattered using ball mill etc. until the average grain diameter of pigment turns into less than 0.2 μm Zuo You.Now, can match somebody with somebody as needed Close part or all of pigment dispersing agent, resin (B).

By mixing the remaining composition of remaining in the dispersible pigment dispersion so obtained, mixed so that as defined Concentration, the red hardening resin composition of target can be prepared.

Compound (IB) be preferably dissolved in advance solvent (E) part or all in prepare solution.With aperture 0.01 ~1 μm or so of filter filters the solution.

It is preferred that mixed red hardening resin composition is filtered with the filter in 0.01~10 μm or so of aperture.

The manufacture method ＞ of ＜ colour filters

As the method for manufacturing colored pattern by the red hardening resin composition of the present invention, photoetching process, spray can be enumerated The method of the use of ink and water, print process etc..Wherein, preferred photoetching process.Photoetching process is that above-mentioned red hardening resin composition is coated on into substrate, is done Method dry and form coloring compositions nitride layer, that the coloring compositions nitride layer is exposed via photomask and developed.In photoetching process, pass through Without using photomask and/or do not develop in exposure, so as to formed the solidfied material as above-mentioned coloring compositions nitride layer Color film.Can be using the colored pattern so formed, coloring film as colour filter of the invention.

The thickness of the colour filter of making is not particularly limited, can suitably be adjusted according to purpose, purposes etc., for example, being 0.1~30 μm, preferably 0.1~20 μm, more preferably 0.5~6 μm.

As substrate, quartz glass, pyrex can be used, alumina silicate glass, silica has been carried out to surface The tree of the glass plate of the soda-lime glass of coating etc., makrolon, polymethyl methacrylate, polyethylene terephthalate etc. Fat plate, silicon, the product for foring on aforesaid substrate aluminium, silver, silver/copper/palldium alloy film etc..It can be formed on these substrates another Outer color-filter layer, resin bed, transistor, circuit etc..

Using photolithographic each color pixel formed can known or usual device, under the conditions of carry out.For example, can It is as described below to make.

First, red hardening resin composition is coated on substrate, passes through heat drying (prebake) and/or decompression Dry, dried so as to which the volatile ingredients such as solvent be removed, obtain smooth coloring compositions nitride layer.

As coating method, spin-coating method, slot coated method, slit and method of spin coating etc. can be enumerated.

Preferably 30~120 DEG C, more preferably 50~110 DEG C of temperature when being thermally dried.In addition, as the heat time, Preferably 10 seconds~60 minutes, more preferably 30 seconds~30 minutes.

In the case of being dried under reduced pressure, enter preferably under 50~150Pa pressure, under 20~25 DEG C of temperature range OK.

The thickness of coloured composition layer is not particularly limited, can suitably be selected according to the thickness of the colour filter of target.

Next, for coloring compositions nitride layer, exposed via the photomask of the colored pattern for forming target.To this Pattern on photomask is not particularly limited, and the pattern being consistent with the purposes of target can be used.

Light source as the light source for exposure, the preferably light of 250~450nm of generation wavelength.Will not for example, can be used The wave-length coverage is blocked to the wave filter that 350nm light blocks, or use by near 436nm, near 408nm, 365nm The bandpass filter that neighbouring light takes out optionally takes out these wave-length coverages.Specifically, as light source, mercury can be enumerated Lamp, light emitting diode, metal halide lamp, Halogen lamp LED etc..

Due to can equably irradiate parallel rays to plane of exposure entirety, carry out photomask and form coloring compositions nitride layer Substrate correct contraposition, therefore preferably using the exposure device such as mask aligner and stepper.

By making the coloring compositions nitride layer after exposure be contacted with developer solution to develop, so as to form color-patch map on substrate Case.By development, the unexposed portion of coloring compositions nitride layer dissolves and is removed in developer solution.As developer solution, preferably for example The aqueous solution of the alkali compounds such as potassium hydroxide, sodium acid carbonate, sodium carbonate, tetramethyl ammonium hydroxide.These alkali compounds Concentration in the aqueous solution is preferably 0.01~10 mass %, more preferably 0.03~5 mass %.And then developer solution can include table Face activating agent.

Developing method can be any of sheathed immersion method, infusion process and spray-on process etc..And then base can be made in development Plate tilts arbitrary angle.Preferably washed after development.

And then the obtained colored pattern of preferred pair carry out after bakee.Preferably 150~250 DEG C of stoving temperature afterwards, more preferably 160~235 DEG C.Preferably 1~120 minute, more preferably 10~60 minutes time is bakeed afterwards.

Using the red hardening resin composition of the present invention, the colour filter that the generation of foreign matter is suppressed can be formed Device.The colour filter can be used as being used for display device (for example, liquid crystal display device, organic el device, Electronic Paper etc.) and solid is taken the photograph The colour filter of element.

Embodiment

Embodiment is exemplified below to further illustrate the present invention, the present invention is not limited by following embodiments certainly, It may be adapted in the range of preceding purport described later suitably be changed to implement also to be possible certainly, these are included in this In the technical scope of invention.% and part of content or usage amount are represented in example, is then quality criteria as long as no special instructions.

In following embodiment, the structure of compound passes through quality analysis (LC；The type of Agilent systems 1200, MASS； Agilent LC/MSD types) confirm.

[synthesis example 1]

350 parts of 50 parts of the compound and isopropanol (and Wako Pure Chemical Industries (strain) manufacture) that will be represented by formula (VI) is at room temperature Mixing.Diethylamine (Tokyo chemical conversion industry (strain) manufacture) 18.1 is instilled at a temperature of no more than 20 DEG C in obtained mixture Part, stirred at 20 DEG C 3 hours.Obtained reactant mixture is added in 2100 parts of 10% hydrochloric acid, separates out solid.Pass through Precipitate is filtrated to get, is dried after obtained solid is eluted with water, has obtained the compound 23.6 represented by formula (I-1-A) Part.Yield is 43%.

The identification of the compound represented by formula (I-1-A)

(quality analysis) ionization mode=ESI+：M/z=[M+H]⁺442.1

Exact mass：441.1

150 parts of 30 parts of the compound and dehydration chloroform (Northeast chemistry (strain) manufacture) that will be represented by formula (I-1-A) is in room temperature Lower mixing.Trimethoxy [3- (methylamino) propyl group] silane is instilled at a temperature of no more than 40 DEG C in obtained mixture 26.3 parts of (Tokyo chemical conversion industry (strain) manufacture), has been stirred 3 hours at 70 DEG C.Obtained reactant mixture is cooled to room Temperature.Obtained mixture is added in 825 parts of ethyl acetate, separates out solid.Obtained precipitate is filtered, consolidated what is obtained Body is cleaned with ethyl acetate, dried, and has obtained 35.5 parts of the compound represented by formula (I-1).Yield is 87%.

The identification of the compound represented by formula (I-1)

(quality analysis) ionization mode=ESI+：M/z=[M+H]⁺599.2

Exact mass：598.2

The compound 0.35g represented by formula (I-1) is dissolved in chloroform, volume is turned into 250cm³, by 2cm therein³With Ion exchange water dilutes, and volume is turned into 100cm³(concentration：0.028g/L), using spectrophotometer (quartz cell, optical path length： 1cm) determine absorption spectrum.The compound is λ max=546nm.

[synthesis example 2]

Flowed into right amount in the flask with agitating device, dropping funel, condenser, thermometer and gas introduction tube Nitrogen, blanket of nitrogen is replaced into, loads 100 parts of propylene glycol monomethyl ether, be heated to 120 DEG C while stirring.Next, by In 13 parts of 7 parts of methacrylic acid tricyclodecyl, 27 parts of benzyl methacrylate, methacrylic acid monomer mixtures formed, with Relative to monomer mixture, 100 parts are added パー Block チ Le O (Nippon Yushi (Co., Ltd.) is made) as 1 part of mode, are leaked from dropping liquid Bucket lasts 2 hours mixed liquors by preparation and instilled in flask.And then stirred 2 hours at 120 DEG C, obtain including copolymer Reaction solution.Next, flowing into appropriate air in flask, air atmosphere is replaced into, by GMA 7 In 0.07 part of part, 0.34 part of triphenylphosphine and the methylnaphthohydroquinone reaction of input comprising above-mentioned copolymer, continue at 120 DEG C anti- Should, room temperature is cooled at the time of solid constituent acid number becomes 105mg-KOH/g, terminates reaction.By adding propane diols 32 parts of monomethyl ether acetate, so as to obtain copolymer (resin B -1) solution.The solid constituent of the solution of resin B -1 is 30%.Tree Fat B-1 weight average molecular weight is 3.0 × 10⁴。

For the polystyrene conversion weight average molecular weight Mw and number-average molecular weight Mn of the resin obtained in above-mentioned synthesis example 2 Measure, using GPC method, carry out under the following conditions.

Device：HLC-8120GPC (eastern Cao's (strain) manufacture)

Post：TSK-GELG2000HXL

Column temperature：40℃

Solvent：THF

Flow velocity：1.0mL/min

Test solution solid component concentration：0.001~0.01 mass %

Injection rate：50μL

Detector：RI

Correction standard substance：TSK STANDARD POLYSTYRENE

F-40、F-4、F-288、A-2500、A-500

(eastern Cao's (strain) manufacture)

The ratio between weight average molecular weight and number-average molecular weight that polystyrene obtained above is converted (Mw/Mn) are set to molecular weight Distribution.

[preparation of red hardening resin composition]

Each composition is mixed in a manner of as the composition shown in table 1, has obtained red hardening resin composition.

【Table 1】

For pigment, with pigment dispersing agent, B-1¹⁾Resin B -1 and E-1 described in column²⁾The propane diols list that column is recorded Methylether acetate mixes, and makes it scattered in advance.

B-1³⁾Column represents the total of the content of resin B -1.

E-1⁴⁾Column represents the total of propylene glycol monomethyl ether content.

It should illustrate, in table 1, each composition represents herein below.It should illustrate, resin (B) represents solid constituent conversion Number.

Dyestuff (A-1)：A-1：The compound represented by formula (I-1)

Dyestuff (A-2)：A-2：C.I. (the beautiful element red 330 difficult to understand of solvent red 130；BASF AG manufactures；Maximum absorption wavelength 495nm；Metallic complex salt dyestuff)

Pigment (A)：A-3：C.I. paratonere 254

Pigment dispersing agent：Acrylic acid series pigment dispersing agent

Resin (B)：B-1：Resin B -1

Polymerizable compound (C)：C-1：Dipentaerythritol acrylate (KAYARAD (registration mark) DPHA；Japanization Medicine (strain) manufactures)

Polymerization initiator (D)：D-1：N- acetoxyl groups -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazoles -3- Base] ethane -1- imines (Irgacure (registration mark) OXE 02；BASF AG manufactures；Oxime compound)

Polymerization initiator (D)：D-2：Compound (the TR-PBG-309 represented by following formula；Changzhou electronic strong new material (having) manufactures)

Antioxidant (J)：J-1：GPA-5001 ((strain) ADEKA manufactures)

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

Solvent (E)：E-2：Diacetone alcohol

Solvent (E)：E-3：Propylene glycol monomethyl ether

Solvent (E)：E-4：Cyclohexanone

Solvent (E)：E-5：Ethyl lactate

Levelling agent (F)：F-1：Organic silicon modified by polyether (Toray Silicone SH8400；Beautiful DOW CORNING (strain) system in east Make)

[formation of colour filter (colored pattern)]

In glass substrate (the EAGLE XG of 2 inch squares；Corning Incorporated manufactures) on, embodiment is coated with using spin-coating method After the colored curable resin composition obtained in 1~10, prebake 3 minutes at 100 DEG C, coloring compositions nitride layer has been obtained. After letting cool, the glass substrate for making to form coloring compositions nitride layer, at intervals of 100 μm, uses exposure with quartz glass photomask Machine (TME-150RSK；トプ Us Application (strain) manufactures), under air atmosphere, use 50mJ/cm²Light exposure (365nm benchmark) carry out Light irradiation.As photomask, the photomask for foring 100 μm of lines and space pattern has been used.By after light irradiation colour cell Compound layer soaks in the water system developer solution comprising nonionic surfactants 0.12% and potassium hydroxide 0.04% at 26 DEG C Stain develop 60 seconds, after washing, in an oven, carried out 20 minutes at 230 DEG C after bakee.

By above-mentioned operation, colored pattern is obtained for by the colored curable resin composition of embodiment 1~10.

[film thickness measuring]

For obtained colored pattern, film thickness measuring device (DEKTAK3 is used；Japanese vacuum technique (strain) manufacture) measure Thickness.Show the result in table 2.

[chromaticity evaluation]

For the colored pattern on obtained glass substrate, colour examining machine (OSP-SP-200 is used；Olympus (strain) is made Make) measure light splitting, waits color function using illuminant-C, determines the xy chromaticity coordinates (x, y) in CIE XYZ color specification systems.Will knot Fruit is shown in Table 2.The color for the colored pattern on glass substrate for confirming to obtain by chromaticity coordinate is red.

[formation of colour filter (coloring film)]

In glass substrate (the EAGLE XG of 2 inch squares；Corning Incorporated manufactures) on, embodiment is coated with using spin-coating method 1~10 and comparative example 1 in after obtained colored curable resin composition, prebake 3 minutes, are coloured at 100 DEG C Composition layer.After letting cool, exposure machine (TME-150RSK is used；トプ Us Application (strain) manufactures), not using photomask, in air Under atmosphere, use 50mJ/cm²Light exposure (365nm benchmark) carried out light irradiation.Coloring compositions nitride layer after light irradiation is being wrapped In water system developer solution containing nonionic surfactants 0.12% and potassium hydroxide 0.04% at 26 DEG C immersion development 60 seconds, After washing, in an oven, carried out 20 minutes at 230 DEG C after bakee, so as to obtain coloring film.

[foreign matter evaluation]

For obtained coloring film, upright microscope (Axio Imager MAT are used；Shimadzu (strain) manufactures), with 50 Multiplying power again observes the foreign matter of coloring film coated surface.

If not observing foreign matter, the coloring film it may be said that have no problem in practical as colour filter.

【Table 2】

Table 2

	Thickness [μm]	×	y	Y
					Embodiment 1	2.2	0.655	0.317	17.7
Embodiment 2	2.2	0.655	0.317	17.7
					Embodiment 3	2.2	0.655	0.317	17.6
Embodiment 4	2.2	0.655	0.317	17.7
					Embodiment 5	2.2	0.655	0.317	17.6
Embodiment 6	2.2	0.655	0.317	17.6
					Embodiment 7	2.2	0.655	0.317	17.7
Embodiment 8	2.2	0.655	0.317	17.6
					Embodiment 9	2.2	0.655	0.317	17.6
Embodiment 10	2.2	0.655	0.317	17.6

【Table 3】

Table 3

〇：There is no foreign matter in observation portion

△：It it is 1~9 in the foreign matter that observation portion is seen

×：It it is more than 10 in the foreign matter that observation portion is seen

The colour filter (coloring film) formed by the colored curable resin composition of inclusion compound (A1) makes colourity It is 10%~78% in the ratio of the propylene glycol monomethyl ether of colored curable resin composition in the case of consistent In the range of, the foreign matter of surplus is not observed in coloring film coated surface.On the other hand, when ratio is 80%, in coloring film Surface observation is not suitable for foreign matter as colour filter.

Industrial applicability

Using the present invention red hardening resin composition, by by the solvent in resist than control in certain model Enclose, can be formed in the colour filter that surface does not produce foreign matter.The colour filter can be used as display device (for example, liquid crystal display fills Put, organic el device, Electronic Paper etc.) and solid-state imager in the colour filter that uses.

Claims

1. red hardening resin composition, which contain toner (A), resin (B), polymerizable compound (C), polymerization initiator (D) and solvent (E), there is the dyestuff (A1) and red that the maximum absorption wavelength in silicon atom and chloroform is 500nm~600nm Pigment (P) is included as colouring agent (A), and propylene glycol monomethyl ether is included as solvent (E), and in solvent (E) containing ratio of propylene glycol monomethyl ether is more than 10 mass % and below 78 mass % in total amount.

2. red hardening resin composition according to claim 1, wherein, in solvent (E) total amount, contain 22 matter Measure more than the % SP values solvent higher than propylene glycol monomethyl ether.

3. red hardening resin composition according to claim 1 or 2, wherein, in solvent (E) total amount, contain 22 More than quality %'s is selected from propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diacetone alcohol, ethyl lactate, 3- methoxyl group -1- fourths Solvent in alcohol, 3- ethoxyl ethyl propionates, cyclohexanone, gamma-butyrolacton, 1-METHYLPYRROLIDONE.

4. red hardening resin composition according to claim 1 or 2, wherein, dyestuff (A1) is with xanthene skeleton Compound.

5. red hardening resin composition according to claim 1 or 2, wherein, also comprising metallic complex salt azo dyes As colouring agent (A).

6. by the colour filter formed according to the red hardening resin composition described in claim 1 or 2.

7. display device, it includes colour filter according to claim 6.