CN107643653A

CN107643653A - Cyan hardening resin composition, colour filter and display device

Info

Publication number: CN107643653A
Application number: CN201710593339.0A
Authority: CN
Inventors: 桥本康弘; 寺川貴清; 中野骏
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2016-07-20
Filing date: 2017-07-19
Publication date: 2018-01-30
Also published as: KR20180010142A; KR102299144B1

Abstract

The colour filter formed by conventional colored curable resin composition has room for improvement in terms of lightness.The cyan hardening resin composition of the present invention includes colouring agent (A), resin (B), polymerizable compound (C) and polymerization initiator (D), as above-mentioned colouring agent (A), the maximum absorption wavelength that the cyan hardening resin composition includes in chloroform is 500nm~600nm and dyestuff (A1) and cyan colorant with silicon atom.Moreover, it relates to the colour filter formed with above-mentioned cyan hardening resin composition, the display device comprising the colour filter.

Description

Cyan hardening resin composition, colour filter and display device

Technical field

The present invention relates to cyan hardening resin composition.

Background technology

Colored curable resin composition is used to manufacture in liquid crystal display device, el display device, plasma The colour filter used in the display devices such as display.As such colored curable resin composition, it is known that comprising by formula (A1-1) mixture and C.I. pigment blue 15s for the compound that~formula (A1-8) represents：6 colored curable resin composition is (specially Sharp document 1).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2011-118369 publications

The content of the invention

The invention problem to be solved

The colour filter formed by above-mentioned colored curable resin composition has room for improvement in terms of lightness.

Means for solving the problems

The present invention includes following invention.

[1] cyan hardening resin composition, which contain toner (A), resin (B), polymerizable compound (C) and polymerization Initiator (D), as above-mentioned colouring agent (A), the cyan hardening resin composition includes：Maximum absorption wavelength in chloroform For 500nm~600nm and with silicon atom dyestuff (A1) and cyan colorant.

[2] the cyan hardening resin composition described in [1], wherein, above-mentioned polymerization initiator (D) is included by following formula (d1) polymerization initiator represented.

[in formula (d1),

R^d1Represent can the aromatic hydrocarbyl with the carbon number 6~18 of substituent, can be with the miscellaneous of the carbon number 3~36 of substituent Ring group, can be with the carbon number 1~15 of substituent saturated hydrocarbyl or can the aralkyl with the carbon number 7~33 of substituent, it is above-mentioned Contained methylene (- CH in saturated hydrocarbyl or aralkyl₂-) it may alternatively be-O- ,-CO- ,-S- ,-SO₂- or-NR^d5-。

R^d2Represent aromatic hydrocarbyl, the heterocyclic radical of carbon number 3~36 or the saturated hydrocarbyl of carbon number 1~10 of carbon number 6~18.

R^d3Represent can the aromatic hydrocarbyl with the carbon number 6~18 of substituent, can be with the miscellaneous of the carbon number 3~36 of substituent Ring group.

R^d4Represent can be with the carbon number 6~18 of substituent aromatic hydrocarbyl or can be with the carbon number 1~15 of substituent Aliphatic alkyl, contained methylene (- CH in above-mentioned aliphatic alkyl₂-)-O- ,-CO- or-S- are may alternatively be, it is above-mentioned Contained methine (- CH ＜) may alternatively be-PO in aliphatic alkyl₃＜, contained hydrogen is former in above-mentioned aliphatic alkyl Son can be substituted by OH bases.

R^d5The saturated hydrocarbyl of carbon number 1~10 is represented, contained methylene (- CH in the saturated hydrocarbyl₂-) can be replaced For-O- or-CO-.]

[3] the cyan hardening resin composition described in [1] or [2], wherein, relative to cyan hardening resin composition Solid constituent total amount, the containing ratio of above-mentioned colouring agent (A) is more than 3 mass % and below 60 mass %.

[4] the cyan hardening resin composition described in any one of [1]~[3], wherein, above-mentioned cyan colorant is tool There is the pigment of phthalocyanine frame.

[5] the cyan hardening resin composition described in any one of [1]~[4], wherein, the content of above-mentioned dyestuff (A1) Mass ratio (dyestuff (A1)/cyan colorant) for the content of above-mentioned cyan colorant is more than 0.01 and less than 2.

[6] colour filter, it is formed as the cyan hardening resin composition described in any one of [1]~[5].

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

The effect of invention

The lightness of the colour filter formed by the cyan hardening resin composition of the present invention is excellent.

Embodiment

The cyan 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, as long as no special instructions, can be used alone or incite somebody to action Multiple combinations use.

The cyan hardening resin composition of the present invention include maximum absorption wavelength in chloroform as 500nm~600nm and Dyestuff (A1) with silicon atom is (below also sometimes referred to as " dyestuff (A1) ".) and cyan colorant (A2) be used as colouring agent (A).As dyestuff (A1), dyestuff that the maximum absorption wavelength preferably in chloroform is 500nm~580nm, in particularly preferred chloroform Maximum absorption wavelength be 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 following 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 being expressed from the next 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.With in the dyestuff of the xanthene skeleton with organic silicon substrate in substituent, preferably have Have has trimethyl silyl alkyl, triethylsilyl alkyl, trimethoxysilyl alkyl, three in substituent 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 following 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 ,-CH adjacent in the alkylidene₂- 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 ,-CH adjacent in the saturated hydrocarbyl₂- 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.]

By formula (IB) represent compound in also include by following 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 ,-CH adjacent in the saturated hydrocarbyl₂- no It can 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, 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, two can be included Methyl fluoride, 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 simultaneously be replaced, end- CH₂- will not also 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 can include：N- Methylsulfamoyls, N- ethylsulfamovls, N- propyl group sulfonamides 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 being preferably expressed from the next.

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 R²⁷、R²⁸、R³⁷And R³⁸- the CO represented₂R¹⁰, such as methoxycarbonyl, ethoxy carbonyl, the third oxygen can be included Base 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 (I-1)~(I-4), (I-13)~(I-16), (I-25)~(I-28), (I-37)~ (I-40), (I-49)~(I-54), (I-117)~(I-119), more preferably (I-1)~(I-4), (I-13)~(I-16), (I- 25)~(I-28), (I-117), (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.]

The compound (hereinafter sometimes referred to as " compound (IV) " of expression.) and by formula (V)

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

The compound (hereinafter sometimes referred to as " compound (V) " of expression.) mix in organic solvent and make its react and Manufacture.

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.) and by formula (III)

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

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

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 cyan hardening resin composition Measure in %, preferably more than 0.1 mass %, more preferably more than 0.5 mass %, more preferably more than 1 mass %, preferably For below 40 mass %, more preferably below 30 mass %, more preferably below 20 mass %.

Wherein, " total amount of solid constituent " in this specification refers to incite somebody to action from the total amount of cyan 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 % More than, it is still more preferably more than 5 mass % more preferably more than 3 mass % more preferably more than 1 mass %, it is excellent Elect as below 90 mass %, more preferably below 80 mass %, more preferably below 60 mass %, still more preferably for Below 50 mass %.

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 50 mass % with On, preferably also 100 mass %, can be 100 more preferably more than 80 mass % more preferably more than 70 mass % Below quality %, can be below 90 mass %.

＜ cyan colorants (A2) ＞

The cyan hardening resin composition of the present invention is in addition to above-mentioned dyestuff (A1), also comprising cyan colorant (A2) As colouring agent (A).

As cyan colorant, the compound that can include the cyan being categorized as in colour index in the compound of dyestuff is (blue or green Color dyestuff (A2-1)) or colour index (The Society of Dyers and Colourists publication) in be categorized as pigment The compound (green pigment (A2-2)) of cyan in compound.

As above-mentioned cyan dye (A2-1), can include

C.I. solvent blue 4,5,37,67,70,90；

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. 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. 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. 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。

As green pigment (A2-2), specifically, the C.I. alizarol saphirols (note of C.I. alizarol saphirols omitted below can be included Carry, only record sequence number.)15、15：3、15：4、15：6th, 16,60,75,80, preferably C.I. pigment blue 15s, 15：3、15：4、15：6、 16th, 75, more preferably C.I. pigment blue 15s, 15：3、15：4、15：6, particularly preferred C.I. pigment blue 15s：6.

Wherein, preferably green pigment (A2-2), the green pigment being more preferably made up of the compound with phthalocyanine frame are (blue or green Color phthalocyanine color).As the green pigment being made up of the compound with phthalocyanine frame, C.I. pigment blue 15s, 15 can be included： 3、15：4、15：6、16、75.

For green pigment (A2-2) containing ratio, in the mass % of cyan colorant (A2) 100, preferably 80 matter More than % is measured, more preferably more than 90 mass %, more preferably more than 95 mass %.

For cyan colorant (A2) containing ratio, in the mass % of colouring agent (A) 100, preferably 0.1 mass % with On, it is still more preferably more than 5 mass %, preferably more preferably more than 3 mass % more preferably more than 1 mass % For below 99 mass %, more preferably below 95 mass %, more preferably below 90 mass %.

And then for total containing ratio of above-mentioned dyestuff (A1) and cyan colorant (A2), in the total of colouring agent (A) Measure in 100 mass %, preferably more than 80 mass %, more preferably more than 90 mass %, more preferably 95 mass % with On.

In addition, mass ratio (dyestuff (A1)/cyan coloring of the content of above-mentioned dyestuff (A1) for the content of cyan colorant Agent (A2)) it is preferably more than 0.01, more preferably more than 0.05, preferably less than 10, more preferably less than 2, particularly preferably Less than 1.8, can be less than 0.7.

Other colorant (A3) ＞ of ＜

The cyan hardening resin composition of the present invention contains the color different from dyestuff (A1) or cyan colorant (A2) Material (A3) is used as colouring agent (A).As other colorants (A3), can include dyestuff (A3-1) (but, with dyestuff (A1) or cyan Colouring agent (A2) is different) and pigment (A3-2) (but, different from cyan colorant (A2)).

As above-mentioned dyestuff (A3-1) (but, different from dyestuff (A1) or cyan colorant (A2)), can enumerate fuel-displaced molten Property dyestuff, acid dyes, basic-dyeable fibre, direct dyes, mordant dye, the amine salt of acid dyes, the sulfonamide of acid dyes spread out The dyestuffs such as biology, such as can include and be categorized as in colour index (The Society ofDyers and Colourists publication) The compound of dyestuff, dyeing take down notes the known dyestuff described in (Se Ran societies).In addition, according to chemical constitution, idol can be included Xanthene dye, phthalocyanine dye, naphthoquinone dyestuff, quinone imines beyond nitrogen dyestuff, cyanine dyes, triphenhlmethane dye, dyestuff (A1) Dyestuff, methine dyes, azomethine dyes, squaraine dye, acridine dye, styryl dye, coumarine dye, quinoline dye Material 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. 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. 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. 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. 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. 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 cudbear and orchil.

These dyestuffs can properly select according to the spectrophotometric spectra of desired colour filter.

For total containing ratio of dyestuff (A3-1), in the mass % of total amount 100 of colouring agent (A), preferably 0.1 More than quality %, more preferably more than 1 mass %, more preferably more than 5 mass %, preferably below 50 mass %, more Preferably below 40 mass %, more preferably below 30 mass %.

As above-mentioned pigment (A3-2) (but, different from cyan colorant (A2)), it is not particularly limited, public affairs can be used The pigment known, such as can include in colour index (The Society of Dyers andColourists publication) and be categorized as face The compound of material.

As pigment (A3-2), such as C.I. pigment yellows 1 can be included and (record of C.I. pigment yellows omitted below, only remembered Carry 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 Red 9,97,105,122,123,144,149,166,168,175,176,177,180,192,209, 215th, the red pigment such as 216,224,242,254,255,264,265；

C.I. 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, the preferably yellow uitramarine such as C.I. pigment yellow 13s 8,139,150, C.I. paratoneres 177,242,254 etc. The violet pigment such as red pigment and C.I. pigment violet 1s, 19,23,29,32,36,38.By comprising above-mentioned pigment, using The optimization through spectrum of the colour filter of the cyan hardening resin composition of the present invention is easy, the light resistance of colour filter and resistance to Chemicals become good.

For total containing ratio of pigment, in the mass % of total amount 100 of colouring agent (A), preferably 1 mass % with On, it is still more preferably more than 30 mass % more preferably more than 20 mass % more preferably more than 10 mass %, Preferably below 99 mass %, more preferably below 95 mass %, more preferably below 90 mass %.

For colouring agent (A) containing ratio, relative to the total amount of solid constituent, preferably more than 1 mass % and 70 matter Below % is measured, more preferably more than 3 mass % and below 60 mass %, more preferably more than 3 mass % and 50 mass % Hereinafter, particularly preferably more than 5 mass % and below 35 mass %.If the containing ratio of colouring agent (A) is in above-mentioned scope, Desired light splitting, colour saturation can then be obtained.

＜ 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 Together.) (hereinafter sometimes referred to " (c) ") construction unit.

As (a), specifically, such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p- vinyl can be included The unsaturated monocarboxylic class such as benzoic 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..

In the case that copolymer includes the construction unit from (a), in the mass % of copolymer 1 00, its ratio is preferably 1 ~50 mass %, more preferably 5~30 mass %.

(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 of " (methyl) acryloyl group " and " (methyl) acrylate " etc. 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.

In the case that copolymer includes the construction unit from (b), in the mass % of copolymer 1 00, its ratio is preferably 50~99 mass %, more preferably 60~95 mass %.

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, it is 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".

In the case that copolymer includes the construction unit from (c), in the mass % of copolymer 1 00, its ratio is preferably 1 ~99 mass %.

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) propylene can be included Acid 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), more preferably Selected from the copolymer from (a) He the construction unit of (b)；And being total to the construction unit from (a), (b) and (c) One kind in polymers, particularly preferably there is the copolymer of the construction unit from (a) and (b).

The weight average molecular weight of the polystyrene conversion of resin (B) is preferably 3000~100000, more preferably 5000~ 50000, more preferably 5000~30000.If molecular weight is in above-mentioned scope, when forming colored pattern, development Front and rear residual film ratio is high, the favorable solubility for developer solution in unexposed portion, and what the resolution ratio with colored pattern improved inclines To.

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 40~170mg-KOH/g, more preferably 50~150mg- KOH/g, more preferably 60~135mg-KOH/g.Wherein, acid number is as the potassium hydroxide neutralized needed for resin (B) 1g The value that is determined of amount (mg), such as can be titrated and be obtained using potassium hydroxide aqueous solution.

For resin (B) content, relative to the total amount of solid constituent, preferably 7~75 mass %, more preferably 13 ~70 mass %, more preferably 17~70 mass %, it is still more preferably 17~65 mass %.If resin (B) Content can then form colored pattern in above-mentioned scope, and the resolution ratio with colored pattern and residual film ratio improve in addition Tendency.

＜ 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 with ethylenic unsaturated bond of 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) propylene can be enumerated Acid esters, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) third Olefin(e) acid ester, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, (first of tetrapentaerythritol ten Base) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2- (methyl) acryloyl-oxyethyl) isocyanuric acid esters, Glycol-modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylate, the third two Alcohol is modified pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, caprolactone and changed Property pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc., wherein, preferably two (methyl) acrylate of pentaerythrite 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.

For polymerizable compound (C) content, relative to the total amount of solid constituent, preferably 4~65 mass %, more Preferably 7~60 mass %, more preferably 10~55 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.

If the content of polymerizable compound (C) is in above-mentioned scope, residual film ratio when being formed with colored pattern The tendency improved with the chemical-resistant of colour filter.

＜ 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- acetoxyl groups -1- [9- ethyls -6- (2- methylbenzenes Formoxyl) -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- { 2- methyl -4- (3,3- diformazans Base -2,4- dioxolyls methoxyl group) benzoyl -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl group -1- [9- Ethyl -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -3- cyclopenta propane -1- imines, N- benzoyloxy -1- [9- Ethyl -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -3- cyclopenta propane -1- ketone -2- imines, [11- (2- ethyl hexyls Base) -5- (2,4,6- trimethylbenzoyls) -11H- benzos [a] carbazole -8- bases]-[2- (2,2,3,3- tetrafluoros propoxyl group) benzene Base] ketoxime O- acetic acid esters etc..Usable IRGACURE (registration mark) OXE01, OXE02 (being that BASF AG manufactures above), The commercially available products such as N-1919 (ADEKA Corp.'s manufacture).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 and [11- (2- Ethylhexyl) -5- (2,4,6- trimethylbenzoyls) -11H- benzos [a] carbazole -8- bases]-[2- (oxygen of 2,2,3,3- tetrafluoros third Base) phenyl] it is at least one kind of in ketoxime O- acetic acid esters, it is more preferably selected from N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) Octane -1- ketone -2- imines and [11- (2- ethylhexyls) -5- (2,4,6- trimethylbenzoyls) -11H- benzos [a] carbazole - 8- yls] it is at least one kind of in-[2- (2,2,3,3- tetrafluoros propoxyl group) phenyl] ketoxime O- acetic acid esters.

As O- acyl group oxime compounds, the compound (hereinafter sometimes referred to " compound preferably represented by following formula (d1) (d1)”。)。

[in formula (d1),

R^d1Represent can the aromatic hydrocarbyl with the carbon number 6~18 of substituent, can be with the miscellaneous of the carbon number 3~36 of substituent Ring group, can be with the carbon number 1~15 of substituent saturated hydrocarbyl or can the aralkyl with the carbon number 7~33 of substituent, it is above-mentioned Contained methylene (- CH in saturated hydrocarbyl or aralkyl₂-)-O- ,-CO- ,-S- ,-SO can be replaced by₂- or-NR^d5-。

It should illustrate, " aromatic hydrocarbyl " means the group for only including aromatic rings position in this specification.

R^d4Represent can be with the carbon number 6~18 of substituent aromatic hydrocarbyl or can be with the carbon number 1~15 of substituent Aliphatic alkyl, contained methylene (- CH in above-mentioned aliphatic alkyl₂-)-O- ,-CO- or-S-, above-mentioned fat can be replaced by Contained methine (- CH ＜) can be replaced by-PO in fat race alkyl₃＜, contained hydrogen atom can in above-mentioned aliphatic alkyl Substituted by OH bases.

R^d5The saturated hydrocarbyl of carbon number 1~10 is represented, contained methylene (- CH in the saturated hydrocarbyl₂-) can be replaced by- O- or-CO-.]

By R^d1The carbon number of the aromatic hydrocarbyl of expression is preferably 6~15, more preferably 6~12, more preferably 6~ 10.As the aromatic hydrocarbyl, such as phenyl, naphthyl, anthryl, phenanthryl, xenyl, terphenyl etc. can be included, more preferably Phenyl, naphthyl, particularly preferred phenyl.

In addition, by R^d1The aromatic hydrocarbyl of expression can have the substituent of more than 1 or 2.Substituent is preferably replaced in virtue α positions, the γ positions of fragrant race's alkyl, are more preferably replaced in γ positions.As the substituent, can include methyl, ethyl, propyl group, butyl, Amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl etc. The saturated hydrocarbyl of carbon number 1~15；Halogen atoms such as fluorine atom, chlorine atom, iodine atom, bromine atoms etc..

Carbon number as the saturated hydrocarbyl of above-mentioned substituent is preferably 1~10, and more preferably 1~7.As the substituent Saturated hydrocarbyl can be any of straight-chain, branch's chain state and ring-type or by the group of chain and the group of ring-type The group combined.As methylene (- CH contained in the saturated hydrocarbyl of the substituent₂-) may alternatively be-O- or- S-.In addition, hydrogen atom contained in the saturated hydrocarbyl can be taken by halogen atoms such as fluorine atom, chlorine atom, iodine atom, bromine atoms In generation, preferably it is replaced by fluorine atoms.But, as in the saturated hydrocarbyl of the substituent, adjacent methylene will not be replaced simultaneously, The methylene of end will not be replaced.

As by R^d1The substituent of the aromatic hydrocarbyl of expression, such as group represented by following formula etc. can be included.Formula In, * represents bonding end.

As by R^d1The aromatic hydrocarbyl with substituent represented, group represented by following formula etc. can be included. In formula, * represents bonding end.

As by R^d1The aromatic hydrocarbyl with substituent represented, the group preferably represented by following formula.

[in formula, R^d6Represent the saturated hydrocarbyl of carbon number more than 1, less than 10 that can be substituted with halogen atoms, R^d6In it is contained Hydrogen atom can be substituted with halogen atoms.M2 represents 1~5 integer.]

As by R^d6The saturated hydrocarbyl of expression, it can include with being used as by R^d1The substituent example of the aromatic hydrocarbyl of expression The same group of the saturated hydrocarbyl that shows.By R^d6The carbon number of the saturated hydrocarbyl of expression be preferably more than 2 and less than 7, more preferably 2 with It is upper and less than 5.In addition, R^d6Saturated hydrocarbyl can be straight-chain, branch's chain state and ring-type any, preferably chain.

As can be by R^d6In contained hydrogen atom substitution halogen atom, can include fluorine atom, chlorine atom, iodine atom, Bromine atoms, particularly preferred fluorine atom.Additionally, it is preferred that by R^d6In more than 2 and less than 10 of contained hydrogen atom be substituted by halogen Plain atom, more than 3 and less than 6 are preferably substituted by halogen atom.R^d6The preferred ortho position of the position of substitution of O- bases, contraposition, it is special Not preferably do not align.

In addition, m2 is preferably 1~2, particularly preferably 1.

By R^d1The carbon number of the heterocyclic radical of expression is preferably 3~20, more preferably 3~10, more preferably 3~5.As The heterocyclic radical, pyrrole radicals, furyl, thienyl, indyl, benzofuranyl, carbazyl etc. can be included.

In addition, R^d1Heterocyclic radical can have the substituent of more than 1 or 2.As the substituent, can include and conduct R^d1The same group of the group that illustrates of the substituent that can have of aromatic hydrocarbyl.

By R^d1The carbon number of the saturated hydrocarbyl of expression is preferably 1~12.As by R^d1The saturated hydrocarbyl of expression, it can include Methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, Myristyl, pentadecyl etc..These saturated hydrocarbyls can be any of straight-chain, branch's chain state and ring-type, can be by The group that the group of chain and the moiety combinations of ring-type form.In addition, in R^d1Saturated hydrocarbyl in, methylene (- CH₂-) can be with It is replaced by-O- ,-CO- ,-S- ,-SO₂- or-NR^d5-, hydrogen atom can be substituted by OH bases or SH bases.But, in the saturated hydrocarbons In base, adjacent methylene will not be replaced simultaneously, and the methylene of end will not be replaced.

R^d5The saturated hydrocarbyl of the saturated hydrocarbyl, preferably carbon number 1~5 of expression carbon number 1~10, more preferably carbon number 1~3 Saturated hydrocarbyl.The saturated hydrocarbyl can be chain (straight-chain or branch's chain state), or ring-type, can be straight-chain, divide Branched and ring-type any or the group for forming the moiety combinations of the group of chain and ring-type.In addition, R^d5's In saturated hydrocarbyl, methylene (- CH₂-) it may alternatively be-O- ,-CO-.But, in the saturated hydrocarbyl, adjacent methylene It will not be replaced simultaneously, the methylene of end will not be replaced.

As by R^d1The saturated hydrocarbyl with substituent represented, specifically, the base represented by following formula can be included Group etc..* bonding end is represented.

And then by R^d1The aralkyl with substituent represented is preferably will be by R^d1The aromatic hydrocarbyl of expression with by Above-mentioned R^d1The group that alkylidene derived from the saturated hydrocarbyl of expression combines.The carbon number of above-mentioned aralkyl is preferably 7~33, more Preferably 7~18, more preferably 7~12.The aralkyl can have the substituent of more than 1 or 2, as the substituent, It can include with being used as by above-mentioned R^d1The aromatic hydrocarbyl of expression and by R^d1The substituent that the saturated hydrocarbyl of expression can have illustrates The same group of group.As will be by the R^d1The aromatic hydrocarbyl of expression with by above-mentioned R^d12 derived from the saturated hydrocarbyl of expression The group that the moiety combinations of valency form, specifically, the group represented by following formula can be included.In formula, * represents bonding end. Contained methylene (- CH in aralkyl₂-) it may alternatively be-O- ,-CO- ,-S- ,-SO₂- or-N (R^d5)-.But, at this In aralkyl, adjacent methylene will not be simultaneously replaced, and the methylene of end will not be replaced.

Wherein, as R^d1, aromatic hydrocarbyl that preferably can be with substituent or can the saturated hydrocarbyl with substituent, more It is preferred that there can be the aromatic hydrocarbyl of substituent.

By R^d2The carbon number of the aromatic hydrocarbyl of expression is preferably 6~15, more preferably 6~12, more preferably 6~ 10.As the aromatic hydrocarbyl, such as phenyl, naphthyl, anthryl, phenanthryl, xenyl, terphenyl etc. can be included.

By R^d2The carbon number of the heterocyclic radical of expression is preferably 3~20, more preferably 3~10, more preferably 3~5.As The heterocyclic radical, such as pyrrole radicals, furyl, thienyl, indyl, benzofuranyl, carbazyl etc. can be included.

By R^d2The carbon number of the saturated hydrocarbyl of expression is preferably 1~7, more preferably 1~5, particularly preferably 1~3.It is used as this Saturated hydrocarbyl, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl etc. can be included.The saturated hydrocarbons Base can be straight-chain, branch's chain state and ring-type any or by the moiety combinations of the group of chain and ring-type and Into group.

Wherein, as R^d2, the preferred chain saturated hydrocarbyl of chain saturated hydrocarbyl, more preferably carbon number 1~5 is further excellent Elect the chain saturated hydrocarbyl of carbon number 1~3, particularly preferably methyl as.

By R^d3The carbon number of the aromatic hydrocarbyl of expression is preferably 6~15, more preferably 6~12, more preferably 6~ 10.As the aromatic hydrocarbyl, such as phenyl, naphthyl, anthryl, phenanthryl, xenyl, terphenyl etc. can be included, more preferably Phenyl, naphthyl.

In addition, by R^d3The aromatic hydrocarbyl of expression can have the substituent of more than 1 or 2.Substituent is preferably replaced in virtue α positions, the γ positions of fragrant race's alkyl.As the aliphatic alkyl of the substituent, preferably carbon number 1~15, specifically, first can be included The alkyl of the carbon numbers such as base, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl 1~15；Vinyl, propylene Alkenyls of carbon number 1~15 such as base, cyclobutenyl, pentenyl, hexenyl, heptenyl, nonenyl, decene base etc..

Carbon number as the aliphatic alkyl of above-mentioned substituent is more preferably 1~7.In addition, the fat as the substituent Race's alkyl can be straight-chain, branch's chain state and ring-type any or by the group of chain and the group group of ring-type Close the group formed.In addition, in the aliphatic alkyl as the substituent, methylene (- CH₂-) may alternatively be-O- ,- CO- or-S-, methine (- CH ＜) may alternatively be-N ＜.But, it is adjacent in the aliphatic alkyl as the substituent Methylene will not be replaced simultaneously, the methylene of end will not be replaced.

As by R^d3The aliphatic alkyl of the substituent of the aromatic hydrocarbyl of expression, such as can include and be represented by following formula Group etc..In formula, * represents bonding end.

As by R^d3The aromatic hydrocarbyl with substituent represented, such as the group represented by following formula can be included Deng.In formula, * represents bonding end.

By R^d3The carbon number of the heterocyclic radical of expression is preferably 3~20, more preferably 3~10, more preferably 3~5.As The heterocyclic radical, such as pyrrole radicals, furyl, thienyl, indyl, benzofuranyl, carbazyl etc. can be included.

In addition, by R^d3The heterocyclic radical of expression can have the substituent of more than 1 or 2, as the substituent, can include and As by R^d1The same group of group that substituent that the aromatic hydrocarbyl of expression can have illustrates.

Wherein, as R^d3, it is however preferred to have the aromatic hydrocarbyl of substituent, as the substituent, preferably carbon number 1~7 (more Preferably carbon number 1~3) chain-like alkyl, the number of substituent is preferably more than 2 and less than 5.

By R^d4The carbon number of the aromatic hydrocarbyl of expression is preferably 6~15, more preferably 6~12, more preferably 6~ 10.As the aromatic hydrocarbyl, such as phenyl, naphthyl, anthryl, phenanthryl, xenyl, terphenyl etc. can be included, more preferably Phenyl, naphthyl, particularly preferred phenyl.

In addition, by R^d4The aromatic hydrocarbyl of expression can have the substituent of more than 1 or 2.As the substituent, can enumerate Go out and R^d1The same group of the substituent that can have of aromatic hydrocarbyl.

By R^d4The carbon number of the aliphatic alkyl of expression is preferably 1~13, more preferably 2~10, more preferably 4~9. As R^d4Aliphatic alkyl, can include methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, The alkyl such as undecyl, dodecyl, tridecyl, myristyl, pentadecyl；Vinyl, acrylic, cyclobutenyl, amylene Base, hexenyl, heptenyl, octenyl, nonenyl, decene base, undecenyl, dodecenyl succinic, tridecylene base, 14 carbon Alkenyls such as alkenyl, 15 carbene bases etc..These aliphatic alkyls can be chain (straight-chain or branch's chain state), or ring Shape, it can also be the group for forming the moiety combinations of the group of chain and ring-type.In addition, by R^d4The aliphatic alkyl of expression In, methylene (- CH₂-)-O- ,-CO- or-S- are may alternatively be, methine (- CH ＜) may alternatively be-PO₃＜.It is above-mentioned Contained hydrogen atom can be substituted by OH bases in aliphatic alkyl.But, in the aliphatic alkyl, adjacent methylene will not Simultaneously it is replaced, the methylene of end will not be replaced.

As by R^d4The aliphatic alkyl with substituent represented, such as the group represented by following formula can be included Deng.In formula, * represents bonding end.

As R^d4, preferably can have substituent chain fatty race alkyl, the chain alkane more preferably without substituent Base, the branch's chain state alkyl more preferably without substituent.

As compound (d1), as shown in table 1 below~7, the compound represented by formula (d1) can be included (d1-1)~(d1-67).In table, * represents bonding end.

【Table 1】

【Table 2】

【Table 3】

【Table 4】

【Table 5】

【Table 6】

【Table 7】

Wherein, preferred compound (d1-3)~(d1-6), (d1-18)~(d1-52), (d1-55), (d1-56), (d1- 60), (d1-61), more preferably compound (d1-3)~(d1-6), (d1-18)~(d1-41), more preferably compound (d1-24), (d1-36)~(d1-40), particularly preferably compound (d1-24).

The containing ratio of the polymerization initiator represented by formula (d1) is preferably 50 matter in the mass % of polymerization initiator (D) 100 Measure more than %, more preferably more than 70 mass %, more preferably more than 90 mass %, particularly preferably 95 mass % with On.

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 ', 5,5 '-tetraphenyl connection miaow can be included 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 The imidazolium compounds substituted by alkoxy carbonyl group is (for example, referring to Japanese Unexamined Patent Publication 7-10913 publications etc..) etc..

As triaizine compounds, double (the trichloromethyl) -6- (4- methoxyphenyls) -1,3,5- tri- of such as 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.

For polymerization initiator (D) content, relative to the matter of total amount 100 of resin (B) and polymerizable compound (C) Measure part, more preferably preferably 0.1~40 mass parts, 1~30 mass parts.

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

＜ solvents (E) ＞

Solvent (E) is not particularly limited, solvent usually used in the field can be used.For example, ester output can be enumerated Solvent (including-COO-, the solvent without-O- in intramolecular), ether solvents (include-O-, molten without-COO- in intramolecular Agent), ether-ether solvent (including-COO- and-O- solvent in intramolecular), ketone solvent (include-CO-, without-COO- in intramolecular Solvent), alcoholic solvent (including OH, the solvent without-O- ,-CO- and-COO- in intramolecular), aromatic hydrocarbon solvents, acid amides it is molten Agent, 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, Acetic acid 3- methoxybutyls, acetic acid 3- methyl -3- methoxybutyls, propylene glycol monomethyl ether, propylene glycol monoethyl Acetic acid esters, propylene glycol monopropyl ether acetic acid esters, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, diethylene glycol (DEG) Single 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, 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-n-butyl alcohol, 3- ethoxy-propionic acid second Ester, 1-METHYLPYRROLIDONE.

For solvent (E) content, relative to the total amount of cyan hardening resin composition, preferably 50~95 matter Measure %, more preferably 55~92 mass %.In other words, the solid constituent of cyan hardening resin composition is preferably 5~50 matter Measure %, more preferably 8~45 mass %.If the content of solvent (E), in above-mentioned scope, flatness during coating becomes good It is good, and when foring colour filter because colour saturation is without deficiency, therefore the tendency that display characteristic becomes good be present.

＜ levelling agents (F) ＞

The cyan 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 include 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), for its content, relative to the total amount of cyan hardening resin composition, Preferably more than 0.001 mass % and below 0.7 mass %, more preferably more than 0.002 mass % and below 0.5 mass %, More preferably more than 0.005 mass % and below 0.3 mass %.If the content of levelling agent (F) in above-mentioned scope, The flatness of colour filter can then be made become good.

＜ other compositions ＞

The present invention cyan 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 ＜ cyan hardening resin compositions

The cyan 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) and the solvent (E) used as needed, levelling agent (F) and other compositions are mixed and made It is standby.

Green pigment (A2-2) and the pigment (A3-2) that uses the as needed preferably part or complete with solvent (E) in advance Portion mixes, and makes it scattered using ball mill etc. until the average grain diameter of pigment turns into less than 0.2 μm Zuo You.Now, as needed Part or all of pigment dispersing agent, resin (B) can be coordinated.

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

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

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

The manufacture method ＞ of ＜ colour filters

As by the present invention cyan hardening resin composition manufacture colored pattern method, can include photoetching process, Ink-jet method, print process etc..Wherein, preferred photoetching process.Photoetching process is that above-mentioned cyan hardening resin composition is coated on into substrate, Dry and form coloring compositions nitride layer, the method that the coloring compositions nitride layer is exposed via photomask and developed.In photoetching process, lead to Cross and without using photomask and/or do not develop in exposure, so as to form the solidfied material as above-mentioned coloring compositions nitride layer Colour 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, cyan 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 included.

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 cyan hardening resin composition of the present invention, the excellent colour filter of lightness can be formed.The colour filter can As the colour filter for display device (for example, liquid crystal display device, organic el device, Electronic Paper etc.) and solid-state imager Device.

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 even 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]

Exist using 40.6 parts of compound (VI), as compound (III) 8 parts of diethylamine (Tokyo chemical conversion industry (strain) manufacture) Mix, stirred at 30 DEG C 3 hours in the presence of 50 parts of 1-Methyl-2-Pyrrolidone, under dark conditions.The reaction that will be obtained After liquid is cooled to room temperature, it is added in the mixed liquor of 400 parts of water, 20 parts of 35% hydrochloric acid, has been stirred at room temperature 1 hour, as a result Crystallization separates out.Dried after the crystallization of precipitation is obtained as the residue of suction strainer, obtained the compound 44 represented by formula (I-1-A) Part.

Next, will be by 44 parts of the compound and trimethoxy [3- (methylamino) propyl group] silane of formula (I-1-A) expression It is small that 21.4 parts of (Tokyo chemical conversion industry (strain) manufacture) heated 5 in the presence of 50 parts of 1-Methyl-2-Pyrrolidone, at 100 DEG C When.After obtained reaction solution is cooled into room temperature, filtering, is cleaned for 100 parts, the crystallizing and drying that will be obtained, obtained by formula with water (I-1) 52 parts of the compound represented.

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

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

Exact mass：598.1

The compound 0.35g represented by formula (I-1) is dissolved in chloroform, volume is turned into 250cm³, by 2cm therein³ Diluted with ion exchange water, volume is turned into 100cm³(concentration：0.028g/L), using spectrophotometer (quartz cell, light path It is long：1cm) determine absorption spectrum.The maximum absorption wavelength X of the compound_maxFor 546nm.

[synthesis of resin]

In the flask of the 1L with reflux cooler, dropping funel and mixer, appropriate nitrogen is set to flow into and be replaced into Blanket of nitrogen, load the parts by weight of propylene glycol monomethyl ether 280, be heated to 80 DEG C while stirring.Next, last 5 hours The parts by weight of acrylic acid 38, the ring [5.2.1.0 of acrylic acid 3,4- epoxies three are instilled^2,6] decane -8 or/and 9- base esters mixture The mixed solution of 289 parts by weight, the parts by weight of propylene glycol monomethyl ether 125.On the other hand, last 6 hours and instill general The parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) 33 are dissolved in the mixing in the parts by weight of propylene glycol monomethyl ether 235 Solution.After instillation terminates, after maintaining 4 hours at the same temperature, room temperature is cooled to, has obtained Type B viscosity (23 DEG C) 125mPas, the weight % of solid constituent 37.0, solution acid number 27mg-KOH/g copolymer (resin B -1).The copolymer of generation Weight average molecular weight Mw is 9200, decentralization 2.08.

For the polystyrene conversion weight average molecular weight Mw and number-average molecular weight Mn of the resin obtained in above-mentioned synthesis example 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 cyan hardening resin composition]

Each composition is mixed in a manner of as the composition shown in table 8, has obtained cyan hardening resin composition.

【Table 8】

In table 8, each composition represents following meanings：

(A) colouring agent：A-1：By C.I. pigment blue 15s：6 12.0 parts of (pigment) and 2.0 parts of acrylic acid series pigment dispersing agent With 80.5 parts of mixing of propylene glycol monomethyl ether, dispersible pigment dispersion scattered in advance

(A) colouring agent：A-2：Will be by 5.0 parts of the compound and propylene glycol monomethyl ether 89.9 of formula (I-1) expression The solution that part mixes

(A) colouring agent：A-3：By dyestuff (A-3) (mixture of the compound represented by formula (A3-1)~formula (A3-8)) 7.2 parts and 92.7 parts of solution mixed of propylene glycol monomethyl ether

(B) resin：B-1：The solution of resin B -1

(C) polymerizable compound：C-1：Dipentaerythritol acrylate (Japanese chemical drug (strain) manufacture；KAYARAD (notes Volume trade mark) DPHA)

(D) polymerization initiator：D-1：By following formula

The compound of expression

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

(F) levelling agent：F-1：Polyether modified silicon oil (TORAY SILICONE SH8400；Beautiful DOW CORNING (strain) manufacture in east)

[formation of 50 μm of square sectional hole patterns]

In glass substrate (the EAGLE XG of 2 inch squares；Corning Incorporated manufactures) on, cyan is coated with using spin-coating method and consolidated After the property changed resin combination, prebake 3 minutes at 100 DEG C.After cooling, cyan hardening resin composition is coated with for this Substrate, via the mask pattern for the square hole for being arranged with 50 μm, use exposure machine (TME-150RSK；トプ Us Application (strain) is made Make), under air atmosphere, with 80mJ/cm²Light exposure (365nm benchmark) carried out light irradiation.After exposure, developer solution is used Carry out developing for 60 seconds at 23 DEG C, after then being rinsed 20 seconds with flowing water, spray drying.Then, after being carried out 30 minutes at 230 DEG C Bakee, form 50 μm of square sectional hole patterns on the glass substrate.

[film thickness measuring]

For obtained pattern, film thickness measuring device (DEKTAK3 is used；Japanese vacuum technique (strain) manufacture) determine film It is thick.Show the result in table 9.

[chromaticity evaluation]

For the pattern on obtained glass substrate, colour examining machine (OSP-SP-200 is used；Olympus (strain) manufactures) survey Fixed light splitting, color function is waited using illuminant-C, determines the xy chromaticity coordinates (x, y) in CIE XYZ color specification systems.Show the result in In table 9.The color for the pattern on glass substrate for confirming to obtain by chromaticity coordinate is cyan.

【Table 9】

By making colourity consistent with the pattern that the colored curable resin composition of (A-2) is formed comprising colouring agent (A-1) In the case of, compared with the pattern formed by the colored curable resin composition of comparative example, it is known that Y is big, and lightness is excellent.

Industrial applicability

Using the cyan hardening resin composition of the present invention, the excellent colour filter of lightness can be formed.The colour filter can As the colour filter used in display device (for example, liquid crystal display device, organic el device, Electronic Paper etc.) and solid-state imager Device.

Claims

1. cyan hardening resin composition, which contain toner (A), resin (B), polymerizable compound (C) and polymerization to trigger Agent (D), as above-mentioned colouring agent (A), the cyan hardening resin composition includes：Maximum absorption wavelength in chloroform is 500nm~600nm and dyestuff (A1) and cyan colorant with silicon atom.

2. cyan hardening resin composition according to claim 1, wherein, the polymerization initiator (D) is included under The polymerization initiator of formula (d1) expression is stated,

In formula (d1),

R^d1Represent can the aromatic hydrocarbyl with the carbon number 6~18 of substituent, can the heterocycle with the carbon number 3~36 of substituent Base, can be with the carbon number 1~15 of substituent saturated hydrocarbyl or can the aralkyl with the carbon number 7~33 of substituent, it is described full With methylene (- CH contained in alkyl or aralkyl₂-) it may alternatively be-O- ,-CO- ,-S- ,-SO₂- or-NR^d5-,

R^d2Aromatic hydrocarbyl, the heterocyclic radical of carbon number 3~36 or the saturated hydrocarbyl of carbon number 1~10 of carbon number 6~18 are represented,

R^d3Represent can the aromatic hydrocarbyl with the carbon number 6~18 of substituent, can the heterocycle with the carbon number 3~36 of substituent Base,

R^d4Represent can be with the carbon number 6~18 of substituent aromatic hydrocarbyl or can the fat with the carbon number 1~15 of substituent Race's alkyl, contained methylene (- CH in the aliphatic alkyl₂-) it may alternatively be-O- ,-CO- or-S-, the fat Contained methine (- CH ＜) may alternatively be-PO in race's alkyl₃＜, contained hydrogen atom can in the aliphatic alkyl To be substituted by OH bases,

R^d5The saturated hydrocarbyl of carbon number 1~10 is represented, contained methylene (- CH in the saturated hydrocarbyl₂-) it may alternatively be-O- Or-CO-.

3. cyan hardening resin composition according to claim 1, wherein, relative to cyan hardening resin composition Solid constituent total amount, the containing ratio of the colouring agent (A) is more than 3 mass % and below 60 mass %.

4. cyan hardening resin composition according to claim 1, wherein, the cyan colorant is cyan phthalocyanine face Material.

5. cyan hardening resin composition according to claim 1, wherein, the content of the dyestuff (A1) is for described The mass ratio (dyestuff (A1)/cyan colorant) of the content of cyan colorant is more than 0.01 and less than 2.

6. colour filter, it according to cyan hardening resin composition according to any one of claims 1 to 5 by forming.

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