CN107522685A

CN107522685A - Compound, colored curable resin composition, colour filter and display device

Info

Publication number: CN107522685A
Application number: CN201710472877.4A
Authority: CN
Inventors: 大垣弘毅; 土谷崇夫
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2016-06-20
Filing date: 2017-06-20
Publication date: 2017-12-29
Anticipated expiration: 2037-06-20
Also published as: KR102211637B1; JP7101295B2; TWI738797B; JP2017226814A; TW201821416A; KR20170142912A; CN107522685B; JP2021176960A; JP6902848B2

Abstract

Using the colored curable resin composition comprising the compounds of this invention, using the teaching of the invention it is possible to provide have the colour filter and display device of good lightness.The formula (I) of the present invention represents, meets at least one in (i)~(vi)：(i)R¹For the saturated hydrocarbyl with COOM, R²~R⁴In at least one be aromatic hydrocarbyl, and COOM is 1；(ii)R¹And R³For the aromatic hydrocarbyl with COOM；(iii)R¹For the aromatic hydrocarbyl with COOM, R³For the saturated hydrocarbyl with COOM；(iv)R¹For the saturated hydrocarbyl with COOM, R³For the saturated hydrocarbyl with COOM；(v)R¹For saturated hydrocarbyl, R²For the aromatic hydrocarbyl with COOM；(vi)R¹And R²For hydrogen atom or saturated hydrocarbyl, R³And R⁴In at least one be the aromatic hydrocarbyl with COOM,

Description

Compound, colored curable resin composition, colour filter and display device

Technical field

The present invention relates to compound and colored curable resin composition.

Background technology

Filter used in the display devices such as liquid crystal display device, el display device and plasma scope Color device has used colored curable resin composition during fabrication.As such colored curable resin composition, it is known that bag Colored curable resin composition containing the compound represented by following formula etc.：

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2010-32999 publications

The content of the invention

The invention problem to be solved

The lightness of the colour filter formed by the colored curable resin composition comprising previously known above-claimed cpd Sometimes fail to fully meet needs.

Means for solving the problems

The present invention includes following invention.

[1] compound represented by formula (I).

[in formula (I), R¹~R⁴Independently of each other represent hydrogen atom, can have substituent carbon number 1~20 saturated hydrocarbyl or Person can have the aromatic hydrocarbyl of the carbon number 6~10 of substituent, contained-CH in the saturated hydrocarbyl₂- can by-O- ,-CO- or- NR¹¹- replace.R¹And R²The ring containing nitrogen-atoms, R can be formed together³And R⁴The ring containing nitrogen-atoms can be formed together.

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

R¹¹Represent hydrogen atom, the saturated hydrocarbyl of carbon number 1~20 or the aralkyl of carbon number 7~10.

But, make to meet at least one in necessary condition (i)~(vi) by the compound that formula (I) represents：

(i)R¹For the saturated hydrocarbyl of the carbon number 1~20 with-COOM, R²~R⁴In at least one can to have substituent Carbon number 6~10 aromatic hydrocarbyl, and contained-COOM in 1 molecule is 1.

(ii)R¹And R³For the aromatic hydrocarbyl of the carbon number 6~10 with-COOM.

(iii)R¹For the aromatic hydrocarbyl of the carbon number 6~10 with-COOM, R³For the full of the carbon number 1~20 with-COOM And alkyl.

(iv)R¹For the saturated hydrocarbyl of the carbon number 3~20 with-COOM, R³For the saturation of the carbon number 1~20 with-COOM Alkyl.

(v)R¹For that can have the saturated hydrocarbyl of the carbon number 1~20 of substituent, R²For the virtue of the carbon number 6~10 with-COOM Fragrant race's alkyl.

(vi)R¹And R²For hydrogen atom or the saturated hydrocarbyl of the carbon number 1~20 can with substituent, R³And R⁴In at least 1 The individual aromatic hydrocarbyl for the carbon number 6~10 with-COOM.

(i) in~(vi), M represents hydrogen atom, Na⁺、K⁺Or⁺N(R¹²)₄, 4 R¹²Can be with identical also different.

R¹²Represent hydrogen atom, the saturated hydrocarbyl of carbon number 1~20 or the aralkyl of carbon number 7~10.]

[2] colored curable resin composition, it is included：[1] compound, resin (B) described in, polymerizable compound And polymerization initiator (D) (C).

[3] colour filter, it is formed as the colored curable resin composition described in [2].

[4] display device, it includes the colour filter described in [3].

The effect of invention

Using the colored curable resin composition of the compound comprising the present invention, the excellent colour filter of lightness can be formed Device.

Embodiment

The formula (I) of the present invention represents.It should illustrate, its tautomerism is also included in compound of the invention Body, stereoisomer, their salt.In addition, each composition illustrated below and functional group each can be used alone or combine Use.

[in formula (I), R¹~R⁴Independently of each other represent hydrogen atom, can have substituent carbon number 1~20 saturated hydrocarbyl, Or can have the aromatic hydrocarbyl of the carbon number 6~10 of substituent, contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- Or-NR¹¹- replace.R¹And R²The ring comprising nitrogen-atoms, R can be formed together³And R⁴The ring comprising nitrogen-atoms can be formed together.

But, the compound represented by formula (I) meets at least one in necessary condition (i)~(vi)：

(i)R¹For the saturated hydrocarbyl of the carbon number 1~20 with-COOM, R²~R⁴In at least one can to have substituent Carbon number 6~10 aromatic hydrocarbyl, and-COOM contained in 1 molecule is 1.

(ii)R¹And R³For the aromatic hydrocarbyl of the carbon number 6~10 with-COOM.

As R¹~R⁴In carbon number 6~10 aromatic hydrocarbyl, such as can include phenyl, tolyl, xylyl, Mesitylene base, propyl group phenyl and butyl phenyl etc..

The substituent that can have as the aromatic hydrocarbyl, halogen atom ,-R can be included⁸、-OH、-OR⁸、-SO₃H、- SO₃ ^-Z⁺、-COOM、-CO₂R⁸、-SR⁸、-SO₂R⁸、-SO₃R⁸Or-SO₂NR⁹R¹⁰, preferably these substituents are by institute in aromatic hydrocarbyl The hydrogen atom substitution contained.In these, as substituent, preferably-SO₃H、-SO₃ ^-Z⁺With-SO₂NR⁹R¹⁰, more preferably-SO₃ ^-Z⁺、- COOM and-SO₂NR⁹R¹⁰.- SO as this situation₃ ^-Z⁺, preferably-SO₃ ^-+N(R¹¹)₄.In the aromatic hydrocarbyl, containing- In the case that COOM is as substituent, preferably-COOM is incorporated into meta or para position relative to bonding end.If R¹~R⁴For these Group, then the generation of foreign matter can be formed less by the colored curable resin composition of the invention of inclusion compound (I) and The colour filter of excellent heat resistance.

R⁸The saturated hydrocarbyl of carbon number 1~20 is represented, contained hydrogen atom can be substituted with halogen atoms in the saturated hydrocarbyl.

R⁹And R¹⁰Hydrogen atom is represented independently of each other or can have the saturated hydrocarbyl of the carbon number 1~20 of substituent, the saturation Contained-CH in aliphatic alkyl₂- can be by-O- ,-CO- ,-NH- or-NR⁸- replace, R⁹And R¹⁰It can be combined with each other and be formed and contained There is the heterocycle of 3~10 yuan of rings of nitrogen-atoms.

As R¹~R⁴And R⁸~R¹²In carbon number 1~20 saturated hydrocarbyl, such as can include methyl, ethyl, propyl group, The straight-chain alkyls such as butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl, eicosyl；It is different Propyl group, isobutyl group, isopentyl, neopentyl, 2- ethylhexyls etc. divide branched-chain alkyl；Cyclopropyl, cyclopenta, cyclohexyl, cycloheptyl The ester ring type saturated hydrocarbyl of the carbon numbers such as base, cyclooctyl, tricyclodecyl 3~20.The carbon number of the saturated hydrocarbyl is more preferably 1~10.

R¹~R⁴In the saturated hydrocarbyl in contained hydrogen atom for example can be by-the COOM as substituent, carbon number 6~10 Aromatic hydrocarbyl or halogen atom substitution.In addition, by R¹~R⁴In the saturated hydrocarbyl of expression, the carbon atom preferably with end The hydrogen atom that (primary carbon atom) combines is substituted with a substituent.As can be by R¹~R⁴Saturated hydrocarbyl hydrogen atom substitution carbon number 6 ~10 aromatic hydrocarbyl, it can include and be used as R¹~R⁴In carbon number 6~10 the aromatic hydrocarbyl group that illustrates it is same Group.

R⁹And R¹⁰In the saturated hydrocarbyl in contained hydrogen atom for example can be by the hydroxyl or halogen atom as substituent Substitution.

As R¹And R²The ring and R formed together³And R⁴The ring formed together, such as following ring can be included.* table Show bonding end.

It is used as-OR⁸, such as methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygen in heptan can be included Alkoxies such as base, octyloxy, 2- ethyl hexyl oxies and eicosane epoxide etc..

It is used as-CO₂R⁸, such as can include methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, Alkoxy carbonyl such as hexyloxy carbonyl and eicosane epoxide carbonyl etc..

It is used as-SR⁸, such as methylsulfanyl, Ethylsulfanyl, butyl sulfanyl, hexyl sulfanyl, decyl can be included Alkyl alkylthio base such as sulfanyl and eicosyl sulfanyl etc..

It is used as-SO₂R⁸, such as methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, the last of the ten Heavenly stems can be included Alkyl sulphonyl such as base sulfonyl and eicosyl sulfonyl etc..

It is used as-SO₃R⁸, such as methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxy can be included Alkyloxysulfonyls such as sulfonyl, hexyloxy sulfonyl and eicosane epoxide sulfonyl etc..

It is used as-SO₂NR⁹R¹⁰, such as sulfamoyl can be included；

N- Methylsulfamoyls, N- ethylsulfamovls, N- propylsulfamovs, N- isopropylsulfamoyls base, N- butyl Sulfamoyl, N- isobutyl groups sulfamoyl, N- sec-butyls sulfamoyl, N- tert-butyls 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) sulfonamides Base, N- (3,3- dimethylbutyls) sulfamoyl, N- heptyl sulfamoyl, N- (1- methylhexyls) sulfamoyl, N- (1,4- bis- Methyl amyl) sulfamoyl, N- octyl groups sulfamoyl, N- (2- ethylhexyls) sulfamoyl, N- (1,5- dimethylhexanyls) ammonia The N-1 such as sulfonyl, N- (1,1,2,2- tetramethyl butyls) sulfamoyl substitute sulfamoyl；

N, N- DimethylsuIfamoyl, N, N- ethyl-methyls sulfamoyl, N, N- diethyl aminos sulfonyl, N, N- propyl group first Base sulfamoyl, N, N- isopropyl methyls sulfamoyl, N, N- tert-butyls Methylsulfamoyl, 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 etc..

As R⁶And R⁷In carbon number 1~6 alkyl, the alkyl of carbon number 1~6 in the above-mentioned alkyl enumerated can be included.Its In, as R⁶、R⁷, preferred hydrogen atom.

As R¹¹~R¹²In carbon number 7~10 aralkyl, benzyl, phenylethyl, phenyl butyl etc. can be included.

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

As above-mentioned⁺N(R¹¹)₄, preferably 4 R¹¹Middle at least two is the saturated hydrocarbyl of carbon number 5~20.In addition, 4 R¹¹'s Total carbon number preferably 20~80, more preferably 20~60.

But, the compound represented by formula (I) meets at least one in necessary condition (i)~(vi), preferably meets necessary At least one in condition (i), (ii), (iv), (v)：

(ii)R¹And R³For the aromatic hydrocarbyl of the carbon number 6~10 with-COOM.

R¹²Represent hydrogen atom, the saturated hydrocarbyl of carbon number 1~20 or the aralkyl of carbon number 7~10.

M is particularly preferably hydrogen atom.

R¹²The preferably saturated hydrocarbyl or benzyl of hydrogen atom, carbon number 1~20.

In necessary condition (i), preferably R¹(it is preferably carbon number 1~10 for the saturated hydrocarbyl of the carbon number 1~20 with COOM Saturated hydrocarbyl), R²~R⁴In at least two for can have substituent carbon number 6~10 aromatic hydrocarbyl.In addition, more preferably R¹For the saturated hydrocarbyl (the preferably saturated hydrocarbyl of carbon number 1~10) of the carbon number 1~20 with COOM, R²And R³For that can have substitution The aromatic hydrocarbyl of the carbon number 6~10 of base.

In necessary condition (ii), preferably R²And R⁴For hydrogen atom or the saturated hydrocarbons of the carbon number 1~20 can with substituent Base, can more preferably have the saturated hydrocarbyl of the carbon number 1~20 of substituent.

As in necessary condition (iv), preferably R²And R⁴For that can have the aromatic hydrocarbyl of the carbon number 6~10 of substituent.Separately Outside, preferably R²For the saturated hydrocarbyl of the carbon number 3~20 with COOM, more preferably R¹And R²For the full of the carbon number 3~10 with COOM And alkyl.

In necessary condition (v), more preferably R³For that can have the saturated hydrocarbyl of the carbon number 1~20 of substituent, R⁴For with COOM Carbon number 6~10 aromatic hydrocarbyl.

As compound (I), the compound (hereinafter sometimes referred to " compound (Ia) " preferably represented by formula (Ia).).Change Compound (Ia) can be its dynamic isomer.

[in formula (Ia), R²¹~R²⁴Hydrogen atom ,-R are represented independently of each other²⁶Or can have the carbon number 6~10 of substituent Aromatic hydrocarbyl.R²¹And R²²The ring containing nitrogen-atoms, R can be formed together²³And R²⁴The ring containing nitrogen-atoms can be formed together.

R²⁶Representing can the saturated hydrocarbyl with COOM carbon number 1~20.

M represents hydrogen atom, Na⁺、K⁺Or⁺N(R¹²)₄, 4 R¹²Can be with identical also different.

But, the compound represented by formula (Ia) meets at least one in necessary condition (ia)~(via)：

(ia)R²¹In at least one be the carbon number 1~20 with COOM saturated hydrocarbyl, R²²~R²⁴In at least one be There can be the aromatic hydrocarbyl of the carbon number 6~10 of substituent, and-COOM contained in 1 molecule is 1.

(iia)R²¹And R²³For the aromatic hydrocarbyl of the carbon number 6~10 with COOM.

(iiia)R²¹For the aromatic hydrocarbyl of the carbon number 6~10 with COOM, R²³For the carbon number 1~20 with COOM Saturated hydrocarbyl.

(iva)R²¹For the saturated hydrocarbyl of the carbon number 3~20 with COOM, R²³For the saturation of the carbon number 1~20 with COOM Alkyl.

(va)R²¹For that can have the saturated hydrocarbyl of the carbon number 1~20 of substituent, R²²For the carbon number 6~10 with COOM Aromatic hydrocarbyl.

(via)R²¹And R²²For hydrogen atom or the saturated hydrocarbyl of the carbon number 1~20 can with substituent, R²³For with COOM Carbon number 6~10 aromatic hydrocarbyl.]

As R²¹~R²⁴In carbon number 6~10 aromatic hydrocarbyl, can include and be used as above-mentioned R¹~R⁴Aromatic series The same group of group that alkyl is enumerated.Contained hydrogen atom can be by-COOM ,-SO in the aromatic hydrocarbyl₃ ^-、-SO₃H、- SO₃ ^-Z1⁺、-SO₃R²⁵Or-SO₂NHR²⁵Substitution.It is excellent in the case that contained hydrogen atom is by-COOM substitutions in the aromatic hydrocarbyl Choosing-COOM is incorporated into meta or para position relative to bonding end.

Z1⁺For⁺N(R²⁷)₄、Na⁺Or K⁺, it is preferably⁺N(R²⁷)₄。

R²⁵Represent the saturated hydrocarbyl of 1 valency of carbon number 1~20.

R²⁷Represent the saturated hydrocarbyl or benzyl of 1 valency of carbon number 1~20.

As R²¹~R²⁴Combination, preferably R²¹And R²³For hydrogen atom, R²²And R²⁴For the aromatic hydrocarbyl of carbon number 6~10, Contained hydrogen atom is by-SO in the aromatic hydrocarbyl₃ ^-、-SO₃H、-SO₃ ^-Z1⁺、-SO₃R²⁶Or-SO₂NHR²⁶Substitution.More preferably It is combined as：R²¹And R²³For hydrogen atom, R²²And R²⁴For the aromatic hydrocarbyl of carbon number 6~10, contained hydrogen is former in the aromatic hydrocarbyl Son is by-SO₃ ^-Z1⁺Or-SO₂NHR²⁶Substitution.

As R²¹And R²²The ring and R containing nitrogen-atoms formed together²³And R²⁴Formed together containing nitrogen-atoms Ring, can be included and R¹And R²The same ring of the ring that is formed together.Wherein, preferred aliphat heterocycle.As the aliphatic heterocycle, Such as following aliphatic heterocycles can be included.* bonding end is represented.

As R²⁵~R²⁷In carbon number 1~20 saturated hydrocarbyl, can include and R⁸~R¹¹It is middle to be enumerated as saturated hydrocarbyl The same group of group.

R²¹~R²⁴For-R²⁶In the case of ,-R²⁶It is preferred that it is each independently methyl or ethyl.R²¹~R²⁴For-R²⁶, R²⁶Tool In the case of having-COOM, preferably-R²⁶Substituted with the hydrogen atom that the carbon atom (primary carbon atom) of end combines by-COOM.

In addition, conduct-SO₃R²⁶With-SO₂NHR²⁶In R²⁶, preferably the branch's chain state alkyl of carbon number 3~20, more preferably carbon The branch's chain state alkyl of number 6~12, further preferred 2- ethylhexyls.

As above-mentioned⁺N(R²⁷)₄, preferably 4 R²⁷Middle at least two is the saturated hydrocarbyl of carbon number 5~20.In addition, 4 R²⁷'s Total carbon number preferably 20~80, more preferably 20~60.Exist in compound (Ia)⁺N(R²⁷)₄In the case of, R²⁷Can be with identical Can be different.

But, the compound represented by formula (Ia) meets at least one in necessary condition (ia)~(via), preferably meets At least one in necessary condition (ia), (iia), (iva), (va)：

(ia)R²¹For the saturated hydrocarbyl of the carbon number 1~20 with-COOM, R²²~R²⁴In at least one for can have substitution The aromatic hydrocarbyl of the carbon number 6~10 of base, and-COOM contained in 1 molecule is 1.

(iia)R²¹And R²³For the aromatic hydrocarbyl of the carbon number 6~10 with-COOM.

(iiia)R²¹For the aromatic hydrocarbyl of the carbon number 6~10 with-COOM, R²³For the carbon number 1~20 with-COOM Saturated hydrocarbyl.

(iva)R²¹For the saturated hydrocarbyl of the carbon number 3~20 with-COOM, R²³For the full of the carbon number 1~20 with-COOM And alkyl.

(va)R²¹For that can have the saturated hydrocarbyl of the carbon number 1~20 of substituent, R²²For the carbon number 6~10 with-COOM Aromatic hydrocarbyl.

(via)R²¹And R²²For hydrogen atom or the saturated hydrocarbyl of the carbon number 1~20 can with substituent, R²³And R²⁴In extremely Few 1 aromatic hydrocarbyl for the carbon number 6~10 with-COOM.

M is particularly preferably hydrogen atom.

In necessary condition (ia), preferably R²¹(it is preferably carbon number 1~10 for the saturated hydrocarbyl of the carbon number 1~20 with-COOM Saturated hydrocarbyl), R²²~R²⁴In at least two for can have substituent carbon number 6~10 aromatic hydrocarbyl.It is preferred that R²¹For The saturated hydrocarbyl (being preferably the saturated hydrocarbyl of carbon number 1~10) of carbon number 1~20 with-COOM, R²²And R²³For that can have substitution The aromatic hydrocarbyl of the carbon number 6~10 of base.

In necessary condition (iia), preferably R²²And R²⁴For hydrogen atom or the saturated hydrocarbons of the carbon number 1~20 can with substituent Base, can more preferably have the saturated hydrocarbyl of the carbon number 1~20 of substituent.

In necessary condition (iva), preferably R²²And R²⁴For that can have the aromatic hydrocarbyl of the carbon number 6~10 of substituent.Separately Outside, preferably R²²For the saturated hydrocarbyl of the carbon number 3~20 with-COOM, more preferably R²¹And R²²For the carbon number 3~10 with-COOM Saturated hydrocarbyl.

In necessary condition (va), more preferably R²³For that can have the saturated hydrocarbyl of the carbon number 1~20 of substituent, R²⁴For with- The aromatic hydrocarbyl of COOM carbon number 6~10.

In addition, as compound (I), it is also preferred that the compound (hereinafter sometimes referred to " compound represented by formula (Ib) (Ib)”.).Compound (Ib) can be its dynamic isomer.

[in formula (Ib), R³¹And R³²The saturated hydrocarbyl of carbon number 1~10, the R are represented independently of each other³¹、R³²Saturated hydrocarbyl In contained hydrogen atom can be substituted by-COOM, the aromatic hydrocarbyl of carbon number 6~10 or halogen atom, in the aromatic hydrocarbyl Contained hydrogen atom can be substituted by-COOM or carbon number 1~3 alkoxy, above-mentioned R³¹、R³²Saturated hydrocarbyl in it is contained- CH₂- can be by-O- ,-CO- or-NR¹¹- replace.

R³³And R³⁴Expression-COOM, the alkyl of carbon number 1~4, the alkyl alkylthio base of carbon number 1~4 or carbon number 1 independently of each other ~4 alkyl sulphonyl.

R³¹And R³³The ring containing nitrogen-atoms, R can be formed together³²And R³⁴The ring containing nitrogen-atoms can be formed together.

P and q represents 0~5 integer independently of each other.When p is more than 2, multiple R³³Can with identical also different, q be 2 with When upper, multiple R³⁴Can be with identical also different.

R¹¹Represent implication same as described above.

But, the compound represented by formula (Ib) meets at least one in necessary condition (ib)~(ivb)：

(ib)R³¹For the saturated hydrocarbyl of the carbon number 1~20 with-COOM, contained-COOM is 1 in 1 molecule.

(iib)R³³And R³⁴In at least one be-COOM.

(iiib)R³¹For the saturated hydrocarbyl of the carbon number 1~20 with-COOM, R³⁴For-COOM.

(ivb)R³¹For the saturated hydrocarbyl of the carbon number 3~20 with-COOM, R³²For the full of the carbon number 1~20 with-COOM And alkyl.]

As R³¹And R³²In carbon number 1~10 saturated hydrocarbyl, R can be included⁸In saturated hydrocarbyl in carbon number 1~10 Group.

As the aromatic hydrocarbyl of the carbon number 6~10 can with substituent, can include and R¹In aromatic hydrocarbyl phase Same group.In addition, by R³¹And R³²In the case that the saturated hydrocarbyl of expression is substituted by-COOM, the carbon atom preferably with end The hydrogen atom that (primary carbon atom) combines is substituted by-COOM.

As the alkoxy of carbon number 1~3, such as methoxyl group, ethyoxyl, propoxyl group etc. can be included.

R³¹And R³²It is preferred that it is independently of one another the saturated hydrocarbyl of carbon number 1~3.

As R³³And R³⁴In carbon number 1~4 alkyl, methyl, ethyl, propyl group, butyl, isopropyl, isobutyl can be included Base, sec-butyl, tert-butyl group etc..

As R³³And R³⁴In carbon number 1~4 alkyl alkylthio base, methylsulfanyl, Ethylsulfanyl, third can be included Base sulfanyl, butyl sulfanyl and isopropyl sulfanyl etc..

As R³³And R³⁴In carbon number 1~4 alkyl sulphonyl, methyl sulphonyl, ethylsulfonyl, third can be included Base sulfonyl, butyl sulfonyl and isopropelsulfonyl etc..

As R³³And R³⁴, the alkyl of preferably-COOM or carbon number 1~4, more preferably-COOM or methyl.In addition, R³³And R³⁴ In the case of for-COOM, preferably-COOM is incorporated into meta or para position relative to the carbon atom combined with N.

P and q preferably 0~2 integer, preferably 1 or 2.

But, the compound represented by formula (Ib) preferably meets at least one in necessary condition (ib)~(ivb), preferably Meet at least one in necessary condition (ib), (iib), (ivb).

(iib)R³³And R³⁴In at least one be-COOM.

(ivb)R³¹For the saturated hydrocarbyl of the carbon number 3~20 with-COOM, R³³For the full of the carbon number 1~20 with-COOM And alkyl.

M is particularly preferably hydrogen atom.

In necessary condition (iib), preferably R³³And R³⁴All it is-COOM.

In necessary condition (ivb), R³³The preferably saturated hydrocarbyl of the carbon number 3~20 with-COOM, R³³And R³⁴More preferably For the saturated hydrocarbyl of the carbon number 3~10 with-COOM.

As compound (I), such as the compound represented by formula (Aa-1)~formula (Aa-52) can be included.

The colored curable resin composition of the present invention is included as colouring agent (A) compound (I), resin (B), polymerization Property compound (C) and polymerization initiator (D).

In the colored curable resin composition of the present invention, relative to the solid constituent of colored curable resin composition Total amount, the containing ratio of compound (I) is preferably 0.1~20 mass %, more preferably 0.5~10 mass %, more preferably 0.5~5 mass %.

＜ colouring agents (A) ＞

Colouring agent (A) can include dyestuff (A1) and pigment (A2) in addition to compound (I).

Dyestuff (A1) is not particularly limited, known dyestuff can be used, such as solvent dye, acid dye can be included Material, direct dyes, mordant dye etc..As dyestuff, such as colour index (The Society of Dyers and can be included Colourists is published) in be categorized as there is tone beyond pigment the compound of material, remember in dyeing notes (Se Ran societies) The known dyestuff carried.In addition, according to chemical constitution, azo dyes, cyanine dyes, triphenhlmethane dye, xanthene can be included Dyestuff, phthalocyanine dye, anthraquinone dye, naphthoquinone dyestuff, quinoneimine dye, methine dyes, azomethine dyes, squaraine dye, Acridine dye, styryl dye, coumarine dye, quinoline dye and nitro dye etc..In these, preferable organic solvent is solvable Property dyestuff.

It should illustrate, compound (I) is included in dyestuff (A1).

Specifically, C.I. solvent yellows 4 can be included and (record of C.I. solvent yellows omitted below, only record sequence number.)、14、 15、23、24、38、62、63、68、82、94、98、99、117、162、163、167、189；

C.I. solvent red 45,49,111,125,130,143,145,146,150,151,155,168,169,172,175, 181、207、218、222、227、230、245、247；

C.I. solvent orange 2,7,11,15,26,56,77,86；

C.I. solvent violet 11,13,14,26,31,36,37,38,45,47,48,51,59,60；

C.I. solvent blue 4,5,14,18,35,36,37,45,58,59,59：1、63、67、68、69、70、78、79、83、 90、94、97、98、100、101、102、104、105、111、112、122、128、132、136、139；

C.I. the green C.I. solvent dyes such as 1,3,4,5,7,28,29,32,33,34,35 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, 4,8,14,17,18,26,27,29,31,33,34,35,37,40,42,44,50,51,52, 57、66、73、76、80、87、88、91、92、94、95、97、98、103、106、111、114、129、133、134、138、143、 145、150、151、155、158、160、172、176、182、183、195、198、206、211、215、216、217、227、228、 249、252、257、258、260、261、266、268、270、274、277、280、281、289、308、312、315、316、339、 341、345、346、349、382、383、388、394、401、412、417、418、422、426；

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, 7,9,15,16,17,19,21,23,24,25,30,34,38,49,72,102；

C.I. Blue VRS, 3,5,7,9,11,13,15,17,18,22,23,24,25,26,27,29,34,38,40,41, 42、43、45、48、51、54、59、60、62、70、72、74、75、78、80、82、83、86、87、88、90、90：1、91、92、93、 93：1、96、99、100、102、103、104、108、109、110、112、113、117、119、120、123、126、127、129、 130、131、138、140、142、143、147、150、151、154、158、161、166、167、168、170、171、175、182、 183、184、187、192、199、203、204、205、210、213、229、234、236、242、243、256、259、267、269、 278、280、285、290、296、315、324：1、335、340；

C.I. acid green 1,3,5,6,7,8,9,11,13,14,15,16,22,25,27,28,41,50,50：1、58、63、 65th, the C.I. acid dyes such as 80,104,105,106,109,

C.I. directly Huang 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98, 102、108、109、129、136、138、141；

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

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

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

C.I. directly indigo plant 1,2,3,6,8,15,22,25,28,29,40,41,42,47,52,55,57,71,76,77,78, 80、81、84、85、86、90、93、94、95、97、98、99、100、101、106、107、108、109、113、114、115、117、 119、120、137、149、150、153、155、156、158、159、160、161、162、163、164、165、166、167、168、 170、171、172、173、188、189、190、192、193、194、195、196、198、199、200、201、202、203、207、 209、210、212、213、214、222、225、226、228、229、236、237、238、242、243、244、245、246、247、 248、249、250、251、252、256、257、259、260、268、274、275、293；

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 51,54,76；

C.I. disperse violet 26,27；

C.I. the C.I. disperse dyes such as disperse blue 1,14,56,60,

C.I. alkali red 1:1,10；

C.I. alkali blue 1,3,5,7,9,19,21,22,24,25,26,28,29,40,41,45,47,54,58,59,60, 64、65、66、67、68、81、83、88、89；

C.I. alkalescence purple 2；

C.I. alkaline red 9；

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 of active red 36 C.I. reactive dye

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

C.I. mordant rouge 1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,27,29,30,32,33, 36、37、38、39、41、42、43、45、46、48、52、53、56、62、63、71、74、76、78、85、86、88、90、94、95；

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 1,1：1、2、3、4、5、6、7、8、10、11、14、15、16、17、18、19、21、22、23、24、27、 28、30、31、32、33、36、37、39、40、41、44、45、47、48、49、53、58；

C.I. mordant dyeing indigo plant 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39, 40、41、43、44、48、49、53、61、74、77、83、84；

C.I. the C.I. such as viridon 1,3,4,5,10,13,15,19,21,23,26,29,31,33,34,35,41,43,53 Mordant dye,

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

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

In dyestuff (A1), relative to dyestuff (A1) total amount, the containing ratio of compound (I) is preferably 1~99 mass %, more Preferably 30~90 mass %, more preferably 40~80 mass %.

Dyestuff (A1) preferably comprises anthraquinone dye (Ad).

As anthraquinone dye (Ad), known material can be used.As anthraquinone dye (Ad), such as can include

C.I. solvent yellow 117 (record of C.I. solvent yellows omitted below, only records sequence number.)、163、167、189、

C.I. solvent orange 77,86,

C.I. solvent red 111,143,145,146,150,151,155,168,169,172,175,181,207,222, 227、230、245、247、

C.I. solvent violet 11,13,14,26,31,36,37,38,45,47,48,51,59,60,

C.I. solvent blue 19 4,18,35,36,45,58,59,59：1、63、68、69、78、79、83、94、97、98、100、 101、102、104、105、111、112、122、128、132、136、139、

C.I. solvent green 3,28,29,32,33,

C.I. acid red 80,

C.I. ACID GREEN 25,27,28,41,

C.I. acid violet 34,

C.I. acid blue 25,27,40,45,78,80,112

C.I. disperse yellow 51,

C.I. disperse violet 26,27,

C.I. disperse blue 1,14,56,60,

C.I. directly indigo plant 40,

C.I. mordant rouge 3,11,

C.I. mordant dyeing indigo plant 8

Deng.Anthraquinone dye (Ad) preferably dissolves in organic solvent, more preferably the anthraquinone dye of cyan, purple or red.

In these, as anthraquinone dye (Ad), the compound (hereinafter sometimes referred to " compound preferably represented by formula (1d) (1d)”。)。

[in formula (1d), R⁹¹And R⁹²Independently of one another represent hydrogen atom, can have substituent carbon number 1~10 aliphatic Alkyl, can have substituent carbon number 3~10 alicyclic type hydrocarbon or by formula (1d ')

(in formula (1d '), R⁹³Represent alkyl, the halogen atom ,-SO of carbon number 1~6₃H、-CO₂H、-CO₂R⁹⁴、-NHCOR⁹⁴、- SO₃R⁹⁴Or-SO₂NR⁹⁴R⁹⁵。

R⁹⁴Represent carbon number 1~10 aliphatic alkyl or carbon number 3~10 alicyclic type hydrocarbon, the aliphatic alkyl or Contained hydrogen atom can be substituted by halogen atom, hydroxyl or amino in alicyclic type hydrocarbon.

R⁹⁵Represent hydrogen atom, the saturated hydrocarbyl of carbon number 1~10.

R represents 0~5 integer.In the case that r is more than 2, multiple R⁹³Can be with identical, also can be different.

X⁹¹Represent the alkylidene of singly-bound or carbon number 1~6.)

The group of expression.]

Compound (1d) has-SO₃H and/or-CO₂In the case of H, they can be with forming salt (such as Na salt, K salt).

In R⁹¹And R⁹²、R⁹⁴And R⁹⁵In, as the aliphatic alkyl of carbon number 1~10, such as methyl, ethyl, third can be included Base, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, new penta Base, 2- ethylhexyls etc..

The substituent that can have as these aliphatic alkyls, hydroxyl, halogen atom or amino etc. can be included, preferably Hydroxyl or halogen atom.

As by R⁹¹、R⁹²And R⁹⁴The alicyclic type hydrocarbon of the carbon number 3~10 of expression, can include cyclopropyl, cyclopenta, ring Hexyl, suberyl, cyclooctyl, tricyclodecyl etc..

The substituent that can have as these alicyclic type hydrocarbons, hydroxyl, halogen atom or amino etc., preferably hydroxyl can be included Base or halogen atom.

As by R⁹³The alkyl of the carbon number 1~6 of expression, for example, can include methyl, ethyl, propyl group, butyl, amyl group, oneself Base, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, neopentyl etc..

It is used as-CO₂R⁹⁴, methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, own oxygen can be included Base carbonyl and eicosane epoxide carbonyl etc..

It is used as-NHCOR⁹⁴, N- acetyl-aminos, N- propanoylaminos, N- bytyries amino, N- isobutyryls can be included Amino and N- valeryl amino etc..

It is used as-SO₃R⁹⁴, methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxy sulphur can be included Acyl group, hexyloxy sulfonyl and eicosane epoxide sulfonyl etc..

It is used as-SO₂NR⁹⁴R⁹⁵, N- Methylsulfamoyls, N- ethylsulfamovls, N- propylsulfamovs, N- can be included Isopropylsulfamoyl base, N- Butylsulfamoyls base, N- isobutyl groups sulfamoyl, N- sec-butyls sulfamoyl, N- tert-butyl group ammonia sulphurs Acyl group, N- amyl groups sulfamoyl, N- (1- ethyl propyls) sulfamoyl, N- (1,1- dimethyl propyls) sulfamoyl, N- (1,2- Dimethyl propyl) sulfamoyl, N- (2,2- dimethyl propyls) sulfamoyl, N- (1- methyl butyls) sulfamoyl, N- (2- first Base butyl) sulfamoyl, N- (3- methyl butyls) sulfamoyl, N- Cyclopentylsulfamoyls base, N- cyclohexylsulfamoyls, N- oneself Base sulfamoyl, N- (1,3- dimethylbutyls) sulfamoyl, N- (3,3- dimethylbutyls) sulfamoyl, N- heptyl sulfonamides Base, N- (1- methylhexyls) sulfamoyl, N- (1,4- dimethyl amyl groups) sulfamoyl, N- octyl groups sulfamoyl, N- (2- ethyls Hexyl) sulfamoyl, N- (1,5- dimethyl) hexyl sulfamoyl, N- (1,1,2,2- tetramethyl butyls) sulfamoyl, N- (5- Aminopentyl) N-1 such as sulfamoyl substitution sulfamoyls；N, N- DimethylsuIfamoyl, N, N- ethyl-methyls sulfamoyl, N, N- diethyl aminos sulfonyl, N, N- hydroxypropyl methyls sulfamoyl, N, N- isopropyl methyls sulfamoyl, N, N- tert-butyl methyl Sulfamoyl, N, N- butyl ethyls sulfamoyl, N, N- double (1- methyl-propyls) sulfamoyl, N, N- hept-ylmethyl sulfamoyls Deng N, N-2 substitution sulfamoyls etc..

X⁹¹In, as the alkylidene of carbon number 1~6, methylene, ethylidene, propane -1,3- diyl, propane -1 can be included, 2- diyls, butane -1,4- diyls, pentane -1,5- diyls, hexane -1,6- diyls, ethane -1,1- diyls, butane -1,3- diyls, 2- methylpropane -1,3- diyls, 2- methylpropane -1,2- diyls, pentane -1,4- diyls, 2- methybutane -1,4- diyls etc..

As R⁹³, preferably can alkyl ,-SO with the carbon number 1~5 of hydroxyl₃R⁹⁴、-SO₂NR⁹⁴R⁹⁵, more preferably- SO₂NR⁹⁴R⁹⁵, further preferred-SO₂NHR⁹⁴(in various, R⁹⁴And R⁹⁵It is as defined above).

As compound (1d), such as the compound represented by formula (3-1)~formula (3-11) can be included.

As anthraquinone dye (Ad), the compound preferably represented by formula (1d) and R⁹¹And R⁹²For hydrogen atom, carbon number 1~5 Alkyl, can have halogen atom phenyl and by formula (1d ') represent group the compound of any one, more preferably by formula The compound that (3-4) and formula (3-11) represent.

In the case of comprising anthraquinone dye (Ad), relative to dyestuff (A1) total amount, its containing ratio is preferably 1~99 matter Measure %, more preferably more preferably 10~70 mass %, 20~60 mass %.

As pigment (A2), it is not particularly limited, known pigment can be used, such as colour index (The can be included Society of Dyers and Colourists are published) in be categorized as the pigment of pigment.

As pigment, for example, can include C.I. pigment yellows 1,3,12,13,14,15,16,17,20,24,31,53,83, 86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、166、173、194、214 Deng yellow uitramarine；

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

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

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..

As pigment, preferably C.I. pigment blue 15s, 15：3、15：4、15：6th, the green pigment such as 60；C.I. pigment violet 1,19, 23rd, the violet pigment such as 29,32,36,38, more preferably C.I. pigment blue 15s：3、15：6 and C.I. pigment Violet 23s, further preferably C.I. pigment blue 15：6.By the way that comprising above-mentioned pigment, the optimization of transmitted spectrum is easy, the light resistance and chemically-resistant of colour filter Moral character becomes good.

For pigment, resin treatment can be implemented as needed, make use of the pigment for having imported acidic-group or basic group The surface treatment of derivative etc., using the grafting processing to surface of pigments such as high-molecular compound, using sulfuric acid particles method Deng micronized processing or for by impurity remove using the cleaning treatment of organic solvent, water etc., using ion-exchange Deng ionic impurity removing processing etc..

Pigment preferable particle size is homogeneous.By carrying out decentralized processing containing pigment dispersing agent, so as to obtain pigment molten The dispersible pigment dispersion of uniformly dispersing state in liquid.

As above-mentioned pigment dispersing agent, such as cation system, anion system, nonionic system, both sexes, polyester can be included Surfactant of system, more amine systems, acrylic acid series etc. etc..These pigment dispersing agents can be used alone, also can be by two or more group Close and use.As pigment dispersing agent, represented with trade name, KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), フローレ can be included Application (common prosperity society chemistry (strain) manufacture), ソ Le スパース (ゼネカ (strain) manufactures), EFKA (manufacture of CIBA companies), アジスパー (aginomoto Off ァイ Application テ Network ノ (strain) manufactures), Disperbyk (manufacture of Bi Ke chemical companies) etc..

In the case of using pigment dispersing agent, relative to pigment (A2) total amount, its usage amount is preferably more than 1 mass % And 100 below mass %, more preferably more than 5 mass % and below 50 mass %.If the usage amount of pigment dispersing agent is upper In the range of stating, then the tendency for the dispersible pigment dispersion for obtaining homogeneous dispersity be present.

In colouring agent (A), the content ratio (dyestuff (A1)/pigment (A2)) of dyestuff (A1) and pigment (A2) is with quality criteria Count, usually 1/99~99/1, preferably 3/97~40/60, more preferably 5/95~30/70.

Relative to the total amount of solid constituent, the containing ratio of colouring agent (A) is preferably 5~60 mass %, and more preferably 8~55 Quality %, more preferably 10~50 mass %.If colour filter is made in above-mentioned scope in the containing ratio of colouring agent (A) Colour saturation during device is abundant, and in composition can the resin containing necessary amount, polymerizable compound, therefore machine can be formed The sufficient pattern of tool intensity.Wherein, " total amount of solid constituent " in this specification refers to from colored curable resin composition Total amount in the content of solvent is removed after amount.The content of the total amount of solid constituent and each composition relative to it, such as can Enough using analysis means measure known to liquid chromatogram or gas-chromatography etc..

＜ resins (B) ＞

Resin (B) is not particularly limited, preferably alkali soluble resin.As resin (B), following tree can be included Fat [K1]~[K6] etc..

Resin [K1]：With (having below from least one (a) selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides When be referred to as " (a) ") construction unit with from the ring-type ether structure of carbon number 2~4 and the monomer (b) of ethylenic unsaturated bond The copolymer of the construction unit of (hereinafter sometimes referred to " (b) ")；

Resin [K2]：With the construction unit from (a) and the construction unit from (b) and from can with (a) be copolymerized Monomer (c) is (but, different from (a) and (b).) (hereinafter sometimes referred to " (c) ") construction unit copolymer；

Resin [K3]：Copolymer with the construction unit from (a) with the construction unit from (c)；

Resin [K4]：Structure list with the construction unit for making (b) and the construction unit addition from (a) and from (c) The copolymer of member；

Resin [K5]：Structure list with the construction unit for making (a) and the construction unit addition from (b) and from (c) The copolymer of member；

Resin [K6]：With make (a) with from (b) construction unit addition so that make the construction unit of carboxylic acid anhydrides addition With the copolymer of the construction unit from (c).

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..

(b) the ring-type ether structure for for example referring to have carbon number 2~4 is (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) preferably there is the ring of carbon number 2~4 The monomer of shape ether 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), such as the monomer (b1) with epoxy ethyl and ethylenic unsaturated bond can be enumerated (hereinafter sometimes referred to " (b1) "), the monomer (b2) (hereinafter sometimes referred to " (b2) ") with oxetanylmethoxy and ethylenic unsaturated bond, with tetrahydrochysene furan Mutter monomer (b3) (hereinafter sometimes referred to " (b3) ") of base and ethylenic unsaturated bond etc..

As (b1), such as the knot that the unsaturated aliphatic hydrocarbon with straight-chain or branch's chain state is at least partially epoxidized can be included The monomer of the monomer (b1-1) (hereinafter sometimes referred to " (b1-1) ") of structure, the structure being at least partially epoxidized with ester ring type unsaturated hydrocarbons (b1-2) (hereinafter sometimes referred to " (b1-2) ").

As (b1-1), can enumerate (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, It is (methyl) propenoic acid beta-ethyl glycidyl ester, glycidyl vinyl ether, o- vinylbenzyl glycidyl base ether, m- Vinylbenzyl glycidyl base ether, p- vinylbenzyl glycidyl base ether, Alpha-Methyl-o- vinylbenzyl glycidyl Base ether, Alpha-Methyl-m- vinylbenzyl glycidyl base ether, Alpha-Methyl-p- vinylbenzyl glycidyl base ether, 2,3- are double Double (glycidoxypropyl methyl) styrene of (glycidoxypropyl methyl) styrene, 2,4-, double (the glycidoxypropyl first of 2,5- Base) styrene, 2,6- double (glycidoxypropyl methyl) styrene, 2,3,4- tri- (glycidoxypropyl methyl) styrene, 2, 3,5- tri- (glycidoxypropyl methyl) styrene, 2,3,6- tri- (glycidoxypropyl methyl) styrene, 3,4,5- tri- (shrink Glycerine epoxide methyl) styrene, 2,4,6- tri- (glycidoxypropyl methyl) styrene etc..

As (b1-2), can include vinylcyclohexene monoxide, 1,2- epoxy -4- vinyl cyclohexanes (for example, セロキサイド2000；(strain) Daicel manufacture), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates are (for example, サイ Network ロマーA400；(strain) Daicel manufacture), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates are (for example, サイ Network ロマー M100；(strain) Daicel manufactures), the compound represented by formula (BI) and the compound etc. represented by formula (BII).

[in formula (BI) and formula (BII), R^aAnd R^bRepresent the alkyl of hydrogen atom or carbon number 1~4, contained hydrogen in the alkyl Atom can be optionally substituted by a hydroxyl group.

X^aAnd X^bRepresent singly-bound, *-R^c-, *-R^c- O-, *-R^c- S- or *-R^c-NH-。

R^cRepresent the alkylidene of carbon number 1~6.

* the bonding end with O is represented.]

As the alkyl of carbon number 1~4, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tertiary fourth can be included Base etc..

The alkyl being optionally substituted by a hydroxyl group as hydrogen atom, hydroxymethyl, 1- hydroxyethyls, 2- hydroxyethyls, 1- can be included Hydroxypropyl, 2- hydroxypropyls, 3- hydroxypropyls, 1- hydroxyl -1- Methylethyls, 2- hydroxyl -1- Methylethyls, 1- hydroxyl fourths Base, 2- hydroxybutyls, 3- hydroxybutyls, 4- hydroxybutyls etc..

As R^aAnd R^b, hydrogen atom, methyl, hydroxymethyl, 1- hydroxyethyls, 2- hydroxyethyls can be preferably included, more Hydrogen atom, methyl can preferably be included.

As alkylidene, methylene, ethylidene, propane -1,2- diyl, propane -1,3- diyl, butane -1 can be included, 4- diyls, pentane -1,5- diyls, hexane -1,6- diyls etc..

As X^aAnd X^b, can preferably include singly-bound, methylene, ethylidene, *-CH₂- O- and *-CH₂CH₂- O-, it is more excellent Choosing can include singly-bound, *-CH₂CH₂- O- (* represents the bonding end with O).

As the compound represented by formula (BI), it can include what is represented by any one of formula (BI-1)~formula (BI-15) Compound etc..Wherein, preferably by formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) or formula (BI-11)~ The compound that formula (BI-15) represents, the chemical combination more preferably represented by formula (BI-1), formula (BI-7), formula (BI-9) or formula (BI-15) Thing.

As the compound represented by formula (BII), any one expression by formula (BII-1)~formula (BII-15) can be included Compound etc..Wherein, preferably by formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formula (BII-11) compound that~formula (BII-15) represents, more preferably by formula (BII-1), formula (BII-7), formula (BII-9) or formula (BII-15) compound represented.

The compound represented by formula (BI) and the compound represented by formula (BII) can each be used alone, also can be by 2 It is used in combination more than kind.In the case of the compound that will be represented by formula (BI) and the compound and use that are represented by formula (BII), they contain There is the ratio [compound represented by formula (BI)：The compound represented by formula (BII)] represented with molar basis, preferably 5：95~ 95：5, more preferably 20：80~80：20.

As (b2), the monomer more preferably with oxetanylmethoxy He (methyl) acryloxy.As (b2), can enumerate Go out 3- methyl -3- methacryloxymethyls oxetanes, 3- methyl -3- acryloyloxymethyls oxetanes, 3- Ethyl -3- methacryloxymethyls oxetanes, 3- ethyl -3- acryloyloxymethyls oxetanes, 3- methyl - 3- methacryloxyethyls oxetanes, 3- methyl -3- acryloyl-oxyethyls oxetanes, 3- ethyl -3- first Base acryloyl-oxyethyl oxetanes, 3- ethyl -3- acryloyl-oxyethyl oxetanes etc..

As (b3), the monomer more preferably with tetrahydrofuran base He (methyl) acryloxy.As (b3), specifically Ground, tetrahydrofurfuryl acrylate (for example, Viscoat V#150, Osaka Organic Chemical Industry (strain) manufacture), metering system can be enumerated Sour tetrahydrochysene chaff ester etc..

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 preferably (b1).And then in terms of the excellent storage stability of colored curable resin composition, more preferably (b1-2).

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 Bicyclic [2.2.1] hept-2-ene" of base -5- methyl bicycles [2.2.1] hept-2-ene", 5- t-butoxy carbonyls, 5- cyclohexyloxy carbonyls Bicyclic [2.2.1] hept-2-ene" of bicyclic [2.2.1] hept-2-ene", 5- phenyloxycarbonyls, 5,6- double (t-butoxy carbonyls) are bicyclic The bicyclic unsaturated compound classes such as double (cyclohexyloxy carbonyl) bicyclic [2.2.1] hept-2-ene"s of [2.2.1] hept-2-ene", 5,6-；

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, N- phenyl horses Come acid imide, N- N-cyclohexylmaleimides, N- benzyl maleimides, bicyclic [2.2.1] hept-2-ene" etc..

In resin [K1], the ratio of the construction unit from each monomer, the entire infrastructure unit of resin [K1] is being formed In, it is preferably

Construction unit from (a)：2~60 moles of %

Construction unit from (b)：40~98 moles of %,

More preferably

Construction unit from (a)：10~50 moles of %

Construction unit from (b)：50~90 moles of %.

If there is colored curable resin composition in the ratio of the construction unit of resin [K1] in above-mentioned scope The tendency of the excellent solvent resistance of developability and obtained colour filter when storage stability, formation colored pattern.

Resin [K1] 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 make Make.

Specifically, ormal weight, polymerization initiator and the solvent of (a) and (b) etc. are fitted into reaction vessel, for example, using nitrogen Oxygen is replaced, so as to form deoxidizing atmosphere, heating while stirring and the method being incubated.It should illustrate, for as used herein poly- Close initiator and solvent etc. to be not particularly limited, material usually used in the field can be used.For example, trigger as polymerization Agent, azo-compound (2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2,4- methyl pentane nitrile) etc.), organic peroxy can be enumerated Compound (benzoyl peroxide etc.), as solvent, as long as each monomer is dissolved, the colored curable resin as the present invention The solvent (E) of composition, can enumerate solvent described later etc..

It should illustrate, for obtained copolymer, reacted solution can be used as former state, it is possible to use concentration or dilution Solution, it is possible to use using the methods of reprecipitation as solid (powder) take out product.Especially, during the polymerization, as Solvent, contained solvent in the colored curable resin composition by using the present invention can as former state will be reacted molten Liquid uses in the modulation of the colored curable resin composition of the present invention, therefore can make the colored curable resin of the present invention The manufacturing process of composition simplifies.

In resin [K2], the ratio of the construction unit from each monomer, the entire infrastructure unit of resin [K2] is being formed In, it is preferably

Construction unit from (a)：2~45 moles of %

Construction unit from (b)：2~95 moles of %

Construction unit from (c)：1~65 mole of %,

More preferably

Construction unit from (a)：5~40 moles of %

Construction unit from (b)：5~80 moles of %

Construction unit from (c)：5~60 moles of %.

If there is colored curable resin composition in the ratio of the construction unit of resin [K2] in above-mentioned scope Solvent resistance, heat resistance and the mechanical strength of developability and obtained colour filter when storage stability, formation colored pattern Excellent tendency.

Resin [K2] can for example manufacture in the same manner as the method for the manufacture method record as resin [K1].

In resin [K3], the ratio of the construction unit from each monomer, the entire infrastructure unit of resin [K3] is being formed In, it is preferably

Construction unit from (a)：2~60 moles of %

Construction unit from (c)：40~98 moles of %,

More preferably

Construction unit from (a)：10~50 moles of %

Construction unit from (c)：50~90 moles of %.

Resin [K3] can for example manufacture in the same manner as the method for the manufacture method record as resin [K1].

Resin [K4] by obtaining (a) and (c) copolymer, can make the cyclic ether and (a) of the carbon number 2~4 that (b) have The carboxylic acid and/or the carboxylic acid anhydrides addition that have and manufacture.

First, (a) and (c) copolymer are manufactured in the same manner as the method for the manufacture method record as resin [K1].This Under kind situation, the ratio of the construction unit from each monomer is preferably the ratio identical ratio with being enumerated in resin [K3].

Next, make the cyclic ether of the carbon number 2~4 that (b) have and the carboxylic acid in above-mentioned copolymer from (a) and/or The part reaction of carboxylic acid anhydrides.

Then (a) and the copolymer of (c) manufacture, is replaced into air, by (b), carboxylic acid or carboxylic by atmosphere in flask by nitrogen The catalysts of acid anhydrides and cyclic ether (such as three (dimethylaminomethyl) phenol etc.) and polymerization inhibitor (such as quinhydrones etc.) etc. Load in flask, for example, being reacted 1~10 hour at 60~130 DEG C, so as to manufacture resin [K4].

Relative to 100 moles of (a), preferably 5~80 moles, more preferably 10~75 moles of the usage amount of (b).By making it For the scope, the developability when storage stability of colored curable resin composition be present, forming pattern and obtained figure The solvent resistance of case, heat resistance, the balance of mechanical strength and sensitivity become good tendency.Because the reactivity of cyclic ether is high, Unreacted (b) is not easy remaining, therefore as (b) for resin [K4], preferably (b1), more preferably (b1-1).

Relative to (a), (b) and (c) mass parts of total amount 100, the usage amounts preferably 0.001 of above-mentioned catalysts~ 5 mass parts.Relative to the mass parts of total amount 100 of (a), (b) and (c), usage amount preferably 0.001~5 matter of above-mentioned polymerization inhibitor Measure part.

For reaction conditions such as feed process, reaction temperature and times, it can be considered that heat release caused by manufacturing equipment, polymerization Amount etc. suitably adjusts.Further, in the same manner as polymerizing condition, it can be considered that thermal discharge etc. caused by manufacturing equipment, polymerization, suitably Ground adjustment feed process, reaction temperature.

For resin [K5], as the first stage, in the same manner as the manufacture method of above-mentioned resin [K1], obtain (b) With the copolymer of (c).As described above, the copolymer obtained can use reacted solution as former state, it is possible to use concentration Or the solution of dilution, it is possible to use using the product taken out the methods of reprecipitation as solid (powder).

Ratio from (b) He the construction unit of (c), relative to the conjunction for the entire infrastructure unit for forming above-mentioned copolymer Molal quantity is counted, is preferably respectively

Construction unit from (b)：5~95 moles of %

Construction unit from (c)：5~95 moles of %,

More preferably

Construction unit from (b)：10~90 moles of %

Construction unit from (c)：10~90 moles of %.

And then under conditions of same with the manufacture method of resin [K4], by make carboxylic acid that (a) have or carboxylic acid anhydrides with (b) reaction of the cyclic ether from (b) having with the copolymer of (c), so as to obtain resin [K5].

Relative to 100 moles of (b), preferably 5~80 moles of the usage amount with (a) of above-mentioned copolymer reaction.Due to ring The reactivity of shape ether is high, and unreacted (b) is not easy remaining, therefore as (b) for being used for resin [K5], preferably (b1), more preferably (b1-1)。

Resin [K6] is carboxylic acid anhydrides is reacted the resin formed with resin [K5].Make carboxylic acid anhydrides with by cyclic ether with Hydroxyl reaction caused by the reaction of carboxylic acid or carboxylic acid anhydrides.

As carboxylic acid anhydrides, maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acids acid anhydride, 4- can be included Vinylphthalic acid acid anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl four Bicyclic [2.2.1] hept-2-ene" acid anhydride of hydrogen phthalic anhydride, 5,6- dicarboxyls etc..Relative to 1 mole of the usage amount of (a), carboxylic acid anhydrides Preferably 0.5~1 mole of usage amount.

As resin (B), specifically, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates/(methyl) propylene can be included Acid copolymer, the ring [5.2.1.0 of acrylic acid 3,4- epoxies three^2.6] resin [K1] such as last of the ten Heavenly stems ester/(methyl) acrylic copolymer；(first Base) acrylic acid/ring [5.2.1.0 of (methyl) acrylic acid 3,4- epoxies three^2.6] last of the ten Heavenly stems ester/vinyl toluene copolymer, (methyl) propylene Acid glycidyl ester/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/benzene second Alkene/(methyl) acrylic copolymer, the ring [5.2.1.0 of acrylic acid 3,4- epoxies three^2.6] last of the ten Heavenly stems ester/(methyl) acrylic acid/N- cyclohexyl Maleimide copolymer, 3- methyl -3- (methyl) acryloyloxymethyls oxetanes/(methyl) acrylic/styrene The resins such as copolymer [K2]；(methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) acrylic acid copolymer The resins such as thing [K3]；(methyl) glycidyl acrylate is set to add with (methyl) benzyl acrylate/(methyl) acrylic copolymer Into into resin, make (methyl) glycidyl acrylate and (methyl) acrylic acid tricyclodecyl/styrene/(methyl) propylene Resin that acid copolymer addition forms, make (methyl) glycidyl acrylate and (methyl) acrylic acid tricyclodecyl/(methyl) The resins [K4] such as the resin that benzyl acrylate/(methyl) acrylic copolymer addition forms；Make (methyl) acrylic acid and (methyl) Resin that the copolymer reaction of acrylic acid tricyclodecyl/(methyl) glycidyl acrylate forms, make (methyl) acrylic acid with Resin that the copolymer reaction of (methyl) acrylic acid tricyclodecyl/styrene/(methyl) glycidyl acrylate forms etc. is set Fat [K5]；Make the copolymer of (methyl) acrylic acid and (methyl) acrylic acid tricyclodecyl/(methyl) glycidyl acrylate anti- Resins [K6] such as the resin that the resin that should be formed further forms with tetrabydrophthalic anhydride reaction etc..

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

The weight average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000~100,000, more preferably 5,000~ 50,000, more preferably 5,000~30,000.If in above-mentioned scope, there is the hardness of colour filter in molecular weight Improve, the tendency that residual film ratio is high, unexposed portion is improved for the favorable solubility of developer solution, the resolution ratio of colored pattern.

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.

In terms of solid constituent conversion, the acid number of resin (B) is preferably 50~170mg-KOH/g, more preferably 60~ 150mg-KOH/g, more preferably 70~135mg-KOH/g.Here, acid number is as the hydrogen neutralized needed for resin (B) 1g The value of amount (mg) measure of potassium oxide, for example, can be titrated and be obtained by using potassium hydroxide aqueous solution.

Relative to the total amount of solid constituent, the containing ratio of resin (B) is preferably 7~65 mass %, and more preferably 13~60 Quality %, more preferably 17~55 mass %.If the containing ratio of resin (B) can be formed in above-mentioned scope Colored pattern, and the resolution ratio of colored pattern and the tendency of residual film ratio raising be present.

＜ polymerizable compounds (C) ＞

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

Wherein, polymerizable compound (C) is preferably the polymerizable compound with the ethylenic unsaturated bond of more than 3.Make For such polymerizable compound, such as trimethylolpropane tris (methyl) acrylate, (first of pentaerythrite three can be included Base) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, the four seasons penta 4 Alcohol ten (methyl) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2- (methyl) acryloyl-oxyethyl) isocyanides Urea acid esters, glycol-modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylic acid Ester, propylene glycol modified pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, oneself Lactone-modified pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc..

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

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

Relative to the total amount of solid constituent, the containing ratio of polymerizable compound (C) is preferably 7~65 mass %, more preferably For 13~60 mass %, more preferably 17~55 mass %.If the containing ratio of polymerizable compound (C) is in above-mentioned model Enclose the tendency that the chemical-resistant of residual film ratio and colour filter interior, when colored pattern formation be present improves.

＜ polymerization initiators (D) ＞

Polymerization initiator (D) triggers polymerization as long as living radical, acid etc. can be produced using light, hot effect Compound, then be not particularly limited, known polymerization initiator can be used.Trigger as the polymerization for producing living radical Agent, for example, can include alkyl phenyl assimilation compound, triaizine compounds, acylphosphine oxide compound, O- acyl groups oxime compound and United imidazole.

Above-mentioned O- acyl groups oxime compound is the compound with the part-structure represented by formula (d1).Hereinafter, * represents key Close end.

As above-mentioned O- acyl groups oxime compound, such as N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) can be included Butane -1- ketone -2- imines, N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) octane -1- ketone -2- imines, N- benzoxies Base -1- (4- Phenylsulfanyls phenyl) -3- cyclopenta propane -1- ketone -2- imines, N- acetoxyl groups -1- [9- ethyls -6- (2- first Base benzoyl) -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- { 2- methyl -4- (3,3- bis- Methyl -2,4- dioxolyl methoxyl group) benzoyl -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -3- cyclopenta propane -1- imines, N- benzoyloxys -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -3- cyclopenta propane -1- ketone -2- imines etc..It can be used The commercially available products such as IRGACURE OXE01, OXE02 (being manufactured above for BASF AG), N-1919 (ADEKA Corp.'s manufacture).Its In, O- acyl group oxime compounds are preferably selected from N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) butane -1- ketone -2- imines, N- Benzoyloxy -1- (4- Phenylsulfanyls phenyl) octane -1- ketone -2- imines and N- benzoyloxys -1- (4- Phenylsulfanyls Phenyl) at least one kind of in -3- cyclopenta propane -1- ketone -2- imines, more preferably N- benzoyloxys -1- (4- Phenylsulfanyls Phenyl) octane -1- ketone -2- imines.If these O- acyl group oxime compounds, it is intended to obtain the colour filter of high brightness.

Abovementioned alkyl phenyl ketone compound is with the part-structure represented by formula (d2) or the part represented by formula (d3) The compound of structure.In these part-structures, phenyl ring can have substituent.

As the compound with the part-structure represented by formula (d2), such as 2- methyl -2- morpholinoes -1- can be included (4- methylsulfanyls phenyl) propane -1- ketone, 2- dimethylaminos -1- (4- morphlinophenyls) -2- benzyl butane -1- ketone, 2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] butane -1- ketone etc..It can be used IRGACURE 369,907,379 (being manufactured above for BASF AG) etc. commercially available product.

As the compound with the part-structure represented by formula (d3), such as 2- hydroxy-2-methyl -1- benzene can be included Base propane -1- ketone, 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] propane -1- ketone, 1- hydroxycyclohexylphenyls Oligomer, the α of ketone, 2- hydroxy-2-methyls -1- (4- isopropenyls phenyl) propane -1- ketone, α-diethoxy acetophenone, benzene are even Acyl dimethyl ketal etc..

In terms of sensitivity, as alkyl phenyl assimilation compound, preferably there is the change of the part-structure represented by formula (d2) Compound.

As above-mentioned triaizine compounds, such as double (the trichloromethyl) -6- (4- methoxyphenyls) -1,3 of 2,4- can be included, Double (trichloromethyl) -6- (4- methoxyl groups the naphthyl) -1,3,5- triazines of 5- triazines, 2,4-, double (the trichloromethyl) -6- peppers of 2,4- Double (trichloromethyl) -6- (4- the methoxyl-styrenes) -1,3,5- triazines of base -1,3,5- triazines, 2,4-, double (three chloromethanes of 2,4- Base) -6- [2- (5- methylfuran -2- bases) vinyl] -1,3,5- triazines, double (trichloromethyl) -6- [2- (furans -2- of 2,4- Base) vinyl] -1,3,5- triazines, double (the trichloromethyl) -6- [2- (4- diethylamino -2- aminomethyl phenyls) vinyl] of 2,4- - Double (trichloromethyl) -6- [2- (3,4- Dimethoxyphenyls) vinyl] -1,3,5- triazines of 1,3,5- triazines, 2,4- etc..

As above-mentioned acylphosphine oxide compound, TMDPO etc. can be included. The commercially available products such as IRGACURE (registration mark) 819 (BASF AG's manufacture) can be used.

As above-mentioned united imidazole, such as 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5 can be included, 5 '-tetraphenyl connection Imidazoles, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (for example, referring to Japanese Unexamined Patent Publication 6-75372 Number 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) bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline (examples Such as, with reference to Japanese Patent Publication 48-38403 publications, Japanese Unexamined Patent Application 62-174204 publications etc..), 4,4 ', 5,5 '-position The imidazolium compounds that phenyl is substituted by alkoxy carbonyl group is (for example, referring to Japanese Unexamined Patent Publication 7-10913 publications etc..) etc..

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..These preferably polymerize with described later Auxiliary agent (D1) (particularly amine) is triggered to be applied in combination.

As acid agent, such as the p- toluene fulfonate of 4- hydroxy phenyl dimethyl sulfoniums, 4- hydroxy phenyl diformazans can be included Base sulfonium hexafluoro antimonate, the p- toluene fulfonate of 4- acetoxyl group phenyl dimethyl sulfoniums, 4- acetoxyl group phenyl methyl benzyls sulfonium six The p- toluene fulfonate of fluorine antimonate, triphenylsulfonium, triphenylsulfonium hexafluoro antimonate, the p- toluene fulfonate of diphenyl iodine, two The salts such as phenyl-iodide hexafluoro antimonate, nitrobenzyl tosylat class, benzoin tosylate class etc..

As polymerization initiator (D), preferably comprise selected from alkyl phenyl assimilation compound, triaizine compounds, acylphosphine oxide The polymerization initiator of at least one of compound, O- acyl groups oxime compound and united imidazole, more preferably comprising O- acyl groups The polymerization initiator of oxime compound.

It is excellent relative to the mass parts of total amount 100 of resin (B) and polymerizable compound (C), the content of polymerization initiator (D) Elect 0.1~30 mass parts, more preferably 1~20 mass parts as.If the content of polymerization initiator (D) in above-mentioned scope, Then there is the tendency for making its high sensitivity, shortening the time for exposure, therefore the productivity ratio of colour filter improves.

＜ polymerizations trigger auxiliary agent (D1) ＞

Polymerization triggers the polymerization that auxiliary agent (D1) is the polymerizable compound for having triggered polymerization for promotion polymerization initiator Compound or sensitizer.In the case of triggering auxiliary agent (D1) comprising polymerization, generally it is applied in combination with polymerization initiator (D).

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

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

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

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

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

In the case of triggering auxiliary agent (D1) using these polymerizations, relative to adding up to for resin (B) and polymerizable compound (C) 100 mass parts are measured, its content is preferably 0.1~30 mass parts, more preferably 1~20 mass parts.If polymerization triggers auxiliary agent (D1) amount within the range, then further can form colored pattern, the productivity ratio of colour filter is tended to improve with high sensitivity.

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

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 and 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 and methyl anisole etc..

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

As alcoholic solvent, methanol, ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propane diols and sweet can be included Oil etc..

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

As amide solvent, DMF, DMA and N- crassitudes can be included Ketone etc..

In above-mentioned solvent, from the boiling point under coating, drying property aspect, preferably 1atm be more than 120 DEG C And less than 180 DEG C of organic solvent.As solvent, preferably propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl Ether, 3- ethoxyl ethyl propionates, ethylene glycol single methyl ether, diethylene glycol monomethyl ether, carbiphene, 4- hydroxyl -4- first Base -2 pentanone and DMF, more preferably propylene glycol monomethyl ether, 4- hydroxy-4-methyl-2-pentanones, Propylene glycol monomethyl ether, ethyl lactate and 3- ethoxyl ethyl propionates.

Relative to the total amount of the colored curable resin composition of the present invention, the containing ratio of solvent (E) is preferably 70~95 Quality %, more preferably 75~92 mass %.In other words, total containing ratio of the solid constituent of colored curable resin composition is excellent Elect 5~30 mass %, more preferably 8~25 mass % as.If the containing ratio of solvent (E) is in above-mentioned scope, during coating Flatness become good, and when foring colour filter because colour saturation is without deficiency, therefore display characteristic be present and become Good tendency.

＜ levelling agents (F) ＞

As levelling agent (F), silicone based surfactants, fluorine system surfactant can be included and there is fluorine atom Silicone based surfactants etc..These can have polymerizable group in side chain.

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 above-mentioned fluorine system surfactant, surfactant that there is fluorocarbon chain in intramolecular etc. can be included.Tool Body, Off ロラー De (registration mark) FC430, FC431 (Sumitomo 3M (strain) manufactures), (registration of メガ Off ァッ Network can be included Trade mark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (DIC (strain) manufactures), エ Off トップ (registration mark) EF301, EF303, EF351, EF352 (Mitsubishi General Materials electronics chemical conversion (strain) manufacture), サー Off ロ Application (note Volume trade mark) S381, S382, SC101, SC105 (Asahi Glass (strain) manufacture) and E5844 ((strain) ダイキ Application Off ァイ Application ケミカ Manufactured by Le research) etc..

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

In the case of containing levelling agent (F), relative to the total amount of colored curable resin composition, its containing ratio is preferably More than 0.001 mass % and below 0.2 mass %, more preferably more than 0.002 mass % and below 0.1 mass %, further Preferably more than 0.01 mass % and below 0.05 mass %.It should illustrate, above-mentioned pigment dispersing agent is free of in the containing ratio Containing ratio.If the containing ratio of levelling agent (F) in above-mentioned scope, can make the flatness of colour filter become good.

＜ other compositions ＞

The colored curable resin composition of the present invention, as needed, filler, other macromolecule chemical combination can be included Known additive in the technical fields such as thing, closely sealed accelerator, antioxidant, light stabilizer, chain-transferring agent.

The manufacture method ＞ of ＜ colored curable resin compositions

The colored curable resin composition of the present invention for example can be by by colouring agent (A), resin (B), polymerism Compound (C), polymerization initiator (D) and the solvent (E) used as needed, levelling agent (F) and other compositions are mixed and adjusted System.

In the case of using pigment (A2), preferably mixed in advance with part or all of solvent (E), use ball mill etc. Make it scattered until the average grain diameter of pigment turns into less than 0.2 μm Zuo You.Now, as needed above-mentioned pigment can be coordinated to disperse Part or all of agent, resin (B).By mixing remaining composition in the dispersible pigment dispersion so obtained with as regulation Concentration, the colored curable resin composition of target can be modulated.

For dyestuff (A1), preferably it is dissolved separately in advance in part or all of solvent (E) and modulates solution.It is preferred that The solution is filtered with 0.01~1 μm or so of the filter in aperture.

It is preferred that mixed colored curable 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 colored curable 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 colored curable resin composition is coated on into substrate, Dry and form coloring compositions nitride layer, the method that the coloring compositions nitride layer is exposed and developed via photomask.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.Colored pattern, the coloring film that can make so to be formed turn into the colour filter of the present invention.

The thickness of the colour filter of making is not particularly limited, can suitably be adjusted according to purpose, purposes etc., be, for example, 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, colored curable 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, mercury vapor lamp can be included, lighted 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 colored curable resin composition of the present invention, the especially excellent colour filter of lightness can be manufactured.The colour filter Device can be used as using in display device (for example, liquid crystal display device, organic el device, Electronic Paper etc.) and solid-state imager Colour filter.

Embodiment

It is exemplified below embodiment to further illustrate the present invention, the present invention is not limited by following embodiments certainly, certainly Also it can suitably be changed and implement in the range of purport described later before it can be adapted to, they are included in the skill of the present invention In the range of art.

It should illustrate, below as long as no special instructions, " part " means " mass parts ", and " % " means " quality % ".

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

[embodiment 1]

In the flask with cooling tube and agitating device, the compound (middle tank formation manufacture) 3 represented by formula (X) is added 1.3 parts of part, 21 parts of 1-METHYLPYRROLIDONE and potassium hydroxide, after being stirred at room temperature 1 hour, 2.3 parts of ethyl acrylate is added, Stir at the same temperature 2 hours.Obtained reaction solution is added in 105 parts of 2N hydrochloric acid, has been stirred at room temperature 30 points Clock, as a result crystallization separate out.The crystallization of precipitation is separated by filtration, is fully cleaned with ion exchange water, is dried under reduced pressure, obtains at 60 DEG C 3.5 parts of the compound represented by formula (Aa-1-IM) is arrived.

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

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺675.3

Exact mass：674.3

1 part of the compound represented by formula (Aa-1-IM), methanol 7 are added in the flask with cooling tube and agitating device 3.0 parts of part and 8% sodium hydrate aqueous solution, have been stirred at room temperature 9 and a half hours.Obtained reaction solution is added to 2N hydrochloric acid In 35 parts, it has been stirred at room temperature 30 minutes, as a result crystallization separates out.The crystallization of precipitation is separated by filtration, washed with ion exchange Only, it is dried under reduced pressure at 60 DEG C, has obtained 0.9 part of the compound represented by formula (Aa-1).

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

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺647.5

Exact mass：646.2

[embodiment 2]

The compound (middle tank formation manufacture) 1 represented by formula (X) is added in the flask with cooling tube and agitating device Part, 7 parts of 1-METHYLPYRROLIDONE, 1.0 parts of potassium carbonate and 2.0 parts of 4- bromobutyrates, have been stirred 7 and a half hours at 100 DEG C. After letting cool, 20 parts of 2N hydrochloric acid is added in obtained reaction solution, 45 parts are extracted 2 times with chloroform, and chloroform is laminated together, with full Clean with saline solution, dried with anhydrous magnesium sulfate.Under reduced pressure by solvent distillation, it is dried under reduced pressure, has been obtained by formula at 60 DEG C (Aa-33-IM) 4.1 parts of the compound runic represented.

The identification of the compound represented by formula (Aa-33-IM)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺803.5

Exact mass：802.3

4.1 parts of the compound represented by formula (Aa-33-IM), first are added in the flask with cooling tube and agitating device 3.5 parts of 9.8 parts of alcohol and 8% sodium hydrate aqueous solution, have been stirred at room temperature 6 hours.Obtained reaction solution is added to 2N salt In 30 parts of acid, it has been stirred at room temperature 30 minutes, as a result crystallization separates out.The crystallization of precipitation is separated by filtration, uses ion exchange water Fully clean, be dried under reduced pressure at 60 DEG C, obtained 1.0 parts of the compound represented by formula (Aa-33).

The identification of the compound represented by formula (Aa-33)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺747.5

Exact mass：746.3

[embodiment 3]

The compound (middle tank formation manufacture) 3 represented by formula (X) is added in the flask with cooling tube and agitating device 1.7 parts of part, 21 parts of 1-METHYLPYRROLIDONE and t-butoxy potassium, after being stirred at room temperature 30 minutes, add 1- N-Propyl Bromides 1.6 parts, stir at the same temperature 1 hour.Obtained reaction solution is added in 21 parts of 2N hydrochloric acid, is stirred at room temperature 1 hour, as a result crystallization separated out.The crystallization of precipitation is separated by filtration, fully cleaned with ion exchange water, is depressurized at 60 DEG C dry It is dry, obtain 3.0 parts of the compound represented by formula (Aa-8-IM1).

The identification of the compound represented by formula (Aa-8-IM1)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺617.5

Exact mass：616.2

1 part of the compound represented by formula (Aa-8-IM1), N- first are added in the flask with cooling tube and agitating device 0.95 part of 7 parts of base pyrrolidones, 0.45 part of potassium carbonate and 4- bromobutyrates, have been stirred 5 and a half hours at 100 DEG C.Will To reaction solution be added in 35 parts of 2N hydrochloric acid, be stirred at room temperature 30 minutes, as a result crystallization separates out.By the crystallization of precipitation Filter separation, is fully cleaned with ion exchange water, is dried under reduced pressure at 60 DEG C, has obtained the chemical combination represented by formula (Aa-8-IM2) 1.2 parts of thing.

The identification of the compound represented by formula (Aa-8-IM2)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺731.5

Exact mass：730.3

1 part of the compound represented by formula (Aa-8-IM2), methanol 7 are added in the flask with cooling tube and agitating device 2.7 parts of part and 8% sodium hydrate aqueous solution, have been stirred at room temperature 3 and a half hours.Obtained reaction solution is added to 2N hydrochloric acid In 21 parts, it has been stirred at room temperature 30 minutes, as a result crystallization separates out.The crystallization of precipitation is separated by filtration, filled with ion exchange water Clean with dividing, be dried under reduced pressure at 60 DEG C, obtained 0.9 part of the compound represented by formula (Aa-8).

The identification of the compound represented by formula (Aa-8)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺703.5

Exact mass：702.3

[embodiment 4]

0.5 part of the compound represented by formula (Aa-1-IM), N- first are added in the flask with cooling tube and agitating device 2.3 parts of 3.5 parts of base pyrrolidones, 0.26 part of potassium carbonate and 1- N-Propyl Bromides, have been stirred at room temperature 80 hours.The reaction that will be obtained Liquid is added in 70 parts of 2N hydrochloric acid, has been stirred at room temperature 30 minutes, as a result crystallization separates out.The crystallization of precipitation is separated by filtration, Fully cleaned with ion exchange water, be dried under reduced pressure at 60 DEG C, obtained the compound 0.5 represented by formula (Aa-4-IM2) Part.

The identification of the compound represented by formula (Aa-4-IM2)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺717.5

Exact mass：716.3

0.5 part of the compound represented by formula (Aa-4-IM2), first are added in the flask with cooling tube and agitating device 1.3 parts of 3.4 parts of alcohol and 8% sodium hydrate aqueous solution, have been stirred at room temperature 2 hours.Obtained reaction solution is added to 2N salt In 70 parts of acid, it has been stirred at room temperature 30 minutes, as a result crystallization separates out.The crystallization of precipitation is separated by filtration, uses ion exchange water Fully clean, be dried under reduced pressure at 60 DEG C, obtained 0.4 part of the compound represented by formula (Aa-4).

The identification of the compound represented by formula (Aa-4)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺689.5

Exact mass：688.3

[embodiment 5]

The compound (middle tank formation manufacture) represented by formula (X) is added in the flask with cooling tube and agitating device 0.5 part of 1.5 parts, 10.5 parts of 1-METHYLPYRROLIDONE, 1.1 parts of potassium carbonate and 4- bromobutyrates, have stirred 4 half at 90 DEG C Hour.Obtained reaction solution is added in 52.5 parts of ion exchange water, has been stirred at room temperature 30 minutes, as a result crystallization analysis Go out.The crystallization of precipitation is separated by filtration, is fully cleaned with ion exchange water, is dried under reduced pressure at 60 DEG C.The runic that will be obtained With silica gel column chromatography (mobile phase：Chloroform/methanol -10/1) it is refined, obtain 0.2 part of the compound represented by formula (Aa-5-IM).

The identification of the compound represented by formula (Aa-5-IM)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺689.5

Exact mass：688.3

0.2 part of the compound represented by formula (Aa-5-IM), methanol are added in the flask with cooling tube and agitating device 1.6 parts and 1.0 parts of 8% sodium hydrate aqueous solution, have been stirred at room temperature 2 and a half hours.Obtained reaction solution is added to 2N 16 parts of hydrochloric acid, it has been stirred at room temperature 30 minutes, as a result crystallization separates out.The crystallization of precipitation is separated by filtration, uses ion exchange water Fully clean, be dried under reduced pressure at 60 DEG C, obtained 0.2 part of the compound represented by formula (Aa-5).

The identification of the compound represented by formula (Aa-5)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺661.5

Exact mass：660.3

[embodiment 6]

In the flask with cooling tube and agitating device add by formula (XX) represent 3,6- dichloros sulfonfluorescein (in Tank formation manufactures) 5 parts, 35 parts of 1-METHYLPYRROLIDONE and 3- amino -12.2 parts of methyl 4 methylbenzoate, are stirred at 130 DEG C Mix 7 hours.After letting cool, obtained reaction solution is added in the aqueous solution of 70 parts of 7.5 parts of concentrated hydrochloric acid and ion exchange water, Stir at room temperature 30 minutes, as a result crystallization separates out.The crystallization of precipitation is separated by filtration, fully cleaned with ion exchange water, It is dried under reduced pressure at 60 DEG C, has obtained 6.6 parts of the compound represented by formula (Aa-41-IM).

The identification of the compound represented by formula (Aa-41-IM)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺663.5

Exact mass：662.2

6 parts of the compound represented by formula (Aa-41-IM), N- first are added in the flask with cooling tube and agitating device 6.6 parts of 42 parts of base pyrrolidones, 5.0 parts of potassium carbonate and 1- N-Propyl Bromides, have been stirred 6 hours at 90 DEG C.After letting cool, by what is obtained Reaction solution is added in 210 parts of ion exchange water, has been stirred at room temperature 30 minutes, as a result crystallization separates out.By the crystallization of precipitation It is separated by filtration, is fully cleaned with ion exchange water, be dried under reduced pressure at 60 DEG C, has obtained the change represented by formula (Aa-44-IM) 5.9 parts of compound.

The identification of the compound represented by formula (Aa-44-IM)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺747.8

Exact mass：746.3

3 parts of the compound represented by formula (Aa-44-IM), methanol are added in the flask with cooling tube and agitating device 21 parts and 8.0 parts of 8% sodium hydrate aqueous solution, have been stirred at room temperature 8 hours.Obtained reaction solution is added to 2N hydrochloric acid In 105 parts, it has been stirred at room temperature 30 minutes, as a result crystallization separates out.The crystallization of precipitation is separated by filtration, filled with ion exchange water Clean with dividing, be dried under reduced pressure at 60 DEG C, obtained 2.5 parts of the compound represented by formula (Aa-44).

The identification of the compound represented by formula (Aa-44)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺719.5

Exact mass：718.2

[embodiment 7]

In the flask with cooling tube and agitating device add by formula (XX) represent 3,6- dichloros sulfonfluorescein (in Tank formation manufactures) 5 parts, 12.2 parts of 35 parts of 1-METHYLPYRROLIDONE and 4-Amino-3-methylbenzoic acid methyl esters, are stirred at 130 DEG C Mix 16 hours.After letting cool, obtained reaction solution is added in the aqueous solution of 70 parts of 7.5 parts of concentrated hydrochloric acid and ion exchange water, It has been stirred at room temperature 30 minutes, as a result crystallization separates out.The crystallization of precipitation is separated by filtration, fully washed with ion exchange water Only, it is dried under reduced pressure at 60 DEG C, has obtained 6.5 parts of the compound represented by formula (Aa-45-IM).

The identification of the compound represented by formula (Aa-45-IM)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺663.8

Exact mass：662.2

6 parts of the compound represented by formula (Aa-45-IM), N- first are added in the flask with cooling tube and agitating device 6.6 parts of 42 parts of base pyrrolidones, 5.0 parts of potassium carbonate and 1- N-Propyl Bromides, have been stirred 8 hours at 90 DEG C.After letting cool, by what is obtained Reaction solution is added in 210 parts of ion exchange water, has been stirred at room temperature 30 minutes, as a result crystallization separates out.By the crystallization of precipitation It is separated by filtration, is fully cleaned with ion exchange water, be dried under reduced pressure at 60 DEG C, has obtained the change represented by formula (Aa-48-IM) 6.0 parts of compound.

The identification of the compound represented by formula (Aa-48-IM)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺747.8

Exact mass：746.3

3 parts of the compound represented by formula (Aa-48-IM), methanol are added in the flask with cooling tube and agitating device 21 parts and 8.0 parts of 8% sodium hydrate aqueous solution, have been stirred at room temperature 8 and a half hours.Obtained reaction solution is added to 2N salt In 105 parts of acid, it has been stirred at room temperature 30 minutes, as a result crystallization separates out.The crystallization of precipitation is separated by filtration, uses ion exchange water Fully clean, be dried under reduced pressure at 60 DEG C, obtained 2.0 parts of the compound represented by formula (Aa-48).

The identification of the compound represented by formula (Aa-48)

(quality analysis) ionization mode=ESI⁺：M/z=[M+H]⁺719.5

Exact mass：718.2

[synthesis example 1]

In the flask with reflux cooler, dropping funel and mixer, appropriate nitrogen is flowed into, is replaced into blanket of nitrogen, 371 parts of 1- methoxyl group -2- propyl-acetic acids ester is put into, is heated to 85 DEG C while stirring.Next, in the flask, 4 hours are lasted Instill 54 parts of acrylic acid, the ring [5.2.1.0 of acrylic acid 3,4- epoxies three^2,6] decane -8 or/and 9- base esters mixture (trade name The manufacture of " E-DCPA ", Co., Ltd. Daicel) 225 parts, 81 parts of vinyltoluene (isomer mixture), 1- methoxyl groups -2- third The mixed solution that 80 parts of yl acetate.On the other hand, lasting 5 hours and having instilled makes polymerization initiator 2,2- azos two (2,4- bis- Methyl valeronitrile) 30 parts of solution being dissolved in 160 parts of 1- methoxyl group -2- propyl-acetic acids ester.Terminate in the instillation of initiator solution Afterwards, after maintaining 4 hours under synthermal, room temperature is cooled to, the viscosity with (23 DEG C) measure of Type B viscosity are 246mPas.Resin (B-1) solid constituent of solution is 37.5 weight %, and the acid number of solid constituent conversion is 115mg-KOH/g.The copolymer of generation Weight average molecular weight Mw be 10600, molecular weight distribution (Mw/Mn) be 2.01.Resin (B-1) has following construction unit.

Resin polystyrene conversion weight average molecular weight (Mw) and number-average molecular weight (Mn) measure use GPC method with Carried out under conditions of lower.

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

Post：TSK-GELG2000HXL

Column temperature：40℃

Solvent：THF

Flow velocity：1.0mL/min

It is detected liquid 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 as molecular weight Distribution.

[embodiment 8]

(preparation of colored curable resin composition)

By (A) colouring agent：C.I. pigment blue 15：6 27 parts of (pigment)

9.5 parts of acrylic acid series pigment dispersing agent

222 parts of propylene glycol monomethyl ether

Mixing, makes pigment fully disperse using ball mill, then, will

(A) colouring agent：1.2 parts of the compound represented by formula (Aa-1)

(A) colouring agent：C.I. 45 1.5 parts of solvent blue

(B) resin：60 parts of resin B 1 (solid constituent conversion)

(C) polymerizable compound：Dipentaerythritol acrylate

(カヤラッ De (registration mark) DPHA；The manufacture of Japanese chemical drug (strain)) 40 parts

(D) polymerization initiator：N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) octane -1- ketone -2- imines (IRGACURE (registration mark) OXE 01；BASF AG manufactures) 9 parts

(F) levelling agent：Polyether modified silicon oil (TORAY SILICONE SH8400：Dong Li-DOW CORNING (strain) is manufactured) 0.15 part

(E) solvent：156 parts of 4- hydroxy-4-methyl-2-pentanones

(E) solvent：401 parts of propylene glycol monomethyl ether

Mixing, has obtained colored curable resin composition.

[comparative example 1]

By (A) colouring agent：C.I. pigment blue 15：6 29 parts of (pigment)

10.1 parts of acrylic acid series pigment dispersing agent

236 parts of propylene glycol monomethyl ether

Mixing, makes pigment fully disperse using ball mill, then, will

(A) colouring agent：1.4 parts of dyestuff (Aa-x)

(A) colouring agent：C.I. 45 1.6 parts of solvent blue

(B) resin：60 parts of resin B 1 (Gu Ti Cheng Fen Change are calculated)

(C) polymerizable compound：Dipentaerythritol acrylate

40 parts of (Japanese chemical drug (strain) manufacture)

(E) solvent：156 parts of 4- hydroxy-4-methyl-2-pentanones

(E) solvent：397 parts of propylene glycol monomethyl ether

Mixing, has obtained colored curable resin composition.

It should illustrate, dyestuff (Aa-x) is by the mixture of following formula (A2-2-1)~(A2-2-8) compounds represented.

Embodiment 9~14, comparative example 1

In addition to as the composition shown in table 1, operation similarly to Example 8 is carried out, it is solid so as to obtain coloring The property changed resin combination.

【Table 1】

It should illustrate, in table 1, " A2-1¹⁾" be and acrylic acid series pigment dispersing agent and " E-1³⁾" column record the third the two of amount The mixing of alcohol monomethyl ether acetate, disperse what is formed in advance.

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

In table 1, each composition represents following implication.In addition, resin (B) represents the mass parts of solid constituent conversion.

Compound (I)：Compound (Aa-1)

Compound (I)：Compound (Aa-33)

Compound (I)：Compound (Aa-8)

Compound (I)：Compound (Aa-4)

Compound (I)：Compound (Aa-5)

Compound (I)：Compound (Aa-44)

Compound (I)：Compound (Aa-48)

Anthraquinone dye (Ad)：Ad-1：C.I. (the Savinyl Blue RS of solvent blue 45；Network ラリア Application ト societies make)

Pigment (A2)：A2-1：C.I. pigment blue 15：6

Resin (B)：B-1：Resin B 1

Polymerizable compound (C)：Dipentaerythritol acrylate (カヤラッ De (registration mark) DPHA；Japanese chemical drug (strain) manufactures)

Polymerization initiator (D)：D-1：N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) octane -1- ketone -2- imines (IRGACURE (registration mark) OXE 01；BASF AG manufactures；O- acyl groups oxime compound)

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

Solvent (E)：E-2：4- hydroxy-4-methyl-2-pentanones

Levelling agent (F)：Polyether modified silicon oil (TORAY SILICONE SH8400；Dong Li-DOW CORNING (strain) is manufactured)

Carried out for the embodiment 8~14 and the colored curable resin composition of comparative example 1 obtained as described above Evaluation.

The making ＞ of ＜ colored patterns

In the glass substrate (EAGLE 2000 of 5cm square；Corning Incorporated manufacture) on using spin-coating method be coated with coloring consolidate After the property changed resin combination, the prebake 3 minutes at 100 DEG C, coloring compositions nitride layer has been obtained.After letting cool, make to form coloring The substrate of composition layer, at intervals of 100 μm, uses exposure machine (TME-150RSK with quartz glass photomask；トプコン (strain) manufactures), under air atmosphere, with 150mJ/cm²Light exposure (365nm benchmark) carried out light irradiation.As photomask, The photomask for foring 100 μm of lines and space pattern is used.Coloring compositions nitride layer after light irradiation is being included into nonionic system In the water system developer solution of surfactant 0.12% and potassium hydroxide 0.04% at 24 DEG C immersion development 60 seconds, after washing, In baking oven, carried out 20 minutes at 230 DEG C after bakee, obtained colored pattern.

＜ film thickness measuring ＞

For obtained colored pattern, film thickness measuring device (DEKTAK3 is used；Japanese vacuum technique (strain) manufacture)) survey Determine thickness.

＜ chromaticity evaluations ＞

For obtained colored pattern, colour examining machine (OSP-SP-200 is used；Olympus (strain) manufactures) measure light splitting, make With the characterisitic function of illuminant-C, xy chromaticity coordinates (x, y) and the values Y in CIE XYZ color specification systems are determined.Y value is bigger, Represent that lightness is higher.Show the result in table 2.

【Table 2】

Confirm to show high lightness using the film that the colored curable resin composition of embodiment obtains.Thus may be used To know, coloring film, the colored pattern obtained by the colored curable resin composition of the present invention can be used as the colour filter of high brightness, The display characteristic of liquid crystal display device comprising the colour filter is excellent.

Industrial applicability

Using the colored curable resin composition of the present invention, the colour filter of high brightness can be formed.The colour filter can use Make the colour filter used in display device (such as liquid crystal display device, organic el device, Electronic Paper etc.) and solid-state imager.

Claims

1. the compound represented by formula (I)：

In formula (I), R¹~R⁴Independently of each other represent hydrogen atom, can have substituent carbon number 1~20 saturated hydrocarbyl or There can be the aromatic hydrocarbyl of the carbon number 6~10 of substituent, contained-CH in the saturated hydrocarbyl₂- can by-O- ,-CO- or- NR¹¹- replace, R¹And R²The ring containing nitrogen-atoms, R can be formed together³And R⁴The ring containing nitrogen-atoms can be formed together,

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

R¹¹Hydrogen atom, the saturated hydrocarbyl of carbon number 1~20 or the aralkyl of carbon number 7~10 are represented,

(i)R¹For the saturated hydrocarbyl of the carbon number 1~20 with-COOM, R²~R⁴In at least one for can have substituent carbon The aromatic hydrocarbyl of number 6~10, and-COOM contained in 1 molecule is 1,

(ii)R¹And R³For the aromatic hydrocarbyl of the carbon number 6~10 with-COOM,

(iii)R¹For the aromatic hydrocarbyl of the carbon number 6~10 with-COOM, R³For the saturated hydrocarbons of the carbon number 1~20 with-COOM Base,

(iv)R¹For the saturated hydrocarbyl of the carbon number 3~20 with-COOM, R³For the saturated hydrocarbyl of the carbon number 1~20 with-COOM,

(v)R¹For that can have the saturated hydrocarbyl of the carbon number 1~20 of substituent, R²For the aromatic series of the carbon number 6~10 with-COOM Alkyl,

(vi)R¹And R²For hydrogen atom or the saturated hydrocarbyl of the carbon number 1~20 can with substituent, R³And R⁴In at least one for tool There is the aromatic hydrocarbyl of-COOM carbon number 6~10,

In (i)~(vi), M represents hydrogen atom, Na⁺、K⁺Or⁺N(R¹²)₄, 4 R¹²Can with identical also different,

2. colored curable resin composition, it includes compound according to claim 1, resin (B), polymerism chemical combination Thing (C) and polymerization initiator (D).

3. colour filter, it is formed by colored curable resin composition according to claim 2.

4. display device, it includes colour filter according to claim 3.