CN106990672A - Colored curable resin composition, colour filter and display device - Google Patents

Abstract

The problem of the present invention is to provide colored curable resin composition, the colour filter of excellent heat resistance and display device.The colored curable resin composition of the present invention includes xanthene compound (A 1), resin (B), polymerizable compound (C) and polymerization initiator (D); it is characterized in that; above-mentioned xanthene compound (A 1) is the compound with cation (AXa) and anion (AXb); cation (AXa) has xanthene skeleton; anion (AXb) contains at least one element and oxygen in tungsten, molybdenum, silicon and phosphorus as essential elements, and above-mentioned xanthene skeleton is the xanthene skeleton with substituted or unsubstituted sulfamoyl.

Description

Colored curable resin composition, colour filter and display device

Technical field

The present invention relates to the colored curable resin composition for including xanthene compound.

Background technology

Xanthene compound is used as what is contained in the various display devices such as liquid crystal display device, solid-state imager etc. The colouring agent of colour filter.For example, having recorded the compound represented by formula (A1) in patent document 1.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2014-88558 publications

The content of the invention

The invention problem to be solved

In the case of using previously known above-claimed cpd, the heat resistance of obtained colour filter not can be fully Meet needs.

Means for solving the problems

The present invention includes following invention.

[1] colored curable resin composition, it is to include xanthene compound (A-1), resin (B), polymerizable compound (C) and polymerization initiator (D) colored curable resin composition, wherein, above-mentioned xanthene compound (A-1) be with cation (AXa) and anion (AXb) compound, cation (AXa) have with substituted or unsubstituted sulfamoyl xanthene bone Frame, anion (AXb) contains at least one element and oxygen in tungsten, molybdenum, silicon and phosphorus as essential elements, above-mentioned xanthene bone Frame is the xanthene skeleton with substituted or unsubstituted sulfamoyl.

[2] colored curable resin composition described in [1], wherein, the cation (AXa) with xanthene skeleton is by formula (I) cation represented.

[in formula (I), R^1a~R^4aIndependently of each other represent hydrogen atom, can have substituent carbon number 6~10 aromatic series Alkyl or can have substituent carbon number 1~20 saturated hydrocarbyl, contained methylene (- CH in the saturated hydrocarbyl₂-) can be with By-O- ,-CO- ,-NR^11a- ,-OCO- ,-COO- ,-OCONH- ,-NHCOO- ,-CONH- or-NHCO- replace, R^1aAnd R^2aCan one Rise and form the ring containing nitrogen-atoms, R^3aAnd R^4aThe ring containing nitrogen-atoms can be formed together.But, adjacent methylene will not be same When be replaced by identical substituent, in addition, the methylene of end will not be also replaced.R^6aAnd R^7aHydrogen is represented independently of each other The alkyl of atom or carbon number 1~6.Ma represents 1~5 integer.R^9aAnd R^10aHydrogen atom is represented independently of each other or there can be substitution Contained methylene (- CH in the saturated hydrocarbyl of the carbon number 1~20 of base, the saturated hydrocarbyl₂-) can by-O- ,-CO- ,- NR^11a- ,-OCO- ,-COO- ,-OCONH- ,-NHCOO- ,-CONH- or-NHCO- replace, R^9aAnd R^10aIt can be combined with each other and be formed The heterocycle of 3~10 yuan of rings containing nitrogen-atoms.But, adjacent methylene will not be replaced by identical substituent simultaneously, separately Outside, the methylene of end will not be also replaced.R^11aRepresent hydrogen atom, the saturated hydrocarbyl or carbon number 7~10 of 1 valency of carbon number 1~20 Aralkyl.]

[3] colored curable resin composition described in [1] or [2], wherein, anion (AXb) is contains tungsten as must Want the heteropoly acid of element or the anion of isopolyacid.

[4] colored curable resin composition described in any one of [1]~[3], wherein, anion (AXb) is phosphorus tungsten Any one among the anion of acid, the anion of the anion of silico-tungstic acid or tungsten system isopolyacid.

[5] colour filter formed as the colored curable resin composition described in any one of [1]~[4].

[6] display device, it includes the colour filter described in [5].

The effect of invention

The colored curable resin composition of the present invention is heat-resisting therefore, it is possible to provide due to comprising specific xanthene compound The excellent colour filter of property.

Embodiment

The colored curable resin composition of the present invention includes xanthene compound (A-1), resin (B), polymerizable compound And polymerization initiator (D) (C).

＜ colouring agents (A) ＞

Xanthene compound (A-1) in the present invention has cation (AXa) and anion (AXb), and cation (AXa) has Xanthene skeleton, anion (AXb) contains at least one element and oxygen in tungsten, molybdenum, silicon and phosphorus as essential elements, above-mentioned Xanthene skeleton has substituted or unsubstituted sulfamoyl.By with：Cation (AXa) with xanthene skeleton and it is cloudy from Sub (AXb), it is possible to increase the heat resistance of xanthene compound.

Cation (AXa) with xanthene skeleton preferably has substituted or unsubstituted sulfamoyl, more preferably by formula (I) cation represented.

[in formula (I),

R^1a~R^4aIndependently of each other represent hydrogen atom, can have substituent carbon number 6~10 aromatic hydrocarbyl or can have Contained methylene (- CH in the saturated hydrocarbyl of the carbon number 1~20 of substituted base, the saturated hydrocarbyl₂-) can by-O- ,-CO- ,- NR^11a- ,-OCO- ,-COO- ,-OCONH- ,-NHCOO- ,-CONH- or-NHCO- replace, R^1aAnd R^2aIt can be formed together containing nitrogen The ring of atom, R^3aAnd R^4aThe ring containing nitrogen-atoms can be formed together.But, adjacent methylene will not be replaced by phase simultaneously Same substituent, in addition, the methylene of end will not be also replaced.

R^6aAnd R^7aThe alkyl of hydrogen atom or carbon number 1~6 is represented independently of each other.

Ma represents 1~5 integer.

R^9aAnd R^10aHydrogen atom is represented independently of each other or can have the saturated hydrocarbyl of the carbon number 1~20 of substituent, the saturation Contained methylene (- CH in alkyl₂-) can be by-O- ,-CO- ,-NR^11a-、-OCO-、-COO-、-OCONH-、-NHCOO-、- CONH- or-NHCO- is replaced, R^9aAnd R^10aIt can be combined with each other and be formed the heterocycle of 3~10 yuan of rings containing nitrogen-atoms.But, it is adjacent The methylene connect will not be while be replaced by identical substituent, in addition, the methylene of end will not be also replaced.

R^11aRepresent the aralkyl of hydrogen atom, the saturated hydrocarbyl of carbon number 1~20 or carbon number 7~10.]

In formula (I) ,-SO₃ ^-In the presence of, its number is 1.

It is used as R^1a~R^4aAnd R^9a~R^11aIn carbon number 1~20 saturated hydrocarbyl, can for example include methyl, ethyl, third The straight-chain alkyls such as base, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl, eicosyl； Point branched-chain alkyl such as isopropyl, isobutyl group, isopentyl, neopentyl, 2- ethylhexyls；Cyclopropyl, cyclopenta, cyclohexyl, ring The ester ring type saturated hydrocarbyl of the carbon numbers such as heptyl, cyclooctyl, tricyclodecyl 3~20.

Contained methylene (- CH in the saturated hydrocarbyl₂-) can be by-O- ,-CO- ,-NR^11a-、-OCO-、-COO-、- OCONH- ,-NHCOO- ,-CONH- or-NHCO- substitutions.But, adjacent methylene will not be replaced by identical substitution simultaneously Base, in addition, the methylene of end will not be also replaced.

It is used as methylene (- CH contained in the saturated hydrocarbyl₂-) group that substituted for Bei-O-, it can such as include following Group (* represents bonding end).

It is used as methylene (- CH contained in the saturated hydrocarbyl₂-) group that substituted for Bei-CO-, can for example include with Under group (* represents bonding end).

It is used as methylene (- CH contained in the saturated hydrocarbyl₂-) by-NR^11a- the group that substituted for, for example, can include Following group (* represents bonding end).

It is used as methylene (- CH contained in the saturated hydrocarbyl₂-) group that substituted for Bei-OCO-, can for example include with Under group (* represents bonding end).

It is used as methylene (- CH contained in the saturated hydrocarbyl₂-) group that substituted for Bei-COO-, can for example include with Under group (* represents bonding end).

It is used as methylene (- CH contained in the saturated hydrocarbyl₂-) group that substituted for Bei-OCONH-, it can such as include Following group (* represents bonding end).

It is used as methylene (- CH contained in the saturated hydrocarbyl₂-) group that substituted for Bei-NHCOO-, it can such as include Following group (* represents bonding end).

It is used as methylene (- CH contained in the saturated hydrocarbyl₂-) group that substituted for Bei-CONH-, it can such as include Following group (* represents bonding end).

It is used as methylene (- CH contained in the saturated hydrocarbyl₂-) group that substituted for Bei-NHCO-, it can such as include Following group (* represents bonding end).

R^1a~R^4aIn the saturated hydrocarbyl can have substituent, as substituent, for example, can include carbon number 6~10 Aromatic hydrocarbyl or halogen atom.It is used as R^1a~R^4aThe aromatic hydrocarbyl of carbon number 6~10 that can have of saturated hydrocarbyl, can arrange Enumerate and as R^1a~R^4aIn carbon number 6~10 the same group of group that illustrates of aromatic hydrocarbyl.

As halogen atom, fluorine atom, chlorine atom, bromine atoms and iodine atom etc. can be included.

R^9aAnd R^10aIn the saturated hydrocarbyl can have substituent, as the substituent, for example, can include fluorine atom, chlorine The halogen atoms such as atom, bromine atoms and iodine atom or hydroxyl.

It is used as R^1aAnd R^2aThe ring and R formed together^3aAnd R^4aThe ring formed together, for example, can include following ring. In formula, * represents bonding end.

It is used as R^1a~R^4aIn carbon number 6~10 aromatic hydrocarbyl, can for example include phenyl, tolyl, dimethylbenzene Base, mesitylene base, propyl group phenyl and butyl phenyl etc..

The aromatic hydrocarbyl of the carbon number 6~10 can have substituent.The substituent that can have as the aromatic hydrocarbyl, can Include halogen atom ,-R^8a、-OH、-OR^8a、-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂R^8a、-SR^8a、-SO₂R^8a、- SO₃R^8aWith-SO₂NR^12aR^13a.In these, substituent, preferably-R are used as^8a、-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺With-SO₂NR^12aR^13a, More preferably-R^8a、-SO₃ ^-Z⁺With-SO₂NR^12aR^13a.It is used as-the R under this situation^8a, the more preferably saturated hydrocarbyl of carbon number 1~10, The alkyl of further preferred carbon number 1~5.In addition, being used as the-SO under this situation₃ ^-Z⁺, preferably-SO₃ ^-N⁺(R^11a)₄。

Z⁺Represent⁺N(R^11a)₄、Na⁺Or K⁺, 4 R^11aCan be with identical, also can be different.

R^8aRepresent the saturated hydrocarbyl of carbon number 1~20 that can be substituted with halogen atoms.

R^12aAnd R^13aHydrogen atom is represented independently of each other or there can be the saturated hydrocarbyl of the carbon number 1~20 of substituent, and this is satisfied With methylene (- CH contained in alkyl₂-) can be by-O- ,-CO- ,-NR^11a-、-OCO-、-COO-、-OCONH-、- NHCOO- ,-CONH- or-NHCO- are replaced, R^12aAnd R^13aIt can be combined with each other and form the miscellaneous of 3~10 yuan of rings containing nitrogen-atoms Ring.But, adjacent methylene will not be replaced by identical substituent simultaneously, in addition, the methylene of end also will not by for Change.

As by R^8a、R^12aAnd R^13aThe saturated hydrocarbyl of the carbon number 1~20 of expression, can be included and by R^1a~R^4aRepresent The saturated hydrocarbyl identical group of carbon number 1~20.

By R^12aAnd R^13aThe saturated hydrocarbyl of the carbon number 1~20 of expression can have substituent, as the substituent, can include The halogen atoms such as fluorine atom, chlorine atom, bromine atoms and iodine atom or hydroxyl.

It is used as-OR^8a, for example, can include methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygen in heptan Alkoxies such as base, octyloxy, 2- ethyl hexyl oxies and eicosane epoxide etc..

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

It is used as-SR^8a, for example, can include methylsulfanyl, Ethylsulfanyl, butyl sulfanyl, hexyl sulfanyl, decyl Alkyl alkylthio base such as sulfanyl and eicosyl sulfanyl etc..

It is used as-SO₂R^8a, for example, can include methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, the last of the ten Heavenly stems Alkyl sulphonyl such as base sulfonyl and eicosyl sulfonyl etc..

It is used as-SO₃R^8a, for example, can include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tertiary fourth oxygen Alkyloxysulfonyls such as base sulfonyl, hexyloxy sulfonyl and eicosane epoxide sulfonyl etc..

It is used as-SO₂NR^12aR^13a, for example, can include：

Sulfamoyl；

N- Methylsulfamoyls, N- ethylsulfamovls, N- propylsulfamovs, N- isopropylsulfamoyls base, N- butyl Sulfamoyl, N- isobutyl groups sulfamoyl, N- sec-butyls sulfamoyl, N- tert-butyl groups sulfamoyl, N- amyl groups sulfamoyl, N- (1- ethyl propyls) sulfamoyl, N- (1,1- dimethyl 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 butyl) sulfamoyl, N- Cyclopentylsulfamoyls base, N- hexyls sulfamoyl, N- (1,3- dimethylbutyls) sulfamoyl, N- (3,3- dimethylbutyls) sulfamoyl, N- heptyl sulfamoyl, N- (1- methylhexyls) sulfamoyl, N- (1,4- diformazans Base amyl group) sulfamoyl, N- octyl groups sulfamoyl, N- (2- ethylhexyls) sulfamoyl, N- (1,5- dimethylhexanyls) ammonia sulphur The N-1 such as acyl group and N- (1,1,2,2- tetramethyl butyls) sulfamoyl replaces sulfamoyl；

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

Ma is preferably 1~4, more preferably 1 or 2.

It is used as R^6aAnd R^7aIn carbon number 1~6 alkyl, the alkyl of carbon number 1~6 in the above-mentioned alkyl enumerated can be included.

R^12aAnd R^13a3~10 member heterocyclic ring containing nitrogens can be represented together with nitrogen-atoms.As the heterocycle, can for example include with Under heterocycle.In formula, * represents bonding end.

It is used as R^11aIn carbon number 7~10 aralkyl, benzyl, phenylethyl and phenyl butyl etc. can be included.

Z⁺Preferably⁺N(R^11a)₄、Na⁺Or K⁺, more preferably⁺N(R^11a)₄。

As above-mentioned⁺N(R^11a)₄, preferably 4 R^11aMiddle at least two is the saturated hydrocarbyl of 1 valency of carbon number 5~20.In addition, 4 Individual R^11aTotal carbon number be preferably 20~80, more preferably 20~60.

It is used as-SO₂NR^9aR^10a, can include and conduct-SO₂NR^12aR^13aThe same group of the group of illustration.In addition, making For R^9aAnd R^10aThe heterocycle of 3~10 yuan of rings containing nitrogen-atoms, can be included and R formed by can be combineding with each other^12aAnd R^13aCan be with The same ring of 3~10 member heterocyclic ring containing nitrogens that are formed together with nitrogen-atoms.

Wherein, as R^1aAnd R^4a, can preferably have the saturated hydrocarbyl of the carbon number 1~20 of substituent and can have substituent Carbon number 6~10 aromatic hydrocarbyl, more preferably can have substituent carbon number 6~10 aromatic hydrocarbyl.R^1a、R^4aIn The carbon number of saturated hydrocarbons is preferably 1~10, and more preferably 1~5, more preferably 1~3, preferably without substituent.In addition, The substituent of above-mentioned aromatic hydrocarbyl is preferably-R^8a。

It is used as R^2aAnd R^3a, can preferably have the saturated hydrocarbyl of the carbon number 1~20 of substituent.R^2aAnd R^3aIn saturated hydrocarbyl Carbon number be preferably 1~10, more preferably 1~5, more preferably 1~3, preferably without substituent.

It is used as R^6aAnd R^7a, preferred hydrogen atom.

R^8aIn the carbon number of saturated hydrocarbyl be preferably 1~10, more preferably 1~5, more preferably 1~3.

It is used as R^9a、R^10a、R^12aAnd R^13a, the preferred saturated hydrocarbyl of hydrogen atom and carbon number 1~12.Additionally, it is preferred that R^9aAnd R^10a At least one be saturated hydrocarbyl, more preferably R^9aAnd R^10aBoth be saturated hydrocarbyl.Additionally, it is preferred that R^12aAnd R^13aAt least one For saturated hydrocarbyl, more preferably R^12aAnd R^13aBoth be saturated hydrocarbyl.

It is used as-SO₂NR^9aR^10a、-SO₂NR^12aR^13a, preferably N-1 substitution sulfamoyls and N-2 replace sulfamoyl.

It is used as R^11a, the preferred saturated hydrocarbyl of carbon number 1~20.

As the cation (AXa) with xanthene skeleton, preferably by formula (I-1) represent have the sun of xanthene skeleton from Son.The cation represented by formula (I-1) can be its dynamic isomer.

[in formula (I-1),

R^1b~R^4bRepresent there can be institute in the saturated hydrocarbyl of the carbon number 1~20 of substituent, the saturated hydrocarbyl independently of each other The methylene (- CH contained₂-) can be by-O- ,-CO- ,-NR^11b- ,-OCO- ,-COO- ,-OCONH- ,-NHCOO- ,-CONH- or- NHCO- is replaced, R^1bAnd R^2bThe ring containing nitrogen-atoms, R can be formed together^3bAnd R^4bThe ring containing nitrogen-atoms can be formed together. But, adjacent methylene will not be replaced by identical substituent simultaneously, in addition, the methylene of end will not be also replaced.

R^6bAnd R^7bThe alkyl of hydrogen atom or carbon number 1~6 is represented independently of each other.

Mb represents 0~5 integer.When mb is more than 2, multiple-SO₂NR^9bR^10bCan be with identical also different.

R^9bAnd R^10bHydrogen atom is represented independently of each other or can have the saturated hydrocarbyl of the carbon number 1~20 of substituent, the saturation Contained methylene (- CH in alkyl₂-) can be by-O- ,-CO- ,-NR^11b-、-OCO-、-COO-、-OCONH-、-NHCOO-、- CONH- or-NHCO- is replaced, R^9bAnd R^10bIt can be combined with each other and be formed the heterocycle of 3~10 yuan of rings containing nitrogen-atoms.But, it is adjacent The methylene connect will not be while be replaced by identical substituent, in addition, the methylene of end will not be also replaced.

R^11bRepresent the aralkyl of hydrogen atom, the saturated hydrocarbyl of carbon number 1~20 or carbon number 7~10.]

R^1b~R^11bPreferred configuration with mb is respectively from above-mentioned R^1a~R^11aWith in ma preferred configuration, no more than R^1b~ R^11bSelected with the range of mb concept.

In addition, as the cation (AXa) with xanthene skeleton, preferably there is xanthene skeleton by what formula (I-2) was represented Cation.The cation represented by formula (I-2) can be its dynamic isomer.

[in formula (I-2),

R^1cAnd R^4cThe alkyl, the alkyl alkylthio base of carbon number 1~4 or carbon number 1~4 of carbon number 1~4 are represented independently of each other Alkyl sulphonyl.

P and q represent 0~5 integer independently of each other.When p is more than 2, multiple R^1cCan with identical also different, q be 2 with When upper, multiple R^4cCan be with identical also different.

R^2cAnd R^3cIndependently of each other represent hydrogen atom, can have substituent carbon number 1~20 1 valency saturated hydrocarbyl, should Contained methylene (- CH in saturated hydrocarbyl₂-) can be by-O- ,-CO- ,-NR^11c-、-OCO-、-COO-、-OCONH-、- NHCOO- ,-CONH- or-NHCO- are replaced.But, adjacent methylene will not be replaced by identical substituent simultaneously, in addition, The methylene of end will not be also replaced.

R^1cAnd R^2cThe ring containing nitrogen-atoms, R can be formed together^3cAnd R^4cThe ring containing nitrogen-atoms can be formed together.

R^6cAnd R^7cThe alkyl of hydrogen atom or carbon number 1~6 is represented independently of each other.

Mc represents 0~5 integer.When mc is more than 2, multiple-SO₂NR^9cR^10cCan be with identical also different.

R^9cAnd R^10cHydrogen atom is represented independently of each other or can have the saturated hydrocarbyl of the carbon number 1~20 of substituent, the saturation Contained methylene (- CH in alkyl₂-) can be by-O- ,-CO- ,-NR^11c-、-OCO-、-COO-、-OCONH-、-NHCOO-、- CONH- or-NHCO- is replaced, R^9cAnd R^10cIt can be combined with each other and be formed the heterocycle of 3~10 yuan of rings containing nitrogen-atoms.But, it is adjacent The methylene connect will not be while be replaced by identical substituent, in addition, the methylene of end will not be also replaced.

R^11cRepresent the aralkyl of hydrogen atom, the saturated hydrocarbyl of 1 valency of carbon number 1~20 or carbon number 7~10.]

R^1c~R^4c、R^6c~R^7c、R^9c~R^11cPreferred configuration with mc is respectively from above-mentioned R^1a~R^11a, ma and R^1aShown virtue In the preferred configuration for the substituent that fragrant race's alkyl can have, no more than R^1c~R^4c、R^6c~R^7c、R^9c~R^11cWith mc concept In the range of select.

As cation (AXa), for example, it can include the cation represented by following formula (AXa-I).It should illustrate, table 1 In, it is expressed as R^2A、R^3A、R^10AR⁴⁰The saturated hydrocarbyl of 1 valency of carbon number 1~20 is represented, the branched chain of carbon number 6~12 is preferably represented Shape alkyl, more preferably represents 2- ethylhexyls.

【Table 1】

In table 1, Me represents methyl, and Et represents ethyl, and Pr represents n-propyl, and iPr represents isopropyl.Ph1~Ph10 is meaned The group represented by following formula, Hc1~Hc4 is respectively R^1AAnd R^2A、R^3AAnd R^4AThe feelings of the ring containing nitrogen-atoms are formed together Shape, is represented corresponding to the respective rings of Hc1~Hc4 by following formula.

Wherein, as cation (AXa), preferred cationic (AXa-1)~(AXa-4), (AXa-27)~(AXa-30).

Above-mentioned cation (AXa) for example can be by will be manufactured by the compound sulfuryl amine that formula (II) is represented.

[in formula (II), R^1a~R^4a、R^6a~R^7aWith ma with it is above-mentioned synonymous.]

Contain with the anion (AXb) that the cation (AXa) with xanthene skeleton is applied in combination and be selected from tungsten, molybdenum, silicon and phosphorus In at least one element and oxygen as essential elements, preferably contain tungsten and oxygen as essential elements.Go out from the viewpoint of heat resistance Hair, preferably these anion.

As anion (AXb), tungsten is preferably comprised as the heteropoly acid of essential elements or the anion of isopolyacid, more preferably The anion of phosphotungstic acid, silico-tungstic acid and tungsten system isopolyacid.

As tungsten is contained as the heteropoly acid of essential elements and the anion of isopolyacid, for example, it can include Keggin-type phosphorus Wolframic acid ion α-[PW₁₂O₄₀]^3-, Dawson type phosphotungstic acid ions α-[P₂W₁₈O₆₂]^6-、β-[P₂W₁₈O₆₂]^6-, Keggin-type silico-tungstic acid Ion α-[SiW₁₂O₄₀]^4-、β-[SiW₁₂O₄₀]^4-、γ-[SiW₁₂O₄₀]^4-, and then, as other examples, it can include [P₂W₁₇O₆₁]^10-、[P₂W₁₅O₅₆]^12-、[H₂P₂W₁₂O₄₈]^12-、[NaP₅W₃₀O₁₁₀]^14-、α-[SiW₉O₃₄]^10-、γ-[SiW₁₀O₃₆]^8-、 α-[SiW₁₁O₃₉]^8-、β-[SiW₁₁O₃₉]^8-、[W₆O₁₉]^2-、[W₁₀O₃₂]^4-、WO₄ ^2-With their mixture.

In addition, it is also preferred that the anion being made up of at least one element and oxygen in silicon and phosphorus.

The anion constituted as such at least one element and oxygen by silicon and phosphorus, can include SiO₃ ^2- And PO₄ ^3-。

As anion (AXb), preferably the phosphotungstic acid such as Keggin-type phosphotungstic acid ion, Dawson type phosphotungstic acid ions it is cloudy from Son；Silico-tungstic acid the anion, [W such as Keggin-type silico-tungstic acid ion₁₀O₃₂]^4-Deng tungsten system isopolyacid anion.Wherein particularly preferred phosphorus Tungsten acid anions, tungsten system isopolyacid anion.

As anion (AXb), further preferably tungsten enters one as the heteropoly acid of essential elements and the anion of isopolyacid Walk the anion of the anion of preferred phosphotungstic acid, the anion of silico-tungstic acid and tungsten system isopolyacid, still more preferably [PW₁₂O₄₀ ]^3-、[P₂W₁₈O₆₂]^6-、[SiW₁₂O₄₀]^4-[W₁₀O₃₂]^4-, particularly preferred [PW₁₂O₄₀]^3-[P₂W₁₈O₆₂]^6-.From the sight of heat resistance Point sets out, and can be used and contains tungsten as the heteropoly acid of essential elements or the anion of isopolyacid.

As compound (A-I), it can include：

Arbitrary 3 cations in above-mentioned cation (AXa-1)~(AXa-52), preferably cation (AXa-1)~ (AXa-4) arbitrary 3 cations and anion α-[PW and in (AXa-27)~(AXa-30)₁₂O₄₀]^3-Combination,

Arbitrary 6 cations in above-mentioned cation (AXa-1)~(AXa-52), preferably cation (AXa-1)~ (AXa-4) arbitrary 6 cations and anion α-[P and in (AXa-27)~(AXa-30)₂W₁₈O₆₂]^6-Combination,

Arbitrary 4 cations in above-mentioned cation (AXa-1)~(AXa-52), preferably cation (AXa-1)~ (AXa-4) arbitrary 4 cations and anion α-[SiW and in (AXa-27)~(AXa-30)₁₂O₄₀]^4-[W₁₀O₃₂]^4-'s Combination etc..

And specifically, it is preferable to be the compound (Xa) being made up of following cations (AXa) and anion (AXb).

【Table 2】

	Axa	Axb
			(Xa-1a)	(Axa-1)	[PW12O40]3-
(Xa-1b)	(Axa-1)	[P2W18O62]6-
			(Xa-1c)	(Axa-1)	[SiW12O40]4-
(Xa-1d)	(Axa-1)	[W10O32]4-
			(Xa-2a)	(Axa-2)	[PW12O40]3-
(Xa-2b)	(Axa-2)	[P2W18O62]6-
			(Xa-2c)	(Axa-2)	[SiW12O40]4-
(Xa-2d)	(Axa-2)	[W10O32]4-
			(Xa-3a)	(Axa-3)	[PW12O40]3-
(Xa-3b)	(Axa-3)	[P2W18O62]6-
			(Xa-3c)	(Axa-3)	[SiW12O40]4-
(Xa-3d)	(Axa-3)	[W10O32]4-
			(Xa-4a)	(Axa-4)	[PW12O40]3-
(Xa-4b)	(Axa-4)	[P2W18O62]6-
			(Xa-4c)	(Axa-4)	[SiW12O40]4-
(Xa-4d)	(Axa-4)	[W10O32]4-
			(Xa-27a)	(Axa-27)	[PW12O40]3-
(Xa-27b)	(Axa-27)	[P2W18O62]6-
			(Xa-27c)	(Axa-27)	[SiW12O40]4-
(Xa-27d)	(Axa-27)	[W10O32]4-
			(Xa-28a)	(Axa-28)	[PW12O40]3-
(Xa-28b)	(Axa-28)	[P2W18O62]6-
			(Xa-28c)	(Axa-28)	[SiW12O40]4-
(Xa-28d)	(Axa-28)	[W10O32]4-
			(Xa-29a)	(Axa-29)	[PW12O40]3-
(Xa-29b)	(Axa-29)	[P2W18O62]6-
			(Xa-29c)	(Axa-29)	[SiW12O40]4-
(Xa-29d)	(Axa-29)	[W10O32]4-
			(Xa-30a)	(Axa-30)	[PW12O40]3-
(Xa-30b)	(Axa-30)	[P2W18O62]6-
			(Xa-30c)	(Axa-30)	[SiW12O40]4-
(Xa-30d)	(Axa-30)	[W10O32]4-

Xanthene compound (A-1) can for example pass through compound and the above-mentioned anion (Axb) that will be represented by formula (III) Alkali metal salt is mixed and manufactured in a solvent.As alkali metal, lithium, sodium and potassium can be included.

[in formula (III), R^1a~R^4a、R^6a~R^7a、R^9a~R^10aWith ma with it is above-mentioned synonymous.]

As solvent, DMF, DMA, 1-METHYLPYRROLIDONE, two can be included Methyl sulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, dioxanes, water and chloroform.

The compound represented by formula (III) can be using known method manufacture.

In the present invention, the color dispersion liquid comprising above-mentioned xanthene compound (A-1) and solvent can be prepared, by obtained coloring Dispersion liquid is used for colored curable resin composition.As the solvent used in color dispersion liquid, can use with it is described later molten The same solvent of agent (E).Additionally, it is preferred that further using pigment dispersing agent in color dispersion liquid, it can wrap in advance as needed Part or all of (being preferably a part) containing the resin (B) used in colored curable resin composition.

As colouring agent (A), can individually contain above-mentioned xanthene compound (A-1), but in order to mix colours, i.e. regulation light splitting it is special Property, it can further include other dyestuffs (A1), pigment (P).

As dyestuff (A1), can include oil-soluble dyes, acid dyes, basic-dyeable fibre, direct dyes, mordant dye, The dyestuffs such as the amine salt of acid dyes, the sulfamide derivative of acid dyes, can include such as colour index (The Society of Dyers and Colourists publish) in be categorized as dyestuff compound, dyeing notes (Se Ran societies) described in it is known Dyestuff.In addition, according to chemical constitution, azo dyes, cyanine dyes, triphenhlmethane dye, xanthene dye, phthalocyanine dye can be included Material, naphthoquinone dyestuff, quinoneimine dye, methine dyes, azomethine dyes, squaraine dye, acridine dye, styryl dye Material, coumarine dye, quinoline dye and nitro dye etc..In these, organic solvent-soluble dyestuff is preferably used.

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

C.I. solvent red 45,49,125,130,218；

C.I. solvent orange 2,7,11,15,26,56；

C.I. solvent blue 4,5,37,67,70,90；

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

C.I. Indian yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98, 99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、 161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、 212、214、220、221、228、230、232、235、238、240、242、243、251；

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

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

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

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

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

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

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

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

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

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

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

C.I. the C.I. disperse dyes such as disperse yellow 54,76,

C.I. alkali red 1:1,10；

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

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

C.I. active yellow 2,76,116；

C.I. reactive orange 16；

C.I. the grade C.I. of active red 36 reactive dye,

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

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

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

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

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

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

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

Wherein, preferably cyan dye, cudbear and orchil.

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

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

As pigment, can for example 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. viridine green such as pigment Green 7,36,58,59 etc..

For pigment, as needed, rosin processing can be implemented, the pigment for having imported acidic-group or basic group has been used The surface treatment of derivative etc., using high-molecular compound etc. to the grafting processing of surface of pigments, using sulfuric acid particles method Deng micronized processing or adopted using the clean processing of the organic solvent, the water that remove impurity etc., ionic impurity is used for Removing processing with ion-exchange etc. etc..The particle diameter of preferred pigments is each homogeneous.

For pigment, by carrying out decentralized processing containing pigment dispersing agent, pigment dispersing agent can be made in the solution The dispersible pigment dispersion for the state being uniformly dispersed.For pigment, decentralized processing each can be individually carried out, a variety of will can also be mixed Close and carry out decentralized processing.

As above-mentioned pigment dispersing agent, for example, it can include cation system, anion system, nonionic system, both sexes, polyester Pigment dispersing agent of system, many amine systems, acrylic acid series etc. etc..These pigment dispersing agents can be used alone or combine two or more Use.As pigment dispersing agent, represented with trade name, KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), FLORENE can be included (altogether Flourish society chemical (strain) manufacture), ソ Le ス パ ー ス (ゼ ネ カ (strain) manufactures), EFKA (BASF AG's manufacture), ア ジ ス パ ー (aginomoto Off ァ イ Application テ Network ノ (strain) manufactures), Disperbyk (manufacture of BYK Chemie companies) etc..

Relative to colouring agent (A) total amount, the containing ratio of above-mentioned xanthene compound (A-1) be usually it is more than 1 mass % and Below 100 mass %, preferably more than 10 mass % and below 100 mass %.Furthermore it is possible to be more than 30 mass %, preferably More than the mass % of ground 50, more preferably more than 70 mass %.

In the case of comprising dyestuff (A1), relative to colouring agent (A) total amount, the containing ratio of dyestuff (A1) is preferably 0.5 More than quality % and 90 below mass %, more preferably more than 40 mass % and below 80 mass %.Include pigment (P) situation Under, relative to colouring agent (A) total amount, the containing ratio of pigment (P) is preferably more than 1 mass % and below 99 mass %, more excellent Elect as more than 1 mass % and below 70 mass %, more preferably more than 1 mass % and below 50 mass %.

Relative to the total amount of solid constituent, the containing ratio of colouring agent (A) be preferably more than 0.1 mass % and 70 mass % with Under, more preferably more than 0.5 mass % and below 60 mass %, more preferably more than 1 mass % and below 50 mass %. If the containing ratio of colouring agent (A) is in above-mentioned scope, desired light splitting, colour saturation can be obtained.

It should illustrate, " total amount of solid constituent " refers to the colored curable resin composition from the present invention in this specification In eliminate the total amount of the composition after solvent (E).The total amount of solid constituent and content relative to its each composition for example can Enough determined using analysis means known to liquid chromatogram or gas-chromatography etc..

＜ resins (B) ＞

Resin (B) is not particularly limited, preferably alkali soluble resin, it is however preferred to have from from unsaturated carboxylic acid and The polymer of the construction unit of at least one monomer (a) selected in unsaturated carboxylic acid anhydrides.

Resin (B) is preferably with the construction unit from above-mentioned monomer (a) and from the cyclic ether with carbon number 2~4 The monomer (b) of structure and ethylenic unsaturated bond and structure list that can be with least one of the monomer (c) of monomer (a) copolymerization The copolymer of member.

To reaction sequence and be not limited, monomer (a) can be made, with least one of monomer (b) and (c) while copolymerization. In addition, in the case of whole using monomer (a)~(c), can make monomer (c) anti-after monomer (a) and monomer (b) copolymerization is made Should, it can also react after by monomer (a) and monomer (c) copolymerization monomer (b).In addition, can also make monomer (a) and monomer (b), list The copolymer reaction of body (c) and then make carboxylic acid anhydride reactant.

As (a), for example, it can include acrylic acid, methacrylic acid, crotonic acid, o-, m-, p- vinyl benzoic acid Deng unsaturated monocarboxylic；

The adjacent benzene two of maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- vinylphthalic acids, 4- vinyl Formic acid, 3,4,5,6- tetrahydrophthalic acids, 1,2,3,6- tetrahydrophthalic acids, dimethyl tetrahydro phthalic acid, 1,4- The unsaturated dicarboxylics 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 Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5- carboxymethyl groups, bicyclic [2.2.1] hept-2-ene" of 5- carboxy ethyls etc. contain There is the bicyclic unsaturated compound of carboxyl；

Carboxylic acid anhydrides such as the acid anhydrides of above-mentioned unsaturated dicarboxylic in addition to fumaric acid and mesaconic acid etc..

Mono succinate [2- (methyl) acryloyl-oxyethyl] ester, phthalic acid list [2- (methyl) propylene can be included Trimethylammonium] more than 2 yuan of the polybasic carboxylic acid such as ester single [(methyl) acryloxyalkyl] esters of unsaturation；

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

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

(b) refer to the ring-type ether structure with carbon number 2~4 (for example, selected from oxirane ring, oxetanes ring and four It is at least one kind of in hydrogen furan nucleus) and ethylenic unsaturated bond polymerizable compound.(b) preferably there is the cyclic ether of carbon number 2~4 The monomer of (methyl) acryloxy.

As (b), for example, it can include the monomer (b1) with epoxy ethyl and ethylenic unsaturated bond (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), for example, it can include the knot that the unsaturated aliphatic hydrocarbon with straight-chain or branch's chain state is at least partially epoxidized Monomer (b1-1) (hereinafter sometimes referred to " (b1-1) "), the monomer for the structure being at least partially epoxidized with ester ring type unsaturated hydrocarbons of structure (b1-2) (hereinafter sometimes referred to " (b1-2) ").

As (b1-1), the monomer preferably with glycidyl and ethylenic unsaturated bond.As (b1-1), specifically, (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) propenoic acid beta-second can be included Base ethylene oxidic ester, glycidyl vinyl ether, vinylbenzyl glycidyl base ether, Alpha-Methyl vinyl benzyl shrink sweet Double (glycidoxypropyl methyl) styrene of oleyl ether, 2,3-, double (glycidoxypropyl methyl) styrene of 2,4-, 2,5- are double (glycidoxypropyl methyl) styrene, 2,6- double (glycidoxypropyl methyl) styrene, (glycidoxypropyls of 2,3,4- tri- Methyl) styrene, 2,3,5- tri- (glycidoxypropyl methyl) styrene, 2,3,6- tri- (glycidoxypropyl methyl) benzene second Alkene, 3,4,5- tri- (glycidoxypropyl 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 De (registration mark) 2000；(strain) Daicel manufacture), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylate (examples Such as, サ イ Network ロ マ ー (registration mark) A400；(strain) Daicel manufacture), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates (for example, サ イ Network ロ マ ー (registration mark) M100；(strain) Daicel manufacture), by formula (BI) represent compound and by formula (BII) compound represented etc..

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

X^aAnd X^bSingly-bound, *-R are represented independently of each other^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 compound represented by formula (BI), any one table among formula (BI-1)~formula (BI-15) can be included Compound shown etc., it is preferable that can include by formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) or The compound that formula (BI-11)~formula (BI-15) is represented, it is highly preferred that can include by formula (BI-1), formula (BI-7), formula (BI- 9) or formula (BI-15) represent compound.

As the compound represented by formula (BII), any one among formula (BII-1)~formula (BII-15) can be included Compound of expression etc., it is preferable that can include by formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula And formula (BII-11) (BII-9) compound that~formula (BII-15) is represented, it is highly preferred that can include by formula (BII-1), formula (BII-7), the compound that formula (BII-9) and formula (BII-15) are represented.

By formula (BI) represent compound and by formula (BII) represent compound can each be used alone, also can by by Compound and be used in combination by the compound of formula (BII) expression that formula (BI) is represented.In the case of by them and use, represented by formula (BI) Compound and by formula (BII) represent compound containing ratio with molar basis, preferably 5：95~95：5, more preferably For 10：90~90：10, more preferably 20：80~80：20.

As above-mentioned (b2), the monomer more preferably with oxetanylmethoxy He (methyl) acryloxy., can as (b2) Include 3- methyl -3- (methyl) acryloyloxymethyls oxetanes, 3- ethyls -3- (methyl) acryloyloxymethyl oxygen Azetidine, 3- methyl -3- (methyl) acryloyl-oxyethyl oxetanes and 3- ethyls -3- (methyl) acryloxy second Base oxetanes etc..

As (c), such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid can 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) Ring [the 5.2.1.0 of acrylic acid three^2,6] decane -8- base esters (and in the technical field, as trivial name, be referred to as " (methyl) acrylic acid Bicyclic pentyl ester ".In addition, sometimes referred to as " (methyl) acrylic acid tricyclodecyl ".), the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] last of the ten Heavenly stems Alkane -9- base esters, the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] decene -8- base esters are (in the technical field, as trivial name, referred to as " (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate ".), the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] decene -9- base esters, (methyl) propylene The bicyclic amoxy ethyl ester of acid, (methyl) isobornyl acrylate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid allyl Ester, (methyl) propargylacrylate, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester and (methyl) benzyl acrylate etc. (methyl) acrylate；

(methyl) propylene containing hydroxyl such as (methyl) acrylic acid 2- hydroxy methacrylates and (methyl) acrylic acid 2- hydroxy propyl esters Acid esters；

The dicarboxylic diesters such as diethyl maleate, diethyl fumarate and 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 such as [2.2.1] hept-2-ene" and double (cyclohexyloxy carbonyl) bicyclic [2.2.1] hept-2-ene"s of 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 Two carbonyls such as acid imide caproate, N- succinimide base -3- maleimidopropionic acids salt and N- (9- acridinyls) maleimide Base imine derivative；

The aromatic series containing vinyl such as styrene, α-methylstyrene, vinyltoluene and p-methoxystyrene Compound；The nitriles containing vinyl such as (methyl) acrylonitrile；The halogenated hydrocarbons such as vinyl chloride and vinylidene chloride；(methyl) acrylamide etc. contains There is the acid amides of vinyl；The esters such as vinylacetate；1,3- butadiene, isoprene and 2,3- dimethyl -1,3- butadiene etc. two Alkene etc..

In these, from copolyreaction and heat resistance aspect, optimization styrene, vinyltoluene, N- phenyl horses Come acid imide, N- N-cyclohexylmaleimides, N- benzyl maleimides and bicyclic [2.2.1] hept-2-ene" etc..

Polymerization initiator and solvent etc. are not particularly limited, material usually used in the field can be used.For example, As polymerization initiator, azo-compound (2,2 '-azodiisobutyronitrile, 2, (2, the 4- dimethyl-pentens of 2 '-azo two can be included Nitrile) etc.), organic peroxide (benzoyl peroxide etc.), as solvent, as long as by each monomer dissolve, work can be included Solvent (E) solvent described later of colored curable resin composition for the present invention etc..

It should illustrate, reacted solution can be used directly in obtained copolymer, it is possible to use the solution of concentration or dilution, It it is also possible to use the product taken out using methods such as reprecipitations as solid.Solvent during particularly as the polymerization, by using Contained solvent in the colored curable resin composition of the present invention, can be by reacted solution directly in the coloring of the present invention Used in the preparation of hardening resin composition, therefore, it is possible to the manufacture work for the colored curable resin composition for simplifying the present invention Sequence.

In addition, catalysts (such as three (the dimethylaminos of carboxylic acid or carboxylic acid anhydrides and cyclic ether can be used as needed Methyl) phenol etc.) and polymerization inhibitor (such as quinhydrones) etc..

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 Hydrogen phthalic anhydride and bicyclic [2.2.1] the hept-2-ene" acid anhydride of 5,6- dicarboxyls etc..The usage amount of carboxylic acid anhydrides, making relative to (a) 1 mole of consumption, preferably 0.5~1 mole.

As resin (B), specifically, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates/(methyl) propylene can be included Acid copolymer, the ring [5.2.1.0 of (methyl) acrylic acid 3,4- epoxies three^2.6] resin such as last of the ten Heavenly stems ester/(methyl) acrylic copolymer；(first Base) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl Ester/styrene/(methyl) acrylic copolymer, the ring [5.2.1.0 of (methyl) acrylic acid 3,4- epoxies three^2.6] last of the ten Heavenly stems ester/(methyl) third Olefin(e) acid/N- N-cyclohexylmaleimides copolymer, the ring [5.2.1.0 of (methyl) acrylic acid 3,4- epoxies three^2.6] last of the ten Heavenly stems ester/(methyl) Acrylic acid/vinyl toluene copolymer, 3- methyl -3- (methyl) acryloyloxymethyls oxetanes/(methyl) acrylic acid/ The resins such as styrol copolymer；(methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) acrylic acid are common The resins such as polymers, (methyl) benzyl acrylate/(methyl) acrylic acid tricyclodecyl/(methyl) acrylic copolymer；Make (methyl) The resin of glycidyl acrylate and (methyl) benzyl acrylate/(methyl) acrylic copolymer addition, make (methyl) Glycidyl acrylate and the tree of (methyl) acrylic acid tricyclodecyl/styrene/(methyl) acrylic copolymer addition Fat, make (methyl) glycidyl acrylate and (methyl) acrylic acid tricyclodecyl/(methyl) benzyl acrylate/(methyl) propylene The resins such as the resin of acid copolymer addition；Make (methyl) acrylic acid and (methyl) acrylic acid tricyclodecyl/(methyl) propylene The resin of the copolymer reaction of acid glycidyl ester, make (methyl) acrylic acid and (methyl) acrylic acid tricyclodecyl/styrene/ The resins such as the resin of copolymer reaction of (methyl) glycidyl acrylate；Make (methyl) acrylic acid and (methyl) propylene The resin of the copolymer reaction of sour tricyclodecyl/(methyl) glycidyl acrylate further with tetrahydrophthalic acid Resins such as the resin of anhydride reactant etc..

The weight average molecular weight of the polystyrene conversion of resin (B) is preferably 3000~100000, more preferably 5000~ 50000, more preferably 5000~30000.If molecular weight is in above-mentioned scope, exist hardness of film improve, it is residual The tendency that film rate is also high, unexposed portion is improved for the favorable solubility of developer solution, the resolution ratio of colored pattern.

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

The acid number of the solid constituent conversion of resin (B) is preferably 50~170mg-KOH/g, more preferably 50~150mg- KOH/g, more preferably 50~135mg-KOH/g.Wherein, acid number is as the potassium hydroxide needed for neutralization resin (B) 1g Amount (mg) determine value, for example, can be titrated and be obtained by using potassium hydroxide aqueous solution.

The containing ratio of resin (B), relative to the total amount of solid constituent, preferably 7~65 mass %, 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, the tendency that the resolution ratio with colored pattern and residual film ratio are improved in addition.

＜ polymerizable compounds (C) ＞

Polymerizable compound (C) is can to utilize the living radical produced by polymerization initiator (D) and/or acid polymerization Compound, can include such as the compound of the ethylenic unsaturated bond with polymerism, can preferably include (methyl) third Enoic acid ester compounds.

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

As the polymerizable compound with 2 ethylenic unsaturated bonds, for example, it can enumerate 1,6- hexylene glycols two (methyl) third Olefin(e) acid ester, ethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylic acid Double (acryloyl-oxyethyl) ethers and 3- methyl pentanediols two (methyl) acrylate etc. of ester, bisphenol-A.

Wherein, polymerizable compound (C) is preferably the polymerizable compound with the ethylenic unsaturated bond of more than 3.Make For such polymerizable compound, for example, it can include trimethylolpropane tris (methyl) acrylate, (first of pentaerythrite three 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 (methyl) acrylate of pentaerythrite four and caprolactone modification dipentaerythritol six (methyl) acrylate etc., preferably Ground can include (methyl) acrylate of dipentaerythritol five and dipentaerythritol six (methyl) acrylate.

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

Relative to the total amount of solid constituent, the containing ratio of polymerizable compound (C) is preferably 7~65 mass %, more preferably For 13~60 mass %, more preferably 17~55 mass %.

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

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

＜ polymerization initiators (D) ＞

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

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

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

As above-mentioned O- acyl groups oxime compound, for example, it can include N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) 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- dioxolyls methoxyl group) benzoyl -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -3- cyclopenta propane -1- imines and 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 product such as Irgacure OXE01, OXE02 (being manufactured above for BASF AG), N-1919 (manufacture of ADEKA companies).Wherein, 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, more preferably N- benzoyloxys -1- (4- phenyl sulfanes in -3- cyclopenta propane -1- ketone -2- imines Base phenyl) octane -1- ketone -2- imines.

In addition, in the mass parts of polymerization initiator 100, the content of O- acyl group oxime compounds is preferably more than 5 mass parts, more It is more than preferably 50 mass parts, it is more than more preferably 70 mass parts, still more preferably for 80 mass parts more than, be preferably Below 100 mass parts.

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

As the compound with the part-structure represented by formula (d2), for example, it can include 2- methyl -2- morpholinoes -1- (4- methylsulfanyls phenyl) propane -1- ketone, 2- dimethylaminos -1- (4- morphlinophenyls) -2- benzyls butane -1- ketone and 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), for example, it can include 2- hydroxy-2-methyl -1- benzene 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 and benzene are even Acyl dimethyl ketal etc..

From sensitivity aspect, as alkyl phenyl assimilation compound, preferably with the part-structure represented by formula (d2) Compound.

As united imidazole, for example, it can enumerate 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (for example, referring to Japanese Unexamined Patent Publication 6-75372 public affairs Report, Japanese Unexamined Patent Publication 6-75373 publications etc..), 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 ' - Double (2- chlorphenyls) -4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (two Alkoxyl phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxalines (for example, ginseng According to Japanese Patent Publication 48-38403 publications, Japanese Unexamined Patent Application 62-174204 publications etc..) and 4,4 ', the phenyl of 5,5 '-position Imidazolium compounds (for example, referring to Japanese Unexamined Patent Publication 7-10913 publications etc.) replaced by alkoxy carbonyl group etc..Wherein, preferably by Compound and their mixture that following formula is represented.

As above-mentioned triaizine compounds, for example, 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- - 1,3,5- triazines and double (trichloromethyl) -6- [2- (3,4- Dimethoxyphenyls) the vinyl] -1,3,5- triazines of 2,4- etc..

As above-mentioned acylphosphine oxide compound, TMDPO etc. can be included.

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

These are preferably applied in combination with the initiation auxiliary agent (D1) described later that polymerize.

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

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

＜ 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 and 4,4 '-bis- (ethylmethylamino) benzophenone Deng can preferably include 4,4 '-bis- (diethylamino) benzophenone.EAB-F (hodogaya chemical industry (strain) systems can be used Make) etc. commercially available product.

As above-mentioned alkoxy anthracene compound, can enumerate 9,10- dimethoxys anthracene, EDMO, 9,10- diethoxies anthracene, 2- ethyl -9,10- diethoxies anthracene, 9,10- dibutoxies anthracene and 2- ethyl -9,10- dibutoxies Anthracene etc..

As above-mentioned thioxanthone compounds, ITX, ITX, 2,4- diethyl can be included Thioxanthones, the clopenthixal ketones of 2,4- bis- and 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 and naphthoxy acetic acid etc..

In the case where triggering auxiliary agent (D1) using these polymerizations, relative to the conjunction of resin (B) and polymerizable compound (C) 100 mass parts are measured, polymerization triggers the content of auxiliary agent (D1) to be preferably 0.1~30 mass parts, more preferably 1~20 mass parts. , can be with more high sensitivity formation colored pattern, the productivity ratio of colour filter if polymerization triggers the amount of auxiliary agent (D1) within the range Tend to improve.

＜ solvents (E) ＞

Solvent (E) is not particularly limited, solvent usually used in the field can be used.Can for example ester output be enumerated molten Agent (intramolecular include-COO-, the solvent without-O-), ether solvents (intramolecular include-O-, the solvent without-COO-), Ether-ether solvent (in solvent of the intramolecular comprising-COO- and-O-), ketone solvent (include-CO-, molten without-COO- in intramolecular Agent), alcoholic solvent (intramolecular include OH, the solvent without-O- ,-CO- and-COO-), aromatic hydrocarbon solvents, amide solvent and Dimethyl sulfoxide (DMSO) etc..

As ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-methyl isobutyl acids, acetic acid second can be included Ester, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, fourth Acid butyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Hexacyclonic Acid Ester 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, diethylene glycol monobutyl ehter acetic acid esters and dipropylene glycol methyl ether acetic acid esters etc..

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

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

Wherein, preferably propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, 3- ethoxy-propionic acid second Ester, ethylene glycol single methyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, carbiphene, acetic acid 3- methoxyl group fourths Ester, 3- methoxyl groups-n-butyl alcohol, 4- hydroxy-4-methyl-2-pentanones, DMF and 1-METHYLPYRROLIDONE etc., more It is preferred that propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetic acid esters, Ethyl lactate, 3- methoxybutyls acetic acid esters, 3- methoxyl groups-n-butyl alcohol, 3- ethoxyl ethyl propionates and 1-METHYLPYRROLIDONE.

Relative to the total amount of colored curable resin composition, the containing ratio of solvent (E) is preferably 70~95 mass %, more Preferably 75~92 mass %.In other words, the solid constituent of colored curable resin composition is preferably 5~30 mass %, more Preferably 8~25 mass %.If the containing ratio of solvent (E) is in above-mentioned scope, flatness during coating becomes good, Colour saturation will not be not enough when being additionally formed colour filter, therefore becomes good tendency with display characteristic.

＜ levelling agents (F) ＞

As levelling agent (F), silicone based surfactants, fluorine system surfactant and having with fluorine atom can be enumerated Machine silicon systems surfactant etc..These can have polymerizable group in side chain.

As silicone based surfactants, can be set forth in intramolecular has surfactant of siloxanes key etc..Specifically Ground, 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, the 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 マ テ リ ア Le electronics chemical conversion (strain) manufacture), サ ー Off ロ Application (registration mark) S381, S382, SC101, SC105 (Asahi Glass (strain) manufacture) and E5844 ((strain) ダ イ キ Application Off ァ イ Application ケ The research of ミ カ Le is manufactured) etc..

As the above-mentioned silicone based surfactants with fluorine atom, can be set forth in intramolecular have siloxanes key and Surfactant of fluorocarbon chain etc..Specifically, can include メ ガ Off ァ ッ Network (registration mark) R08, BL20, F475, F477 and F443 (DIC (strain) manufactures) etc..

In the case of containing levelling agent (F), relative to the total amount of colored curable resin composition, levelling agent (F) Containing ratio is preferably more than 0.001 mass % and below 0.2 mass %, more preferably more than 0.002 mass % and 0.1 mass % Hereinafter, more preferably more than 0.005 mass % and below 0.07 mass %.If the containing ratio of levelling agent (F) is above-mentioned In the range of, then can make the flatness of colour filter becomes good.

＜ other compositions ＞

The colored curable resin composition of the present invention, as needed, can include filler, other macromolecule chemical combination 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 use as needed, solvent (E), levelling agent (F), polymerization trigger auxiliary agent (D1) and Other compositions are mixed and prepared.

In the case that colouring agent (A) beyond xanthene compound (A-1) includes pigment (P), the pigment (P) preferably in advance with Part or all of mixing of solvent (E), it is scattered until the average grain diameter of pigment turns into less than 0.2 μm journey using ball mill etc. Degree.Now, part or all of above-mentioned pigment dispersing agent, resin (B) can be coordinated as needed.

The filter for preferably using 0.01~10 μm or so of aperture filters mixed colored curable resin composition.

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 via photomask and developed.In photoetching process, lead to Cross and without using photomask and/or do not develop in exposure, so as to form the solidfied material as above-mentioned coloring compositions nitride layer Colour film.The colored pattern so formed, coloring film can be made as colour filter of the invention.

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

As substrate, can be used glass plate, resin plate, silicon and formd on the substrate of above-mentioned material aluminium, silver and silver/ The product of copper/palldium alloy film etc..Other color-filter layer, resin bed, transistor and circuit etc. can be formed on these substrates.

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, by heat drying (prebake) and/ Or be dried under reduced pressure, so that the volatile ingredients such as solvent be removed and dried, obtain smooth coloring compositions nitride layer.It is used as coating side Method, can enumerate spin-coating method, slot coated method, slit and method of spin coating etc..

Next, being exposed via the photomask of the colored pattern for forming target to coloured composition layer.Due to Parallel rays can equably be irradiated to plane of exposure entirety, carry out the correct of substrate of the photomask with foring coloring compositions nitride layer Contraposition, therefore preferably use the exposure devices such as mask aligner and stepper.

Developed by making the coloring compositions nitride layer after exposure be contacted with developer solution, 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, for example preferably The aqueous solution of the alkali compounds such as potassium hydroxide, sodium acid carbonate, sodium carbonate and tetramethyl ammonium hydroxide.Developing method can be rotation Cover any of immersion method, infusion process and spray-on process etc..And then, in development substrate can be made to tilt arbitrary angle.After development It is preferred that being washed.

The colored pattern that preferred pair is obtained is bakeed after further carrying out.

The colored pattern enabled to is constituted as colour filter.

Using the colored curable resin composition of the present invention, heat resistance especially excellent colour filter can be manufactured.The filter Color device can be used as making in display device (for example, liquid crystal display device, organic el device, Electronic Paper etc.) and solid-state imager Colour filter.

Embodiment

Embodiment is exemplified below to further illustrate the present invention, but the present invention is not limited fundamentally by following embodiments System, is suitably changed to implement also it is of course possible to which they are all wrapped in the range of main contents described later before being adapted to In the technical scope for being contained in the present invention.Should illustrate, below in, as long as no special instructions, " part " means " mass parts ", " % " Mean " quality % ".

(synthesis example 1)

10 parts of the compound represented by formula (AXa-1), chloroform 300 are put into possessing the flask of cooling tube and agitating device 12.6 parts of thionyl chloride is added dropwise in 5.7 parts of part and DMF, less than 20 DEG C of side maintenance under agitation, side, and maintenance 5 is small When react it.Then, side maintains less than 20 DEG C under agitation, and 11.5 parts of 6.7 parts of N- ethyl dimethylamines and triethylamine is added dropwise in side Mixed liquor.Then, react it within 5 hours in synthermal lower stirring.Next obtained reaction is mixed with rotary evaporator Thing is carried out after solvent distillation, is added a small amount of methanol, is vigorously stirred.Ion exchange water 375 is added the mixture to while stirring In the mixed liquor of part, separate out crystallization.The crystallization of precipitation is separated by filtration, fully cleaned with ion exchange water, is subtracted at 60 DEG C Press dry it is dry, obtained by formula (AXa-1a) represent 10.7 parts of compound.

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

(quality analysis) ionization mode=ESI+：M/Z=701.9 [M-Cl]⁺

Definite quality：736.4

400 parts of methanol is added in 7.3 parts of the compound represented by formula (AXa-1a), 1 is stirred at 20 DEG C~30 DEG C small When, obtain solution.400 parts of ion exchange water is added in the solution, stirs 2 hours, has obtained solution (AXa-1aKA).

On the other hand, 28.8 parts of ion exchange water is added in 9.6 parts of 12 wolframic acid of phosphorus, 3 hydrogen, 1 is stirred at 20 DEG C~30 DEG C Hour, next, adding 28.8 parts of methanol, stir 2 hours, obtained solution (AXa-1aKB).In solution (AXa-1aKA) Solution (AXa-1aKB) is added, is stirred 12 hours at 20 DEG C~30 DEG C.By filtering the sediment leaching of generation, ion is used 200 parts of exchanged water is cleaned 2 times, next with the cleaning 2 times of 200 parts of methanol.The crystallization of leaching is dried 24 hours at 60 DEG C, obtained 10.2 parts of the compound represented by formula (AXa-1A) is arrived.

(synthesis example 2)

N- ethyl dimethylamines are replaced in synthesis example 1 and are used beyond 2 ethyl hexylamine, synthesizes, obtains in the same manner as synthesis example 1 10.2 parts of the compound represented by formula (AXa-2A) is arrived.

(synthesis example 3)

In the flask with reflux cooler, dropping funel and agitator, flow into appropriate nitrogen and turn into blanket of nitrogen, Load 100 parts of propylene glycol monomethyl ether, 85 DEG C are heated to while stirring.Next, in the flask, using dropping liquid pump Last about 5 hours and instill 19 parts of methacrylic acid, the ring [5.2.1.0 of acrylic acid 3,4- epoxies three^2,6] decane -8- base esters and third Ring [the 5.2.1.0 of olefin(e) acid 3,4- epoxies three^2,6] decane -9- base esters mixture (contain than being represented with mol ratio, be 50：50) (business The name of an article " E-DCPA ", the manufacture of Co., Ltd. Daicel) 171 parts of solution for being dissolved in 40 parts of propylene glycol monomethyl ether. On the other hand, about 5 hours are lasted using other dropping liquid pump to instill polymerization initiator 2,2 '-azo two (2,4- into flask Methyl pentane nitrile) 26 parts of solution for being dissolved in 120 parts of propylene glycol monomethyl ether.The instillation of polymerization initiator terminates Afterwards, kept for about 3 hours synthermal, be then cooled to room temperature, obtained copolymer, the resin (B-1) of solid constituent 43.5% Solution.The weight average molecular weight of obtained resin (B-1) is 8000, and decentralization is 1.98, and the acid number of solid constituent conversion is 53mg-KOH/g。

(synthesis example 4)

In the flask with reflux cooler, dropping funel and agitator, flow into appropriate nitrogen and turn into blanket of nitrogen, Load 280 parts of propylene glycol monomethyl ether, 80 DEG C are heated to while stirring.Next, in the flask, using dropping liquid pump Last about 5 hours and instill 38 parts of acrylic acid, the ring [5.2.1.0 of acrylic acid 3,4- epoxies three^2,6] decane -8 and 9- base esters mixing Thing (is contained than being represented with mol ratio, is 50：50) 289 parts of (trade name " E-DCPA ", Co., Ltd. Daicel manufacture) is dissolved in Solution in 125 parts of propylene glycol monomethyl ether.On the other hand, about 6 hours are lasted to flask using other dropping liquid pump Polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) is dissolved in propylene glycol monomethyl ether 235 for 33 parts by interior instillation Solution in part.After the instillation of polymerization initiator terminates, kept for about 4 hours synthermal, be then cooled to room temperature, consolidate The copolymer (resin (B-2)) of body composition 35.1%.The weight average molecular weight of obtained resin (B-2) is 9200, and decentralization is 2.08, the acid number of solid constituent conversion is 77mg-KOH/g.

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

Test solution solid component concentration：0.001~0.01 mass %

Injection rate：50μL

Detector：RI

Correction standard substance：TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500 (eastern Cao's (strain) manufacture)

The ratio between weight average molecular weight and number-average molecular weight that polystyrene obtained above is converted (Mw/Mn) are as scattered Degree.

[preparation of colored curable resin composition]

Embodiment 1,2, comparative example 1

Composition shown in following tables is mixed, colored curable resin composition has been obtained.

【Table 3】

In table, each composition is as described below.

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

Dyestuff (A-2)：The compound represented by formula (AXa-2A)

Dyestuff (A-3)：Rhodamine B (Tokyo chemical conversion industry (strain) manufacture)

Resin (B)：Resin (B-1) (solid constituent conversion)

Polymerizable compound (C)：Dipentaerythritol acrylate (KAYARAD (registration mark) DPHA；Japanese chemical drug (strain) is manufactured)

Polymerization initiator (D)：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-1)：Propylene glycol monomethyl ether

Solvent (E-2)：Propylene glycol monomethyl ether

Solvent (E-3)：Ethyl lactate

Solvent (E-4)：Dimethylformamide

Levelling agent (F)：メ ガ Off ァ ッ Network (registration mark) F554 (DIC (strain) manufactures)

[formation of pattern]

In the glass substrate (イ ー グ Le XG of 2 inch squares；Corning Incorporated manufacture) on color sensation is coated with using spin-coating method After photosensitiveness composition, prebake 3 minutes, have obtained composition layer at 100 DEG C.After cooling, make the glass for foring composition layer The interval of glass substrate and quartz glass photomask turns into 100 μm, uses exposure machine (TME-150RSK；ト プ Us Application (strain) is made Make) under air atmosphere, with 150mJ/cm²Light exposure (365nm benchmark) carry out light irradiation.As photomask, formation is used The photomasks of 100 μm of lines and space pattern.After light irradiation, above-mentioned film is being included into nonionic surfactants 0.12% With in the water system developer solution of potassium hydroxide 0.04% at 23 DEG C immersion development 80 seconds, after washing, enter in an oven, at 220 DEG C Row is bakeed after 20 minutes, has obtained pattern.

[Evaluation of Heat Tolerance]

In the formation of above-mentioned pattern, carry out light irradiation when not via photomask beyond, obtain as described above Film.Use colour examining machine (OSP-SP-200；OLYMPUS companies manufacture) determine the colourity of obtained film.Then, will be identical Film heated at 230 DEG C after 20 minutes, use colour examining machine (OSP-SP-200；OLYMPUS companies manufacture) determine again Colourity, obtains the aberration (Δ Eab*) of the film before and after heating.By the colored curable resin composition shape of Examples 1 and 2 Into the aberration (Δ Eab*) of film be respectively 4.5 and 3.8.In addition, by the colored curable resin composition shape of comparative example 1 Into film aberration (Δ Eab*) be 80.1.It follows that the painting formed by the colored curable resin composition of the present invention The excellent heat resistance of film and pattern.

Comparative example 2

(making of dispersion liquid)

The pigment red 81 of 10.0 parts of weighing, dispersant DISPERBYK-LPN6919 (the propane diols list first of solid constituent 38% Base ether acetic acid ester solution) 10.5 parts, as dispersion resin (resin B -2) propylene glycol monomethyl ether solution (solid Composition 35%) 5.7 parts, after 163.7 parts of propylene glycol monomethyl ether, load 0.4 μm of 300 parts of zirconium oxide bead, use Coating conditioner (manufacture of LAU companies) vibrates 3 hours, makes dispersion liquid.

(making of colored curable resin composition)

By above-mentioned dispersion liquid：15 parts；

Alkali soluble resin (B)：1.0 parts of resin (B-1) (solid constituent conversion)；

Polymerizable compound (C)：Dipentaerythritol acrylate (KAYARAD (registration mark) DPHA；Japanese chemical drug (strain) is manufactured) 2.0 parts；

Polymerization initiator (D)：N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) octane -1- ketone -2- imines (Irgacure (registration mark) OXE-01；BASF AG manufactures；O- acyl groups oxime compound) 0.3 part；

Solvent (E)：18 parts of propylene glycol monomethyl ether；

Levelling agent (H)：Polyether modified silicon oil (solid constituent conversion)

(TORAY SILICONE SH8400；East beautiful DOW CORNING (strain) manufacture) 0.09 part

Mixing, has obtained colored curable resin composition.

Heat resistance is have rated using with embodiment 1,2 and the same method of comparative example 1, as a result aberration (Δ Eab*) is 17.7。

Industrial applicability

If using the colored curable resin composition of the present invention, the colour filter with good heat resistance can be provided Device.The colour filter can be used as in display device (for example, liquid crystal display device, organic el device, Electronic Paper etc.) and solid-state image pickup The colour filter used in element.

Claims (6)

1. colored curable resin composition, its be comprising xanthene compound (A-1), resin (B), polymerizable compound (C) and The colored curable resin composition of polymerization initiator (D), xanthene compound (A-1) is with cation (AXa) and anion (AXb) compound, cation (AXa) has the xanthene skeleton with substituted or unsubstituted sulfamoyl, anion (AXb) Contain at least one element and oxygen in tungsten, molybdenum, silicon and phosphorus as essential elements.

2. colored curable resin composition according to claim 1, wherein, the cation (AXa) with xanthene skeleton For the cation represented by formula (I)：

In formula (I),

R^1a~R^4aIndependently of each other represent hydrogen atom, can have substituent carbon number 6~10 aromatic hydrocarbyl or can have take Contained methylene (- CH in the saturated hydrocarbyl of Dai Ji carbon number 1~20, the saturated hydrocarbyl₂-) can by-O- ,-CO- ,- NR^11a- ,-OCO- ,-COO- ,-OCONH- ,-NHCOO- ,-CONH- or-NHCO- replace, R^1aAnd R^2aIt can be formed together containing nitrogen The ring of atom, R^3aAnd R^4aThe ring containing nitrogen-atoms can be formed together, and but, adjacent methylene will not be replaced by phase simultaneously Same substituent, in addition, the methylene of end will not be also replaced,

R^6aAnd R^7aThe alkyl of hydrogen atom or carbon number 1~6 is represented independently of each other,

Ma represents 1~5 integer,

R^9aAnd R^10aHydrogen atom is represented independently of each other or can have the saturated hydrocarbyl of the carbon number 1~20 of substituent, the saturated hydrocarbyl In contained methylene (- CH₂-) can be by-O- ,-CO- ,-NR^11a-、-OCO-、-COO-、-OCONH-、-NHCOO-、-CONH- Or-NHCO- is replaced, R^9aAnd R^10aThe heterocycle of 3~10 yuan of rings containing nitrogen-atoms can be combined with each other and be formed, but, adjacent Asia Methyl will not be replaced by identical substituent simultaneously, in addition, the methylene of end will not be also replaced,

R^11aRepresent the aralkyl of hydrogen atom, the saturated hydrocarbyl of 1 valency of carbon number 1~20 or carbon number 7~10.

3. colored curable resin composition according to claim 1, wherein, anion (AXb) is contains tungsten as must Want the heteropoly acid of element or the anion of isopolyacid.

4. colored curable resin composition according to claim 1, wherein, anion (AXb) for phosphotungstic acid it is cloudy from Any one among son, the anion of the anion of silico-tungstic acid or tungsten system isopolyacid.

5. the colour filter formed as the colored curable resin composition according to any one of Claims 1 to 4.

6. display device, it includes colour filter according to claim 5.