CN103454859A

CN103454859A - Colored curable resin composition

Info

Publication number: CN103454859A
Application number: CN2013102012776A
Authority: CN
Inventors: 市冈贤二
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2012-05-29
Filing date: 2013-05-27
Publication date: 2013-12-18
Also published as: KR20130133675A; TWI592751B; JP6777129B2; JP2014005451A; TW201411283A; KR102155239B1; JP2018012839A; JP2019065288A

Abstract

Provided is a colored curable resin composition, comprising a coloring agent, resin, polymer compound and polymerization initiator, wherein the coloring agent has xanthene dyes, tetrazaporphyri dyes containing the compound expressed by the following formula (1b) and pigment. In the formula (1b), R41-R48 respectively represents hydrogen atom, halogen atom, cyano group, replaced or non-replaced alkyl group, replaced or non-replaced alkoxy, replaced or non-replaced aryl group, replaced or non-replaced aryloxy, replaced or non-replaced aralkyl oxygroup, replaced or non-replaced amine; M represents two hydrogen atoms, two mono-valence metallic atoms, a bivalence metallic atom, a trivalence replaced metallic atom or an oxidized metallic atom.

Description

Colored curable resin composition

Technical field

The present invention relates to colored curable resin composition.

Background technology

Colored curable resin composition is used to the manufacture of the color filter that the display device of display panels, electroluminescence panel and plasma display device etc. used.As such colored curable resin composition, be known that: only comprise xanthene dye and C.I. pigment blue 15: 6 colored curable resin compositions as colorant (JP2010-32999-A), and comprise xanthene dye, C.I. pigment blue 15: 6 and phthalocyanine dye as the colored curable resin composition (JP2011-28236-A) of colorant.

Yet the contrast of the color filter obtained by the past known above-mentioned colored curable resin composition may not fully be satisfied the demand.

Summary of the invention

The inventor is studied in order to address the above problem, and result has completed the present invention.

The present invention comprises following scheme.

[1] a kind of colored curable resin composition, it contains colorant, resin, polymerizable compound and polymerization initiator,

Wherein, colorant comprises xanthene dye, contains the compound shown in following formula (1b) tetraazatetradecane porphyrin dyestuff and pigment.

In formula (1b), R ⁴¹～R ⁴⁸mean independently of one another hydrogen atom, halogen atom, cyano group, nitro, replacement or unsubstituted alkyl, replacement or unsubstituted alkoxy, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy group, replacement or unsubstituted aralkoxy or replacement or unsubstituted amino, M means 2 hydrogen atoms, 21 valency metallic atoms, divalent metallic atom, 3 valency substituted metal atoms or oxidized metal atoms.

[2] according to [1] described colored curable resin composition, wherein,

With respect to xanthene dye 100 mass parts, the content of tetraazatetradecane porphyrin dyestuff is more than 1 mass parts and below 100 mass parts.

[3] according to [1] or [2] described colored curable resin composition, wherein,

With respect to the total amount of colorant, the content of xanthene dye is more than 0.1 quality % and below 50 quality %.

[4] according to the described colored curable resin composition of any one in [1]～[3], wherein,

Xanthene dye contains the compound meaned by following formula (1a),

In formula (1a), R ¹～R ⁴the 1 valency saturated hydrocarbyl that mean independently of one another hydrogen atom, can have a substituent carbon number 1～20 maybe can have 1 valency aromatic hydrocarbyl of substituent carbon number 6～10, contained in this saturated hydrocarbyl-CH ₂-can by-O-,-CO-or-NR ¹¹-replace.R ¹and R ²can form the ring that comprises nitrogen-atoms, R with together with adjacent nitrogen-atoms ³and R ⁴can form the ring that comprises nitrogen-atoms with together with adjacent nitrogen-atoms.

R ⁵expression-OH ,-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-z ⁺,-CO ₂h ,-CO ₂ ^-z ⁺,-CO ₂r ⁸,-SO ₃r ⁸or-SO ₂nR ⁹r ¹⁰.

R ⁶and R ⁷the alkyl that means independently of one another hydrogen atom or carbon number 1～6.

M means 0～5 integer.At m, be 2 when above, a plurality of R ⁵can be the same or different.

A means 0 or 1 integer.

X means halogen atom.

Z ⁺mean ⁺n(R ¹¹) ₄, Na ⁺or K ⁺, 4 R ¹¹can be the same or different.

R ⁸mean 1 valency saturated hydrocarbyl of carbon number 1～20, hydrogen atom contained in this saturated hydrocarbyl can be replaced by halogen atom.

R ⁹and R ¹⁰mean that independently of one another hydrogen atom maybe can have 1 valency saturated hydrocarbyl of substituent carbon number 1～20, contained in this saturated hydrocarbyl-CH ₂-can by-O-,-CO-,-NH-or-NR ⁸-replace R ⁹and R ¹⁰can mutually combine and form 3～10 member heterocyclic ring containing nitrogens together with nitrogen-atoms.

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

[5] a kind of color filter, its described colored curable resin composition of any one in [1]～[4] forms.

[6] a kind of display device, it comprises [5] described color filter.

According to the present invention, can provide the colored curable resin composition of the color filter that can form high-contrast.

The accompanying drawing explanation

Fig. 1 is the sketch of the manufacture method of explanation color filter of the present invention.

Fig. 2 is the sketch of the manufacture method of explanation color filter of the present invention.

Fig. 3 is the sketch of the manufacture method of explanation color filter of the present invention.

Embodiment

Colored curable resin composition of the present invention comprises colorant (A), resin (B), polymerizable compound (C) and polymerization initiator (D).

Colorant (A) comprises xanthene dye (Aa), tetraazatetradecane porphyrin dyestuff (Ab) and pigment (Ad).Further, colorant (A) can also comprise the dyestuff different from xanthene dye (Aa) and tetraazatetradecane porphyrin dyestuff (Ab) (below be sometimes referred to as " dyestuff (Ac) ".)。

Colored curable resin composition of the present invention preferably also contains solvent (E) and/or levelling agent (F).

Colored curable resin composition of the present invention can contain polymerization and cause auxiliary agent (D1).

Colored curable resin composition of the present invention is by containing xanthene dye (Aa), tetraazatetradecane porphyrin dyestuff (Ab) and pigment (Ad) as colorant (A), thereby can manufacture the color filter of high-contrast.

Xanthene dye (Aa) is the dyestuff that comprises in molecule the compound with xanthene skeleton.As xanthene dye (Aa), for example can list, the C.I. CI 45430 (below, the record of omitting the C.I. acid red, only put down in writing sequence number.Other too.), 52,87,92,94,289,388, the xanthene dye put down in writing in the xanthene dye put down in writing in C.I. acid violet 9,30,102, C.I. alkali red 1:1 (rhodamine 6G), 2,3,4,8, C.I. alkali red 1:1 0 (rhodamine B), 11, C.I. alkaline purple 10,11,25, C.I. solvent red 218, C.I. mordant rouge 27, C.I. reactive red 36 (rose-bengal B), sulfo group Rhodamine G, JP2010-32999-A and JP4492760-B etc., be preferably dissolved in the dyestuff of organic solvent.

In the middle of these, as xanthene dye (Aa), preferably comprise the compound shown in formula (1a) (below, be sometimes referred to as " compound (1a) ".) dyestuff.Compound (1a) can be its dynamic isomer.In the situation that use compound (1a), the content of the compound (1a) in xanthene dye (Aa) be preferably 50 quality % above, more preferably 70 quality % above, more preferably more than 90 quality %.Particularly, as xanthene dye (Aa), preferably only use compound (1a).

A means 0 or 1 integer.

X means halogen atom.

As R ¹～R ⁴in 1 valency aromatic hydrocarbyl of carbon number 6～10, for example can list, phenyl, tolyl, xylyl,

base, propyl group phenyl and butyl phenyl etc.

The substituting group that can have as this aromatic hydrocarbyl, can list halogen atom ,-R ⁸,-OH ,-OR ⁸,-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-z ⁺,-CO ₂h ,-CO ₂r ⁸,-SR ⁸,-SO ₂r ⁸,-SO ₃r ⁸or-SO ₂nR ⁹r ¹⁰.In the middle of these, as substituting group, preferably-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-z ⁺and-SO ₂nR ⁹r ¹⁰, more preferably-SO ₃ ^-z ⁺and-SO ₂nR ⁹r ¹⁰.As now-SO ₃ ^-z ⁺, preferably-SO ₃ ^-+n(R ¹¹) ₄.If R ¹～R ⁴for these groups, can, by the colored curable resin composition of the present invention of inclusion compound (1a), form impurity and produce less and the color filter of excellent heat resistance.

As R ¹～R ⁴and R ⁸～R ¹¹in 1 valency saturated hydrocarbyl of carbon number 1～20, for example can list the straight chain shape alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl, eicosyl; The branched-chain alkyls such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl; The ester ring type saturated hydrocarbyl of the carbon numbers 3～20 such as cyclopropyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, three ring decyls.

R ¹～R ⁴in this saturated hydrocarbyl in contained hydrogen atom can be replaced by the aromatic hydrocarbyl of carbon number 6～10 or halogen atom.

R ⁹and R ¹⁰in this saturated hydrocarbyl in contained hydrogen atom can be replaced by hydroxyl or halogen atom.

As R ¹and R ²with the ring that comprises nitrogen-atoms and the R that form together with adjacent nitrogen-atoms ³and R ⁴the ring that comprises nitrogen-atoms with forming together with adjacent nitrogen-atoms, for example can list, below ring.

As-OR ⁸, for example can list, methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy, eicosane oxygen base etc.

As-CO ₂r ⁸, for example can list methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxy carbonyl, eicosane oxygen base carbonyl etc.

As-SR ⁸, for example can list methyl sulfenyl, ethyl sulfenyl, butyl sulfenyl, hexyl sulfenyl, decyl sulfenyl, eicosyl sulfenyl etc.

As-SO ₂r ⁸, for example can list methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, decyl sulfonyl, eicosyl sulfonyl etc.

As-SO ₃r ⁸, for example can list methoxyl sulfonyl, ethoxy sulfonyl, propoxyl group sulfonyl, tert-butoxy sulfonyl, own oxygen base sulfonyl, eicosane oxygen base sulfonyl etc.

As-SO ₂nR ⁹r ¹⁰, for example can list sulfamoyl;

N-methyl nitrogen sulfonyl, N-ethyl sulfamoyl, N-propyl group sulfamoyl, N-isopropyl sulfamoyl, N-butyl sulfamoyl, N-isobutyl sulfamoyl, N-sec-butyl sulfamoyl, N-tert-butyl group sulfamoyl, N-amyl group sulfamoyl, N-(1-ethyl propyl) sulfamoyl, N-(1,1-dimethyl propyl) sulfamoyl, N-(1,2-dimethyl propyl) sulfamoyl, N-(2,2-dimethyl propyl) sulfamoyl, N-(1-methyl butyl) sulfamoyl, N-(2-methyl butyl) sulfamoyl, N-(3-methyl butyl) sulfamoyl, N-cyclopentyl sulfamoyl, N-hexyl sulfamoyl, N-(1,3-dimethylbutyl) sulfamoyl, N-(3,3-dimethylbutyl) sulfamoyl, N-heptyl sulfamoyl, N-(1-methyl hexyl) sulfamoyl, N-(Isosorbide-5-Nitrae-dimethyl amyl group) sulfamoyl, N-octyl group sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1,5-dimethyl) hexyl sulfamoyl, the N-1 such as N-(1,1,2,2-tetramethyl butyl) sulfamoyl replace sulfamoyl,

N; N-dimethylamino sulfonyl, N; N-ethyl-methyl sulfamoyl, N, N-diethyl amino sulfonyl, N, N-propyl group methyl sulfamoyl, N; N-isopropyl methyl sulfamoyl, N; N-tert-butyl group methyl sulfamoyl, N, N-butyl ethyl sulfamoyl, N, two (1-methyl-propyl) sulfamoyls of N-, N; the N such as N-heptyl methyl sulfamoyl, N-2 replaces sulfamoyl etc.

As R ⁵, be preferably-CO ₂h ,-CO ₂ ^-z ⁺,-CO ₂r ⁸,-SO ₃ ^-,-SO ₃ ^-z ⁺,-SO ₃h and SO ₂nHR ⁹, SO more preferably ₃ ^-,-SO ₃ ^-z ⁺,-SO ₃h and SO ₂nHR ⁹.

M is preferably 1～4, more preferably 1 and 2.

As R ⁶and R ⁷in the alkyl of carbon number 1～6, in the above-mentioned alkyl of enumerating, can list the alkyl of carbon number 1～6.

As R ¹¹in the aralkyl of carbon number 7～10, can list benzyl, phenethyl, benzene butyl etc.

Z ⁺for ⁺n(R ¹¹) ₄, Na ⁺or K ⁺, be preferably ⁺n(R ¹¹) ₄.

As above-mentioned ⁺n(R ¹¹) ₄, preferred 4 R ¹¹in at least 21 valency saturated hydrocarbyls that are carbon number 5～20.In addition, 4 R ¹¹total carbon number be preferably 20～80, more preferably 20～60.In compound (1a), exist ⁺n(R ¹¹) ₄situation under, if R ¹¹for these groups, can form the color filter that impurity is few by the colored curable resin composition of the present invention of inclusion compound (1a).

As compound (1a), the compound shown in preferred formula (2a) (below be sometimes referred to as " compound (2a) ".)。Compound (2a) can be its dynamic isomer.

[in formula (2a), R ²¹～R ²⁴mean independently of one another hydrogen atom ,-R ²⁶the 1 valency aromatic hydrocarbyl that maybe can there is substituent carbon number 6～10.R ²¹and R ²²can form the ring that comprises nitrogen-atoms, R with together with adjacent nitrogen-atoms ²³and R ²⁴can form the ring that comprises nitrogen-atoms with together with adjacent nitrogen-atoms.

R ²⁵expression-SO ₃ ^-,-SO ₃h ,-SO ₃-Z1 ⁺or-SO ₂nHR ²⁶.

M1 means 0～5 integer.At m1, be 2 when above, a plurality of R ²⁵can be the same or different.

A1 means 0 or 1 integer.

X1 means halogen atom.

R ²⁶the 1 valency saturated hydrocarbyl that means carbon number 1～20.

Z1 ⁺mean ⁺n(R ²⁷) ₄, Na ⁺or K ⁺, 4 R ²⁷can be the same or different.

R ²⁷1 valency saturated hydrocarbyl or the benzyl that means carbon number 1～20.]

As R ²¹～R ²⁴in 1 valency aromatic hydrocarbyl of carbon number 6～10, can list with as above-mentioned R ¹～R ⁴the cited identical group of group of aromatic hydrocarbyl.In this aromatic hydrocarbyl, contained hydrogen atom can be by-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-z1 ⁺,-SO ₃r ²⁶or-SO ₂nHR ²⁶replace.

As R ²¹～R ²⁴combination, preferred R ²¹and R ²³for hydrogen atom, R ²²and R ²⁴for 1 valency aromatic hydrocarbyl of carbon number 6～10, and contained hydrogen atom quilt-SO in this aromatic hydrocarbyl ₃ ^-,-SO ₃h ,-SO ₃ ^-z1 ⁺,-SO ₃r ²⁶or-SO ₂nHR ²⁶replace.Further preferred combination is as described below: R ²¹and R ²³for hydrogen atom, R ²²and R ²⁴for 1 valency aromatic hydrocarbyl of carbon number 6～10, and contained hydrogen atom quilt-SO in this aromatic hydrocarbyl ₃ ^-z1 ⁺or-SO ₂nHR ²⁶replace.

If R ²¹～R ²⁴for these groups, can be formed by the colored curable resin composition of the present invention of inclusion compound (2a) color filter of excellent heat resistance.

As R ²¹and R ²²with the ring that comprises nitrogen-atoms and the R that form together with adjacent nitrogen-atoms ²³and R ²⁴the ring that comprises nitrogen-atoms with forming together with adjacent nitrogen-atoms, can list and R ¹and R ²the ring that the ring that comprises nitrogen-atoms formed together with adjacent nitrogen-atoms is identical.Wherein, preferred aliphat heterocycle.As this aliphatics heterocycle, can list for example following ring.

As R ²⁶and R ²⁷in 1 valency saturated hydrocarbyl of carbon number 1～20, can list and R ⁸～R ¹¹the middle group identical group cited as saturated hydrocarbyl.

At R ²¹～R ²⁴for-R ²⁶situation under ,-R ²⁶be preferably methyl or ethyl independently of one another.In addition, as-SO ₃r ²⁶and-SO ₂nHR ²⁶in R ²⁶, the preferably branched-chain alkyl of carbon number 3～20, more preferably branched-chain alkyl, the further preferred 2-ethylhexyl of carbon number 6～12.If R ²⁶for these groups, can be formed by the colored curable resin composition of the present invention of inclusion compound (2a) the few color filter of generation of impurity.

Z1 ⁺for ⁺n(R ²⁷) ₄, Na ⁺or K ⁺, be preferably ⁺n(R ²⁷) ₄.

As above-mentioned ⁺n(R ²⁷) ₄, preferred 4 R ²⁷in at least 21 valency saturated hydrocarbyls that are carbon number 5～20.In addition, 4 R ²⁷total carbon number be preferably 20～80, more preferably 20～60.In compound (2a), exist ⁺n(R ²⁷) ₄situation under, if R ²⁷for these groups, can be formed by the colored curable resin composition of the present invention of inclusion compound (2a) the few color filter of generation of impurity.

M1 is preferably 1～4, more preferably 1 and 2.

In addition, as compound (1a), also be preferably the compound shown in formula (3a) (below be sometimes referred to as " compound (3a) ".)。Compound (3a) can be its dynamic isomer.

[in formula (3a), R ³¹and R ³²the 1 valency saturated hydrocarbyl that means independently of one another carbon number 1～10, hydrogen atom contained in this saturated hydrocarbyl can be replaced by the aromatic hydrocarbyl of carbon number 6～10 or halogen atom, hydrogen atom contained in this aromatic hydrocarbyl can be replaced by the alkoxy of carbon number 1～3, contained in above-mentioned saturated hydrocarbyl-CH ₂-can by-O-,-CO-or-NR11-replaces.

R ³³and R ³⁴mean independently of one another the alkyl of carbon number 1～4, the alkyl sulfenyl of carbon number 1～4 or the alkyl sulphonyl of carbon number 1～4.

R ³¹and R ³³can form the ring that comprises nitrogen-atoms, R with together with adjacent nitrogen-atoms ³²and R ³⁴can form the ring that comprises nitrogen-atoms with together with adjacent nitrogen-atoms.

P and q mean 0～5 integer independently of one another.At p, be 2 when above, a plurality of R ³³can be the same or different, be 2 when above at q, a plurality of R ³⁴can be the same or different.

R ¹¹mean the meaning same as described above.]

As R ³¹and R ³²in 1 valency saturated hydrocarbyl of carbon number 1～10, can list R ⁸in the group of carbon number 1～10.

The aromatic hydrocarbyl of the carbon number 6～10 had as can be used as substituting group, can list and R ¹in the identical group of group.

As the alkoxy of carbon number 1～3, can list such as methoxyl, ethoxy, propoxyl group etc.

R ³¹and R ³²be preferably 1 valency saturated hydrocarbyl of carbon number 1～3 independently of each other.

As R ³³and R ³⁴in the alkyl of carbon number 1～4, can list methyl, ethyl, propyl group, butyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group etc.

As R ³³and R ³⁴in the alkyl sulfenyl of carbon number 1～4, can list methyl sulfenyl, ethyl sulfenyl, propyl group sulfenyl, butyl sulfenyl, isopropyl sulfenyl etc.

As R ³³and R ³⁴in the alkyl sulphonyl of carbon number 1～4, can list methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, butyl sulfonyl, isopropyl sulfonyl etc.

R ³³and R ³⁴be preferably the alkyl of carbon number 1～4, methyl more preferably.

P and q are preferably 0～2 integer, more preferably 0 and 1.

As compound (1a), can list for example compound shown in formula (1-1)～formula (1-43).In addition, in formula, R ⁴⁰the 1 valency saturated hydrocarbyl that means carbon number 1～20, be preferably the branched-chain alkyl of carbon number 6～12,2-ethylhexyl more preferably.

In above-claimed cpd, compound shown in formula (1-1)～formula (1-23) or formula (1-37)～formula (1-43) is equivalent to compound (2a), and in formula (1-24)～formula (1-36), the compound shown in any one is equivalent to compound (3a).

In the middle of these, sulfonamide compound, the quaternary ammonium salt of C.I. acid red 289, the sulfonamide compound of C.I. acid violet 102 or the quaternary ammonium salt of C.I. acid violet 102 of preferred C.I. acid red 289.As such compound, can list compound shown in formula (1-1)～formula (1-8), formula (1-11), formula (1-12) etc.

In addition, from the viewpoint of the dissolubility excellence organic solvent, go back the compound shown in any one in preferred formula (1-24)～formula (1-33).

Xanthene dye (Aa) can be used commercially available xanthene dye (for example China and foreign countries change into " the Chugai Aminol Fast Pink R-H/C " of (strain) system, " Rhodamin6G " of ridge, field chemical industry (strain) system).In addition, can also, using commercially available xanthene dye as initial feed, with reference to JP2010-32999-A, be synthesized.

Tetraazatetradecane porphyrin dyestuff (Ab) is for having the compound of tetraazatetradecane porphyrin skeleton in molecule.In addition, in the situation that the tetraazatetradecane porphyrin dyestuff is acid dyes or basic-dyeable fibre, can also be with kation or negative ion form salt arbitrarily.Tetraazatetradecane porphyrin dyestuff (Ab) is preferably the dyestuff that is dissolvable in water organic solvent.Particularly, in the situation that colored curable resin composition of the present invention is prepared into to blue-colored hardening resin composition, the tetraazatetradecane porphyrin dyestuff is preferably at least a kind of dyestuff be selected from blueness, purple and redness.

With regard to colored curable resin composition of the present invention, in the middle of these, in tetraazatetradecane porphyrin dyestuff (Ab), comprise the compound shown in formula (1b) (below, be sometimes referred to as " compound (1b) ".)。The content of the compound (1b) in tetraazatetradecane porphyrin dyestuff (Ab) be preferably 50 quality % above, more preferably 70 quality % above, more preferably more than 90 quality %.Particularly, preferably as tetraazatetradecane porphyrin dyestuff (Ab), only use compound (1b).

[in formula (1b), R ⁴¹～R ⁴⁸mean independently of one another hydrogen atom, halogen atom, cyano group, nitro, replacement or unsubstituted alkyl, replacement or unsubstituted alkoxy, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy group, replacement or unsubstituted aralkoxy or replacement or unsubstituted amino, M means substituted metal atom or the oxidized metal atom of 2 hydrogen atoms, 21 valency metallic atoms, divalent metallic atom, 3 valencys.

In this instructions, the aryl representation case is as carbon-ring type aromatic series bases such as phenyl, naphthyls.Such as being the hetero ring type aromatic series bases such as furyl, thienyl, pyridine radicals, be preferably carbon-ring type aromatic series base.

In formula (1b), R ⁴¹～R ⁴⁸preferably be expressed as independently of one another replacement or unsubstituted aryloxy group, the replacement of carbon number 5～30 or the substituted-amino of unsubstituted aralkoxy or carbon number 1～30 of the replacement of the replacement of the replacement of hydrogen atom, halogen atom, cyano group, nitro, carbon number 1～24 or unsubstituted alkyl, carbon number 1～24 or unsubstituted alkoxy, carbon number 4～30 or unsubstituted aryl, carbon number 4～30.

R ⁴¹～R ⁴⁸be more preferably replacement or unsubstituted aryloxy group, the replacement of carbon number 7～24 or the substituted-amino of unsubstituted aralkoxy or carbon number 1～16 of the replacement of the replacement of the replacement of hydrogen atom, fluorine atom, chlorine atom, bromine atoms, cyano group, carbon number 1～16 or unsubstituted alkyl, carbon number 1～16 or unsubstituted alkoxy, carbon number 6～24 or unsubstituted aryl, carbon number 6～24 independently of one another.

R ⁴¹～R ⁴⁸be further preferably replacement or unsubstituted aryloxy group, the replacement of carbon number 7～16 or the substituted-amino of unsubstituted aralkoxy or carbon number 1～12 of the replacement of the replacement of the replacement of hydrogen atom, fluorine atom, bromine atoms, cyano group, carbon number 1～10 or unsubstituted alkyl, carbon number 1～10 or unsubstituted alkoxy, carbon number 6～16 or unsubstituted aryl, carbon number 6～16 independently of one another.

R in formula (1b) below is shown ⁴¹～R ⁴⁸concrete example.

As halogen atom, can list for example fluorine atom, the chlorine atom, bromine atoms, as unsubstituted alkyl, can list for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, tertiary pentyl, n-hexyl, the 1-methyl amyl, 4-methyl-2-amyl group, the 2-ethyl-butyl, n-heptyl, 1-methyl hexyl, n-octyl, the 1-methylheptyl, the 2-ethylhexyl, 2-propyl group amyl group, n-nonyl, 2,2-dimethyl heptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethyl hexyl, positive decyl, 1-ethyl octyl group, the n-undecane base, 1-methyl decyl, dodecyl, the n-tridecane base, 1-hexyl heptyl, the n-tetradecane base, the n-pentadecane base, 1-heptyl octyl group, n-hexadecyl, the n-heptadecane base, 1-octyl group nonyl, the n-octadecane base, the 1-nonadecyl, 1-decyl undecyl, the n-eicosane base, the n-docosane base, the n-tetracosane base, the 1-adamantyl, cyclopentyl, cyclohexyl, the straight chain that norborny etc. only consist of carbon atom and hydrogen atom, the alkyl of side chain or ring-type.

As the substituting group had in substituent alkyl, can list alkylthio group, the halogen atom of aryloxy group, the carbon number 1～10 of aralkoxy, the carbon number 6～16 of alkoxy alkoxy, the carbon number 7～9 of alkoxy, the carbon number 2～12 of carbon number 1～14, halogenated alkoxy of carbon number 1～10 etc.

As the concrete example with substituent alkyl, for example can list methoxy, ethoxyl methyl, the n-butoxy methyl, just own oxygen ylmethyl, (2-ethyl butoxy) methyl, the n-octyloxy methyl, the n-decyloxy methyl, the 2-methoxy ethyl, the 2-ethoxyethyl group, 2-positive propoxy ethyl, 2-isopropoxy ethyl, 2-n-butoxy ethyl, 2-n-pentyloxy ethyl, the just own oxygen base of 2-ethyl, 2-(2 '-the ethyl butoxy) ethyl, 2-oxygen base in positive heptan ethyl, 2-n-octyloxy ethyl, 2-(2 '-ethyl hexyl oxy) ethyl, 2-n-decyloxy ethyl, 2-n-dodecane oxygen base ethyl, 2-n-tetradecane oxygen base ethyl, 2-cyclohexyloxy ethyl, the 2-methoxy-propyl, the 3-methoxy-propyl, the 3-ethoxycarbonyl propyl, 3-positive propoxy propyl group, the 3-isopropoxide propyl, 3-(n-butoxy) propyl group, 3-(n-pentyloxy) propyl group, 3-(just own oxygen base) propyl group, 3-(2 '-the ethyl butoxy) propyl group, 3-(n-octyloxy) propyl group, 3-(2 '-ethyl hexyl oxy) propyl group, 3-(n-decyloxy) propyl group, 3-(n-dodecane oxygen base) propyl group, 3-(n-tetradecane oxygen base) propyl group, 3-cyclohexyloxy propyl group, 4-methoxyl butyl, 4-ethoxy butyl, 4-positive propoxy butyl, 4-isopropoxy butyl, 4-n-butoxy butyl, the just own oxygen Ji Dingji of 4-, 4-n-octyloxy butyl, 4-n-decyloxy butyl, 4-n-dodecane oxygen Ji Dingji, 5-methoxyl amyl group, 5-ethoxy amyl group, 5-positive propoxy amyl group, 6-ethoxy hexyl, 6-isopropoxy hexyl, 6-n-butoxy hexyl, the just own oxygen base of 6-hexyl, 6-n-decyloxy hexyl, 4-methoxyl cyclohexyl, 7-ethoxy heptyl, 7-isopropoxy heptyl, 8-methoxyl octyl group, 10-methoxyl decyl, 10-n-butoxy decyl, 12-ethoxy dodecyl, 12-isopropoxy dodecyl, tetrahydrofurfuryls etc. have the alkyl of alkoxy,

For example, (2-methoxy ethoxy) methyl, (2-ethoxy ethoxy) methyl, (2-n-butoxy ethoxy) methyl, (the just own oxygen base oxethyl of 2-) methyl, (3-methoxy propoxy) methyl, (3-ethoxy propoxyl group) methyl, (3-n-butoxy propoxyl group) methyl, (3-n-pentyloxy propoxyl group) methyl, (4-methoxyl butoxy) methyl, (the own oxygen base of 6-methoxyl) methyl, (10-ethoxy oxygen in last of the ten Heavenly stems base) methyl, 2-(2 '-methoxy ethoxy) ethyl, 2-(2 '-ethoxy ethoxy) ethyl, 2-(2 '-n-butoxy ethoxy) ethyl, 3-(2 '-ethoxy ethoxy) propyl group, 3-(2 '-methoxy propoxy) propyl group, 3-(2 '-isopropoxy propoxyl group) propyl group, 3-(3 '-methoxy propoxy) propyl group, 3-(3 '-ethoxy propoxyl group) propyl group etc. has the alkyl of alkoxy alkoxy,

For example, benzyloxymethyl, 2-benzyloxy ethyl, 2-benzene ethoxyethyl group, 2-(4 '-methyl benzyloxy) ethyl, 2-(2 '-methyl benzyloxy) ethyl, 2-(4 '-fluorine benzyloxy) ethyl, 2-(4 '-chlorine benzyloxy) ethyl, 3-benzyloxy propyl group, 3-(4 '-methoxyl benzyloxy base) propyl group, 4-benzyloxy butyl, 2-(benzyloxy methoxyl) ethyl, 2-(4 '-methyl benzyloxy methoxyl) ethyl etc. have the alkyl of aralkoxy;

For example, phenoxymethyl, 4-methylenedioxy phenoxy ylmethyl, 3-methylenedioxy phenoxy ylmethyl, 2-methylenedioxy phenoxy ylmethyl, 4-ethyl phenoxymethyl, 4-n-pro-pyl phenoxymethyl, 4-normal-butyl phenoxymethyl, 4-tert-butyl group phenoxymethyl, 4-n-hexyl phenoxymethyl, 4-n-octyl phenoxymethyl, the positive decyl phenoxymethyl of 4-, 4-methoxyphenoxy methyl, 4-phenoxy ethoxy ylmethyl, 4-phenoxy butoxy ylmethyl, 4-n-pentyloxy phenoxymethyl, 3-fluorophenoxy methyl, 2-fluorophenoxy methyl, 4-fluorophenoxy methyl, 4-chlorophenoxy methyl, 2-chlorophenoxy methyl, 3,4-difluoro phenoxymethyl, 4-phenyl phenoxymethyl, 1-naphthoxy methyl, 2-naphthoxy methyl, 2-furans oxygen ylmethyl, 1-phenoxy group ethyl, 2-phenoxy group ethyl, 2-(4 '-methylphenoxy) ethyl, 2-(4 '-the ethyl phenoxy group) ethyl, 2 (4 '-the n-hexyl phenoxy group) ethyl, 2-(4 '-methoxyphenoxy) ethyl, 2-(4 '-the n-butoxy phenoxy group) ethyl, 2-(4 '-fluorophenoxy) ethyl, 2-(4 '-chlorophenoxy) ethyl, 2-(4 '-bromine phenoxy group) ethyl, 2-(1 '-naphthoxy) ethyl, 2-(2 '-naphthoxy) ethyl, the 2-phenoxy propyl, the 3-phenoxy propyl, 3-(4 '-methylphenoxy) propyl group, 3-(2 '-naphthoxy) propyl group, 4-phenoxy group butyl, 4-(2 '-ethyl phenoxy group) butyl, 4-phenoxy group amyl group, 5-phenoxy group amyl group, 5-(4 '-tert-butyl group phenoxy group) amyl group, 6-phenoxy group hexyl, 6-(2 '-chlorophenoxy) hexyl, 8-phenoxy group octyl group, 10-phenoxy group decyl, 10-(3 '-methylphenoxy) decyl, 10-(3 '-chlorophenoxy) decyl, 2-(2 '-the phenoxy group ethoxy) ethyl, 3-(2 '-the phenoxy group ethoxy) propyl group, 4-(2 '-phenoxy group ethoxy) butyl etc. has the alkyl of aryloxy group,

For example, normal-butyl sulfidomethyl, n-hexyl sulfidomethyl, 2-methyl sulphur ethyl, 2-ethyl sulphur ethyl, 2-normal-butyl sulphur ethyl, 2-n-hexyl sulphur ethyl, 2-n-octyl sulphur ethyl, the positive decyl sulphur of 2-ethyl, 3-methyl thiopropyl, 3-ethyl thiopropyl, 3-normal-butyl thiopropyl, 4-ethyl sulphur butyl, 4-n-pro-pyl sulphur butyl, 4-normal-butyl sulphur butyl, 5-ethyl sulphur amyl group, 6-methyl sulphur hexyl, 6-ethyl sulphur hexyl, 6-normal-butyl sulphur hexyl, 8-methyl sulphur octyl group etc. have the alkyl of alkyl sulfenyl;

For example, methyl fluoride, the 3-fluoropropyl, 6-fluorine hexyl, 8-fluorine octyl group, trifluoromethyl, 1, 1-dihydro-perfluor ethyl, 1, 1-dihydro-perfluor-n-pro-pyl, 1, 1, 3-tri-hydrogen-perfluor-n-pro-pyl, 2-hydrogen-perfluor-2-propyl group, 1, 1-dihydro-perfluor-normal-butyl, 1, 1-dihydro-perfluor-n-pentyl, 1, 1-dihydro-perfluor-n-hexyl, 6-fluorine hexyl, 4-fluorine cyclohexyl, 1, 1-dihydro-perfluor-n-octyl, 1, 1-dihydro-perfluor-positive decyl, 1, 1-dihydro-perfluor-dodecyl, 1, 1-dihydro-perfluor-n-tetradecane base, 1, 1-dihydro-perfluor-n-hexadecyl, the perfluor ethyl, perfluor-n-pro-pyl, perfluor-n-pentyl, perfluor-n-hexyl, 2, two (trifluoromethyl) propyl group of 2-, dichloromethyl, the 2-chloroethyl, the 3-chloropropyl, 4-chlorine cyclohexyl, 7-chlorine heptyl, 8-chlorine octyl group, 2, 2, 2-tri-chloroethyls etc. have the alkyl of halogen atom,

For example, fluorine methoxy, the fluoro-n-propoxymethyl of 3-, the fluoro-just own oxygen ylmethyl of 6-, the trifluoromethoxy methyl, 1,1-dihydro-perfluor ethoxyl methyl, 1,1-dihydro-perfluor-n-propoxymethyl, 2-hydrogen-perfluor-2-propoxyl group methyl, 1,1-dihydro-perfluor-n-butoxy methyl, 1,1-dihydro-perfluor-n-pentyloxy methyl, 1,1-dihydro-perfluor-just own oxygen ylmethyl, 1,1-dihydro-perfluor-n-octyloxy methyl, 1,1-dihydro-perfluor-n-decyloxy methyl, 1,1-dihydro-perfluor-n-tetradecane oxygen ylmethyl, two (trifluoromethyl) propoxyl group methyl of 2,2-, the chloro-n-propoxymethyl of 3-, 2-(the fluoro-n-octyloxy of 8-) ethyl, 2-(1,1-dihydro-perfluor ethoxy) ethyl, 2-(1,1,3-, tri-hydrogen-perfluor-positive propoxy) ethyl, 2-(1,1-dihydro-perfluor-n-pentyloxy) ethyl, 2-(the fluoro-just own oxygen base of 6-) ethyl, 2-(1,1-dihydro-perfluor-n-octyloxy) ethyl, 3-(4-fluorine cyclohexyloxy) propyl group, 3-(1,1-dihydro-perfluor ethoxy) propyl group, 3-(1,1-dihydro-perfluor-n-dodecane oxygen base) propyl group, 4-(perfluor-just own oxygen base) butyl, 4-(1,1-dihydro-perfluor ethoxy) butyl, 6-(2-chloroethoxy) hexyl, 6-(1,1-dihydro-perfluor ethoxy) hexyl etc. has the alkyl of halogenated alkoxy.

As replacing or unsubstituted alkoxy, for thering is the substituent alkoxy identical with above-mentioned cited alkyl, can list the alkoxy derived by the illustrated alkyl of the concrete example as abovementioned alkyl.

As unsubstituted aryl, can list for example phenyl, 1-naphthyl, 2-naphthyl, 2-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 1-pyrenyl, 2-pyrenyl, 2-perylene base, 3-perylene base, 2-fluoranthene base, 3-fluoranthene base, 7-fluoranthene base, 8-fluoranthene base.

As the substituting group had in substituent aryl, can list alkylthio group, cyano group of alkylhalide group, the carbon number 1～2 of aryl, halogen atom, the carbon number 1～2 of alkoxy, phenoxy group, the carbon number 6～10 of alkyl, the carbon number 1～5 of carbon number 1～6 etc.

As the concrete example with substituent aryl, for example can list 1-methyl-2-pyrenyl, 2-aminomethyl phenyl, 4-ethylphenyl, 4-(4 '-tert-butylcyclohexyl) phenyl, 3-cyclohexyl phenyl, 2-cyclohexyl phenyl, 4-ethyl-1-naphthyl, 6-normal-butyl-2-naphthyl, 2,4-3,5-dimethylphenyl etc. has the aryl of alkyl;

For example, 4-methoxyphenyl, 3-ethoxyl phenenyl, 2-ethoxyl phenenyl, 4-positive propoxy phenyl, 3-positive propoxy phenyl, 4-isopropyl phenyl, 3-isopropyl phenyl, 2-isopropyl phenyl, 2-sec-butoxy phenyl, 4-n-pentyloxy phenyl, 4-isoamoxy phenyl, 2-methyl-5-methoxyphenyl, 2-Phenoxyphenyl etc. have the aryl of alkoxy and aryloxy group;

For example, 4-phenyl, 3-phenyl, 2-phenyl, 2,6-diphenyl phenyl, 4-(2 '-naphthyl) phenyl, 2-phenyl-1-naphthyl, 1-phenyl-2-naphthyl, 7-phenyl-1-pyrenyl etc. have the aryl of aryl;

For example, 4-fluorophenyl, 3-fluorophenyl, 2-fluorophenyl, 4-chlorphenyl, 4-bromophenyl, the chloro-5-aminomethyl phenyl of 2-, the chloro-6-aminomethyl phenyl of 2-, 2-methyl-3-chlorphenyl, 2-methoxyl-4-fluorophenyl, the fluoro-4-methoxyphenyl of 2-etc. have the aryl of halogen atom;

Also have 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 3, two (trifluoromethyl) phenyl of 5-, 4-perfluor ethylphenyl, 4-methyl thio phenyl, 4-ethyl sulfur phenenyl, 4-cyano-phenyl, 3-cyano-phenyl etc.

As replacing or unsubstituted aryloxy group, for thering is the substituent aryloxy group identical with the aryl of above-mentioned cited replacement, can list by the concrete example of the aryl as above-mentioned cited replacement and replacement or unsubstituted aryloxy group that illustrative substituting group derives.

As replacing or unsubstituted aralkoxy, can list for example benzyloxy, Alpha-Methyl benzyloxy, benzene ethoxy, Alpha-Methyl benzene ethoxy, α, alpha-alpha-dimethyl benzyloxy, α, alpha-alpha-dimethyl benzene ethoxy, 4-methylbenzene ethoxy, 4-methyl benzyloxy, 4-isopropyl benzyloxy etc. do not replace or have the aralkoxy of alkyl;

4-benzyl benzyloxy, 4-phenethyl benzyloxy, 4-phenyl benzyloxy etc. have the aralkoxy of aryl or aralkyl;

4-methoxyl benzyloxy base, 4-n-tetradecane oxygen base benzyloxy, 4-n-heptadecane oxygen base benzyloxy, 3,4-dimethoxy benzyloxy, 4-methoxy benzyloxy, 4-ethyleneoxy methyl benzyloxy, 4-benzyloxy benzyloxy, 4-benzene ethoxy benzyloxy base etc. have the aralkoxy of substituted oxy;

4-hydroxyl benzyloxy, 4-hydroxy-3-methoxy benzyloxy etc. have the aralkoxy of hydroxyl;

4-fluorine benzyloxy, 3-chlorine benzyloxy, 3,4-dichloro-benzyloxy etc. has the aralkoxy of halogen atom;

2-chaff oxygen base, diphenyl methoxy base, 1-naphthyl methoxyl, 2-naphthyl methoxyl etc.

As the substituting group in substituted-amino, can list alkyl, the benzyl of carbon number 1～12, aryl of carbon number 6～10 etc.

As substituted-amino, can list the amino that such as N-methylamino, N-ethylamino, N-normal-butyl amino, N-cyclohexyl amino, N-n-octyl amino, the positive decyl amino of N-etc. has alkyl;

For example, N-benzylamino, N-phenyl amino, N-(3-aminomethyl phenyl) amino, N-(4-aminomethyl phenyl) amino, N-(4-n-butylphenyl) amino, N-(4-methoxyphenyl) amino, N-(3-fluorophenyl) amino, N-(4-chlorphenyl) amino, N-(1-naphthyl) amino, N-(2-naphthyl) amino etc. have the amino of aralkyl or aryl;

For example, N, N-dimethylamino, N, N-diethylamino, N, the N-di-n-butyl is amino, N, and N-bis--n-hexyl is amino, N, and N-bis--n-octyl is amino, N, N-bis--positive decyl is amino, N, the amino after alkyl and aryl two replacements such as N-bis--dodecyl amino, N-methyl-N-ethylamino, N-ethyl-N-normal-butyl amino, N-methyl-N-phenyl amino, N-ethyl-N-phenyl amino, N-normal-butyl-N-phenyl amino;

For example, N, N-diphenyl amino, N, N-bis-(3-aminomethyl phenyl) amino, N, N-bis-(4-aminomethyl phenyl) amino, N, N-bis-(4-ethylphenyl) amino, N, N-bis-(4-tert-butyl-phenyl) amino, N, N-bis-(4-n-hexyl phenyl) amino, N, N-bis-(4-methoxyphenyl) amino, N, N-bis-(4-ethoxyl phenenyl) amino, N, N-bis-(4-n-butoxy phenyl) amino, N, N-bis-(the just own oxygen base of 4-phenyl) amino, N, N-bis-(1-naphthyl) amino, N, N-bis-(2-naphthyl) amino, N-phenyl-N-(3-aminomethyl phenyl) amino, N-phenyl-N-(4-aminomethyl phenyl) amino, N-phenyl-N-(4-octyl phenyl) amino, N-phenyl-N-(4-methoxyphenyl) amino, N-phenyl-N-(4-ethoxyl phenenyl) amino, N-phenyl-N-(the just own oxygen base of 4-phenyl) amino, N-phenyl-N-(4-fluorophenyl) amino, N-phenyl-N-(1-naphthyl) amino, N-phenyl-N-(2-naphthyl) amino, N-phenyl-N-(3-phenyl) amino, N-phenyl-N-(4-phenyl) amino waits the amino after being replaced by aryl two etc.

In formula (1b), M means substituted metal atom or the oxidized metal atom of 2 hydrogen atoms, 21 valency metallic atoms, divalent metallic atom, 3 valencys, more preferably 2 hydrogen atoms, divalent metallic atom or oxidized metal atoms, more preferably divalent metallic atom or oxidized metal atom.

The 1 valency metallic atom as shown in M, can list such as Na, K, Li etc.

As the divalent metallic atom shown in M, can list such as Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb, Sn etc.

The 3 valency substituted metal atoms as shown in M, can list for example Al-Cl, Ga-Br, Ga-I, In-Cl, Al-C ₆h ₅, In-C ₆h ₅, Mn (OH), Mn[OSi (CH ₃) ₃], Fe-Cl etc.

As the oxidized metal atom shown in M, can list such as VO, MnO, TiO etc.

In formula (1b), M is Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, VO and TiO more preferably, and more preferably Cu, Ni, Pd and VO, be particularly preferably Cu, Pd and VO.

As the concrete example of the compound the present invention relates to (1b), can list for example compound shown in formula (2-1)～formula (2-38), but the present invention is not limited to these compounds.

As tetraazatetradecane porphyrin dyestuff (Ab), preferably comprise (compound shown in formula (2-29)).If the composition that comprises this tetraazatetradecane porphyrin dyestuff, can form the filming of high-contrast, pattern, and the generation of impurity is also few.

As dyestuff (Ac), so long as the dyestuff different from xanthene dye (Aa) and tetraazatetradecane porphyrin dyestuff (Ab), just be not particularly limited, can list the amine salt of oil-soluble dyes, acid dyes, basic-dyeable fibre, direct dyes, mordant dye, acid dyes, the dyestuffs such as sulfamide derivative of acid dyes, can list in color index (The Society of Dyers and Colourists publication) for example and be classified as dyestuff be beyond C.I. pigment and there is the compound of material of form and aspect and dyeing handbook (look dyes society) in the known dyestuff of record.In addition, according to chemical constitution, can list azo dyes, cyanine dye, triphenhlmethane dye, anthraquinone dye, phthalocyanine dye, naphthoquinone dyestuff, quinoneimine dye, methine dyes, azomethine dyes, squaraine dye (squarylium dye), acridine dye, styryl dye, coumarine dye, quinoline dye and nitro dye etc.In the middle of these, preferred organic solvent-soluble dye.

Specifically, can list C.I. solvent yellow 4,14,15,23,24,38,62,63,68,82,94,98,99,162,

C.I. solvent red 45,49,125,130,

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

C.I. solvent blue 4,5,25,35,37,45,67,70,90,

C.I. the C.I. solvent dye such as solvent green 1,4,5,7,34,35;

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, 57, 66, 73, 80, 81, 82, 83, 88, 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, 308, 312, 315, 316, 339, 341, 345, 346, 349, 356, 382, 383, 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, 7,17,19,29,31,33,34,36,36:1,39,41,42,43,47,48,51,63,76,103,109,118,126,

C.I. acid blue 2, 8, 14, 18, 23, 25, 27, 29, 35, 37, 41, 42, 43, 45, 47, 49, 50, 51, 52, 53, 55, 56, 57, 58, 59, 60, 62, 62:1, 63, 64, 65, 68, 69, 70, 72, 74, 78, 79, 80, 81, 81:1, 82, 87, 92, 96, 102, 111, 113, 117, 120, 122, 124, 126, 127, 127:1, 129, 129:1, 130, 131, 137, 138, 140, 142, 143, 145, 145:1, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 176, 182, 183, 184, 187, 192, 198, 199, 203, 204, 205, 208, 210, 220, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335,

C.I. the C.I. acid dyes such as acid green 1,58,63,65,80,104,105,106,109;

It is C.I. directly yellow 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 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107,

It is 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 blue 2, 6, 8, 15, 22, 25, 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. direct dyes such as direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82;

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

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

C.I.

mordant rouge

1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94,95

C.I. the

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

As pigment (Ad), can be not particularly limited to use known pigment, can list the pigment that for example in color index (The Society ofDyers and Colourists publication), is classified as pigment.

As pigment, can list such as yellow uitramarines such as 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;

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

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

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

pigment violet

1,19,23,29,32,36, the violet pigments such as 38;

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

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

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

As pigment, be preferably C.I. pigment blue 15,15:3,15:4,15:6, the blue pigments such as 60; C.I.

pigment violet

1,19,23,29,32,36, the violet pigments such as 38, more preferably C.I. pigment blue 15: 3,15:6 and C.I. pigment Violet 23, more preferably C.I. pigment blue 15: 6.By comprising above-mentioned pigment, thereby the optimization of transmitted spectrum is become easily, it is good that the photostability of color filter and chemical proofing become.

Pigment can also be implemented as required rosin process, use the surface treatment of the pigment derivative that has been imported into acidic groups or basic group etc., utilize macromolecular compound etc. to the grafting of surface of pigments process, utilize the micronize of sulfuric acid micronize method etc. process or utilize the carrying out washing treatment of organic solvent for removing impurity or water etc., utilize ion exchange process etc. ionic impurity remove processing etc.

The pigment preferable particle size is even.Carry out dispersion treatment by containing pigment dispersing agent, can obtain the dispersible pigment dispersion of pigment homodisperse state in solution.

As above-mentioned pigment dispersing agent, can list pigment dispersing agent such as kation system, negative ion system, nonionic system, both sexes, polyester system, polyamine system, acrylic acid series etc. etc.These pigment dispersing agents can be used separately also can combine two or more use.As pigment dispersing agent, can list the pigment dispersing agents such as commodity KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Floren by name (common prosperity society chemistry (strain) system), Solsperse (Zeneca (strain) system), EFKA (CIBA company system), Ajisper (aginomoto Fine Techno (strain) system), Disperbyk (Byk Chemie company system).

In the situation that use pigment dispersing agent, its use amount with respect to the total amount of pigment (Ad) be preferably that 1 quality % is above and 100 quality % are following, more preferably 5 quality % are above and below 50 quality %.If, in above-mentioned scope, there is the tendency of the dispersible pigment dispersion that obtains uniform disperse state in the use amount of pigment dispersing agent.

The content of xanthene dye (Aa) is with respect to the total amount of colorant (A), more than being preferably 0.1 quality % and below 50 quality %, more preferably more than 0.5 quality % and below 50 quality %.

The content of tetraazatetradecane porphyrin dyestuff (Ab) is with respect to xanthene dye (Aa) 100 mass parts, more than being preferably 1 mass parts and below 100 mass parts, more preferably more than 10 mass parts and below 100 mass parts.

The content of pigment (Ad) is with respect to the total amount of colorant (A), more than being preferably 10 quality % and below 99.9 quality %, more preferably more than 30 quality % and below 99 quality %.

In the situation that colorant (A) comprises dyestuff (Ac), the content of dyestuff (Ac) is with respect to the total amount of colorant (A), more than being preferably 0.1 quality % and below 50 quality %, more preferably more than 0.5 quality % and below 30 quality %.

Colorant (A) preferably comprises xanthene dye (Aa), tetraazatetradecane porphyrin dyestuff (Ab) and pigment (Ad).In the case, the content of these each compositions, with respect to the total amount of colorant (A), is preferably respectively

Xanthene dye (Aa): more than 0.1 quality % and below 50 quality %

Tetraazatetradecane porphyrin dyestuff (Ab): more than 0.1 quality % and below 50 quality %

Pigment (Ad): more than 49.9 quality % and below 99.8 quality %;

More preferably

Xanthene dye (Aa): more than 0.5 quality % and below 50 quality %

Tetraazatetradecane porphyrin dyestuff (Ab): more than 0.5 quality % and below 50 quality %

Pigment (Ad): more than 49.5 quality % and below 99 quality %.

The content of colorant (A) is with respect to the total amount of solid constituent, is preferably 5～60 quality %, more preferably 8～55 quality %, 10～50 quality % more preferably.If the content of colorant (A) is in above-mentioned scope, the colour saturation while making color filter is abundant, and can make in composition the resin (B), the polymerizable compound (C) that contain aequum, thereby can form the sufficient pattern of physical strength.Here, " total amount of solid constituent " in this instructions refer to, by the total amount of colored curable resin composition deduct solvent content and amount.The total amount of solid constituent reaches with respect to the content of this each composition and can be measured by known analytical equipments such as liquid chromatography or gas chromatography.

Resin (B) is not particularly limited, and is preferably alkali soluble resin.As resin (B), can list following resin [K1]～[K6] etc.

Resin [K1]: be selected from least a kind (a) in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides (below be sometimes referred to as " (a) "), with the multipolymer with the cyclic ether structure of carbon number 2～4 and monomer (b) of ethylenic unsaturated bond (below be sometimes referred to as " (b) ");

Resin [K2]: (a) and (b), with can with the monomer (c) of (a) copolymerization, (still, (c) with (a), reach (b) different.) multipolymer of (below be sometimes referred to as " (c) ");

Resin [K3]: (a) with multipolymer (c);

Resin [K4]: make (a) and the multipolymer of (c) and (b) react the resin formed;

Resin [K5]: make (b) and the multipolymer of (c) and (a) react the resin formed;

Resin [K6]: make the multipolymer of (b) and (c) and (a) react, further with carboxylic acid anhydrides, reacting the resin formed.

As (a), specifically, can list such as acrylic acid, methacrylic acid, crotonic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, to unsaturated monocarboxylic classes such as vinyl benzoic acids;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2, the unsaturated dicarboxylic classes such as 3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norborene-2,3-dicarboxylic acid, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", the dicyclo unsaturated compound class that the 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene" etc. contains carboxyl;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2, the unsaturated dicarboxylic class acid anhydrides such as 3,6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5,6 dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides;

Unsaturated list ((methyl) acryloxyalkyl) the ester class of the polybasic carboxylic acids more than 2 yuan such as mono succinate (2-(methyl) acryloxy ethyl) ester, phthalic acid list (2-(methyl) acryloxy ethyl) ester;

Acrylic acid α-(methylol) ester is such, unsaturated esters of acrylic acid contain hydroxyl and carboxyl in same a part etc.

In the middle of these, from the viewpoint of copolyreaction and the deliquescent viewpoint of resin aqueous alkali of gained, preferred acrylic acid, methacrylic acid, maleic anhydride etc.

(b) refer to the cyclic ether structure (for example being selected from least a kind in oxirane ring, oxetanes ring and tetrahydrofuran ring) that for example there is carbon number 2～4 and the polymerizable compound of ethylenic unsaturated bond.(b) be preferably the monomer of cyclic ether with carbon number 2～4 and (methyl) acryloxy.

In addition, in this instructions, " (methyl) acrylic acid " means to be selected from least a kind in acrylic acid and methacrylic acid.The mark such as " (methyl) acryloyl group " and " (methyl) acrylate " also has the same meaning.

As (b), can list such as the monomer with Oxyranyle and ethylenic unsaturated bond (b1) (below be sometimes referred to as " (b1) "), have oxetanyl and ethylenic unsaturated bond monomer (b2) (below be sometimes referred to as " (b2) "), there is monomer (b3) (below be sometimes referred to as " (b3) ") of tetrahydrofuran base and ethylenic unsaturated bond etc.

As (b1), can list for example there is straight chain shape or chain unsaturated aliphatic hydrocarbon by epoxidation and structure monomer (b1-1) (below be sometimes referred to as " (b1-1) "), there is the ester ring type unsaturated hydrocarbon by epoxidation and the monomer (b1-2) (below be sometimes referred to as " (b1-2) ") of structure.

As (b1-1), can list (methyl) glycidyl acrylate, (methyl) acrylic acid Beta-methyl ethylene oxidic ester, (methyl) propenoic acid beta-ethyl ethylene oxidic ester, the glycidyl vinyl ether, adjacent vinyl benzyl glycidol ether, between the vinyl benzyl glycidol ether, to the vinyl benzyl glycidol ether, Alpha-Methyl-adjacent vinyl benzyl glycidol ether, an Alpha-Methyl-vinyl benzyl glycidol ether, Alpha-Methyl-to the vinyl benzyl glycidol ether, two (glycidoxypropyl methyl) styrene of 2,3-, two (glycidoxypropyl methyl) styrene of 2,4-, two (glycidoxypropyl methyl) styrene of 2,5-, two (glycidoxypropyl methyl) styrene of 2,6-, 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-(glycidoxypropyl methyl) styrene, 2,4,6-tri-(glycidoxypropyl methyl) styrene etc.

As (b1-2), can list vinyl cyclohexene monoxide, 1,2-epoxy-4-vinyl cyclohexane (Celloxide2000 for example; (strain) Daicel system), 3,4-epoxycyclohexyl methyl (methyl) acrylate (Cyclomer A400 for example; (strain) Daicel system), 3,4-epoxycyclohexyl methyl (methyl) acrylate (Cyclomer M100 for example; (strain) Daicel system), compound shown in the compound shown in formula (I), formula (II) etc.

[in formula (I) and formula (II), R ^aand R ^bmean the alkyl of hydrogen atom or carbon number 1～4, hydrogen atom contained in this alkyl can be replaced by hydroxyl.

X ^aand X ^bthe expression singly-bound ,-R ^c-, *-R ^c-O-, *-R ^c-S-or *-R ^c-NH-.

R ^cthe alkylidene that means carbon number 1～6.

* mean the binding end with O.]

As the alkyl of carbon number 1～4, can list methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc.

Alkyl after being replaced by hydroxyl as hydrogen atom, can list methylol, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxyl butyl, 2-hydroxyl butyl, 3-hydroxyl butyl, 4-hydroxyl butyl etc.

As R ^aand R ^b, preferably can list hydrogen atom, methyl, methylol, 1-hydroxyethyl, 2-hydroxyethyl, more preferably can list hydrogen atom, methyl.

As alkylidene, can list methylene, ethylidene, propane-1,2-bis-bases, propane-1,3-bis-bases, butane-Isosorbide-5-Nitrae-bis-base, pentane-1,5-bis-bases, hexane-1,6-bis-bases etc.

As X ^aand X ^b, preferably can list singly-bound, methylene, ethylidene, *-CH ₂-O-and *-CH ₂cH ₂-O-, more preferably can list singly-bound and *-CH ₂cH ₂-O-(* means the binding end with O).

As the compound shown in formula (I), can list the compound shown in the middle any one of formula (I-1)～formula (I-15) etc.Wherein, compound shown in preferred formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11)～formula (I-15), the more preferably compound shown in formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

As the compound shown in formula (II), can list the compound shown in the middle any one of formula (II-1)～formula (II-15) etc.Wherein, be preferably the compound shown in formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)～formula (II-15), more preferably the compound shown in formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

Compound shown in compound shown in formula (I) and formula (II) can be distinguished use separately, and also two or more kinds may be used.In the situation that also with the compound shown in formula (I) and the compound shown in formula (II), they contain ratio (compound shown in formula (I): the compound shown in formula (II)) in molar basis be preferably 5: 95～95: 5, more preferably 20: 80～80: 20.

As (b2), more preferably there is the monomer of oxetanyl and (methyl) acryloxy.As (b2), can list 3-methyl-3-methacryloxy methyl oxetanes, 3-methyl-3-acryloyl-oxy ylmethyl oxetanes, 3-ethyl-3-methacryloxy methyl oxetanes, 3-ethyl-3-acryloyl-oxy ylmethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloxy Ethyloxetane, 3-ethyl-3-methacryloxyethyl oxetanes, 3-ethyl-3-acryloxy Ethyloxetane etc.

As (b3), more preferably there is the monomer of tetrahydrofuran base and (methyl) acryloxy.As (b3), specifically, can list tetrahydrofurfuryl acrylate (such as Viscoat V#150, Osaka organic chemistry industry (strain) system), tetrahydrofurfuryl methacrylate etc.

As (b), the viewpoint from the reliability of the thermotolerance that can further improve the color filter of gained, chemical proofing etc., be preferably (b1).Further, such viewpoint from the excellent storage stability of colored curable resin composition, more preferably (b1-2).

As (c), for example can list (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, 2-ethylhexyl (methyl) acrylate, (methyl) acrylic acid dodecane ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, 2-methylcyclohexyl (methyl) acrylate, three ring [5.2.1.0 ^2,6] decane-8-base (methyl) acrylate (is called as " (methyl) acrylic acid two ring pentyl esters " as trivial name in the art.In addition, be sometimes referred to as " (methyl) acrylic acid three ring esters in the last of the ten Heavenly stems ".), three the ring [5.2.1.0 ^2,6] decene-8-base (methyl) acrylate (is called as " (methyl) acrylic acid two cyclopentene esters " as trivial name in the art.), (methyl) esters of acrylic acid such as (methyl) acrylic acid two cyclopentyloxy ethyl esters, (methyl) isobornyl acrylate, (methyl) acrylic acid diamantane ester, (methyl) allyl acrylate, (methyl) acrylic acid alkynes propyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate;

(methyl) esters of acrylic acid that (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl ester etc. contain hydroxyl;

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

Dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-methylol dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-methoxyl dicyclo [2.2.1] hept-2-ene", 5-ethoxy dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxy dicyclo [2.2.1] hept-2-ene", 5,6-bis-(methylol) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-methylol-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyloxy carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", two (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene"s of 5,6-, the dicyclo unsaturated compound classes such as two (cyclohexyloxy carbonyl) dicyclo [2.2.1] hept-2-ene"s of 5,6-,

The dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimide-3-maleimide benzoic ether, N-succinimide-4-maleimide butyric ester, N-succinimide-6-maleimide capronate, N-succinimide-3-maleimide propionic ester, N-(9-acridinyl) maleimide;

Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.

In the middle of these, from copolyreaction and stable on heating viewpoint, optimization styrene, vinyltoluene, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene" etc.

In resin [K1], from the ratio of the structural unit of each monomer, in the entire infrastructure unit that forms resin [K1], be preferably

Structural unit from (a): 2～60 % by mole

Structural unit from (b): 40～98 % by mole

More preferably

Structural unit from (a): 10～50 % by mole

Structural unit from (b): 50～90 % by mole.

If in above-mentioned scope, there is the tendency of solvent resistance excellence of storage stability, the developability while forming colored pattern and the gained color filter of colored curable resin composition in the ratio of the structural unit of resin [K1].

Resin [K1] can be manufactured as the citing document of putting down in writing in document " experimental method of Polymer Synthesizing " (Tianjin outstanding sale room of grand row (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people greatly) the middle method of putting down in writing and the document by reference example.

Specifically, can list (a) and ormal weight, polymerization initiator and solvent etc. (b) are put into to reaction vessel, for example, by utilizing the nitrogen replace oxygen, thereby make deoxidation atmosphere, the method that heats while stirring and be incubated.In addition, polymerization initiator used herein and solvent etc. can be not particularly limited to use material usually used in this field.For example, as polymerization initiator, can list azo-compound (2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitriles) etc.), organic peroxide (benzoyl peroxide etc.), as solvent, get final product so long as dissolve the solvent of each monomer, can list solvent (E) as colored curable resin composition of the present invention and the solvent of aftermentioned record etc.

In addition, the multipolymer of gained can directly be used reacted solution, also can use the solution after concentrated or dilution, can also use the material after with the taking-up of solid (powder) form by methods such as precipitations again.Particularly, by solvent contained in using colored curable resin composition of the present invention when this polymerization as solvent, and reacted solution can be directly used in to the preparation of colored curable resin composition of the present invention, thereby can make the manufacturing process of colored curable resin composition of the present invention oversimplify.

In resin [K2], from the ratio of the structural unit of each monomer, in the entire infrastructure unit that forms resin [K2], be preferably

Structural unit from (a): 2～45 % by mole

Structural unit from (b): 2～95 % by mole

Structural unit from (c): 1～65 % by mole

More preferably

Structural unit from (a): 5～40 % by mole

Structural unit from (b): 5～80 % by mole

Structural unit from (c): 5～60 % by mole.

If in above-mentioned scope, there is the tendency of solvent resistance, thermotolerance and physical strength excellence of storage stability, the developability while forming colored pattern and the gained color filter of colored curable resin composition in the ratio of the structural unit of resin [K2].

Can with for example as the manufacture method of resin [K1] and the method for putting down in writing is manufactured resin [K2] in the same manner.

In resin [K3], from the ratio of the structural unit of each monomer, in the entire infrastructure unit that forms resin [K3], be preferably

Structural unit from (a): 2～60 % by mole

Structural unit from (c): 40～98 % by mole

More preferably

Structural unit from (a): 10～50 % by mole

Structural unit from (c): 50～90 % by mole.

Can with for example as the manufacture method of resin [K1] and the method for putting down in writing is manufactured resin [K3] in the same manner.

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

At first, manufacture in the same manner (a) and multipolymer (c) with the method for manufacture method as resin [K1] record.In the case, the ratio from the structural unit of each monomer is preferably the ratio identical with ratio cited in resin [K3].

The cyclic ether of the carbon number 2～4 that then, the part of the carboxylic acid from (a) in above-mentioned multipolymer and/or carboxylic acid anhydrides is had with (b) reacts.

After the manufacture of (a) and multipolymer (c), atmosphere in flask is replaced into to air by nitrogen, the catalysts of (b), carboxylic acid or carboxylic acid anhydrides and cyclic ether (such as three (dimethylaminomethyl) phenol etc.) and polymerization inhibitor (such as quinhydrones etc.) etc. are put into to flask, by for example reacting 1～10 hour, can manufacture resin [K4] under 60～130 ℃.

(b) use amount, with respect to (a) 100 moles, is preferably 5～80 moles, more preferably 10～75 moles.Use amount by making (b) in this scope, the tendency that exists the balance of solvent resistance, thermotolerance, physical strength and light sensitivity of storage stability, the developability while forming pattern and the gained pattern of colored curable resin composition to become good.Due to the reactivity of cyclic ether is high, be difficult for remained unreacted (b), thereby as (b) for resin [K4], preferably (b1), further preferably (b1-1).

The use amount of above-mentioned catalysts, with respect to (a), (b) and 100 mass parts of total amount (c), is preferably 0.001～5 mass parts.The use amount of above-mentioned polymerization inhibitor, with respect to (a), (b) and 100 mass parts of total amount (c), is preferably 0.001～5 mass parts.

Suitably adjust add that the reaction conditionss such as method, temperature of reaction and time can be considered manufacturing equipment, the thermal value that produces because of polymerization etc.In addition, can also with polymerizing condition similarly, the thermal value that consider manufacturing equipment, produces because of polymerization etc. is suitably adjusted and is added method, temperature of reaction.

For resin [K5], as the first stage, with the manufacture method of above-mentioned resin [K1] similarly, obtain (b) and multipolymer (c).With similarly above-mentioned, the multipolymer of gained can directly be used reacted solution, can use the solution after concentrated or dilution, can also use the material after with the taking-up of solid (powder) form by methods such as precipitations again.

Reach the total mole number of the ratio of structural unit (c) with respect to the entire infrastructure unit that forms above-mentioned multipolymer from (b), be preferably respectively

Structural unit from (b): 5～95 % by mole

Structural unit from (c): 5～95 % by mole

More preferably

Structural unit from (b): 10～90 % by mole

Structural unit from (c): 10～90 % by mole.

Further, can by under the condition identical in the manufacture method with resin [K4], the cyclic ether from (b) that (b) has with the multipolymer of (c) be reacted with carboxylic acid or carboxylic acid anhydrides that (a) has, thereby obtain resin [K5].

With respect to (b) 100 moles, be preferably 5～80 moles with the use amount of (a) of above-mentioned copolymer reaction.Because the reactivity of cyclic ether is high, be difficult for (b) of remained unreacted, thereby, as (b) for resin [K5], be preferably (b1), more preferably (b1-1).

Resin [K6] is for to make resin [K5] further with carboxylic acid anhydrides, react the resin formed.

Make the hydroxyl produced with reacting of carboxylic acid or carboxylic acid anhydrides by cyclic ether, react with carboxylic acid anhydrides.

As carboxylic acid anhydrides, can list maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2,3,6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides (carbic anhydride) etc.The use amount of carboxylic acid anhydrides, with respect to 1 mole of the use amount of (a), is preferably 0.5～1 mole.

As resin (B), specifically, can list 3,4-epoxycyclohexyl methyl (methyl) acrylate/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0 ^2,6] decyl acrylate/resins [K1] such as (methyl) acrylic copolymer; (methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/styrene/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0 ^2,6] decyl acrylate/(methyl) acrylic acid/N-N-cyclohexylmaleimide multipolymer, 3-methyl-3-(methyl) acryloyl-oxy ylmethyl oxetanes/resins [K2] such as (methyl) acrylic acid/styrol copolymer; (methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/resins [K3] such as (methyl) acrylic copolymer; The resin that (methyl) benzyl acrylate/(methyl) acrylic copolymer and the addition of (methyl) glycidyl acrylate are formed, the resin that (methyl) acrylic acid three ring ester/styrene in the last of the ten Heavenly stems/(methyl) acrylic copolymer and the addition of (methyl) glycidyl acrylate are formed, the resins such as resin [K4] that (methyl) acrylic acid three ring esters in the last of the ten Heavenly stems/(methyl) benzyl acrylate/(methyl) acrylic copolymer and the addition of (methyl) glycidyl acrylate are formed; The multipolymer that makes (methyl) acrylic acid three encircle esters in the last of the ten Heavenly stems/(methyl) glycidyl acrylate reacts the resin formed with (methyl) acrylic acid, the multipolymer that makes (methyl) acrylic acid three encircle ester/styrene in the last of the ten Heavenly stems/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid the resins such as resin [K5] that form; Make the multipolymer of (methyl) acrylic acid three ring esters in the last of the ten Heavenly stems/(methyl) glycidyl acrylate react with (methyl) acrylic acid the resin formed, further with tetrabydrophthalic anhydride, react the resins such as resin [K6] that form etc.

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

The weight-average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000～100, and 000, more preferably 5,000～50,000, more preferably 5,000～30,000.The tendency that the hardness of color filter improves if molecular weight, in above-mentioned scope, exists, the exploring degree of the favorable solubility of high, the unexposed section of residual film ratio in developer solution, colored pattern improves.

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

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 be in and the measured value of amount (mg) of the necessary potassium hydroxide of resin (B) 1g, for example can obtain by with potassium hydroxide aqueous solution, carrying out titration.

The content of resin (B), with respect to the total amount of solid constituent, is preferably 7～65 quality %, more preferably 13～60 quality %, more preferably 17～55 quality %.If the content of resin (B) is in above-mentioned scope, existence can form the exploring degree of colored pattern and colored pattern and the tendency that residual film ratio improves.

Polymerizable compound (C) is can be by the living radical and/or the sour compound that carries out polymerization that are produced by polymerization initiator (D), can list compound such as the ethylenic unsaturated bond with polymerism etc., be preferably (methyl) acrylate compounds.

Wherein, polymerizable compound (C) is preferably the polymerizable compound with 3 above ethylenic unsaturated bonds.As such polymerizable compound, can list for example trimethylolpropane tris (methyl) acrylate, three (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, the four seasons penta tetrol ten (methyl) acrylate, the four seasons penta tetrol nine (methyl) acrylate, three (2-(methyl) acryloxy ethyl) isocyanuric acid ester, glycol-modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylate, propylene glycol modified pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, caprolactone modification pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc.

Wherein, preferred dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate.

The weight-average molecular weight of polymerizable compound (C) be preferably more than 150 and 2,900 following, more preferably 250～1, below 500.

The content of polymerizable compound (C), with respect to the total amount of solid constituent, is preferably 7～65 quality %, more preferably 13～60 quality %, more preferably 17～55 quality %.If the content of polymerizable compound (C) in above-mentioned scope, the tendency that the residual film ratio while exist forming colored pattern and the chemical proofing of color filter improve.

Polymerization initiator (D) is so long as the effect by light, heat produces living radical, acid etc., and compound that can initiated polymerization, just is not particularly limited, and can use known polymerization initiator.

Polymerization initiator as producing living radical, can list for example O-acyl group oxime compound, alkyl phenones compound, triaizine compounds, acylphosphine oxide compound and united imidazole.

Above-mentioned O-acyl group oxime compound is for having the compound of the part-structure shown in formula (d1).Below, * means binding end.

As above-mentioned O-acyl group oxime compound, can list for example N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) octane-1-ketone-2-imines, N-benzoyloxy-1-(4-phenyl sulfenyl phenyl)-3-cyclopentyl propane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3, 3-dimethyl-2, 4-dioxane amyl group methoxyl) benzoyl }-9H-carbazole-3-yl] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl]-3-cyclopentyl propane-1-imines, N-benzoyloxy-1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl]-3-cyclopentyl propane-1-ketone-2-imines etc.Can also use the commercially available products such as IRGACUREOXE01, OXE02 (more than, BASF AG's system), N-1919 (ADEKA company system).Wherein, O-acyl group oxime compound is preferably at least a kind that is selected from N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) octane-1-ketone-2-imines and N-benzoyloxy-1-(4-phenyl sulfenyl phenyl)-3-cyclopentyl propane-1-ketone-2-imines, more preferably N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) octane-1-ketone-2-imines.If these O-acyl group oxime compounds, existence obtains the tendency of the color filter of high brightness.

Abovementioned alkyl benzophenone compound is for having the compound of the part-structure shown in the part-structure shown in formula (d2) or formula (d3).In these part-structures, phenyl ring can have substituting group.

As the compound with the part-structure shown in formula (d2), can list such as 2-methyl-2-morpholino-1-(4-methyl sulfenyl phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl] butane-1-ketone etc.Can use the commercially available products such as IRGACURE369,907,379 (more than, BASF AG's system).

As the compound with the part-structure shown in formula (d3), can list for example 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl) propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenyl phenyl) propane-oligomer of 1-ketone, α, α-diethoxy acetophenone, benzil dimethyl ketal etc.

On the viewpoint of light sensitivity, as the alkyl phenones compound, preferably there is the compound of the part-structure shown in formula (d2).

As above-mentioned triaizine compounds, for example can list 2, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-piperonyls-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(2-(5-methylfuran-2-yl) vinyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(2-(furans-2-yl) vinyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-1 of 4-, 3, the 5-triazine, 2, (2-(3 for two (the trichloromethyl)-6-of 4-, the 4-Dimethoxyphenyl) vinyl)-1, 3, 5-triazine etc.

As above-mentioned acylphosphine oxide compound, can list 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide etc.Can use the commercially available products such as IRGACURE (registered trademark) 819 (BASF AG's system).

As above-mentioned united imidazole, can list for example 2,2 '-bis-(2 chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline (such as reference JPH06-75372-A, JPH06-75373-A etc.), 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetra-(alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2 chlorphenyl)-4,4 ', 5,5 '-tetra-(dialkoxy phenyl) bisglyoxaline, 2,2 '-bis-(2 chlorphenyl)-4,4 ', 5,5 '-tetra-(tri-alkoxy phenyl) bisglyoxaline (such as reference JPS48-38403-B, JPS62-174204-A etc.), the imidazolium compounds that replaced by alkoxy carbonyl group of phenyl of 4,4 ', 5,5 '-position (such as reference JPH07-10913-A etc.) etc.

Be further used as polymerization initiator (D), can list the benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, o-benzoyl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide, 3,3 ', 4,4 '-tetra-(tert-butyl peroxide carbonyl) benzophenone, 2, the benzophenone cpds such as 4,6-tri-methyl benzophenone; The naphtoquinone compounds such as 9,10-phenanthrenequione, 2-EAQ, camphorquinone; 10-butyl-2-chloro-acridine ketone, benzyl, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.They preferably cause auxiliary agent (D1) (particularly amine) with the aftermentioned polymerization and are used in combination.

The acid producing agent played a role as polymerization initiator as producing acid, can list salts such as 4-hydroxy phenyl dimethyl sulfonium tosilate, 4-hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium tosilate, 4-acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine hexafluoro antimonate, nitrobenzyl toluenesulfonic acid salt, benzoin toluenesulfonic acid salt etc.

As polymerization initiator (D); be preferably and comprise the polymerization initiator of at least a kind be selected from alkyl phenones compound, triaizine compounds, acylphosphine oxide compound, O-acyl group oxime compound and united imidazole, more preferably comprise the polymerization initiator of O-acyl group oxime compound.

The content of polymerization initiator (D), with respect to total amount 100 mass parts of resin (B) and polymerizable compound (C), is preferably 0.1～30 mass parts, more preferably 1～20 mass parts.The tendency that time shutter shortens if, in above-mentioned scope, there is ISO in the content of polymerization initiator (D), thereby the throughput rate of color filter improves.

It is compound or the sensitizer by the polymerization of the polymerizable compound of polymerization initiator initiated polymerization for promotion that polymerization causes auxiliary agent (D1).Polymerization causes auxiliary agent (D1) usually and polymerization initiator (D) is used in combination.

Cause auxiliary agent (D1) as polymerization, can list amines, alkoxy anthracene compound, thioxanthones compound and carboxylic acid compound etc.

As above-mentioned amines, can list triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamino benzoic acid methyl esters, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylamino benzoic acid 2-Octyl Nitrite, N, the N-dimethyl-p-toluidine, 4, 4 '-bis-(dimethylamino) benzophenone (common name Michler's keton), 4, 4 '-bis-(diethylamino) benzophenone, 4, 4 '-bis-(ethylmethylamino) benzophenone etc., wherein preferably 4, 4 '-bis-(diethylamino) benzophenone.Can use the commercially available products such as EAB-F (hodogaya chemical industry (strain) system).

As above-mentioned alkoxy anthracene compound, can list 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene etc.

As above-mentioned thioxanthones compound, can list ITX, ITX, 2,4-diethyl thioxanthone, 2,4-bis-clopenthixal ketones, the chloro-4-propoxyl group of 1-thioxanthones etc.

As above-mentioned carboxylic acid compound, can list phenyl sulfenyl acetic acid, aminomethyl phenyl sulfenyl acetic acid, ethylphenyl sulfenyl acetic acid, Methylethyl phenyl sulfenyl acetic acid, 3,5-dimethylphenyl sulfenyl acetic acid, methoxyphenyl sulfenyl acetic acid, Dimethoxyphenyl sulfenyl acetic acid, chlorphenyl sulfenyl acetic acid, dichlorophenyl sulfenyl acetic acid, N-phenylglycine, phenoxyethanoic acid, naphthyl thioacetic acid, N naphthyl glycocoll, naphthoxy acetic acid etc.

In the situation that use these polymerizations to cause auxiliary agents (D1), its content is with respect to total amount 100 mass parts of resin (B) and polymerizable compound (C), is preferably 0.1～30 mass parts, 1～20 mass parts more preferably.If polymerization causes the amount of auxiliary agent (D1) in this scope, exist and can further with high sensitivity, form the tendency of the throughput rate raising of colored pattern and color filter.

Solvent (E) can be not particularly limited to use solvent usually used in this field.For example, can list ester solvent (solvent of comprise in molecule-COO-and do not comprise-O-), ether solvents (solvent of comprise in molecule-O-and do not comprise-COO-), ether-ether solvent (comprise in molecule-COO-and-solvent of O-), ketone solvent (solvent of comprise in molecule-CO-and do not comprise-COO-), alcoholic solvent (in molecule, comprise OH and do not comprise-O-,-CO-and-solvent of COO-), aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide (DMSO) etc.

As ester solvent, can list methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyl isobutyl alkanoic acid methyl esters, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate and gamma-butyrolacton etc.

As ether solvents, can list the glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, the diethylene glycol single-butyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, the propylene glycol single-butyl ether, 3-methoxyl-n-butyl alcohol, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, 1, the 4-diox, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, the diethylene glycol dipropyl ether, the diethylene glycol dibutyl ethers, anisole, phenetol and methyl anisole etc.

As the ether-ether solvent, can list Methoxy Methyl Acetate, the Methoxy acetic acid ethyl ester, the Methoxy acetic acid butyl ester, the ethoxy methyl acetate, the ethoxy ethyl acetate, the 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy 2 Methylpropionic acid ethyl ester, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, the ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, the TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters etc.

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

As alcoholic solvent, can list methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerine etc.

As aromatic hydrocarbon solvents, can list benzene,toluene,xylene,

deng.

As amide solvent, can list DMF, DMA, 1-METHYLPYRROLIDONE etc.

In above-mentioned solvent, viewpoint from coating, drying property, the boiling point be preferably under 1atm is more than 120 ℃ and the organic solvent below 180 ℃, more preferably propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, glycol monomethyl methyl ether, diethylene glycol monomethyl ether, TC, 4-hydroxy-4-methyl-2-pentanone and N, dinethylformamide, more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl lactate and 3-ethoxyl ethyl propionate.

The content of solvent (E) is with respect to the total amount of colored curable resin composition of the present invention, is preferably 70～95 quality %, 75～92 quality % more preferably.In other words, the total amount of the solid constituent of colored curable resin composition is preferably 5～30 quality %, 8～25 quality % more preferably.If the content of solvent (E) is in above-mentioned scope, the flatness while being coated with becomes well, and while forming color filter in addition, colour saturation does not have deficiency, thereby the tendency that exists display characteristic to become good.

As levelling agent (F), can list the silicone-based surfactant, fluorine is surfactant and the silicone-based surfactant with fluorine atom etc.They can have polymerizable group at side chain.

As the silicone-based surfactant, can list in molecule surfactant with siloxane bond etc.Specifically, can list Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (trade name: Dow Corning Toray Co., Ltd. make), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Janpan contract commercial firm system) etc.

Be surfactant as above-mentioned fluorine, can list in molecule surfactant with fluorocarbon chain etc.Specifically, can list Fluorad (registered trademark) FC430, Fluorad FC431 (Sumitomo 3M (strain) system), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (DIC (strain) system), EFtop (registered trademark) EF301, EFtop EF303, EFtop EF351, EFtop EF352 (Mitsubishi's material electronics changes into (strain) system), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (strain) system), E5844 ((strain) DAIKIN FINE CHEMICAL institute system) etc.

As the above-mentioned silicone-based surfactant with fluorine atom, can list in molecule surfactant with siloxane bond and fluorocarbon chain etc.Specifically, can list Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, MegafacF443 (DIC (strain) system) etc.

The content of levelling agent (F) is with respect to the total amount of colored curable resin composition, more than being preferably 0.001 quality % and below 0.2 quality %, more preferably more than 0.002 quality % and below 0.1 quality %, more preferably more than 0.01 quality % and below 0.05 quality %.In addition, this content does not comprise the content of above-mentioned pigment dispersing agent.If the content of levelling agent (F) in above-mentioned scope, can make the flatness of color filter become good.

Colored curable resin composition of the present invention can also comprise the adjuvants as known in the art such as filling agent, other macromolecular compounds, closely sealed promoter, antioxidant, light stabilizer, chain-transferring agent as required.

The manufacture method of<colored curable resin composition >

Colored curable resin composition of the present invention can by mixing, for example colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D) and the solvent (E) used as required, levelling agent (F), polymerization cause auxiliary agent (D1) and other one-tenth assigns to prepare.

Pigment (A2) preferably mixes with part or all of solvent (E) in advance, uses ball mill etc. that it is disperseed, until the averaged particles footpath of pigment is the following degree of 0.2 μ m.Now, can also coordinate as required part or all of above-mentioned pigment dispersing agent, resin (B).Mode by the concentration according to becoming regulation is mixed residual composition in the dispersible pigment dispersion obtained as mentioned above, thereby can prepare the target colored curable resin composition.

Dyestuff (A1) can also be dissolved in respectively in advance part or all of solvent (E) and prepare solution.Preferably utilize the filtrator of 0.01～1 μ m left and right, aperture to filter this solution.

Preferably utilize the filtrator of 0.1～10 μ m left and right, aperture to filter mixed colored curable resin composition.

The manufacture method of<color filter >

As by colored curable resin composition of the present invention, manufacturing the method that colored pattern is filmed, can list photoetching process, ink-jet method, print process etc.Wherein, preferred photoetching process.Photoetching process is method as described below: above-mentioned colored curable resin composition is coated to substrate, make it dry and form the coloured composition layer, across photomask, this coloured composition layer is exposed and develops.In photoetching process, by exposure, the time do not use photomask and/or do not developed, thereby the solidfied material that can form above-mentioned coloured composition layer is painted filming.The colored pattern formed is like this filmed, painted filming is color filter of the present invention.

The thickness of the color filter of made can be not particularly limited suitably to adjust according to purpose, purposes etc., is for example 0.1～30 μ m, is preferably 0.1～20 μ m, 0.5～6 μ m more preferably.

As substrate, the glass plates such as soda-lime glass that can use quartz glass, pyrex, alumina silicate glass, effects on surface to be coated with silicon dioxide and obtain, the resin plates such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate, silicon is formed with the substrate of aluminium, silver, silver/copper/palldium alloy film etc. on aforesaid substrate.Can also on these substrates, be formed with other color-filter layers, resin bed, transistor, circuit etc.

Utilize the formation of photolithographic each color pixel to carry out under known or habitual device, condition.For example, can be made as described below.

At first, by colored curable resin composition being applied on substrate and carrying out heat drying (baking and banking up with earth in advance) and/or drying under reduced pressure, thereby, except volatile ingredients such as desolventizings, make its drying, obtain level and smooth coloured composition layer.

As coating process, can list spin-coating method, slot coated method, slit and spin-coating method etc.

Temperature while carrying out heat drying is preferably 30～120 ℃, more preferably 50～110 ℃.In addition, as heat time heating time, be preferably 10 second～60 minute, more preferably 30 second～30 minute.

Carry out in the situation of drying under reduced pressure, preferably under the pressure of 50～150Pa, the temperature range of 20～25 ℃ carries out.

The thickness of coloured composition layer is not particularly limited, as long as carry out suitably selecting according to the thickness of the color filter as target.

Then, the coloured composition layer is exposed across being used to form the photomask that the target colored pattern films.Pattern on this photomask is not particularly limited, and can use the pattern corresponding to the target purposes.

As the light source that is used to exposure, be preferably the light source of the light of the wavelength that produces 250～450nm.For example, for the light of not enough 350nm, can block with the wave filter that blocks this wavelength region may, or, near near near light 436nm, 408nm, 365nm, use the bandpass filter of extracting these wavelength region may selectively to extract.Specifically, can list mercury lamp, light emitting diode, metal halide lamp, Halogen lamp LED etc.

Due to can be to the whole uniform irradiation parallel rays of plane of exposure, or make photomask and the substrate that is formed with the coloured composition layer carry out correct contraposition, therefore preferably use the exposure devices such as mask aligner and stepper.

By make the exposure after composition layer contact and develop with developer solution, thereby form colored pattern on substrate.By developing, the unexposed portion of coloured composition layer is dissolved in developer solution and is removed.

As developer solution, preference is as the aqueous solution of the alkali compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, Tetramethylammonium hydroxide.Concentration in the aqueous solution of these alkali compounds is preferably 0.01～10 quality %, more preferably 0.03～5 quality %.Further, developer solution can contain surfactant.

Developing method can be any in paddling process (paddle method), infusion process and gunite etc.Further can when developing, substrate be tilted arbitrarily angled.

Preferably washing after developing.

Further, preferably resulting colored pattern is filmed after carrying out and baked and banked up with earth.After bake and bank up with earth temperature and be preferably 150～250 ℃, more preferably 160～235 ℃.After the time of baking and banking up with earth be preferably 1～120 minute, more preferably 10～60 minutes.

According to the present invention, can provide and can make the particularly colored curable resin composition of the color filter of contrast excellence.This color filter is as being useful for display device (such as liquid crystal indicator, organic El device, Electronic Paper etc.) and the color filter of solid-state imager.

In addition, according to the present invention, can also provide the colored curable resin composition of the color filter that can form pattern distinctness (for example the brachmorphy shape is good) and fine.

Embodiment

Below, by embodiment, to colored curable resin composition of the present invention, illustrate in greater detail.

" % " in example and " part ", as long as no being particularly limited, are quality % and mass parts.

In following synthesis example, compound is by quality analysis (LC; Agilent system 1200 types, MASS; Agilent LC/MSD type processed) or ultimate analysis (VARIO-EL; (Elementar (strain) system)) identified.

(synthesis example 1)

To the compound shown in throw-in type (A0-1) in the flask with condenser pipe and stirring apparatus and potpourri (the trade name Chugai Aminol Fast Pink R of the compound shown in formula (A0-2); China and foreign countries change into system) 8.9 parts of 15 parts, 150 parts of chloroforms and DMFs, under agitation limit maintains below 20 ℃, and limit adds 10.9 parts of thionyl chlorides.After drip finishing, be warming up to 50 ℃, maintain 5 hours under synthermal to make its reaction, then be cooled to 20 ℃.Cooled reaction solution limit is under agitation maintained below 20 ℃, and limit adds the mixed liquor of 22.1 parts of 12.5 parts of 2-DEHAs and triethylamines.Then, within 5 hours, make its reaction in synthermal lower stirring.Then, from the reaction mixture of gained heats up in a steamer desolventizing, add a small amount of methyl alcohol, high degree of agitation with rotary evaporator.This potpourri is joined while stirring in the mixed liquor of 375 parts of ion exchange waters, make its crystallize out.Filter the crystal of separating out, fully wash with ion exchange water, at 60 ℃ of lower drying under reduced pressure, obtain dyestuff (Aa-1) (potpourri of the compound shown in formula (A1-1)～formula (A1-8)) 11.3 parts.

(synthesis example 2)

200 parts of 20 parts of compounds shown in hybrid under the shading condition (1x) and N-ethyl-ortho-aminotoluenes (with the pure pharmaceutical worker's industry of light (strain) system) stir the solution of gained 6 hours under 110 ℃.After the reactant liquor of gained is cooled to room temperature, add in the mixed liquor of 800 parts, water, 50 parts of 35% hydrochloric acid, at room temperature stir 1 hour, as a result crystallize out.Carry out drying, 24 parts of the compounds shown in acquisition formula (1-24) after the crystal of separating out of the residue form of acquisition suction filtration.Yield is 80%.

The structure of the compound shown in formula (1-24) is by quality analysis (LC; Agilent system 1200 types, MASS; Agilent LC/MSD type processed) confirm.

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

Exact?Mass：602.2

(synthesis example 3)

Except replacing N-ethyl-ortho-aminotoluene, use N-propyl group-2, beyond the 6-xylidin, with synthesis example 1, obtain in the same manner the compound shown in formula (1-32).

The evaluation of the compound shown in formula (1-32)

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

Exact?Mass：658.9

(synthesis example 4)

Specially permit the synthetic method of record in No. 3961078 according to Japan, obtain dyestuff (Ab-1) (potpourri of the compound shown in formula (2-29), formula (2-39), formula (2-40), formula (2-41)).

(synthesis example 5)

Flow into proper N in the flask with reflux condenser, tap funnel and stirring machine, be replaced into blanket of nitrogen, add 371 parts of propylene glycol monomethyl ether, be heated to 85 ℃ while stirring.Then, with 4 hours to dripping and make 54 parts, acrylic acid, 3 in flask, 4-epoxy three ring [5.2.1.0 ^2, ⁶] decane-8-base acrylate and 3,4-epoxy, three ring [5.2.1.0 ^2,6] 81 parts of 225 parts, potpourri (contain than for molar ratio computing 50: 50), the vinyltoluenes (isomer mixture) of decane-9-base acrylate be dissolved in 80 parts of mixed solutions of preparing of propylene glycol monomethyl ether.

On the other hand, with 5 hours, drip and make polymerization initiator 2, two (2, the 4-methyl pentane nitriles) 30 parts of 2-azo are dissolved in 160 parts of solution that form of propylene glycol monomethyl ether.After the dropping of initiator solution finishes, under 85 ℃, keep, after 4 hours, being cooled to room temperature, obtain copolymer solution.Using this multipolymer as resin B 2.The viscosity that the solid constituent of resin B 2 solution is 37.5%, measure by Brookfield viscometer (23 ℃) is 246mPas.The weight-average molecular weight of resin B 1 is 1.06 * 10 ⁴, the acid number that converts of solid constituent is that 115mg-KOH/g, molecular weight distribution are 2.01.Resin B 1 has following structural unit.

(synthesis example 6)

To thering is stirring machine, thermometer, reflux condensing tube, import propylene glycol monomethyl ether 182g in the flask of tap funnel and nitrogen ingress pipe, after atmosphere in flask is become to nitrogen by air, be warming up to 100 ℃, then drip and comprising benzyl methacrylate 70.5g (0.40 mole), methacrylic acid 43.0g (0.5 mole), add 2 in the potpourri of the monomethacrylates of tricyclodecane skeleton (Hitachi changes into (strain) FA-513M processed) 22.0g (0.10 mole) and propylene glycol monomethyl ether 136g, the solution that 2 '-azobis isobutyronitrile 3.6g forms, further under 100 ℃, continue to stir.

Then, atmosphere in flask is become to air by nitrogen, to drop into 35.5g[0.25 mole of glycidyl methacrylate, (being 50 % by mole) in flask for the carboxyl of the methacrylic acid for this reaction], three (dimethylaminomethyl) phenol 0.9g and quinhydrones 0.145g, continue reaction under 110 ℃, resin B 2 solution that acquisition solid constituent 29%, solid constituent acid number are 79mgKOH/g.The weight-average molecular weight of the polystyrene conversion of measuring by GPC is 30,000.

Use the GPC method, carry out under the following conditions the weight-average molecular weight (Mw) of the resin that obtains in synthesis example and the mensuration of number-average molecular weight (Mn).

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

Post: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: THF (tetrahydrofuran)

Flow velocity: 1.0mL/min

Detecting device: RI

Proofread and correct and use standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (eastern Cao (strain) system)

Using the ratio (Mw/Mn) of the weight-average molecular weight of the polystyrene conversion of above-mentioned acquisition and number-average molecular weight as molecular weight distribution.

Use the GPC method, carry out the weight-average molecular weight (Mw) of resin and the mensuration of number-average molecular weight (Mn) under following condition.

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

Post: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: THF (tetrahydrofuran)

Flow velocity: 1.0mL/min

Detecting device: RI

(embodiment 1)

(preparation of colored curable resin composition)

By (A) colorant: C.I. pigment blue 15: 6 (pigment) 33.8 parts

12.8 parts of acrylic acid series pigment dispersing agents

225 parts of propylene glycol monomethyl ether

Mix, use ball mill that pigment is fully disperseed, then,

By (A) colorant: 4.0 parts of xanthene dyes (Aa-1)

(A) colorant: 2.0 parts of tetraazatetradecane porphyrin dyestuffs (Ab-1)

(B) resin: 50 parts of resin B 1 (solid constituent conversion)

(C) polymerizable compound: dipentaerythritol acrylate

(KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system) 50 parts

(D) polymerization initiator: N-benzoyloxy-1-(4-phenyl sulfenyl phenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE01; BASF AG's system) 10 parts

(D1) polymerization initiator: 2,4-diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; Japan's chemical drug (strain) system; The thioxanthones compound) 5 parts

(F) levelling agent: 0.2 part of polyether modified silicon oil (Toray silicone SH8400:Dow Corning Toray Co., Ltd. system)

(E) solvent: 477 parts of 4-hydroxy-4-methyl-2-pentanones

(E) solvent: 204 parts of propylene glycol monomethyl ether

Mix, obtain colored curable resin composition.

The making of<colored pattern >

Use spin-coating method that colored curable resin composition is applied to the square glass substrate (EAGLE2000 of 5cm; Corning company system), after upper, 100 ℃ of lower prebake 3 minutes, obtain dyed layer.

After letting cool, make to be formed with the 100 μ m that are spaced apart of the substrate of dyed layer and quartz glass photomask processed, use exposure machine (TME-150RSK; Topcon (strain) system), under air atmosphere, with 150mJ/cm ²exposure (365nm benchmark) carry out irradiation.As photomask, used the mask that is formed with 100 μ m lines and intermittent pattern.By the dyed layer after irradiation in comprising the water system developer solution that nonionic is surfactant 0.12% and potassium hydroxide 0.04% 24 ℃ of 60 seconds of lower immersion development, after washing, in stove, under 230 ℃, carry out curing after 30 minutes, obtain colored pattern.

For the colored pattern of gained, use determining film thickness device (DEKTAK3; Japan's vacuum technique (strain) system)), measure thickness.

For the colored pattern of gained, use colour examining machine (OSP-SP-200; Olympus (strain) system), measure light splitting, use the characteristic function of illuminant-C, xy chromaticity coordinate (x, y) and tristimulus values Y in the XYZ chromatic diagram of mensuration CIE.The value of Y more means that brightness is higher.The results are shown in table 1.

Do not use during except exposure photomask, carry out the operation identical with the making of colored pattern, make painted filming.Film for the painted of gained, use contrast meter (CT-1; Kettle slope motor company system, color colour difference meter BM-5A; Topcon company system, light source; F-10, polarizing coating; Kettle slope motor (strain) system), making blank value is 30000, measures contrast.If the contrast in filming is high, can think in colored pattern it is also same high-contrast.The results are shown in table 1.

(embodiment 2)

(preparation of colored curable resin composition)

By (A) colorant: C.I. pigment blue 15: 6 (pigment) 17.2 parts

6.5 parts of acrylic acid series pigment dispersing agents

114 parts of propylene glycol monomethyl ether

Mix, use ball mill, pigment is fully disperseed, then,

By (A) colorant: 3.4 parts of xanthene dyes (1-24)

(A) colorant: 2.3 parts of tetraazatetradecane porphyrin dyestuffs (Ab-1)

(B) resin: 50 parts of resin B 1 (solid constituent conversion)

(C) polymerizable compound: dipentaerythritol acrylate

(F) levelling agent: 0.1 part of polyether modified silicon oil (Toray silicone SH8400:Dow Corning Toray Co., Ltd. system)

(E) solvent: 510 parts of 4-hydroxy-4-methyl-2-pentanones

(E) solvent: 201 parts of propylene glycol monomethyl ether

Mix, obtain colored curable resin composition.

For this colored curable resin composition, carry out the operation identical with embodiment 1, further carry out identical evaluation.The results are shown in table 1.

(embodiment 3)

Except xanthene dye (1-24) being replaced with to xanthene dye (1-32), carry out the operation identical with embodiment 2, obtain colored curable resin composition.For this colored curable resin composition, carry out the evaluation identical with embodiment 1.The results are shown in table 1.

(comparative example 1)

By (A) colorant: C.I. pigment blue 15: 6 (pigment) 20 parts

5 parts of acrylic acid series pigment dispersing agents

137 parts of propylene glycol monomethyl ether

Mix, use ball mill, pigment is fully disperseed, then,

By (A) colorant: 3.5 parts of xanthene dyes (Aa-1)

(B) resin: 157 parts of resin B 2 solution

(C) polymerizable compound: dipentaerythritol acrylate

(Japanese chemical drug (strain) system) 50 parts

(D) 15 parts of polymerization initiator: OXE01 (BASF AG's system)

(E) solvent: 289 parts of mixing of 4-hydroxy-4-methyl-2-pentanone obtain colored curable resin composition.For this colored curable resin composition, carry out the evaluation identical with embodiment 1.The results are shown in table 1.

(comparative example 2)

By (A) colorant: C.I. pigment blue 15: 6 (pigment) 25 parts

8.4 parts of acrylic acid series pigment dispersing agents

181 parts of propylene glycol monomethyl ether

Mix, use ball mill that pigment is fully disperseed, then,

By (A) colorant: 4.8 parts of xanthene dyes (Aa-1)

(A) 2.3 parts of the salt (Orient chemical industry (strain) system) of colorant: C.I. direct blue 264 and dodecylbenzene sulfonic acid

(B) resin: 152 parts of resin B 2 solution

(C) polymerizable compound: dipentaerythritol acrylate

(Japanese chemical drug (strain) system) 50 parts

(D) 15 parts of polymerization initiator: OXE 01 (BASF AG's system)

(E) solvent: 308 parts of ethyl lactates

Mix, obtain colored curable resin composition.For this colored curable resin composition, carry out the evaluation identical with embodiment 1.The results are shown in table 1.

(comparative example 3)

By (A) colorant: C.I. pigment blue 15: 6 (pigment) 25 parts

8.4 parts of acrylic acid series pigment dispersing agents

181 parts of propylene glycol monomethyl ether

Mix, use ball mill that pigment is fully disperseed, then,

By (A) colorant: 4.8 parts of xanthene dyes (Aa-1)

(A) colorant: tetraazatetradecane porphyrin dyestuff

(B90401 processed of (strain) Kyung In Synthetic Corp.) 2.3 parts

(B) resin: 152 parts of resin B 2 solution

(C) polymerizable compound: dipentaerythritol acrylate

(Japanese chemical drug (strain) system) 50 parts

(D) 15 parts of polymerization initiator: OXE 01 (BASF AG's system)

(E) solvent: 308 parts of ethyl lactates

[table 1]

According to embodiment, obtained by colored curable resin composition of the present invention film to be identified out demonstrates high-contrast.Hence one can see that, by colored curable resin composition of the present invention, obtained paintedly film, color filter that colored pattern is filmed as high-contrast is useful, and comprises the display characteristic excellence of the liquid crystal indicator of this color filter.

According to colored curable resin composition of the present invention, can form the color filter of high-contrast.

Symbol description

21: glass substrate

22:TFT (on-off element)

22a: gate electrode

22b: gate insulating film

22c: polysilicon film

22d: diaphragm

23: color-filter layer

23A: colored curable resin composition layer (color filter)

23a: red filtrator

23b: green filters

23c: blue filter

24: pixel electrode

27: signal wire

29: photosensitive resin film (diaphragm)

201,202: connecting hole

Claims

1. a colored curable resin composition, it contains colorant, resin, polymerizable compound and polymerization initiator,

Wherein, tetraazatetradecane porphyrin dyestuff and pigment that colorant contains xanthene dye, comprises the compound shown in following formula (1b),

In formula (1b), R ⁴¹～R ⁴⁸mean independently of one another hydrogen atom, halogen atom, cyano group, nitro, replacement or unsubstituted alkyl, replacement or unsubstituted alkoxy, replacement or unsubstituted aryl, replacement or unsubstituted aryloxy group, replacement or unsubstituted aralkoxy or replacement or unsubstituted amino, M means substituted metal atom or the oxidized metal atom of 2 hydrogen atoms, 21 valency metallic atoms, divalent metallic atom, 3 valencys.

2. colored curable resin composition according to claim 1, wherein,

3. colored curable resin composition according to claim 1 and 2, wherein,

4. according to the described colored curable resin composition of any one in claim 1～3, wherein, xanthene dye comprises the compound shown in following formula (1a),

In formula (1a), R ¹～R ⁴the 1 valency saturated hydrocarbyl that mean independently of one another hydrogen atom, can have a substituent carbon number 1～20 maybe can have 1 valency aromatic hydrocarbyl of substituent carbon number 6～10, contained in this saturated hydrocarbyl-CH ₂-can by-O-,-CO-or-NR ¹¹-replace R ¹and R ²can form the ring that comprises nitrogen-atoms, R with together with adjacent nitrogen-atoms ³and R ⁴can form the ring that comprises nitrogen-atoms with together with adjacent nitrogen-atoms,

R ⁵expression-OH ,-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-z ⁺,-CO ₂h ,-CO ₂ ^-z ⁺,-CO ₂r ⁸,-SO ₃r ⁸or-SO ₂nR ⁹r ¹⁰,

R ⁶and R ⁷the alkyl that means independently of one another hydrogen atom or carbon number 1～6,

M means 0～5 integer, at m, is 2 when above, a plurality of R ⁵can be the same or different,

A means 0 or 1 integer,

X means halogen atom,

Z ⁺mean ⁺n(R ¹¹) ₄, Na ⁺or K ⁺, 4 R ¹¹can be the same or different,

R ⁸mean 1 valency saturated hydrocarbyl of carbon number 1～20, hydrogen atom contained in this saturated hydrocarbyl can be replaced by halogen atom,

R ⁹and R ¹⁰mean that independently of one another hydrogen atom maybe can have 1 valency saturated hydrocarbyl of substituent carbon number 1～20, contained in this saturated hydrocarbyl-CH ₂-can by-O-,-CO-,-NH-or-NR ⁸-replace R ⁹and R ¹⁰can mutually combine and form 3～10 member heterocyclic ring containing nitrogens together with nitrogen-atoms,

5. a color filter, it is formed by the described colored curable resin composition of any one in claim 1～4.

6. a display device, it comprises color filter claimed in claim 5.