CN104865796B - Colored curable resin composition - Google Patents

Abstract

A kind of colored curable resin composition, containing colorant, resin, polymerizable compound and polymerization initiator, colorant is containing the colorant selected from least one of weld and yellow uitramarine and blue dyes, viridine green.

Description

Colored curable resin composition

Technical field

The present invention relates to colored curable resin compositions.

Background technique

Colored curable resin composition in liquid crystal display device, el display and plasma for showing The manufacture of colour filter used in the display devices such as device.In order to reduce the power consumption of display device, seek transmissivity height, high brightness Colour filter.As the colored curable resin composition for manufacturing colour filter, in Japanese Unexamined Patent Publication 2013-231165 bulletin In recite the colored curable resin composition for containing halogenated phthalo-cyanine pigment and coumarine dye as colorant.

Summary of the invention

The present invention includes invention below.

[1] a kind of colored curable resin composition causes containing colorant, resin, polymerizable compound and polymerization Agent,

Colorant is containing selected from least one of weld and yellow uitramarine and blue dyes and viridine green Colorant.

[2] colored curable resin composition according to [1], wherein the containing ratio of blue dyes is relative to coloring Total content of agent is 0.1 mass % or more and 20 mass % or less.

[3] colored curable resin composition according to [1] or [2], wherein blue dyes is selected from formula (Ab1) At least one kind of dyestuff in represented compound, methine dyestuff and azomethine dyes,

(in formula, R^1A~R^8ASeparately indicate hydrogen atom, halogen atom, nitro, hydroxyl, carbon atom number 1~20 alkane Base (can be inserted into oxygen atom between the carbon atom for constituting the alkyl).R^4AIt can be with R^5ABe mutually bonded and formed-NH- ,-S-, Or-SO₂-。

R^9A~R^12ASeparately indicate hydrogen atom；Can by amino or can by carbon atom number 1 that halogen atom replaces~ 20 alkyl (can be inserted into oxygen atom between the carbon atom for constituting the alkyl；It can be with substituted aralkyl；Or it can be substituted Aryl.R^9AIt can be with R^10AThe nitrogen-atoms for being bonded and being bonded with them is formed together ring, R^11AIt can be with R^12ABonding and and he The nitrogen-atoms that is bonded be formed together ring.

A is indicated can be with substituted aromatic hydrocarbyl or can be with substituted aromatic heterocycle.

G^g-Indicate counter anion.

G indicates 0 or arbitrary natural number.When g is 0, indicate do not have counter anion.)

[4] colored curable resin composition according to any one of [1]~[3], wherein polymerization initiator be containing There is the polymerization initiator of O- acyl group oxime compound.

[5] a kind of colour filter, by the described in any item colored curable resin composition shapes in any one of [1]~[4] At.

[6] a kind of display device, it includes the colour filters described in [5].

Colored curable resin composition according to the present invention can form the excellent colour filter of brightness (lightness).

Specific embodiment

Colored curable resin composition of the invention contains colorant (A), resin (B), polymerizable compound (C) and gathers It closes initiator (D), colorant (A) contains selected from least one of weld and yellow uitramarine and blue dyes and green Pigment.

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

Colored curable resin composition of the invention can contain polymerization trigger auxiliary agent (D1) and/or mercaptan compound (T)。

It in the present specification, can individually or will be more if the compound illustrated as each ingredient is without special provision Kind is applied in combination.

<colorant (A)>

Colorant (A) containing blue dyes (A1), viridine green (A2) and in weld and yellow uitramarine extremely Few one kind (hereinafter sometimes referred to " yellow colorants (A3) ").

In the present invention, blue dyes (A1) refers in 580nm or more and 650nm range below, preferably in 600nm or more And with maximum absorption wavelength and to the soluble pigment of solvent in the range of 645nm or less.

As blue dyes (A1), can enumerate compound represented by phthalocyanine dye, formula (Ab1), triarylmethane colouring matters, Anthraquinone dye, methine dyestuff, azomethine dyes etc..Wherein, preferably phthalocyanine dye, compound, methine represented by formula (Ab1) Dyestuff and azomethine dyes, compound, methine dyestuff and azomethine dyes represented by more preferable formula (Ab1).

Phthalocyanine dye (Aa) is the dyestuff containing the compound in the molecule with phthalocyanine frame.As phthalocyanine dye (Aa), can enumerating カ ラ ー イ Application デ ッ Network ス (color index), (The Society of Dyers and Colourists goes out Version) in record C.I. solvent blue 67,70；C.I. direct indigo plant 86,87,189,199；C.I. acid blue 249；C.I. medium is blue 77；Japanese Unexamined Patent Publication 5-333207 bulletin, Japanese Unexamined Patent Publication 6-51115 bulletin, Japanese Unexamined Patent Publication 6-194828 bulletin The dyestuff etc. of middle record.

As compound represented by formula (Ab1) (hereinafter, sometimes referred to as " compound (Ab1) ".), it also include color index (カ ラ ー イ Application デ ッ Network ス) (The Society of Dyers and Colourists publication) middle C.I. solvent recorded Indigo plant 2,4,5,43,124；C.I. alkali blue 1,5,7,26；C.I. Blue VRS, 3,5,7,9,11,13,15,17,22,24,26, 34,48,75,83,86,88,90,91,99,100,103,104,108,109,110,119,123,147,213,269 and Japan The dyestuff etc. recorded in No. 4492760 bulletin of patent.

In formula (Ab1), R^1A~R^8ASeparately indicate hydrogen atom, halogen atom, nitro, hydroxyl, carbon atom number 1~20 Alkyl (can constitute the alkyl carbon atom between be inserted into oxygen atom).R^4AIt can be with R^5ABe mutually bonded and formed-NH- ,- S- or-SO₂-。

R^9A~R^12ASeparately indicating can (can be with by the alkyl for the carbon atom number 1~20 that amino or halogen atom replace Be inserted into oxygen atom between the carbon atom for constituting the alkyl), can be with substituted aralkyl or can be with substituted aryl or hydrogen Atom, preferably separately indicates hydrogen atom, can (can by the alkyl for the carbon atom number 1~20 that amino or halogen atom replace To be inserted into oxygen atom between the carbon atom for being constituted the alkyl) or can be with substituted aryl.R^9AIt can be with R^10ABonding and and it The nitrogen-atoms that is bonded be formed together ring, R^11AIt can be with R^12AThe nitrogen-atoms for being bonded and being bonded with them is formed together ring.

A is indicated can be with substituted aromatic hydrocarbyl or can be with substituted aromatic heterocycle.

G^g-Indicate counter anion.

G indicates 0 or arbitrary natural number.When g is 0, indicate do not have counter anion.

It further include its tautomer in the compound represented by formula (Ab1).

R^1A~R^8ASeparately preferred hydrogen atom and the alkyl of carbon atom number 1~20.In R^1A~R^8AIn, as carbon original The alkyl of the carbon atom numbers such as the alkyl of subnumber 1~20, preferably methyl, ethyl, propyl, butyl 1~4.

R^9A~R^12AIn, as the alkyl of carbon atom number 1~20, the preferably carbon atom numbers such as methyl, ethyl, propyl, butyl 1 ~4 alkyl.As the phenyl that can be replaced by halogen atom, nitro, hydroxyl can be enumerated with substituted aryl.R^9A~R^12A In, as aralkyl, benzyl, phenylethyl etc. can be enumerated.As can with substituted aralkyl, can enumerate can have- SO₃ ^-、-SO₃Aralkyl of the J (J indicates cation) as substituent group.

R^9A~R^12ASeparately preferred hydrogen atom, carbon atom number 1~20 alkyl and can be with substituted benzyl.

In A, as aromatic hydrocarbyl, the carbon atom numbers such as phenyl, naphthalene, toluyl groups, xylyl 6~10 can be enumerated Aromatic hydrocarbyl.As aromatic heterocycle, can enumerate pyrrole radicals, oxazolyl, imidazole radicals, thiazolyl, indyl etc. includes The aromatic heterocycle of the heterocycle of 5 member rings containing aerobic, nitrogen, sulphur.

In A, as the substituent group that aromatic hydrocarbyl and aromatic heterocycle can have, halogen atom can be enumerated, can be by Substituted amino, hydroxyl, sulfo group ,-SO₃ ^-、-SO₃J (J indicates cation) etc..

As the substituent group in above-mentioned amino, the alkyl of carbon atom number 1~4 can be enumerated；It can have carbon atom number 1~4 Aryl of the alkoxy as substituent group；It can have-SO₃ ^-、-SO₃Benzyl of the J as substituent group；Deng.

As J, inorganic cation or organic cation can be enumerated.As inorganic cation, can enumerate alkali metal cation, Ammonium cation.As organic cation, it can be mentioned, for example organoammonium cations, the glyoxaline cations such as cation of following formula.

As G^g-, anion represented by formula (y1), formula (y2) or formula (y3) can be enumerated.

In formula, R^B1Indicate the organic group of 1 valence.As the organic group, the carbon such as methyl, ethyl, propyl, butyl can be enumerated The aliphatic alkyl of atomicity 1~20；The aromatic hydrocarbyl of the carbon atom numbers such as phenyl, naphthalene, toluyl groups 6~20, the rouge The hydrogen atom for including in fat race alkyl and the aromatic hydrocarbyl can be replaced by halogen atom etc..

R^B2And R^B3Indicate halogen atom or halohydrocarbyl, R^B2And R^B3It can be mutually bonded and be formed comprising-SO₂-N^--SO₂ Ring.Above-mentioned halohydrocarbyl is preferably fluoro alkyl, more preferably the fluoro-alkyl of carbon atom number 1~4, further preferably perfluor Alkyl.

R^B4And R^B5Indicate the organic group of divalent.The organic group is preferably the aromatic series base of divalent.As the aromatic series Base can enumerate the aromatic hydrocarbyl of the carbon atom number 6~10 of the divalents such as phenylene, naphthylene, the hydrogen for including in the aromatic hydrocarbyl Atom can be replaced by hydroxyl etc..

M indicates aluminium atom or boron atom.

As anion represented by formula (y1), methane sulfonate anions, toluenesulfonate anion, dodecyl can be enumerated Benzene sulfonate anion, trifluoromethayl sulfonic acid anion, perfluorobutane anion etc..

As anion represented by formula (y2), the anion etc. of following formula can be enumerated.

As anion represented by formula (y3), the anion etc. of following formula can be enumerated.

Further, as G^g-, can enumerate with halide ion, silico-tungstic acid anion, the resin of sulfonic acid anion, three entirely Oroalkane sulfonyl methide acid anion (ト リ ス ペ Le Off Le オ ロ ア Le キ Le ス Le ホ ニ Le メ チ De acid ア ニ オ Application) etc..

G^g-Preferably anion, more preferably halide ion represented by halide ion or formula (y2) or formula (y3) And anion represented by formula (y2).

When A is aromatic hydrocarbyl in formula (Ab1), as compound (Ab1), it can be mentioned, for example the compounds of following formula.Under State in formula J with it is above-mentioned synonymous.

Compound (Ab1) is preferably compound represented by formula (Ab2) (hereinafter, sometimes referred to as " compound (Ab2) ".). It also include its tautomer in compound represented by formula (Ab2).

In formula (Ab2), m indicates arbitrary natural number.

X indicates oxygen atom ,-NR⁵⁶Or sulphur atom.

[Y]^m-Indicate the anion of m valence.

R⁵⁶Indicate the alkyl of hydrogen atom or carbon atom number 1~10.

R⁴¹~R⁴⁶Separately indicating can (can be with by the alkyl for the carbon atom number 1~20 that amino or halogen atom replace Be inserted into oxygen atom between the carbon atom for constituting the alkyl), can with substituted aralkyl, can be former with substituted aryl or hydrogen Son, preferably indicate can by the carbon atom number 1~20 that amino or halogen atom replace alkyl (can constitute the alkyl carbon original Oxygen atom is inserted between son), can be with substituted aryl or hydrogen atom.R⁴¹It can be with R⁴²The nitrogen for being bonded and being bonded with them is former Son is formed together ring, R⁴³It can be with R⁴⁴The nitrogen-atoms for being bonded and being bonded with them is formed together ring, R⁴⁵It can be with R⁴⁶Bonding and The nitrogen-atoms being bonded with them is formed together ring.

R⁴⁷~R⁵⁴Separately indicate hydrogen atom, halogen atom, nitro, hydroxyl, carbon atom number 1~8 alkyl (can be with Oxygen atom is inserted between the carbon atom for constituting the alkyl).R⁴⁸It can be with R⁵²It is mutually bonded and forms-NH- ,-S- or-SO₂-。

R⁵⁵Indicate hydrogen atom, carbon atom number 1~20 alkyl or can be with substituted aryl.

It should be noted that containing multiple in 1 molecule

When, they can may be different structures for identical structure.

R⁴¹~R⁴⁶It is preferred that separately for can with substituted benzyl, carbon atom number 1~20 alkyl or can be taken The aryl in generation, or the ring to be formed together with above-mentioned nitrogen-atoms, the more preferably alkyl of carbon atom number 1~20 or can be by Substituted aryl, or the ring to be formed together with above-mentioned nitrogen-atoms.

R^41A~R^46AIn, as the alkyl of carbon atom number 1~20, the preferably carbon atom numbers such as methyl, ethyl, propyl, butyl 1 ~4 alkyl.

R^41A~R^46AIn, as aryl, the preferably aryl of the carbon atom numbers such as phenyl, toluyl groups 6~10.

R^41A~R^46AIn, as can be with substituted benzyl, can enumerate can have-SO₃-、-SO₃J (J indicates cation) Benzyl as substituent group.

R⁴⁷~R⁵⁴Separately preferred hydrogen atom and the alkyl of carbon atom number 1~4.

R⁵⁵Preferably hydrogen atom, carbon atom number 1~4 alkyl or can be with substituted phenyl.As taking in the phenyl Dai Ji can enumerate halogen atom, methyl, the alkyl sulphonyl of carbon atom number 1~4, trifluoromethyl etc..

As the cationic portion of formula (Ab2), can enumerate cation 1 represented by the formula (Ab2-0) being shown in table 1~ Cation 12 etc..In table, * indicates bonding end.

[table 1]

Wherein, the cationic portion as formula (Ab2), preferred cationic 1~cation 6, cation 8, cation 11 or Cation 12, particularly preferably cation 1, cation 2, cation 8 or cation 12.

As [Y]^m-Well known anion can be enumerated.From the aspect of heat resistance, preferred [Y]^m-For containing boron anion, Anion containing aluminium, fluo anion and at least one kind of element and oxygen contained in tungsten, molybdenum, silicon and phosphorus are used as necessary element Anion.

As compound (Ab2), it can be mentioned, for example the compounds represented by following formula.

It can be reacted by compound represented by compound represented by formula (B-I) and formula (C-I) to manufacture chemical combination Object (Ab2).The reaction can carry out in presence of organic solvent, can also carry out in the absence of a solvent.

[in formula (B-I) and formula (C-I), each symbol respectively indicates the meaning same as described above.]

Compound represented by compound represented by formula (B-II), formula (C-II) and formula (C-II ') can also be passed through Represented compound reacts to manufacture compound (Ab2).The reaction can carry out in presence of organic solvent, can also be It is carried out under the conditions of solvent-free.

[in formula (B-II), formula (C-II) and formula (C-II '), each symbol respectively indicates the meaning same as described above.]

As the manufacturing method of compound (B-I) and compound (B-II), well known various methods can be enumerated, for example, western The method recorded in German patent application P3928243.0.

Can be by well known various method manufactures compound (C-I) and compound (C-II), they are also possible to city Sell the compound that the form of product obtains.

For arbitrary compound (Ab2), desired chemical combination can be further manufactured by anion exchange Object (Ab2).Anion exchange for example can be by the compound (Ab2) that will manufacture in above-mentioned method and desired [Y]^m-'s Alkali metal salt mixes to carry out in a solvent.

As alkali metal, lithium, sodium and potassium can be enumerated.

As [Y]^m-Alkali metal salt, can enumerate Japanese Patent No. 4097704, Japanese Patent No. 4341251 and Journal of The Electrochemical Society, the 1st phase of volume 148, in 2001, International Publication 2008/ No. 075672, Japanese Unexamined Patent Publication 2010-280586 bulletin record alkali metal salt.

Methine dyestuff is the dyestuff of the compound containing the tool structure that there are two groups to be connected by odd number methine chain, should The methine dyestuff (is also known as " poly- methine dyestuff (Port リ メ チ Application sometimes for heterocycle or aromatic rings by least one of two groups Dyestuff) ").

As above compound, specifically, can enumerate with Xa-CH (=CH-CH)_x(Xa and Xb are respectively indicated=Xb Arbitrary group.X be 0 or more integer) shown in structure compound.

Azomethine dyes refers to that 1 or 2 or more in above-mentioned methine chain methine is replaced into the dye of nitrogen-atoms Material.

Methine dyestuff and azomethine dyes (hereinafter, sometime collectively referred to as " methine dyestuff (Ac) ") preferably have above-mentioned two The compound for the structure that a group is connected by 1 methine or 1 imino group, more there is compound represented by the formula of being selected as (Ac1).

[in formula (Ac1), X⁶¹Indicate nitrogen-atoms or CH.

R⁶¹Indicate the alkyl of hydrogen atom or carbon atom number 1~4.

R⁶²Indicate the alkoxy carbonyl of hydrogen atom, cyano, carbamoyl, carboxyl or carbon atom number 1~4.

R⁶³Indicate oxygen atom, C (CN)₂、C(CN)CO₂L¹Or C (CO₂L¹)₂。L¹It indicates the alkyl of carbon atom number 1~8, constitutes 1 of the methylene units of the alkyl or 2 can be replaced by oxygen atom.

R⁶⁴~R⁶⁶Separately indicate can by the alkyl for the carbon atom number 1~20 that amino or halogen atom replace, can be with Substituted amino can be inserted into oxygen between the carbon atom for constituting the alkyl with substituted aryl, hydrogen atom or hydroxyl Atom.]

X⁶¹Preferably nitrogen-atoms.

R⁶¹The preferably alkyl of carbon atom number 1~3, more preferably methyl.

R⁶²Preferably cyano.

R⁶³Preferably oxygen atom.

R⁶⁴Preferably methyl, ethyl or-CH (L²)(L³)。-CH(L²)(L³) in, L²And L³Separately indicate alkyl, L²And L³Total number of carbon atoms be 2~19, more preferably 2~9.In addition, L²And L³Preferably straight-chain alkyl.

R⁶⁵Preferably by the alkyl of 2 carbon atom numbers 1~10 (the more preferably alkyl of carbon atom number 3~6) instead of Amino, more preferably N, N- diisopropylaminoethyl, N, N- di-n-butyl amino, N, bis- n-pentyl amino of N-, N, N- di-n-hexyl Amino.

R⁶⁶Preferably the alkyl, naphthalene, phenyl of the carbon atom number 1~8 of hydrogen atom, straight-chain or branched or have 1 The branched alkane of the phenyl of above halogen atom (preferably fluorine atom, chlorine atom), more preferably hydrogen atom, carbon atom number 3~5 Base (preferably isopropyl, isopentyl, tert-butyl), phenyl or chlorphenyl.

As compound represented by formula (Ac1), it can be mentioned, for example compounds below.It can be for example, by Japanese Unexamined Patent Publication Method that flat 3-166268 bulletin is recorded manufactures compound represented by formula (Ac1).

In the present invention, viridine green (A2) refers to has maximum absorption wave in the range of 650nm or more and 700nm or less It is long and to water, organic solvent equal solvent is insoluble or the pigment of indissoluble.It can be mentioned, for example in color index (The Society of Dyers and Colourists is published) in be classified as the pigment of pigment.

As viridine green, C.I. pigment Green 7,36,58,59, Japanese Unexamined Patent Publication 2004-70342 bulletin, Japan can be enumerated The halogenated phthalo-cyanines pigment such as the viridine green that special open 2008-19383 bulletin, Japanese Unexamined Patent Publication 2007-320986 bulletin are recorded.It is excellent It is selected as C.I. pigment Green 7,36,58,59.

Yellow colorants (A3) are selected from least one of weld and yellow uitramarine.In the present invention, yellow coloring Agent (A3) refers to be had in the range of 400nm or more and 470nm or less, preferably in the range of 430nm or more and 470nm or less There is the pigment of maximum absorption wavelength.

As weld, azo dyes, metal complex dyes, methine dyestuff, coumarine dye, styrene can be enumerated Dyestuff.Wherein, preferred coumarine dye.

Coumarine dye is the dyestuff containing the compound in the molecule with coumarin skeleton.As coumarine dye, The C.I. Indian yellow recorded in color index (The Society of Dyers and Colourists publication) can be enumerated 227,250, C.I. disperse yellow 82,184, C.I. solvent orange 112, C.I. solvent yellow 16 0,172, Japanese Patent No. 1299948 The coumarine dye etc. recorded in bulletin.The coumarine dye is preferably dissolved in organic solvent.

In them, as coumarine dye, compound represented by preferred formula (Ad1) or formula (Ad2) (is distinguished sometimes below Referred to as " compound (Ad1) ", " compound (Ad2) ").

[in formula (Ad1), Q^1BAnd Q^2BSeparately indicate hydrogen atom or-CO₂M^1B, but Q^1BAnd Q^2BAny of indicate- CO₂M^1B。

R^1B~R^4BSeparately indicate the alkyl or R of 1 valence of hydrogen atom or carbon atom number 1~20^1BAnd R^3BTogether Ring, R are formed together with the nitrogen-atoms of carbon atom and adjoining on adjacent phenyl ring^2BAnd R^4BTogether with the carbon on adjacent phenyl ring Atom and the nitrogen-atoms of adjoining are formed together ring or R^1BAnd R^2BIt is bonded and is formed together ring with adjacent nitrogen-atoms.Constitute this 1 The methylene of the alkyl of valence can be replaced into oxygen atom, sulphur atom ,-N (R^5B)-, sulfonyl or carbonyl, in the alkyl of 1 valence The hydrogen atom for including can be substituted by halogen atom, cyano, nitro, carbamoyl, amino-sulfonyl ,-SO₃M^1B、-CO₂M^1B、 Hydroxyl or amino.

R^5BIndicate the alkyl of 1 valence of hydrogen atom or carbon atom number 1~20.There are multiple R^5BWhen, they are same to each other or not Together.

M^1BIndicate hydrogen atom or alkali metal atom.]

R^1BAnd R^2BIt is separately preferably the aliphatic alkyl of 1 valence of carbon atom number 1~10, more preferably ethyl, fourth Base, hexyl, 2- ethylhexyl or octyl, further preferably ethyl, butyl, hexyl and 2- ethylhexyl.

R^3BAnd R^4BPreferably hydrogen atom.

R^1BAnd R^3BWhen forming the ring of the nitrogen-atoms and carbon atom that are bonded comprising them together or R^2BAnd R^4BIt is formed together When the ring of the nitrogen-atoms and carbon atom that are bonded comprising them, as-R^1B-R^3BAnd-R^2B-R^4B,-CH can be enumerated₂-CH₂-、- CF₂-CF₂Or-CH₂-C(CH₃)₂Etc. preferably-CH₂-CH₂Or-CH₂-C(CH₃)₂, more preferably-CH₂-C(CH₃)₂-。

As R^1BAnd R^2BBonding and-R when being formed together ring with adjacent nitrogen-atoms^1B-R^2B,-(CH can be enumerated₂)₂-、- (CH₂)₃-、-(CH₂)₄-、-(CH₂)₅-、-(CH₂)₆-、-(CH₂)₇-、-(CF₂)₂-、-(CF₂)₃-、-(CF₂)₄-、-(CF₂)₅-、- (CF₂)₆-、-(CF₂)₇Etc. preferably-(CH₂)₄-、-(CH₂)₅-、-(CH₂)₆-、-(CF₂)₄-、-(CF₂)₅Or-(CF₂)₆, more Preferably-(CH₂)₄-、-(CH₂)₅Or-(CH₂)₆, further preferably-(CH₂)₄Or-(CH₂)₅-。

M^1BPreferably hydrogen atom, sodium atom or potassium atom, more preferably hydrogen atom.

As compound (Ad1), it can be mentioned, for example the compounds of following formula and Japanese Unexamined Patent Publication 2013-231165 bulletin to remember The compound of load.

In formula (Ad2), L^CIndicate the alkyl or sulfonyl of the divalent of carbon atom number 1~20, the hydrogen atom for including in the alkyl It can be replaced by fluorine atoms.

X^CIndicate oxygen atom or sulphur atom.

R^1CAnd R^2CIt separately indicates to can have the phenyl of substituent group or the alkyl of carbon atom number 1~20, Ke Yi It constitutes and is inserted into oxygen atom between the carbon atom of the alkyl.

R^7C~R^13CSeparately indicate hydrogen atom, halogen atom, cyano, nitro, carbamoyl, amino-sulfonyl ,- SO₃M^C、-CO₂M^C, hydroxyl, formoxyl, amino, carbon atom number 1~20 1 valence alkyl, constitute the alkyl carbon atom between Oxygen atom, sulphur atom ,-N (R can be inserted^14C)-, sulfonyl or carbonyl, the hydrogen atom for including in the alkyl can by halogen atom, Cyano, nitro, carbamoyl, amino-sulfonyl ,-SO₃M^C、-CO₂M^C, hydroxyl, formoxyl or amino replaces.

R^14CIndicate the alkyl of 1 valence of hydrogen atom or carbon atom number 1~20, there are multiple R^14CWhen, they can be identical, It can be different.

M^CIndicate hydrogen atom or alkali metal atom.

As R^1CAnd R^2CThe substituent group that can have of phenyl, can enumerate halogen atom, cyano, nitro, carbamoyl, Amino-sulfonyl ,-SO₃M^C、-CO₂M^C, hydroxyl, formoxyl, amino, the alkyl of 1 valence of carbon atom number 1~20 etc..

L^CThe alkyl or sulfonyl of the divalent for the carbon atom number 1~5 that can be preferably replaced by fluorine atoms, more preferably third Alkane -2,2- diyl, hexafluoropropane -2,2- diyl or sulfonyl.

X^CPreferably oxygen atom.

As compound (Ad2), it can be mentioned, for example the compounds represented by following formula.

As yellow uitramarine, color index (The Society of Dyers and Colourists publication) can be enumerated The C.I. pigment yellow 1 of middle record, 3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117, 125,128,129,137,138,139,147,148,150,153,154,166,173,180,185,194,214 etc..Wherein, excellent Select C.I. pigment Yellow 12 9,138,139,150.

Yellow colorants (A3) are preferably weld.If yellow colorants (A3) are weld, presence can subtract The tendency of the content of few yellow colorants (A3), therefore the resin (B) in colored curable resin composition, polymerization can be increased Property compound (C) content, the durabilities such as heat resistance, chemical-resistant of the colour filter that can make improve.

Colorant (A) can also contain it in the degree of performance for not damaging the application colored curable resin composition His dyestuff and/or pigment.As other dyestuffs, can enumerate in color index (The Society of Dyers and Colourists is published) in be classified as the compound of the dyestuff other than the pigment with tone, in dyeing notes (Se Ran society) Dyestuff in the well known dyestuff recorded other than blue dyes (A1) and yellow colorants (A3).According to chemical structure, can enumerate Azo dyes, phthalocyanine dye, anthraquinone dye, cyanine dye, naphthoquinone dyestuff, quinoneimine dye, methine dyestuff, squaraine dye, Acridine dye, styryl dye, quinoline dye and nitro dye etc..

As other pigment, if viridine green (A2), yellow colorants (A3) yellow uitramarine other than pigment, just do not have It is particularly limited to and well known pigment can be used, it can be mentioned, for example in color index (The Society of Dyers and Colourists is published) in be classified as the pigment of pigment.

As pigment, C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71,73 can be enumerated Etc. orange pigment；

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

C.I. the blue pigments such as pigment blue 15,15:3,15:4,15:6,60；C.I. pigment violet 1,19,23,29,32,36, 38 equal violet pigments etc..

In colorant (A), the containing ratio of blue dyes (A1), viridine green (A2) and yellow colorants (A3) is preferably distinguished In following range.

Blue dyes (A1): 0.1 mass % or more and 20 mass % or less (more preferably 0.5 mass % or more and 15 matter % is measured hereinafter, further preferably 1 mass % or more and 10 mass % or less)

Viridine green (A2): 30 mass % or more and 85 mass % or less (more preferably 45 mass % or more and 75 matter % is measured hereinafter, further preferably 50 mass % or more and 70 mass % or less)

Yellow colorants (A3): 5 mass % or more and 60 mass % or less (more preferably 10 mass % or more and 50 matter % is measured hereinafter, further preferably 15 mass % or more and 45 mass % or less)

The content of blue dyes (A1) relative to 100 mass parts of content of viridine green (A2) be preferably 0.2 mass parts with It is upper and 100 below the mass, more than more preferably 0.4 mass parts and 50 below the mass, further preferably 0.6 mass parts with It is upper and 20 below the mass.

The content of yellow colorants (A3) relative to 100 mass parts of content of viridine green (A2) be preferably 10 mass parts with It is upper and 200 below the mass, more than more preferably 20 mass parts and 150 below the mass, further preferably 30 mass parts with It is upper and 120 below the mass.

If the containing ratio of blue dyes (A1) is in above-mentioned range, since the brightness of obtained colour filter exists into one It is therefore preferred to walk the tendency improved.

In colorant (A), the combination of blue dyes (A1), viridine green (A2) and yellow colorants (A3) is preferably phthalocyanine Dyestuff (Aa)/C.I. pigment Green 7/coumarine dye, phthalocyanine dye (Aa)/58/ coumarine dye of C.I. naphthol green, phthalocyanine dye (Aa) represented by/C.I. pigment Green 7/azo dyes, phthalocyanine dye (Aa)/58/ azo dyes of C.I. naphthol green, formula (Ab1) Compound represented by compound/C.I. pigment Green 7/coumarine dye, formula (Ab1)/C.I. pigment green 36/coumarine dye, Compound/C.I. pigment represented by compound represented by formula (Ab1)/58/ coumarine dye of C.I. naphthol green, formula (Ab1) Represented by compound represented by green 7/ azo dyes, formula (Ab1)/C.I. pigment Green 7/C.I. pigment Yellow 12 9, formula (Ab1) Compound represented by compound/C.I. pigment Green 7/C.I. pigment yellow 13 8, formula (Ab1)/C.I. naphthol green 58/C.I. pigment Compound/C.I. naphthol green 58/C.I. pigment yellow 13 8 represented by Huang 129, formula (Ab1), compound represented by formula (Ab1)/ C.I. 58/ azo dyes of naphthol green, methine dyestuff (Ac)/C.I. pigment Green 7/coumarine dye, methine dyestuff (Ac)/C.I. face Expect green 36/ coumarine dye, methine dyestuff (Ac)/58/ coumarine dye of C.I. naphthol green, methine dyestuff (Ac)/C.I. pigment Green 7/ azo dyes, methine dyestuff (Ac)/58/ azo dyes of C.I. naphthol green, methine dyestuff (Ac)/C.I. pigment Green 7/C.I. Pigment Yellow 12 9, methine dyestuff (Ac)/C.I. pigment Green 7/C.I. pigment yellow 13 8, methine dyestuff (Ac)/C.I. naphthol green 58/ C.I. pigment Yellow 12 9, methine dyestuff (Ac)/C.I. naphthol green 58/C.I. pigment yellow 13 8, further preferably formula (Ab1) institute table 58/ tonka-bean uniformly dyeing of compound/C.I. naphthol green represented by the compound shown /C.I. pigment Green 7/coumarine dye, formula (Ab1) Material, methine dyestuff (Ac)/C.I. pigment Green 7/coumarine dye, methine dyestuff (Ac)/58/ coumarine dye of C.I. naphthol green.

Rosin processing can be implemented, using having imported acidic groups or basic group in the pigment such as viridine green (A2) as needed The surface treatment of pigment derivative etc., the grafting to surface of pigments based on high-molecular compound etc. handle, are based on sulfuric acid particles The micronized of change method etc. handles or the carrying out washing treatment based on organic solvent, water for removing impurity etc., is based on ionic impurity The removing processing of ion-exchange etc. etc..

Pigment preferable particle size is uniform.By carrying out decentralized processing containing pigment dispersing agent, available pigment is in solution In it is evenly dispersed after state dispersible pigment dispersion.

As above-mentioned pigment dispersing agent, it can be mentioned, for example cationic system, anionic system, nonionic system, both sexes, polyesters, Surfactants such as polyamines class, acrylic acid series etc..These pigment dispersing agents may be used alone, can also be used in combination 2 kinds with On.As pigment dispersing agent, trade name KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), FLOWLEN (common prosperity society chemistry (strain) can be enumerated System), SOLSPERSE (Jie Likang (strain) system), EFKA (BASF AG's system), AJISPER (aginomoto fine chemistry (strain) system), Disperbyk (Bi Ke chemical company system) etc..

When using pigment dispersing agent, usage amount is preferably 1 mass % or more and 100 mass % relative to the total amount of pigment Hereinafter, more preferably 5 mass % or more and 50 mass % or less.If the usage amount of pigment dispersing agent is within the above range, deposit In the tendency for the dispersible pigment dispersion that can obtain uniform dispersity.

The content of colorant (A) is preferably 5~65 mass %, more preferably 8~60 matter relative to the total amount of solid component Measure %, further preferably 10~55 mass %.If the content of colorant (A) is in above-mentioned range, when colour filter is made Color density it is abundant, and can the resin containing necessary amount, polymerizable compound in the composition, therefore machinery can be formed The sufficient pattern of intensity.

Herein, in this specification " total amount of solid component " refer to from the total amount of colored curable resin composition remove it is molten Amount after the content of agent.The total amount of solid component and relative to its each ingredient content can for example, by liquid chromatography or The measurement of analysis method well known to gas chromatography etc..

<resin (B)>

Resin (B) is preferably alkali soluble resin.As resin (B), resin below [K1]~[K6] etc. can be enumerated.

Resin [K1]: at least one kind of (a) in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides is (hereinafter sometimes referred to " (a) ") and cyclic annular ether structure and ethylenic unsaturated bond with carbon atom number 2~4 monomer (b) (hereinafter sometimes referred to " (b) ") copolymer；

Resin [K2]: (a), (b) He Nengyu (a) copolymerization monomer (c) (but from (a) and (b) different) (hereinafter sometimes referred to " (c) ") copolymer；

Resin [K3]: (a) with the copolymer of (c)；

Resin [K4]: make resin obtained from the copolymer reaction of (b) with (a) and (c)；

Resin [K5]: make resin obtained from the copolymer reaction of (a) with (b) and (c)；

Resin [K6]: making (a) and (b) and copolymer reaction (c), then with resin obtained from carboxylic acid anhydride reactant.

It is specific enumerable as (a): acrylic acid, methacrylic acid, crotonic acid, o-, m-, p- vinyl benzoic acid etc. Unsaturated monocarboxylic acid class；

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

Methyl -5- norbornene -2,3- dioctyl phthalate, bicyclic [2.2.1] hept-2-ene" of 5- carboxyl, 5,6- dicarboxyl are bicyclic [2.2.1] hept-2-ene", 5- carboxyl -5- methyl bicycle [2.2.1] hept-2-ene", bicyclic [2.2.1] the hept- 2- of 5- carboxyl -5- ethyl Alkene, 5- carboxyl -6- methyl bicycle [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene" of 5- carboxyl -6- ethyl etc. are carboxylic Bicyclic unsaturated compound；

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

Mono succinate [2- (methyl) acryloyloxyethyl ester], phthalic acid list [2- (methyl) acryloyloxyethyl ester] Deng single [(methyl) acryloxyalkyl] ester of unsaturation of 2 yuan or more of polybasic carboxylic acids；

Unsaturated acrylate etc. as α-(hydroxymethyl) acrylic acid in same molecule containing hydroxyl and carboxyl.

In them, dissolubility in aqueous alkali of the viewpoint of copolyreaction, gained resin, preferably Acrylic acid, methacrylic acid, maleic anhydride etc..

(b) refer to the cyclic annular ether structure for example with carbon atom number 2~4 (for example, selected from oxirane ring, oxa- ring fourth It is at least one kind of in alkane ring and tetrahydrofuran ring) and ethylenic unsaturated bond monomer.(b) preferably there is carbon atom number 2~4 The monomer of cyclic annular ether structure and (methyl) acryloxy.

It should be noted that " (methyl) acrylic acid " indicates in acrylic acid and methacrylic acid in this specification It is at least one kind of.The statements such as " (methyl) acryloyl group " and " (methyl) acrylate " also have same meaning.

As (b), can enumerate: the monomer (b1) with Oxyranyle and ethylenic unsaturated bond is (hereinafter sometimes referred to " (b1) "), the monomer (b2) (hereinafter sometimes referred to " (b2) ") with oxetanyl and ethylenic unsaturated bond, have tetrahydro Furyl and the monomer (b3) (hereinafter sometimes referred to " (b3) ") of ethylenic unsaturated bond etc..

As (b1), the list of the structure after the unsaturated aliphatic hydrocarbon with straight-chain or branched is at least partially epoxidized can be enumerated Body (b1-1) (hereinafter sometimes referred to " (b1-1) "), be at least partially epoxidized with ester ring type unsaturated hydrocarbons after structure monomer (b1-2) (hereinafter sometimes referred to " (b1-2) ").

As (b1-1), can enumerate (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl ester, glycidyl vinyl ether, adjacent vinylbenzyl glycidyl base ether, second Alkenyl benzyl glycidyl ether, to vinylbenzyl glycidyl base ether, Alpha-Methyl neighbour's vinylbenzyl glycidyl base ether, Vinylbenzyl glycidyl base ether, Alpha-Methyl are to vinylbenzyl glycidyl base ether, the bis- (glycidols of 2,3- between Alpha-Methyl Oxygroup methyl) styrene, bis- (glycidoxypropyl methyl) styrene of 2,4-, bis- (glycidoxypropyl methyl) the benzene second of 2,5- Bis- (glycidoxypropyl methyl) styrene of alkene, 2,6-, 2,3,4- tri- (glycidoxypropyl methyl) styrene, 2,3,5- tri- (glycidoxypropyl methyl) styrene, 2,3,6- tri- (glycidoxypropyl methyl) styrene, (the glycidol oxygen of 3,4,5- tri- Ylmethyl) styrene, 2,4,6- tri- (glycidoxypropyl methyl) styrene etc..

As (b1-2), can enumerate vinylcyclohexene monoxide, 1,2- epoxy -4- vinyl cyclohexane (for example, Celloxide (registered trademark) 2000；(strain) Daicel system), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylate (for example, Cyclomer (registered trademark) A400；(strain) Daicel system), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylate (for example, Cyclomer (registered trademark) M100；(strain) Daicel system), chemical combination represented by compound and formula (II) represented by formula (I) Object etc..

[in formula (I) and formula (II), R^aAnd R^bIndicate the alkyl of hydrogen atom or carbon atom number 1~4, the hydrogen for including in the alkyl Atom can be optionally substituted by a hydroxyl group.

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

R^cIndicate the alkylidene of carbon atom number 1~6.

* the bonding end with O is indicated.]

As the alkyl of carbon atom number 1~4, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, uncle can be enumerated Butyl etc..

Alkyl after being optionally substituted by a hydroxyl group as hydrogen atom can enumerate hydroxymethyl, 1- hydroxyethyl, 2- hydroxyethyl, 1- Hydroxypropyl, 2- hydroxypropyl, 3- hydroxypropyl, 1- hydroxyl -1- Methylethyl, 2- hydroxyl -1- Methylethyl, 1- hydroxyl fourth Base, 2- hydroxybutyl, 3- hydroxybutyl, 4- hydroxybutyl etc..

As R^aAnd R^b, hydrogen atom, methyl, hydroxymethyl, 1- hydroxyethyl, 2- hydroxyethyl are preferably enumerated, it can be more excellent Hydrogen atom, methyl are enumerated in choosing.

As alkylidene, methylene, ethylidene, propane -1,2- diyl, propane -1,3- diyl, butane-Isosorbide-5-Nitrae-can be enumerated Diyl, pentane -1,5- diyl, hexane -1,6- diyl etc..

As X^aAnd X^b, preferably enumerate singly-bound, methylene, ethylidene, *-CH₂- O- and *-CH₂CH₂- O-, it may be more preferable to Enumerate singly-bound, *-CH₂CH₂- O- (* indicates the bonding end with O).

As compound represented by formula (I), compound represented by any of formula (I-1)~formula (I-15) can be enumerated Deng.Wherein, preferred formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11)~formula (I-15) are represented Compound, compound represented by more preferable formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

As compound represented by formula (II), change represented by any of formula (II-1)~formula (II-15) can be enumerated Close object etc..Wherein, preferred formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)~formula (II-15) compound represented by, chemical combination represented by more preferable formula (II-1), formula (II-7), formula (II-9) or formula (II-15) Object.

Compound represented by compound represented by formula (I) and formula (II) can use individually, and also can be used together 2 Kind or more.By compound represented by compound represented by formula (I) and formula (II) and used time, their containing ratio (formula (I) Represented compound: compound represented by formula (II)) it with molar basis is preferably 5:95~95:5, more preferably 20: 80~80:20.

As (b2), more preferably with the monomer of oxetanylmethoxy and (methyl) acryloxy.As (b2), can enumerate 3- methyl -3- methacryloxymethyl oxetanes, 3- methyl -3- acryloyloxymethyl oxetanes, 3- ethyl -3- Methacryloxymethyl oxetanes, 3- ethyl -3- acryloyloxymethyl oxetanes, 3- methyl -3- metering system Acyloxyethyl oxetanes, 3- methyl -3- acrylyl oxy-ethyl oxetanes, 3- ethyl -3- methylacryoyloxyethyl Oxetanes, 3- ethyl -3- acrylyl oxy-ethyl oxetanes etc..

As (b3), more preferably with the monomer of tetrahydrofuran base and (methyl) acryloxy.As (b3), it is specific and Speech can enumerate tetrahydrofurfuryl acrylate (for example, biscoat V#150, Osaka Organic Chemical Industry (strain) system), methacrylic acid Tetrahydrochysene chaff ester etc..

As (b), in the side of the reliability of heat resistance, the chemical-resistant of the colour filter that can be further improved etc. Face, preferably (b1).Further, in terms of the excellent storage stability of colored curable resin composition, more preferable (b1-2).

As (c), can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 12 Arrcostab, (methyl) lauryl acrylate, (methyl) stearyl acrylate, (methyl) acrylic acid ring pentyl ester, (methyl) acrylic acid Cyclohexyl, (methyl) acrylic acid 2- methyl cyclohexyl, (methyl) acrylic acid tricyclic [5.2.1.0^2,6] decane -8- base ester is (in this skill In art field, as popular name, referred to as " (methyl) acrylic acid Bicvclopentyl ester ".In addition, being sometimes referred to as " (methyl) acrylic acid tricyclic Decyl ester "), (methyl) acrylic acid tricyclic [5.2.1.0^2,6] decene -8- base ester is (in the art, as popular name, referred to as " (methyl) acrylic acid double cyclopentenyl ester "), the bicyclic amoxy ethyl ester of (methyl) acrylic acid, (methyl) isobornyl acrylate, (methyl) adamantyl acrylate, (methyl) allyl acrylate, (methyl) acrylic acid propargyl ester, (methyl) acrylic acid (methyl) acrylate such as phenyl ester, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate；

(methyl) propylene of the hydroxyls such as (methyl) acrylic acid 2- hydroxyethyl ester, (methyl) acrylic acid 2- hydroxy-propyl ester Acid esters；

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

Bicyclic [2.2.1] hept-2-ene", 5- methyl bicycle [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene" of 5- ethyl, Bicyclic [2.2.1] hept-2-ene" of 5- hydroxyl, bicyclic [2.2.1] hept-2-ene" of 5- hydroxymethyl, 5- (2 '-hydroxyethyl) are bicyclic Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5- methoxyl group, bicyclic [2.2.1] hept-2-ene" of 5- ethyoxyl, 5,6- dihydroxy Bicyclic [2.2.1] hept-2-ene" of base, bicyclic [2.2.1] hept-2-ene" of 5,6- bis- (hydroxymethyl), 5,6- bis- (2 '-hydroxyethyl) are double Bicyclic [2.2.1] hept-2-ene" of ring [2.2.1] hept-2-ene", 5,6- dimethoxy, bicyclic [2.2.1] the hept- 2- of 5,6- diethoxy Bicyclic [2.2.1] hept-2-ene" of alkene, 5- hydroxy-5-methyl base, bicyclic [2.2.1] hept-2-ene" of 5- hydroxyl -5- ethyl, 5- hydroxyl first Bicyclic [2.2.1] hept-2-ene" of base -5- methyl bicycle [2.2.1] hept-2-ene", 5- tert-butoxycarbonyl, 5- cyclohexyl Epoxide carbonyl Bicyclic [2.2.1] hept-2-ene" of bicyclic [2.2.1] hept-2-ene", 5- phenyloxycarbonyl, 5,6- bis- (tert-butoxycarbonyl) are bicyclic The bicyclic unsaturated compounds such as [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene" of 5,6- bis- (cyclohexyl Epoxide carbonyl)；

N-phenylmaleimide, N- N-cyclohexylmaleimide, N- benzyl maleimide, N- succinimido- 3- maleimidobenzoyl ester, N- succinimido -4- malimidobutanoate, the Malaysia N- succinimido -6- The dicarbapentaborane such as acid imide capronate, N- succinimido -3- maleimidopropionic acid ester, N- (9- acridinyl) maleimide Imide derivative；

Styrene, α-methylstyrene, m-methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene second Alkene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3- Butadiene, isoprene, 2,3- dimethyl -1,3- butadiene etc..

In them, from the viewpoint of copolyreaction and heat resistance, optimization styrene, vinyltoluene, N- phenyl horse Come acid imide, N- N-cyclohexylmaleimide, N- benzyl maleimide, bicyclic [2.2.1] hept-2-ene" etc..

In resin [K1], for the ratio from respective structural unit, in the entire infrastructure unit for constituting resin [K1] In, preferably:

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

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

It is more preferable:

Structural unit from (a)；10~50 moles of %

Structural unit from (b)；50~90 moles of %.

If the ratio of the structural unit of resin [K1] is within the above range, there are the guarantors of colored curable resin composition Deposit stability, formed colored pattern when developability and obtained colour filter excellent solvent resistance tendency.

Can by reference to for example document " experimental method of Polymer Synthesizing " (the big grand row of saliva sale room (strain) chemistry it is same The 1st printing of people the 1st edition distribution on March 1st, 1972) in the method recorded and the citation recorded in the publication manufacture Resin [K1].

It is added in reaction vessel specifically, specified amount by (a) and (b), polymerization initiator and solvent etc. can be enumerated, example Such as, with nitrogen displacement oxygen, thus it is arranged to deoxidizing atmosphere, the method for heating and keeping the temperature while stirring.It should be noted that make herein Polymerization initiator and solvent etc. are not particularly limited, and usually used in this field polymerization initiator and molten can be used Agent.For example, azo-compound (2,2 '-azodiisobutyronitriles, 2,2 '-azos two (2,4- bis- can be enumerated as polymerization initiator Methyl valeronitrile) etc.), organic peroxide (benzoyl peroxide etc.), as solvent, as long as dissolving the solvent of each monomer i.e. Can, the solvent (E) as colored curable resin composition of the invention can enumerate aftermentioned solvent etc..

It should be noted that concentration or dilute can also can be used directly using the solution after reaction in obtained copolymer Solution after releasing can also use the substance taken out in the form of solid (powder) the methods of reprecipitation.Especially by Use the solvent that includes in colored curable resin composition of the invention as solvent in the polymerization, it can will be after reaction Solution directly uses in the preparation of colored curable resin composition of the invention, therefore it is solid to can simplify coloring of the invention The manufacturing process of the property changed resin combination.

In resin [K2], for the ratio from respective structural unit, in the entire infrastructure unit for constituting resin [K2] In, preferably:

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

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

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

It is more preferable:

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

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

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

If the ratio of the structural unit of resin [K2] is within the above range, there are the guarantors of colored curable resin composition Developability and the solvent resistance of obtained colour filter, heat resistance and mechanical strength when depositing stability, forming colored pattern is excellent Different tendency.

Such as resin [K2] is manufactured in the same manner as the method that can be recorded with the manufacturing method as resin [K1].

In resin [K3], for the ratio from respective structural unit, in the entire infrastructure unit for constituting resin [K3] In, preferably:

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

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

It is more preferable:

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

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

Such as resin [K3] is manufactured in the same manner as the method that can be recorded with the manufacturing method as resin [K1].

Can by obtaining the copolymer of (a) Yu (c), make the cyclic ether addition of carbon atom number 2~4 possessed by (b) in (a) carboxylic acid and/or carboxylic acid anhydrides possessed by manufacture resin [K4].

The copolymer of (a) and (c) are manufactured in the same manner as the method for the manufacturing method record as resin [K1] first.This When, for the ratio from respective structural unit, ratio preferably identical with the ratio enumerated in resin [K3].

Then, make the cyclic ether of carbon atom number 2~4 possessed by (b) and the carboxylic acid from (a) in above-mentioned copolymer And/or a part reaction of carboxylic acid anhydrides.

And then the manufacture of the copolymer of (a) and (c), is replaced into air by nitrogen for atmosphere in flask, by (b), carboxylic acid or The catalysts (such as three (dimethylaminomethyl) phenol etc.) and polymerization inhibitor (such as quinhydrones etc.) of carboxylic acid anhydrides and cyclic ether Deng investment flask in, 60~130 DEG C react 1~10 hour, it is possible thereby to manufacture resin [K4].

(b) usage amount is relative to preferably 5~80 moles, more preferably 10~75 moles of 100 moles of (a).By setting For the range, there are the developability when storage stability of colored curable resin composition, formation pattern and obtained figures Solvent resistance, heat resistance, mechanical strength and the balance of sensitivity of case become well to be inclined to.Since the reactivity of cyclic ether is high, It is difficult to (b) of remained unreacted, therefore preferably (b1) as used in resin [K4] (b), further preferred (b1-1).

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

It is contemplated that calorific value caused by manufacturing equipment, polymerization etc. comes suitably, to adjust feeding method, reaction temperature timely Between equal reaction conditions.It should be noted that with polymerizing condition likewise it is possible to fever caused by considering manufacturing equipment, polymerizeing Amount etc. suitably to adjust feeding method, reaction temperature.

For resin [K5], as the first step, (b) and (c) are got similarly with the manufacturing method of above-mentioned resin [K1] Copolymer.As described above, concentration or dilute can also can be used directly using the solution after reaction in the copolymer obtained Solution after releasing can also use the substance after the methods of reprecipitation is taken out in the form of solid (powder).

The ratio of structural unit from (b) and (c) is relative to the total of the entire infrastructure unit for constituting above-mentioned copolymer Molal quantity, preferred respectively:

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

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

It is more preferable:

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

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

Further, under the conditions of same as the manufacturing method of resin [K4], by making carboxylic acid or carboxylic acid possessed by (a) Cyclic ether possessed by copolymer of the acid anhydride with (b) and (c) from (b) reacts, available resin [K5].

With the usage amount of (a) of above-mentioned copolymer reaction relative to 100 moles preferably 5~80 moles of (b).Due to ring-type The reactivity of ether is high, it is difficult to (b) of remained unreacted, therefore preferably (b1) as (b) used in resin [K5], it is further excellent It selects (b1-1).

Resin [K6] is resin made of reacting carboxylic acid anhydrides with resin [K5].Make carboxylic acid anhydrides and passes through cyclic ether With carboxylic acid or reacting for carboxylic acid anhydrides and the hydroxyl that generates reacts.

As carboxylic acid anhydrides, maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acid acid anhydride, 4- second can be enumerated Alkenyl phthalic anhydride, 3,4,5,6- tetrabydrophthalic anhydride, 1,2,3,6- tetrabydrophthalic anhydride, dimethyl tetrahydro Bicyclic [2.2.1] hept-2-ene" acid anhydrides of phthalic anhydride, 5,6- dicarboxyl etc..Use of the usage amount of carboxylic acid anhydrides relative to (a) Preferably 0.5~1 mole of 1 mole of amount.

As resin (B), specifically, (methyl) acrylic acid 3 can be enumerated, 4- epoxycyclohexanecarboxylate/(methyl) propylene Acid copolymer, 3,4- epoxy tricyclic [5.2.1.0^2.6] resins [K1] such as decyl acrylate/(methyl) acrylic copolymer；(first Base) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl Ester/styrene/(methyl) acrylic copolymer, 3,4- epoxy tricyclic [5.2.1.0^2.6] decyl acrylate/(methyl) propylene Acid/N- N-cyclohexylmaleimide copolymer, 3- methyl -3- (methyl) acryloyloxymethyl oxetanes/(methyl) propylene The resins such as acid/styrol copolymer [K2]；(methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) third The resins such as olefin(e) acid copolymer [K3]；Make (methyl) glycidyl acrylate and (methyl) benzyl acrylate/(methyl) acrylic acid Resin obtained by copolymer addition, make (methyl) glycidyl acrylate and (methyl) tricyclodecyl acrylate/styrene/ Resin obtained by (methyl) acrylic copolymer addition makes (methyl) glycidyl acrylate and (methyl) acrylic acid tricyclic last of the ten Heavenly stems The resins [K4] such as resin obtained by ester/(methyl) benzyl acrylate/(methyl) acrylic copolymer addition；Make (methyl) acrylic acid With resin made of (methyl) tricyclodecyl acrylate/(methyl) glycidyl acrylate copolymer reaction, make (methyl) Made of acrylic acid and (methyl) tricyclodecyl acrylate/styrene/(methyl) glycidyl acrylate copolymer reaction The resins such as resin [K5]；Make (methyl) acrylic acid and (methyl) tricyclodecyl acrylate/(methyl) glycidyl acrylate Resins such as resin made of resin made of copolymer reaction is further reacted with tetrabydrophthalic anhydride [K6] etc..

Wherein, as resin (B), preferred resin [K1], resin [K2] and resin [K3], more preferable resin [K1] and resin [K2]。

The weight average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000~100,000, more preferably 5,000~ 50,000, further preferably 5,000~30,000.If molecular weight, in the range, there are the hardness of colour filter to mention Height, residual film ratio is high, favorable solubility of the unexposed portion to developer solution, the tendency that the resolution ratio of colored pattern improves.

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

The acid value of resin (B) is preferably 50~170mg-KOH/g, more preferably 60~150mg-KOH/g, further preferably For 70~135mg-KOH/g.Acid value is measured as the amount (mg) for potassium hydroxide needed for neutralizing resin (B) 1g herein Value, such as can be titrated by using potassium hydroxide aqueous solution to find out.

The content of resin (B) is preferably 7~65 mass %, more preferably 13~60 matter relative to the total amount of solid component Measure %, further preferably 17~55 mass %.If the content of resin (B), in the range, presence can be formed Colored pattern, the tendency that in addition resolution ratio of colored pattern and residual film ratio improve.

<polymerizable compound (C)>

Polymerizable compound (C) can polymerize and being the living radical and/or acid by being generated by polymerization initiator (D) Compound, it can be mentioned, for example compounds of the ethylenic unsaturated bond with polymerism etc., preferably (methyl) acroleic acid esterification Close object.

Wherein, polymerizable compound (C) is preferably the polymerizable compound with 3 or more ethylenic unsaturated bonds.As Such polymerizable compound, it can be mentioned, for example trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) third Olefin(e) acid ester, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) Acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, tetrapentaerythritol ten (methyl) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2- (methyl) acrylyl oxy-ethyl) isocyanuric acid esters, Glycol-modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylate, the third two Alcohol is modified pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, caprolactone and changes Property pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc..

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

The weight average molecular weight of polymerizable compound (C) is preferably 150 or more and 2, and 900 hereinafter, more preferably 250~1, 500 or less.

The content of polymerizable compound (C) is preferably 7~65 mass % relative to the total amount of solid component, and more preferably 13 ~60 mass %, further preferably 17~55 mass %.If the content of polymerizable compound (C) in the range, There are the tendencies that the chemical-resistant of residual film ratio and colour filter when colored pattern formation improves.

<polymerization initiator (D)>

Polymerization initiator (D) as long as by light, the effect generation living radical of heat, acid etc. and polymerization can be caused Compound is just not particularly limited, and well known polymerization initiator can be used.As generate living radical polymerization initiator, It can be mentioned, for example O- acyl group oxime compound, alkyl phenones compound, triaizine compounds, acylphosphine oxide compound and bisglyoxalines Compound.

Above-mentioned O- acyl group oxime compound is the compound with partial structurtes represented by formula (d1).Hereinafter, * indicates bonding End.

As O- acyl group oxime compound, it can be mentioned, for example N- benzoyloxy -1- (4- Phenylsulfanylphenyl) butane -1- ketone - 2- imines, N- benzoyloxy -1- (4- Phenylsulfanylphenyl) octane -1- ketone -2- imines, N- benzoyloxy -1- (4- thiophenyl Phenyl) -3- cyclopenta propane -1- ketone -2- imines, N- acetoxyl group -1- [9- ethyl -6- (2- methyl benzoyl) -9H- click Azoles -3- base] ethane -1- imines, N- acetoxyl group -1- [9- ethyl -6- { 2- methyl -4- (3,3- dimethyl -2,4- dioxane Phenyl-methyl oxygroup) benzoyl } -9H- carbazole -3- base] ethane -1- imines, N- acetoxyl group -1- [9- ethyl -6- (2- first Base benzoyl) -9H- carbazole -3- base] -3- cyclopenta propane -1- imines, N- benzoyloxy -1- [9- ethyl -6- (2- first Base benzoyl) -9H- carbazole -3- base] -3- cyclopenta propane -1- ketone -2- imines etc..Irgacure (registrar can be used Mark) OXE01, OXE02 (more than, BASF AG's system), the commercially available products such as N-1919 (ADEKA corporation).Wherein, O- acyl group oximate is closed Object is preferably selected from N- benzoyloxy -1- (4- Phenylsulfanylphenyl) butane -1- ketone -2- imines, N- benzoyloxy -1- (4- Phenylsulfanylphenyl) octane -1- ketone -2- imines and N- benzoyloxy -1- (4- Phenylsulfanylphenyl) -3- cyclopenta propane -1- ketone - It is at least one kind of in 2- imines, more preferably N- benzoyloxy -1- (4- Phenylsulfanylphenyl) octane -1- ketone -2- imines.If These O- acyl group oxime compounds are then in the tendency of the colour filter of available high brightness.

Abovementioned alkyl benzophenone compound is that have the knot of part represented by partial structurtes represented by formula (d2) or formula (d3) The compound of structure.In these partial structurtes, phenyl ring can have substituent group.

As the compound with partial structurtes represented by formula (d2), 2- methyl -2- morpholino -1- (4- first can be enumerated Sulfenyl phenyl) propane -1- ketone, 2- dimethylamino -1- (4- morphlinophenyl) -2- benzyl butane -1- ketone, 2- (dimethylamino Base) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholinyl) phenyl] butane -1- ketone, irgacure (registered trademark) 369, 907,379 (more than, BASF AG's system).

As the compound with partial structurtes represented by formula (d3), it can be mentioned, 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, The oligomer, α of 2- hydroxy-2-methyl -1- (4- isopropyl phenyl) propane -1- ketone, α-diethoxy acetophenone, benzil diformazan Base ketal etc..

As above-mentioned triaizine compounds, it can be mentioned, for example bis- (the trichloromethyl) -6- (4- methoxyphenyl) -1,3,5- of 2,4- Triazine, 2,4- bis- (trichloromethyl) -6- (4- methoxyl group naphthalene) -1,3,5- triazine, bis- (the trichloromethyl) -6- piperonyls-of 2,4- Bis- (trichloromethyl) -6- (4- the methoxyl-styrene) -1,3,5- triazines of 1,3,5- triazine, 2,4-, 2,4- bis- (trichloromethyls) - 6- (2- (5- methylfuran -2- base) vinyl) -1,3,5- triazine, bis- (the trichloromethyl) -6- of 2,4- (2- (furans -2- base) second Alkenyl) -1,3,5- triazine, bis- (the trichloromethyl) -6- of 2,4- (2- (4- diethylamino -2- aminomethyl phenyl) vinyl) -1,3, Bis- (the trichloromethyl) -6- of 5- triazine, 2,4- (2- (3,4- Dimethoxyphenyl) vinyl) -1,3,5- triazine etc..

As acylphosphine oxide compound, 2,4,6- trimethylbenzoyldiphenyl oxides etc. can be enumerated.It can To use the commercially available products such as irgacure (registered trademark) 819 (BASF AG's system).

As united imidazole, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines, 2,2 '-can be enumerated Bis- (2,3- dichlorophenyls) -4,4 ' 5,5 '-tetraphenyl bisglyoxaline is (for example, referring to Japanese Unexamined Patent Publication 6-75372 bulletin, Japan Japanese Laid-Open Patent Publication 6-75373 bulletin etc..), 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines, 2,2 '-bis- (2- chlorine Phenyl) -4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxalines, 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-four (dialkoxies Phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxalines are (for example, referring to Japan Examined patent publication 48-38403 bulletin, Japanese Unexamined Patent Application 62-174204 bulletin etc..), the phenyl of 4,4 ', 5,5 '-positions is by carbonyl alkane Oxygroup instead of imidazolium compounds (for example, referring to Japanese Unexamined Patent Publication 7-10913 bulletin etc..) etc..

It is further used as polymerization initiator (D), benzoin, benzoin methylether, benzoin ethyl ether, benzoin isopropyl can be enumerated The benzoins compound such as ether, benzoin isobutyl ether；Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- phenyl benzophenone, 4- Benzoyl -4 '-methyldiphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6- front three The benzophenone cpds such as base benzophenone；The naphtoquinone compounds such as 9,10- phenanthrenequione, 2- ethyl hydrazine, camphorquinone；10- butyl -2- chlorine Acridine, dibenzoyl, phenylglyoxalates methyl esters, titanocenes compound etc..It is preferred that by them and aftermentioned polymerization trigger auxiliary agent (D1) (especially amine) is applied in combination.

It as acid agent, can enumerate: 4- hydroxy phenyl dimethyl sulfonium tosilate, 4- hydroxy phenyl dimethyl sulfonium six Fluorine antimonate, 4- acetoxyl group phenyl dimethyl sulfonium tosilate, 4- acetoxyl group phenyl methyl benzyl sulfonium hexafluoro-antimonic acid Salt, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine The salt such as hexafluoro antimonate or nitrobenzyl tosylat, benzoin tosylate etc..

Polymerization initiator (D) preferably containing selected from O- acyl group oxime compound, alkyl phenones compound, triaizine compounds, The polymerization initiator of at least one of acylphosphine oxide compound and united imidazole more preferably contains O- acyl group oxime The polymerization initiator of compound.

The content of polymerization initiator (D) is excellent relative to 100 mass parts of total amount of resin (B) and polymerizable compound (C) It is selected as 0.1~30 mass parts, more preferably 1~20 mass parts.If the content of polymerization initiator (D) in above-mentioned range, Due to the tendency of time for exposure shortening there are high-sensitivity, the productivity of colour filter is improved.

<polymerization trigger auxiliary agent (D1)>

Polymerization trigger auxiliary agent (D1) is the polymerization for promoting to have been caused by polymerization initiator the polymerizable compound of polymerization Compound or sensitizer.When containing polymerization trigger auxiliary agent (D1), usually it is applied in combination with polymerization initiator (D).

As polymerization trigger auxiliary agent, amine compounds, alkoxy anthracene compound, thioxanthone compound and Carboxylation can be enumerated Close object etc..

As above-mentioned amine compounds, triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylamino can be enumerated Methyl benzoate, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, benzoic acid 2- dimethylamino Ethyl ester, 4- dimethylaminobenzoic acid 2- ethylhexyl, N, N- dimethyl-p-toluidine, 4,4 '-bis- (dimethylamino) hexichol Ketone (common name Michler's keton), 4,4 '-bis- (diethylamino) benzophenone, 4,4 '-bis- (ethylmethylamino) benzophenone etc., Wherein preferably 4,4 '-bis- (diethylamino) benzophenone.It is commercially available that EAB-F (hodogaya chemical industry (strain) system) etc. can be used Product.

As above-mentioned alkoxy anthracene compound, can enumerate 9,10- dimethoxy anthracene, 2-ethyl-9,10-dimethoxypyrene, 9,10- diethoxy anthracene, 2- ethyl -9,10- diethoxy anthracene, 9,10- dibutoxy anthracene, 2- ethyl -9,10- dibutoxy anthracene Deng.

As above-mentioned thioxanthone compound, 2- isopropyl thioxanthone, 4- isopropyl thioxanthone, 2,4- bis- can be enumerated Ethyl thioxanthone, bis- chlorothiaxanthenone of 2,4-, the chloro- 4- propoxyl group thioxanthone of 1- etc..

As above-mentioned carboxylic acid compound, thiophenyl acetic acid, methylphenyl-sulfanyl acetic acid, ethylthiophenyl acetic acid, first can be enumerated Base ethylthiophenyl acetic acid, dimethyl benzene ethyl thioglycollic acid, Methoxv-phenylsulfanvl acetic acid, dimethoxyphenylthio acetic acid, chlorobenzene sulphur Guanidine-acetic acid, dichloro-benzenes ethyl thioglycollic acid, N-phenylglycine, phenoxyacetic acid, naphthalene ethyl thioglycollic acid, N- naphthalene glycine, naphthoxy Acetic acid etc..

When using these polymerization trigger auxiliary agent (D1), content is relative to the total of resin (B) and polymerizable compound (C) Measuring 100 mass parts is preferably 0.1~30 mass parts, more preferably 1~20 mass parts.If the amount of polymerization trigger auxiliary agent (D1) is at this Tendency in range, then in the productivity raising that can form colored pattern, colour filter with further high sensitivity.

<mercaptan compound (T)>

Mercaptan compound (T) is compound in the molecule with sulfydryl (- SH).

As with the compound of 1 sulfydryl, it can be mentioned, for example 2- sulfydryl oxazole, 2- thyroidan, 2- mercaptos in the molecule Base benzimidazole, 2-mercaptobenzothiazole, 2- mercaptobenzoxazole, 2- mercaptonicotinic acid, 2- mercaptopyridine, 2- mercaptopyridine -3- Alcohol, pyrithione, 4- Amide-6-hydroxy-2-mercaptopyrimidine, 4- Amide-6-hydroxy-2-mercaptopyrimidine, 4- ammonia Base -2- mercaptopyrimidine, 6- amino -5- nitroso -2- deracil, 4,5- diamino -6- hydroxyl -2- mercaptopyrimidine, 4,6- bis- Amino-2-mercapto phenyl formic pyrimidine, 2,4- diamino -6- mercaptopyrimidine, 4,6- dihydroxy -2- mercaptopyrimidine, 4,6- dimethyl -2- sulfydryl Pyrimidine, 4- hydroxyl -2- sulfydryl -6- methylpyrimidine, 4- hydroxyl -2- sulfydryl -6- propyl pyrimidine, 2- sulfydryl -4- methylpyrimidine, 2- mercapto Yl pyrimidines, 2- deracil, 3,4,5,6- tetrahydropyrimidine -2- mercaptan, 4,5- diphenyl-imidazole -2- mercaptan, 2- mercaptoimidazole, 2- Sulfydryl -1- methylimidazole, 4- amino -3- diazanyl -5- sulfydryl -1,2,4- triazole, 3- amino -5- sulfydryl -1,2,4- triazole, 2- first Base -4H-1,2,4- triazole -3- mercaptan, 4- methyl -4H-1,2,4- triazole -3- mercaptan, 3- sulfydryl -1H-1,2,4- triazole -3- sulphur Alcohol, 2- amino -5- sulfydryl -1,3,4- thiadiazoles, 5- amino -1,3,4- thiadiazoles -2- mercaptan, 2,5- dimercapto -1,3,4- thiophene Diazole, (furans -2- base) methyl mercaptan, 2- sulfydryl -5- thiazolidone, 2- sulfydryl thiazoline, 2- sulfydryl -4 (3H)-quinazoline Ketone, 1- phenyl -1H-TETRAZOLE -5- mercaptan, 2- quinoline thiol, 2- sulfydryl -5- tolimidazole, 2- sulfydryl -5- nitro benzo miaow Azoles, 6- amino-2-mercapto phenyl formic benzothiazole, the chloro- 2-mercaptobenzothiazole of 5-, 6- ethyoxyl -2-mercaptobenzothiazole, 6- nitro - 2-mercaptobenzothiazole, 2- sulfydryl naphtho- imidazoles, 2- sulfydryl aphthoxazoles, 3- sulfydryl -1,2,4- triazole, 4- amino -6- sulfydryl Pyrazolo [2,4-d] pyridine, 2- amino -6- purine mercaptan, Ismipur, 4- sulfydryl -1H- pyrazolo [2,4-d] pyrimidine etc..

As the compound of the sulfydryl in the molecule with 2 or more, it is bis- that ethanthiol, two mercaptan of the last of the ten Heavenly stems, Isosorbide-5-Nitrae-can be enumerated (methyl mercapto) benzene, butanediol bis- (3-thiopropionates), butanediol bis- (3- mercaptoacetates), bis- (the 3- sulfydryl second of ethylene glycol Acid esters), trimethylolpropane tris (3- mercaptoacetate), butanediol bis- (3-thiopropionates), trimethylolpropane tris (3- mercapto Base propionic ester), trimethylolpropane tris (3- mercaptoacetate), pentaerythrite four (3-thiopropionate), four (3- of pentaerythrite Mercaptoacetate), trihydroxy ethyl three (3-thiopropionate), pentaerythrite four (3- mercaptobutylate), bis- (the 3- sulfydryls of 1,4- Butoxy) butane etc..

The content of mercaptan compound (T) is preferably 0.5~20 mass parts relative to 100 mass parts of polymerization initiator (D), more Preferably 1~15 mass parts.If the content of mercaptan compound (T) is in the range, got higher there are sensitivity and developability Become good tendency.

<solvent (E)>

Solvent (E) is not particularly limited, and solvent usually used in this field can be used.As the solvent, can enumerate Ester solvent (containing-COO-, the solvent without-O- in the molecule), ether solvents are (molten without-COO- in the molecule containing-O- Agent), the ether-ether solvent solvent of-COO- and-O- (in the molecule contain), ketone solvent (contain-CO- in the molecule, without-COO- Solvent), alcoholic solvent (containing OH in the molecule, the solvent without-O- ,-CO- and-COO-), aromatic hydrocarbon solvents, amide it is molten Agent, dimethyl sulfoxide etc..

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

As ether solvents, can enumerate glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol Single propyl ether, propylene glycol monobutyl ether, 3- methoxyl group-n-butyl alcohol, 3- methoxyl group -3- methyl butanol, tetrahydrofuran, oxinane, 1, 4- dioxanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol dipropyl ether, diethylene glycol Butyl oxide, methyl phenyl ethers anisole, phenetole, methylanisole etc..

As ether-ether solvent, methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy can be enumerated Acetic acid methyl ester, ethoxy ethyl acetate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, 2- methoxy methyl propionate, 2- methoxypropionate, 2- methoxy propyl propyl propionate, 2- ethyoxyl Methyl propionate, 2- ethoxyl ethyl propionate, 2- methoxyl group -2 Methylpropionic acid methyl esters, 2- ethyoxyl -2 Methylpropionic acid ethyl ester, 3- Methoxybutyl acetic acid esters, 3- methyl -3- methoxybutyl acetic acid esters, propylene glycol methyl ether acetate, dihydroxypropane single-ether second Acid esters, propylene glycol monopropyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol monoethyl ether Acetic acid esters and butyl carbitol acetate etc..

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

As alcoholic solvent, methanol, ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol can be enumerated Deng.

As aromatic hydrocarbon solvents, benzene,toluene,xylene and mesitylene etc. can be enumerated.

As amide solvent, n,N-Dimethylformamide, n,N-dimethylacetamide and N-Methyl pyrrolidone can be enumerated Deng.

In above-mentioned solvent, from the aspect of coating, drying property, boiling point preferably at 1atm be 120 DEG C or more and 180 DEG C of organic solvents below.As solvent, preferably propylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3- Ethoxyl ethyl propionate, glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4- hydroxy-4-methyl -2- penta Ketone and n,N-Dimethylformamide, more preferable propylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and 4- hydroxyl- 4-methyl-2 pentanone.

The content of solvent (E) is preferably 70~95 matter relative to the total amount of colored curable resin composition of the invention Measure %, more preferably 75~92 mass %.In other words, the total amount of the solid component of colored curable resin composition is preferably 5 ~30 mass %, more preferably 8~25 mass %.If flatness of the content of solvent (E) in above-mentioned range, when being coated with Become good, color density will not be insufficient when being additionally formed colour filter, therefore there are display characteristics to become good tendency.

<levelling agent (F)>

As levelling agent (F), silicone-based surfactant, fluorine system surfactant and the silicone with fluorine atom can be enumerated It is surfactant etc..They can have polymerizable group in side chain.

As silicone-based surfactant, surfactant etc. in the molecule with siloxanes key can be enumerated.It is specific and Speech, can enumerate 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: east beautiful DOW CORNING (strain) system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (step contract commercial firm, figure new high-tech material Japan system) Deng.

As above-mentioned fluorine system surfactant, surfactant etc. in the molecule with fluorocarbon chain can be enumerated.Specifically For, fluorad (registered trademark) FC430, fluorad FC431 (Sumitomo 3M (strain) system), megafac (registrar can be enumerated Mark) 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 Materials electronics is melted into (strain) system), surflon (registered trademark) S381, surflon S382, surflon SC101, surflon SC105 (Asahi Glass (strain) system) and E5844 ((strain) big aurin Thin chemical institute system) etc..

As the above-mentioned silicone-based surfactant with fluorine atom, can enumerate has siloxanes key and fluorine in the molecule The surfactant etc. of carbochain.Specifically, megafac (registered trademark) R08, megafac BL20, megafac can be enumerated F475, megafac F477 and megafac F443 (DIC (strain) system) etc..

The content of levelling agent (F) is preferably 0.001 mass % or more relative to the total amount of colored curable resin composition And 0.2 mass % hereinafter, preferably 0.002 mass % or more and 0.1 mass % hereinafter, more preferably 0.01 mass % or more and 0.05 mass % or less.It should be noted that not including the content of above-mentioned pigment dispersing agent in the content.If levelling agent (F) Content then can make the flatness of colour filter good in above-mentioned range.

<other compositions>

Colored curable resin composition of the invention as needed can containing filler, other high-molecular compounds, The additive well-known in the art such as closely sealed promotor, antioxidant, light stabilizer, chain-transferring agent.

<manufacturing method of colored curable resin composition>

Can by mix for example colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D) and Solvent (E), levelling agent (F), polymerization trigger auxiliary agent (D1), mercaptan compound (T) and other compositions used as needed are made Standby colored curable resin composition of the invention.

The pigment such as viridine green (A2) are preferably mixed with part or all of solvent (E) in advance, use ball mill equal part The average grain diameter for being dissipated to pigment is 0.2 μm of degree below.At this point, above-mentioned pigment dispersing agent, resin can be cooperated as needed (B) part or all.Mixing remaining in a manner of reaching defined concentration in the dispersible pigment dispersion obtained in this way Ingredient can prepare target coloration hardening resin composition.

Can make the dyestuffs such as blue dyes (A1) be dissolved separately in solvent (E) part or all and it is previously prepared molten Liquid.It is preferred that filtering the solution with the filter in 0.01~1 μm or so of aperture.

It is preferred that filtering mixed colored curable resin composition with the filter in 0.01~10 μm or so of aperture.

<manufacturing method of colour filter>

Colour filter of the invention is formed by colored curable resin composition of the invention.It can be by making the staining and curing Property resin combination solidification to form the colour filter.

As the method by colored curable resin composition manufacture colored pattern of the invention, photoetching process, spray can be enumerated The method of the use of ink and water, print process etc..Wherein, preferred photoetching process.Photoetching process is following methods: above-mentioned colored curable resin composition is coated with It in substrate, makes it dry and forms coloring compositions nitride layer, expose the coloring compositions nitride layer across photomask, development.

In photoetching process, by not using photomask in exposure and/or not developing, it can be formed as above-mentioned coloring compositions The coloring film of the solidfied material of nitride layer.Colored pattern, the coloring film formed like this is colour filter of the invention.

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

As substrate, quartz glass can be used, pyrex, alumina silicate glass, titanium dioxide has been carried out to surface The glass plates such as the soda-lime glass of silicon coating；The resins such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate Plate；Silicon, the substrate for aluminium, silver, silver/copper/palldium alloy film being formd on aforesaid substrate etc..On these substrates, it can be formed Other colour filters, resin layer, transistor, circuit etc..

It can be carried out with known or usual device, condition based on the formation of photolithographic colored pattern.For example, can be with Following production.

Firstly, by the way that colored curable resin composition to be coated on substrate, heat drying (prebake) and/or decompression It dries and removes the volatile ingredients such as solvent and make it dry, obtain smooth coloring compositions nitride layer.

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

Temperature when being thermally dried is preferably 30~120 DEG C, and more preferably 50~110 DEG C.When additionally as heating Between, preferably 10 seconds~60 minutes, more preferably 30 seconds~30 minutes.

When being dried under reduced pressure, carried out within the temperature range of preferably under the pressure of 50~150Pa, 20~25 DEG C.

The film thickness of coloring compositions nitride layer is not particularly limited, if suitably selected according to the film thickness of the colour filter of target be It can.

Then, coloring compositions nitride layer is exposed across the photomask for being used to form target coloration pattern.On the photomask Pattern is not particularly limited, and uses the pattern for corresponding to intended applications.

As light source used in exposure, the preferably light source of the light of the wavelength of 250~450nm of sending.It is, for example, possible to use It intercepts light of the filter intercepts lower than 350nm of the wavelength region or is selected using the bandpass filter for taking out these wavelength regions Take out to selecting property the light of 436nm nearby, near 408nm, near 365nm.Specifically, mercury lamp, light emitting diode, gold can be enumerated Belong to halide lamp, halogen lamp etc..

Due to whole to plane of exposure can equably irradiate parallel rays or progress photomask and form coloured composition The correct aligned in position of the substrate of layer, therefore it is preferable to use the exposure devices such as mask aligner and stepper.

By making the coloring compositions nitride layer after exposure and developer solution develop and contact, colored pattern is formed on substrate.It is logical Development is crossed, the unexposed portion of coloring compositions nitride layer dissolves in developer solution and is removed.As developer solution, for example, it is preferable to hydrogen-oxygen Change the aqueous solution of the alkali compounds such as potassium, sodium bicarbonate, sodium carbonate, tetramethyl ammonium hydroxide.These alkali compounds it is water-soluble Concentration in liquid is preferably 0.01~10 mass %, more preferably 0.03~5 mass %.Developer solution can also contain surface-active Agent.

Developing method can be any in paddle board method, infusion process and spray-on process etc..Development when can also by substrate with Arbitrary angle tilt.

It is preferably washed after development.

Further, it is baked after preferably being carried out to obtained colored pattern.Stoving temperature is preferably 150~250 DEG C afterwards, more excellent It is selected as 160~235 DEG C.Baking time is preferably 1~120 minute afterwards, and more preferably 10~60 minutes.

Using colored curable resin composition of the invention, the especially excellent colour filter of brightness can be manufactured.The colour filter Device is as colour filter used in display device (liquid crystal display device, organic el device, Electronic Paper etc.) and solid-state imager It is useful.Wherein, useful as color filter for liquid crystal display, especially as using LED as the liquid crystal display of backlight The colour filter of device and it is useful.

Embodiment

Hereinafter, being illustrated in more details by embodiment to colored curable resin composition of the invention.

" % " and " part " in example refers to quality % and mass parts without special provision.

In synthesis example below, pass through mass spectral analysis (LC；1200 type of Agilent system, MASS；Agilent LC/MSD Type) or elemental analysis (VARIO-EL；(elemental (strain) system)) identify compound.

(synthesis example 1)

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, potassium rhodanide is put into After 36.3 parts and 160 parts of acetone, it is stirred at room temperature 30 minutes.Then, with 10 minutes instillation chlorobenzoyl chlorides, (Tokyo was melted into (strain) Corporation) 50 parts.After completion of dropwise addition, further it is stirred at room temperature 2 hours.Then, it by after the cooling of reaction mixture ice bath, drips Enter 45.7 parts of N- ethyl-ortho-toluidine (Tokyo is melted into (strain) corporation).After completion of dropwise addition, it is further stirred at room temperature 30 points Clock.Then, by after the cooling of reaction mixture ice bath, 34.2 parts of 30% sodium hydrate aqueous solution is instilled.After completion of dropwise addition, further It is stirred at room temperature 30 minutes.Then, 35.3 parts of monoxone are instilled at room temperature.After completion of dropwise addition, under reflux condition Stirring 7 hours.Then, after reaction mixture placement being cooled to room temperature, after reaction solution is injected in 120 parts of tap water, add Enter 200 parts of toluene and stirs 30 minutes.Then stop stirring, stand 30 minutes, be as a result separated into organic layer and water layer.By dividing After water layer is discarded in liquid operation, finally used full with 1 equivalent hydrochloric acid, 200 parts of washing organic layers then with 200 parts of tap water washings It is washed with 200 parts of saline solution.After suitable saltcake is added and stirs 30 minutes to organic layer, filters and be removed after moisture Organic layer.Solvent is distilled off in obtained organic layer with evaporator, obtains weak yellow liquid.It is refining to obtain with column chromatography Weak yellow liquid.Weak yellow liquid after 60 DEG C of dry purifications at reduced pressure conditions, obtains compound represented by formula (B-I-1) 52 parts.Yield is 50%.

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, throw-in type (B-I-1) Represented 9.3 parts of compound, 4,4 ' -10 parts of bis- (diethylamino) benzophenone (Tokyo is melted into (strain) corporation) and toluene After 20.0 parts, then, 14.8 parts of phosphorous oxychloride is added and is stirred 3 hours at 95~100 DEG C.Then, reaction mixture is cooling To room temperature, diluted with 170 parts of isopropanol.Then, after the reaction solution after dilution being injected in 300 parts of saturated salt solution, add Enter 100 parts of toluene and stirs 30 minutes.Then stop stirring, stand 30 minutes, be as a result separated into organic layer and water layer.By dividing After water layer is discarded in liquid operation, with 300 parts of washing organic layers of saturated salt solution.Suitable saltcake is added to organic layer and stirs 30 After minute, filter and the organic layer after the moisture that is removed.Solvent is distilled off in obtained organic layer with evaporator, obtains indigo plant Violet solid.Further 60 DEG C of dry bluish violet solids at reduced pressure conditions, obtain compound represented by formula (A-II-1) 19.8 parts.Yield is 100%.

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

(mass spectrum) ionization mode=ESI+:m/z=601.3 [M-Cl]⁺

Exact mass: 636.3

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, throw-in type (A-II- 1) 4.5 parts of 10 parts of compound, bis- (trifluoromethane sulfonyl group) imide lis (Tokyo is melted into (strain) corporation) and N represented by, After 100 parts of dinethylformamide, stirred 3 hours at 50~60 DEG C.Then, after reaction mixture being cooled to room temperature, while stirring It mixes side to be added drop-wise in 2000 parts of tap water with 1 hour, obtains skipper suspension.The suspension being obtained by filtration, obtains blue-green Solid.Further 60 DEG C of dry blue-green solids at reduced pressure conditions, obtain represented by formula (Ab2-1) 11.3 parts of compound. Yield is 82%.

Compound 0.35g represented by formula (Ab2-1) is dissolved in chloroform and sets 250cm for volume³, will be therein 2cm³It is diluted with ion exchange water and sets 100cm for volume³(concentration: 0.028g/L) uses spectrophotometer (quartzy ratio Color ware, optical length；1cm) determine absorption spectrum.The compound shows absorbance 2.9 in maximum absorption wavelength λ max=628nm (arbitrary unit).

(synthesis example 2)

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, potassium rhodanide is put into After 11 parts and 39.4 parts of acetone, it is stirred at room temperature 30 minutes.Then, with 13 parts of chlorobenzoyl chloride of instillation in 10 minutes.Completion of dropwise addition Afterwards, it is further stirred at room temperature 2 hours.Then, by after the cooling of reaction solution ice bath, two (2- ethylhexyl) amine 23 are instilled Part.After completion of dropwise addition, further it is stirred at room temperature 30 minutes.Then, by after the cooling of reaction solution ice bath, 30% hydrogen-oxygen is instilled Change 30 parts of sodium water solution.After completion of dropwise addition, further it is stirred at room temperature 30 minutes.Then, monoxone 9.2 is instilled at room temperature Part.After completion of dropwise addition, stir 7 hours under reflux condition.It then, will be anti-after reaction solution placement being cooled to room temperature After answering solution to inject in 13 parts of tap water, 26 parts of ethyl acetate is added and stirs 30 minutes.Then stop stirring, stand 30 points As a result clock is separated into organic layer and water layer.By liquid separation operation by water layer it is discarded after, with 1 equivalent hydrochloric acid, 13 parts of washing organic layers, Then it with 13 parts of tap water washings, is finally washed with 13 parts of saturated salt solution.Suitable saltcake is added to organic layer and stirs 30 After minute, filter and the organic layer after the moisture that is removed.Solvent is distilled off in obtained organic layer with evaporator, is obtained light Yellow liquid.Further 60 DEG C of dry weak yellow liquids at reduced pressure conditions, obtain compound 14 represented by formula (B-I-2) Part.Yield is 48%.

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, n-amyl alcohol is put into After 250 parts of hydrazine of 1000 parts, 133 parts of 3- aminochlotononitlile and N- Cyanoacetyl-N '-(2- ethyl hexyl), it is being heated to reflux Under the conditions of stir 2 hours.Then, it after being added 166.4 parts of zinc chloride, further stirs 4 hours under reflux condition.It connects , instill 225 parts of concentrated hydrochloric acid.After completion of dropwise addition, n-amyl alcohol is distilled off together with vapor.Remaining suspension is filtered, Residual component is washed with water, obtains faint yellow solid.Further 60 DEG C of dry faint yellow solids at reduced pressure conditions, obtain formula (C-II-1) 215 parts of the compound represented by.Yield is 71%.

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, throw-in type (C-II- 1) it after 1200 parts of 120 parts of compound, glacial acetic acid represented by and 1200 parts of concentrated hydrochloric acid, is stirred at room temperature 30 minutes.Then, will After reaction solution ice bath is cooling, 28.5 parts of 23% sodium nitrite in aqueous solution is added and stirs 3 hours, obtains bronzing suspension. After filtering obtained bronzing suspension.Residual component is washed with water, obtains red brown solid.Further at reduced pressure conditions 60 DEG C dry red brown solid, obtains represented by formula (C-I-1) 120 parts of compound.Yield is 90%.

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, concentrated hydrochloric acid 2 is added 1.5 parts of compound represented by part, 7 parts of acetic acid and formula (C-I-1) is simultaneously stirred at room temperature 30 minutes.Then, in reaction solution After 1.6 parts of compound represented by middle addition formula (B-I-2) and 0.5 part of water, it is stirred at room temperature 30 minutes.Then, it is reacting After being added 0.05 part of sulfamic acid in solution, it is stirred at room temperature 20 minutes.Then, 30% hydroxide is added in reaction solution After 7 parts of sodium water solution, stirred 4 hours at 60 DEG C.Then, after reaction solution placement being cooled to room temperature, reaction solution is injected After in 15 parts of tap water, 15 parts of ethyl acetate is added and stirs 30 minutes.Then stop stirring, stand 30 minutes, as a result separate For organic layer and water layer.After being discarded water layer by liquid separation operation, solvent is distilled off in obtained organic layer with evaporator, is obtained To blue-green solid.Blue-green solid further is refined with silica gel column chromatography, obtains compound represented by formula (Ac1-7) 1.2 part.Yield is 36%.

Compound 0.35g represented by formula (Ac1-7) is dissolved in chloroform and sets 250cm for volume³, will be therein 2cm³It is diluted with ion exchange water and sets 100cm for volume³(concentration: 0.028g/L) uses spectrophotometer (quartzy ratio Color ware, optical length；1cm) measure absorption spectrum.The compound shows absorbance 2.6 (arbitrary unit) in λ max=621nm.

The identification of compound represented by formula (Ac1-7)

(mass spectrum) ionization mode=ESI+:m/z=684.4 [M+H]⁺

Exact mass: 683.4

(synthesis example 3)

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, 2- bromo- 3 '-is put into After 50 parts of 5 parts of nitro-acetophenone (Tokyo is melted into (strain) corporation) and 50% isopropanol water solution, it is stirred at room temperature 30 minutes. Then, with 3 parts of potassium rhodanide of addition in 10 minutes.After completion of dropwise addition, further it is stirred at room temperature 3 hours.Then, it instills originally 50 parts of water.After completion of dropwise addition, further it is stirred at room temperature 30 minutes.After the yellow solid for filtering out precipitation, column chromatography is used The yellow solid being refining to obtain.The yellow solid of 60 DEG C of dry purifications at reduced pressure conditions, obtains represented by formula (B-II-21) 4.2 parts of compound.Yield is 92%.

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, throw-in type (B-II- 13) it after 5 parts of the compound represented by and 50 parts of ethyl alcohol, is stirred at room temperature 30 minutes.Then, respectively with 10 minutes instillation piperidines 2.9 parts and 1.4 parts of glacial acetic acid of (Tokyo is melted into (strain) corporation).After completion of dropwise addition, 2 are further stirred under reflux condition Hour.After the placement of reaction liquid is cooled to room temperature, 70 parts of tap water are instilled.After completion of dropwise addition, further it is stirred at room temperature 30 minutes.After the yellow solid for filtering out precipitation, the yellow solid that is refining to obtain with column chromatography.It does for 60 DEG C at reduced pressure conditions Yellow solid after dry purification obtains represented by formula (B-I-21) 4.2 parts of compound.Yield is 64%.

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, throw-in type (B-I- 21) 10.4 parts of compound represented by, 4,4 ' -10 parts of bis- (diethylamino) benzophenone (Tokyo is melted into (strain) corporation) and After 20.0 parts of toluene, then, 14.8 parts of phosphorous oxychloride is added and is stirred 3 hours at 95~100 DEG C.Then, by reaction mixture After being cooled to room temperature, diluted with 170 parts of isopropanol.Then, the reaction solution after dilution is injected in 300 parts of saturated salt solution Afterwards, 100 parts of toluene is added and stirs 30 minutes.Then stop stirring, stand 30 minutes, be as a result separated into organic layer and water layer. After being discarded water layer by liquid separation operation, with 300 parts of washing organic layers of saturated salt solution.Suitable saltcake is added simultaneously to organic layer After stirring 30 minutes, filter and the organic layer after the moisture that is removed.Solvent is distilled off in obtained organic layer with evaporator, Obtain bluish violet solid.The bluish violet solid being refining to obtain with column chromatography.Indigo plant after 60 DEG C of dry purifications at reduced pressure conditions Violet solid obtains represented by formula (A-II-21) 10.2 parts of compound.Yield is 52%.

The identification of compound represented by formula (A-II-21)

(mass spectrum) ionization mode=ESI+:m/z=596.3 [M-Cl]⁺

Exact mass: 631.3

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, throw-in type (A-II- 21) 5.9 parts of 10 parts of compound, bis- (trifluoromethane sulfonyl group) imide lis (Tokyo is melted into (strain) corporation) and N represented by, After 30 parts of dinethylformamide, stirred 3 hours at 40 DEG C.Then, it after reaction mixture being cooled to room temperature, uses while stirring It is added drop-wise within 1 hour in 500 parts of tap water, obtains skipper suspension.The suspension being obtained by filtration, obtains blue-green solid.Into One step, 60 DEG C of dry blue-green solids at reduced pressure conditions, obtain represented by formula (Ab2-21) 11.5 parts of compound.Yield is 83%.

Compound 0.35g represented by formula (Ab2-21) is dissolved in chloroform and sets 250cm for volume³, will wherein 2cm³It is diluted with ion exchange water and sets 100cm for volume³(concentration: 0.028g/L) uses spectrophotometer (quartz Cuvette, optical length；1cm) measure absorption spectrum.The compound shows absorbance 3.0 (arbitrary unit) in λ max=634nm.

(synthesis example 4)

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, potassium rhodanide is put into After 33 parts and 160 parts of acetone, it is stirred at room temperature 30 minutes.Then, with 10 minutes instillation 2- methyl benzoyl chlorides, (Tokyo was melted into (strain) corporation) 50 parts.After completion of dropwise addition, further it is stirred at room temperature 2 hours.Then, reaction mixture ice bath is cooling Afterwards, 41.6 parts of N- ethyl-ortho-toluidine (Tokyo is melted into (strain) corporation) is instilled.After completion of dropwise addition, further it is stirred at room temperature 30 minutes.Then, by after the cooling of reaction mixture ice bath, 34.2 parts of 30% sodium hydrate aqueous solution is instilled.After completion of dropwise addition, into One step is stirred at room temperature 30 minutes.Then, 32.1 parts of monoxone are instilled at room temperature.After completion of dropwise addition, in heated reflux condition Lower stirring 7 hours.Then, after reaction mixture placement being cooled to room temperature, after reaction solution is injected in 120 parts of tap water, 200 parts of toluene is added and stirs 30 minutes.Then stop stirring, stand 30 minutes, be as a result separated into organic layer and water layer.Pass through After water layer is discarded in liquid separation operation, finally used with 1 equivalent hydrochloric acid, 200 parts of washing organic layers then with 200 parts of tap water washings 200 parts of saturated salt solution washings.

After suitable saltcake is added and stirs 30 minutes to organic layer, is filtered and remove the organic layer after moisture.With Solvent is distilled off in obtained organic layer by evaporator, obtains weak yellow liquid.The light yellow liquid being refining to obtain with column chromatography Body.Weak yellow liquid after 60 DEG C of dry purifications at reduced pressure conditions, obtains represented by formula (B-I-9) 40.5 parts of compound. Yield is 41%.

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, throw-in type (B-I-9) Represented 9.7 parts of compound, 4,4 ' -10 parts of bis- (diethylamino) benzophenone (Tokyo is melted into (strain) corporation) and toluene After 20 parts, then, 14.8 parts of phosphorous oxychloride is added and is stirred 3 hours at 95~100 DEG C.Then, reaction mixture is cooled to After room temperature, diluted with 170 parts of isopropanol.Then, it after the reaction solution after dilution being injected in 300 parts of saturated salt solution, is added 100 parts of toluene simultaneously stirs 30 minutes.Then stop stirring, stand 30 minutes, be as a result separated into organic layer and water layer.Pass through liquid separation After water layer is discarded in operation, with 300 parts of washing organic layers of saturated salt solution.Suitable saltcake is added to organic layer and stirs 30 points Zhong Hou is filtered and the organic layer after the moisture that is removed.Solvent is distilled off in obtained organic layer with evaporator, obtains royal purple Color solid.The bluish violet solid being refining to obtain with column chromatography.Bluish violet solid after 60 DEG C of dry purifications at reduced pressure conditions, 15.1 parts of compound are obtained represented by formula (A-II-9).Yield is 75%.

The identification of compound represented by formula (A-II-9)

(mass spectrum) ionization mode=ESI+:m/z=615.4 [M-Cl]⁺

Exact mass: 650.3

Reaction below carries out under nitrogen atmosphere.In the flask for having condenser pipe and agitating device, throw-in type (A-II- 9) 5.7 parts of 10 parts of compound, bis- (trifluoromethane sulfonyl group) imide lis (Tokyo is melted into (strain) corporation) and N represented by, After 30 parts of dinethylformamide, stirred 3 hours at 40 DEG C.Then, it after reaction mixture being cooled to room temperature, uses while stirring It is added drop-wise within 1 hour in 500 parts of tap water, obtains skipper suspension.The suspension being obtained by filtration, obtains blue-green solid.Into One step, 60 DEG C of dry blue-green solids at reduced pressure conditions, obtain represented by formula (Ab2-9) 13.2 parts of compound.Yield is 96%.

Compound 0.35g represented by formula (Ab2-9) is dissolved in chloroform and sets 250cm for volume³, will be therein 2cm³It is diluted with ion exchange water and sets 100cm for volume³(concentration: 0.028g/L) uses spectrophotometer (quartzy ratio Color ware, optical length；1cm) measure absorption spectrum.The compound shows absorbance 2.7 (arbitrary unit) in λ max=627nm.

(synthesis example 5)

By 10 parts of 4- amino-3-hydroxy formic acid (Tokyo chemical conversion industry (strain) system), 4- (diethylamino) salicylide (east Capital chemical conversion industry (strain) system) 12.8 parts, 2.73 parts of benzoic acid (Tokyo chemical conversion industry (strain) system), 1- amylalcohol (Tokyo chemical conversion industry (strain) system) 157 parts and 7.43 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system) mixing, 120 DEG C stirring 3 hours.Add Enter 7.46 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system), 2.79 parts of benzoic acid (Tokyo chemical conversion industry (strain) system), 1- 49.8 parts of amylalcohol (Tokyo chemical conversion industry (strain) system) and 4- (diethylamino) salicylide (Tokyo chemical conversion industry (strain) system) 12.7 Part, it is stirred 14 hours at 120 DEG C.3.76 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system), benzoic acid (Tokyo is added At industrial (strain) system) 1.41 parts, 52.5 parts of 1- amylalcohol (Tokyo chemical conversion industry (strain) system) and 4- (diethylamino) salicylide it is (eastern Capital chemical conversion industry (strain) system) 6.35 parts, it is stirred 8 hours at 120 DEG C.After above-mentioned reaction solution is cooled to room temperature, with the residual of suction filtration The crystal that the form of slag is precipitated.140 parts of tetrahydrofuran are added in the residue, after 70 DEG C are stirred 1 hour, with suction filtration The form of residue obtains insoluble matter.120 parts of tetrahydrofuran are added in the residue, after 70 DEG C are stirred 1 hour, with the residual of suction filtration The form of slag obtains insoluble matter.340 parts of n,N-Dimethylformamide are added in the residue, is made it dissolve in 90 DEG C of heating Afterwards, it is stood at 0 DEG C~5 DEG C.The crystal being precipitated in the form of the residue of suction filtration.The residue is dried under reduced pressure at 60 DEG C, is obtained To 5.69 parts of compound represented by formula (Ad1-1).With¹H-NMR confirmed structure.

<identification of compound represented by formula (Ad1-1)>

¹H-NMR (500MHz, DMSO-d6): 1.14 (6H, t), 3.47 (4H, q), 6.57 (1H, d), 6.78 (1H, dd), 7.68(1H,d),7.79(1H,d),7.96(1H,dd),8.15(1H,d),8.80(1H,s),13.11(1H,s).

(synthesis example 6)

By 275 parts of resorcinol (Tokyo chemical conversion industry (strain) system) and 101 parts of n-hexylamine (Tokyo chemical conversion industry (strain) system) Mixing, side remove the waterside generated and stir 20 hours at 150~155 DEG C.After placing cooling, reaction mixture is dissolved in toluene In 433 parts, 1000 parts of warm water of 40 DEG C of the toluene solution are washed 3 times.Anhydrous magnesium sulfate 50 is added in the toluene solution After part and stirring, filtering.The solvent of filtrate is distilled off and obtains crude product.The crude product is dissolved in 234 parts of toluene, 0 It is DEG C stirred below, crystallization object is filtered, is thus recycled.The crystallization object is dried under reduced pressure at 50 DEG C, obtains formula (pt1) institute 95.7 parts of the compound of expression.

<identification of compound represented by formula (pt1)>

(mass spectrum) ionization mode=ESI+:m/z=[M+H]⁺194.2

Exact mass: 193.2

By 95.3 parts and 48.0 parts of water mixing of compound represented by formula (pt1), stirred at 80 DEG C.Then, 1- is added in side 48% sodium hydroxide water is added after 80 DEG C are stirred 3 hours in bromo- 107 parts of sides of 2- ethyl hexane (Tokyo chemical conversion industry (strain) system) 22.4 parts of solution.The mixture is stirred 18 hours at 110 DEG C.After placing cooling, it will be reacted with 10% sodium hydrate aqueous solution The pH of mixture is adjusted to 5, and 130 parts of toluene is added and stirs, extracts toluene layer.Toluene extract liquor is washed 2 with 500 parts of warm water It is secondary, 25 parts of anhydrous magnesium sulfate is added and stirs, filters.The solvent of filtrate is distilled off, obtains containing change represented by formula (pt2) Close 154 parts of residue of object as principal component.

<identification of compound represented by formula (pt2)>

(mass spectrum) ionization mode=ESI+:m/z=[M+H]⁺306.3

Exact mass: 305.3

Using compound represented by the formula contained (pt2) as 154 parts of the residue and N of principal component, N-dimethyl methyl 597 parts of amide mixing, are stirred at -6 DEG C~3 DEG C.Be added wherein when liquid temperature is maintained at -6 DEG C~3 DEG C phosphorus oxychloride (and Wako Pure Chemical Industries (strain) system) 258 parts.After the mixture is stirred at room temperature 1 hour, stirred 4 hours at 60 DEG C.Place cooling Afterwards, reaction mixture is added in 1500 parts of ice, is neutralized using 48% sodium hydrate aqueous solution.Toluene is added wherein 867 parts, extract toluene layer.With 1200 parts of 15% sodium-chloride water solution washings, 2 toluene extract liquors.In the toluene extract liquor After 60 parts of anhydrous magnesium sulfate is added and stirs, filtering.The solvent of filtrate is distilled off and obtains residue.It should with column chromatography purification Residue obtains represented by formula (pt3) 94.4 parts of compound.

<identification of compound represented by formula (pt3)>

(mass spectrum) ionization mode=ESI+:m/z=[M+H]⁺334.3

Exact mass: 333.3

Will be bis- 10.6 parts of (3- amino-4-hydroxylphenyl) sulfone (Tokyo chemical conversion industry (strain) system), change represented by formula (pt3) Close 25.3 parts of object, 3.2 parts of benzoic acid (Tokyo chemical conversion industry (strain) system), 184 parts of 1- amylalcohol (Tokyo chemical conversion industry (strain) system) and 8.59 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system) mixing, are stirred 3 hours at 120 DEG C.It is mixed in the reaction solution 3.21 parts of 25.4 parts of compound, benzoic acid represented by box-like (pt3) (Tokyo chemical conversion industry (strain) system), 1- amylalcohol (Tokyo At industrial (strain) system) 90 parts and 8.59 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system), 120 DEG C stirring 12 hours. It after above-mentioned reaction solution is cooled to room temperature, is added into 1800 parts of methanol, the crystal being precipitated in the form of the residue of suction filtration. The residue is refined by column chromatography, obtains represented by formula (Ad2-10) 20.6 parts of compound.Pass through¹H-NMR confirmation finishes Structure.

<identification of compound represented by formula (Ad2-10)>

¹H-NMR(500MHz,DMSO-d₆): 0.85 (6H, t), 0.87 (6H, t), 0.87 (6H, t), 1.20~1.40 (28H),1.56(4H,tt),1.75(2H,ttt),3.34(4H,d),3.43(4H,t),6.55(2H,d),6.79(2H,dd), 7.64(2H,d),7.91(2H,d),8.01(2H,dd),8.36(2H,d),8.73(2H,s)

(synthesis example 7)

Suitable nitrogen is flowed into the flask for having reflux condenser, dropping funel and blender and is replaced into nitrogen atmosphere, 371 parts of propylene glycol methyl ether acetate are added, is heated to 85 DEG C while stirring.Then, make 54 parts of acrylic acid, 3,4- epoxy tricyclic [5.2.1.0^2,6] decane -8- base acrylate and 3,4- epoxy tricyclic [5.2.1.0^2,6] decane -9- base acrylate mixing 225 parts of object (containing than being 50:50 with molar ratio computing), 81 parts of vinyltoluene (isomer mixture) are dissolved in propylene glycol list first 80 parts of ether acetic acid ester are prepared into mixed solution, are instilled the mixed solution in flask with 4 hours.

On the other hand, make polymerization initiator 2,30 parts of 2- azo two (2,4- methyl pentane nitrile) is dissolved in propylene glycol monomethyl ether 160 parts of acetic acid esters and obtain solution, the solution was added dropwise with 5 hours.It is small in 85 DEG C of holdings 4 after the completion of dropwise addition of initiator solution Shi Hou is cooled to room temperature, and obtains copolymer (resin B a) solution.The solid component of resin B a solution is 37%, passes through Type B viscosity The viscosity of (23 DEG C) measurements of meter is 246mPas.The weight average molecular weight of resin B a is 1.06 × 10⁴, the acid of solid component conversion Value is 115mg-KOH/g, molecular weight distribution 2.01.

Resin B a has structural unit below.

Using GPC method, the survey of the weight average molecular weight (Mw) and number-average molecular weight (Mn) of resin is carried out under the following conditions It is fixed.

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

Column；SHIMADZU Shim-pack GPC-80M

Column temperature；40℃

Solvent；THF (tetrahydrofuran)

Flow velocity；1.0mL/min

Detector；RI

Standard substance is used in correction；TSK STANDARD POLYSTYRENE F-40,F-4,F-288,A-2500,A-500 (Tosoh (strain) system)

The ratio between the weight average molecular weight to be converted by polystyrene obtained above and number-average molecular weight (Mw/Mn) is used as and is divided Son amount distribution.

<preparation of dispersible pigment dispersion>

Preparation example 1

By viridine green (A2): C.I. pigment Green 7 (pigment；λ max=660nm) 27 parts,

12 parts of acrylic acid series pigment dispersing agent,

Resin (B): methacrylic acid/benzylmethacrylate copolymers (copolymerization ratio (mass ratio)；30/70, Mw；1.2× 10⁴) 9.5 parts of (solid component conversion) and

Solvent (E): 180 parts of propylene glycol methyl ether acetate

Mixing, keeps pigment fully dispersed, is thus prepared for dispersible pigment dispersion 1 using ball mill.

Preparation example 2

In addition to by C.I. pigment Green 7 (pigment) instead of 58 (pigment of C.I. naphthol green；λ max=675nm) other than, it carries out It is similarly operated with preparation example 1, is prepared for dispersible pigment dispersion 2.

Examples 1 to 8 and comparative example 1~2

<preparation of colored curable resin composition>

Each ingredient of table 2 is mixed, green coloring hardening resin composition is obtained.In table 2, the number of resin shows solid The value of body ingredient conversion.

Table 2

<blue dyes (A1)>

Aa；Compound represented by formula (Ab2-1) (λ max=628nm)

Ab；Compound represented by formula (Ac1-7) (λ max=621nm)

Ac；Compound represented by formula (Ab2-21) (λ max=634nm)

Ad；Compound represented by formula (Ab2-9) (λ max=627nm)

Ae；C.I. Blue VRS (λ max=639nm)

Af；Compound represented by formula (Ad1-1) (λ max=453nm)

Ag；Compound represented by formula (Ad2-10) (λ max=455nm)

<resin (B)>

Ba；Resin B a

<polymerizable compound (C)>

Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA；Japanese chemical drug (strain) system)

<polymerization initiator (D)>

N- benzoyloxy -1- (4- phenylmercapto phenyl) octane -1- ketone -2- imines (irgacure (registered trademark) OXE-01；BASF AG's system；O- acyl group oxime compound)

<solvent (E)>

Ea；Propylene glycol methyl ether acetate

Eb；Ethyl lactate

Ec；4- hydroxy-4-methyl-2-pentanone

<levelling agent (F)>

Polyether modified silicone oil (toray silicone SH8400；Beautiful DOW CORNING (strain) system in east)

<production of colored pattern>

In the glass substrate (eagle 2000 of 5cm square；Corning Incorporated's system) on, colored curable is coated with by spin-coating method After resin combination, coloring compositions nitride layer is formed in 100 DEG C of prebakes 3 minutes.After placing cooling, coloring compositions will be formed with The substrate of nitride layer is set to 100 μm with quartz glass photomask, uses exposure machine (TME-150RSK；Open up Pu Kang (strain) system), under air atmosphere, light irradiation has been carried out with light quantity (365nm benchmark).As photomask, using foring 100 μm Line width/intermittent pattern photomask.Coloring compositions nitride layer after light is irradiated is containing nonionic surfactants 0.12% With in the water system developer solution of potassium hydroxide 0.04% 24 DEG C immersion development 60 seconds, after washing, in an oven, 210 DEG C into Row bakes after 30 minutes.

Colored pattern is obtained by the colored curable resin composition of Examples 1 to 8 and comparative example 1.For comparative example 2 For colored curable resin composition, the removing in the unexposed portion of the coloring compositions nitride layer based on development carries out insufficient, It could not obtain colored pattern.It is formed in column in the pattern in table 3, zero will be recorded as the case where obtaining colored pattern, could not obtained To the case where be recorded as ×.

<film thickness measuring>

To obtained colored pattern, with film thickness measuring device (DEKTAK3；Japanese vacuum technique (strain) system) measurement film thickness.

<chromaticity evaluation>

To obtained film, with colour examining machine (OSP-SP-200；Olympus (strain) system) measurement light splitting, and with illuminant-C Characterisitic function measures xy chromaticity coordinate (x, y) and tristimulus values Y in the XYZ colour system of CIE.The value of Y is bigger, indicates brightness It is higher.As a result it is shown in table 3.

Table 3

Industrial availability

Using colored curable resin composition of the invention, the excellent colour filter of brightness can be manufactured.

Claims (4)

1. a kind of colored curable resin composition, containing colorant, resin, polymerizable compound and polymerization initiator,

The colorant is containing selected from least one of weld and yellow uitramarine and blue dyes and viridine green Colorant,

The containing ratio of the blue dyes relative to total content of colorant be 0.1 mass % or more and 20 mass % hereinafter,

The blue dyes is at least one kind of in compound, methine dyestuff and azomethine dyes represented by formula (Ab1) Blue dyes,

In formula (Ab1), R^1A~R^8ASeparately indicate hydrogen atom, halogen atom, nitro, hydroxyl, carbon atom number 1~20 alkane Base, wherein oxygen atom, R can be inserted between the carbon atom for constituting the alkyl^4AIt can be with R^5ABe mutually bonded and formed-NH- ,- S- or-SO₂,

R^9A~R^12AIt separately indicates: hydrogen atom；It can be by amino or can be by carbon atom number 1~20 that halogen atom replaces Alkyl, can constitute the alkyl carbon atom between be inserted into oxygen atom；It can be with substituted aralkyl；Or it can be substituted Aryl,

R^9AIt can be with R^10AThe nitrogen-atoms for being bonded and being bonded with them is formed together ring, R^11AIt can be with R^12ABonding and and they The nitrogen-atoms being bonded is formed together ring,

A indicate can with substituted aromatic hydrocarbyl or can with substituted aromatic heterocycle,

G^g-Indicate counter anion,

G indicates 0 or arbitrary natural number, when g is 0, indicates do not have counter anion.

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

Polymerization initiator is the polymerization initiator containing O- acyl group oxime compound.

3. a kind of colour filter is formed by colored curable resin composition of any of claims 1 or 2.

4. a kind of display device, it includes colour filters described in claim 3.