CN103732692A

CN103732692A - Colored curable composition, color filter, method for producing color filter, and display device

Info

Publication number: CN103732692A
Application number: CN201280037215.XA
Authority: CN
Inventors: 片山晃男; 両角一真; 八木一成; 新居一巳; 福重裕一
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2011-09-30
Filing date: 2012-09-24
Publication date: 2014-04-16
Anticipated expiration: 2032-09-24
Also published as: JP2013083916A; JP5775482B2; WO2013047454A1; KR101703680B1; TWI558692B; CN103732692B; KR20140072009A; TW201319039A

Abstract

Provided is a colored curable composition with which brightness is increased while obtaining high contrast and which is useful in colored pattern formation for a color filter. Also provided are a color filter and a display device. The colored curable composition comprises: one or more dye compounds selected from (A-1) a dipyrromethene metal complex compound wherein the structure represented by general formula (I) is coordinated to a metal or metal compound and (A-2) azapyrromethene metal complex compounds wherein the structure represented by general formula (II) is coordinated to a metal or metal compound; and (B) a porphyrin compound represented by general formula (III). R1-R6 and R21-R26 are hydrogen atoms or monovalent substitution groups. R7 is a hydrogen atom, halogen atom, alkyl group or the like. In general formula (III), Z1-Z4 are N or C-R, A1-A8 are hydrogen atoms, alkyl groups or the like, and at least one pair from the pairs A1 and A2, A3 and A4, A5 and A6, and A7 and A8 does not have a cyclic structure. M is a divalent metal ion or the like.

Description

The manufacture method of painted curable adhensive compositions, colored filter, colored filter and display unit

Technical field

The present invention relates to a kind of dyestuff that comprises as manufacture method and the display unit of the painted curable adhensive compositions of coloring compound, colored filter, colored filter.

Background technology

As making one of method of the colored filter using in liquid crystal indicator or solid photographic element etc., extensively utilize colo(u)rant dispersion method.Colo(u)rant dispersion method has the painted curable adhensive compositions that uses colo(u)rant dispersion to form in various photosensitive composites, the method for making colored filter by optical micro-image method.The method owing to containing pigment to light or thermally-stabilised, and carry out patterning by optical micro-image method, therefore fully guarantee positional precision, become and be suitable for the method for the making of colored filter etc. for the color monitor that uses in liquid crystal indicator, electroluminescent (electroluminescent, EL) display unit etc.

The coloring compound using in making as colored filter, is not only pigment, also broad research the dye compound beyond the pigment such as dyestuff.Wherein, dyestuff known have there is pyrroles's methylene radical based dye, compound (for example, with reference to Japanese Patent Laid-Open 2008-292970 communique, Japanese Patent Laid-Open 2007-039478 communique and No. 3387541 communique of Japanese Patent) that pyrimidine azo based dye, pyrazoles azo based dye, dibenzo piperazine are muttered various pigment precursors such as based dye.Wherein, in Japanese Patent Laid-Open 2008-292970 communique, introduced following technology: by and use multiple dyestuff, for example pyrroles's methylene radical based dye is obtained to high purity of color with having the dyestuff of phthalocyanine structure use.

If use dyestuff as coloring compound, although useful for the tone of demonstration image while improving image demonstration with regard to utilizing the purity of color of dyestuff self or the vividness of its tone or the aspect of brightness, even yet present situation is to have the leeway of improvement in the picture characteristics of colored filter of using dyestuff, and require further improvement in contrast gradient, brightness characteristics.

Summary of the invention

The problem that invention will solve

The present invention is in view of the above-mentioned prior art person of forming.That is, the problem of one aspect of the present invention be to provide makes brightness improve, obtain high contrast gradient in order to form the painted curable adhensive compositions of the colored pattern of colored filter.

And the problem of other aspects of the present invention is to provide uses described painted curable adhensive compositions of the present invention and can be with colored filter and the manufacture method thereof of the high image of high brightness display comparison degree and the display unit of using the demonstration of carrying out good image quality that this colored filter forms.

The technique means of dealing with problems

The people such as the inventor make great efforts research in order to reach described problem, found that by by pyrroles's methylene radical based dye and particular dye combinations, can realize very high brightness and high contrast gradient simultaneously, thereby complete the present invention.

Concrete aspect of the present invention is as described below.

< 1 > painted curable adhensive compositions, it contains: choosing freely the represented structure of (A-1) following general formula (I) be coordinated in two pyrroles's methylene radical (dipyrromethene) metal complex compounds of forming on metal or metallic compound and (A-2) the represented structure of following general formula (II) be coordinated in a kind of above dye compound of the group that azepine pyrroles methylene radical (azapyrrornethene) metal complex compounds that forms on metal or metallic compound forms, (B) represented porphyrin (porphyrin) compound of following general formula (III).

[changing 1]

In described general formula (I), R ¹, R ², R ³, R ⁴, R ⁵, and R ⁶represent independently of one another hydrogen atom or 1 valency substituting group, R ⁷represent hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical.

[changing 2]

In described general formula (II), R ²¹, R ²², R ²³, R ²⁴, R ²⁵and R ²⁶represent independently of one another hydrogen atom or 1 valency substituting group.

[changing 3]

In described general formula (III), Z ¹, Z ², Z ³and Z ⁴all represent N, or Z ¹and Z ³, and Z ²and Z ⁴the both sides of any a group all represent N, another group represents C-R, R represents respectively hydrogen atom, alkyl or aryl independently.A ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A ⁷and A ⁸represent independently of one another alkyl, thiazolinyl, aryl, alkoxyl group, alkylthio, aryloxy, arylthio, halogen atom, hydroxyl, alkoxy carbonyl, aryloxycarbonyl, amino, carbamyl, sulfamyl, acyl group, silicon alkoxyl group, cyano group, nitro or heterocyclic radical.A ¹with A ², A ³with A ⁴, A ⁵with A ⁶, or A ⁷with A ⁸also can be separately bond and form ring structure mutually, but in these at least one group do not form ring structure.M represents divalent atoms metal or the divalent atoms metal being substituted or the divalent atomic group that comprises atoms metal.

The painted curable adhensive compositions of < 2 > as described in < 1 >, the represented porphyrin compound of wherein said (B) general formula (III) is the represented porphyrin compound of following general formula (III-2).

[changing 4]

In described general formula (III-2), A ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A ⁷, A ⁸and the A in M and general formula (III) ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A7, A ⁸and M synonym separately.

The painted curable adhensive compositions of < 3 > as described in < 1 > or < 2 >, it also contains (C) polymerizable compound and (D) Photoepolymerizationinitiater initiater, and is photosensitivity.

The painted curable adhensive compositions of < 4 > as described in any one in < 1 >～< 3 >, wherein, for the total amount of coloring compound contained in painted curable adhensive compositions, the content of the porphyrin compound that described (B) general formula (III) is represented is more than 0.1 quality %, below 50 quality %.

The painted curable adhensive compositions of < 5 > as described in any one in < 1 >～< 4 >, the represented porphyrin compound of wherein said (B) general formula (III) is the A in general formula (III) ¹with A ², A ³with A ⁴, A ⁵with A ⁶, and A ⁷with A ⁸any person of group all form the compound of ring structure in end.

The painted curable adhensive compositions of < 6 > as described in any one in < 1 >～< 5 >, wherein for the total solids composition of described painted curable adhensive compositions, comprise the described represented structure of (A) general formula (I) and be coordinated in the two pyrroles's methylene radical metal complex compounds that form on metal or metallic compound, the total content that the represented structure of general formula (II) is coordinated in the coloring compound of the azepine pyrroles methylene radical metal complex compounds that forms on metal or metallic compound and the represented porphyrin compound of described (B) general formula (III) is more than 0.2 quality %, below 50 quality %.

< 7 > colored filter, it is the painted curable adhensive compositions person of forming who uses as described in any one in < 1 >～< 6 >.

The manufacture method of a < 8 > colored filter, it comprises: pigmented layer forms step, the painted curable adhensive compositions as described in any one in < 1 >～< 6 > is imparted on supporter and forms pigmented layer; Step of exposure is pattern apperance by formed pigmented layer exposure; Development step, develops and forms colored pattern the pigmented layer after exposure.

< 9 > display unit, the colored filter that it comprises the colored filter as described in < 7 > or obtains by the manufacture method as described in < 8 >.

The effect of invention

By one aspect of the present invention, can provide make brightness improve, obtain high contrast gradient in order to form the painted curable adhensive compositions of the colored pattern of colored filter.

And, by other aspects of the present invention, can provide use described painted curable adhensive compositions of the present invention can be with colored filter and the manufacture method thereof of the high image of high brightness display comparison degree and the display unit of using the demonstration of carrying out good image quality that this colored filter forms.

Accompanying drawing explanation

Fig. 1 means the main electrode of made and the general view of guarded electrode in the mensuration of the relative permittivity in embodiments of the invention.

Embodiment

Below, painted curable adhensive compositions of the present invention is described in detail, and to using the colored filter of the present invention of this painted curable adhensive compositions and manufacture method thereof and display unit to be described in detail.

Painted curable adhensive compositions

Painted curable adhensive compositions of the present invention be at least contain the represented structure of the following general formula of shown below being selected from (A-1) (I) be coordinated in two pyrroles's methylene radical metal complex compounds of forming on metal or metallic compound and (A-2) the represented structure of following general formula (II) be coordinated in a kind of above dye compound of the azepine pyrroles methylene radical metal complex compounds forming on metal or metallic compound, (B) the represented porphyrin compound of following general formula (III) is as the composition of coloring compound, preferably further contain (C) polymerizable compound and (D) Photoepolymerizationinitiater initiater, there is photosensitive curable adhensive compositions.

Only otherwise undermine effect of the present invention, painted curable adhensive compositions of the present invention also can optionally further contain the binder resins such as alkali soluble resin, organic solvent and various additive.

Below, to forming each composition of painted curable adhensive compositions of the present invention, described in detail.In addition, with lower, sometimes by painted curable adhensive compositions of the present invention referred to as " coloured composition of the present invention " or " coloured composition ".

In addition, in this manual, use "～" and numerical value that front and back that the numerical range that represents represents to comprise "～" are recorded as the scope of lower value and higher limit.And, as the amount of each composition in composition, while there is the situation of the multiple material suitable with each composition in composition, as long as no special instructions, represent the total amount of existing this many kinds of substance in composition.

In this manual, " alkyl " is the general name of the alkyl of " straight chain, branch and ring-type ".And the substituting group in this specification sheets (atomic group) is used to comprise the person of being unsubstituted and further to have substituting group person's implication.That is in this manual, so-called " alkyl " used with the implication that comprises the alkyl being unsubstituted and the alkyl being substituted, other substituting groups too.

Painted curable adhensive compositions of the present invention contain be selected from the represented structure of (A-1) following general formula (I) be coordinated in two pyrroles's methylene radical metal complex compounds of forming on metal or metallic compound and (A-2) the represented structure of following logical formula II be coordinated in a kind of above dye compound of the azepine pyrroles methylene radical metal complex compounds forming on metal or metallic compound.Below, successively this dye compound is illustrated.

(A-1) the represented structure of general formula (I) is coordinated in the metal complex compounds forming on metal or metallic compound

First, the represented structure of mutual-through type (I) is coordinated in the two pyrroles's methylene radical metal complex compounds (following suitable being called " two pyrroles's methylene radical metal complex compounds " or " particular dye (A-1) ") that form on metal or metallic compound and is illustrated.

[changing 5]

In general formula (I), R ¹～R ⁶the 1 valency substituting group representing separately can be enumerated halogen atom and (for example can enumerate fluorine atom, chlorine atom, bromine atoms), alkyl (the straight chain that preferably carbon number is 1～48, the alkyl of branched chain or ring-type, the straight chain that more preferably carbon number is 1～24, the alkyl of branched chain or ring-type, for example, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, tributyl, amyl group, hexyl, heptyl, octyl group, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norcamphyl, and 1-adamantyl), (thiazolinyl that preferably carbon number is 2～48, the thiazolinyl that more preferably carbon number is 2～18 for example can be enumerated vinyl to thiazolinyl, allyl group, and 3-butene-1-yl), (aryl that preferably carbon number is 6～48, the aryl that more preferably carbon number is 6～24 for example can be enumerated phenyl to aryl, and naphthyl), (heterocyclic radical that preferably carbon number is 1～32, the heterocyclic radical that more preferably carbon number is 1～18 for example can be enumerated 2-thienyl to heterocyclic radical, 4-pyridyl, 2-furyl, 2-pyrimidyl, 1-pyridyl, 2-[4-morpholinodithio base, 1-imidazolyl, 1-pyrazolyl, and benzotriazole-1-yl), (silylation that preferably carbon number is 3～38, the silylation that more preferably carbon number is 3～18 for example can be enumerated TMS to silylation, triethyl silyl, tributyl silylation, tributyl dimethylsilyl, and the 3rd hexyl dimethylsilyl), hydroxyl, cyano group, nitro, (alkoxyl group that preferably carbon number is 1～48, the alkoxyl group that more preferably carbon number is 1～24 for example can be enumerated methoxyl group to alkoxyl group, oxyethyl group, 1-butoxy, 2-butoxy, isopropoxy, the 3rd butoxy, and dodecyloxy, and cyclopentyloxy for example, or the cycloalkyloxy such as cyclohexyloxy),

(aryloxy that preferably carbon number is 6～48, the aryloxy that more preferably carbon number is 6～24 for example can be enumerated phenoxy group to aryloxy, and 1-naphthyloxy), (heterocyclic oxy group that preferably carbon number is 1～32, the heterocyclic oxy group that more preferably carbon number is 1～18 for example can be enumerated 1-phenyltetrazole-5-oxygen base to heterocyclic oxy group, and 2-THP trtrahydropyranyl oxygen base), (the silicon alkoxyl group that preferably carbon number is 1～32, the silicon alkoxyl group that more preferably carbon number is 1～18 for example can be enumerated TMS oxygen base to silicon alkoxyl group, tributyl dimethyl-silicon alcoxyl base, and diphenylmethylsilane oxygen base), (acyloxy that preferably carbon number is 2～48, the acyloxy that more preferably carbon number is 2～24 for example can be enumerated acetoxyl group to acyloxy, pivaloyl oxygen base, benzoyloxy, and dodecanoyl oxygen base), alkoxyl group carbonyl oxygen base (the alkoxyl group carbonyl oxygen base that preferably carbon number is 2～48, the alkoxyl group carbonyl oxygen base that more preferably carbon number is 2～24, for example, can enumerate oxyethyl group carbonyl oxygen base, and the 3rd butoxy carbonyl oxy, and such as cycloalkyloxy carbonyl oxygen bases such as cyclohexyloxy carbonyl oxygens), aryloxy carbonyl oxygen base (the aryloxy carbonyl oxygen base that preferably carbon number is 7～32, the aryloxy carbonyl oxygen base that more preferably carbon number is 7～24, for example, can enumerate phenoxy group carbonyl oxygen base), carbamyl oxygen base (the carbamyl oxygen base that preferably carbon number is 1～48, the carbamyl oxygen base that more preferably carbon number is 1～24, for example, can enumerate N, N-dimethylamino formyl radical oxygen base, N-butyl carbamyl oxygen base, N-phenylamino formyl radical oxygen base, and N-ethyl-N-phenylamino formyl radical oxygen base), sulfamyl oxygen base (the sulfamyl oxygen base that preferably carbon number is 1～32, the sulfamyl oxygen base that more preferably carbon number is 1～24, for example, can enumerate N, N-diethyl amino alkylsulfonyl oxygen base, and N-propyl group sulfamyl oxygen base),

(alkylsulfonyloxy that preferably carbon number is 1～38, the alkylsulfonyloxy that more preferably carbon number is 1～24 for example can be enumerated sulfonyloxy methyl oxygen base to alkylsulfonyloxy, hexadecyl sulfonyloxy, and cyclohexyl sulfonyloxy), aryl-sulfonyl oxygen (aryl-sulfonyl oxygen that preferably carbon number is 6～32, the aryl-sulfonyl oxygen that more preferably carbon number is 6～24 for example can be enumerated phenyl sulfonyloxy), (acyl group that preferably carbon number is 1～48, the acyl group that more preferably carbon number is 1～24 for example can be enumerated formyl radical to acyl group, ethanoyl, pivaloyl group, benzoyl, myristoyl, and hexamethylene acyl group), (alkoxy carbonyl that preferably carbon number is 2～48, the alkoxy carbonyl that more preferably carbon number is 2～24 for example can be enumerated methoxycarbonyl to alkoxy carbonyl, ethoxy carbonyl, octadecane oxygen base carbonyl, cyclohexyloxy carbonyl, and 2,6-, bis--tributyl-4-methyl cyclohexane oxygen base carbonyl), aryloxycarbonyl (aryloxycarbonyl that preferably carbon number is 7～32, the aryloxycarbonyl that more preferably carbon number is 7～24 for example can be enumerated phenyloxycarbonyl), (carbamyl that preferably carbon number is 1～48, the carbamyl that more preferably carbon number is 1～24 for example can be enumerated carbamyl to carbamyl, N, N-diethyl amino formyl radical, N-ethyl-N-octyl group carbamyl, N, N-dibutylamine formyl radical, N-propyl group carbamyl, N-phenylamino formyl radical, N-methyl-N-phenylamino formyl radical, and NN-dicyclohexyl carbamyl),

It is amino that (preferably carbon number is the amino below 32, and more preferably carbon number is the amino below 24, for example, can enumerate amino, methylamino, N, N-dibutylamino, tetradecyl is amino, 2-ethylhexyl is amino, and cyclohexyl is amino), anilino (anilino that preferably carbon number is 6～32, more preferably 6～24 anilino, for example, can enumerate anilino, and methylphenylamine base), heterocyclic amino group (heterocyclic amino group that preferably carbon number is 1～32, more preferably 1～18 heterocyclic amino group, for example, can enumerate 4-pyridinylamino), carboxamide groups (carboxamide groups that preferably carbon number is 2～48, more preferably 2～24 carboxamide groups, for example, can enumerate acetamido, benzoylamino, tetradecyl amide group, pivaloyl group amide group, and cyclohexyl amide base), (urea groups that preferably carbon number is 1～32, the urea groups that more preferably carbon number is 1～24 for example can be enumerated urea groups to urea groups, N, N-dimethyl urea groups, and N-phenyl urea groups), imide (preferably carbon number is the imide below 36, and more preferably carbon number is the imide below 24, for example, can enumerate N-succinimido and N phlhalimide base), (alkoxycarbonyl amino that preferably carbon number is 2～48, the alkoxycarbonyl amino that more preferably carbon number is 2～24 for example can be enumerated methoxycarbonyl amino to alkoxycarbonyl amino, ethoxy carbonyl is amino, the 3rd butoxy carbonyl is amino, octadecane oxygen base carbonylamino, and cyclohexyloxy carbonyl is amino),

Aryloxycarbonyl amino (aryloxycarbonyl that preferably carbon number is 7～32 is amino, and the aryloxycarbonyl that more preferably carbon number is 7～24 is amino, for example, can enumerate phenyloxycarbonyl amino), (sulfoamido that preferably carbon number is 1～48, the sulfoamido that more preferably carbon number is 1～24 for example can be enumerated sulfonyloxy methyl amido to sulfoamido, butyl sulfonamide base, benzene sulfonamido, hexadecyl sulfoamido, and cyclohexyl sulfonamide base), (sulfamoylamino group that preferably carbon number is 1～48, the sulfamoylamino group that more preferably carbon number is 1～24 for example can be enumerated N to sulfamoylamino group, N-dipropyl sulfamoylamino group, and N-ethyl-N-dodecyl sulfamoylamino group), (azo-group that preferably carbon number is 1～32, the azo-group that more preferably carbon number is 1～24 for example can be enumerated phenylazo to azo-group, and 3-pyrazolyl azo-group), (alkylthio that preferably carbon number is 1～48, the alkylthio that more preferably carbon number is 1～24 for example can be enumerated methylthio group to alkylthio, ethylmercapto group, pungent sulfenyl, and hexamethylene sulfenyl), arylthio (arylthio that preferably carbon number is 6～48, the arylthio that more preferably carbon number is 6～24 for example can be enumerated thiophenyl), (the heterocycle sulfenyl that preferably carbon number is 1～32, the heterocycle sulfenyl that more preferably carbon number is 1～18 for example can be enumerated 2-[4-morpholinodithio base sulfenyl to heterocycle sulfenyl, 2-pyridyl sulfenyl, and 1-phenyltetrazole base sulfenyl), alkyl sulphinyl (alkyl sulphinyl that preferably carbon number is 1～32, the alkyl sulphinyl that more preferably carbon number is 1～24 for example can be enumerated dodecyl sulfinyl), aryl sulfonyl kia (aryl sulfonyl kia that preferably carbon number is 6～32, the aryl sulfonyl kia that more preferably carbon number is 6～24 for example can be enumerated phenyl sulfinyl), (alkyl sulphonyl that preferably carbon number is 1～48, the alkyl sulphonyl that more preferably carbon number is 1～24 for example can be enumerated methyl sulphonyl to alkyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, butyl alkylsulfonyl, sec.-propyl alkylsulfonyl, 2-ethylhexyl alkylsulfonyl, hexadecyl alkylsulfonyl, octyl group alkylsulfonyl, and cyclohexyl alkylsulfonyl), (aryl sulfonyl that preferably carbon number is 6～48, the aryl sulfonyl that more preferably carbon number is 6～24 for example can be enumerated phenyl sulfonyl to aryl sulfonyl, and 1-naphthyl alkylsulfonyl), (preferably carbon number is the sulfamyl below 32 to sulfamyl, and more preferably carbon number is the sulfamyl below 24, for example, can enumerate sulfamyl, N, N-dipropyl sulfamyl, N-ethyl-N-dodecyl sulfamyl, N-ethyl-N-phenyl sulfamoyl base, and N-cyclohexyl sulfamyl), sulfo group, (phosphono that preferably carbon number is 1～32, the phosphono that more preferably carbon number is 1～24 for example can be enumerated phenoxy group phosphono to phosphono, octyloxy phosphono, and Phenylphosphine acyl group), phosphono is amino, and (phosphono that preferably carbon number is 1～32 is amino, and the phosphono that more preferably carbon number is 1～24 is amino, for example, can enumerate diethoxy phosphonium mesitoyl base amino, and two octyloxy phosphono amino).Below, sometimes these substituting groups are called to " substituent R ".

Above-mentioned 1 valency substituting group be can further substituted group situation time, also can further be replaced by any person of above-mentioned each group.In addition, when above-mentioned 1 valency substituting group has 2 above further substituent situations, these substituting groups can be identical also can be different.

In general formula (I), R ¹with R ²also can be independently of one another bond and form 5 members, 6 members or 7 s' ring, R mutually ²with R ³also can be independently of one another bond and form 5 members, 6 members or 7 s' ring, R mutually ⁴with R ⁵also can be independently of one another bond and form 5 members, 6 members or 7 s' ring, R mutually ⁵with R ⁶also can be independently of one another bond and form 5 members, 6 members or 7 s' ring mutually.In addition, formed ring can be any person of saturated rings or unsaturated ring.These 5 members, 6 members or 7 s' saturated rings or unsaturated ring for example can be enumerated pyrrole ring, furan nucleus, thiphene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, Pyrrolizidine ring, piperidine ring, cyclopentenes ring, cyclohexene ring, phenyl ring, pyridine ring, pyrazine ring, pyridazine ring, preferably enumerate phenyl ring, pyridine ring.

In addition, when the situation that formed 5 members, 6 members and 7 s' ring can be further substituted, can be used as 1 valency substituting group in described general formula (I) and any person of illustrative group (that is substituent R) replaces, when the situation being replaced by more than 2 substituting group (that is substituent R), these substituting groups can be identical also can be different.

In addition, R preferably ¹with R ⁶do not form ring.

And, in general formula (I), at R ⁷during for the situation of halogen atom, alkyl, aryl or heterocyclic radical, the preferable range of these bases (comprising preference) with as aforesaid R ¹～R ⁶the preferable range of halogen atom, alkyl, aryl or heterocyclic radical identical.

In general formula (I), described R ¹and R ⁶preferably alkylamino, arylamino, carboxamide groups, urea groups, imide, alkoxycarbonyl amino or sulfoamido independently of one another in above-mentioned, more preferably carboxamide groups, urea groups, alkoxycarbonyl amino or sulfoamido, further more preferably carboxamide groups, urea groups, alkoxycarbonyl amino or sulfoamido, particularly preferably be carboxamide groups or urea groups.

In general formula (I), described R ²and R ⁵preferably alkoxy carbonyl, aryloxycarbonyl, carbamyl, alkyl sulphonyl, aryl sulfonyl, itrile group, imide or carbamyl alkylsulfonyl independently of one another in above-mentioned; more preferably alkoxy carbonyl, aryloxycarbonyl, carbamyl, alkyl sulphonyl, itrile group, imide or carbamyl alkylsulfonyl; further more preferably alkoxy carbonyl, aryloxycarbonyl, carbamyl, itrile group, imide or carbamyl alkylsulfonyl, particularly preferably be alkoxy carbonyl, aryloxycarbonyl or carbamyl.

In general formula (I), described R ³and R ⁴in above-mentioned, be preferably substituted independently of one another or the alkyl being unsubstituted, the aryl that is substituted or is unsubstituted or the heterocyclic radical, the alkyl that is more preferably substituted or is unsubstituted or the aryl that is substituted or is unsubstituted that are substituted or are unsubstituted.

In general formula (I), R ³and R ⁴the alkyl that is substituted or is unsubstituted of represented alkyl straight chain, branched chain or ring-type that preferably carbon number is 1～12, more specifically for example can enumerate methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, tributyl, cyclobutyl, cyclopentyl, cyclohexyl and benzyl.R ³and R ⁴the alkyl that is substituted or is unsubstituted of the represented alkyl branched chain that more preferably carbon number is 1～12 or ring-type, more specifically for example can enumerate sec.-propyl, cyclopropyl, isobutyl-, tributyl, cyclobutyl, cyclopentyl and cyclohexyl.R ³and R ⁴the represented alkyl secondary that further more preferably carbon number is 1～12 or the alkyl that is substituted or is unsubstituted of three grades, more specifically for example can enumerate sec.-propyl, cyclopropyl, isobutyl-, tributyl, cyclobutyl and cyclohexyl.

In general formula (I), R ³and R ⁴the naphthyl that represented aryl can preferably be enumerated the phenyl that is substituted or is unsubstituted and be substituted or be unsubstituted.R ³and R ⁴the phenyl that represented aryl is more preferably substituted or is unsubstituted.

At R ³and R ⁴this heterocyclic radical while representing the situation of heterocyclic radical can preferably be enumerated the 2-thienyl that is substituted or is unsubstituted, the 4-pyridyl that is substituted or is unsubstituted, the 3-pyridyl that is substituted or is unsubstituted, the 2-pyridyl that is substituted or is unsubstituted, the 2-furyl that is substituted or is unsubstituted, the 2-pyrimidyl that is substituted or is unsubstituted, the 2-[4-morpholinodithio base that is substituted or is unsubstituted, the 1-imidazolyl that is substituted or is unsubstituted, the 1-pyrazolyl that is substituted or is unsubstituted, and the benzotriazole-1-base that is substituted or is unsubstituted.The 1-pyridyl that above-mentioned heterocyclic radical can more preferably be enumerated the 2-thienyl that is substituted or is unsubstituted, the 4-pyridyl that is substituted or is unsubstituted, the 2-furyl that is substituted or is unsubstituted, the 2-pyrimidyl that is substituted or is unsubstituted and be substituted or be unsubstituted.

Secondly, to forming metal or the metallic compound of two pyrroles's methylene radical metal complex compounds, be illustrated.

As metal or metallic compound, if can form metal or the metallic compound of complex compound, can be any person, comprise divalent atoms metal, divalent metal oxide, divalent metal hydroxides or divalent metal chloride.Such as except Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B etc., also comprise AlCl, InCl, FeCl, TiCl ₂, SnCl ₂, SiCl ₂, GeCl ₂deng metal chloride, the metal oxides such as TiO, VO, Si (OH) ₂deng metal hydroxides.

In these metals or metallic compound, from the stability of complex compound, dichroism, heat-resisting, photostabilization and manufacture the viewpoints such as suitability and consider, preferably Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B or VO, more preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO, most preferably Fe, Zn, Cu, Co, B or VO.Especially preferred in these metals or metallic compound is Zn.

It is as follows that the represented structure of described general formula (I) is coordinated in the two pyrroles's methylene radical metal complex compounds that form on metal or metallic compound preferred aspect.

That is, the aspect that can be listed below: in general formula (I), R ¹and R ⁶represent that independently of one another hydrogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, silylation, hydroxyl, cyano group, alkoxyl group, aryloxy, heterocyclic oxy group, acyl group, alkoxy carbonyl, carbamyl, amino, anilino, heterocyclic amino group, carboxamide groups, urea groups, imide, alkoxycarbonyl amino, aryloxycarbonyl amino, sulfoamido, azo-group, alkylthio, arylthio, heterocycle sulfenyl, alkyl sulphonyl, aryl sulfonyl or phosphono are amino, R ²and R ⁵represent independently of one another hydrogen atom, halogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, hydroxyl, cyano group, nitro, alkoxyl group, aryloxy, heterocyclic oxy group, acyl group, alkoxy carbonyl, aryloxycarbonyl, carbamyl, imide, alkoxycarbonyl amino, sulfoamido, azo-group, alkylthio, arylthio, heterocycle sulfenyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl, R ³and R ⁴represent that independently of one another hydrogen atom, halogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, silylation, hydroxyl, cyano group, alkoxyl group, aryloxy, heterocyclic oxy group, acyl group, alkoxy carbonyl, carbamyl, anilino, carboxamide groups, urea groups, imide, alkoxycarbonyl amino, sulfoamido, azo-group, alkylthio, arylthio, heterocycle sulfenyl, alkyl sulphonyl, aryl sulfonyl, sulfamyl or phosphono are amino, R ⁷represent hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical, metal or metallic compound represent with Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B or VO.

The preferred aspect of two pyrroles's methylene radical metal complex compounds is as follows.

That is, the aspect that can be listed below: in described general formula (I), R ¹and R ⁶represent that independently of one another hydrogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, cyano group, acyl group, alkoxy carbonyl, carbamyl, amino, heterocyclic amino group, carboxamide groups, urea groups, imide, alkoxycarbonyl amino, aryloxycarbonyl amino, sulfoamido, azo-group, alkyl sulphonyl, aryl sulfonyl or phosphono are amino, R ²and R ⁵represent independently of one another alkyl, thiazolinyl, aryl, heterocyclic radical, cyano group, nitro, acyl group, alkoxy carbonyl, aryloxycarbonyl, carbamyl, imide, alkyl sulphonyl, aryl sulfonyl or sulfamyl, R ³and R ⁴represent independently of one another hydrogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, cyano group, acyl group, alkoxy carbonyl, carbamyl, carboxamide groups, urea groups, imide, alkoxycarbonyl amino, sulfoamido, alkylthio, arylthio, heterocycle sulfenyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl, R ⁷represent hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical, metal or metallic compound represent with Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO.

The preferred aspects of two pyrroles's methylene radical metal complex compounds that described general formula (I) is represented can be enumerated the compound that is selected from the represented compound of the represented compound of following general formula (I-2), general formula (I-3) and the represented compound of general formula (I-4).

[changing 6]

In described general formula (I-2), R ¹, R ², R ³, R ⁴, R ⁵, R ⁶and R ⁷with the R in general formula (I) ¹, R ², R ³, R ⁴, R ⁵, R ⁶and R ⁷synonym separately.Ma represents metal or metallic compound, X ¹expression can with the group of Ma bond, X ²expression in order in and the necessary group of electric charge of Ma.In addition, X ¹with X ²also bond and together form 5 members, 6 members or 7 s' ring with Ma mutually.

In general formula (I-2), R ¹～R ⁷with the R in general formula (I) ¹～R ⁷difference synonym, preferred aspects is also identical.

In general formula (I-2), Ma represents metal or metallic compound, with metal or metallic compound synonym in described " general formula (I) represented compound be coordinated in the two pyrroles's methylene radical metal complex compounds that form on metal or metallic compound ", its preferred scope is also identical.

X in general formula (I-2) ¹if can be any person with the group of Ma bond, can enumerate and be derived from water, ferment class (first ferment for example, ethanol, the third ferment) etc., and the flat work of wild scenery (nineteen ninety-five Nan Jiangtang) on < < metallo-chelate > > [1] slope mouth force one, < < metallo-chelate > > [2] (1996), the group of the compound of recording in < < metallo-chelate > > [3] (1997) etc.Wherein, certainly manufacture suitable positive viewpoint and consider, be preferably derived from the group of water, carboxylic acid cpd, ferment class, amine compound or amide compound, be more preferably derived from the group of water, carboxylic acid cpd, amide compound.

X in general formula (I-2) ²expression in order in and the necessary group of electric charge of Ma, for example can enumerate halogen atom, hydroxyl, carboxylic acid group, phosphate, sulfonic group, be derived from the group of R-CONHCO-R (R represents alkyl, aryl or heterocyclic radical independently of one another) and be derived from R-CONIISO ₂the group of-R (R represents alkyl, aryl or heterocyclic radical independently of one another) etc., wherein with regard to the aspect of manufacturing, preferably halogen atom, hydroxyl, carboxylic acid group, sulfonic group, be derived from the group of R-CONHCO-R and be derived from R-CONHSO ₂the group of-R, more preferably hydroxyl, carboxylic acid group and be derived from the group of R-CONIICO-R.In addition, the group that what is called is derived from R-CONHCO-R refers to from R-CONHCO-R removes 1 hydrogen atom and the 1 valency base that forms, and there is no particular restriction to remove the position of hydrogen atom.

X in general formula (I-2) ¹with X ²also bond and together form 5 members, 6 members or 7 s' ring with Ma mutually.Formed 5 members, 6 members and 7 s' ring can be saturated rings and also can be unsaturated ring.And 5 members, 6 members and 7 s' ring can only comprise carbon atom and hydrogen atom, or also can be and there is at least 1 heterocycle that is selected from the atom of nitrogen-atoms, Sauerstoffatom and sulphur atom.

[changing 7]

In described general formula (I-3), R ¹, R ², R ³, R ⁴, R ⁵and R ⁶with the R in general formula (I) ¹, R ², R ³, R ⁴, R ⁵and R ⁶synonym separately.In described general formula (I-3), R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹²and R ¹³represent independently of one another hydrogen atom or 1 valency substituting group.Ma represents metal or metallic compound.

In general formula (I-3), R ¹～R ⁶with the R in general formula (I) ¹～R ⁶synonym, preferred aspects is also identical.

In general formula (I-3), R ⁸～R ¹³the R of the compound that 1 represented valency substituting group and general formula (I) are represented ¹～R ⁶1 represented valency substituting group is synonym separately, and its preferred aspects is also identical.

R at the represented compound of general formula (I-3) ⁸～R ¹³during situation that 1 represented valency substituting group can be further substituted, can be replaced by any person of aforementioned substituent R, when the situation being replaced by more than 2 substituent R, these substituent R can be identical also can be different.

R in general formula (I-3) ⁷with the R in general formula (I) ⁷synonym, preferred aspects is also identical.

R in general formula (I-3) ¹⁴represent hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical, R ¹⁴preferable range and described R ⁷preferable range identical.At R ¹⁴for can further substituted group situation time, also can be replaced by any person of aforementioned substituent R, when the situation being replaced by more than 2 substituent R, these substituent R can be identical also can be different.

In general formula (I-3), Ma represents metal or metallic compound, and with metal or metallic compound synonym in described " general formula (I) represented compound be coordinated in the complex compound forming on metal or metallic compound ", its preferred scope is also identical.

In general formula (I-3), R ⁸with R ⁹also can be independently of one another bond and form 5 members, 6 members or 7 s' saturated rings or unsaturated ring, R mutually ⁹with R ¹⁰also can be independently of one another bond and form 5 members, 6 members or 7 s' saturated rings or unsaturated ring, R mutually ¹¹with R ¹²also can be independently of one another bond and form 5 members, 6 members or 7 s' saturated rings or unsaturated ring, R mutually ¹²with R ¹³also can be independently of one another bond and form 5 members, 6 members or 7 s' saturated rings or unsaturated ring mutually.Formed saturated rings or unsaturated ring with by R ¹with R ², R ²with R ³, R ⁴with R ⁵, or R ⁵with R ⁶formed saturated rings or unsaturated ring synonym, preference is also identical.

And, in general formula (I-3), R preferably ¹not with R ⁸or R ¹³form ring, and R preferably ⁶not with R ⁸or R ¹³form ring.

[changing 8]

In described general formula (I-4), R ², R ³, R ⁴, and R ⁵represent independently of one another hydrogen atom or substituting group, R ⁷represent hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical.R ⁸and R ⁹represent independently of one another alkyl, thiazolinyl, aryl, heterocyclic radical, alkoxyl group, aryloxy, alkylamino, arylamino or heterocyclic amino group.Ma represents metal or metallic compound.X ³and X ⁴represent independently of one another NR ^a(R ^arepresent hydrogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl), Sauerstoffatom or sulphur atom.Y ¹and Y ²represent independently of one another NR ^b(R ^brepresent hydrogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl), Sauerstoffatom, sulphur atom or carbon atom.

X ⁵expression can with the group of Ma bond, a represents 0,1 or 2.R ⁸with Y ¹also bond and form 5 members, 6 members or the ring of 7 Yuans, R mutually ⁹with Y ²also bond and form 5 members, 6 members or the ring of 7 Yuans mutually.

R in general formula (I-4) ²～R ⁵, and R ⁷with the R in general formula (I) ²～R ⁵, and R ⁷synonym, preferred aspects is also identical.

Ma in general formula (I-4) represents metal or metallic compound, and the compound represented with described general formula (I) is coordinated in metal or the metallic compound synonym in the complex compound forming on metal or metallic compound, and its preferred scope is also identical.

In general formula (I-4), R ⁸and R ⁹represent independently of one another the alkyl (straight chain that preferably carbon number is 1～36, branched chain, or the alkyl of ring-type, more preferably 1～12 straight chain, branched chain, or the alkyl of ring-type, for example can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, tributyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, and 1-adamantyl), thiazolinyl (thiazolinyl that preferably carbon number is 2～24, more preferably 2～12 thiazolinyl, for example, can enumerate vinyl, allyl group, and 3-butene-1-yl), aryl (aryl that preferably carbon number is 6～36, more preferably 6～18 aryl, for example, can enumerate phenyl, and naphthyl), heterocyclic radical (heterocyclic radical that preferably carbon number is 1～24, more preferably 1～12 heterocyclic radical, for example, can enumerate 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidyl, 1-pyridyl, 2-[4-morpholinodithio base, 1-imidazolyl, 1-pyrazolyl, and benzotriazole-1-yl), alkoxyl group (alkoxyl group that preferably carbon number is 1～36, more preferably 1～18 alkoxyl group, for example, can enumerate methoxyl group, oxyethyl group, propoxy-, butoxy, hexyloxy, 2-ethyl hexyl oxy, dodecyloxy, and cyclohexyloxy), aryloxy (aryloxy that preferably carbon number is 6～24, more preferably 1～18 aryloxy, for example, can enumerate phenoxy group, and naphthyloxy), alkylamino (alkylamino that preferably carbon number is 1～36, more preferably 1～18 alkylamino, for example, can enumerate methylamino, ethylamino, propyl group is amino, butyl is amino, hexyl is amino, 2-ethylhexyl is amino, isopropylamino, tributyl is amino, trioctylphosphine is amino, cyclohexyl is amino, N, N-diethylamino, N, N-dipropyl is amino, N, N-dibutylamino, and N-methyl-N-ethylamino), arylamino (arylamino that preferably carbon number is 6～36, more preferably 6～18 arylamino, for example, can enumerate phenyl amino, naphthyl is amino, NN-diphenyl amino, and N-ethyl-N-phenyl amino), or heterocyclic amino group (heterocyclic amino group that preferably carbon number is 1～24, more preferably 1～12 heterocyclic amino group, for example, can enumerate 2-amino-pyrroles base, 3-amino-pyrazol base, PA base, and 3-aminopyridine base).

In general formula (I-4), R ⁸and R ⁹when represented alkyl, thiazolinyl, aryl, heterocyclic radical, alkoxyl group, aryloxy, alkylamino, arylamino or heterocyclic amino group can further substituted situations, can be replaced by any person of described substituent R, when the situation being replaced by more than 2 substituent R, these substituent R can be identical also can be different.

In general formula (I-4), X ³and X ⁴represent independently of one another NR ^a, Sauerstoffatom or sulphur atom.R ^arepresent hydrogen atom, alkyl (the straight chain that preferably carbon number is 1～36, branched chain, or the alkyl of ring-type, more preferably 1～12 straight chain, branched chain, or the alkyl of ring-type, for example can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, tributyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, and 1-adamantyl), thiazolinyl (thiazolinyl that preferably carbon number is 2～24, more preferably 2～12 thiazolinyl, for example, can enumerate vinyl, allyl group, and 3-butene-1-yl), aryl (aryl that preferably carbon number is 6～36, more preferably 6～18 aryl, for example, can enumerate phenyl, and naphthyl), heterocyclic radical (heterocyclic radical that preferably carbon number is 1～24, more preferably 1～12 heterocyclic radical, for example, can enumerate 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidyl, 1-pyridyl, 2-[4-morpholinodithio base, 1-imidazolyl, 1-pyrazolyl, and benzotriazole-1-yl), acyl group (acyl group that preferably carbon number is 1～24, more preferably 2～18 acyl group, for example, can enumerate ethanoyl, pivaloyl group, 2-ethyl hexyl acyl group, benzoyl, and hexamethylene acyl group), alkyl sulphonyl (alkyl sulphonyl that preferably carbon number is 1～24, more preferably 1～18 alkyl sulphonyl, for example, can enumerate methyl sulphonyl, ethylsulfonyl, sec.-propyl alkylsulfonyl, and cyclohexyl alkylsulfonyl), aryl sulfonyl (aryl sulfonyl that preferably carbon number is 6～24, more preferably 6～18 aryl sulfonyl, for example, can enumerate phenyl sulfonyl, and naphthyl alkylsulfonyl).

And, at R ^ain the time of can substituted situation, can further be substituted base and replace, when the situation being replaced by a plurality of substituting groups, these substituting groups can be identical also can be different.Further substituting group when Ra can substituted situation can be enumerated: halogen atom (for example can be enumerated fluorine atom, chlorine atom, bromine atoms), alkyl (the straight chain that preferably carbon number is 1～48, branched chain, or the alkyl of ring-type, the straight chain that more preferably carbon number is 1～24, branched chain, or the alkyl of ring-type, for example can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, tributyl, amyl group, hexyl, heptyl, octyl group, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norcamphyl, and 1-adamantyl), (thiazolinyl that preferably carbon number is 2～48, the thiazolinyl that more preferably carbon number is 2～18 for example can be enumerated vinyl to thiazolinyl, allyl group, and 3-butene-1-yl), (aryl that preferably carbon number is 6～48, the aryl that more preferably carbon number is 6～24 for example can be enumerated phenyl to aryl, and naphthyl), (heterocyclic radical that preferably carbon number is 1～32, the heterocyclic radical that more preferably carbon number is 1～18 for example can be enumerated 2-thienyl to heterocyclic radical, 4-pyridyl, 2-furyl, 2-pyrimidyl, 1-pyridyl, 2-[4-morpholinodithio base, 1-imidazolyl, 1-pyrazolyl, and benzotriazole-1-yl), (silylation that preferably carbon number is 3～38, the silylation that more preferably carbon number is 3～18 for example can be enumerated TMS to silylation, triethyl silyl, tributyl silylation, tributyl dimethylsilyl, and the 3rd hexyl dimethylsilyl), hydroxyl, cyano group, nitro, (alkoxyl group that preferably carbon number is 1～48, the alkoxyl group that more preferably carbon number is 1～24 for example can be enumerated methoxyl group to alkoxyl group, oxyethyl group, 1-butoxy, 2-butoxy, isopropoxy, the 3rd butoxy, and dodecyl oxygen base, and cyclopentyloxy for example, or the cycloalkyloxy such as cyclohexyloxy), (aryloxy that preferably carbon number is 6～48, the aryloxy that more preferably carbon number is 6～24 for example can be enumerated phenoxy group to aryloxy, and 1-naphthyloxy), (heterocyclic oxy group that preferably carbon number is 1～32, the heterocyclic oxy group that more preferably carbon number is 1～18 for example can be enumerated 1-phenyltetrazole-5-oxygen base to heterocyclic oxy group, and 2-THP trtrahydropyranyl oxygen base), (the silicon alkoxyl group that preferably carbon number is 1～32, the silicon alkoxyl group that more preferably carbon number is 1～18 for example can be enumerated trimethyl silicane alcoxyl base to silicon alkoxyl group, tributyl dimethyl-silicon alcoxyl base, and diphenylmethylsilane oxygen base), (acyloxy that preferably carbon number is 2～48, the acyloxy that more preferably carbon number is 2～24 for example can be enumerated acetoxyl group to acyloxy, pivaloyl oxygen base, benzoyloxy, and lauroyl oxygen base), alkoxyl group carbonyl oxygen base (the alkoxyl group carbonyl oxygen base that preferably carbon number is 2～48, the alkoxyl group carbonyl oxygen base that more preferably carbon number is 2～24, for example, can enumerate oxyethyl group carbonyl oxygen base, and the 3rd butoxy carbonyl oxy, and such as cycloalkyloxy carbonyl oxygen bases such as cyclohexyloxy carbonyl oxygens), aryloxy carbonyl oxygen base (the aryloxy carbonyl oxygen base that preferably carbon number is 7～32, the aryloxy carbonyl oxygen base that more preferably carbon number is 7～24, for example, can enumerate phenoxy group carbonyl oxygen base), carbamyl oxygen base (the carbamyl oxygen base that preferably carbon number is 1～48, the carbamyl oxygen base that more preferably carbon number is 1～24, for example, can enumerate N, N-dimethylamino formyl radical oxygen base, N-butyl carbamyl oxygen base, N-phenylamino formyl radical oxygen base, and N-ethyl-N-phenylamino formyl radical oxygen base), sulfamyl oxygen base (the sulfamyl oxygen base that preferably carbon number is 1～32, the sulfamyl oxygen base that more preferably carbon number is 1～24, for example, can enumerate N, N-diethyl amino alkylsulfonyl oxygen base, and N-propyl group sulfamyl oxygen base), (alkylsulfonyloxy that preferably carbon number is 1～38, the alkylsulfonyloxy that more preferably carbon number is 1～24 for example can be enumerated sulfonyloxy methyl oxygen base to alkylsulfonyloxy, hexadecyl sulfonyloxy, and cyclohexyl sulfonyloxy), aryl-sulfonyl oxygen (aryl-sulfonyl oxygen that preferably carbon number is 6～32, the aryl-sulfonyl oxygen that more preferably carbon number is 6～24 for example can be enumerated phenyl sulfonyloxy), (acyl group that preferably carbon number is 1～48, the acyl group that more preferably carbon number is 1～24 for example can be enumerated formyl radical to acyl group, ethanoyl, pivaloyl group, benzoyl, myristoyl, and hexamethylene acyl group), (alkoxy carbonyl that preferably carbon number is 2～48, the alkoxy carbonyl that more preferably carbon number is 2～24 for example can be enumerated methoxycarbonyl to alkoxy carbonyl, ethoxy carbonyl, octadecane oxygen base carbonyl, cyclohexyloxy carbonyl, and 2,6-, bis--tributyl-4-methyl cyclohexane oxygen base carbonyl), aryloxycarbonyl (aryloxycarbonyl that preferably carbon number is 7～32, the aryloxycarbonyl that more preferably carbon number is 7～24 for example can be enumerated phenyloxycarbonyl), (carbamyl that preferably carbon number is 1～48, the carbamyl that more preferably carbon number is 1～24 for example can be enumerated carbamyl to carbamyl, N, N-diethyl amino formyl radical, N-ethyl-N-octyl group carbamyl, N, N-dibutylamine formyl radical, N-propyl group carbamyl, N-phenylamino formyl radical, N-methyl-N-phenylamino formyl radical, and N, N-dicyclohexyl carbamyl).

X ³and X ⁴preferably independent is separately Sauerstoffatom or sulphur atom, X ³and X ⁴particularly preferably be and be Sauerstoffatom.

In general formula (I-4), Y ¹and Y ²represent independently of one another NR ^b, sulphur atom or carbon atom, R ^bwith described X ³or X ⁴in R ^asynonym.

Y ¹and Y ²preferably independent is separately NR ^b(R ^bfor hydrogen atom or the carbon number alkyl that is 1～8), Y ¹and Y ²particularly preferably be and be NH.

In general formula (I-4), R ⁸with Y ¹also bond and make R mutually ⁸, Y ¹, and the carbon atom of adjacency together form 5 Yuans rings (for example pentamethylene, Pyrrolizidine, tetrahydrofuran (THF), dioxolane, tetramethylene sulfide, pyrroles, furans, thiophene, indoles, cumarone or thionaphthene), 6 Yuans rings (for example hexanaphthene, piperidines, piperazine, morpholine, tetrahydropyrans, dioxan, sulfuration pentamethylene, dithiane, benzene, piperidines, piperazine, pyridazine, quinoline or quinazoline) or 7 Yuans rings (for example suberane or hexamethylene imine).

In general formula (I-4), R ⁹with Y ²also bond and make R mutually ⁹, Y ², and the carbon atom of adjacency together form 5 members, 6 members or 7 s' ring.The example of formed 5 members, 6 members and 7 s' ring can enumerate make described by R ⁸with Y ¹and 1 key in the formed ring of carbon atom is changed to the ring of two keys.

In general formula (I-4), R ⁸with Y ¹, or R ⁹with Y ²during situation that bond and 5 members forming, 6 members and 7 s' ring can be further substituted, can be replaced by the illustrated group of any person of described substituent R, when the situation being replaced by more than 2 substituent R, these substituent R can be identical also can be different.

In general formula (I-4), X ⁵expression can with the group of Ma bond, can enumerate with described general formula (I-1) in X ²identical group.A represents 0,1 or 2.

The preferred aspects that below represents the compound that general formula (I-4) is represented.That is following aspect: R ²～R ⁵, R ⁷, and Ma the preferred aspects of the complex compound of the compound represented with comprising general formula (I) and metal or metallic compound is identical respectively, X ³and X ⁴independent is separately NR ^a(R ^arepresent hydrogen atom, alkyl or heterocyclic radical) or Sauerstoffatom, Y ¹and Y ²independent is separately NR ^b(R ^brepresent hydrogen atom or alkyl), nitrogen-atoms or carbon atom, X ⁵for the group via Sauerstoffatom or nitrogen-atoms bond, R ⁸and R ⁹represent independently respectively alkyl, aryl, heterocyclic radical, alkoxyl group or alkylamino, or R ⁸with Y ¹mutual bond and form 5 Yuans or 6 Yuans rings, R ⁹with Y ²mutual bond and form 5 members, 6 Yuans rings, a represents 0 or 1.

The more preferably aspect that below represents the compound that general formula (I-4) is represented.That is following aspect: R ²～R ⁵, R ⁷, the preferred aspects of the complex compound of the compound represented with comprising general formula (I) and metal or metallic compound is identical respectively for Ma, X ³and X ⁴for Sauerstoffatom, Y ¹for NH, Y ²for nitrogen-atoms, X ⁵for the group via Sauerstoffatom or nitrogen-atoms bond, R ⁸and R ⁹represent independently respectively alkyl, aryl, heterocyclic radical, alkoxyl group or alkylamino, or R ⁸with Y ¹mutual bond and form 5 Yuans or 6 Yuans rings, R ⁹with Y ²mutual bond and form 5 members, 6 Yuans rings, a represents 0 or 1.

Described general formula (I-2) to the represented compound of described general formula (I-4) in the represented complex compounds of general formula (I-4) (that is, be coordinated in the preferred aspects of the dyestuff of the metal complex compounds forming on metal or metallic compound as the represented structure of described general formula (I)) is particularly preferred sample state.

Below, the concrete example that represents the particular dye (A-1) that the described general formula (I) that uses in the present invention is represented.Wherein, the present invention is not limited to these concrete examples.

In addition, as shown in following concrete example, particular dye of the present invention (A-1) is not only two represented pyrroles's methylene radical metal complex compounds (monomer) of described general formula (I), also comprises and contains this structure as the polymer of part-structure.

In addition, in following exemplary compounds 43～exemplary compounds 45, a/b and a/b/c represent the mass ratio of each constituent.

[changing 9]

[changing 10]

[changing 11]

[changing 12]

[changing 13]

[changing 14]

[changing 15]

In the exemplary compounds of these two pyrroles methylene radical metal complex compounds, exemplary compounds (46)～exemplary compounds (50) is also the exemplary compounds of general formula (I-2), exemplary compounds (51) is also the compound that shows of general formula (I-3), and exemplary compounds (1)～exemplary compounds (45) is also the exemplary compounds of general formula (I-4).

And, except above-mentioned exemplary compounds, also can enumerate exemplary compounds (Ia-3)～exemplary compounds (Ia-83) of recording in Japanese Patent Laid-Open 2008-292970 communique, exemplary compounds (Ia-1)～exemplary compounds (IIa-20), exemplary compounds (I-1)～exemplary compounds (I-36), exemplary compounds (II-1)～exemplary compounds (II-11), and exemplary compounds (III-1)～exemplary compounds (III-103), exemplary compounds (I-1)～exemplary compounds (I-35) of recording in No. 3324279 communique of Japanese Patent, exemplary compounds (I-1)～exemplary compounds (I-13) of recording in No. 3279035 communique of Japanese Patent, the exemplary compounds of recording in Japanese patent laid-open 11-256057 communique (2-1)～exemplary compounds (2-32), exemplary compounds (3-1)～exemplary compounds (3-32), exemplary compounds (4-1)～exemplary compounds (4-26), and exemplary compounds (5-1)～exemplary compounds (5-26), the exemplary compounds of recording in Japanese Patent Laid-Open 2005-77953 communique (I-1)～exemplary compounds (I-6), and exemplary compounds (VII-1)～exemplary compounds (VII-8), the exemplary compounds of recording in Japanese patent laid-open 11-352686 communique (1-1)～exemplary compounds (1-45), the exemplary compounds of recording in Japanese Patent Laid-Open 2000-19729 communique (1-1)～exemplary compounds (1-50), and exemplary compounds (1-1)～exemplary compounds (1-45) of recording in Japanese patent laid-open 11-352685 communique etc. is coordinated in the example of the dyestuff (two pyrroles's methylene radical metal complex compounds) of the metal complex compounds forming on metal or metallic compound as the represented structure of general formula (I).

(A-2) the represented structure of general formula (II) is coordinated in the azepine pyrroles methylene radical metal complex compounds forming on metal or metallic compound

Secondly, the represented azepine pyrroles methylene radical metal complex compounds (following suitable being called " azepine pyrroles methylene radical metal complex compounds " or " particular dye (A-2) ") of mutual-through type (II) is illustrated.

[changing 16]

In described general formula (II), R ²¹, R ²², R ²³, R ²⁴, R ²⁵and R ²⁶represent independently respectively hydrogen atom or 1 valency substituting group.

Above-mentioned R ²¹～R ²⁶1 valency substituting group while representing the substituent situation of 1 valency can be enumerated the R in described general formula (I) ¹～R ⁶in illustrated 1 valency substituting group, preference is also identical.

In addition, R ²¹with R ²², R ²²with R ²³, R ²⁴with R ²⁵, and R ²⁵with R ²⁶at least one group also can distinguish mutual bond and form 5 members, 6 members or saturated rings or the unsaturated ring of 7 Yuans.During situation that formed 5 members, 6 members and 7 s' ring can be further substituted, can be by the R in described general formula (I) ¹～R ⁶in illustrated substituting group (substituent R) further replace, when the situation being replaced by more than 2 substituting group (substituent R), these substituting groups (substituent R) can be identical also can be different.

The represented compound of described general formula (II) is following general formula (II-1) or the represented compound of general formula (II-2) preferably.

[changing 17]

[changing 18]

In described general formula (II-1) and general formula (II-2), R ^arepresent independently respectively aryl or alkyl.R ^brepresent independently respectively 2,6-, bis--tributyl-4-methyl cyclohexane oxygen base carbonyl or cyano group, R ^drepresent independently respectively alkyl, aryl, heteroaryl or thiazolinyl.

Other preferred aspects of the azepine pyrroles methylene radical metal complex compounds that described general formula (II) is represented can be enumerated the represented metal complex of following general formula (II-3).

[changing 19]

In described general formula (II-3), R ²¹, R ²², R ²³, R ²⁴, R ²⁵and R ²⁶represent independently respectively hydrogen atom or substituting group.Ma represents atoms metal or metallic compound, and X represents respectively substituting group independently.Between Ma and X, be covalent linkage, coordinate bond or ionic linkage.N is 2～4 integer.

In described general formula (II-3), dotted line represents coordinate bond.Below, about general formula (II-4)～general formula (II-9) and exemplary compounds, also represent same implication.

R in general formula (II-3) ²¹, R ²², R ²³, R ²⁴, R ²⁵and R ²⁶respectively with general formula (II) in R ²¹, R ²², R ²³, R ²⁴, R ²⁵and R ²⁶synonym, preferred scope is also identical.

Herein, R ²¹with X also bond and together form 5 members, 6 members or 7 s' ring, R with Ma mutually ²⁶with X also bond and together form 5 members, 6 members or 7 s' ring with Ma mutually.

Ma and X preferably at least 1 by coordinate bond, carry out bond.N is 2～4 integer, preferably 3.In molecule, multiple X are can be mutually identical also can be different.

Ma is Zn, Mg, Sc, Fe, Al, Cr, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO or VO preferably, and more preferably Zn, Mg, Sc, Fe, Al, Mn, Cu, Ni, Co, TiO or VO, particularly preferably be Zn, Cu or Co.

The represented metal complex compounds of general formula (II) is that the represented metal complex compounds of general formula (II-4) is also preferred aspects.

[changing 20]

In described general formula (II-4), r ²², R ²³, R ²⁴, R ²⁵and R ²⁶represent independently respectively hydrogen atom or substituting group.R ²⁷represent alkyl, thiazolinyl, aryl, heterocyclic radical, alkoxyl group, aryloxy, alkylamino, arylamino or heterocyclic amino group.Ma represents atoms metal or metallic compound, and X represents respectively substituting group independently.X ¹¹represent NR, nitrogen-atoms, Sauerstoffatom or sulphur atom, R represents hydrogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl.Y ¹represent NRc, nitrogen-atoms or carbon atom, Rc represents hydrogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl.Between Ma and X, by covalent linkage, coordinate bond or ionic linkage, carry out bond.N1 is 2～4 integer, and in molecule, multiple X are can be mutually identical also can be different.

R ²⁷with Y ¹also bond and form 5 members, 6 members or the ring of 7 Yuans, R mutually ²⁷with X ¹¹also bond and form 5 members, 6 members or the ring of 7 Yuans, X mutually ¹¹with X also bond and form 5 members, 6 members or the ring of 7 Yuans mutually.

R in general formula (II-4) ²², R ²³, R ²⁴, R ²⁵and R ²⁶respectively with general formula (II) in R ²², R ²³, R ²⁴, R ²⁵and R ²⁶synonym, preferred scope is also identical.

R in general formula (II-4) ²⁷alkyl or aryl preferably, aryl more preferably, further phenyl more preferably.These bases also can further have substituting group.Further substituting group is alkyl preferably, the alkyl that more preferably carbon number is 1～3.

Ma synonym in Ma in general formula (II-4) and general formula (II-3), preferred scope is also identical.

X in general formula (II-4) ¹¹sauerstoffatom preferably.

Y in general formula (II-4) ¹nRc preferably.Rc is hydrogen atom preferably.

The represented metal complex compounds of general formula (II) can be enumerated the represented metal complex compounds of general formula (II-5) as more preferably aspect.

[changing 21]

In general formula (II-5), R ²², R ²³, R ²⁴and R ²⁵represent independently respectively hydrogen atom or substituting group.R ²⁷and R ²⁸represent independently respectively alkyl, thiazolinyl, aryl, heterocyclic radical, alkoxyl group, aryloxy, alkylamino, arylamino or heterocyclic amino group.Ma represents atoms metal or metallic compound.X ^youngster, X ^northrepresent independently respectively NR (R represents hydrogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl), ammonia atom, Sauerstoffatom or sulphur atom.Y ¹, Y ²represent independently respectively NRc (Rc represents hydrogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl), ammonia atom or carbon atom.Z ¹expression can with the group of Ma bond, a represents 0,1 or 2.

R ²⁷with Y ¹also bond and form 5 members, 6 members or the ring of 7 Yuans, R mutually ²⁸with Y ²also bond and form 5 members, 6 members or the ring of 7 Yuans mutually.And, R ²⁷with X ¹¹also bond and form 5 members, 6 members or the ring of 7 Yuans, R mutually ²⁸with X ¹²also bond and form 5 members, 6 members or the ring of 7 Yuans, R mutually ²⁷with Z ¹also bond and form 5 members, 6 members or the ring of 7 Yuans, RR mutually ²⁸with Z ¹also bond and form 5 members, 6 members or the ring of 7 Yuans mutually.

R in general formula (II-5) ²², R ²³, R ²⁴and R ²⁵respectively with general formula (II) in R ²², R ²³, R ²⁴and R ²⁵synonym, preferred scope is also identical.

R in general formula (II-5) ²⁷and R ²⁸alkyl or aryl preferably independently respectively, aryl more preferably, further phenyl more preferably.These groups also can further have substituting group.Further substituting group is alkyl preferably, the alkyl that more preferably carbon number is 1～3.

Ma synonym in Ma in general formula (II-5) and general formula (II-2), preferred scope is also identical.

X in general formula (II-5) ¹¹, X ¹²difference is Sauerstoffatom preferably.

Y in general formula (II-5) ¹, Y ²nRc preferably independently respectively.Rc is hydrogen atom preferably.

Z ¹expression can with the group of Ma ion bond or covalency bond.Z ¹tetrafluoro boron ion, hexafluoro phosphonium ion, hexafluoro antimony ion, three (trifluoromethanesulfonic acid) methide ion be can enumerate, chlorate ions, cyano group, halogen (preferably chlorine), alkyl carboxylic acid base (the alkyl carboxylic acid base that preferably carbon number is 2～20 crossed, the alkyl carboxylic acid base that more preferably carbon number is 2～12, particularly preferably is carbon number and is 2～8 alkyl carboxylic acid base.Such as enumerating acetoxyl, lactyl, decane carboxylic acid group etc.), (the aryl carboxylic acid base that preferably carbon number is 2～20, the aryl carboxylic acid base that more preferably carbon number is 2～11 particularly preferably are carbon number and are 2～7 aryl carboxylic acid base to aryl carboxylic acid.Such as enumerating benzoyloxy, anthraquinone carboxylic acids base, naphthalene monocarboxylic acid base etc.), alkylsulphonic acid base (the alkylsulphonic acid base that preferably carbon number is 2～20, the alkylsulphonic acid base that more preferably carbon number is 2～12, particularly preferably is carbon number and is 2～8 alkylsulphonic acid base.For example can enumerate methylsulphonic acid base, trifluoromethane sulfonic acid base), (aryl sulfonic acid groups that preferably carbon number is 2～20, the aryl sulfonic acid groups that more preferably carbon number is 2～11 particularly preferably are carbon number and are 2～7 aryl sulfonic acid groups to aryl sulfonic acid groups.For example can enumerate Phenylsulfonic acid base, tosic acid base, naphthene sulfonic acid base), hydroxyl, the imide (imide that preferably carbon number is 2～20, the imide that more preferably carbon number is 2～12, particularly preferably is carbon number and is 2～8 imide.Such as enumerating phthalimide-based, diacetyl imide, two fluoroform sulfimide bases etc.), the aryloxy (aryloxy that preferably carbon number is 2～20, the aryloxy that more preferably carbon number is 2～12, particularly preferably is carbon number and is 2～8 aryloxy.Such as enumerating phenoxy group etc.), (alkylthio that preferably carbon number is 2～20, the alkylthio that more preferably carbon number is 2～12 particularly preferably are carbon number and are 2～8 alkylthio to alkylthio.Such as enumerating dodecane sulfenyl etc.), (arylthio that preferably carbon number is 2～20, the arylthio that more preferably carbon number is 2～12 particularly preferably are carbon number and are 2～8 arylthio to arylthio.Such as enumerating thiophenyl) etc.Wherein preferably alkyl carboxylic acid base, aryl carboxylic acid base, aryl sulfonic acid groups, imide, more preferably alkyl carboxylic acid base, imide, particularly preferably be alkyl carboxylic acid base.

A preferably 1.

And the represented metal complex of general formula (II) is the represented metal complex of general formula (II-6) preferably also.

[changing 22]

In general formula (II-6), R ²², R ²³, R ²⁴and R ²⁵represent independently respectively hydrogen atom or substituting group.R ²⁷and R ²⁸represent independently respectively alkyl, thiazolinyl, aryl, heterocyclic radical, alkoxyl group, aryloxy, alkylamino, arylamino or heterocyclic amino group.Ma represents atoms metal or metallic compound.X ¹¹¹represent NR (R represents hydrogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl), ammonia atom, Sauerstoffatom or sulphur atom, X ¹¹²represent NRa (Ra represents hydrogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl), Sauerstoffatom or sulphur atom.Y ¹¹represent NRc (Rc represents hydrogen atom, alkyl, thiazolinyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl), nitrogen-atoms or carbon atom, Y ¹²represent nitrogen-atoms or carbon atom.Z ²expression can with the group of Ma bond, a represents 0,1 or 2.

R ²⁷with Y ¹¹also bond and form 5 members, 6 members or the ring of 7 Yuans, R mutually ²⁸with Y ¹²also bond and form 5 members, 6 members or the ring of 7 Yuans mutually.And, R ²⁷with X ¹¹¹also bond and form 5 members, 6 members or the ring of 7 Yuans, R mutually ²⁸with X ¹²²also bond and form 5 members, 6 members or the ring of 7 Yuans, R mutually ²⁷with Z ²also bond and form 5 members, 6 members or the ring of 7 Yuans, R mutually ²⁸with Z ²also bond and form 5 members, 6 members or the ring of 7 Yuans mutually.

R in general formula (II-6) ²², R ²³, R ²⁴and R ²⁵respectively with general formula (II) in R ²², R ²³, R ²³and R ²⁵synonym, preferred scope is also identical.

R in general formula (II-6) ⁷and R ⁸respectively with general formula (II-5) in R ⁷and R ⁸synonym, preferred scope is also identical.

Y in general formula (II-6) ¹¹preferably NRc or nitrogen-atoms.Rc is hydrogen atom preferably.

Y in general formula (II-6) ¹²nitrogen-atoms preferably.

X in general formula (II-6) ¹¹¹and X ¹¹²sauerstoffatom preferably.

Z in general formula (II-6) ²expression can with the group of Ma coordination bond.Z ²(alkyl carboxylic acid that preferably carbon number is 2～20, the alkyl carboxylic acid that more preferably carbon number is 2～12 particularly preferably are carbon number and are 2～8 alkyl carboxylic acid can to enumerate ether (for example tetrahydrofuran (THF), diethyl ether), alkyl carboxylic acid.Such as enumerating acetic acid, lactic acid, decane carboxylic acid etc.), (aryl carboxylic acid that preferably carbon number is 6～20, the aryl carboxylic acid that more preferably carbon number is 6～11 particularly preferably are carbon number and are 6～7 aryl carboxylic acid to aryl carboxylic acid.Such as enumerating phenylformic acid, anthraquinone carboxylic acids, naphthalene monocarboxylic acid etc.), (alkylsulphonic acid that preferably carbon number is 2～20, the alkylsulphonic acid that more preferably carbon number is 2～12 particularly preferably are carbon number and are 2～8 alkylsulphonic acid to alkylsulphonic acid.For example can enumerate methylsulphonic acid, trifluoromethane sulfonic acid), (aryl sulfonic acid that preferably carbon number is 6～20, the aryl sulfonic acid that more preferably carbon number is 6～11 particularly preferably are carbon number and are 6～7 aryl sulfonic acid to aryl sulfonic acid.For example can enumerate Phenylsulfonic acid, tosic acid, naphthene sulfonic acid), (imide that preferably carbon number is 2～20, the imide that more preferably carbon number is 2～12 particularly preferably are carbon number and are 2～8 imide for water, imide.Such as enumerating phthalic imidine, diacetyl imide, two fluoroform sulfimides etc.), (alcohol that preferably carbon number is 2～20, the alcohol that more preferably carbon number is 2～12 particularly preferably are carbon number and are 1～8 alcohol to alkyl alcohol.Such as methyl alcohol, butanols, Virahol etc.), (aryl alcohol that preferably carbon number is 6～20, the aryl alcohol that more preferably carbon number is 6～12 particularly preferably are carbon number and are 6～8 aryl alcohol to aryl alcohol.Such as enumerating phenol etc.), (aryl mercaptan that preferably carbon number is 6～20, the aryl mercaptan that more preferably carbon number is 6～12 particularly preferably are carbon number and are 6～8 aryl mercaptan to aryl mercaptan.Such as enumerating thiophenol etc.), (alkyl sulfhydryl that preferably carbon number is 2～20, the alkyl sulfhydryl that more preferably carbon number is 2～12 particularly preferably are carbon number and are 2～8 alkyl sulfhydryl to alkyl sulfhydryl.Such as enumerating dodecyl mercaptans) etc.Wherein, preferably water, alkyl carboxylic acid, aryl carboxylic acid, aryl sulfonic acid, imide, more preferably alkyl carboxylic acid, water, particularly preferably be alkyl carboxylic acid.

A preferably 1.

The represented compound of general formula (II) particularly preferably is general formula (II-7) or the represented compound of general formula (II-8).

[changing 23]

[changing 24]

R in general formula (II-7) and general formula (II-8) ^a, R ^band R ^dwith the R in described general formula (II-1) and general formula (II-2) ^a, R ^band R ^ddifference synonym.Ma is atoms metal or metallic compound, Z ¹expression can with the group of Ma bond.

In above-mentioned general formula (II-7) or general formula (II-8), R ^aaryl preferably independently respectively.

By R ^athe represented benzonitrile base that also can there is the phenyl that substituent aryl is preferably substituted or is unsubstituted, the tolyl that is substituted or is unsubstituted, the chloro-phenyl-that is substituted or is unsubstituted, the bromophenyl that is substituted or is unsubstituted, be substituted or be unsubstituted, the phenyl that is more preferably substituted or is unsubstituted, the tolyl that is substituted or is unsubstituted, the phenyl that is further more preferably substituted or is unsubstituted.

By R ^arepresented alkyl is methyl, ethyl, butyl, sec.-propyl, tributyl preferably, more preferably ethyl, sec.-propyl.

In general formula (II-7) or general formula (II-8), R ^bpreferably 2,6-bis--tributyl-4-methyl cyclohexane oxygen base carbonyl.

In general formula (II-7) or general formula (II-8), R ^drespectively preferably alkyl or aryl, more preferably aryl independently.

By R ^drepresented also can have substituent alkyl preferably secondary alkyl, three grades of alkyl, and more preferably three grades of alkyl, particularly preferably are tributyl.By R ^drepresented aryl is phenyl, tolyl, xylyl or naphthyl preferably, and more preferably tolyl, phenyl, particularly preferably be tolyl.

By R ^drepresented thiazolinyl is β-styryl preferably.

Ma in general formula (II-7) or general formula (II-8) and the Ma synonym in general formula (II-3), preferred scope is also identical.

Z in general formula (II-7) or general formula (II-8) ¹with the Z in general formula (II-5) ¹synonym, preferred scope is also identical.

The represented compound of general formula (II) particularly preferably is the represented compound of general formula (II-9).

[changing 25]

In general formula (II-9), R ³⁰for comprising the substituting group of nitrogen-atoms, R ³¹for substituting group, R ³⁰with R ³¹also bond and form ring mutually.Nd is 0 or 1.In addition, in described formula, " t-Bu " represents tributyl.

The concrete example that below represents the azepine pyrroles methylene radical metal complex compounds that the general formula (II) that uses in the present invention is represented, but self-evident the present application is not limited to these concrete examples.In addition, " t-Bu " in following compound represents tributyl.

[changing 26]

[changing 27]

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[changing 31]

[changing 32]

[changing 33]

[changing 34]

[changing 35]

Painted curable adhensive compositions of the present invention can comprise only a kind of dye compound that is selected from described particular dye (A-1) and particular dye (A-2), also can comprise two or more.When comprising situation of more than two kinds, can comprise two or more particular dye (A-1), also can comprise two or more particular dye (A-2), and can comprise the both sides of particular dye (A-1) and particular dye (A-2).

As in the present invention, use be selected from the represented structure of (A-1) described general formula (I) be coordinated in two pyrroles's methylene radical metal complex compounds of forming on metal or metallic compound and (A-2) the represented structure of described general formula (II) be coordinated in the content of the dye compound of the azepine pyrroles methylene radical metal complex compounds forming on metal or metallic compound, for the total solids composition of painted curable adhensive compositions, in quality criteria preferably 0.2%～50%, more preferably 0.5%～30%.By being made as this scope, can obtain good depth of shade (being for example suitable for the depth of shade of liquid-crystal display), particularly by being made as below 30 quality %, favourable with regard to the patterning of pixel becomes good aspect.

In addition, the total solids composition of so-called painted curable adhensive compositions refers to the total total amount except the composition of desolventizing from all the components that forms painted curable adhensive compositions in the present invention.

(B) the represented porphyrin compound of following general formula (III)

Painted curable adhensive compositions of the present invention need to together contain the represented porphyrin compound of (B) following general formula (III) (following suitable being called " porphyrin compound " or " particular dye (B) ") with particular dye (A).

[changing 36]

In described general formula (III), Z ¹, Z ², Z ³and Z ⁴all represent N, or Z ¹and Z ³, and Z ²and Z ⁴any one group all represent N, remain one group and all represent C-R, R represents respectively hydrogen atom, alkyl or aryl independently.

A ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A ⁷and A ⁸represent independently of one another hydrogen atom, alkyl, thiazolinyl, aryl, alkoxyl group, alkylthio, aryloxy, arylthio, halogen atom, hydroxyl, alkoxy carbonyl, aryloxycarbonyl, amino, carbamyl, sulfamyl, acyl group, silicon alkoxyl group, cyano group, nitro or heterocyclic radical.A ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A ⁷and A ⁸also can further there is separately substituting group.

A ¹with A ², A ³with A ⁴, A ⁵with A ⁶, or A ⁷with A ⁸also can be separately bond and form ring structure mutually, but at least one group for not forming the aspect of ring structure.And, in forming the group of ring structure, preferably form alicyclic structure and do not form aromatic ring structure, more preferably A ¹with A ², A ³with A ⁴, A ⁵with A ⁶, and A ⁷with A ⁸any person all do not form the aspect of ring structure.

M represents divalent atoms metal or the divalent atoms metal being substituted or the divalent atomic group that comprises atoms metal.

Painted curable adhensive compositions of the present invention is by least a kind and particular dye (B) containing described particular dye (A-1) and particular dye (A-2), although reason is still uncertain, while forming the situation of colored filter using formed painted cured film, can effectively improve brightness and contrast gradient.

A in mutual-through type (III) ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A ⁷and A ⁸represented substituting group is illustrated.

A in general formula (III) ¹～A ⁸the alkyl that represents independently of any person can preferably enumerate the alkyl that carbon number is 1～48 straight chain, branched chain or ring-type, can more preferably enumerate carbon number and be the alkyl of 1～24 straight chain, branched chain or ring-type.Particularly such as enumerating methyl, ethyl, propyl group, sec.-propyl, butyl, tributyl, amyl group, hexyl, heptyl, octyl group, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norcamphyl, 1-adamantyl etc.It is 2～48 thiazolinyl that thiazolinyl can preferably be enumerated carbon number, can more preferably enumerate carbon number and be 2～18 thiazolinyl.Particularly such as enumerating vinyl, allyl group, 3-butene-1-Ji etc.It is 6～48 aryl that aryl can preferably be enumerated carbon number, can more preferably enumerate carbon number and be 6～24 aryl.Particularly such as enumerating phenyl, naphthyl etc.It is 1～48 alkoxyl group that alkoxyl group can preferably be enumerated carbon number, can more preferably enumerate carbon number and be 1～24 alkoxyl group.Particularly such as enumerating methoxyl group, oxyethyl group, 1-butoxy, 2-butoxy, isopropoxy, the 3rd butoxy, dodecyloxy etc.And, if cycloalkyloxy, such as enumerating cyclopentyloxy, cyclohexyloxy etc.It is 1～48 alkylthio that alkylthio can preferably be enumerated carbon number, can more preferably enumerate carbon number and be 1～24 alkylthio.Particularly such as enumerating methylthio group, ethylmercapto group, pungent sulfenyl, cyclohexyl sulfenyl etc.It is 6～48 aryloxy that aryloxy can preferably be enumerated carbon number, can more preferably enumerate carbon number and be 6～24 aryloxy.Particularly such as enumerating phenoxy group, 1-naphthyloxy etc.It is 6～48 arylthio that arylthio can preferably be enumerated carbon number, can more preferably enumerate carbon number and be 6～24 arylthio.Particularly such as enumerating thiophenyl etc.Halogen atom can preferably be enumerated fluorine atom, chlorine atom, bromine atoms, iodine atom.Can preferably enumerate fluorine atom, chlorine atom, bromine atoms.It is 2～48 alkoxy carbonyl that alkoxy carbonyl can preferably be enumerated carbon number, can more preferably enumerate carbon number and be 2～24 alkoxy carbonyl.Particularly for example can enumerate methoxycarbonyl, ethoxy carbonyl, octadecane oxygen base carbonyl, cyclohexyloxy carbonyl, 2,6-bis--tributyl-4-methyl cyclohexane oxygen base carbonyl etc.

It is 7～32 aryloxycarbonyl that aryloxycarbonyl can preferably be enumerated carbon number, can more preferably enumerate carbon number and be 7～24 aryloxycarbonyl.Particularly such as enumerating phenyloxycarbonyl etc.It is the amino below 32 that amino can preferably be enumerated carbon number, and can more preferably enumerate carbon number is the amino below 24.Particularly for example can enumerate amino, methylamino, N, N-dibutylamino, tetradecyl are amino, 2-ethylhexyl is amino, cyclohexyl is amino etc.It is 1～48 carbamyl that carbamyl can preferably be enumerated carbon number, can more preferably enumerate carbon number and be 1～24 carbamyl.Particularly for example can enumerate carbamyl, N; N-diethyl amino formyl radical, N-ethyl-N-octyl group carbamyl, N; N-dibutylamine formyl radical, N-propyl group carbamyl, N-phenylamino formyl radical, N-methyl-N-phenylamino formyl radical, N, N-dicyclohexyl carbamyl alkoxy carbonyl etc.It is the sulfamyl below 32 that sulfamyl can preferably be enumerated carbon number, and can more preferably enumerate carbon number is the sulfamyl below 24.Particularly for example can enumerate sulfamyl, N, N-dipropyl sulfamyl, N-ethyl-N-dodecyl sulfamyl, N-ethyl-N-phenyl sulfamoyl base, N-cyclohexyl sulfamyl etc.It is 1～48 acyl group that acyl group can preferably be enumerated carbon number, can more preferably enumerate carbon number and be 1～24 acyl group.Particularly such as enumerating formyl radical, ethanoyl, pivaloyl group, benzoyl, myristoyl, hexamethylene acyl group etc.It is 1～32 silicon alkoxyl group that silicon alkoxyl group can preferably be enumerated carbon number, can more preferably enumerate carbon number is 1～18 silicon alkoxyl group.Particularly such as enumerating TMS oxygen base, tributyl dimethyl-silicon alcoxyl base, diphenylmethylsilane oxygen base etc.It is 1～32 heterocyclic radical that heterocyclic radical can preferably be enumerated carbon number, can more preferably enumerate carbon number and be 1～18 heterocyclic radical.Particularly such as enumerating 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidyl, 1-pyridyl, 2-[4-morpholinodithio base, 1-imidazolyl, 1-pyrazolyl, benzotriazole-1-base etc.

These A ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A ⁷and A ⁸represented substituting group also can be further substituted separately.The substituting group that can import (can preferably be enumerated carbon number and is the alkyl of 1～48 straight chain, branched chain or ring-type, can more preferably enumerate carbon number and be the alkyl of 1～24 straight chain, branched chain or ring-type such as enumerating halogen atom (such as fluorine atom, chlorine atom, bromine atoms etc.), alkyl.Particularly such as enumerating methyl, ethyl, propyl group, sec.-propyl, butyl, tributyl, amyl group, hexyl, heptyl, octyl group, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norcamphyl, 1-adamantyl etc.), thiazolinyl (can preferably enumerate carbon number and be 2～48 thiazolinyl, can more preferably enumerate carbon number and be 2～18 thiazolinyl.Particularly such as enumerating vinyl, allyl group, 3-butene-1-Ji etc.), aryl (can preferably enumerate carbon number and be 6～48 aryl, can more preferably enumerate carbon number and be 6～24 aryl.Particularly such as enumerating phenyl, naphthyl etc.), heterocyclic radical (can preferably enumerate carbon number and be 1～32 heterocyclic radical, can more preferably enumerate carbon number and be 1～18 heterocyclic radical.Particularly such as enumerating 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidyl, 1-pyridyl, 2-[4-morpholinodithio base, 1-imidazolyl, 1-pyrazolyl, benzotriazole-1-base etc.), silylation (can preferably enumerate carbon number and be 3～38 silylation, can more preferably enumerate carbon number and be 3～18 silylation.Particularly such as enumerating TMS, triethyl silyl, tributyl silylation, tributyl dimethylsilyl, the 3rd hexyl dimethylsilyl etc.), hydroxyl, cyano group, nitro,

Alkoxyl group (can preferably be enumerated carbon number and is 1～48 alkoxyl group, can more preferably enumerate carbon number and be 1～24 alkoxyl group.Particularly such as enumerating the cycloalkyloxies such as methoxyl group, oxyethyl group, 1-butoxy, 2-butoxy, isopropoxy, the 3rd butoxy, dodecyloxy and cyclopentyloxy or cyclohexyloxy), aryloxy (can preferably enumerate carbon number and be 6～48 aryloxy, can more preferably enumerate carbon number and be 6～24 aryloxy.Particularly such as enumerating phenoxy group, 1-naphthyloxy etc.), heterocyclic oxy group (can preferably enumerate carbon number and be 1～32 heterocyclic oxy group, can more preferably enumerate carbon number and be 1～18 heterocyclic oxy group.Particularly such as enumerating 1-phenyltetrazole-5-oxygen base, 2-THP trtrahydropyranyl oxygen base etc.), silicon alkoxyl group (can preferably enumerate carbon number and be 1～32 silicon alkoxyl group, can more preferably enumerate carbon number and be 1～18 silicon alkoxyl group.Particularly such as enumerating TMS oxygen base, tributyl dimethyl-silicon alcoxyl base, diphenylmethylsilane oxygen base etc.), acyloxy (can preferably enumerate carbon number and be 2～48 acyloxy, can more preferably enumerate carbon number and be 2～24 acyloxy.Particularly such as enumerating acetoxyl group, pivaloyl oxygen base, benzoyloxy, dodecanoyl oxygen base etc.), alkoxyl group carbonyl oxygen base (can preferably enumerate carbon number and be 2～48 alkoxyl group carbonyl oxygen base, can more preferably enumerate carbon number and be 2～24 alkoxyl group carbonyl oxygen base.Particularly such as enumerating the cycloalkyloxy carbonyl oxygen bases such as oxyethyl group carbonyl oxygen base, the 3rd butoxy carbonyl oxy and cyclohexyloxy carbonyl oxygen), aryloxy carbonyl oxygen base (can preferably enumerate carbon number and be 7～32 aryloxy carbonyl oxygen base, can more preferably enumerate carbon number and be 7～24 aryloxy carbonyl oxygen base.Particularly such as enumerating phenoxy group carbonyl oxygen base etc.), carbamyl oxygen base (can preferably enumerate carbon number and be 1～48 carbamyl oxygen base, can more preferably enumerate carbon number and be 1～24 carbamyl oxygen base.Particularly for example can enumerate N; N-dimethylamino formyl radical oxygen base, N-butyl carbamyl oxygen base, N-phenylamino formyl radical oxygen base, N-ethyl-N-phenylamino formyl radical oxygen base etc.), sulfamyl oxygen base (can preferably enumerate carbon number and be 1～32 sulfamyl oxygen base, can more preferably enumerate carbon number and be 1～24 sulfamyl oxygen base.Particularly for example can enumerate N, N-diethyl amino alkylsulfonyl oxygen base, N-propyl group sulfamyl oxygen base etc.), alkylsulfonyloxy (can preferably be enumerated carbon number and be 1～38 alkylsulfonyloxy, can more preferably enumerate carbon number and be 1～24 alkylsulfonyloxy, it is for example particularly sulfonyloxy methyl oxygen base, hexadecyl sulfonyloxy, cyclohexyl sulfonyloxy etc.), aryl-sulfonyl oxygen (can preferably be enumerated carbon number and be 6～32 aryl-sulfonyl oxygen, can more preferably enumerate carbon number and be 6～24 aryl-sulfonyl oxygen, particularly such as being phenyl sulfonyloxy etc.), acyl group (the acyl group that preferably carbon number is 1～48, the acyl group that more preferably carbon number is 1～24, for example can enumerate formyl radical, ethanoyl, pivaloyl group, benzoyl, myristoyl, hexamethylene acyl group), alkoxy carbonyl (can preferably be enumerated carbon number and be 2～48 alkoxy carbonyl, can more preferably enumerate carbon number and be 2～24 alkoxy carbonyl.Particularly for example can enumerate methoxycarbonyl, ethoxy carbonyl, octadecane oxygen base carbonyl, cyclohexyloxy carbonyl, 2,6-bis--tributyl-4-methyl cyclohexane oxygen base carbonyls etc.), aryloxycarbonyl (can preferably be enumerated carbon number and is 7～32 aryloxycarbonyl, can more preferably enumerate carbon number and be 7～24 aryloxycarbonyl.Particularly such as enumerating phenyloxycarbonyl etc.),

Carbamyl (can preferably be enumerated carbon number and is 1～48 carbamyl, can more preferably enumerate carbon number and be 1～24 carbamyl.Particularly for example can enumerate carbamyl, N; N-diethyl amino formyl radical, N-ethyl-N-octyl group carbamyl, N; N-dibutylamine formyl radical, N-propyl group carbamyl, N-phenylamino formyl radical, N-methyl-N-phenylamino formyl radical, N; it is N-dicyclohexyl carbamyls etc.), amino that (can preferably enumerate carbon number is the amino below 32, and can more preferably enumerate carbon number is the amino below 24.Particularly for example can enumerate amino, methylamino, N, N-dibutylamino, tetradecyl are amino, 2-ethylhexyl is amino, cyclohexyl is amino etc.), anilino (can preferably enumerate carbon number and be 6～32 anilino, can more preferably enumerate 6～24 anilino.Particularly such as enumerating anilino, methylphenylamine base etc.), heterocyclic amino group (can preferably enumerate carbon number and be 1～32 heterocyclic amino group, can more preferably enumerate 1～18 heterocyclic amino group.Particularly such as enumerating 4-pyridinylamino etc.), carboxamide groups (can preferably enumerate carbon number and be 2～48 carboxamide groups, can more preferably enumerate 2～24 carboxamide groups.Particularly such as enumerating acetamido, benzoylamino, myristoyl amido, pivaloyl group amide group, Cyclohexamide base etc.), urea groups (can preferably enumerate carbon number and be 1～32 urea groups, can more preferably enumerate carbon number and be 1～24 urea groups.Particularly for example can enumerate urea groups, N, N-dimethyl urea groups, N-phenyl urea groups etc.), (can preferably enumerate carbon number is the imide below 36 to imide, and can more preferably enumerate carbon number is the imide below 24.Particularly such as enumerating N-succinimido, N phlhalimide base etc.), alkoxycarbonyl amino (can preferably enumerate carbon number and be 2～48 alkoxycarbonyl amino, can more preferably enumerate carbon number and be 2～24 alkoxycarbonyl amino.Particularly such as enumerating methoxycarbonyl amino, ethoxy carbonyl amino, the 3rd butoxy carbonyl amino, octadecane oxygen base carbonylamino, cyclohexyloxy carbonyl amino etc.), aryloxycarbonyl is amino (can preferably enumerate carbon number and be 7～32 aryloxycarbonyl amino, can more preferably enumerate carbon number and be 7～24 aryloxycarbonyl amino.Particularly such as enumerating phenyloxycarbonyl amino etc.), sulfoamido (can preferably enumerate carbon number and be 1～48 sulfoamido, can more preferably enumerate carbon number and be 1～24 sulfoamido.Particularly such as enumerating sulfonyloxy methyl amido, butyl sulfonamide base, benzene sulfonamido, hexadecyl sulfoamido, cyclohexyl sulfonamide base etc.), sulphonamide amido (can preferably enumerate carbon number and be 1～48 sulphonamide amido, can more preferably enumerate carbon number and be 1～24 sulphonamide amido.Particularly for example can enumerate N, N-dipropyl sulphonamide amido, N-ethyl-N-dodecyl sulphonamide amido etc.), azo-group (can preferably enumerate carbon number and be 1～32 azo-group, can more preferably enumerate carbon number and be 1～24 azo-group.Particularly such as enumerating phenylazo, 3-pyrazolyl azo-group etc.),

Alkylthio (can preferably be enumerated carbon number and is 1～48 alkylthio, can more preferably enumerate carbon number and be 1～24 alkylthio.Particularly such as enumerating methylthio group, ethylmercapto group, pungent sulfenyl, hexamethylene sulfenyl etc.), arylthio (can preferably enumerate carbon number and be 6～48 arylthio, can more preferably enumerate carbon number and be 6～24 arylthio.Particularly such as enumerating thiophenyl etc.), heterocycle sulfenyl (can preferably enumerate carbon number and be 1～32 heterocycle sulfenyl, can more preferably enumerate carbon number and be 1～18 heterocycle sulfenyl.Particularly such as enumerating 2-[4-morpholinodithio base sulfenyl, 2-pyridyl sulfenyl, 1-phenyltetrazole base sulfenyl etc.), alkyl sulphinyl (can preferably enumerate carbon number and be 1～32 alkyl sulphinyl, can more preferably enumerate carbon number and be 1～24 alkyl sulphinyl.Particularly such as enumerating dodecyl sulfinyl etc.), aryl sulfonyl kia (can preferably enumerate carbon number and be 6～32 aryl sulfonyl kia, can more preferably enumerate carbon number and be 6～24 aryl sulfonyl kia.Particularly such as enumerating phenyl sulfinyl etc.), alkyl sulphonyl (can preferably enumerate carbon number and be 1～48 alkyl sulphonyl, can more preferably enumerate carbon number and be 1～24 alkyl sulphonyl.Particularly such as enumerating methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, butyl alkylsulfonyl, sec.-propyl alkylsulfonyl, 2-ethylhexyl alkylsulfonyl, hexadecyl alkylsulfonyl, octyl group alkylsulfonyl, cyclohexyl alkylsulfonyl etc.), aryl sulfonyl (can preferably enumerate carbon number and be 6～48 aryl sulfonyl, can more preferably enumerate carbon number and be 6～24 aryl sulfonyl.Particularly such as enumerating phenyl sulfonyl, 1-naphthyl alkylsulfonyl etc.), (can preferably enumerate carbon number is the sulfamyl below 32 to sulfamyl, and can more preferably enumerate carbon number is the nitrogen alkylsulfonyl below 24.Particularly for example can enumerate sulfamyl, N; N-dipropyl sulfamyl, N-ethyl-N-dodecyl sulfamyl, N-ethyl-N-phenyl sulfamoyl base, N-cyclohexyl sulfamyl etc.), sulfo group, phosphono (can preferably enumerate carbon number and be 1～32 phosphono, can more preferably enumerate carbon number and be 1～24 phosphono.Particularly such as enumerating phenoxy group phosphono, octyloxy phosphono, Phenylphosphine acyl group etc.), phosphono is amino (can preferably enumerate carbon number and be 1～32 phosphono amino, can more preferably enumerate carbon number and be 1～24 phosphono amino.Particularly such as enumerating diethoxy phosphonium mesitoyl base amino, two octyloxy phosphono amino etc.).

Z ¹, Z ², Z ³or Z ⁴in represented C-R, the alkyl that R is represented and aryl and as A ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A ⁷and A ⁸represented substituting group and the alkyl and the aryl synonym that illustrate.

The represented atoms metal of M preferably represents Al, Si, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Mo, Ru, Rh, Pd, In, Sn, Pt, Pb, Mg, preferred Al, V, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, the Mg of meaning, further preferred Al, V, Mn, Fe, Co, Ni, Cu, Zn, the Mg of meaning, particularly preferred V, Co, Ni, Cu, the Zn of meaning.

The concrete example during situation of the divalent atoms metal being substituted that M is represented or the divalent atomic group that comprises atoms metal can be enumerated metal halide atom (for example Al-F, Al-Cl, Al-Br, AI-I, In-F, In-Cl, Fe-Cl, In-Br, In-I, SiF ₂, SiCl ₂, SiBr ₂, SiI ₂, TiF ₂, TiCl ₂, TiBr ₂, TiI ₂deng), (B is the substituting groups such as alkyl, aryl, naphthyl, alkoxyl group, hydroxyl to M-B, is for example particularly Si (CH ₃) ₃, Si (C ₂h ₅) ₃, Al-C ₆h ₅, In-C ₆h ₅, Al (OH), Mn (OH), Si (OH) ₂, Zr (OH) ₂, Al-OCH ₃, Al-O (C ₆h ₅) etc.), metal oxide (such as TiO, MnO, VO etc.).

The porphyrin compound using in the present invention is Z preferably ¹, Z ², Z ³and Z ⁴all represent the assorted porphyrin compound of tetrahydrochysene of N, can preferably enumerate the represented compound of general formula (III-2).

[changing 37]

In described general formula (III-2), A ¹, A ², A ³, A4, A ⁵, A ⁶, A ⁷, A ⁸and the A in M and general formula (III) ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A ⁷, A ⁸and M synonym separately.

Maximum value as the absorption spectrum of the represented compound of the general formula using in the present invention (III), viewpoint from the transmissivity of formed colored filter is considered, 550nm to 650nm preferably, more preferably 570nn to 630nm, particularly preferably is 570nm to 610nm.

The concrete example that below represents the particular dye (B) in the present invention.But be not restricted in the present invention these concrete examples.

In addition, isomer about following illustrated compound, and unreceipted description, but make in fact as described below dicyano vinyl compound and reacting metal salt and make its cyclisation, therefore as shown in following flow process, in each exemplary compounds, there are 4 kinds of isomer, become the mixture of these isomer.

And; in concrete example; R represents hydrogen atom, alkyl, thiazolinyl, aryl, alkoxyl group, alkylthio, aryloxy, arylthio, halogen atom, hydroxyl, alkoxy carbonyl, aryloxycarbonyl, amino, carbamyl, sulfamyl, acyl group, silicon alkoxyl group, cyano group, nitro or heterocyclic radical, and D1 is illustrated in the bond position on porphyrin skeleton.

And in following concrete example, " t-Bu " represents tributyl, " Me " represents methyl, and " Et " represents ethyl, and " Pr " represents propyl group, and " Pe " represents phenyl.

[changing 38]

X in described flow process ¹, X ², X ³, X ⁴, Y ¹, Y ², Y ³, and Y ⁴respectively with general formula (III) in A ¹to A ⁸in illustrated group synonym, at X ¹with Y ¹, X ²with Y ², X ³with Y ³, X ⁴with Y ⁴during different situation, can form above-mentioned 4 kinds of isomer.

[changing 39]

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[changing 43]

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[changing 45]

[changing 46]

[changing 47]

[changing 48]

[changing 49]

[changing 50]

[changing 51]

[changing 52]

[changing 53]

Content as the represented porphyrin compound of described (B) general formula (III), more than preferably comprising 0.1 quality % for the total amount of coloring compound contained in painted curable adhensive compositions, more preferably more than 0.5 quality %, more than particularly preferably being 1 quality %.Even porphyrin compound trace of the present invention is used, also can when making colored filter, obtain good colourity, contrast gradient, so cost effect is excellent.The users' such as the requirement of colourity when if the upper limit of the concentration of using is applicable to making colored filter or resist performance demander, be not particularly limited, if the balance of consideration and described (A) two pyrroles's methylene radical metal complex compounds and azepine pyrroles methylene radical metal complex compounds is preferably below 50 quality % for the total amount of coloring compound.

Other dyestuffs

In painted curable adhensive compositions of the present invention, also can comprise described two pyrroles's methylene radical metal complex compounds and azepine pyrroles methylene radical metal complex compounds known dyestuff in addition.

In painted hardening constituent of the present invention other dyestuffs that also can comprise be pyrazoles azo system, anilino azo system, triphenyl methane system, anthraquinone system, anthrapyridone system, α-tolylene system, oxygen be, Pyrazolotriazole azo system, pyridone azo system, cyanine system, thiodiphenylamine system, pyrrolo-pyrazoles methyne azo system, dibenzo piperazine mutter be, the dyestuff such as side sour cyanines system, phthalocyanine system, chromene system, indigo system.

As in painted curable adhensive compositions of the present invention the concrete example of other dyestuffs that also can comprise, be for example the clear 64-90403 communique of Japanese Patent Laid-Open, the clear 64-91102 communique of Japanese Patent Laid-Open, Japanese patent laid-open 1-94301 communique, Japanese patent laid-open 6-11614 communique, Japanese Patent spy steps on No. 2592207, United States Patent (USP) the 4th, 808, No. 501 specification sheetss, United States Patent (USP) the 5th, 667, No. 920 specification sheetss, United States Patent (USP) the 5th, 059, No. 500 specification sheets, Japanese patent laid-open 5-333207 communique, Japanese patent laid-open 6-35183 communique, Japanese patent laid-open 6-51115 communique, Japanese patent laid-open 6-194828 communique, Japanese patent laid-open 8-211599 communique, Japanese patent laid-open 4-249549 communique, Japanese patent laid-open 10-123316 communique, Japanese patent laid-open 11-302283 communique, Japanese patent laid-open 7-286107 communique, Japanese Patent Laid-Open 2001-4823 communique, Japanese patent laid-open 8-15522 communique, Japanese patent laid-open 8-29771 communique, Japanese patent laid-open 8-146215 communique, Japanese patent laid-open 11-343437 communique, Japanese patent laid-open 8-62416 communique, Japanese Patent Laid-Open 2002-14220 communique, Japanese Patent Laid-Open 2002-14221 communique, Japanese Patent Laid-Open 2002-14222 communique, Japanese Patent Laid-Open 2002-14223 communique, Japanese patent laid-open 8-302224 communique, Japanese patent laid-open 8-73758 communique, Japanese patent laid-open 8-179120 communique, Japanese patent laid-open 8-151531 communique, the dyestuff of recording in Japanese patent laid-open 6-230210 communique etc.

(pigment)

In painted curable adhensive compositions of the present invention, also can and use pigment as coloring compound.

Pigment optimization be that average primary particle diameter is that 10nm is above, the pigment below 30nm.If above-mentioned aspect, acquisition can form the painted curable adhensive compositions of the colored filter of brightness and contrast gradient excellence.

Pigment can be used known various mineral dyes or pigment dyestuff in the past, but considers from the viewpoint of reliability, preferably uses pigment dyestuff.In the present invention, pigment dyestuff for example can be enumerated the pigment dyestuff of recording in the paragraph [0093] of Japanese Patent Laid-Open 2009-256572 communique.

And particularly pigment shown below is suitable with regard to the viewpoint of colorrendering quality, but be not limited in the present invention these pigment.These pigment dyestuffs can be used alone, or also can combine in order to improve purity of color multiple use.

C.I. Pigment red 177,224,242,254,255,264

C.I. pigment yellow 13 8,139,150,180,185

C.I. pigment orange 36,38,71,

C.I. pigment Green 7,36,58,

C.I. pigment Blue 15: 6,

C.I. pigment Violet 23

When using the situation of pigment, as the content of the pigment in painted curable adhensive compositions of the present invention, for the total solids composition of said composition, preferably 0.5 quality %～50 quality %, more preferably 1 quality %～30 quality %.If the content of pigment is in described scope, can effectively guarantee excellent colour characteristics.

As two pyrroles's methylene radical metal complex compounds contained in painted curable adhensive compositions of the present invention, azepine pyrroles methylene radical metal complex compounds, and the total content of porphyrin compound, the all coloring compounds that comprise with respect to painted curable adhensive compositions (that is comprise two pyrroles's methylene radical metal complex compounds, azepine pyrroles methylene radical metal complex compounds, and porphyrin compound, and other pigment or dyestuff while using the situation of other pigment or dyestuff), 1 quality %～90 quality % preferably, 10 quality %～70 quality % more preferably.

(C) polymerizable compound

Painted curable adhensive compositions of the present invention preferably contains at least a kind of polymerizable compound.

If polymerizable compound for example has the polymerizable compound of at least 1 ethene unsaturated double-bond, there is no particular restriction, can in the composition of the painted curable adhensive compositions of known formation, select and use.For example can enumerate the composition of recording in paragraph numbering [0027]～paragraph numbering [0053] of the composition recorded in paragraph numbering [0010]～paragraph numbering [0020] of Japanese Patent Laid-Open 2006-23696 communique or Japanese Patent Laid-Open 2006-64921 communique.

And, addition has the polymerizable compound of the carbamate that utilizes the addition reaction of isocyanic ester and hydroxyl and manufacture also suitable, the clear 51-37193 communique of Japanese Patent Laid-Open, Japanese Patent JP 2-32293 communique, the propenoic methyl carbamate class of recording in Japanese Patent JP 2-16765 communique or Japanese Patent examined patent publication 58-49860 communique, Japanese Patent examined patent publication 56-17654 communique, Japanese Patent examined patent publication 62-39417 communique, the carbamate compounds class with oxyethane skeleton of recording in Japanese Patent examined patent publication 62-39418 communique is also suitable.

Other examples can be enumerated polyfunctional acrylate or the methacrylic esters such as Epoxy Acrylates that polyester acrylate class, the epoxy resin recorded in each communique of the clear 48-64183 communique of Japanese Patent Laid-Open, Japanese Patent examined patent publication 49-43191 communique, Japanese Patent examined patent publication 52-30490 communique react with (methyl) vinylformic acid and obtain.Also can use in addition Japan then in association's magazine the 20th volume, No.7, the 300th page～the 308th page (1984) as photo-hardening monomer and oligomer and the person of introduction.

The concrete example of polymerizable compound can be enumerated tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, three ((methyl) acryloxy ethyl) isocyanuric acid ester, tetramethylolmethane four (methyl) acrylate oxyethane (EO) modifier, Dipentaerythritol six (methyl) acrylate EO modifier etc., and as the NK Ester A-TMMT of commercially available product, NK Ester A-TMM-3, NK Oligo UA-32P, NK Oligo UA-7200 (is trade(brand)name above, Xin Zhong village chemical industry limited-liability company manufactures), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronix M-402, TO _-1382, TO-2349 (being that the synthetic limited-liability company in trade(brand)name, East Asia manufactures above), V#802 (trade(brand)name, Osaka organic chemistry Industries, Inc manufacture) are as preference.

These polymerizable compounds can be used alone, or two or more are used and use.

While using the situation of polymerizable compound in painted curable adhensive compositions, the content of the polymerizable compound in total solids composition (being total content during situation of more than two kinds) is 10 quality %～80 quality % preferably, more preferably 15 quality %～75 quality %, particularly preferably are 20 quality %～60 quality %.

(D) Photoepolymerizationinitiater initiater

Painted curable adhensive compositions of the present invention preferably contains at least a kind of Photoepolymerizationinitiater initiater.

If Photoepolymerizationinitiater initiater makes described polymerizable compound polymerization person, there is no particular restriction, preferably from viewpoints such as characteristic, efficiency of initiation, absorbing wavelength, acquired, costs, selects.

Photoepolymerizationinitiater initiater is the sensitization by the light of exposure, causes, promotes the compound of the polymerization of polymerizable compound.It is actinic rays more than 300nm that Photoepolymerizationinitiater initiater is preferably responded to wavelength, causes, promotes the compound of the polymerization of polymerizable compound.And, about directly not responding to wavelength, be photoactinic Photoepolymerizationinitiater initiater more than 300nm, also can preferably use with sensitizing agent combination.

Photoepolymerizationinitiater initiater particularly for example can be enumerated oxime ester compound, organic halogenation compound, oxadiazole compound, carbonyl compound, ketal compound, st-yrax compound, acridine compounds, organo-peroxide, azo-compound, coumarin compound, trinitride, metallocene compound, six aryl united imidazoles, organic boronic compound, disulfonic acid compound, salt compound, acylphosphanes (oxide compound), benzophenone cpd, acetophenone compound and derivative etc. thereof.

In these compounds, from the aspect of light sensitivity, consider, preferably oxime ester compound, six aryl united imidazoles.

Oxime ester compound can be used Japanese Patent Laid-Open 2000-80068 communique, Japanese Patent Laid-Open 2001-233842 communique, the special table of Japanese Patent 2004-534797 communique, No. 2005/080337th, International Publication, No. 2006/018973 specification sheets of International Publication, Japanese Patent Laid-Open 2007-210991 communique, Japanese Patent Laid-Open 2007-231000 communique, Japanese Patent Laid-Open 2007-269779 communique, Japanese Patent Laid-Open 2009-191061 communique, the compound of recording in No. 2009/131189 specification sheets of International Publication.

Concrete example can be enumerated 2-(O-benzoyl oxime)-1-[4-(thiophenyl) phenyl]-1,2-dimethyl diketone, 2-(O-benzoyl oxime)-1-[4-(thiophenyl) phenyl]-1,2-diacetylmethane, 2-(O-benzoyl oxime)-1-[4-(thiophenyl) phenyl]-1,2-hexanedione, 2-(O-benzoyl oxime)-1-[4-(thiophenyl) phenyl]-1,2-heptadione, 2-(O-benzoyl oxime)-1-[4-(thiophenyl) phenyl]-1,2-acetyl caproyl, 2-(O-benzoyl oxime)-1-[4-(methylbenzene sulfenyl) phenyl]-1,2-dimethyl diketone, 2-(O-benzoyl oxime)-1-[4-(ethylbenzene sulfenyl) phenyl]-1,2-dimethyl diketone, 2-(O-benzoyl oxime)-1-[4-(butylbenzene sulfenyl) phenyl]-1,2-dimethyl diketone, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone, 1-(O-acetyl oxime)-1-[9-methyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone, 1-(O-acetyl oxime)-1-[9-propyl group-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-ethylamino benzonitrile acyl group)-9H-carbazole-3-yl] ethyl ketone, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-butylbenzene formyl radical)-9H-carbazole-3-yl] ethyl ketone etc.But be not limited to these compounds.

And in the present invention, the painted viewpoint when light sensitivity, ageing stability, later stage heating considers, as for the oxime ester compound as Photoepolymerizationinitiater initiater, the represented compound of following general formula (A) is also suitable.

[changing 54]

In general formula (A), X ¹, X ², and X ³represent independently respectively hydrogen atom, halogen atom or alkyl, R ¹expression-R ,-OR ,-COR ,-SR ,-CONRR ' or-CN, R ²and R ³respectively independently expression-R ,-OR ,-COR ,-SR or-NRR '.R and R ' represent respectively alkyl, aryl, aralkyl or heterocyclic radical independently.These groups can selected free halogen atom and 1 above replacement of the group that forms of heterocyclic radical, 1 of the carbon atom of the formation alkyl chain in this alkyl and aralkyl also can be replaced into unsaturated link(age), ehter bond or ester bond above, and R and R ' be bond and form ring mutually also.

In general formula (A), X ¹, X ², or X ³halogen atom while representing the situation of halogen atom can be enumerated fluorine, chlorine, bromine, iodine, X ¹, X ², or X ³alkyl while representing the situation of alkyl for example can be enumerated methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the second butyl, tributyl, amyl group, isopentyl, the 3rd amyl group, hexyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, trioctylphosphine, nonyl, different nonyl, decyl, isodecyl, vinyl, allyl group, butenyl, ethynyl, proyl, methoxy ethyl, ethoxyethyl group, propoxy-ethyl, methoxyethoxyethyl, ethoxy ethoxy ethyl, propoxy-ethoxyethyl group, methoxy-propyl, single methyl fluoride, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, 2-(benzoxazoles-2 '-Ji, ) vinyl etc.

X preferably wherein ¹, X ², and X ³all represent hydrogen atom, or X ¹represent alkyl, X ²and X ³all represent hydrogen atom.

In general formula (A), the represented alkyl of R or R ' for example can be enumerated methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the second butyl, tributyl, amyl group, isopentyl, the 3rd amyl group, hexyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, trioctylphosphine, nonyl, different nonyl, decyl, isodecyl, vinyl, allyl group, butenyl, ethynyl, proyl, methoxy ethyl, ethoxyethyl group, propoxy-ethyl, methoxyethoxyethyl, ethoxy ethoxy ethyl, propoxy-ethoxyethyl group, methoxy-propyl, single methyl fluoride, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl, 2-(benzoxazoles-2 '-yl) vinyl etc.

The represented aryl of R or R ' is such as enumerating phenyl, tolyl, xylyl, ethylphenyl, chloro-phenyl-, naphthyl, anthryl, phenanthryl etc.

The represented aralkyl of R or R ' is such as enumerating benzyl, chlorobenzyl, α-methylbenzyl, alpha, alpha-dimethylbenzyl, phenylethyl, phenyl vinyl etc.

The represented heterocyclic radical of R or R ' is such as enumerating pyridyl, pyrimidyl, furyl, thienyl etc.

And, R and R ' mutually bond and the ring that forms such as enumerating piperidine ring, morpholine ring etc.

The R that comprises above-mentioned R and R ' and form ²and R ³respectively independent for methyl, hexyl, cyclohexyl ,-S-Ph ,-S-Ph-C1 and-S-Ph-Br is particularly preferred sample state.

In Photoepolymerizationinitiater initiater, in general formula (A), X ¹, X ²and X ³the person that is hydrogen atom; R ¹for alkyl, particularly methyl person; R ²for alkyl, particularly methyl person; R ³for alkyl, particularly ethyl person suitable especially as Photoepolymerizationinitiater initiater.

Therefore, the preferred concrete example of the represented Photoepolymerizationinitiater initiater of above-mentioned general formula (A) can be enumerated following illustrated compd A～compound F 17-hydroxy-corticosterone.But the present invention is not subject to any restriction of following compound.

[changing 55]

[changing 56]

[changing 57]

The represented Photoepolymerizationinitiater initiater of general formula (A) for example can synthesize by the method for recording in Japanese Patent Laid-Open 2005-220097 communique.

In the present invention the represented compound of general formula (A) of suitable use in the wavelength region may of 250nm～500nm, there is absorbing wavelength.Can more preferably be set forth in the compound in the wavelength region may of 300nm～380nm with absorbing wavelength.Particularly preferably be the high compound of absorbancy of 308nm and 355nm.

And in the present invention, the painted viewpoint when light sensitivity, ageing stability, later stage heating considers, as for the oxime ester compound as Photoepolymerizationinitiater initiater, the represented compound of following general formula (B) is also suitable.

[changing 58]

In general formula (B), R ²²represent 1 valency substituting group.A ²²represent divalent concatenating group, Ar represents aryl.N is 0～5 integer.X ²²represent 1 valency substituting group, during the situation of the integer that is 2～4 at n, multiple X ²²can be identical also can be different.

Described R ²²1 represented valency substituting group is 1 valency nonmetallic atom group shown below preferably.

That is, R ²²the nonmetallic atom group of 1 represented valency can be enumerated also can have substituent alkyl, also can have substituent aryl, also can have substituent alkyl sulphonyl, also can have substituent aryl sulfonyl, also can have substituent acyl group, also can have substituent heterocyclic radical etc.

Also can there is the substituent alkyl alkyl that preferably carbon number is 1～30, such as enumerating methyl, ethyl, propyl group, butyl, hexyl, cyclopentyl, cyclohexyl, trifluoromethyl etc.

Also can there is the substituent aryl aryl that preferably carbon number is 6～30, such as enumerating phenyl, xenyl, 1-naphthyl, 2-naphthyl etc.

Also can there is the substituent alkyl sulphonyl alkyl sulphonyl that preferably carbon number is 1～20, such as enumerating methyl sulphonyl, ethylsulfonyl etc.

Also can there is the substituent aryl sulfonyl aryl sulfonyl that preferably carbon number is 6～30, such as enumerating phenyl sulfonyl, 1-naphthyl alkylsulfonyl etc.

Also can there is the substituent acyl group acyl group that preferably carbon number is 2～20, for example can enumerate ethanoyl, propionyl, butyryl radicals, trifluoromethyl carbonyl, pentanoyl, benzoyl, 1-naphthoyl, 2-naphthoyl, 4-methyl sulfenyl benzoyl, 4-phenyl sulfenyl benzoyl, 4-dimethylamino benzoyl, 4-diethylamino benzoyl, 2-chlorobenzene formacyl, 2-methyl benzoyl, 2-anisoyl, 2-butyl phenyl ether formyl radical, 3-chlorobenzene formacyl, 3-trifluoromethyl benzoyl, 3-cyano group benzoyl, 3-nitro benzoyl, 4-fluoro benzoyl, 4-cyano group benzoyl, 4-anisoyl etc.

Also can there is aromatic series or aliphatic heterocycle that substituent heterocyclic radical preferably comprises nitrogen-atoms, Sauerstoffatom, sulphur atom, phosphorus atom.Such as enumerating thienyl, furyl, pyranyl etc.

As described R ²², with regard to the aspect of ISO, be more preferably unsubstituted or there is substituent acyl group, be particularly preferably unsubstituted or there is substituent ethanoyl, propionyl, benzoyl, toluyl.

Described R ²²substituting group while having substituent situation for example can be enumerated the represented group of following structural formula.Wherein preferably (d-1), (d-4) and any person (d-5).

[changing 59]

Described A ²²represented divalent concatenating group can be enumerated also can be had substituent carbon number and be 1～12 alkylidene group, also can have substituent cyclohexylidene, also can have substituent alkynylene.

Can be directed into the substituting group of these bases such as enumerating the halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom, the alkoxyl groups such as methoxyl group, oxyethyl group, the 3rd butoxy, phenoxy group, to aryloxy such as tolyloxys, the alkoxy carbonyls such as methoxycarbonyl, butoxy carbonyl, phenyloxycarbonyl etc.

Wherein, as described A ²²from improving light sensitivity, suppress heating and pass through in time caused painted aspect and consider, the alkylidene group being preferably unsubstituted, the alkylidene group for example, replacing through alkyl (methyl, ethyl, tributyl, dodecyl), the alkylidene group for example, replacing through thiazolinyl (vinyl, allyl group), the alkylidene group for example, replacing through aryl (phenyl, p-methylphenyl, xylyl, cumyl, naphthyl, anthryl, phenanthryl, styryl).

The aryl aryl that preferably carbon number is 6～30 that described Ar is represented, and can there is substituting group.

Ar particularly can enumerate phenyl, xenyl, 1-naphthyl, 2-naphthyl, terphenylyl, connection tetraphenyl, o-tolyl, a tolyl and p-methylphenyl, xylyl, adjacent cumyl, a cumyl and to cumyl, mesityl etc.Wherein, with regard to causing painted aspect through in raising light sensitivity, inhibition heating in time, the phenyl that is preferably substituted or is unsubstituted.

When above-mentioned phenyl has substituent situation, this substituting group is such as enumerating the halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom; The alkoxyl groups such as methoxyl group, oxyethyl group, the 3rd butoxy; Phenoxy group, to aryloxy such as tolyloxys; The alkoxy carbonyls such as methoxycarbonyl, butoxy carbonyl, phenyloxycarbonyl; The acyloxy such as acetoxyl group, propionyloxy, benzoyloxy; The acyl groups such as ethanoyl, benzoyl, isobutyryl, acryl, methacryloyl, methoxalyl; The alkylaminos such as methylamino, cyclohexyl amino; The dialkyl amidos such as dimethylamino, diethylamino, N-morpholinyl, N-piperidyl; Phenyl amino; The alkyl such as methyl, ethyl, tributyl, dodecyl; Hydroxyl, carboxyl etc.

In general formula (B), if be structure shown below by the structure of the S of described Ar and adjacency formed " SAr ", preferred with regard to the aspect of light sensitivity.

[changing 60]

Described X ²²1 represented valency substituting group can be enumerated also can have substituent alkyl, also can have substituent aryl, also can have substituent thiazolinyl, also can have substituent alkynyl, also can have substituent alkoxyl group, also can have substituent aryloxy, also can have substituent alkylthio oxygen base, also can have substituent arylthio oxygen base, halogen atom etc.

Also can there is the substituent alkyl alkyl that preferably carbon number is 1～30, such as enumerating methyl, ethyl, propyl group, butyl, hexyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, phenacyl etc.

Also can there is the substituent aryl aryl that preferably carbon number is 6～30, such as enumerating phenyl, xenyl, 1-naphthyl, 2-naphthyl, terphenylyl, connection tetraphenyl, o-tolyl, a tolyl and p-methylphenyl, xylyl etc.

Also can there is the substituent thiazolinyl thiazolinyl that preferably carbon number is 2～10, such as enumerating vinyl, allyl group, styryl etc.

Also can there is the substituent alkynyl alkynyl that preferably carbon number is 2～10, such as enumerating ethynyl, proyl, propargyl etc.

Also can there is the substituent alkoxyl group alkoxyl group that preferably carbon number is 1～30, such as enumerating methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, benzyloxy etc.

Also can there is the substituent aryloxy aryloxy that preferably carbon number is 6～30, such as enumerating phenoxy group, 1-naphthyloxy, 2-naphthyloxy, 2-chlorophenoxy, 2-methylphenoxy, 2-methoxyphenoxy etc.

Also can there is the substituent alkylthio oxygen base sulfenyl alkoxyl group that preferably carbon number is 1～30, such as enumerating methylthio group oxygen base, ethylmercapto group oxygen base, rosickyite base oxygen base, isopropyl sulfenyl oxygen base, butylthio oxygen base, isobutyl sulfenyl oxygen base, the second butylthio oxygen base, the 3rd butylthio oxygen base, penta sulfenyl oxygen base, isoamyl sulfenyl oxygen base, own sulfenyl oxygen base, heptan sulfenyl oxygen base, pungent sulfenyl oxygen base, 2-ethyl hexyl sulfenyl oxygen base, last of the ten Heavenly stems sulfenyl oxygen base, dodecane sulfenyl oxygen base, octadecane sulfenyl oxygen base, benzylthio-oxygen base etc.

Also can there is the substituent arylthio oxygen base arylthio oxygen base that preferably carbon number is 6～30, for example have thiophenyl oxygen base, 1-naphthalene sulfenyl oxygen base, 2-naphthalene sulfenyl oxygen base, 2-chlorobenzene sulfenyl oxygen base, 2-methylbenzene sulfenyl oxygen base, 2-anisole sulfenyl oxygen base, 2-butyl phenyl ether sulfenyl oxygen base, 3-chlorobenzene sulfenyl oxygen base, 3-trifluoromethyl thiophenyl oxygen base, 3-cyano group thiophenyl oxygen base, 3-nitrophenylsulfenyl oxygen base, 4-fluorobenzene sulfenyl oxygen base, 4-cyano group thiophenyl oxygen base, 4-anisole sulfenyl oxygen base, 4-dimethylamino thiophenyl oxygen base, 4-methyl sulfenyl thiophenyl oxygen base, 4-phenyl sulfenyl thiophenyl oxygen base etc.

Halogen atom has fluorine atom, chlorine atom, bromine atoms, iodine atom etc.

Also can there is substituent halogenated alkyl and can enumerate single methyl fluoride, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, single brooethyl, two brooethyls, trisbromomethyl etc.

On N, also can there is substituent amide group and can enumerate N, N-dimethylformamide base, N, N-diethylamide base etc.

In these substituting groups, as X ²², the aspect that assimilated efficiency from solvent solubility and long wavelength region improves is considered, preferably also can there is substituent alkyl, also can there is substituent aryl, also can there is substituent thiazolinyl, also can there is substituent alkynyl, also can there is substituent alkoxyl group, also can there is substituent aryloxy, also can there is substituent alkylthio oxygen base, also can there is substituent arylthio oxygen base, also can there is substituent halogenated alkyl, also can there is substituent amino, or also can there is substituent amide group on N, wherein more preferably also can there is substituent alkyl.

And the n in general formula (B) represents 0～5 integer, the consideration of the viewpoint of certainly synthetic easiness, preferably 0～3 integer, more preferably 0～2 integer.

In general formula (B), there are a plurality of X ²²situation time, a plurality of X ²²can be identical also can be different.

The concrete example that below represents the oxime Photoepolymerizationinitiater initiater that above-mentioned general formula (B) is represented.

[changing 61]

[changing 62]

In the present invention, the represented compound of the general formula of suitable use (B) is that wavelength region may at 250nm～500nm has absorbing wavelength person.The wavelength region may that can more preferably be set forth in 300nm～380nm has the compound of absorbing wavelength.Particularly preferably be the high compound of absorbancy of 308nm and 355nm.

Example as organic halogenation compound, if particularly can enumerate woods etc., circular (Bull Chem.Soc.Japan) the > > 42 of < < Japan Chemical Society, 2924 (1969), United States Patent (USP) the 3rd, 905, No. 815 specification sheetss, Japanese Patent examined patent publication 46-4605 communique, the clear 48-36281 communique of Japanese Patent Laid-Open, the clear 55-32070 communique of Japanese Patent Laid-Open, the clear 60-239736 communique of Japanese Patent Laid-Open, the clear 61-169835 communique of Japanese Patent Laid-Open, the clear 61-169837 communique of Japanese Patent Laid-Open, the clear 62-58241 communique of Japanese Patent Laid-Open, the clear 62-212401 communique of Japanese Patent Laid-Open, the clear 63-70243 communique of Japanese Patent Laid-Open, the clear 63-298339 communique of Japanese Patent Laid-Open, M _-p Hart (M.P.Hutt) < < heterocyclic chemistry magazine (Journal ofHeterocyclic Chemistry) two > > 1 (No3), etc. (1970) compound of recording in, particularly can enumerate the oxazoline compound, the s-triazine that through trihalogenmethyl, replace.

As the example of six aryl united imidazoles, for example, can enumerate Japanese Patent JP 6-29285 communique, United States Patent (USP) the 3rd, 479, No. 185, United States Patent (USP) the 4th, 311, No. 783, United States Patent (USP) the 4th, the various compounds of recording in each specification sheets of 622, No. 286 grades, be particularly 2,2 '-bis-(Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(o-bromophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(neighbour, santochlor bases)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(Chloro-O-Phenyl)-4,4 ', 5,5 '-tetra-(m-methoxyphenyl) bisglyoxaline, 2,2 '-bis-(neighbour, neighbour '-dichlorophenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(O-Nitrophenylfluorone)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(o-methyl-phenyl-)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(adjacent trifluorophenyls, )-4,4 ', 5,5 '-tetraphenyl bisglyoxaline etc.

Photoepolymerizationinitiater initiater can be used a kind or two or more is used in combination.When using situation of more than two kinds, can use the represented compound of multiple general formula (B), also can use the represented compound of multiple general formula (A).And, also can self-drifting (A) and the represented compound of general formula (B) in use at least a kind respectively.And, the oxime compound beyond the represented compound of at least a kind of difference also can using the represented compound of general formula (A) and general formula (B) and general formula (A) and general formula (B) or the Photoepolymerizationinitiater initiater beyond oxime compound.And, also can and use sensitizing agent.

The total content of Photoepolymerizationinitiater initiater is preferably 0 in the total solids composition in painted curable adhensive compositions _-1 quality %～20 quality %, more preferably 0 _-5 quality %～10 quality %, most preferably 1 quality %～5 quality %.If within the scope of this, light sensitivity while exposing is high and colour characteristics is also good.

(E) binder resin

In painted curable adhensive compositions of the present invention, for overlay film formative is improved, also can use binder resin.As binder resin, from the viewpoint of pattern formative, consider, preferably use alkali-soluble tackiness agent.

Alkali-soluble tackiness agent

Alkali-soluble tackiness agent, except having alkali-soluble, is not particularly limited, and preferably can select according to thermotolerance, developability, the viewpoint such as acquired.

Alkali-soluble tackiness agent is wire organic high molecular polymer, and preferably dissolves in organic solvent, can pass through weak alkaline aqueous solution and development person.This kind of wire organic high molecular polymer can be set forth in the polymkeric substance that side chain has carboxylic acid, for example Japanese Patent Laid-Open is clear No. 59-44615, No. 54-34327, Japanese Patent examined patent publication, No. 58-12577, Japanese Patent examined patent publication, No. 54-25957, Japanese Patent examined patent publication, clear No. 59-53836 of Japanese Patent Laid-Open, the Sipacril 2739OF of recording in each communique that Japanese Patent Laid-Open is clear No. 59-71048, acrylic copolymer, Yi Kang acid copolymer, β-crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc., the acid cellulose derivative at side chain with carboxylic acid is useful similarly.

Except above-mentioned person, alkali-soluble tackiness agent also can be used having on the polymkeric substance of hydroxyl that the addition acid anhydrides person of forming waits or polycarboxylated styrene is resin, polysiloxane series resin, poly-((methyl) 2-Hydroxy ethyl acrylate), polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol etc.And wire organic high molecular polymer also can be has the hydrophilic monomer copolymerization person of forming.Its example can be enumerated (methyl, ) alkoxyalkyl acrylate, (methyl) vinylformic acid hydroxyalkyl acrylate, glycerol (methyl) acrylate, (methyl) acrylamide, N hydroxymethyl acrylamide, the alkyl acrylamide of secondary or three grades, (methyl, ) propenoic acid dialkyl aminoalkyl ester, morpholine (methyl, ) acrylate, NVP, N-caprolactam, vinyl imidazole, vinyl triazole, (methyl, ) methyl acrylate, (methyl, ) ethyl propenoate, (methyl) propyl acrylate of branch or straight chain, (methyl) butyl acrylate of branch or straight chain, or (methyl) vinylformic acid phenoxy group hydroxy propyl ester etc.In addition, there is hydrophilic monomer and also can use monomer that the group that comprises tetrahydrofuran methyl, phosphate, phosphate-based, quarternary ammonium salt base, ethyleneoxy group chain, propylidene oxygen base chain, sulfonic group and be derived from its salt, morpholinyl ethyl etc. form etc.

And alkali-soluble tackiness agent, in order to improve cross-linking efficiency, also can have polymerizability base at side chain, such as also using polymkeric substance that contains allyl group, (methyl) propenyl or allyloxy alkyl etc. at side chain etc.The example of the polymkeric substance that contains above-mentioned polymerizability base can be enumerated Dianal NR series (trade(brand)name, Li Yang limited-liability company of Mitsubishi manufacture), Photomer6173 (the polyurethane acroleic acid oligomer that contains COOH (polyurethane acrylic oligomer), trade(brand)name, (the Diamond Shamrock Co of Ultramar Diamond Shamrock limited-liability company _-ltd _-) manufacture), ViscoatR-264, KS resist106 (be trade(brand)name, Osaka organic chemistry Industries, Inc manufactures), Cyclomer P series, PLACCEL CF200 series (be trade(brand)name, Daicel chemical industry limited-liability company manufactures), Ebecryl3800 (trade(brand)name, Daicel-UCB (Daicel-UCB) limited-liability company manufacture) etc.And, in order to improve sclerosis skin film strength, also can use the polyethers of alcohol soluble nylon or 2,2-XX-(4-hydroxy phenyl)-propane and Epicholorohydrin etc.

In these various alkali-soluble tackiness agents; from stable on heating viewpoint, consider; preferably polycarboxylated styrene is resin, polysiloxane series resin, acrylic resin, acrylamide resin, acryl/acrylamide copolymer resin; the viewpoint consideration of self-acting control developability, preferably acrylic resin, acrylamide resin, acryl/acrylamide copolymer resin.

Described acrylic resin preferably comprises the multipolymer of the monomer that is selected from (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid, hydroxyl (methyl) ethyl propenoate, (methyl) acrylamide etc. or described Photomer6173, KS resist-106, Cyclomer P series (trade(brand)name) etc.

The viewpoint such as autography, liquid viscosity is considered, alkali-soluble tackiness agent preferably weight average molecular weight (the polystyrene conversion value of measuring by gel permeation chromatography (Gel Permeation Chromatography, GPC) method) is 1000～2 * 10 ⁵polymkeric substance, more preferably 2000～1 * 10 ⁵polymkeric substance, particularly preferably be 5000～5 * 10 ⁴polymkeric substance.Can be used alone and also can and use two or more.

Other compositions

Painted curable adhensive compositions of the present invention also can further optionally contain known additive in the scope that does not undermine effect of the present invention, for example multi-functional thiol's compound, chain-transfer agent, polymerization retarder, organic solvent, tensio-active agent, connect airtight modifying agent, linking agent, development accelerant and other additives.

Below, these compositions are illustrated.

Multi-functional thiol's compound

Painted curable adhensive compositions of the present invention also can contain multi-functional thiol's compound.

Painted curable adhensive compositions of the present invention can improve light sensitivity by containing multi-functional thiol's compound, inhibition is by caused ion stripping of the colored materials such as dyestuff etc., while using painted curable adhensive compositions of the present invention in the making of the colored filter of liquid crystal indicator, the deteriorated of image quality such as (crosstalk) of crosstalking can be prevented, thereby become, distinct high image quality can be shown.

In the present invention, so-called " multi-functional thiol's compound " means the compound in molecule with more than 2 sulfydryl.Above-mentioned multi-functional thiol's compound is more than 100 low molecular compound of molecular weight preferably, and particularly preferably molecular weight is 100～1500, and more preferably 150～1000.Above-mentioned multi-functional thiol's compound preferably has 2～10 sulfydryls in molecule, more preferably has 2～6, particularly preferably is to have 2～4.And these compounds are preferably made as the system of auxiliarily using when above-mentioned free radical polymerization monomer polymerization.Particularly, preferably make the addition of multi-functional thiol's compound is 1 quality %～20 quality % in the total solids composition of composition, or is made as more simultaneously than the addition of the above-mentioned free radical polymerization monomer containing addition still less.

As in the present invention the concrete example of spendable multi-functional thiol's compound, for example can enumerate trimethylolpropane tris (3-thiohydracrylic acid) ester, tetramethylolmethane four (3-thiohydracrylic acid) ester, two (3-thiohydracrylic acid) esters of TEG, Dipentaerythritol six (3-thiohydracrylic acid) ester, tetramethylolmethane four (Thiovanic acid) ester, tetramethylolmethane four (3-sulfydryl butyric acid) ester, two (the 3-sulfydryl butyric acid) esters of butyleneglycol, 1, two (the 3-sulfydryl butoxy) butane of 4-, 1, 3, 5-tri-(3-sulfydryl butoxyethyl group)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketones etc. are as suitable multi-functional thiol's compound.Particularly preferably be the compound that comprises secondary SH base (sulfydryl).And, from the viewpoint of liquid stabilising, consider preferably there is triazine skeleton.Particularly can enumerate Karenz MT series (trade(brand)name, Zhao He electrician limited-liability company manufacture) etc.

The content of multi-functional thiol's compound is preferably 0 in the total solids composition in painted curable adhensive compositions _-01 quality %～20 quality %, more preferably 0 _-1 quality %～10 quality %.If the content of multi-functional thiol's compound is within the scope of this, can provide the light sensitivity of painted curable adhensive compositions good, and storage stability is good, good and the pattern-free defect of the adhesion of the pixel in the colored filter obtaining, the good painted curable adhensive compositions of electrical specification during the situation of using in liquid crystal indicator.

Sensitizing agent

Painted curable adhensive compositions of the present invention also can contain sensitizing agent.In the present invention the typical sensitizing agent of suitable use can be set forth in sieve Ke Liwei (Crivello) [J.V gram of Li Weiluo (J.V.Crivello), polymer science progress (Adv.in Polymer Sci), 62,1 (1984)] sensitizing agent disclosing in.Particularly can enumerate Bi, perylene, acridine, thioxanthone, CTX, benzoflavine, N-vinylcarbazole, 9,10-dibutoxy anthracene, anthraquinone, benzophenone, tonka bean camphor, ketone tonka bean camphor, phenanthrene, camphorquinone, phenothiazine derivative etc.As sensitizing agent, preferably take for Photoepolymerizationinitiater initiater as the ratio of 50 quality %～200 quality % is added.

Chain-transfer agent

Painted curable adhensive compositions of the present invention also can contain chain-transfer agent.In the present invention, the chain-transfer agent of suitable use for example can be enumerated N, the N such as N-dimethylaminobenzoic acid ethyl ester, N-dialkyl amido phenylformic acid alkyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenyl mercaptobenzimidazole etc. have the sulfhydryl compound of heterocycle etc.

Chain-transfer agent can be used alone a kind, also can and use two or more.

As the content (total amount) of chain-transfer agent, certainly lower the uneven first-class viewpoint of light sensitivity and consider, in the total solids composition of painted curable adhensive compositions of the present invention, be preferably 0 _-the scope of 01 quality %～15 quality %, more preferably 0 _-1 quality %～10 quality %, particularly preferably is 0 _-5 quality %～5 quality %.

Polymerization retarder

Painted curable adhensive compositions of the present invention also can contain polymerization retarder.

So-called polymerization retarder is the material functioning as follows: by light or heat, the polymerizations such as the free radical producing in painted curable adhensive compositions are caused and kind implement to supply with a hydrogen (or authorizing hydrogen), supply with energy (or authorizing energy), supply with electronics (or authorizing electronics) etc., make polymerization cause kind of inactivation and suppress polymerization and unexpectedly cause.Can use polymerization retarder of recording in the paragraph 0154～paragraph 0173 of Japanese Patent Laid-Open 2007-334322 communique etc.

In these compounds, polymerization retarder can preferably be enumerated p methoxy phenol.

Content (total amount) as the polymerization retarder in painted curable adhensive compositions of the present invention, in the total mass of polymerizable compound, be preferably 0.0001 quality %～5 quality %, more preferably 0.001 quality %～5 quality %, particularly preferably is 0.001 quality %～1 quality %.

Organic solvent

Painted curable adhensive compositions of the present invention can contain organic solvent.

If organic solvent can meet and the solvability of each composition of depositing or the coating person while making painted curable adhensive compositions, there is no particular restriction substantially, particularly preferably is to consider the solvability, coating, security of solids component and select.

Organic solvent can be enumerated ester class, ethers, ketone, aromatic hydrocarbon based etc.

Ester class for example can be enumerated ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, Isoamyl Acetate FCC, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, acetic oxide alkyl esters (acetic oxide methyl esters for example, acetic oxide ethyl ester, acetic oxide butyl ester (particularly can be enumerated methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate etc.)), 3-oxygen base alkyl propionates class, 2-oxygen base alkyl propionates class, 2-oxygen base-2 Methylpropionic acid methyl esters, 2-oxygen base-2 Methylpropionic acid ethyl ester, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, Propyl pyruvate, methyl acetoacetate, methyl aceto acetate, 2-side oxy butyrate methyl esters, 2-side oxy butyrate ethyl ester etc.

And ethers is such as enumerating diethylene glycol dimethyl ether, tetrahydrofuran (THF), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethylmethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester etc.

Ketone is such as enumerating methyl ethyl ketone, pimelinketone, 2-heptanone, 3-heptanone etc.

Aromatic hydrocarbon based such as can suitablely enumerating toluene, dimethylbenzene etc.

As these organic solvents, its solvability during from the solvability of described each composition and in the situation that comprises caustic solubility tackiness agent, be coated with the viewpoints such as planar improvement and consider, also preferably mix two or more.When this situation, particularly preferably be the mixing solutions of more than two kinds that comprises the choosing group that freely solvent forms as follows: 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, butylacetate, 3-methoxy methyl propionate, 2-heptanone, pimelinketone, ethyl carbitol acetic ester, acetate of butyl carbitol, propylene glycol monomethyl ether and propylene glycol methyl ether acetate.

Content as organic solvent in painted curable adhensive compositions, preferably the total solids constituent concentration in painted curable adhensive compositions becomes the amount of 10 quality %～80 quality %, more preferably becomes the amount of 15 quality %～60 quality %.

Tensio-active agent

Painted curable adhensive compositions of the present invention also can contain tensio-active agent.

Tensio-active agent can be used any person of negatively charged ion system, positively charged ion system, nonionic system or both sexes, and preferred tensio-active agent is non-ionization series tensio-active agent.Particularly can enumerate the nonionic of recording in the paragraph 0058 of Japanese Patent Laid-Open 2009-098616 communique is tensio-active agent, and wherein preferably fluorine is tensio-active agent.

In the present invention spendable tensio-active agent for example can enumerate the Megafac F142D as commercially available product, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F183, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781, Megafac F781-F, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac R-90 (trade(brand)name, Di Aisheng (DIC) limited-liability company manufactures), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, Novec FC-4430 (trade(brand)name, Sumitomo 3M limited-liability company manufactures), Asahi GuardAG7105, 7000, 950, 7600, Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (trade(brand)name, Asahi Glass limited-liability company manufactures), Eftop EF351, Eftop352, Eftop801, Eftop802 (trade(brand)name, Mitsubishi General Materials electronics changes into limited-liability company and manufactures), Ftergent250 (manufacture of Ni Ousi (Neos) limited-liability company) etc.

And, tensio-active agent can be enumerated following multipolymer as preference: described multipolymer comprises the represented structural unit A of following formula (W) and structural unit B, using tetrahydrofuran (THF) as solvent, the weight average molecular weight of the polystyrene conversion of measuring by gel permeation chromatography (Mw) is 1, more than 000, below 10,000.

[changing 63]

In formula (W), R ¹and R ³represent independently respectively hydrogen atom or methyl, R ²represent that carbon number is the straight-chain alkyl-sub-more than 1, below 4, R ⁴represent that hydrogen atom or carbon number are the alkyl more than 1, below 4, L represents that carbon number is the alkylidene group more than 3, below 6, p and q mean the quality percentage of polymerization ratio, p represents that 10 quality % are above, the numerical value below 80 quality %, q represents that 20 quality % are above, the numerical value below 90 quality %, r represents the integer more than 1, below 18, and n represents the integer more than 1, below 10.

Described L is the represented branch's alkylidene group of following formula (W-2) preferably.R in formula (W-2) ⁵represent that carbon number is the alkyl more than 1, below 4, with regard to intermiscibility and to regard to the aspect of the wettability of applied, preferably carbon number is the alkyl more than 1, below 3, more preferably carbon number is 2 or 3 alkyl.

P in formula (W) and q and (p+q) p+q=100 preferably, that is 100 quality %.

The weight average molecular weight of described multipolymer (Mw) more preferably more than 1,500, below 5,000.

[changing 64]

These tensio-active agents can be used alone a kind or use two or more.

As the addition (total amount) of the tensio-active agent in painted curable adhensive compositions of the present invention, in the total solids composition of painted curable adhensive compositions, be preferably 0.01 quality %～2.0 quality %, particularly preferably be 0.02 quality %～1 _-0 quality %.If addition is this scope, the homogeneity of coating and cured film becomes better.

Connect airtight modifying agent

Painted curable adhensive compositions of the present invention also can contain and connect airtight modifying agent.

Connecting airtight modifying agent is to use so that become the compound that the adhesion of the inorganics (silicon compounds such as glass, silicon, silicon oxide, silicon nitride, gold, copper, aluminium etc.) of supporter and the cured film of painted curable adhensive compositions improves.Particularly can enumerate silane coupling agent etc.As the silane coupling agent that connects airtight modifying agent, be to take surperficial upgrading as object person, be not particularly limited, can use known person.

The silane coupling agent that silane coupling agent is preferably recorded in the paragraph 0048 of Japanese Patent Laid-Open 2009-98616 communique, wherein more preferably γ-glycidoxypropyl trialkoxy silane or γ-methacryloxypropyl trialkoxy silane.These silane coupling agents can be used alone a kind or and use two or more.

As the content that connects airtight modifying agent (total amount) in painted curable adhensive compositions of the present invention, for the total solids of the raw composition of painted sclerosis becomes component, preferably 0.1 quality %～20 quality %, more preferably 0.2 quality %～5 quality %.

Linking agent

In painted curable adhensive compositions of the present invention, also can use to supplemental linking agent, thus the hardness of the painted cured film that further raising is hardened painted curable adhensive compositions to be formed.

If linking agent carries out film sclerosis person by crosslinking reaction, be not particularly limited, for example, can enumerate: (a) epoxy resin, (b) are through being selected from melamine compound, guanidine amine compound, glycoluril compounds or the carbamide compound of at least 1 substituting group replacement of methylol, alkoxy methyl and acyloxy methyl, phenolic compound, naphthol compound or the hydroxyl anthracene compound that (c) replaces through being selected from least 1 substituting group of methylol, alkoxy methyl and acyloxy methyl.

Wherein, (a) epoxy resin can by with can be used as stiffening agent and be present in reacting of acidic component (such as resin, monomer etc.) in painted curable adhensive compositions or SH compound (sulfhydryl compound) and form the painted cured film of more consolidating, therefore particularly preferably.In addition, in epoxy resin, from the viewpoint of low viscosity, thermotolerance, stability, consider, preferably cycloaliphatic epoxy resin.

About the detailed contents such as concrete example of linking agent, can be with reference to the record of paragraph [the 0134]～paragraph [0147] of Japanese Patent Laid-Open 2004-295116 communique.

Development accelerant

The alkali dissolution in the territory, non-exposed area when the situation in order to promote painted curable adhensive compositions layer to expose, while realizing the situation further improving of developability of painted curable adhensive compositions, also can in painted curable adhensive compositions of the present invention, add development accelerant.Development accelerant preferably molecular weight is that lower molecular weight organic carboxyl acid compound or molecular weight below 1000 is the lower molecular weight phenolic compound below 1000.

Particularly, such as enumerating formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethylacetic acid, enanthic acid, the aliphatic monocarboxylic acid such as sad; The aliphatic dicarboxylic acids such as oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane dicarboxylic acid, Methylpropanedioic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl-succsinic acid, citraconic acid; The aliphatic tricarboxylic acids such as propanetricarboxylic acid, equisetic acid, Norcamphor three acid; The aromatic monocarboxylates such as phenylformic acid, toluic acid, fencholic acid, mesitylenic acid, xylic acid; The aromatic multi-carboxy acids such as phthalic acid, m-phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid; Toluylic acid, hydratropic acid, phenylpropionic acid, mandelic acid, phenylsuccinic acid, atropic acid, styracin, methyl cinnamate, styracin benzyl ester, inferior cinnamyl acetic acid, coumaric acid, umbellic acid (umbellic acid) etc.

Other additives

Painted curable adhensive compositions of the present invention also can optionally contain various additives, such as weighting agent, macromolecular compound beyond above-mentioned, UV light absorber, antioxidant etc.These additives can be enumerated the middle record person of paragraph [0155]～paragraph [0156] of Japanese Patent Laid-Open 2004-295116 communique.

In painted curable adhensive compositions of the present invention, can contain the thermal polymerization inhibitor of recording in the paragraph [0081] of the photostabilizer recorded in the paragraph [0078] of Japanese Patent Laid-Open 2004-295116 communique, Japanese Patent Laid-Open 2004-295116 communique.

The modulator approach of painted curable adhensive compositions

Painted curable adhensive compositions of the present invention can be by being mixed aforesaid each essential component to be modulated with any composition optionally.

In addition, when modulating painted curable adhensive compositions, can, by the blanket allotment of each composition that forms painted curable adhensive compositions, also each composition can be dissolved, be scattered in solvent and successively allocate afterwards.And ordering in launching during allotment or operating condition are not subject to special restriction.For example all the components can be dissolved simultaneously, be scattered in solvent and modulation group compound, also can optionally each composition be made to two or more solution, dispersion liquid aptly in advance, in use (during coating) these solution, dispersion liquid are mixed and are modulated to painted curable adhensive compositions.

As mentioned above and the painted curable adhensive compositions of modulation preferably can to use aperture be that the strainer etc. of 0.01 about μ m～3.0 μ m carries out after filtering separation, for extremely.

Painted curable adhensive compositions of the present invention can form the painted cured film of the colored filter that can form brightness and contrast gradient excellence, therefore can as colored pixels such as the colored filters using in liquid crystal indicator, form purposes aptly, and can the suitable making purposes as printing ink, ink for ink-jet print and coating etc.

Colored filter and manufacture method thereof

Colored filter of the present invention is to comprise the constitutor by the formed painted areas of painted curable adhensive compositions of the present invention set on substrate, this substrate.Painted areas on substrate by form colored filter each pixel pigmented layers such as red (R), green (G), blue (B) and form.

The manufacture method of colored filter of the present invention comprises following steps: pigmented layer forms step (A), described painted curable adhensive compositions is imparted on supporter and forms pigmented layer (painted curable adhensive compositions layer); Step of exposure (B), carries out the exposure of pattern apperance to the pigmented layer forming by step (A); Development step (C), develops and forms pattern the pigmented layer after described exposure.

And, in the manufacture method of colored filter of the present invention, particularly preferably being the aspect of further setting steps (D), described step (D) is that the colored pattern of gained in step (C) is carried out to heat treated.

Below, the manufacture method of colored filter of the present invention is carried out to more specific description.In addition, except the manufacture method of in the past mainly using, to certainly improving the viewpoint of brightness and yield, consider that the enamel method for manufacturing colored filtering substrate of spectral filter (Color Filter onArray, COA) mode of effective array is also illustrated.

The method for manufacturing colored filtering substrate of previous type

Step (A)

In the manufacture method of colored filter of the present invention, first by rotary coating, slot coated, curtain coating coating, roller coat, rod, be coated with or the coating process such as ink-jet is imparted to described of the present invention painted curable adhensive compositions on supporter and forms pigmented layer, thereafter this pigmented layer heated to (pre-baked) or vacuum-drying etc. and it is dried.

Supporter is such as enumerating the soda glass that uses in liquid crystal indicator, non-alkali glass, borosilicate glass, silica glass, silicon substrate, resin substrate etc.And, on these supporters, also lower coating can be optionally set and in order to improvement with top layer the diffusion of connecting airtight, prevent material or realize surperficial planarization.In addition, described supporter also can be the TFT substrate that is formed with thin film transistor (thin-film transistor, TFT) film on supporter.

Pre-baked condition can be enumerated and use hot-plate (hot plate) or baking oven (oven), heats the condition about 0.5 minute～15 minutes at 70 ℃～130 ℃.

And, can be according to object and suitable selection by the thickness of the formed pigmented layer of painted curable adhensive compositions.At liquid crystal indicator, use in colored filter, preferably the scope of 0.2 μ m～5.0 μ m, the more preferably scope of 1.0 μ m～4.0 μ m.In addition, the thickness of pigmented layer is dried thickness.

Step (B)

Then,, in the manufacture method of colored filter of the present invention, formed pigmented layer on supporter is carried out to the exposure of pattern apperance.Light or radioactive rays preferably g line, h line, i line, various laser light applicable to exposure, particularly preferably be i line.When irradiating the situation of light use i line, preferably pass through 5mJ/cm ²～500mJ/cm ²exposure irradiate.

And other exposure light sources can be used each mercuryvapour lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halid lamp, various LASER Light Source of ultra-high voltage, high pressure, middle pressure, low pressure etc.

Use the step of exposure of LASER Light Source

In using the Exposure mode of LASER Light Source, irradiate the ultraviolet laser of the wavelength region of the light scope that preferably wavelength is 300nm～410nm, more preferably the wavelength of the scope of 300nm～360nm.The third harmonic (355nm) of neodymium yttrium aluminium garnet laser (Nd:YAG laser) or the XeCl (308nm) of excimer laser, the XeF (353nm) of particularly, particularly can suitable use output rating large, less expensive Solid State Laser.As the exposure of pattern, from productive viewpoint, consider, preferably 1mJ/cm ²～100mJ/cm ²scope, 1mJ/cm more preferably ²～50mJ/cm ²scope.

There is no particular restriction for exposure apparatus, and commercially available exposure apparatus can be used Callisto (trade(brand)name, (the V Technology Co of V Science and Technology Co., Ltd. _-, Ltd _-) manufacture) or EGIS (trade(brand)name, V Technology Co., Ltd. manufactures) or DF2200G (trade(brand)name, Dainippon Screen Manufacturing Co (Dainippon Screen) limited-liability company manufacture) etc.And, also can the above-mentioned device in addition of suitable use.

Step (C)

Then, to the pigmented layer after exposure, utilize developing solution to develop.Can form colored pattern thus.If developing solution dissolves the unhardened portion of pigmented layer and do not dissolve the person of sclerosis portion, can use combination or the alkaline aqueous solution of various organic solvents.During the situation that is alkaline aqueous solution at developing solution, alkali concn can be adjusted into preferably pH becomes 10～13.Described alkaline aqueous solution for example can be enumerated sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, water glass, Starso, ammoniacal liquor, ethylamine, diethylamide, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1, the alkaline aqueous solution of 8-diazabicyclo-[5.4.0]-7-undecylene etc.

Development time preferably 30 seconds～300 seconds, more preferably 30 seconds～120 seconds.Preferably 20 ℃～40 ℃ of development temperatures, more preferably 23 ℃.

Development can be undertaken by covering liquid mode, spray mode, spray pattern etc.

And, after using alkaline aqueous solution to develop, preferably by water, clean.

In the manufacture method of colored filter of the present invention, particularly preferably be the post-exposure that the colored pattern (pixel) also forming using painted curable adhensive compositions utilizes uviolizing.

Step (D)

Preferably the colored pattern after developing is further carried out to heat treated, or further carry out heat treated to having carried out the colored pattern of the post-exposure of uviolizing that utilizes as above.By formed colored pattern being carried out to heat treated (so-called rear baking processing), can further make colored pattern sclerosis.This heat treated is such as being undertaken by hot-plate, various well heater, baking oven etc.

Preferably 100 ℃～300 ℃ of temperature during heat treated, more preferably 150 ℃～250 ℃.And, about preferably 10 minutes～120 minutes heat-up time.

As mentioned above and colored pattern form the pixel in colored filter.In the making of colored filter of pixel with multiple color tones, according to desired number of colours, repeatedly carry out above-mentioned steps (A), step (B), step (C) and step optionally (D).

In addition, can finish in formation, exposure, the development of each monochromatic pigmented layer to carry out described step (D) after (every 1 look), also after can finishing in formation, exposure, the development of all pigmented layers of desired number of colours, the blanket described step (D) of carrying out.

The manufacture method of COA mode colored filter

The manufacture method of the colored filter of COA mode of the present invention comprises following steps: pigmented layer forms step (A), use TFT substrate as supporter, described painted curable adhensive compositions is imparted on the TFT substrate of supporter and forms pigmented layer (painted curable adhensive compositions layer); Step of exposure (B), carries out the exposure of pattern apperance to the pigmented layer forming by step (A); Development step (C), develops and forms colored pattern the pigmented layer after described exposure.And, particularly preferably being the aspect of further setting steps (D), described step (D) is that the colored pattern of gained in step (C) is carried out to heat treated.

In the manufacture method of the colored filter of COA mode, after forming desired colored pattern (pixel) as described above on TFT substrate, more comprise following steps: step (E) forms ELD in formed pixel; Step (F), carries out patterned process and forms pixel electrode described ELD.

At pigmented layer, form in step (A), on TFT substrate, give painted curable adhensive compositions and form pigmented layer.The formation of pigmented layer for example can be carried out in the following way: be coated with painted curable adhensive compositions, be optionally dried (pre-baked) and process and formation coated film.The coating of painted curable adhensive compositions can directly or be situated between and on TFT substrate, carry out by rotary coating (spin coating), slot coated, curtain coating coating or roller coat etc. every other layers.

When being dried the situation that (pre-baked) process, its condition can be according to the formation of painted curable adhensive compositions and suitable selection.Such as carrying out at the temperature of 50 ℃～140 ℃ 10 seconds～300 seconds by hot-plate, baking oven etc.And, in recent years, the maximization development of substrate, therefore, as the formation method of coated film, slot coated is also effective, and this coating process becomes general method gradually.

Pigmented layer in the manufacture method of the colored filter of COA mode forms step (A) can be with reference to the record of the step in the method for manufacturing colored filtering substrate of described previous type (A).

In step of exposure (B), described pigmented layer is carried out to pattern exposure.When the pattern exposure of pigmented layer is for example the situation of minus, can be situated between and exposes every the mask pattern of regulation, only make to have carried out light-struck pigmented layer partially hardened and carry out.Spendable radioactive rays during as exposure, particularly can preferably be used the ultraviolet rays such as g line, i line.

Step of exposure in the manufacture method of the colored filter of COA mode (B) can be with reference to the record of the step in the method for manufacturing colored filtering substrate of described previous type (B).

In development step (C), make non-sclerosis portion stripping after described step of exposure for example, to developing solution (alkaline aqueous solution), form the colored pattern that comprises sclerosis portion.During the situation that is minus at described painted curable adhensive compositions, do not carry out the non-sclerosis portion stripping of described exposure to developing solution, only remaining part of carrying out photo-hardening.Developing solution it is desirable to circuit of substrate etc. not caused the organic basic developing solution of damage.Organic basic developing solution for example can be used and with pure water, following organic basic compound is diluted to concentration and become 0 _-001 quality %～10 quality %, preferably 0 _-the alkaline aqueous solution of 01 quality %～1 quality %: ammoniacal liquor, ethylamine, diethylamide, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicyclo-[5.4.0]-7-undecylene etc.In addition, during the situation of the developing solution that comprises this kind of alkaline aqueous solution in use, generally, after development treatment, by pure water, clean (flushing).

Development temperature is generally 20 ℃～30 ℃, and development time is 20 seconds～90 seconds.

Development step in the manufacture method of the colored filter of COA mode (C) can be with reference to the record of the step in the method for manufacturing colored filtering substrate of described previous type (C).

In carrying out the step (D) of heat treated, formed colored pattern in development step (C) is carried out to heat treated (baking afterwards).Rear baking be with so that the heat treated of the sclerosis of colored pattern after developing completely conventionally carry out the heat embrittlement of 200 ℃～240 ℃ and process.The mode that this rear baking processing can become described condition is used the heating arrangements such as hot-plate or convection oven (hot air circulation type drying machine), high frequency heating machine, with continous way or batch-type, the coated film after developing is carried out.

About forming each color of colored filter, can repeatedly carry out in turn as described above described step (A)～step (C) and step optionally (D) and manufacture the painted cured film with desired colored pattern.Obtain therefrom colored filter.

In forming the step (E) of ELD, carry out as described above and on TFT substrate the upper ELD that forms of formed desired colored pattern (pixel).The material that forms ELD for example can be enumerated tin indium oxide (ITO).By formed ELD such as ITO, for example can be formed by sputter.The condition of sputter can be according to common used condition and suitable selection.

In forming the step (F) of pixel electrode, formed ELD in pixel is carried out patterned process and formed pixel electrode.The patterned process of transparent electrode layer for example can be carried out as described below.In ELD, form eurymeric light blockage coating film, this photoresistance film is implemented, after pattern exposure, development treatment, further to use the chemical such as hydrofluoric acid to carry out etch processes and form pixel electrode pattern necessary ELD (preferably ITO)., by stripping liquid this pixel electrode pattern in remaining photoresistance film removed, can form pixel electrode thus thereafter.

Form the eurymeric photoresist that the photoresist using in the step of pixel electrode preferably has elching resistant.And generally well-known gimmick can and be unrestrictedly used in pattern exposure or development, etching.

By stripping liquid, photoresistance film residual on formed pixel electrode is peeled off and removed.This stripping liquid can there is no particular restriction ground use known stripping liquid in the past.The various organic solvents that disclose in each specification sheets such as No. 0119337th, each communique of can use Japanese Patent Laid-Open clear No. 51-72503, clear No. 57-84456 of Japanese Patent Laid-Open, No. 6-222573, Japanese patent laid-open etc. or No. 4165294th, United States Patent (USP) and European patent.Representational stripping liquid can be enumerated the mixed solvent of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO) (DMSO).And, by use, be heated to 60 ℃ of above organic solvents as stripping liquid, strip step can be made as to the short period of time, and can further eliminate the problem of development residue.

Therefore described painted curable adhensive compositions is the resistance to fluidity excellence of peeling off particularly, even if use, is heated to 60 ℃ of above organic solvents, also can not produce that filming of colored filter peeled off, swelling, expansion photoresistance film be removed.

The colored filter of the COA mode of manufacturing is as mentioned above conventionally with as the graphic structure being disclosed of Japanese patent laid-open 9-311347 communique and for various display unit such as TFT liquid crystal indicators.Described colored filter is suitable for COA mode, therefore easily aims at, and can improve numerical aperture.And, use described painted curable adhensive compositions and form pixel, therefore the resistance to fluidity of peeling off is high, so yield is high, and production efficiency is also high.And the heat-resisting discolouration that colored filter requires conventionally, low-k, thickness homogeneity, analyticity, voltage retention, photostabilization etc. are also good.

The structure of colored filter can be the form that only comprises as described above 1 layer of pixel; and can between substrate and pixel electrode, comprise following 2 layers: by the formed colored pattern of painted curable adhensive compositions for pixel, with the formed pixel protective membrane that comprises pixel protective membrane use optothermal polymerization composition on this colored pattern.

Form thickness preferably 0.3 μ m～5.0 μ m, the more preferably 0.5 μ m～3.5 μ m of colored pattern of the colored filter of described COA mode.The thicker person of coating thickness can realize high chroma, if but coating thickness is thicker, the analyticity variation of contact hole, so necessary balance.And the thickness of described pixel protective membrane is 0.2 μ m～5.0 μ m preferably, 0.2 μ m～3.0 μ m more preferably.And, it is desirable to make become the concavo-convex planarization of the colored pattern of substrate, surface smoothing.

Display unit

The colored filter (colored filter of the present invention) being obtained by the manufacture method of colored filter of the present invention is used painted curable adhensive compositions of the present invention, so brightness and contrast gradient excellence.

Display unit of the present invention comprises colored filter of the present invention.

As display unit of the present invention, particularly suitable is liquid-crystal display (liquid crystal indicator; LCD), the display unit of display unit etc. for the used for mobile terminal display unit such as OLED display (organic EL display), liquid crystal projection apparatus, display device for game computer, mobile telephone, display unit for digital camera, auto navigation, suitable is especially colour display device.

Colored filter of the present invention during for the situation of organic EL display or liquid crystal indicator etc., can realized to good tone, and becoming and can show the image of dichroism and contrast gradient excellence.

Liquid crystal indicator

To using the liquid crystal indicator of colored filter of the present invention to be illustrated.About the definition of organic EL display or liquid crystal indicator or each display unit in detail, such as recording to some extent in < < electronic display unit (the wooden clear husband's work of assistant assistant, the census of manufacturing can limited-liability company's nineteen ninety distribution) > >, < < display unit (she blows along chapter work, industry books limited-liability company and puts down into the first year (1989) distribution) > > etc.And, about liquid crystal indicator, for example, in < < LCD Technology of future generation (Uchida Tatsuo compiles, the census of manufacturing can limited-liability company's distribution in 1994) > >, record to some extent.There is no particular restriction for applicable liquid crystal indicator of the present invention, for example, in the liquid crystal indicator applicable to the variety of way of recording in above-mentioned < < LCD Technology > of future generation >.

Wherein, colored filter of the present invention is effective especially for the liquid crystal indicator of colored TFT mode.About the liquid crystal indicator of colored TFT mode, for example, in < < color TFT-LCD indicating meter (the vertical limited-liability company that publishes issues for 1996 altogether) > >, record to some extent.In addition, the present invention is also applicable to copline and switches (In-plane Switching, the transverse electric field type of drive such as IPS), multiregional vertical align (Multi-domain VerticalAlignment, MVA) etc. the visual angles such as pixel partitioning scheme obtain the liquid crystal indicator expanding, or STN Super TN (Super Twisted Nematic, STN), twisted nematic (Twisted Nematic, TN), vertical orientation (Vertical Alignment, VA), optical compensation inclination (Optically Compensated Splay, OC S), fringing field switches (Fringe Field Switching, FFS), and reflective optics compensated bend (Reflective Optically Compenated Bend, R-OCB) etc. in.And colored filter of the present invention also can be for enameling in spectral filter (Color-filter On Array, COA) mode to array.

If colored filter of the present invention is used for to liquid crystal indicator, during with the three-wavelength pipe combination of in the past known cold-cathode tube, can realize high contrast gradient, in addition by providing brightness colorrendering quality high and that purity of color is high good liquid crystal indicator as backlight the photodiode of red, green, blue (Light Emitting Diode, LED) light source (RGB-LED).

Embodiment

Below, by embodiment to the present invention's more specific description in addition, as long as but the present invention is no more than its purport, be not limited to following examples.In addition, unless otherwise noted, " part ", " % " are quality criterias.

Embodiment 1-1

The modulation of painted curable adhensive compositions

Following each composition is mixed, dissolved and modulated painted curable adhensive compositions.

8 parts of organic solvents 1 (propylene glycol methyl ether acetate)

26 parts of organic solvents 2 (diethylene glycol ethylmethyl ether)

The alkali-soluble tackiness agent 1 (affixture of cyclohexyl methacrylate/methacrylic acid/glycidyl methacrylate and methacrylic acid (30/30/40[mol ratio], 45% propylene glycol monomethyl ether solution)

1 part

2 parts, alkali-soluble tackiness agent 2 (allyl methacrylate(AMA)/Sipacril 2739OF=mol ratio 70/30, weight average molecular weight are 26800)

5 parts of polymerizable compounds 1 (Japanese chemical drug limited-liability company manufactures, KAYARAD DPHA (trade(brand)name))

2 parts of polymerizable compounds 2 (manufacture of the synthetic limited-liability company in East Asia, Aronix TO-2349 (trade(brand)name))

0.003 part of polymerization retarder (p methoxy phenol)

0.5 part of Photoepolymerizationinitiater initiater 1 (1-(O-acetyl oxime)-1-[9-ethyl-6-(thiophene acyl group)-9H-card azoles-3-yl] acetone)

0.1 part of Photoepolymerizationinitiater initiater 2 (1,3-dihydro-1-phenyl-2H-benzimidazolyl-2 radicals-thioketones)

0.3 part of multi-functional thiol's compound 1 (Isosorbide-5-Nitrae-bis-(3-sulfydryl butyryl acyloxy) butane)

Connect airtight 0.2 part of modifying agent (3-methacryloxypropyl trimethoxy silane)

Fluorine is 5.1 parts, tensio-active agent (Megafac F-554 (trade(brand)name), 0.2% propylene glycol methyl ether acetate solution that DIC company manufactures)

Blue pigments dispersion liquid 1 (pigment Blue 15: 6 dispersion liquids) 25 parts

Dye solution 1 0-1 part

Dye solution 2 1-5 parts

In addition, described blue pigments dispersion liquid can be modulated as described below.

By 12.8 parts of C.I. pigment Blue 15s: 6 with 7.2 parts of dispersion agents (Japanese Lu Borun (Lubrizol) company manufactures, trade(brand)name: Solsperse 5500), mix with 80.0 parts of propylene glycol methyl ether acetates, use ball mill and pigment is fully disperseed, adjust blue pigments dispersion liquid.

Dye solution 1 is mixed following each composition, dissolved and is made.In embodiment 1, the dye strength of dye solution 1 is 0.1% for the colored materials in painted curable adhensive compositions.

44.6 parts of organic solvents 1 (propylene glycol methyl ether acetate)

2.4 parts of dyestuffs (P-26)

Dye solution 2 is mixed following each composition, dissolved and is made.

48.0 parts of organic solvents 1 (propylene glycol methyl ether acetate)

2.6 parts of dyestuffs [exemplary compounds (11)]

In dye solution 1, comprise (P-26) as (B) porphyrin compound, in dye solution 2, comprise the exemplary compounds (11) as the general formula (I) of (A-1) two pyrroles's methylene radical metal complex compounds.In addition, in following table 1, for example, the exemplary compounds (x) that belongs to general formula (I) is recited as to " (I-x) ".

The formation of painted curable adhensive compositions layer (pigmented layer)

By spin-coating method at glass (#1737 (trade(brand)name); Corning Incorporated manufactures) be coated with after above-mentioned modulated painted curable adhensive compositions on substrate, at room temperature dry 30 minutes and make volatile component volatilization, form pigmented layer A.This pigmented layer A is irradiated to i line (wavelength is 365 nm) and form latent image.The light source of i line is used extra-high-pressure mercury vapour lamp, irradiates after being made as directional light.Now, irradiating light quantity is 40mJ/cm ².Secondly, for this, be formed with the pigmented layer of latent image, use the aqueous solution (concentration is 2-4%) of sodium carbonate/bicarbonate and at 26 ℃, carry out the development of 45 seconds, secondly by flowing water, undertaken after the flushing of 20 seconds, after spraying, make it dry, obtain thread pattern image.The thread pattern image of gained is carried out at 230 ℃ to the rear baking processing of 20 minutes, obtaining thickness is pigmented layer (painted cured film) B of 2 μ m.

Evaluate

About contrast gradient and the dichroism of the pigmented layer of above-mentioned gained, by method shown below, evaluate.Evaluation result is shown in following table 2.

(1) contrast gradient

And, by the substrate clamping with each pigmented layer B of gained between 2 pieces of light polarizing film, use chroma-luminance meter (to open up that Pu Kang (TOPCON) limited-liability company manufactures, model: the brightness value of BM-5A) measuring the parallel situation of the polarizing axis of 2 pieces of light polarizing film and vertical situation, the brightness of the situation that the polarizing axis of 2 pieces of light polarizing film is parallel, divided by the brightness of vertical situation, is obtained the value of gained and is spent as a comparison.Contrast gradient is higher, as liquid crystal indicator, with colored filter, more shows good performance.

(2) dichroism (brightness)

Use the micro-spectral determinator OSP-SP200 (trade(brand)name) that Olympic Ba Si limited-liability company manufactures and measure the transmitted spectrum of the pigmented layer B of above-mentioned gained.By the transmitted spectrum of gained, obtain chromaticity coordinates x value, y value, Y value in CIE 1931 (CIEl931) colour system.

As dichroism, in (x, y)=(0 _-138,0 _-085) during the high situation of the Y value in (brightness), there is excellent dichroism, when this kind of pigmented layer is applicable to colored filter, obtain good image.

Embodiment 1-2～embodiment 1-4

In embodiment 1, as recorded in table 1, change the usage quantity of dye solution 1, similarly carry out with embodiment 1-1 in addition and modulate painted curable adhensive compositions, form pigmented layer, and evaluate.Evaluation result is recorded in table 2 in the lump.

Embodiment 1-5

The modulation of painted curable adhensive compositions

Following each composition is mixed, dissolved and modulate painted curable adhensive compositions.

8 parts of organic solvents 1 (propylene glycol methyl ether acetate)

26 parts of organic solvents 2 (diethylene glycol ethylmethyl ether)

Alkali-soluble tackiness agent 1 (affixture of cyclohexyl methacrylate/methacrylic acid/glycidyl methacrylate and methacrylic acid (30/30/40[mol ratio]), 45% propylene glycol monomethyl ether solution)

1 part

0.003 part of polymerization retarder (p methoxy phenol)

0.5 part of Photoepolymerizationinitiater initiater 1 (1-(O-acetyl oxime)-l-[9-ethyl-6-(thiophene acyl group)-9H-card azoles-3-yl] acetone)

3 0.1 parts of dye solutions

2 1.5 parts of dye solutions

Carry out similarly to Example 1 the evaluation of the painted curable adhensive compositions of gained.Evaluation result is shown in Table 2.

Dye solution 3 is that following each composition is mixed, dissolved and makes.In embodiment 1, the dye strength of dye solution 1 is for the colored materials in painted curable adhensive compositions, to be 0.1%.

44.6 parts of organic solvents 1 (propylene glycol methyl ether acetate)

2.4 parts of dyestuffs (P-32)

And dye solution 2 is dye solutions identical with the user of institute in embodiment 1.

48.0 parts of organic solvents 1 (propylene glycol methyl ether acetate)

2.6 parts of dyestuffs (I-11)

In dye solution 3, comprise (P-32) as (B) porphyrin compound, in dye solution 2, comprise (exemplary compounds (I-11)) as (A-1) two pyrroles's methylene radical metal complex compounds.

Embodiment 1-6～embodiment 1-8

In embodiment 1-5, in table l, institute changes the usage quantity of the particular dye (B) in dye solution 1 recording, and similarly carries out in addition and modulates painted curable adhensive compositions, formation pigmented layer and evaluating with embodiment 1-l.Evaluation result is shown in following table 2.

Embodiment 1-9～embodiment 1-12

In embodiment 1-3, in table l, institute changes kind and the usage quantity of the particular dye (B) in dye solution 1 recording, and similarly carries out in addition and modulates painted curable adhensive compositions, formation pigmented layer and evaluating with embodiment 1-1.Evaluation result is shown in following table 2.

Embodiment 1-13～embodiment 1-18

In embodiment 1-3, as recorded in table 1, change particular dye (A-I), particular dye (A-2) in dye solution 2, similarly carry out with embodiment 1-1 in addition and modulate painted curable adhensive compositions, form pigmented layer and evaluate.Evaluation result is shown in following table 2.

Embodiment 1-19～embodiment 1-24

In embodiment 1-7, as recorded in table 1, change particular dye (A-1), particular dye (A-2) in dye solution 2, similarly carry out with embodiment 1-1 in addition and modulate painted curable adhensive compositions, form pigmented layer and evaluate.Evaluation result is shown in following table 2.

Embodiment 1-25～embodiment 1-33

In embodiment 1-3, as recorded in table 1, change particular dye (A-1), particular dye (A-2) in dye solution 2, similarly carry out with embodiment 1-1 in addition and modulate painted curable adhensive compositions, form pigmented layer and evaluate.In addition, the ratio of mixture of the dyestuff when also with 2 kinds of dyestuffs is 1:1.Evaluation result is shown in following table 2.

Comparative example 1-1

8 parts of organic solvents 1 (propylene glycol methyl ether acetate)

26 parts of organic solvents 2 (diethylene glycol ethylmethyl ether)

1 part

0.003 part of polymerization retarder (p methoxy phenol)

Blue pigments dispersion liquid (pigment Blue 15: 6 dispersion liquids) 28 parts

21 parts of dye solutions

After modulation, similarly evaluate with embodiment 1-1.Evaluation result is shown in following table 2.

Comparative example 1-2

8 parts of organic solvents 1 (propylene glycol methyl ether acetate)

26 parts of organic solvents 2 (diethylene glycol ethylmethyl ether)

1 part

0.003 part of polymerization retarder (p methoxy phenol)

0.5 part of Photoepolymerizationinitiater initiater 1 (1-(O-acetyl oxime)-1-[9-ethyl-6-(thiophene acyl group)-9H-I card azoles-3-yl] acetone)

0.1 part of Photoepolymerizationinitiater initiater 2 (1,3-dihydro-l-phenyl-2H-benzimidazolyl-2 radicals-thioketones)

11 parts of dye solutions

Comparative example 1-3

8 parts of organic solvent l (propylene glycol methyl ether acetate)

26 parts of organic solvents 2 (diethylene glycol ethylmethyl ether)

1 part

0.003 part of polymerization retarder (p methoxy phenol)

0.3 part of multi-functional thiol's compound 1 (l, two (3-sulfydryl the butyryl acyloxy) butane of 4-)

Fluorine is tensio-active agent (the Megafac F-554 (trade(brand)name), 0 that DIC company manufactures _-2% propylene glycol methyl ether acetate solution) 5.1 parts

Blue pigments dispersion liquid (pigment Blue 15: 6 dispersion liquids) 25 parts

1 1.5 parts of dye solutions

4 0.1 parts of dye solutions

In addition, dye solution 4 is that following each composition is mixed, dissolved and makes.

44.6 parts of organic solvent l (propylene glycol methyl ether acetate)

2.4 parts of the exemplary compounds CB-34 recording in Japanese Patent Laid-Open 2008-292970

After adjustment, similarly evaluate with embodiment 1-1.Show the result in table 2.

In addition, in dye solution 4, contained porphyrin compound is the A in general formula (III) ¹with A ², A ³with A ⁴, A ⁵with A ⁶, and A ⁷with A ⁸the of the present invention extraneous dyestuff of whole formation aromatic ring structures.

[table 1]

[table 2]

According to the evaluation result person of being known as below of table 2.

The formed painted cured film of painted curable adhensive compositions that known two pyrroles's methylene radical metal complexs by embodiment 1-1～embodiment 1-33 and/or azepine pyrroles methylene radical metal complex and porphyrin compound combine can be realized high contrast gradient and dichroism simultaneously, as shown in embodiment 1-1 or embodiment 1-5, even if the content of particular dye (A) is trace, with the comparative example 1-1 that does not use particular dye (A) Comparatively speaking, also there is high contrast gradient and brightness and improve effect.

According to comparative example 1-1, when not using the situation of porphyrin compound, the contrast gradient of painted curable adhensive compositions is low, and performance is also insufficient.And according to comparative example 1-2, when not using the situation of two pyrroles's methylene radical metal complex compounds, dichroism (Y value) is low.

As described in as shown in each embodiment, by and with the represented porphyrin compound of pyrroles's methylene radical based dye and general formula (III), can obtain the painted curable adhensive compositions with good colourity, contrast gradient, but at also the phthalocyanine based compound of the similar compound of use porphyrin compound that is the A in general formula (III) as shown in comparative example 1-3 ¹with A ², A ³with A ⁴, A ⁵with A ⁶, and A ⁷with A ⁸whole mutually bonds and while forming the situation of compound of ring structure, brightness, contrast gradient are slightly low for embodiment group, performance is also insufficient.Its reason is still not clear, supposition is that Comparatively speaking molecular structure is little with the comparison dyestuff with phthalocyanine structure due to the compound with the represented porphyrin structure of general formula (III) of the present invention, movability is high, therefore suppress dye molecule each other, the pigment particles effect of condensing is each other high.

Embodiment 1-34

The making of liquid crystal indicator

The liquid crystal indicator of being made colored filter and being comprised this colored filter by following gimmick is evaluated.

The making of red colored photosensitive polymer combination R

The pigment dispensing composition of following composition is mixed, used homogenizer and with 3, the rotating speed of 000r.p.m. carries out the stirring of 3 hours.By as mentioned above and mixing solutions further using 0.3mm

the particle dispersion machine Dispermat (trade(brand)name, Gus graceful (GETZMANN) company manufacture) of zirconia particles in carry out the dispersion treatment of 12 hours, further use thereafter high pressure dispersion machine NANO-3000-10 (trade(brand)name, Japan finish (BEE) limited-liability company and manufactures) with the mechanism of decompressor and at 2000kg/cm ³pressure under with the flow of 500g/min, carry out dispersion treatment.Repeat this dispersion treatment l0 time and obtain pigment dispensing composition.

The composition of red pigment dispersion

254 75 parts of Pigment reds

177 50 parts of Pigment reds

70 parts of benzyl methacrylate/Sipacril 2739OFs

(copolymerization ratio of components is that 70/30 weight average molecular weight is 30000, acid number be 40)

800 parts of propylene glycol methyl ether acetates

In the colo(u)rant dispersion thing of gained, further add the composition of following composition, make red colored photosensitive polymer combination R.

The composition of red colored photosensitive polymer combination R

100 parts of above-mentioned red pigment dispersions

12 parts of the propylene glycol methyl ether acetate solution (solids component is 50%) of benzyl methacrylate/methacrylic acid (=70/30[mol ratio]) multipolymer (Mw:30,000)

12.1 parts of polymerizable compound I (Japanese chemical drug limited-liability company manufactures, KAYARAD DPHA (trade(brand)name))

3.1 parts of Photoepolymerizationinitiater initiaters (2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole base dimer)

4.2 parts of 4,4 '-bis-(diethylamino) benzophenone (sensitizing coloring matter)

2.1 parts of 2-mercaptobenzothiazoles (hydrogen supply compound)

Polymerization retarder: 0.001 part of p methoxy phenol

Fluorine is 0.5 part, tensio-active agent (trade(brand)name: Megafac R08 (trade(brand)name), DIC limited-liability company manufacture)

60 parts of propylene glycol methyl ether acetates

The making of green chromatic colorant photosensitive polymer combination G

In the making of red colored photosensitive polymer combination R, use the Pigment green 58 of 103 parts to replace Pigment reds 254, uses the Pigment Yellow 73 150 replacement Pigment reds 177 of 19 parts, similarly carry out in addition and make green coloring photosensitive polymer combination G.

The making of black colorant photosensitive polymer combination K

Adjust the pigment dispensing composition of following composition, while making with red pigment dispersion, similarly carry out dispersion treatment and make black pigment dispersion.

The composition of black pigment dispersion

13.1 parts of carbon blacks (trade(brand)name: Nipex35, Japanese Degussa (Degussa Japan) limited-liability company manufacture)

6.7 parts, polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid one 72/28 mol ratios, molecular weight are 3.7 ten thousand)

79.1 parts of propylene glycol methyl ether acetates

0.65 part of dispersion agent (following compound)

[changing 65]

Use the black pigment dispersive composition of gained, by following composition, adjust black colorant photosensitive polymer combination K.

The composition of black colorant photosensitive polymer combination K

25 parts of above-mentioned black pigment dispersions

8.5 parts of propylene glycol methyl ether acetates

53 parts of methyl ethyl ketones

The tackiness agent mixture of 73 parts of propylene glycol methyl ether acetates (27 parts, the polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=78/22 mol ratio, molecular weight are 3.8 ten thousand) with)

9.1 part

0.002 part of hydroquinone monomethyl ether

12 parts of DPHA (trade(brand)name, Japanese chemical drug company manufacture)

Two (three the chloroethyls)-6-[4 ' of 2,4--(N, the two ethoxy carbonyl methyl of N-) amino-3 '-bromophenyl]-s-triazine

0.16 part

0.042 part of 30 % by weight methyl ethyl ketone solution of tensio-active agent (following compound)

[changing 66]

(n=6、x=55、y=5、

Mw=33940Mw／Mn=2.55

PO: propylene oxide, EO: oxyethane

The shape system of colored filter

The shape system of black matrix"

After alkali-free glass substrate is cleaned in UV-light (UV) washing unit, use clean-out system to be cleaned with brush, further in ultrapure water, carry out ultrasonic cleaning.This substrate carried out to the thermal treatment of 3 minutes at 120 ℃ and make after condition of surface stabilization, making this substrate cooling and temperature is adjusted to 23 ℃.

By having the coating machine for glass substrate of slit-shaped ozzle, (F.A.S. industry continent (F.A.S.Asia) company manufactures, trade(brand)name: MH-1600), described black colorant photosensitive polymer combination K is coated on this substrate.Then by VCD (Minton dryer; Tokyo answers chemical industry limited-liability company to manufacture) within 30 seconds, to make the part of solvent dry and make coating layer without after mobility, at 120 ℃, carrying out 3 minutes pre-baked and obtaining thickness is the black-colored photosensitive resin layer of 2.4 μ m.

By thering is the type that closely the connects exposure machine (manufacture of high-new electronic engineering limited-liability company of Hitachi) of extra-high-pressure mercury vapour lamp, under the state that substrate and shade (the quartz exposure shade with picture pattern) are vertically erect, distance between exposure shade face and this photo-sensitive resin is set as to 200 μ m, passes through 300mJ/cm ²exposure carry out pattern exposure.

Secondly, by the spray ozzle pure water of spraying, make after the uniform surface ground humidity of this black-colored photosensitive resin layer, by KOH, be that developing solution (KOH, contains nonionogenic tenside, trade(brand)name: CDK-1, (the FUJIFILM Electronic materials Co. of electronic material limited-liability company of Fuji, Ltd.) manufacture) and at 23 ℃, with flat type nozzle (flat nozzle) pressure of 0.04VPa, carry out spray development and the acquisition patterning image of 80 seconds.Then, by ultra-high voltage, clean ozzle, with the pressure injection ultrapure water of 9.8MPa, carry out residue and remove, obtain the image K of black (K).The last thermal treatment of 30 minutes, the formation black matrix" of carrying out at 220 ℃.

The formation of rgb pixel

On the described glass substrate that is formed with black matrix", made blue-colored curable adhensive compositions and carry out patterning in the same red colored photosensitive polymer combination R of step lamination, green coloring photosensitive polymer combination G, embodiment 1 when forming with black matrix" in turn, obtains the colored filter of RGB3 color pixel respectively.Now, RGB painted portion thickness of all kinds is 1.6 μ m.

The formation of ITO electrode

The glass substrate that is formed with colored filter is put into sputter equipment, and after the ITO that is 1300A to whole vacuum evaporation thickness at 100 ℃, the annealing of carrying out at 240 ℃ 90 minutes makes ITO crystallization, forms ito transparent electrode.

The formation of spacer

The same method of spacer formation method by recording in [embodiment 1] with Japanese Patent Laid-Open 2004-240335 communique forms spacer on the ito transparent electrode of above-mentioned made.

LCD alignment is controlled the formation by projection

Use following positive-working photosensitive resin layer coating fluid, on the described ito transparent electrode that is formed with spacer, form LCD alignment control projection.

Wherein, exposure, development and baking procedure are used following method.

The mode that becomes the distance of 100 μ m with the light shield of stipulating from the surface of photo-sensitive resin configures close induction type exposure machine (trade(brand)name, (the Hitachi High-Tech Electronics Engineering Co. of high-new electronic engineering limited-liability company of Hitachi, Ltd.) manufacture), be situated between every this light shield by extra-high-pressure mercury vapour lamp with 150mJ/cm ²irradiation energy carry out close induction type exposure.

Then, simultaneously by spray-type developing apparatus, 2.38% tetramethylammonium hydroxide aqueous solution being sparged to substrate upper 30 second of one side at 33 ℃ develops.As described above part (exposure portion) development that do not need of photo-sensitive resin is removed, obtain therefrom and on colored filter side group plate, be formed with the base plate for liquid crystal display device that projection is used in the LCD alignment control that comprises the photo-sensitive resin that is patterned as desired shape.

Secondly, this is formed with to LCD alignment control and with the base plate for liquid crystal display device of projection, at 230 ℃, carries out the baking of 30 minutes, on base plate for liquid crystal display device, form therefrom the LCD alignment control projection of sclerosis.

Positive-working photosensitive resin layer is filled a prescription with coating fluid

Eurymeric anti-corrosion liquid (FH-2413F (trade(brand)name) that electronic material limited-liability company of Fuji manufactures)

53.0 parts

46.5 parts of methyl ethyl ketones

0.05 part of Megafac F-780F (trade(brand)name, DIC limited-liability company manufacture)

The making of liquid crystal indicator

The alignment film that comprises polyimide is further set on the base plate for liquid crystal display device of above-mentioned gained.Thereafter, to surround the mode of the pixel group of colored filter, be located at position, that be equivalent to black matrix" housing around, printing epoxy encapsulant, and drip MVA pattern liquid crystal, by after subtend baseplate-laminating, fitted substrate is heat-treated and made hardening seal.

As mentioned above and two faces of liquid crystal cells attach the Polarizer HLC2-2518 (trade(brand)name) that San Li limited-liability company manufactures.Secondly, LED light source as light source (back light of the LCD TV that company of Sony (Sony) manufactures, trade(brand)name, KDL-40ZXl) is disposed to a side that becomes the back side of the liquid crystal cells that is provided with described Polarizer, makes liquid crystal indicator (LCD).

The liquid crystal indicator of making as mentioned above has high contrast gradient and brightness, is suitable for as display unit.In addition, carried out in the present embodiment the evaluation in MVA mode LCD, if think and use coloring effect composition of the present invention in the liquid crystal indicator of other patterns or the colored filter of OLED display, also can similarly obtain good image quality.

Embodiment 2-1

Following each composition is mixed, dissolved and modulates painted curable adhensive compositions 2-1 and evaluate.

21 parts of organic solvents (propylene glycol methyl ether acetate)

25 parts of organic solvents (diethylene glycol ethylmethyl ether)

1 part of alkali soluble resin 1 (allyl methacrylate(AMA)/Sipacril 2739OF=mol ratio 70/30, weight average molecular weight are 26800)

2.2 parts of blocked isocyanate B1 (trade(brand)name: TPA-B80X, chemistry (Asahi Kasei Chemicals) limited-liability company of Asahi Chemical Industry manufacture)

1 3.3 parts of monomer M

(Japanese chemical drug limited-liability company manufactures, KAYARAD DPHA (trade(brand)name))

3.2 part

0.003 part of polymerization retarder (p methoxy phenol)

0.4 part of Photoepolymerizationinitiater initiater 1 (1-(O-acetyl oxime)-1-[9-ethyl-6-(thiophene acyl group)-9H-carbazole-3-yl] acetone)

0.4 part of multifunctional SH compound S 1 (manufacture of Zhao He electrician limited-liability company, trade(brand)name, Karenz MTBDl)

Connect airtight 0.15 part of modifying agent (3-methacryloxypropyl trimethoxy silane)

Fluorine is 5.5 parts, tensio-active agent (Megafac F-554 (trade(brand)name), 0.2% propylene glycol methyl ether acetate solution that DIC company manufactures)

Blue pigments dispersion liquid (with the same person of blue pigments dispersion phase, the pigment Blue 15 that in embodiment 1-1, use: 6 dispersion liquids) 25 parts

16 parts of dye solutions

2 25 parts of dye solutions

Dye solution 1 is that following each composition is mixed, dissolved and modulates.

44.6 parts of organic solvents 1 (propylene glycol methyl ether acetate)

2.4 parts of dyestuffs (P-26)

Dye solution 2 is that following each composition is mixed, dissolved and making dye solution.

48.0 parts of organic solvents 1 (propylene glycol methyl ether acetate)

2.6 parts of dyestuffs [exemplary compounds (11)]

In dye solution 1, comprise (P-26) as (B) porphyrin compound, in dye solution 2, comprise the exemplary compounds (11) as the general formula (I) of (A-1) two pyrroles's methylene radical metal complex compounds.

The formation of painted formation composition layer (pigmented layer)

Upper at the coated glass substrate (1 limit is that the thickness of 75mm, chromium film is 0.3 μ m) of chromium, the painted curable adhensive compositions 2-1 that the spin coater that the mode that becomes 3.0 μ m by the thickness with (after rear baking) after heat hardening is adjusted rotating speed is coated with above-mentioned gained forms coated film.

Secondly, by the coated glass substrate of the chromium that is formed with coated film on hot-plate, carry out under the condition of 100 ℃, 120 seconds pre-bakedly, except desolventizing, make it dry.

After pre-baked, use the extra-high-pressure mercury vapour lamp of 2.5kW, with 200mJ/cm ²exposure the whole face of coated film is carried out to rayed.

Secondly, by hot air circulation type drying machine, the coated glass substrate of the chromium that is formed with coated film after exposure is carried out to heat hardening (baking afterwards) under the condition of 220 ℃, 60 minutes, make the test piece that is formed with pigmented layer.

Evaluate

The mensuration of relative permittivity

The pigmented layer that reams a corner, place of the test piece that is formed with pigmented layer after the rear baking of above-mentioned gained, exposes chromium film surface.Secondly, at the back side of test piece spin coating silver paste it is air-dry.By described silver paste surperficial chromium exposed to the silver paste coated face conducting (be connected) at face and the back side thereafter.Table coated surface in the test piece of gained, use vacuum deposition apparatus (trade(brand)name: ion sputtering E1030 (trade(brand)name), Hitachi Co., Ltd manufacture), by Pt/Pd target, in test piece (substrate) 1, make as shown in Figure 1 main electrode 2 (inner circle) and guarded electrode (guard electrode) 3 (cylindricals) that evaporation thickness is about 50nm.In addition, in test piece 1, expose the chromium film surface 4 reaming.

After electrode fabrication, by contact pin type surface shape measuring device (manufacture of trade(brand)name: DEKTAK3, Ai Fake (ULVAC) limited-liability company) measure test piece not with the thickness of the pigmented layer of the part of electrode.

Secondly, at electrostatic capacitance tester (accurate impedance analysis device 4294A, trade(brand)name, Agilent (agilent) Science and Technology Co., Ltd. manufacture) the upper measurement fixture 16451B (trade(brand)name) of installation and electrode, the test piece 1 of above-mentioned gained is further installed, relative permittivity ε ' when mensuration applies the voltage of alternating current of 1kHz, 0.5V, evaluates according to following metewand.Evaluation result is shown in following table 3.

Metewand

A: relative permittivity ε ' < 3.0

B: relative permittivity ε '=3.0～5.0

C: relative permittivity ε ' > 5.0

The resistance to fluidity of peeling off

By following order a)～e) be determined at the thickness of formed pigmented layer in test piece and calculate swelling rate, using this value of calculating as evaluating the resistance to index of peeling off fluidity.Wherein, resistance to, there is following phenomenon while peeling off the poor situation of fluidity: in the time of in impregnated in stripping liquid, film to be dissolved in and in stripping liquid or on substrate, peel off and cannot measure thickness.This kind of situation is evaluated as to " C ".Evaluation result is shown in following table 3.

A) use contact pin type surface shape measuring device (manufacture of trade(brand)name: DEKTAK3, Ai Fake (ULVAC) limited-liability company) and measure the thickness (FT0) of pigmented layer of the test piece that is formed with pigmented layer of above-mentioned gained.

B) after mensuration, use the mixture (MEA/DMSO=7/3 mass ratio) of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO) (DMSO) as stripping liquid, at 80 ℃, above-mentioned test piece is flooded 120 seconds in stripping liquid.

C) in groove, be full of the liquid of MEA/DMSO=7/3, further flood described b) dipping after test piece.Thereafter, on the test piece brace table of contact pin type surface shape measuring device (manufacture of trade(brand)name: DEKTAK3, Ai Fake (ULVAC) limited-liability company), place the test piece with the state of stripping liquid covering surfaces, measure the thickness (FTl) (measuring the thickness due to the caused swelling state of stripping liquid) of pigmented layer.

D) in other grooves, be full of pure water, impregnated in described c) in the test piece of swelling, standing 1 evening and by after stripping liquid contained in filming and water displacement, test piece is dried to 30 minutes at 200 ℃, again measure the thickness (FT2) of pigmented layer.

E) use by the above-mentioned FT0 measuring, FTl, FT2, according to following formula, calculate respectively swelling rate and the film decrement of test piece, based on following metewand, evaluate the resistance to fluidity of peeling off.In addition, be (FTl-FT0) to measure the apparent swelling causing due to stripping liquid, therefore by being stripped from the film minimizing part (FT2-FT0) of liquid erosion, proofread and correct, thereby calculate real swelling rate.

Real swelling rate (%)=100 * (FTl-FT2)/FT0

Film decrement (%)=100 * (FT2-FT0)/FT0

Metewand

A: real swelling rate≤40%, film decrement≤5%, resistance to peel off fluidity good.

B: real swelling rate≤40%, film decrement > 5%, resistance to peeling off in the scope of fluidity for license.

C: film and dissolve or peel off, resistance to peel off fluidity poor.

[embodiment 2-2～embodiment 2-6]

In embodiment 2-1, as recorded in table 3, change the kind of the particular dye (B) in dye solution 1, similarly carry out with embodiment 2-1 in addition and modulate coloring photosensitive combination, form pigmented layer and evaluate.Evaluation result is shown in following table 3.

[embodiment 2-7～embodiment 2-12]

In embodiment 2-1, as recorded in table 3, change particular dye (A-1), particular dye (A-2) in dye solution 2, similarly carry out with embodiment 2-1 in addition and modulate coloring photosensitive combination, form pigmented layer and evaluate.Evaluation result is shown in following table 3.

[table 3]

It is known according to table 3: even if the painted curable adhensive compositions of the combination that comprises particular dye of the present invention is used and also can show suitable performance in the making of the colored filter of COA mode.

As the announcement of No. 2012-077759, No. 2011-218598, Japanese patent application and Japanese patent application, by with reference to and it is all incorporated in this specification sheets.

As all documents, patent application and the technical specification recorded in this specification sheets, and specifically and severally record by the situation equal extent ground with reference to being incorporated to each document, patent application and technical specification, by with reference to being incorporated in this specification sheets.

Claims

1. a painted curable adhensive compositions, contains:

Choosing freely the represented structure of (A-1) following general formula (I) be coordinated in two pyrroles's methylene radical metal complex compounds of forming on metal or metallic compound and (A-2) the represented structure of following general formula (II) be coordinated in a kind of above dye compound of the group that the azepine pyrroles methylene radical metal complex compounds that forms on metal or metallic compound forms; And

(B) the represented porphyrin compound of following general formula (III),

[changing 1]

In described general formula (I), R ¹, R ², R ³, R ⁴, R ⁵, and R ⁶represent independently of one another hydrogen atom or 1 valency substituting group, R ⁷represent hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical;

[changing 2]

In described general formula (II), R ²¹, R ²², R ²³, R ²⁴, R ²⁵and R ²⁶represent independently of one another hydrogen atom or 1 valency substituting group;

[changing 3]

In described general formula (III), Z ¹, Z ², Z ³and Z ⁴all represent N, or Z ¹and Z ³, and Z ²and Z ⁴the both sides of any a group all represent N, another group represents C-R, R represents respectively hydrogen atom, alkyl or aryl independently; A ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A ⁷and A ⁸represent independently of one another alkyl, thiazolinyl, aryl, alkoxyl group, alkylthio, aryloxy, arylthio, halogen atom, hydroxyl, alkoxy carbonyl, aryloxycarbonyl, amino, carbamyl, sulfamyl, acyl group, silicon alkoxyl group, cyano group, nitro or heterocyclic radical; A ¹with A ², A ³with A ⁴, A ⁵with A ⁶, or A ⁷with A ⁸also can be separately bond and form ring structure mutually, but in these at least one group do not form ring structure; M represents divalent atoms metal or the divalent atoms metal being substituted or the divalent atomic group that comprises atoms metal.

2. painted curable adhensive compositions according to claim 1, the represented porphyrin compound of wherein said (B) general formula (III) is the represented porphyrin compound of following general formula (III-2):

[changing 4]

In described general formula (III-2), A ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A ⁷, A ⁸and the A in M and described general formula (III) ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A7, A ⁸and M synonym separately.

3. painted curable adhensive compositions according to claim 1 and 2, wherein also contains (C) polymerizable compound and (D) Photoepolymerizationinitiater initiater, and is photosensitivity.

4. according to the painted curable adhensive compositions described in any one in claims 1 to 3, wherein, for the total amount of coloring compound contained in described painted curable adhensive compositions, the content of the porphyrin compound that described (B) general formula (III) is represented is more than 0.1 quality %, below 50 quality %.

5. according to the painted curable adhensive compositions described in any one in claim 1 to 4, the represented porphyrin compound of wherein said (B) general formula (III) is the A in described general formula (III) ¹with A ², A ³with A ⁴, A ⁵with A ⁶, and A ⁷with A ⁸any person of group all do not form the compound of ring structure.

6. according to the painted curable adhensive compositions described in any one in claim 1 to 5, wherein for the total solids composition of described painted curable adhensive compositions, comprise the described represented structure of (A-1) general formula (I) and be coordinated in the two pyrroles's methylene radical metal complex compounds that form on metal or metallic compound, the total content that the represented structure of described (A-2) general formula (II) is coordinated in the coloring compound of the azepine pyrroles methylene radical metal complex compounds that forms on metal or metallic compound and the represented porphyrin compound of described (B) general formula (III) is more than 0.2 quality %, below 50 quality %.

7. a colored filter, it is to use according to the painted curable adhensive compositions person of forming described in any one in claim 1 to 6.

8. a manufacture method for colored filter, comprises:

Pigmented layer forms step, by being imparted to according to the painted curable adhensive compositions described in any one in claim 1 to 6, forms pigmented layer on supporter;

Step of exposure is pattern apperance by formed described pigmented layer exposure; And

Development step, develops and forms colored pattern the described pigmented layer after exposure.

9. a display unit, the colored filter that comprises colored filter according to claim 7 or obtain by manufacture method according to claim 8.