CN103571219A

CN103571219A - Dye compound and method of manufacturing the same, colored curable composition, colored cured film, color filter and method of manufacturing the same, and display device

Info

Publication number: CN103571219A
Application number: CN201310317046.1A
Authority: CN
Inventors: 藤田明徳; 石地洋平
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2012-07-27
Filing date: 2013-07-25
Publication date: 2014-02-12
Also published as: JP2014025010A; TWI630240B; TW201404833A; KR20140013993A; JP5642739B2

Abstract

The present invention relates to a dye compound and a method of manufacturing the same, a colored curable composition, a colored cured film, a color filter and a method of manufacturing the same, and a display device. The present invention provides the dye compound which is high in color purity and excellent in heat resistance and the method of manufacturing the same, and the colored curable composition capable of obtaining the colored cured film having good hue, high brightness and excellent heat resistance. The dye compound and the colored curable composition comprising the dye compound are represented by the following general formula (1), wherein R1 and R2 are SO2R3 and COR3, R3 is an alkyl group of which the number of carbons is 1-18 or an aryl group of which the number of carbons is 6-18.

Description

Dye composition and method for making thereof, painted curable adhensive compositions, painted cured film, colored filter and method for making and display unit

Technical field

The present invention relates to a kind of dye composition and manufacture method thereof, painted curable adhensive compositions, painted cured film, colored filter and manufacture method and display unit.

Background technology

Since before, mobile phone, mobile game machine, personal digital assistant (Personal Digital Assistant, PDA) small-scale liquid crystal device, organic electric-excitation luminescent (the Electro Luminescent such as, EL) display unit comprises light source for backlight (back light), and the light irradiating from this light source shows desired image by colored filter.As forming the colored materials (color material) of using in the colored filter of this kind of display unit, advantageously brightness open-wire line high, that can make backlight sees through well and carries out the colored tinting material showing.And, in recent years, the maximization of liquid crystal indicator, organic EL display develops in the purposes such as the display monitor (display monitor) of PC (personal computer) or TV, importantly, in thering is the display unit of large-scale picture, there is color reproduction more than compact display apparatus.For the tinting material using in colored filter, except brightness, must be able to improve purity of color, contrast gradient that left and right picture quality (quality) improves.

For this kind of requirement, carry out following research: use adjustment of color to be relatively easy to that dyestuff replaces the pigment that used since before and as tinting material.By using dyestuff as tinting material, the purity of color that can have due to dyestuff self or the bright-coloured degree of its form and aspect improve form and aspect or the brightness of carrying out the demonstration image of image while showing, and and but the worry that the oversize particle in the situation of use pigment brings has advantages of easy acquisition high-contrast.

As the example of dyestuff, since before, just proposed to there are two pyrroles's methylene dyes, the dye composition of the diversified dye matrix such as pyrimidine azoic dyestuff, pyrazoles azoic dyestuff, xanthene dye, triarylmethane dye (triarylmethane dye).

Except above-mentioned dyestuff, the example as the dyestuff of hot stability or light stability excellence, has disclosed the methine pigment (methine dye) (for example, with reference to patent documentation 1) with ad hoc structure.In addition, as ink-vapor recording kind of dyes, disclosed the dyestuff (for example, with reference to patent documentation 2) that links the structure that has 2 Pyrazolotriazole rings with methyne.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2005-250420 communique

Patent documentation 2: Japanese Patent Laid-Open 2011-12256 communique

Summary of the invention

Up to now, although proposed diversified dyestuff according to various uses or object etc., truth is according to the viewpoint of recording materials purposes, may not reach and meet sufficient characteristic.In the performance that colored materials should have, particularly purity of color is of crucial importance as the characteristic of left and right picture quality, and desired display goes out the form and aspect of absorption peak sharp keen (sharp).

In addition, colored materials not only requires purity of color self good, and require to have can be through maintaining steadily in the long term the weather resistance of its form and aspect, particularly, for example, for being exposed to the stability in hot situation.The colored materials with weather resistance can maintain the desired tone of formed image or brightness, contrast gradient.

The present invention forms in view of above-mentioned, its object is to provide that purity of color is high, the dye composition of excellent heat resistance and manufacture method thereof, obtain form and aspect good and there is the painted curable adhensive compositions of the painted cured film of high brightness, excellent heat resistance, form and aspect are good and have a painted cured film of high brightness, excellent heat resistance, form and aspect are good and have colored filter and a manufacture method thereof of high brightness, contrast gradient, excellent heat resistance, and the display unit that can show through carrying out steadily in the long term distinct image, take and reach this object as problem.

As described below in order to reach the concrete means of described problem.

<1> dye composition, is characterized in that representing with following general formula (1).In following general formula (1), R ¹and R ²represent independently of one another SO ₂r ³or COR ³.R ³the aryl that the alkyl that expression carbon number is 1～18 or carbon number are 6～18.

[changing 1]

<2>, according to the dye composition described in above-mentioned <1>, is characterized in that: in general formula (1), and R ¹and R ²represent independently of one another SO ₂r ³, R ³represent the alkyl that carbon number is 4～18.

<3>, according to the dye composition described in above-mentioned <1>, is characterized in that: in general formula (1), and R ¹and R ²represent independently of one another COR ³, R ³represent the alkyl that carbon number is 6～18.

<4>, according to the dye composition described in any one in above-mentioned <1>～above-mentioned <3>, is characterized in that: have the structure that is selected from following structure.

[changing 2]

<5>, according to the dye composition described in any one in above-mentioned <1>～above-mentioned <4>, is characterized in that: the R in general formula (1) ¹and R ²represent identical base, described dye composition has symmetrical structure.

The manufacture method of a <6> dye composition, is characterized in that: make the represented compound of following general formula (2) react and manufacture according to the dye composition described in any one in above-mentioned <1>～above-mentioned <5> with ortho-formiate compound.In following general formula (2), R ⁵represent SO ₂r ³or COR ³.R ³the aryl that the alkyl that expression carbon number is 1～18 or carbon number are 6～18.

[changing 3]

The manufacture method of a <7> dye composition, is characterized in that: make the represented aldehyde cpd of the represented compound of following general formula (2) and following general formula (3) or its tautomerism precursor reactant and manufacture according to the dye composition described in any one in above-mentioned <1>～above-mentioned <5>.

In following general formula (2), R ⁵represent SO ₂r ³or COR ³.R ³the aryl that the alkyl that expression carbon number is 1～18 or carbon number are 6～18.And, in following general formula (3), R ⁶represent SO ₂r ³or COR ³, R ³the aryl that the alkyl that expression carbon number is 1～18 or carbon number are 6～18.

[changing 4]

<8> painted curable adhensive compositions, is characterized in that: at least comprise according to dye composition and polymerizable compound described in any one in above-mentioned <1>～above-mentioned <5>.

<9>, according to the painted curable adhensive compositions described in above-mentioned <8>, is characterized in that: also comprise polymerization starter.

<10>, according to the painted curable adhensive compositions described in above-mentioned <8> or above-mentioned <9>, is characterized in that: also comprise phthalocyanine pigment or derivatives thereof.

<11>, according to the painted curable adhensive compositions described in any one in above-mentioned <8>～above-mentioned <10>, is characterized in that: also comprise and be selected from triarylmethane dye, indolenium squaraine cyanine dye (squarylium dye) and phthalocyanine pigment (phthalocyanine dye) at least a kind.

<12> painted cured film, is characterized in that: comprise according to the dye composition described in any one in above-mentioned <1>～above-mentioned <5>.

<13> colored filter, is characterized in that: comprise according to the painted cured film described in above-mentioned <12>.

The manufacture method of a <14> colored filter, is characterized in that comprising:

To be applied on supporter according to the painted curable adhensive compositions described in any one in above-mentioned <8>～above-mentioned <11>, form the step of coloring film; And

By being pattern-like by the exposure of described coloring film, developing and form the step of painted cured film.

<15> display unit, is characterized in that: comprise according to the colored filter described in above-mentioned <13> or by the colored filter of manufacturing according to the manufacture method of the colored filter described in above-mentioned <14>.

The effect of invention

According to the present invention, provide that purity of color is high, the dye composition of excellent heat resistance and manufacture method thereof.And,

According to the present invention, provide the painted curable adhensive compositions that can obtain form and aspect well and there is the painted cured film of high brightness, excellent heat resistance.In addition,

According to the present invention, provide form and aspect good and there is colored filter and the manufacture method thereof of high brightness, contrast gradient, excellent heat resistance.In addition,

According to the present invention, provide the display unit that can show through carrying out steadily in the long term distinct image.

Embodiment

Below, to the dye composition of novelty of the present invention and manufacture method thereof and use the painted curable adhensive compositions of this dye composition, painted cured film, colored filter and manufacture method thereof and display unit to be described in detail.

In addition; in this manual; (methyl) acrylate is the both sides' that comprise acrylate and methacrylic ester implication; and (methyl) propenyl is with the both sides' that comprise propenyl and methylpropenyl implication and use, (methyl) acryl is with the both sides' that comprise acryl and methacryloyl implication and use.

< dye composition and manufacture method > thereof

Dye composition of the present invention is the represented compound of following general formula (1).This dye composition presents yellow form and aspect.

Since before, the known compound that has various structures of dye compound with Pyrazolotriazole ring, but to show image colour characteristics require highly, must further improve yellow purity of color, thermotolerance.Given this plant situation, dye composition of the present invention is characterised in that: in the Pyrazolotriazole ring in molecule, have following structure, that is, there is the tertiary butyl and in para-orientation, have the structure of the amino phenyl being substituted, if this kind of structure, the absorption peak that presents the maximum absorption wavelength in yellow wavelength region may (400nm～500nm) is sharp keen, the high and excellent heat resistance of purity of color.

[changing 5]

In general formula (1), R ¹and R ²represent independently of one another SO ₂r ³or COR ³.R ³the aryl that the alkyl that expression carbon number is 1～18 or carbon number are 6～18.

R ³represented carbon number is that 1～18 alkyl can be any number of of linear chain structure or branched structure, can be unsubstituted also can further be substituted base and replace.R ³the concrete example of represented alkyl can be enumerated methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, hexyl, cyclohexyl, heptyl, 3-heptyl, octyl group, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, methoxyethoxyethyl, ethoxy carbonyl ethyl etc.Wherein, as R ³represented alkyl, considers from purity of color or stable on heating viewpoint, is preferably carbon number and is 4～18 alkyl, the alkyl that more preferably carbon number is 6～18, the alkyl that further more preferably carbon number is 6～12.

And, at alkyl, having in substituent situation, this substituting group is such as enumerating halogen atom, alkoxyl group, ester group, amide group, sulfoamido etc.

R ³represented carbon number is that 6～18 aryl can be unsubstituted and also can further be substituted base and replace.R ³the concrete example of represented aryl can be enumerated phenyl, 2-aminomethyl phenyl, 4-ethoxy carbonyl phenyl, 4-chloro-phenyl-, 3-(2-ethyl hexyl oxy carbonyl) phenyl.Wherein, from purity of color or stable on heating viewpoint, consider R ³it is 8～18 aryl that represented aryl is preferably carbon number, the aryl that more preferably carbon number is 10～18.

And, at aryl, there is in substituent situation this substituting group and above-mentioned similarly such as enumerating halogen atom, alkoxyl group, ester group, amide group, sulfoamido etc.

The concrete example of the dye composition that general formula (1) is represented can be enumerated the concrete example (exemplary compounds Y-1～exemplary compounds Y-26) of following structure.But in the present invention, not limited by those compounds.

[changing 6]

[changing 7]

[changing 8]

In above-mentioned, as the R in general formula (1) ¹, R ², in presenting yellow wavelength region may, show sharper keen absorption peak, the aspect that purity of color and thermotolerance are more excellent, preferably R ¹and R ²both sides all represent SO ₂r ³situation, R in such cases ³be preferably carbon number and be 4～18 alkyl, the alkyl that more preferably carbon number is 6～18, the alkyl that further more preferably carbon number is 8～12.

And, as the R in general formula (1) ¹, R ², in presenting yellow wavelength region may, show sharper keen absorption peak, the aspect that purity of color and thermotolerance are more excellent, also preferred R ¹and R ²both sides all represent COR ³situation, R in such cases ³be preferably carbon number and be 6～18 alkyl, the alkyl that more preferably carbon number is 6～12.

In addition, in general formula (1), preferred R ¹and R ²all represent SO ₂r ³(R ³for the carbon number alkyl that is 8～12) situation, further R particularly preferably ¹and R ²all represent SO ₂r ³, R ¹in R ³with R ²in R ³the situation that represents identical alkyl.Wherein, particularly preferably above-mentioned exemplary compounds Y-1, exemplary compounds Y-3, exemplary compounds Y-6, most preferably exemplary compounds Y-1, exemplary compounds Y-3.

The synthetic of the dye composition that general formula (1) is represented can carry out according to existing known method, in the present invention, can utilize following method A, method B and carries out aptly.

< method A (symmetrical structure) >

The represented dye composition of general formula of the present invention (1) can be by making the represented compound of following general formula (2) and ortho-formiate compound (HC (OR) ₃, R is alkyl) reaction synthesizes.

In general formula (2), R ⁵represent SO ₂r ³or COR ³, R ³the aryl that the alkyl that expression carbon number is 1～18 or carbon number are 6～18.Herein, SO ₂r ³and COR ³and R ³details and the SO of described general formula (1) ₂r ³and COR ³and R ³identical, preferred form is also identical.

[changing 9]

Concrete synthesis method is in such cases shown in following flow process 1.

As shown in flow process 1, make pre-prepd for example compd A and there is desired SO ₂r ³or COR ³the compound reaction at position, generate the represented compound (intermediate) of general formula (2).Secondly, this compound is reacted with ortho-formiate compound, make therefrom the represented compound dimerization (dimerization) of general formula (2), the synthetic dye composition with symmetrical structure.

Herein, compd A can utilize european patent application to disclose the method for recording in No. 0571959 specification sheets.

Ortho-formiate compound is such as enumerating trimethyl orthoformate, triethyl orthoformate etc.

[changing 10]

< method B (unsymmetric structure) >

The represented dye composition of general formula of the present invention (1) can be by synthesizing the represented aldehyde cpd of the represented compound of above-mentioned general formula (2) and following general formula (3) or its tautomerism precursor reactant.

In general formula (3), R ⁶represent SO ₂r ³or COR ³, R ³the aryl that the alkyl that expression carbon number is 1～18 or carbon number are 6～18.Herein, SO ₂r ³and COR ³and R ³details and the SO of described general formula (1) ₂r ³and COR ³and R ³identical, preferred form is also identical.

[changing 11]

Concrete synthesis method is in such cases shown in following flow process 2.

As shown in flow process 2, make pre-prepd for example compd A and above-mentioned flow process 1 similarly with there is desired SO ₂r3 or COR ³the 1st compound reaction at position, generate the represented compound (intermediate 1) of general formula (2).In contrast to this, similarly make compd A and there is desired SO with above-mentioned flow process 1 ₂r ³or COR ³the 2nd compound reaction at position, generate after the represented compound (intermediate 2) of general formula (2), generate the aldehyde body of this intermediate 2.Secondly, make the dye composition of intermediate 1 unsymmetric structure synthetic with the aldehyde precursor reactant of intermediate 2.

[changing 12]

The painted curable adhensive compositions > of <

Painted curable adhensive compositions of the present invention is at least used described dye composition of the present invention (the represented dye composition of general formula (1)) to form with polymerizable compound.Painted curable adhensive compositions of the present invention is owing to containing as described above dye composition of the present invention, so the absorption peak under maximum absorption wavelength is sharp keen and form and aspect are excellent, has high brightness.

And painted curable adhensive compositions of the present invention preferably more contains polymerization starter, also can optionally further contain other compositions such as tackiness agent, linking agent or tensio-active agent, organic solvent etc.

-dyestuff-

Painted curable adhensive compositions use of the present invention is selected from the one kind or two or more of described dye composition and forms as coloring components, also can be also by other colored materials beyond this dye composition.In addition, about details and the preferred configuration of dye composition of the present invention, as mentioned above.

Content as the represented dye composition of described general formula (1) in painted curable adhensive compositions is preferably 5 quality %～50 quality %, more preferably 10 quality %～30 quality % for the total solid of painted curable adhensive compositions.

If the ratio that contains of dye composition is more than 5 quality %, obtain good yellow form and aspect, there is high brightness, and thermotolerance is more excellent.And, if the ratio that contains of dye composition is below 50 quality %, suppressing to separate out in dyestuff self-hardening composition, the aspect of the developability when patterning is favourable.

As in painted curable adhensive compositions of the present invention can and other colored materials of use, the tinting material (below also referred to as " other tinting materials ") that the structure that can enumerate the compound represented from described general formula (1) is different, have different form and aspect.If other tinting materials are selected from known dyestuff, dye derivate, pigment and the colo(u)rant dispersion thing at visible light wave range with absorption.

In addition, the represented compound of described general formula (1) has maximum absorption peak wavelength (λ at the wave band of 400nm～500nm _max), so other tinting materials can suitablely be used in the tinting material that surpasses the wave band of 500nm as the absorption peak of the maximum absorption wavelength below the above 800nm of 380nm of the wave band of visible ray.

In the present invention, the absorption peak of the compound that described general formula (1) is represented and the maximum absorption wavelength of other tinting materials is, with solvent, the dye solution that comprises colored materials or the dispersible pigment dispersion adjustment that become determination object are become to measurable concentration (for example absorbancy becomes 0.8～1.0 concentration), the value of using CARY5/ ultraviolet ray (Ultra Violet, UV)-visible spectrophotometer (manufacture of Varian (Varian) company) and measuring.

As the dyestuff that can be used as other tinting materials, can select to be suitable for form and aspect not being impacted or being formed the dyestuff of desired form and aspect, can be structure arbitrarily, for example can enumerate triarylmethane dye, indolenium squaraine cyanine dye, phthalocyanine pigment.

The dyestuff of recording in the preferred Japanese Patent Laid-Open 2007-94187 communique of triarylmethane dye, Japanese Patent Laid-Open 2008-304766 communique.The dyestuff of recording in No. 4413193rd, the preferred Japanese Patent Laid-Open 2004-099713 communique of indolenium squaraine cyanine dye, Japanese Patent.The dyestuff of recording in the preferred Japanese Patent Laid-Open 2009-51896 communique of phthalocyanine pigment, Japanese Patent Laid-Open 2011-197670 communique.

And, as the pigment that can be used as other tinting materials, such as can Lie Ju perylene (perylene), purple cyclic ketones, quinacridone, quinacridone quinone, anthraquinone, anthracene form anthrone (anthanthrone), benzimidazolone, disazo condensation thing, tetrazo, azo, indanthrene, phthalocyanine, triaryl carbonium ion (triaryl carbonium), dioxazine, aminoanthraquinone, diketopyrrolopyrrolecocrystals, indigo, thioindigo, isoindoline, isoindolinone, pyranthrone or iso-violanthrone etc.More specifically, for example can enumerate Pigment red 190, Pigment red 224, pigment violet 29 pigment such as compound such as perylene such as Deng, pigment orange 43, or the purple cyclic ketones compound such as Pigment red 194 pigment, pigment violet 19, pigment violet 42, pigment red 122, Pigment red 192, Pigment red 202, Pigment Red 207, or the quinacridone compound pigment such as Pigment red 209, Pigment red 206, pigment orange 48, or the quinacridone naphtoquinone compounds pigment such as pigment orange 49, the anthraquinone compounds pigment such as pigment yellow 147, Pigment red 168 anthracenes such as grade are formed anthrone compound pigment, pigment brown 25, pigment violet 32, pigment orange 36, pigment Yellow 12 0, Pigment Yellow 73 180, Pigment Yellow 73 181, pigment orange 62, or the benzimidazolone compound pigment such as Pigment red 185, Pigment Yellow 73 93, Pigment Yellow 73 94, Pigment Yellow 73 95, pigment Yellow 12 8, Pigment Yellow 73 166, pigment orange 34, pigment Orange 13, pigment orange 31, Pigment red 144, Pigment red 166, Pigment red 220, Pigment red 221, Pigment red 242, Pigment red 248, Pigment red 262, or the disazo condensation compound pigment such as pigment brown 23, pigment yellow 13, pigment yellow 83, or the tetrazo compound pigment such as Pigment Yellow 73 188, Pigment red 187, Pigment red 170, Pigment Yellow 73 74, Pigment Yellow 73 150, pigment red 48, Pigment red 53, pigment orange 64, or the azo-compound pigment such as Pigment red 247, the indanthrene compound pigment such as pigment blue 60, pigment Green 7, pigment green 36, Pigment green 37, Pigment green 58, pigment blue 16, Pigment blue 75, or the phthalocyanine compound pigment such as pigment Blue 15, Pigment blue 56, or the triaryl carbonium ion compound pigment such as pigment Blue-61, pigment Violet 23, or pigment violet 37 dioxazine compound pigment, Pigment red 177 pigment such as compound such as aminoanthraquinone such as grade, Pigment red 254, Pigment red 255, Pigment red 264, Pigment red 272, pigment orange 71, or the Diketopyrrolo-pyrrole compounds pigment such as pigment orange 73, the thioindigo compound pigment such as pigment Red 88, pigment yellow 13 9, pigment orange 66 pigment such as isoindoline compounds such as grade, Pigment Yellow 73 109, or the isoindoline ketone compound pigment such as pigment orange 61, pigment orange 40, or the pyranthrone compound pigment such as pigment red 21 6, or the iso-violanthrone compound pigment such as pigment violet 31.

If be conceived to the structure of preferred pigment, preferably painted curable adhensive compositions of the present invention contains phthalocyanine pigment or derivatives thereof as other tinting materials.By comprising phthalocyanine pigment or derivatives thereof, can obtain the painted curable adhensive compositions that dispersion stabilization or tinting strength are excellent, can form the painted cured film with high brightness.

Phthalocyanine pigment or derivatives thereof can be enumerated copper phthalocyanine, ZnPc pigment, copper halide phthalocyanine pigment and zinc halide phthalocyanine pigment.The concrete example of those pigment can be enumerated pigment Blue 15: 6, pigment Green 7, pigment green 36, Pigment green 58.In the situation that forming green coloring cured film, the halogenated phthalocyanines pigment such as preferred pigments green 58 or pigment green 36.

Preferred phthalocyanine pigment can be enumerated the represented ZnPc compound of following general formula (P).

[changing 13]

In general formula (P), A ¹, A ², A ³, A ⁴, A ⁵, A ⁶, A ⁷, A ⁸, A ⁹, A ¹⁰, A ¹¹, A ¹², A ¹³, A ¹⁴, A ¹⁵, and A ¹⁶represent independently of one another halogen atom, alkyl, alkoxyl group or thio alkoxy.

A in general formula (P) ¹～A ¹⁶preferably represent independently of one another hydrogen atom, chlorine atom or bromine atoms, preferably at least 8 in those are bromine atoms.By making A ¹～A ¹⁶in 8 be above bromine atoms, present with the high green of the brightness of yellow hue, be suitable for forming the green coloring region of colored filter.In addition, there is the ZnPc compound of 10 above bromine atoms comparatively suitable.

The average composition of ZnPc compound can easily be obtained with utilizing the content of halogen analysis of flask combustion ion chromatography (flask combustion and ion chromatography) according to the mass analysis based on mass spectroscopy (mass spectrometry).

ZnPc compound is manufactured such as utilizing the known manufacture method such as chlorosulfonic acid method, halogenation phthalonitrile method, scorification.About manufacture method more specifically, in Japanese Patent Laid-Open 2008-19383 communique, Japanese Patent Laid-Open 2007-320986 communique, Japanese Patent Laid-Open 2004-70342 communique etc., record to some extent in detail.

Other tinting materials that are used in combination as the represented dye composition of the described general formula (1) with presenting yellow form and aspect, from the viewpoint that is suitable for colored filter purposes, consider, in wave band more than 380nm, below 800nm, preferably the wave band more than 500nm, below 800nm has the tinting material of maximum absorption wavelength, and more preferably the wave band more than 600nm, below 700nm has the tinting material of maximum absorption wavelength.Particularly preferably green hue that is the wave band more than 600nm, below 700nm have the tinting material of maximum absorption wavelength, such as enumerating pigment green 36 or Pigment green 58 etc.

In addition, as Pigment green 58 and known pigment is the pigment being contained in bromination phthalocyanine pigment.

The scope that the preferred average primary particle diameter of phthalocyanine pigment or derivatives thereof is 10nm～40nm.By by the ZnPc compound of the average primary particle diameter of this scope and represented dye composition the use of described general formula (1), can obtain the painted curable adhensive compositions that dispersion stabilization or tinting strength are excellent and brightness is high, contrast gradient is high.

In addition, average primary particle diameter is with transmission electron microscope, the particle in the visual field to be photographed, primary particle to the ZnPc series pigments of the formation aggregate on 100 two dimensional images, obtain respectively the mean value of long diameter (major diameter) and short diameter (minor axis), the value that it is averaged.

In the situation that using pigment as other tinting materials, preferred previously prepared colo(u)rant dispersion thing and using.Colo(u)rant dispersion thing for example can be prepared according to the record of Japanese patent laid-open 9-197118 communique or Japanese Patent Laid-Open 2000-239544 communique.

In the situation that and be used as the dyestuff of other tinting materials or the content of pigment, as long as in not undermining the scope of effect of the present invention, particularly, for the total solid of painted curable adhensive compositions of the present invention, be preferably 0.5 quality %～70 quality %.For represented dye composition 100 mass parts of described general formula (1), the ratio that contains of other tinting materials is preferably 20 mass parts～500 mass parts.

-polymerizable compound-

At least one that painted curable adhensive compositions of the present invention contains polymerizable compound.By comprising polymerizable compound, can form cured film.Polymerizable compound for example can be enumerated the addition polymerization compound with at least 1 ethene unsaturated double-bond.

The polymerizable compound with at least 1 ethene unsaturated double-bond, can suitable selection in known compound, for example can enumerate the compound of recording in paragraph numbering [0027]～paragraph numbering [0053] of the compound recorded in paragraph numbering [0010]～paragraph numbering [0020] of Japanese Patent Laid-Open 2006-23696 communique or Japanese Patent Laid-Open 2006-64921 communique.

About polymerizable compound, its structure, separately use or and the details of the using method such as use, addition can be according to the final functional design of painted curable adhensive compositions and at random setting.For example, in the viewpoint of sensitivity, consider, preferred many structures of unsaturated group content in every 1 molecule, in the situation that unsaturated group content is many, preferably 2 officials can more than.And, in the viewpoint that improves painted sclerosis film strength, consider, the polymerizable compound that preferably 3 officials can be above, in addition by and for example, with the polymerizable compound of different functional number, different polymerizability base (acrylate, methacrylic ester, polystyrene compound, Vinyl Ether based compound), regulate both sides' the method for sensitivity and intensity also effective.And, for with painted curable adhensive compositions in for the consistency, dispersiveness of contained other compositions (such as Photoepolymerizationinitiater initiater, tinting material (pigment), binder polymer etc.), the selection of polymerizable compound, to make usage be important factor, sometimes for example by using low-purity compound or and can making consistency improve with two or more.And the viewpoint improving in the adhesion making with the hard surface of substrate etc., also can select specific structure.

As polymerizable compound, the carbamate addition polymerization compound that uses the addition reaction of isocyanic ester and hydroxyl and manufacture is 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 the polyester acrylate class 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, epoxy resin is reacted and polyfunctional acrylate or the methacrylic esters such as Epoxy Acrylates of gained with (methyl) vinylformic acid.In addition, also can be set forth in the compound that Japan is then introduced as photo-hardening monomer and oligomer in association's magazine the 20th volume, No. 7, the 300th page～the 308th page (1984).

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) upgrading thing, Dipentaerythritol six (methyl) acrylate EO upgrading thing etc.And polymerizable compound also can be used the commercially available product of selling on market.Example as this commercially available product, can enumerate NK ESTER A-TMMT, NK ESTER A-TMM-3, NK Oligo UA-32P, NK Oligo UA-7200 (manufacture of above You Xinzhong village chemical industry Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronix M-402, TO-1382 (being manufactured by Toagosei Co., Ltd above), V#802 (Osaka Organic Chemical Industry Co., Ltd.'s manufacture), Kayarad D-330, Kayarad D-320, Kayarad D-310, Kayarad DPHA (being manufactured by Nippon Kayaku K. K above) etc. are as preference.

And, polymerizable compound also can be also with two or more, the viewpoint that for example self-hardening exposure sensitivity and developability are adjusted considers, preferably the EO upgrading things such as dipentaerythritol acrylate and tetramethylolmethane four (methyl) acrylate EO upgrading thing, Dipentaerythritol six (methyl) acrylate EO upgrading thing is used in combination.By those combinations, can make patterning suitability further improve.

Polymerizable compound contained in painted curable adhensive compositions can be only a kind, also can be according to object and and use two or more.

In the aspect that more effectively plays effect of the present invention, for the total solid of painted curable adhensive compositions, the content (comprising of more than two kinds situation in is total content) of polymerizable compound in painted curable adhensive compositions is preferably 10 quality %～80 quality %, more preferably 15 quality %～75 quality %, are particularly preferably 20 quality %～60 quality %.

-polymerization starter-

At least one that preferred painted curable adhensive compositions of the present invention contains polymerization starter.If the form that the sclerosis form in the present invention is hardened by the polyreaction of polymerizable compound is also unrestricted, can be by thermopolymerization or photopolymerisable any number of form of hardening.Painted curable adhensive compositions of the present invention is preferably configured to the composition of photopolymerization sclerosis, preferably contains Photoepolymerizationinitiater initiater as the composition of polymerization starter.

Below, centered by Photoepolymerizationinitiater initiater, be illustrated.Photoepolymerizationinitiater initiater is induction light and cause, promote the compound of the polymerization of polymerizable compound.Wherein, preferably responding to wavelength is the compound that more than 300nm active ray causes, promotes the polymerization of polymerizable compound.If Photoepolymerizationinitiater initiater can make the compound of polymerizable compound polymerization, there is no particular restriction, the generation efficiency that be preferably consideration characteristics, causes kind, absorbing wavelength, acquired, cost etc. and select.

And, about directly not responding to the Photoepolymerizationinitiater initiater that wavelength is active ray more than 300nm, can be by preferably using with sensitizing agent combination.

Photoepolymerizationinitiater initiater such as can enumerate be selected from halogen Jia oxadiazole (halomethyl oxadiazole) compound and monochloromethyl s-triazine at least a kind of active halogen compound, 3-aryl substituted cumarin compound, cough up fen dimer, benzophenone cpd, acetophenone compound and derivative thereof, cyclopentadiene-benzene-iron misfit thing and salt, oxime compound etc.The concrete example of Photoepolymerizationinitiater initiater can be enumerated the middle compound of recording of paragraph [0070]～paragraph [0077] of Japanese Patent Laid-Open 2004-295116 communique.Wherein, preferred organic halogenated compound, Hexaarylbiimidazole compound, oxime compound (being also called below oxime is Photoepolymerizationinitiater initiater) etc., the considerations such as the willing aspect of auto-polymerization, preferably oxime is Photoepolymerizationinitiater initiater.

Oxime is that Photoepolymerizationinitiater initiater is not particularly limited, such as enumerating the oxime compound of recording in Japanese Patent Laid-Open 2000-80068 communique, WO02/100903A1, Japanese Patent Laid-Open 2001-233842 communique etc.

Concrete example can be enumerated 2-(O-benzoyl oxime)-1-[4-(phenyl sulfenyl) phenyl]-1, 2-dimethyl diketone, 2-(O-benzoyl oxime)-1-[4-(phenyl sulfenyl) phenyl]-1, 2-diacetylmethane, 2-(O-benzoyl oxime)-1-[4-(phenyl sulfenyl) phenyl]-1, 2-hexanedione, 2-(O-benzoyl oxime)-1-[4-(phenyl sulfenyl) phenyl]-1, 2-heptadione, 2-(O-benzoyl oxime)-1-[4-(phenyl sulfenyl) phenyl]-1, 2-acetyl caproyl, 2-(O-benzoyl oxime)-1-[4-(aminomethyl phenyl sulfenyl) phenyl]-1, 2-dimethyl diketone, 2-(O-benzoyl oxime)-1-[4-(ethylphenyl sulfenyl) phenyl]-1, 2-dimethyl diketone, 2-(O-benzoyl oxime)-1-[4-(butyl phenyl 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, 2-(benzoyloxy imino-)-1-[4-(phenyl sulfenyl) phenyl]-1-octanone, 2-(acetoxyl group imino-)-4-(4-chloro-phenyl-sulfenyl)-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-butanone etc.But be not limited to those compounds.

And, in the present invention, painted viewpoint when sensitivity, ageing stability, later stage heating considers, oxime is the compound that Photoepolymerizationinitiater initiater more preferably selects the group that free following formula (1) or the represented compound of following formula (2) form.

[changing 14]

In formula (1), R and X represent the substituting group of 1 valency independently of one another, and A represents the organic radical of divalent, and Ar represents aryl.N is 0～5 integer.

From the aspect of high-sensitivity, the preferred acyl group of R, for example more preferably ethanoyl, propionyl, benzoyl, toluyl.

From improving sensitivity, suppress to pass through in time caused painted aspect and consider due to heating the alkylene that A is preferably unsubstituted, the alkylene for example, replacing through alkyl (methyl, ethyl, the tertiary butyl, dodecyl), the alkylene for example, replacing through thiazolinyl (vinyl, allyl group), the alkylene for example, replacing through aryl (phenyl, p-methylphenyl, xylyl, cumenyl, naphthyl, anthryl, phenanthryl, styryl).

From improving sensitivity, suppressing because caused painted aspect consideration, the phenyl that Ar is preferably substituted or is unsubstituted are passed through in heating in time.In the situation that the phenyl being substituted, its substituting group is such as being preferably the halogens such as fluorine atom, chlorine atom, bromine atoms, iodine atom.

The aspect that assimilated efficiency from solvent solubility and long wavelength region improves, X is preferably 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 alkyl sulfide ketone group, also can have substituent aryl thioketones base, also can have substituent amino.

And the n in formula (1) is preferably 0～2 integer.

The example of the compound that formula (1) is represented is the compound of following (D-2) represented structure preferably.

[changing 15]

[changing 16]

In formula (2), X ¹, X ², and X ³represent independently of one another hydrogen atom, halogen atom or alkyl.R ¹expression-R ,-OR ,-COR ,-SR ,-CONRR ' or-CN, R ²and R ³independently of one another expression-R ,-OR ,-COR ,-SR or-NRR '.R and R ' represent alkyl, aryl, aralkyl or heterocyclic radical independently of one another, and those bases also can be through selecting a kind of above replacement of the group that free halogen atom and heterocyclic radical form.1 of carbon atom who forms the represented alkyl of R, R ' and the alkyl chain in aralkyl also can be substituted by unsaturated link(age), ehter bond or ester bond above, and R and R ' be bond and form ring mutually also.

The example of the compound that formula (2) is represented is preferably the compound of following (D-3) represented structure.

[changing 17]

If the example of organic halogenation compound can be enumerated Lin Dengren, 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.Hutt < < heterocyclic chemistry magazine (Journal of Heterocyclic Chemistry) > > 1 (No3), etc. (1970) compound of recording in, particularly can enumerate through trihalogenmethyl and replace oxazole compounds, s-triazine is as suitable example.

The example of Hexaarylbiimidazole compound can be enumerated 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, 622, the various compounds of recording in No. 286 each specification sheetss such as grade, particularly can enumerate 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-(neighbours, p-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis-(Chloro-O-Phenyl)-4, 4 ', 5, 5 '-tetra-(m-methoxyphenyl) bisglyoxaline, 2, 2 '-bis-(neighbours, neighbour '-dichlorophenyl)-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.

And, also can use the known Photoepolymerizationinitiater initiater of recording in the paragraph numbering 0079 of Japanese Patent Laid-Open 2004-295116 communique.

Wherein, as Photoepolymerizationinitiater initiater, suitable is oxime compound, more preferably above-mentioned (D-2), (D-3) represented compound.

Photoepolymerizationinitiater initiater can contain separately a kind or combination contain two or more.

From the viewpoint that more effectively plays effect of the present invention, consider, for the total solid of painted curable adhensive compositions, the content (of more than two kinds situation in be total content) of Photoepolymerizationinitiater initiater in painted curable adhensive compositions is preferably 0.5 quality %～30 quality %, 3 quality %～20 quality % more preferably, further 4 quality %～19 quality % more preferably, are particularly preferably 5 quality %～18 quality %.

-tackiness agent-

Painted curable adhensive compositions of the present invention can be used tackiness agent and form.Tackiness agent preferably has the alkali-soluble tackiness agent of alkali-soluble, can select according to thermotolerance, developability, the viewpoint such as acquired.

Alkali-soluble tackiness agent is wire organic high molecular polymer, preferably dissolves in organic solvent and available weak base aqueous solution develops.This kind of wire organic high molecular polymer can be recited in the polymkeric substance that side chain has carboxylic acid, such as the Sipacril 2739OF of recording in each communiques such as 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, clear No. 59-71048 of Japanese Patent Laid-Open that can be recited in Japanese Patent Laid-Open, acrylic copolymer, itaconic acid copolymer, β-crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc.And the acid cellulose derivative in side chain with carboxylic acid is also suitable.In addition, can suitablely be recited in compound that on the polymkeric substance with hydroxyl, addition acid anhydrides forms etc., or polycarboxylated styrene is resin, polysiloxane series resin, poly-((methyl) 2-Hydroxy ethyl acrylate), polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol etc.

In above-mentioned, from stable on heating viewpoint, to consider, it is resin, polysiloxane series resin, acrylic resin, acrylamide resin, acrylic acid/acrylamide copolymer resin that alkali-soluble tackiness agent is preferably polycarboxylated styrene.And the viewpoint that autography is controlled is considered, preferred acrylic resin, acrylamide resin, acrylic acid/acrylamide copolymer resin.

In those alkali-soluble tackiness agents, acrylic resin can be enumerated the multipolymer that forms by being selected from the monomer of (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid, (methyl) Hydroxyethyl Acrylate, (methyl) acrylamide etc. (for example benzyl methacrylate/methacrylic acid (=65/35[mol ratio]) multipolymer), or as KS-RESIST-106 (Osaka Organic Chemical Industry Co., Ltd.'s manufacture), the CYCLOMER-P series (Daisel chemical industry Co., Ltd) of the example of the commercially available product of selling on market etc. as suitable acrylic resin.

And in the situation that painted curable adhensive compositions is configured to positive type composition, alkali-soluble tackiness agent can be used alkali-soluble phenol resins.Alkali-soluble phenol resins is such as enumerating resol, vinyl polymer etc.

Resol for example can be enumerated and make phenols and aldehydes carry out condensation and the resin of gained under the existence of acid catalyst.Herein, the example of phenols can be enumerated phenol, cresols, diethylstilbestrol, fourth phenol, xylenol, phenylphenol, pyrocatechol, Resorcinol, pyrogallol (pyrogallol), naphthols, dihydroxyphenyl propane etc.The example of aldehydes can be enumerated formaldehyde, paraformaldehyde, acetaldehyde, propionic aldehyde, phenyl aldehyde etc.Phenols and aldehydes can be used alone a kind of or are used in combination two or more.

The concrete example of resol can be enumerated the condensation product of meta-cresol, p-cresol or those mixture and formalin.

And, also can in resol, mix bisphenol-c or dihydroxyphenyl propane etc. and there is the low molecular weight compositions that phenol is hydroxyl.

The weight average molecular weight of tackiness agent (the polystyrene conversion value of measuring by gel permeation chromatography (Gel-Permeation Chromatography, GPC) method) is preferably 1000～2 * 10 ⁵, more preferably 2000～1 * 10 ⁵, be particularly preferably 5000～5 * 10 ⁴.

The viewpoints such as self-hardening, developability, film strength and shape are considered, for the total solid of painted curable adhensive compositions, the content of tackiness agent in painted curable adhensive compositions is preferably 10 quality %～90 quality %, 20 quality %～80 quality % more preferably, further 30 quality %～70 quality % more preferably.

-other compositions-

Painted curable adhensive compositions of the present invention, except mentioned component, also can optionally comprise sensitizing agent, chain-transfer agent, polymerization retarder, organic solvent, linking agent, tensio-active agent, connects airtight modifying agent and development accelerant and packing material, various additives such as antioxidant, UV light absorber, aggregation inhibitor etc.

(sensitizing agent)

Painted curable adhensive compositions of the present invention also can comprise sensitizing agent.Sensitizing agent can be set forth in Ke Liweinuo (Crivello) [J.V gram of Li Weinuo (J.V.Crivello), polymer science (Adv.in Polymer Sci), 62,1 (1984)] sensitizing agent of recording in etc., 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.Be preferably the ratio of take for Photoepolymerizationinitiater initiater as 50 quality %～200 quality % and add sensitizing agent.

Sensitizing agent has advantages of as follows: the sensitivity of coexisted Photoepolymerizationinitiater initiater is improved, also with suitable sensitizing agent, also the Photoepolymerizationinitiater initiater of directly not responding to exposure wavelength can be applicable in painted curable adhensive compositions as described above.

(chain-transfer agent)

Painted curable adhensive compositions of the present invention also can contain chain-transfer agent.Chain-transfer agent 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, 1; 3; 5-tri-(3-sulfydryl butoxyethyl group)-1; 3; 5-triazine-2,4,6 (1H; 3H; 5H)-triketone etc. has the sulfhydryl compound of heterocycle, and the multifunctional sulfhydryl compound of aliphatics such as tetramethylolmethane four (3-sulfydryl butyric ester), Isosorbide-5-Nitrae-bis-(3-sulfydryl butyryl radicals oxygen base) butane etc.

Chain-transfer agent can be used alone a kind, also can and use two or more.In the inhomogenous aspect of desensitization, for the total solid of painted curable adhensive compositions, the content of chain-transfer agent is preferably 0.01 quality %～15 quality %, and more preferably 0.1 quality %～10 quality %, is particularly preferably 0.5 quality %～5 quality %.

(polymerization retarder)

Painted curable adhensive compositions of the present invention also can contain polymerization retarder.So-called polymerization retarder refers to the material functioning as follows: the polymerizations such as free radical that produce in painted curable adhensive compositions due to light or heat are caused and kind implement hydrogen for giving (or hydrogen is authorized), energy for giving (or energy is authorized), electronics for giving (or electronics is authorized) etc., polymerization initiation kind is deactivated, suppress the polyreaction unexpectedly causing.The example of polymerization retarder can be enumerated polymerization retarder of recording in the paragraph 0154～paragraph 0173 of Japanese Patent Laid-Open 2007-334322 communique etc.Wherein, preferred polymerization retarder can be enumerated p methoxy phenol.

Content as polymerization retarder in painted curable adhensive compositions is preferably 0.0001 quality %～5 quality % for polymerizable compound, and more preferably 0.001 quality %～5 quality %, is particularly preferably 0.001 quality %～1 quality %.

(organic solvent)

Painted curable adhensive compositions of the present invention can contain organic solvent.The solvent of coating when if organic solvent can meet the solvability of each composition or make painted curable adhensive compositions, there is no particular restriction, can consider the solvability, coating, security of the solid substances such as tackiness agent and select.

As the example of organic solvent, 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, ethoxyacetic acid alkyl esters (oxygen base (oxy) methyl acetate for example, ethoxyacetic acid ethyl ester, ethoxyacetic acid butyl ester (methoxy menthyl acetate for example, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate etc.)), 3-oxygen base alkyl propionates class (3-oxygen base methyl propionate for example, (the 3-methoxy methyl propionate for example such as 3-oxygen base ethyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate etc.)), 2-oxygen base alkyl propionates class (2-oxygen base methyl propionate for example, 2-oxygen base ethyl propionate, (the 2-methoxy methyl propionate for example such as 2-oxygen base propyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate etc.)), 2-oxygen base-2 Methylpropionic acid methyl esters, 2-oxygen base-2 Methylpropionic acid ethyl ester (2-methoxyl group-2 Methylpropionic acid methyl esters for example, 2-oxyethyl group-2 Methylpropionic acid ethyl ester etc.), Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, Propyl pyruvate, methyl acetoacetate, methyl aceto acetate, 2-Oxobutyric acid methyl esters, 2-Oxobutyric acid 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, 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 (methyl ethyl ketone), pimelinketone, 2-heptanone, 3-heptanone etc.

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

From the solvability of each composition and in the situation that comprising alkali-soluble tackiness agent from its solvability, be coated with the viewpoint such as planar improvement and consider, those organic solvents also preferably mix two or more.In this case, be particularly preferably and comprise the mixing solutions of more than two kinds that is selected from 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl 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, total solid concentration in preferred composition becomes the amount of 5 quality %～80 quality %, more preferably the total solid concentration in composition becomes the amount of 5 quality %～60 quality %, and particularly preferably the total solid concentration in composition becomes the amount of 10 quality %～60 quality %.

(linking agent)

Painted curable adhensive compositions of the present invention can contain to supplemental linking agent.By containing linking agent, can further improve, make the sclerosis of painted curable adhensive compositions and the hardness of the painted cured film of gained.

If the linking agent that linking agent can carry out film sclerosis by crosslinking reaction is not particularly limited, for example, can enumerate (a) epoxy resin, (b) is selected from the melamine compound that at least 1 substituting group replaced, guanidine amine compound, glycoluril compounds or the carbamide compound of methylol, alkoxy methyl and acyloxy methyl, the phenolic compound that at least 1 substituting group replaced, naphthol compound or the hydroxyl anthracene compound that (c) is selected from methylol, alkoxy methyl and acyloxy methyl.Preferred polyfunctional epoxy resin wherein.

About the details of the concrete example of linking agent etc., can be with reference to the record of paragraph numbering 0134～paragraph numbering 0147 of Japanese Patent Laid-Open 2004-295116 communique.

(tensio-active agent)

Painted curable adhensive compositions of the present invention also can comprise tensio-active agent.Tensio-active agent can be any number of of negatively charged ion system, positively charged ion system, nonionic system or both sexes, and preferred tensio-active agent is that nonionic is tensio-active agent.

Nonionic is that can to enumerate polyoxyethylene senior alkyl ethers, polyoxyethylene senior alkyl phenyl ethers, the higher fatty acid diester class of polyoxyethylene glycol, silicone-based, fluorine be tensio-active agent to the example of tensio-active agent.And, tensio-active agent also can be used the commercially available product of selling on market, and the example of commercially available product can be enumerated each series such as commodity KP (Shin-Etsu Chemial Co., Ltd's manufactures) by name, Polyflow (Kyoeisha Chemical Co., Ltd.'s manufacture), Eftop (Ji Mu can the manufacture of (JEMCO) company), Megafac (Dainippon Ink Chemicals's manufacture), Fluorad (manufacture of Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (Asahi Glass Co., Ltd's manufacture), PolyFox (manufacture of Ou Nuofa (OMNOVA) company).

Tensio-active agent can be enumerated and comprise the represented structural unit A of following formula (1) and structural unit B, and the weight average molecular weight of the polystyrene conversion that the gel permeation chromatography of take is measured (Mw) is 1, multipolymer more than 000, below 10,000 is as preference.

[changing 18]

In formula (1), R ¹and R ³represent independently of one another hydrogen atom or methyl, R ²represent that carbon number is the straight chain alkylene 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 alkylene more than 3, below 6.P and q mean the quality criteria percentage of polymerization ratio, and p represents that 10 quality % are above, the numerical value below 80 quality %, and q represents that 20 quality % are above, the numerical value below 90 quality %.R represents the integer more than 1, below 18.N represents the integer more than 1, below 10.

L in formula (1) is preferably the represented branch's alkylene of following formula (2).

[changing 19]

In formula (2), R ⁵represent that carbon number is the alkyl more than 1, below 4, in consistency and the aspect for the wettability of applied, being preferably carbon number is the alkyl more than 1, below 3, and more preferably carbon number is the alkyl more than 2, below 3.

As the weight average molecular weight (Mw) of the multipolymer of the represented tensio-active agent of formula (1) more preferably more than 1,500, below 5,000.

Tensio-active agent can be used alone a kind or two or more mix is used.The content of tensio-active agent in painted curable adhensive compositions can suitable selection in the scope that does not undermine effect of the present invention.

(connecting airtight modifying agent)

Painted curable adhensive compositions of the present invention also can contain and connect airtight modifying agent.Connect airtight modifying agent and be the compound that the adhesion of the inorganics (silicon compounds such as glass, silicon, silicon oxide, silicon nitride, gold, copper, aluminium etc.) that makes to become base material and cured film improves.Particularly can enumerate silane coupling agent, mercaptan based compound etc.As the object of connecting airtight the silane coupling agent of modifying agent, be that effects on surface carries out upgrading, be not particularly limited, can use known silane coupling agent.

Silane coupling agent is preferably the silane coupling agent of recording in the paragraph 0048 of Japanese Patent Laid-Open 2009-98616 communique, wherein more preferably γ-glycidoxypropyl trialkoxy silane or γ-methacryloxypropyl trialkoxy silane.

Connect airtight modifying agent and can be used alone a kind or be mixed with two or more.For the total solid amount of painted curable adhensive compositions, connect airtight the content of modifying agent in painted curable adhensive compositions and be preferably 0.1 quality %～20 quality %, more preferably 0.2 quality %～5 quality %.

(development accelerant)

Painted curable adhensive compositions of the present invention also can contain development accelerant.By containing development accelerant, can promote the alkali dissolution in territory, non-exposed area, realize the further raising of the developability of painted curable adhensive compositions.It is that lower molecular weight organic carboxyl acid compound, molecular weight below 1000 is the lower molecular weight phenolic compound below 1000 that development accelerant is preferably molecular weight.

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 tricarballylic acid (tricarballylic acid), equisetic acid (aconitic acid), camphoronic acid (camphoronic acid); Phenylformic acid, tolyl acid (toluic acid), cuminic acid (cumic acid), adjoin the aromatic monocarboxylates such as a batch formic acid (hemellitic acid), 3,5-xylic acid (mesitylenic acid); The aromatic multi-carboxy acids such as phthalic acid, m-phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, mellophanic acid (mellophanic acid), Pyromellitic Acid; Toluylic acid, hydratropic acid (hydratropic acid), benzylacetic acid (hydrocinnamic acid), mandelic acid (mandelic acid), phenylsuccinic acid (phenylsuccinic acid), atropic acid, TRANSCINNAMIC ACID, Methyl cinnamylate, cinnamein, sub-cassia bark guanidine-acetic acid (cinnamylidene acetic acid), coumaric acid, umbellic acid etc.

(other additives)

Painted curable adhensive compositions of the present invention can optionally add other various additives, such as weighting agent, macromolecular compound beyond above-mentioned, UV light absorber, antioxidant, aggregation inhibitor etc.Those additives can be enumerated the compound of recording in paragraph [the 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 preparation of～painted curable adhensive compositions～

Painted curable adhensive compositions of the present invention for example can by by the represented dye composition of described general formula (1), polymerizable compound, Photoepolymerizationinitiater initiater or tackiness agent optionally, various additive is mixed prepares.

In preparation during painted curable adhensive compositions, for after removing foreign matter or lower defect etc., being preferably each composition being mixed, with strainer, filter.Strainer can be not particularly limited use existing in filtration applications etc. the user of institute.Particularly, such as enumerating to use, be selected from the fluoro-resin such as PTFE (tetrafluoroethylene), nylon-6, nylon-6, the polyamide-based resins such as 6, the resinogen material of the polyolefin resines such as polyethylene, polypropylene (PP) (polyolefin resin that comprises high-density, ultra-high molecular weight) etc. and the strainer that forms.In those strainer starting material, be preferably nylon-6, nylon-6, polyamide-based resin, the polypropylene (comprising high density poly propylene) such as 6.

As the aperture of strainer, 0.01 μ m～7.0 μ m left and right is comparatively suitable, is preferably 0.01 μ m～2.5 μ m left and right, more preferably 0.01 μ m～2.0 μ m left and right.By making the aperture of strainer, be above-mentioned scope, the fine foreign matter that becomes the preparation that hinders the painted curable adhensive compositions of homogeneous in aftertreatment is positively removed, and can form the painted curable adhensive compositions of homogeneous and level and smooth painted curable adhensive compositions layer.

When using strainer, also different strainer capable of being combined.Now, use the filtration of the 1st strainer only to carry out 1 time, also can carry out more than 2 times.And, also can in above-mentioned scope, the different strainer in aperture be combined, the 1st strainer is made as to the strainer that comprises a plurality of strainers and carries out the 1st time and filter.So-called aperture can be with reference to the nominal value of filter manufacturer's herein.Commercially available strainer for example can be selected in Japan's various strainers that quite your (PALL) Co., Ltd., Bang get Ke Toyo Co., Ltd. of IDALL (Advantec Toyo Kaisha, Ltd.), Japanese Ying Tege (Entegris) Co., Ltd. (former days this microlith (microlith) Co., Ltd.) or northern damp micro-strainer (KITZ MICRO FILTER) Co., Ltd. etc. provide.

The 2nd strainer can use and utilize the formed strainers such as material same with above-mentioned the 1st strainer.

And, for example only colo(u)rant dispersion thing is utilized the filtration of the 1st strainer, in this colo(u)rant dispersion thing, mix other compositions and make after painted curable adhensive compositions, also can carry out the 2nd and filter.

Painted curable adhensive compositions of the present invention is applicable to colored filter for solid-state imager, colored filter for liquid crystal indicator, for printing in the various uses such as ink, ink for inkjet.

The painted cured film of < and colored filter >

Painted cured film of the present invention is at least used described dye composition of the present invention and forms.And, this painted cured film supporter of this painted cured film (and be preferably formed) also can be set and form colored filter of the present invention.Painted cured film of the present invention contains dye composition of the present invention, so the absorption peak under maximum absorption wavelength is sharp keen and form and aspect are excellent, has high brightness.And colored filter of the present invention contains dye composition of the present invention, so the form and aspect of painted areas are good and present high brightness, and contrast gradient is excellent.

About forming details and the preferred form of each composition of the dye composition of painted cured film of the present invention and colored filter or polymerizable compound etc., as mentioned above.

Painted cured film of the present invention and colored filter are except comprising described dye composition of the present invention, and there is no particular restriction, can utilize known method and manufacture.

The in the situation that of forming painted cured film on supporter, by being coated with the coating method of painted curable adhensive compositions or supporter being impregnated in to pickling process in painted curable adhensive compositions etc., form the coloring film that comprises painted curable adhensive compositions, make this coloring film sclerosis and obtain painted cured film.And, in the situation that form the painted cured film of pattern-like, also can utilize the desired regioselectivity of ink jet method on supporter and use painted curable adhensive compositions, form therefrom coloring film, make this coloring film sclerosis.And, also the known print process such as applicable printing and dyeing or offset printing and desired regioselectivity form coloring film, make the sclerosis of this coloring film.

Particularly in the situation that manufacturing colored filter, the viewpoint of the pattern of self-forming fine considers, suitable is method (manufacture method of colored filter of the present invention) shown below.That is, colored filter of the present invention can be manufactured by the manufacture method that comprises following steps optimum: painted curable adhensive compositions is applied on supporter, form the step (coloring film formation step) of coloring film, by coloring film exposure, be pattern-like, develop and form the step (painted cured film formation step) of painted cured film.

-coloring film formation step-

In the manufacture method of colored filter of the present invention, first directly or across other layers, utilize desired method and described painted curable adhensive compositions of the present invention is applied on supporter, forming the coloring film (painted curable adhensive compositions layer) that comprises painted curable adhensive compositions.Also can optionally carry out pre-hardening (preliminary drying) and make it dry formed coloring film.

Supporter is such as enumerating the non-alkali glass, the soda glass that use in liquid crystal indicator etc., send Simon Rex (Pyrex, registered trademark) glass, silica glass and those persons that is attached with nesa coating on glass, or the photo-electric conversion element substrate using in solid-state imager etc., such as silicon substrate or plastic base etc.And, also can on those supporters, form the black matrix" of each pixel of isolation, transparent resin layer is set in order to promote to connect airtight etc.And, in order to improve with the material that connects airtight, prevents of upper layer, to spread or make flattening surface, also undercoat can be optionally set on supporter.Plastic base preferably further comprises at least 1 layer that is selected from gas barrier layer and solvent resistance layer in its surface.

As supporter, use has configured thin film transistor (Thin-Film Transistor, TFT) substrate for driving of the thin film transistor of mode color liquid crystal display arrangement (TFT) (hereinafter referred to as " TFT mode liquid crystal drive substrate "), also can on substrate, form the colored pattern that uses painted curable adhensive compositions of the present invention to form for this driving, thereby make colored filter.

TFT mode liquid crystal drive with the substrate in substrate such as enumerating glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc.Those substrates also can optionally implement to utilize the suitable pre-treatment such as the chemicals treatment, Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum evaporation of silane coupling agent etc. in advance.For example, can use in TFT mode liquid crystal drive and with the surface of substrate, form the substrate of the passive films such as silicon nitride film.

The method that painted curable adhensive compositions is applied on supporter can be enumerated the coating processes such as rotary coating, slot coated, curtain coating coating, roller coat, rod painting, ink-jet.Utilize in the method for slot coated, preferably slit spin-coating method, non-rotating coating method etc. are used the method (hereinafter referred to as gap nozzle coating method) of gap nozzle.In gap nozzle coating method, slit spin-coating method from non-rotating coating method according to the size of coated substrates and condition is different, for example, the in the situation that of being coated with painted curable adhensive compositions utilizing non-rotating coating method on the 5th generation glass substrate (1100mm * 1250mm), from the spray volume of painted curable adhensive compositions that gap nozzle sprays, be generally 500 microlitres/second～2000 microlitre/seconds, be preferably 800 microlitres/second～1500 microlitre/seconds, and surface covered is generally 50mm/ second～300mm/ second, be preferably 100mm/ second～200mm/ second.

And the solid concentration of painted curable adhensive compositions is generally 10 quality %～20 quality %, be preferably 13 quality %～18 quality %.

After forming coloring film, preferably implement preliminary drying and process, also can before preliminary drying, implement vacuum-treat.Vacuum drying condition is that vacuum tightness is generally 13.33Pa (0.1torr)～133.32Pa (1.0torr), is preferably 26.66Pa (0.2torr)～66.66Pa (0.5torr) left and right.And preliminary drying is processed can use hot plate, baking oven etc., in the temperature range of 50 ℃～140 ℃, is preferably 70 ℃～110 ℃ left and right, carries out under the condition of 10 seconds～300 seconds.In addition, in preliminary drying is processed, also can be in heat treated further and with high frequency waves processing etc.And, in the situation that carry out the dry of painted curable adhensive compositions layer, also can carry out high frequency waves processing separately and replace preliminary drying to process.

And, utilize painted curable adhensive compositions and the thickness of the coloring film that forms can be according to object and suitable selection.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, the most preferably scope of 1.5 μ m～3.5 μ m.And, at solid-state imager, use in colored filter, preferably the scope of 0.2 μ m～5.0 μ m, the more preferably scope of 0.3 μ m～2.5 μ m, the most preferably scope of 0.3 μ m～1.5 μ m.In addition, the thickness of painted curable adhensive compositions layer is pre-baked thickness.

-painted cured film formation step-

At painted cured film, form in step, formed coloring film on supporter (painted curable adhensive compositions layer) is carried out to the exposure (pattern exposure) and development of pattern-like.

Pattern exposure for example can be undertaken by carrying out rayed across photomask.In order to suppress the oxidation of the colored materials in coloring film, fade, can one towards flowing into nitrogen in chamber, simultaneously expose.

Light or radioactive rays applicable to exposure are preferably g line, h line, i line, j line, KrF light, ArF light, particularly preferably i line.In the situation that irradiating light use i line, preferably with 100mJ/cm ²～10000mJ/cm ²exposure irradiate.Light source also can use each mercuryvapour lamp, chemical lamp, carbon arc lamp, xenon lamp, Metal-halogen lamp of ultra-high voltage, high pressure, middle pressure, low pressure, the various LASER Light Source of visible and ultraviolet, luminescent lamp, tengsten lamp, sunlight etc.

In using the Exposure mode of LASER Light Source, preferably use ultraviolet laser as light source.Irradiate the ultraviolet laser of the scope that light optimal wavelength is 300nm～380nm, the ultraviolet laser of the scope that wavelength is 300nm～360nm meet resist (resist) wavelength photoreceptor aspect more preferably.Particularly, especially can be suitable the triple-frequency harmonics (355nm) of Nd:YAG laser or the XeCl (308nm) of excimer laser, the XeF (353nm) of large, the less expensive Solid State Laser of use output.

The exposure that is exposed thing (pattern) is 1mJ/cm ²～100mJ/cm ²scope, more preferably 1mJ/cm ²～50mJ/cm ²scope.If exposure is this scope, preferred aspect the productivity of pattern formation.

There is no particular restriction for exposure apparatus, commercially available exposure apparatus can be used LE5565A (manufacture of high and new technology company of Hitachi), Callisto (Wei Jiyan limited-liability company (V Technology Co., Ltd.) manufacture) or EGIS (manufacture of Wei Jiyan limited-liability company) or DF2200G (manufacture of Dainippon Screen Manufacturing Co Co., Ltd.) etc.And, also can use above-mentioned device in addition.

When the manufacture method of colored filter of the present invention being applicable to the manufacture of liquid crystal indicator use colored filter, preferably utilize close induction type exposure machine, mirror surface projection exposure machine, mainly irradiate the exposure method of h line, i line.And, when the manufacture method of colored filter of the present invention being applicable to the manufacture of solid-state imager use colored filter, preferably utilize stepping exposure machine mainly to irradiate the exposure method of i line.In addition, when using TFT mode liquid crystal drive to manufacture colored filter with substrate, the photomask using can be used except in order to form the pattern of pixel (colored pattern), is also provided with to form the photomask of pattern in the hole, low-lying area of through hole or U font.

And, photodiode (Light-Emitting Diode, LED) and laser diode (Laser Diode, LD) can be used as to active radiation source.Particularly, the in the situation that of essential ultraviolet source, can use ultraviolet LED and ultraviolet LD.The main emmission spectrum that for example can use You Ya chemical industrial company to sell on market has the purple LED of the wavelength between 365nm and 420nm.In the situation that wavelength that further must be shorter can be enumerated United States Patent (USP) the 6th, in 084, No. 250 specification sheets, record can the active radioactive rays of launching centre between 300nm and 370nm LED.And, also can use obtainable other ultraviolet LEDs.Particularly preferred active radiation source is UV-LED, wherein preferably at 340nm～370nm, has the UV-LED of peak wavelength.

The parallelism of ultraviolet laser is good, even if therefore do not use mask when exposure, also can expose for pattern-like.But the in the situation that of pattern exposure using mask, the rectilinearity of pattern further uprises, therefore more preferably.

Secondly, with developing solution, the coloring film after exposing is developed.Can form the colored pattern of minus or eurymeric thus.In development, make exposure after the stripping of unhardened portion to developing solution, only make sclerosis portion remain on substrate.

Can utilize the methods such as Jin Stains mode, spray mode, spray pattern and develop.And, also mode, rotation mode, ultrasonic wave mode etc. of waving capable of being combined.Also can before coloring film contacts with developing solution, take the moistening faces that are developed such as water in advance, thereby prevent the uneven processing of developing, then develop.And, also can make the supporter with the coloring film after exposure tilt and carry out development treatment.In the situation that manufacturing solid-state imager and use colored filter, also applicable one side stirs in developing bath that simultaneously carrying out soaking of development treatment puts development (puddle development).

If developing solution dissolves the coloring film (painted curable adhensive compositions layer) of unhardened portion, do not dissolve on the other hand the developing solution of sclerosis portion, can use.For example, can use combination or the alkaline aqueous solution of various organic solvents.Spendable described organic solvent when organic solvent can be set forth in preparation painted curable adhensive compositions of the present invention.

Alkaline aqueous solution for example can enumerate by following basic cpd with concentration become 0.001 quality %～10 quality %, the mode that is preferably 0.01 quality %～1 quality % dissolves the alkaline aqueous solution forming: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, water glass, Starso (sodium metasilicate), ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicyclo-[5,4,0]-7-undecylene etc.In this case, with preferred pH become 11～13, more preferably pH becomes 11.5～12.5 mode and adjusts alkali concn.

In alkaline aqueous solution such as also adding in right amount the water-miscible organic solvents such as methyl alcohol, ethanol or tensio-active agent etc.

Development temperature is the temperature range of preferably 20 ℃～30 ℃ conventionally, and development time is preferably 20 seconds～and 90 seconds.

After development treatment, preferably carry out that remaining developing solution is cleaned to the flushing of removing and process.Conventionally with pure water, rinse processing, but in order to save liquid, also can use used pure water at the cleaning initial stage, or substrate is tilted and clean, and also can and use ultrasonic irradiation.

And, after rinse processing, also preferably implemented dry after, in order to promote sclerosis, implement heat treated (drying afterwards).Conventionally by the heat treated of approximately 150 ℃～250 ℃, carry out rear baking.For the coated film after developing, the mode that can become above-mentioned condition is used the heating arrangements such as hot plate or convection oven (hot air circulation type drying machine), high frequency machine, and continous way or batch-type ground carry out rear baking.

According to desired form and aspect number, according to every kind of color, repeatedly carry out in turn one by one above each step, can make thus and be formed with the painted cured film (colored pattern) of multiple color as the colored filter of colored pixels.

Except above-mentioned steps, in the manufacture method of colored filter of the present invention, also can further carry out uviolizing and implement post-exposure formed painted cured film (colored pixels).

Also can further carry out heat treated to having carried out the painted cured film (colored pixels) of post-exposure.By further carrying out heat treated, can make painted cured film further harden.Such as utilizing hot plate, various well heater, baking oven etc., carry out heat treated.Temperature during heat treated is preferably 100 ℃～300 ℃, more preferably 150 ℃～250 ℃.And, be preferably 10 minutes heat-up time～about 120 minutes.

Painted cured film of the present invention and colored filter are used painted curable adhensive compositions of the present invention, therefore carry out bright in luster while showing of image and contrast gradient is high, excellent heat resistance.And, as described later, not only in the situation that use known cold-cathode fluorescence lamp (Cold Cathode Fluorescent Lamp, CCFL) as backlight, and in the situation that using White LED as backlight, also play the excellent effect that can reproduce good form and aspect.

Colored filter of the present invention can be used for, in liquid crystal indicator or solid-state imager, being particularly suitable for the purposes of liquid crystal indicator.The in the situation that of use in liquid crystal indicator, use dyestuff as tinting material, thereby reach good form and aspect, and become and can show the image of dichroism and contrast gradient excellence, in addition the suitability of White LED is become to excellent.

Purposes as painted curable adhensive compositions of the present invention, in above-mentioned, centered by the formation purposes of the main colored pattern by colored filter, be illustrated, but also applicable to the formation of isolating the black matrix" of the colored pattern (pixel) that forms colored filter.Black matrix" can form in the following way: use the painted curable adhensive compositions of the Opacifying pigment contain the black pigments such as carbon black, titanium be black, through coating, exposure and each step of developing, optionally carry out thereafter rear baking.

Painted curable adhensive compositions of the present invention is applied on substrate and forms in the situation of coloring film, the dry thickness of coloring film is generally 0.3 μ m～5.0 μ m, is preferably 0.5 μ m～3.5 μ m, it would be desirable 1.0 μ m～2.5 μ m.

< display unit >

Display unit of the present invention comprises described colored filter of the present invention or utilizes the manufacture method of described colored filter of the present invention and the colored filter manufactured.The colored filter that display unit of the present invention comprises the painted curable adhensive compositions of the present invention that comprises the represented dye composition of general formula (1) described in use, therefore shows that image is bright-coloured and contrast gradient is high, can be through showing long-term and stably image.

The definition of display unit or the illustrative examples of each display unit are as record to some extent in < < electronic display unit (the wooden clear husband's work of assistant assistant, the nineteen ninety distribution of census of manufacturing meeting Co., Ltd.) > >, < < display unit (she blows along chapter work, the distribution in the first year of industry books K.K. Hiranari) > > etc.And, about liquid crystal indicator, for example record to some extent in < < LCD Technology of future generation (Uchida Tatsuo edit, the census of manufacturing can Co., Ltd.'s distribution in 1994) > >.To the present invention's liquid crystal indicator applicatory, there is no particular restriction, for example, in the liquid crystal indicator applicable to the variety of way of recording in above-mentioned " LCD Technology of future generation ".

As colored filter of the present invention, while wherein particularly using in the liquid crystal indicator of colored TFT mode, its effect is remarkable.About the liquid crystal indicator of colored TFT mode, for example, in < < color TFT-LCD indicating meter (the vertical Co., Ltd. that publishes issues for 1996 altogether) > >, record to some extent.In addition, colored filter of the present invention also switches (In-Plane Switching applicable to plane, the transverse electric field type of drive such as IPS), multi-zone vertical alignment nematic (Multi-domain Vertical Alignment, MVA) etc. the visual angles such as pixel partitioning scheme obtain the liquid crystal indicator expanding, or supertwist is to row (Super Twisted Nematic, STN), twisted-nematic (Twisted Nematic, TN), vertical orientation (Vertical Alignment, VA), optical compensation inclination (Optically Compensated Splay, OCS), fringe field switching (Fringe Field Switching, FFS), and reflective optics compensated bend (Reflected-Optically Compensated Bend, R-OCB) etc. in.

And colored filter of the present invention is also available in colour filter matrix (Color-filter On Array, the COA) mode of bright and fine.In the liquid crystal indicator of COA mode, to colored filter require characteristic except common requirement characteristic as above, must be to interlayer dielectric require characteristic that is low-k and the resistance to fluidity of peeling off.As colored filter of the present invention, except utilizing the exposure method of ultraviolet laser, by selecting form and aspect or the thickness of pixel given to this invention, and improve the perviousness as the ultraviolet laser of exposure light.Make therefrom the hardening of colored pixels improve, can form and N/D or peel off, the pixel of fold, the pigmented layer therefore particularly arranging directly or indirectly on TFT substrate resistance to peels off fluidity raising, useful in the liquid crystal indicator of COA mode.For the characteristic that requires of low-k is further improved, also resin coating can be further set in color filter layers.

In the pigmented layer forming utilizing COA mode, in order to make to be configured in the terminal conducting of substrate for the driving of ITO electrode on pigmented layer and pigmented layer below, must form length is on one side the through hole of rectangle or the guiding paths such as hole, low-lying area of U font of 1 μ m～15 μ m left and right, particularly preferably making the size (that is length on one side) of guiding path is below 5 μ m, but the colored filter of the present invention by use with the good pigmented layer of hardening, can easily form the guiding path below 5 μ m.

About described image display pattern, in the 43rd page of the up-to-date trend in < < EL, PDP, LCD display-technology and market-(eastern beautiful research centre investigation department calendar year 2001 distribution) > > etc., record to some extent.

Liquid crystal indicator of the present invention and organic EL display, except colored filter of the present invention, also comprise the various members such as electrode base board, light polarizing film, phase retardation film, backlight, distance piece, compensation film for angular field of view.Colored filter of the present invention is applicable in the liquid crystal indicator that comprises those known members and organic EL display.

About those members, for example, in the present situation in the market of < < ' 94 liquid-crystal display periphery materials, chemical (island Itou Kentaro ,CMC Co., Ltd., distribution in 1994) > >, the associated markets of < < 2003 liquid crystal with record to some extent in prospect (last volume) ((Fuji Chimera Research Institute, Inc.), distribution in 2003 are always ground by Biao Liangji, Fuji) > > in the future.

About backlight, the 25th page of the 18th page～the 24th page (island health is abundant) in SID conference summary 1380 (SID meeting Digest1380) (2005) people such as () modern wild apricot south (A.Konno) or indicating meter monthly magazine in December, 2005 number, indicating meter monthly magazine in December, 2005 number～record to some extent in the 30th page (Yagi spark gap is grand bright) etc.

If colored filter of the present invention for liquid crystal indicator, can be realized to high contrast gradient during with the three-wavelength pipe of cold-cathode tube as backlight or the combination of the LED light source (RGB-LED) of red, green, blue.Comprise use painted curable adhensive compositions of the present invention and the colored filter of the colored pixels of gained in the situation that take near 450nm with 550nm near the wavelength LED light source with emmission spectrum be backlight, obtain particularly preferred form and aspect, obtain high color reproduction.

Particularly preferred backlight can be set forth in the LED light source in the scope of 430nm～470nm with the peak wavelength of emissive porwer.

That is, comprise to have and use painted curable adhensive compositions of the present invention and the colored filter of the colored pixels of gained, the liquid crystal indicator in LED-backlit source in the scope of 430nm～470nm with the peak wavelength of emissive porwer become the liquid crystal indicator of the image that can provide good especially.

And, comprise to have and use painted curable adhensive compositions of the present invention and the colored filter of the colored pixels of gained, the organic EL display of fluor in the scope of 430nm～470nm with the peak wavelength of emissive porwer become the display unit that the image that brightness is high, color reproduction is good can be provided.

It is that fluor, TAG are fluor, α-SiAlON fluor that Y fluor: YAG can be enumerated in the LED-backlit source in the scope of 430nm～470nm with the peak wavelength of emissive porwer; G fluor: β-SiAlON fluor, silicate fluor, BSS fluor, BSON fluor; R fluor: CASN fluor, SCASN fluor etc., all applicable in display unit of the present invention.

[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 embodiment.In addition, unless otherwise specified, " part " is quality criteria.

(embodiment 1)

With reference to synthesis flow shown below and synthetic dyestuff Y-1～dyestuff Y-7 (the represented dye composition of described general formula (1)).

[changing 20]

The synthetic > of < dyestuff Y-1

-intermediate A synthetic-

Prepare following compound (A) (utilize european patent application to disclose the method for recording in No. 0571959 specification sheets and synthesize), according to above-mentioned synthesis flow, first the mixing solutions of compound (A) 100 mass parts and pyridine 390ml is cooled to 5 ℃, in temperature of reaction, be below 25 ℃, in wherein dripping octyl group SULPHURYL CHLORIDE 87 mass parts.Reaction solution is at room temperature carried out, after the stirring of 2 hours, add 4N aqueous hydrochloric acid 2L and at room temperature stir.Carry out leaching thereafter.After the crystallization of institute's leaching is cleaned with methyl alcohol 500ml, be dried, obtain thus the intermediate A (productive rate is 91%) of 153g.

Utilize NMR to carry out the result of structural confirmation of intermediate A of gained as follows.

¹H-NMR(300MHz、CDCl ₃)δ0.8(t，3H)，1.0-1.4(m，19H)，1.6(m，2H)，3.2(t，2H)，5.6(s，1H)，7.3(d，2H)，7.9(d，2H)，10.2(s，1H)，12.9(s，1H)

[changing 21]

-Y-1 synthetic-

Then, according to above-mentioned synthesis flow, at room temperature, in the aaerosol solution of intermediate A 110g and acetic acid 650ml, add triethyl orthoformate 68g, reaction solution is carried out the stirring of 3 hours at 80 ℃.In reaction solution, add methyl alcohol 1.1L, carry out leaching after in addition cooling, carry out washed with methanol and obtain the Y-1 (productive rate is 88%) of 96g.

Utilize NMR to carry out the result of structural confirmation of Y-1 of gained as follows.

¹H-NMR(300MHz、CDCl ₃)δ0.8(t，6H)，1.2-2.0(m，41H)，3.3(t，4H)，7.3(d，4H)，7.6(br，2H)，7.8(d，4H)，8.4(s，1H)

The synthetic > of < dyestuff Y-2

In above-mentioned dyestuff Y-1 synthetic, octyl group SULPHURYL CHLORIDE is replaced by butyl sulfochlorides, similarly carry out and synthetic dyestuff Y-2 with the synthetic of dyestuff Y-1 in addition.

Utilize NMR to carry out the result of structural confirmation of Y-2 of gained as follows.

¹H-NMR(300MHz、CDCl ₃)δ0.9(t，6H)，1.1-1.8(m，26H)，3.3(t，4H)，7.3(d，4H)，7.6(br，2H)，7.8(d，4H)，8.4(s，1H)

The synthetic > of < dyestuff Y-3

In above-mentioned dyestuff Y-1 synthetic, octyl group SULPHURYL CHLORIDE is replaced by octadecyl sulfonyl chloride, similarly carry out and synthetic dyestuff Y-3 with the synthetic of dyestuff Y-1 in addition.

Utilize NMR to carry out the result of structural confirmation of Y-3 of gained as follows.

¹H-NMR(300MHz、CDCl ₃)δ0.8(t，6H)，1.1-2.0(m，58H)，3.3(t，4H)，7.3(d，4H)，7.6(br，2H)，7.8(d，4H)，8.4(s，1H)

The synthetic > of < dyestuff Y-4

In above-mentioned dyestuff Y-1 synthetic, octyl group SULPHURYL CHLORIDE is replaced by 2-ethyl hexanoyl chloro, similarly carry out and synthetic dyestuff Y-4 with the synthetic of dyestuff Y-1 in addition.

Utilize NMR to carry out the result of structural confirmation of Y-4 of gained as follows.

¹H-NMR(300MHz、CDCl ₃)δ0.8-0.9(m，12H)，1.0-1.6(m，34H)，2.9(m，2H)，7.5(d，4H)，7.8(d，4H)，8.5(s，1H)，9.8(br，2H)

The synthetic > of < dyestuff Y-5

-intermediate B synthetic-

The mixing solutions of above-mentioned intermediate A 43 mass parts and dimethyl formamide 500ml is cooled to 5 ℃, shown in synthesis flow described above, is below 15 ℃ at reacting liquid temperature, in wherein adding phosphoryl chloride 17 mass parts.At room temperature carry out, after the stirring of 2 hours, adding 2N aqueous sodium hydroxide solution 2L and carrying out the stirring of 1 hour.Thereafter, the crystallization that leaching is separated out, is cleaned and is obtained the intermediate B (productive rate is 76%) of 35g with methyl alcohol 300ml.

Utilize NMR to carry out the result of structural confirmation of intermediate B of gained as follows.

¹H-NMR(300MHz、CDCl ₃)δ0.8(t，3H)，1.1-1.8(m，21H)，3.1(t，2H)，7.2(d，2H)，7.9(d，2H)，8.1(s，1H)，9.9(s，1H)

-Y-5 synthetic-

Secondly, according to above-mentioned synthesis flow, during by the intermediate B 5g of gained, synthetic dyestuff Y-2, make butyl sulfochlorides reaction and intermediate A (butyl sulfonamide body) 4g of gained, the mixing solutions of acetic acid 20ml carry out the stirring of 3 hours at 120 ℃.After stirring finishes, reaction soln is added in water 100m1 and makes crystallization.The crystallization of leaching gained, is cleaned with methyl alcohol, obtains thus the dyestuff Y-5 (productive rate is 96%) of 8g.

Utilize NMR to carry out the result of structural confirmation of Y-5 of gained as follows.

¹H-NMR(300MHz、CDCl ₃)δ0.8-0.9(m，6H)，1.2-2.0(m，34H)，3.3(m，4H)，7.3(d，4H)，7.6(br，2H)，7.8(d，4H)，8.4(s，1H)

The synthetic > of < dyestuff Y-6

In above-mentioned dyestuff Y-5 synthetic, intermediate A (butyl sulfonamide) is replaced by and makes octadecyl sulfonyl chloride reaction and the dodecyl sulphonamide body of gained similarly carries out and synthetic dyestuff Y-6 with the synthetic of dyestuff Y-5 in addition.

Utilize NMR to carry out the result of structural confirmation of Y-6 of gained as follows.

¹H-NMR(300MHz、CDCl ₃)δ0.8(t，6H)，1.2-2.0(m，49H)，3.3(t，4H)，7.3(d，4H)，7.6(br，2H)，7.8(d，4H)，8.4(s，1H)

The synthetic > of < dyestuff Y-7

In above-mentioned dyestuff Y-5 synthetic, following intermediate C when intermediate A (butyl sulfonamide) is replaced by synthetic dyestuff Y-4, similarly carries out and synthetic dyestuff Y-7 with the synthetic of dyestuff Y-5 in addition.

Utilize NMR to carry out the result of structural confirmation of Y-7 of gained as follows.

¹H-NMR(300MHz、CDCl ₃)δ0.8-0.9(m，9H)，1.0-1.8(m，38H)，2.9(m，1H)，3.3(t，2H)，7.3(d，2H)，7.5(d，2H)，7.7(d，2H)，7.8(m，3H)，8.4(s，1H)，9.8(s，1H)

[changing 22]

(embodiment 2)

-making of yellow filter-

The solid substance that the THF solution of the dyestuff Y-1 of above-mentioned synthesized is mixed in to benzyl methacrylate/Sipacril 2739OF (=80/20[mol ratio], weight average molecular weight be 30000) is in the PGMEA solution of 30 quality %.Now, make dyestuff Y-1 shared concentration in total solid become 10 quality %.Utilize spin coater that the mixing solutions of gained is become to 1.6g/m with drying coated amount ²the mode of (coating film thickness is approximately 2 μ m) is coated on glass substrate, and it is dried and making yellow filter (yellow filter).

And, dyestuff Y-1 is replaced by turn to dyestuff Y-2～dyestuff Y-6 of above-mentioned synthesized, utilize with above-mentioned same method and further make 5 kinds of yellow filters.

In addition, for comparison yellow filter, prepare following comparative compound 1～comparative compound 2, dyestuff Y-1 is replaced by comparative compound 1～comparative compound 2 in turn, utilize with above-mentioned same method and 2 kinds of yellow filters that comparison is used.

-evaluation of filbtercharacteristic-

For each yellow filter of made, at 230 ℃, implement the heat treated of 60 minutes.

Secondly, use UV-2400PC (manufacture of Shimadzu company), the transmitted spectrum of the yellow filter after heat treated is carried out to instrumentation, according to this transmitted spectrum, obtain respectively the 490nm of heating front and back and the dulling luminosity ratio (absorbancy under the absorbancy/460nm under 490nm) of 460nm.Dulling luminosity ratio is shown in following table 1.

[changing 23]

[table 1]

As described in as shown in table 1, the known yellow filter that comprises dye composition of the present invention (the represented dye composition of general formula (1)) with relatively with yellow filter Comparatively speaking, dulling luminosity ratio before and after heat treated is high, as spectral filter excellence.

(embodiment 3)

-preparation of painted curable adhensive compositions-

With the amount shown in following table 1, allocate each composition in composition shown below, under room temperature (25 ℃), mix after 10 minutes, carry out 10 minutes standing, with HDC II (Japanese Solution manufactures), filter and prepare painted curable adhensive compositions A1 and painted curable adhensive compositions B～these 5 kinds of painted curable adhensive compositions E.

In addition, in following table 1, the content of each composition of numeric representation (quality %), "-" represents not containing this composition.

< forms >

The dyestuff Y-1 of above-mentioned synthesized (the represented dye composition of general formula (1))

By 5814.9 parts of C.I. Pigment greens and acrylic acid series pigment dispersing agent [methyl methacrylate/Sipacril 2739OF (=80/20[mass ratio], weight average molecular weight, be 12,000)] 7.1 parts are mixed with 78.0 parts of propylene glycol methyl ether acetates, use ball mill and pigment is disperseed and the dispersible pigment dispersion of gained fully

The phthalocyanine pigment derivative of recording in the paragraph 0350 of Japanese Patent Laid-Open 2011-197670 communique

[ZnPc-{α-(4-COOC ₂H ₄OCH ₃)C ₆H ₄O} _x，{β-(4-COOC ₂H ₄OCH ₃)C ₆H ₄O} _3.8-xH _0.8Cl _11.4](0≤x＜3.8)

(Japanese chemical drug company manufactures Kayarad DPHA; Polymerizable compound)

2-(benzoyloxy imino-)-1-[4 '-(phenyl sulfenyl) phenyl] (IRGACURE OXE01, BASF (BASF) company manufacture-1-octanone; Photoepolymerizationinitiater initiater)

Following Compound D-2 (Photoepolymerizationinitiater initiater of oxime system)

Following Compound D-3 (Photoepolymerizationinitiater initiater of oxime system)

Propylene glycol methyl ether acetate (solvent)

3-ethoxyl ethyl propionate (solvent)

Tetramethylolmethane four (3-sulfydryl butyric ester) [multifunctional sulfhydryl compound; Chain-transfer agent]

Benzyl methacrylate/Sipacril 2739OF (=65/35[mol ratio]; Tackiness agent)

P methoxy phenol (polymerization retarder)

(DIC manufactures Megafac F781-F; Tensio-active agent)

[changing 24]

[table 2]

(embodiment 4)

In the preparation of the painted curable adhensive compositions A1 of embodiment 3, dyestuff Y-1 is replaced by dyestuff Y-2～dyestuff Y-7 of above-mentioned synthesized, similarly carries out and prepare painted curable adhensive compositions A2～these 6 kinds of painted curable adhensive compositions A7 with the preparation of the painted curable adhensive compositions A1 of embodiment 3 in addition.

(evaluation)

Painted curable adhensive compositions A1 prepared in embodiment 3～embodiment 4～painted curable adhensive compositions A7 and painted curable adhensive compositions B～painted curable adhensive compositions E are carried out to following evaluation.Evaluation result is shown in following table 3.

-1. thermotolerance-

At glass, [Corning Incorporated manufactures; EAGLE-XG (trade(brand)name; Thickness is 0.7mm)] on, with spin-coating method, be coated with in turn painted curable adhensive compositions A1～painted curable adhensive compositions A7 and the painted curable adhensive compositions B～painted curable adhensive compositions E of above-mentioned gained, then under the condition of 80 ℃, 2 minutes, make volatile component volatilization and formation coated film (coloring film) 1.After cooling, this coated film 1 is irradiated to i line [wavelength is 365nm].I line irradiates with using extra-high-pressure mercury vapour lamp in light source, irradiates after being adjusted into directional light.Irradiation light quantity is now made as 50mJ/cm ².Secondly, the rear baking that postradiation coated film 1 is carried out 90 minutes at 230 ℃ is processed, and obtaining thickness is the painted cured film 1 of 2 μ m.Measure the aberration (Δ Eab) before and after rear baking of painted cured film of gained and evaluate.The numerical value of Δ Eab is less, and foxy is less, demonstrates excellent heat resistance.

-2. contrast gradient, brightness-

Similarly carry out and form after painted cured film with above-mentioned " 1. thermotolerance ", this painted cured film is clipped between 2 pieces of light polarizing film, with chroma-luminance meter (Topcon Co., Ltd manufacture, model be BM-5A), measures while making the polarizing axis of 2 pieces of light polarizing film parallel brightness value in two kinds of situations when vertical.And the value of the brightness of the brightness when polarizing axis of 2 pieces of light polarizing film is parallel when vertical and gained is as the index of evaluating contrast gradient.Contrast gradient is higher, as color light filter used for LCD device, more shows good performance.

-3. patterning suitability-

For " 1. thermotolerance " with above-mentioned, similarly with spin-coating method, be coated with in turn painted curable adhensive compositions A1～painted curable adhensive compositions A7 and painted curable adhensive compositions B～painted curable adhensive compositions E, the coated film (coloring film) 1 that makes volatile component volatilization and form, across having formed live width, be the mask of the pattern of 20 μ m, with " 1. thermotolerance " same condition under irradiate i line [wavelength is 365nm].With developing solution (concentration be the aqueous solution of the sodium carbonate/bicarbonate of 2.4 quality %s) develop and washed thereafter., with opticmicroscope with the multiplying power of 200 times observe the fine rule of formed pattern-like painted cured film, according to following metewand evaluation, whether form the pattern as shown in design load thereafter.A grade～B grade is the level of permitting in practicality.

< metewand >

A: the live width of fine rule is more than 19 μ m

B: the live width of fine rule is more than 17 μ m and less than 19 μ m

C: the live width less than 17 μ m of fine rule

[table 3]

As described in as shown in table 3, painted curable adhensive compositions of the present invention with relatively with curable adhensive compositions Comparatively speaking, the brightness of image is high, contrast gradient is excellent, patterning suitability is also good.And thermotolerance is also excellent.

On the other hand, do not use the represented dye composition of general formula (1) relatively by the low lightness of painted curable adhensive compositions and explain aobvious very poor in the aspect of contrast gradient.And although have patterning suitability to a certain degree, thermotolerance is obviously very poor.

Claims

1. a dye composition, is characterized in that representing with following general formula (1):

general formula (1)

In formula, R ¹and R ²represent independently of one another SO ₂r ³or COR ³; R ³the aryl that the alkyl that expression carbon number is 1～18 or carbon number are 6～18.

2. dye composition according to claim 1, is characterized in that:

In described general formula (1), R ¹and R ²represent independently of one another SO ₂r ³, R ³represent the alkyl that carbon number is 4～18.

3. dye composition according to claim 1, is characterized in that:

In described general formula (1), R ¹and R ²represent independently of one another COR ³, R ³represent the alkyl that carbon number is 6～18.

4. dye composition according to claim 1, is characterized in that:

There is the structure that is selected from following structure,

5. dye composition according to claim 1, is characterized in that:

R in described general formula (1) ¹and R ²represent identical base, described dye composition has symmetrical structure.

6. a manufacture method for dye composition, is characterized in that:

The represented compound of following general formula (2) is reacted with ortho-formiate compound and manufactures according to claim 1 to the dye composition described in any one in claim 5,

general formula (2)

In formula, R ⁵represent SO ₂r ³or COR ³; R ³the aryl that the alkyl that expression carbon number is 1～18 or carbon number are 6～18.

7. a manufacture method for dye composition, is characterized in that:

Make the represented aldehyde cpd of the represented compound of following general formula (2) and following general formula (3) or its tautomerism precursor reactant and manufacture according to claim 1 to the dye composition described in any one in claim 5,

general formula (2)

In formula, R ⁵represent SO ₂r ³or COR ³; R ³the aryl that the alkyl that expression carbon number is 1～18 or carbon number are 6～18;

general formula (3)

In formula, R ⁶represent SO ₂r ³or COR ³, R ³the aryl that the alkyl that expression carbon number is 1～18 or carbon number are 6～18.

8. a painted curable adhensive compositions, is characterized in that: at least comprise according to claim 1 to dye composition and polymerizable compound described in any one in claim 5.

9. painted curable adhensive compositions according to claim 8, is characterized in that:

Also comprise polymerization starter.

10. painted curable adhensive compositions according to claim 8, is characterized in that:

Also comprise phthalocyanine pigment or derivatives thereof.

11. painted curable adhensive compositions according to claim 8, is characterized in that:

Also comprise and be selected from triarylmethane dye, indolenium squaraine cyanine dye and phthalocyanine pigment at least a kind.

12. 1 kinds of painted cured films, is characterized in that: comprise according to claim 1 to the dye composition described in any one in claim 5.

13. 1 kinds of colored filters, is characterized in that: comprise painted cured film according to claim 12.

The manufacture method of 14. 1 kinds of colored filters, is characterized in that comprising:

Painted curable adhensive compositions according to claim 8 is applied on supporter, forms the step of coloring film; And

15. 1 kinds of display unit, is characterized in that: comprise colored filter according to claim 13.