CN101959923A

CN101959923A - Curable composition and color filter

Info

Publication number: CN101959923A
Application number: CN2009801073505A
Authority: CN
Inventors: 中村秀之; 池田秀夫; 根本洋一; 冈部孝太郎
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2008-03-03
Filing date: 2009-03-02
Publication date: 2011-01-26
Anticipated expiration: 2029-03-02
Also published as: CN101959923B; JP2010024434A; WO2009110434A1; KR20100131437A

Abstract

Disclosed is a curable composition comprising (A) a coloring agent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a hexaarylbiimidazole-type polymerization initiator, (E) at least one component selected from an oxime-type initiator and a triazine-type initiator, and (F) a multifunctional epoxy compound having a functionality of 4 or more, wherein the content of the multifunctional epoxy compound (F) and the content of the coloring agent (A) are 2 to 20% by mass and 25 to 50% by mass, respectively, relative to the total solid content.

Description

Solidification compound and colour filter

Technical field

The present invention relates to solidification compound, be specifically related to be applicable to the solidification compound of manufacturing of colour filter and the colour filter that has used this solidification compound.

Background technology

Usually, liquid crystal indicator is by making filter substrate and TFT (Thin-Film-Tra nsistor) substrate respectively, the liquid crystal clamping being fitted make.At this moment, filter substrate is coated with the alignment films such as polyimide that are used to make liquid crystal aligning on pigmented layer.Therefore, pigmented layer need have tolerance for the strong solvent of NMP contained in the polyimide resin (N-methyl-pyrrolidone) isopolarity.

In addition, pigmented layer forms pixel with per a kind of color according to bar (stripe) shape or mosaic (mosaic) shape independently.Therefore, form concavo-convexly on pigmented layer surface, thereby use resin coating sometimes ((followingly be also referred to as sometimes " outside cover (overcoat) layer ") is as planarization film on the surface of pigmented layer.For this resin coating, also require anti-NMP equally with pigmented layer.

In addition, in the liquid crystal indicator of COA (Color-filter On Array, color filter array) mode, on TFT, form the pigmented layer of the effect that has interlayer dielectric concurrently.Therefore, to pigmented layer require characteristic except above-mentioned common requiring the characteristic, also appended for interlayer dielectric require characteristic, be that the anti-fluidity etc. peeled off is as the essential characteristic that requires.Require characteristic in order to satisfy these, also can resin coating be set on pigmented layer as protective layer.

Usually, the anti-NMP that in the evaluation of colour filter, uses be by 50 ℃ down the colourity of the front and back that obtain of dipping 10min change and estimate, with respect to this, the above-mentioned anti-fluidity of peeling off is to estimate by the swelling ratio behind dipping 2min under 80 ℃, therefore, common pigmented layer can't be used for the colour filter of COA mode.

In the patent documentation 1,, proposed to comprise the composition of six aryl bisglyoxalines as the photosensitive composite that the colour filter pigmented layer is used.This photosensitive composite is so that sensitivity is good, make solvent resistance be optimized for purpose.But, in this photosensitive composite, have the insufficient problem of anti-NMP in the high zone of pigment concentration.

In addition, in patent documentation 2, proposed to comprise the photosensitive composite that the colour filter of Resins, epoxy is used, still, be anything but anti-NMP, with fluid preservation stability, painted good composition.

And then, following problems is still arranged in this photosensitive composite: the zone that pigment concentration is high or in the making of colour filter the colored pixels of next step making of black matrix" before the completing of colour filter in developing procedure by multiple-exposure (repetition) thus become shaggy state.

As mentioned above, also can't provide to form to make all good resin involucra of anti-NMP and fluid preservation stability, ITO evaporation adaptability and painted both sides or the liquid against corrosion of color-filter layer, wish to develop to comprise the curable resin composition that can form the tinting material of the resin involucra that possesses this performance.

Patent documentation 1: Japanese kokai publication hei 6-148417 communique

Patent documentation 2: TOHKEMY 2006-28455 communique

Summary of the invention

The present invention is in order to address the above problem, and purpose is to provide high NMP tolerance, ITO evaporation adaptability, the curable resin composition that fluid preservation has good stability, contrast gradient is high and the colour filter that has used this curable resin composition.

The inventor furthers investigate the back and finds, by use comprise (A) tinting material, (B) alkali soluble resins, (C) optical polymerism compound, (D) six aryl bisglyoxalines be polymerization starter, (E) be selected from oxime series initiators and the triazine series initiators more than one, and (F) multi-functional epoxy compound's that 4 officials can be above solidification compound, can solve above-mentioned problem, thereby finish the present invention.

That is, problem of the present invention realizes by following means.

＜1〉a kind of solidification compound, its comprise (A) tinting material, (B) alkali soluble resins, (C) optical polymerism compound, (D) six aryl bisglyoxalines be polymerization starter, (E) be selected from oxime series initiators and the triazine series initiators more than one, and (F) 4 officials can above multi-functional epoxy compound, with respect to the total solids composition, this (F) multi-functional epoxy compound's content is the scope of 2～20 quality %, and the content of this (A) tinting material is the scope of 25～50 quality %.

＜2〉according to＜1〉described solidification compound, wherein, above-mentioned (F) multi-functional epoxy compound is the compound of following general formula (I) expression.

In the formula, 1 is 5～100, and R is hydrogen atom or methyl independently of one another.

＜3〉according to＜1〉described solidification compound, wherein, above-mentioned (D) six aryl bisglyoxalines are that Photoepolymerizationinitiater initiater is the Photoepolymerizationinitiater initiater of following general formula (II) or general formula (III) expression.

In the general formula (II), X represents that hydrogen atom, halogen atom, cyano group, carbonatoms are that 1～4 alkyl or carbonatoms are 6～9 aryl, A represent independently of one another carbonatoms be 1～12 replacement or the alkoxyl group that does not have replacement or-COO-R ⁹(wherein, R ⁹The expression carbonatoms is that 1～4 alkyl or carbonatoms are 6～9 aryl), n is 1～3 integer, m is 1～3 integer.

In the general formula (III), X ¹, X ²And X ³Represent that independently of one another hydrogen atom, halogen atom, cyano group, carbonatoms are that 1～4 alkyl or carbonatoms are 6～9 aryl.Wherein, X ¹, X ²And X ³In be not hydrogen atom simultaneously more than 2.

＜4〉according to＜1〉described solidification compound, wherein, above-mentioned (A) tinting material is pigment, C.I. pigment green 36 or the C.I. pigment Green 7 of following general formula (IV) expression, and to be the primary particle size be less than 10 quality % and primary particle size are less than 5 quality % greater than the particle of 0.08 μ m pigment less than the particle of 0.02 μ m.

In the general formula (IV), R ^CRepresent independently of one another hydrogen atom, methyl, ethyl, propyl group ,-N (CH ₃) ₂,-N (C ₂H ₅) ₂,-CF ₃, chlorine atom or bromine atoms.

＜5〉according to＜1〉described solidification compound, wherein, and then, above-mentioned (A) tinting material is the pigment that comprises C.I. Pigment green 58, and is that the primary particle size is less than 10 quality % and primary particle size are less than 5 quality % greater than the particle of 0.08 μ m pigment less than the particle of 0.02 μ m in the total amount of this pigment.

＜6〉according to＜1 〉～＜5 in each described solidification compound, wherein, above-mentioned (A) tinting material is by resin-coated pigment.

＜7〉a kind of colour filter, it directly or across other layers ground (not comprising liquid crystal layer) is formed with pixel electrode on each colored pixels, above-mentioned each colored pixels directly or across other layers ground is formed on the TFT substrate, and above-mentioned each colored pixels is by＜1 〉～＜6 in each described solidification compound form.

According to the present invention, can provide NMP tolerance height, ITO evaporation adaptability, the curable resin composition that fluid preservation has good stability, contrast gradient is high and the colour filter that has used said composition.

Embodiment

Below, embodiment is elaborated.

The present invention by comprise (A) tinting material, (B) alkali soluble resins, (C) optical polymerism compound, (D) six aryl bisglyoxalines be polymerization starter, (E) be selected from oxime series initiators and the triazine series initiators more than one, and (F) multi-functional epoxy compound's that 4 officials can be above solidification compound constitute.Below each integrant that constitutes raw material, the best is described.

(A) tinting material

As the tinting material that can in solidification compound of the present invention, use, can use known in the past various mineral dyes or pigment dyestuff.In addition, also can use dyestuff as required.

No matter pigment mineral dye or pigment dyestuff, if consider that pigment optimization is this point of high-transmission rate, then preferably use the small pigment of the as far as possible little size of particles of particle diameter, if also consider operability, then preferred average primary particle diameter is 0.01 μ m～0.3 μ m, the pigment of 0.0 μ m～0.15 μ m more preferably.If this particle diameter is in above-mentioned scope, then for form the transmissivity height, colour characteristics is good and the high colour filter of contrast gradient is effective.

In the observation of the primary particle size of pigment, transmission electron microscope is suitable, for example by calculate in the observation sample under 3～100,000 times total population with less than 0.02 μ m and greater than the population of the pigment of 0.08 μ m, just can hold size-grade distribution.

About the primary particle size, less than the ratio of the primary particle of 0.02 μ m and greater than as described below the trying to achieve of ratio of the primary particle of 0.08 μ m: observe the pigment powder with transmission electron microscope, measure the major diameter of each primary particle, calculate less than 0.02 μ m and greater than the ratio (number %) of the particle of the pigment of 0.08 μ m.More specifically, observe the pigment powders with 3～100,000 times, take pictures, measure the major diameter of 1000 primary particles, calculate less than 0.02 μ m and greater than the ratio of the primary particle of 0.08 μ m with transmission electron microscope.This operation is carried out to amounting to 3 places in the position that changes the pigment powder, with results averaged.

As above-mentioned mineral dye, can enumerate metallic compound with expressions such as metal oxide, metallic complex salts, particularly, can enumerate the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. and the composite oxides of above-mentioned metal.

As the pigment that can preferably use, can enumerate following material.But, be not limited to these among the present invention.

C.I. Pigment Yellow 73 11,24,108,109,110,138,139,150,151,154,167,180,185;

C.I. pigment orange 36;

C.I. pigment red 122,150,171,175,177,209,224,242;

C.I. pigment violet 19,23,32;

C.I. pigment Blue 15: 1,15:3,15:6,16,22,60,66;

C.I. pigment Green 7,36,37;

C.I. Pigment black 1,7;

C.I. Pigment green 58.

The present invention particularly use C.I. pigment Green 7, C.I. pigment green 36, and during the pigment of the structure of following formula (IV) expression, effect is remarkable.

And then when using C.I. Pigment green 58, effect is remarkable.

In addition, among the present invention, consider from the viewpoint of contrast gradient and fluid preservation stability, be selected from C.I. pigment Green 7, C.I. pigment green 36, C.I. Pigment green 58 and be less than 10 quality % and primary particle size are less than 5 quality % greater than the particle of 0.08 μ m pigment for primary particle size in the pigment total amount less than the particle of 0.02 μ m by the pigment optimization in the pigment of following formula (IV) expression.

In the formula (IV), R ^CRepresent independently of one another hydrogen atom, methyl, ethyl, propyl group ,-N (CH ₃) ₂,-N (C ₂H ₅) ₂,-CF ₃, chlorine atom or bromine atoms.Be preferably hydrogen atom, methyl and chlorine atom especially.

Among the present invention, can use pigment dyestuff fine and the whole granulation of warp as required.The miniaturization of pigment can be following operation: pigment is modulated into full-bodied liquid composition with water-miscible organic solvent and water-soluble inorganic salt, grinds then.

As water-miscible organic solvent, can enumerate methyl alcohol, ethanol, Virahol, n-propyl alcohol, isopropylcarbinol, propyl carbinol, ethylene glycol, glycol ether, diglycol monotertiary methyl ether, carbiphene, diglycol monotertiary butyl ether, propylene glycol, propylene glycol monomethyl ether etc.But, if be adsorbed in pigment by a small amount of use, and be not lost in the waste water, also can use benzene, toluene, dimethylbenzene, ethylbenzene, chlorobenzene, oil of mirbane, aniline, pyridine, quinoline, tetrahydrofuran (THF), dioxane, ethyl acetate, isopropyl acetate, butylacetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, hexanaphthene, methylcyclohexane, halohydrocarbon, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone, dimethyl formamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone etc., and also two or more solvent can be used as required.

Among the present invention,, can enumerate sodium-chlor, Repone K, calcium chloride, bariumchloride, sodium sulfate etc. as water-soluble inorganic salt.

The usage quantity of water-soluble inorganic salt is preferably 1～50 times of quality of pigment, though more amount grinds effect, considers that from the aspect of productivity preferred amount is 1～10 times of quality, and moisture is preferably below 1%.

The usage quantity of water-miscible organic solvent is the scope of 50 quality % to 300 quality % with respect to pigment, is preferably the scope of 100 quality % to 200 quality %.Operating condition to the case of wet attrition device among the present invention has no particular limits, but, for make utilize crushing medium grind effectively and carry out, at the rotating speed that installs to the blade in the operating condition preferred embodiment under the situation of kneader is 10～200rpm, in addition, grind effective, therefore preferred under the relatively large situation of the speed ratio of twin shaft.Runtime and dry type pulverizing time add up to be preferably 1 hour～8 hours, the internal temperature of device is preferably 50～150 ℃.In addition, be the narrowly distributing of 5～50 μ m, particle diameter and as the preferred grinding particle size of the water-soluble inorganic salt of crushing medium for spherical.

These pigment dyestuffs can use separately or be used in combination various in order to improve purity of color.The concrete example of aforesaid combination is as follows, but is not limited thereto.

For example, as red pigment, can use separately or in them at least a kind of anthraquione pigmentss, perylene pigments, diketopyrrolopyrrolecocrystals series pigments, be that yellow ultramarine, isoindoline are that yellow ultramarine, quinophthalone are that yellow ultramarine Huo perylene is that red pigment, anthraquinone are that red pigment, diketopyrrolopyrrolecocrystals are mixing of red pigment etc. with tetrazo.For example, as anthraquione pigmentss, can enumerate C.I. Pigment red 177 Zuo is perylene pigments, C.I. Pigment red 155, C.I. Pigment red 224 can be enumerated,, C.I. Pigment red 254 can be enumerated as the diketopyrrolopyrrolecocrystals series pigments, consider from the viewpoint of color reproducibility, preferred C.I. pigment yellow 13 9 or C.I. Pigment red 177, with the mixing of C.I. Pigment red 254.In addition, the mass ratio of red pigment and other pigment be preferably 100: 5～100: 80.Above-mentioned mass ratio is 100: 4 when following, is difficult to suppress the transmittance from 400nm to 500nm sometimes, can't improve purity of color.In addition, above-mentioned mass ratio is 100: 81 when above, and colour developing power sometimes reduces.Especially, above-mentioned mass ratio is that 100: 10～100: 65 scope is the most desirable.In addition, under the situation of red pigment combination with one another, mass ratio can be adjusted according to colourity.

In addition, as veridian, can use a kind of halogenated phthalocyanines series pigments separately, perhaps can be that yellow ultramarine, quinophthalone are that yellow ultramarine, azomethine are that yellow ultramarine or isoindoline are that yellow ultramarine mixes use with this halogenated phthalocyanines series pigments and tetrazo.For example, as such example, preferred C.I. pigment Green 7, C.I. pigment green 36 mix with C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. Pigment Yellow 73 150, C.I. Pigment Yellow 73 180 or C.I. Pigment Yellow 73 185.The mass ratio of veridian and yellow ultramarine is preferably 100: 5～and 100: 200.By being set in the above-mentioned scope, can effectively suppress the transmittance of 400～450nm, purity of color becomes well, can obtain desirable NTSC target form and aspect.As above-mentioned mass ratio, be preferably 100: 20～100: 150 scope especially.

In addition, as veridian, can use a kind of zinc phthualocyanine pigment separately, perhaps can be that yellow ultramarine, quinophthalone are that yellow ultramarine, azomethine are that yellow ultramarine or isoindoline are that yellow ultramarine mixes use with this zinc phthualocyanine pigment and tetrazo.For example, as such example, preferred C.I. Pigment green 58 mixes with C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. Pigment Yellow 73 150, C.I. Pigment Yellow 73 180 or C.I. Pigment Yellow 73 185.The mass ratio of veridian and yellow ultramarine is preferably 100: 5～and 100: 200.By being set in the above-mentioned scope, can effectively suppress the transmittance of 400～450nm, purity of color becomes well, can obtain desirable NTSC target form and aspect.As above-mentioned mass ratio, be preferably 100: 20～100: 150 scope especially.

As blue pigments, can use a kind of phthualocyanine pigment separately, can be that violet pigment mixes use with this phthualocyanine pigment Yu dioxazine perhaps.As more preferred example, can enumerate the C.I. pigment Blue 15: 6 with the mixing of C.I. pigment Violet 23.

The mass ratio of blue pigments and violet pigment is preferably 100: 0～and 100: 100, more preferably below 100: 70.

In addition, as the pigment that is suitable for the black matrix" purposes, can carbon black, graphite, titanium is black, ferric oxide, titanium oxide uses separately or mix use, the combination that preferred carbon black and titanium are deceived.

In addition, the mass ratio that carbon black and titanium are black is preferably 100: 0～100: 60 scope.By being set in the above-mentioned scope, it is good that dispersion stabilization becomes.

Among the present invention,, under the situation of using dyestuff, can obtain dissolved Photocurable composition equably as tinting material.

Can be not particularly limited as the dyestuff that tinting material uses, can use the known dyestuff that in the past adopted as the colour filter purposes.For example, can enumerate Japanese kokai publication sho 64-90403 communique, the spy opens clear 64-91102 communique, Japanese kokai publication hei 1-94301 communique, Te Kaiping 6-11614 communique, the spy steps on No. 2592207, United States Patent (USP) the 4th, 808, No. 501 specification sheetss, United States Patent (USP) the 5th, 667, No. 920 specification sheetss, United States Patent (USP) the 5th, 059, No. 500 specification sheets, Te Kaiping 5-333207 communique, Te Kaiping 6-35183 communique, Te Kaiping 6-51115 communique, Te Kaiping 6-194828 communique, Te Kaiping 8-211599 communique, Te Kaiping 4-249549 communique, Te Kaiping 10-123316 communique, Te Kaiping 11-302283 communique, Te Kaiping 7-286107 communique, the spy opens the 2001-4823 communique, Te Kaiping 8-15522 communique, Te Kaiping 8-29771 communique, Te Kaiping 8-146215 communique, Te Kaiping 11-343437 communique, Te Kaiping 8-62416 communique, the spy opens the 2002-14220 communique, the spy opens the 2002-14221 communique, the spy opens the 2002-14222 communique, the spy opens the 2002-14223 communique, Te Kaiping 8-302224 communique, Te Kaiping 8-73758 communique, Te Kaiping 8-179120 communique, the pigment of record in the Te Kaiping 8-151531 communique etc.

As chemical structure, can enumerate dyestuffs such as pyrazoles azo system, aniline azo system, triphenyl methane system, anthraquinone system, anthrapyridone system, benzal base system, oxonols system, Pyrazolotriazole azo system, pyridylazo system, cyanines system, thiodiphenylamine system, pyrrolo-pyrazoles azomethine system, xanthene system, phthalocyanine system, chromene system, indigo system.

As the content of the tinting material in the solidification compound of the present invention, be preferably 25～50 quality % with respect to the total solids composition (quality) of said composition, more preferably 30～45 quality %.If the content of tinting material is in above-mentioned scope, then fully and guarantee that aspect the good colour characteristics be effective in depth of shade.

In the present invention, especially preferably use pigment dyestuff, and in the miniaturization operation or dispersion step of pigment, use the material that pigment is obtained with the macromolecular compound lining as tinting material.By using the macromolecular compound coated pigment, even in the pigment of miniaturization, also can suppress the formation of 2 aggregates, thereby can use the coated pigment that can be improved with 1 particle state dispersive dispersiveness, the coated pigment of dispersion stabilization excellence that 1 particle after disperseing can stably be kept.

So-called coated pigment as optimal way among the present invention is meant that pigment is covered by macromolecular compound and the pigment that obtains.So-called lining is meant, the new interface of the pigment that the surfactivity that produces through miniaturization is high forms the firm coating of this macromolecular compound by having the strong electrostatic interaction of heterocyclic macromolecular compound with of the present invention at side chain.Thus, be considered to obtain have the coated pigment of higher dispersion stabilization.That is, in the present invention, even the pigment after lining is handled with the organic solvent washing of solubilized macromolecular compound, the macromolecular compound of lining also can dissociate hardly.

So-called coated pigment is characterised in that among the present invention, the i of pigment dyestuff etc.) pigment particles is covered by the macromolecular compound that iv) has a heterocycle isopolarity group at side chain, part or all that is overlayed on the pigment particles surface by this macromolecular compound securely reaches effect of the present invention, is different from that common macromolecule dispersing agent is adsorbed on the pigment and the pigment that obtains.This lining state can be measured by the free amount (ionization rate) of macromolecular compound that the washing that utilizes organic solvent shown below is obtained and confirm.That is, only be adsorbed on macromolecular compound on the pigment through its major part of washing of organic solvent, specifically have and take place free more than 65% and be removed, but as the present invention by the situation of surface-coated pigment, ionization rate is few, is below 30%.

Pigment after the lining processing of the present invention with 1-methoxyl group-2-propyl alcohol washing, is calculated free amount.This method is that pigment 10g is dropped among 1-methoxyl group-2-propyl alcohol 100ml, at room temperature vibrates 3 hours with vibrating machine.Made the pigment sedimentation with separating centrifuge through 8 hours with 80000rpm afterwards, the solids component of supernatant liquor part is obtained by desiccating method.Obtain the quality of free macromolecular compound from pigment,, calculate ionization rate (%) by the ratio of the quality of the macromolecular compound that uses in handling with the initial stage.

The ionization rate of the pigment of commercially available grade can be measured by the following method.Promptly, with the solvent (for example dimethyl sulfoxide (DMSO), dimethyl formamide, formic acid, sulfuric acid etc.) of dissolving pigment with the whole dissolving of pigment after, it is deliquescent poor to utilize, with an organic solvent macromolecular compound is separated with pigment, calculate as " quality of the macromolecular compound that uses in the initial stage processing ".With 1-methoxyl group-2-propyl alcohol washing pigment, the above-mentioned free amount that obtains is obtained ionization rate (%) divided by this " quality of the macromolecular compound that uses in the initial stage processing " in addition.

Ionization rate is more little, and is high more to the lining rate of pigment, dispersed, dispersion stabilization is good more.The preferable range of ionization rate is below 30%, is more preferably below 20%, and most preferably be below 15%.It is desirable to 0%.

Lining is handled and is preferably carried out simultaneously in the miniaturization operation of pigment, specifically, implement through following operation: add i) pigment, ii) water miscible inorganic salt, iii) do not dissolve ii) a spot of water-miscible organic solvent and iv) macromolecular compound in fact, carry out the operation (being called salt grinder preface) of mechanically mixing with kneader etc.; This mixture is dropped in water, make the operation of pulp-like with stirring such as super mixer; And, carry out the exsiccant operation as required with this slurries filtration, washing.

Salt mill for above-mentioned further is specifically described.At first, at i) pigment dyestuff and ii) in the mixture of water-soluble inorganic salt, add a spot of iii) water-miscible organic solvent as wetting agent, after mixing with brute forces such as kneaders, this mixture is dropped in water, make pulp-like with stirring such as super mixer.Then,, carry out drying as required, obtain the pigment of miniaturization thus this slurries filtration, washing.In addition, under the situation that colo(u)rant dispersion is used in butyrous varnish, also can be with the method that is commonly referred to as flash evaporation (flashing) of the processing pigment (being called filter cake) before dry, the limit is removed the waterside and is dispersed in the butyrous varnish.In addition, under the situation in being dispersed in water system varnish, handle the pigment drying-free, filter cake directly can be dispersed in the varnish.

In the present invention, when salt grinds,, further obtain fine, surface thus by the iv) partly soluble at least resin-coated few pigment of cohesion of pigment when dry by in above-mentioned iii) pigment dyestuff and with iv) partly soluble at least resin.

In addition, add the iv) opportunity of macromolecular compound, can add all at the initial stage of salt grinder preface, also can portion-wise addition.In addition, can also in dispersion step, add.

The macromolecular compound that in the lining of pigment, uses so long as the macromolecular compound that has the adsorptivity group of pigment get final product.Especially preferably be used in side chain and have the pigment that the heterocyclic macromolecular compound is covered and handles and obtain.As such macromolecular compound, be preferably the polymkeric substance that comprises the monomeric polymerized unit that derives from the monomer shown in the following general formula (1) or constitute by maleimide, maleimide derivatives, be preferably especially and comprise the polymkeric substance that derives from the monomeric polymerized unit shown in the following general formula (1).

General formula (1)

In the above-mentioned general formula (1), R ¹Expression hydrogen atom or replace or do not have the alkyl of replacement.R ²The linking group of expression singly-bound or divalent.Y represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.Z represents to have the group of nitrogen heterocyclic ring structure.

As R ¹Alkyl, be preferably carbonatoms and be 1～12 alkyl, more preferably carbonatoms is 1～8 alkyl, is preferably carbonatoms especially and is 1～4 alkyl.

R ¹When shown alkyl has substituting group,, for example can enumerate hydroxyl, alkoxyl group (preferred carbonatoms is 1～5, and more preferably carbonatoms is 1～3) as this substituting group, as methoxyl group, oxyethyl group, cyclohexyloxy etc.

As R ¹Shown preferred alkyl particularly, for example can be enumerated methyl, ethyl, propyl group, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl.

As R ¹, most preferably be hydrogen atom or methyl.

In the general formula (1), R ²The concatenating group of expression singly-bound or divalent.As the concatenating group of this divalent, be preferably the alkylidene group that replaces or do not have replacement.As this alkylidene group, be preferably carbonatoms and be 1～12 alkylidene group, more preferably carbonatoms is 1～12 alkylidene group, more preferably carbonatoms is 1～8 alkylidene group, is preferably carbonatoms especially and is 1～4 alkylidene group.

R ²Shown alkylidene group also can be the group that 2 above alkylidene groups link via heteroatoms (for example, Sauerstoffatom, nitrogen-atoms or sulphur atom).

As R ²Shown preferred alkylidene group particularly, for example can be enumerated methylene radical, ethylidene, propylidene, trimethylene, tetramethylene.

R ²Shown preferred alkylidene group has under the substituent situation, as this substituting group, for example can enumerate hydroxyl etc.

As R ²The concatenating group of represented divalent, also can be end at above-mentioned industry alkyl have be selected from-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-, and-heteroatoms among the NHCO-or comprise heteroatomic part-structure and via this heteroatoms or comprise heteroatomic part-structure and come and Z banded group.

In the general formula (1), Z represents to have the group of heterocycle structure.As group, for example can enumerate phthalocyanine system with heterocycle structure, insoluble azo is, azo lake system, anthraquinone system, quinacridone dioxazine system, diketopyrrolopyrrolecocrystals system, anthra pyridine (anthrapyridine) is, anthracene is formed anthrone (anthanthrone), indanthrone system, flavanthrone system, purple cyclic ketones (perinone) is perylene system, the pigment structure that thioindigo (thioindigoid) is, perhaps thiophene for example, furans, xanthene, the pyrroles, pyrroline, tetramethyleneimine, dioxolane, pyrazoles, pyrazoline, pyrazolidine, imidazoles oxazole, thiazole oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithian, isoindoline, isoindolinone, Benzimidazolinone, benzothiazole, succinimide, phthalic imidine, naphthalimide, glycolylurea, indoles, quinoline, carbazole, acridine, dihydroketoacridine, anthraquinone, pyrazine, tetrazolium, thiodiphenylamine phenoxazine, benzoglyoxaline, benzotriazole, cyclic amide, the ring-type urea, heterocycle structures such as cyclic imide.These heterocycle structures can have substituting group, as this substituting group, for example, can enumerate alkyl, alkoxyl group, halogen atom, aliphatics ester group, aromatic series ester group, alkoxy carbonyl etc.

Z more preferably has the group that carbonatoms is the nitrogen heterocyclic ring structure more than 6, is preferably especially that to have carbonatoms be more than 6 and the group of 12 following nitrogen heterocyclic ring structures.As carbonatoms is nitrogen heterocyclic ring structure more than 6, particularly, be preferably thiodiphenylamine ring, phenoxazine ring, dihydroketoacridine ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, ring-type urea structure and cyclic imide structure, be preferably the structure of following general formula (2), (3) or (4) expression especially.

General formula (2) general formula (3) general formula (4)

In the general formula (2), E represent to be selected from singly-bound, alkylidene group (for example methylene radical, ethylidene, propylidene, trimethylene, tetramethylene etc.) ,-O-,-S-,-NR ^A-and-C (=O)-in any.Here, R ^AExpression hydrogen atom or alkyl.R ^AAlkyl under the expression alkyl situation is preferably that carbonatoms is 1～18 alkyl, more preferably carbonatoms is 1～6 alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-hexyl, n-octyl, 2-ethylhexyl, Octadecane base etc.

In above-mentioned, as the E in the general formula (2), be preferably singly-bound, methylene radical ,-O-or-C (=O)-, be preferably especially-C (=O)-.

In the general formula (4), Y ¹And Y ²Independently of one another expression-N=,-NH-,-N (R ^B)-,-S-or-O-.R ^BThe expression alkyl, R ^BIt is 1～18 alkyl that alkyl under the situation of expression alkyl is preferably carbonatoms, more preferably carbonatoms is 1～6 alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-hexyl, n-octyl, 2-ethylhexyl, Octadecane base etc.

In above-mentioned, as the Y in the general formula (4) ¹And Y ², be preferably especially-N=,-NH-and-N (R ^B)-.As Y ¹And Y ²Combination, can enumerate Y ¹And Y ²In the either party be-N=, the opposing party be-combination of NH-, be imidazolyl.

In general formula (2), (3) and (4), ring B ¹, the ring B ², the ring C, and the ring D represent aromatic nucleus independently of one another.As this aromatic nucleus, for example, can enumerate phenyl ring, naphthalene nucleus, indenes ring, azulene, fluorenes ring, anthracene nucleus, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, thiodiphenylamine ring, phenoxazine ring, dihydroketoacridine ring, anthraquinone ring etc., wherein be preferably phenyl ring, naphthalene nucleus, anthracene nucleus, pyridine ring, phenoxazine ring, acridine ring, thiodiphenylamine ring, phenoxazine ring, dihydroketoacridine ring, anthraquinone ring, be preferably phenyl ring, naphthalene nucleus, pyridine ring especially.

Particularly, as the ring B in the general formula (2) ¹And ring B ², for example, can enumerate phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring etc.As the ring C in the general formula (3), for example, can enumerate phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring etc.As the ring D in the general formula (4), for example, can enumerate phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring etc.

In the structure of general formula (2), (3) and (4) expression, from the viewpoint of the ageing stability of dispersed, dispersion liquid, more preferably phenyl ring, naphthalene nucleus, in general formula (2) or (4), phenyl ring more preferably, in general formula (3), naphthalene nucleus more preferably.

These concrete compounds for example can use disclosed compound in [0045]～[0047] of [0044]～[0047], Japanese Patent Application 2007-231695 number of TOHKEMY 2008-083089 number [0029]～[0030], TOHKEMY 2008-266627 number and [0075]～[0076].

The rerum natura of above-mentioned specific dispersion resin determines that method is as follows.In addition, the physics value of the resin of putting down in writing among the present invention etc. unless otherwise specified, can make use the same method definite.

(weight-average molecular weight and number-average molecular weight)

Carry out by GPC (gel permeation chromatography) mensuration of following condition and by polystyrene conversion.

Use post: TSKgel Multipore HXL-M (pore polydispersion type linear columns) TOSOH system

Elutriant: THF

Flow: 1.0ml/min

Temperature: 40 ℃

Testing conditions: RI

System: the high speed GPC device same form (TOSOH makes HLC-8220)

(acid number)

1-methoxyl group-2-the propanol solution of resin is carried out neutralization titration with 1 equivalent (1N) potassium hydroxide aqueous solution to be obtained.

Even under the situation of the pigment of the coated processing of stating in the use, also more preferably use at least a dispersion agent that pigment is disperseed, use as pigment dispensing composition.By containing this dispersion agent, can improve dispersing of pigments.

As dispersion agent, for example can suitably select to use known pigment dispersing agent or tensio-active agent.

Particularly, the compound of numerous species be can use, organosiloxane polymer KP341 (Shin-Etsu Chemial Co., Ltd's system), (methyl) acrylic acid series (being total to) polymer P OLYFLOW No.75, No.90, No.95 (chemical industry Co., Ltd. of common prosperity society system) for example can be enumerated, W001 positively charged ions such as (Yu Business Co., Ltd's systems) is a tensio-active agent; Nonionics such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan-fatty acid ester are tensio-active agent; W004, W005, W017 negatively charged ion such as (Yu Business Co., Ltd's systems) are tensio-active agent; EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER100, EFKA POLYMER 400, EFKA POLYMER 401, the contour molecular dispersion of EFKA POLYMER 450 (being Ciba Specialty Chemicals corporate system); SOLSPERSE3000,5000,9000,12000,13240,13940,17000,24000,26000, various SOLSPERSE dispersion agents such as 28000 (Japanese Lubrizol Co., Ltd. system); アデカプ Le ロニ Star Network L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (rising sun electrification Co., Ltd. system) and ISONET S-20 (Sanyo Chemical Industries Co., Ltd.'s manufacturing), Disperbyk 101,103,106,108,109,111,112,116,130,140,142,162,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (BYK-Chemie Co., Ltd. systems).In addition, can also enumerate acrylic copolymer etc. has polar group on molecular end or side chain oligopolymer or polymkeric substance.

As the content of dispersion agent in pigment dispensing composition, with respect to the quality of above-mentioned pigment, be preferably 1～100 quality %, more preferably 3～70 quality %.

Can add pigment derivative as required in the above-mentioned pigment dispensing composition.Make to have imported and have the part of affinity with dispersion agent or the pigment derivative of polar group is adsorbed in surface of pigments, adsorption site used as dispersion agent, thereby can make pigment be dispersed in solidification compound as fine particle, prevent that it from condensing again, it is effective for the colour filter that forms contrast gradient height, transparency excellence.

Pigment derivative particularly is is precursor skeleton with the pigment dyestuff, imported acidic groups or basic group, aromatic series base as substituent compound at side chain.Pigment dyestuff specifically can be enumerated quinacridone pigment, phthualocyanine pigment, azo pigment, quinophthalone series pigments, isoindoline series pigments, isoindolinone pigment, quinoline pigment, diketo pyrrolo-pyrrole pigment(DPP pigment), benzimidazolone pigment etc.Usually also comprise faint yellow aromatic series polynuclear compounds such as the naphthalene system that is not called as pigment, anthraquinone system, triazine system, quinoline system.As pigment derivative, can use Japanese kokai publication hei 11-49974 communique, spy to open flat 11-189732 communique, spy and open flat 10-245501 communique, spy and open 2006-265528 communique, spy and open flat 8-295810 communique, spy and open flat 11-199796 communique, spy and open 2005-234478 communique, spy and open the pigment derivative that 2003-240938 communique, spy are opened record in the 2001-356210 communique etc.

As the content of the pigment derivative among the present invention in pigment dispensing composition, with respect to the quality of pigment, be preferably 1～30 quality %, more preferably 3～20 quality %.This content is if in above-mentioned scope, then when viscosity inhibition ground is lower, can disperse well, and can improve dispersion stabilization after disperseing, thereby make transmissivity increase, excellent colour characteristics can be obtained, when making colour filter, high-contrast can be constituted with good colour characteristics.

The dispersive method for example can be carried out according to as described below: with pigment with dispersion agent is pre-mixed and disperse in advance with homogenizer etc., then the material that obtains is adopted the bead dispersion machine that used zirconium white bead etc. etc. to carry out differential and loose.

As (B) alkali soluble resins, be the wire organic high molecular polymer, can from the alkali soluble resins that molecule (being the molecule of main chain preferably), has at least 1 alkali-soluble group of promotion (for example carboxyl, phosphate, sulfonic group etc.), suitably select with acrylic copolymer, styrene based copolymer.Wherein, more preferably solvable in organic solvent, the resin that can develop by weak base aqueous solution.

In the manufacturing of alkali soluble resins, for example can use the method for utilizing known radical polymerization.The kind and the polymerizing conditions such as amount, solvent types thereof of the temperature during with radical polymerization manufactured alkali soluble resins, pressure, radical initiator can easily be set by those skilled in the art, also can determine condition experimentally.

As above-mentioned wire organic high molecular polymer, preferred side chain has the polymkeric substance of carboxylic acid.For example; can enumerate Japanese kokai publication sho 59-44615 number; special public clear 54-34327 number; special public clear 58-12577 number; special public clear 54-25957 number; the spy opens clear 59-53836 number; the spy opens the Sipacril 2739OF of putting down in writing in each communique of clear 59-71048 number; acrylic copolymer; itaconic acid copolymer; the Ba Dousuan multipolymer; maleic acid; partial esterification maleic acid etc.; and the acid cellulose derivative that on side chain, has carboxylic acid; addition acid anhydrides in having the polymkeric substance of hydroxyl and polymkeric substance of obtaining etc., and then preferably enumerate on side chain high molecular polymer with (methyl) acryl.

Wherein, preferred especially (methyl) benzyl acrylate/(methyl) acrylic copolymer or by multiple copolymer that (methyl) benzyl acrylate/(methyl) vinylformic acid/other monomer constitutes.

In addition, as useful polymkeric substance, also can enumerate polymkeric substance that obtains by the 2-hydroxyethyl methacrylate copolymerization etc.This polymkeric substance can mix with any amount and uses.

Except that above-mentioned polymkeric substance, can enumerate (methyl) vinylformic acid 2-hydroxy propyl ester/polystyrene macromolecular monomer/benzyl methacrylate/Sipacril 2739OF of putting down in writing in the Japanese kokai publication hei 7-140654 communique, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester/polymethylmethacrylate macromonomer/benzyl methacrylate/Sipacril 2739OF, 2-hydroxyethyl methacrylate/polystyrene macromolecular monomer/methyl methacrylate/Sipacril 2739OF, 2-hydroxyethyl methacrylate/polystyrene macromolecular monomer/benzyl methacrylate/Sipacril 2739OF etc.

For the concrete formation unit of alkali soluble resins, preferred especially (methyl) vinylformic acid and other the monomeric multipolymer that can follow (methyl) acrylic acid copolymer.Herein, (methyl) vinylformic acid is the general name of vinylformic acid and methacrylic acid, below, (methyl) acrylate also is the general name of acrylate and methacrylic ester in the same manner.

As can with other monomer of (methyl) acrylic acid copolymer, can enumerate (methyl) alkyl acrylate, (methyl) aryl acrylate, vinyl compound etc.Herein, the hydrogen atom of alkyl and aryl can be substituted the base replacement.

As the concrete example of above-mentioned (methyl) alkyl acrylate and (methyl) aryl acrylate, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) CA, (methyl) vinylformic acid naphthalene ester, (methyl) cyclohexyl acrylate etc.

In addition, as above-mentioned vinyl compound, for example can enumerate vinylbenzene, alpha-methyl styrene, Vinyl toluene, glycidyl methacrylate, vinyl cyanide, vinyl-acetic ester, N-vinyl pyrrolidone, methacrylic acid tetrahydro furfuryl ester, polystyrene macromolecular monomer, polymethylmethacrylate macromonomer, CH ₂=CR ¹R ², CH ₂=C (R ¹) (COOR ³) [R herein, ¹Expression hydrogen atom or carbonatoms are 1～5 alkyl, R ²The expression carbonatoms is 6～10 aromatic hydrocarbons ring, R ³The expression carbonatoms is that 1～8 alkyl or carbonatoms are 6～12 aralkyl] etc.

In addition; in order to improve the cross-linking efficiency of solidification compound of the present invention; can use the resin that in alkali soluble resins, has polymerizable group separately; perhaps also can with its with do not have the alkali soluble resins and the usefulness of polymerizable group, the polymkeric substance etc. that contains aryl, (methyl) acryl, aryloxy alkyl etc. at side chain is useful.Alkali soluble resins with the two keys of polymerizability can develop with alkaline developer, and has light solidified and Thermocurable.Show the example of the polymkeric substance that contains these polymerizable groups below, but so long as in 1 molecule, contain the compound of caustic solubility group such as COOH base, OH base and carbon-to-carbon unsaturated bond, just be not subjected to following qualification.

(1) by following compound and the reactive acrylic resin that contains carboxyl are obtained through the urethane-modified acrylic resin that contains the two keys of polymerizability, wherein, above-claimed cpd is to make isocyanate group and OH radical reaction in advance and stay next unreacted isocyanate group and contain the compound of at least 1 (methyl) acryl;

(2) acrylic resin by will containing carboxyl and intramolecularly have the acrylic resin that contains unsaturated group that the compound reaction of epoxy group(ing) and the two keys of polymerizability obtains simultaneously;

(3) sour side chain (pendant) type Epocryl;

(4) acrylic resin that contains the two keys of polymerizability that the acrylic resin that contains the OH base is obtained with 2 yuan of anhydride reactions with the two keys of polymerizability.

In above-mentioned, the resin of preferred especially (1) and (2).

As concrete example, can use: will by for example vinylformic acid 2-hydroxyl ethyl ester with OH base, contain for example methacrylic acid of COOH base and the multipolymer that can form with the monomer of the acrylic acid or the like of their copolymerization or vinylic chemical compound etc. with have compound that the oxirane ring of responding property of OH base and the compound of carbon carbon unsaturated link(age) compounds such as (for example) glycidyl acrylates reaction is obtained etc.With the reaction of OH base in, except oxirane ring, can also use compound with acid anhydrides, isocyanate group, acryl.

In addition, can also use the reaction of following compound and saturated or unsaturated multi-anhydride and reactant, above-claimed cpd reacts the compound that gets for the unsaturated carboxylic acid of the compound with oxirane ring that will put down in writing and vinylformic acid and so in Japanese kokai publication hei 6-102669 communique, Japanese kokai publication hei 6-1938 communique.

As the compound of alkali soluble groups that has COOH Kina sample concurrently and carbon carbon unsaturated group, for example, can enumerate DIANAL NR series (Mitsubishi Rayon Co., Ltd. system); Photomer6173 (the polyurethane acroleic acid oligopolymer that contains the COOH base, Diamond Shamrock Co.Ltd. system); VISCOTE R-264, KS resist 106 (being Osaka Organic Chemical Industry Co., Ltd.'s system); CYCLOMER P series, PLACCEL CF200 series (being DAICEL Chemical Industries Co., Ltd. system); Ebecryl 3800 (DAICEL-UCB Co., Ltd. system) etc.

As the content of alkali soluble resins in solidification compound, with respect to the total solids composition of said composition, be preferably 1～15 quality %, more preferably 2～12 quality % are preferably 3～10 quality % especially.

As (C) optical polymerism compound, but the ethylenic unsaturated group, the boiling point that preferably have at least one addition polymerization are the compound more than 100 ℃ under normal pressure, and wherein, more preferably 4 officials can above acrylic compound.

But under the normal pressure be compound more than 100 ℃ as above-mentioned ethylenic unsaturated group with at least one addition polymerization, boiling point, for example can enumerating the acrylate or the methacrylic ester of simple functions such as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) vinylformic acid phenoxy ethyl; Polyoxyethylene glycol two (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, hexylene glycol two (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanuric acid ester, the compound that in polyfunctional alcohols such as glycerol or trimethylolethane, carries out (methyl) acroleic acid esterification behind addition of ethylene oxide or the propylene oxide and obtain, poly-(methyl) acroleic acid esterification of tetramethylolmethane or Dipentaerythritol and the compound that obtains, Japanese Patent Publication 48-41708 number, special public clear 50-6034 number, the spy opens the urethane acrylate class of putting down in writing in the clear 51-37193 communique, the spy opens clear 48-64183 number, special public clear 49-43191 number, the polyester acrylate class of putting down in writing in the special public clear 52-30490 communique, Resins, epoxy is polyfunctional acrylate or methacrylic esters such as epoxy acrylate class with (methyl) acrylic acid reaction product.

In addition, also can use Japan then the will Vol.20 of association, No.7, in 300～308 pages as light solidified monomer and oligopolymer and recommended compound.

In addition, also can use the compound that behind addition of ethylene oxide of putting down in writing as the concrete example of general formula (1) and (2) in above-mentioned polyfunctional alcohol or propylene oxide, carries out (methyl) acroleic acid esterification in the Japanese kokai publication hei 10-62986 communique and obtain.

Wherein, the structure that connects via ethylene glycol, propylene glycol residue of preferred Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate and their acryl.Also can use their oligomeric.

In addition, the carbamate compounds class with oxyethane pastern bone frame of record in the urethane acrylate class of record in clear 51-37193 number, special fair 2-32293 number, special fair 2-16765 number or special public clear 58-49860 number, special public clear 56-17654 number, special public clear 62-39417 number, special public clear 62-39418 number is opened in also preferred Japanese Patent Publication 48-41708 number, spy.And then, open clear 63-260909 number, spy and open addition polymerization compounds record, that intramolecularly has amino structure or sulfide structure in flat 1-105238 number by using the spy to open clear 63-277653 number, spy, can obtain the very excellent optical polymerism composition of film speed.As commercially available product, can enumerate oligourethane UAS-10, UAB-140 (adret state basic policy PULP corporate system), UA-7200 (Xin Zhong village chemical company system), DPHA-40H (Japanese chemical drug corporate system), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (common prosperity corporate system) etc.

In addition, the ethylenically unsaturated compounds class that also preferably has acidic group, as commercially available product, the conduct that for example can enumerate Toagosei Co., Ltd's system contain carboxyl 3 functional acrylates TO-756 and as 5 functional acrylates' of containing carboxyl TO-1382 etc.

The optical polymerism compound also can will be used in combination more than 2 kinds except a kind of independent use.As the content of optical polymerism compound in solidification compound,, be preferably 3～55 parts, more preferably 10～50 parts with respect to 100 parts of the total solids compositions of said composition.If the content of optical polymerism compound is in the above-mentioned scope, then can fully be cured reaction.

As (D) six aryl bisglyoxalines is polymerization starter, so long as replace and the dimer of the imidazole ring that obtains get final product with 3 aryl, still, the polymerization starter that preferred especially following general formula (II) or general formula (III) are represented.

In addition, under the situation that has a plurality of A, X, can be identical or different mutually, but consider from the viewpoint of sensitivity and thermostability, preferably identical.

As six aryl bisglyoxaline based compounds, for example, can enumerate 2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2,4 dichloro benzene bases)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-cyano-phenyls)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-cyano-phenyls)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-aminomethyl phenyls)-4,4 ', 5,5 '-four (4-methoxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-aminomethyl phenyls)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-aminomethyl phenyls)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-ethylphenyls)-4,4 ', 5,5 '-four (4-methoxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-ethylphenyls)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-ethylphenyls)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-phenyl)-4,4 ', 5,5 '-four (4-methoxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-phenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-phenyl)-4, bisglyoxaline based compounds such as 4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline;

2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four-(p-methoxyphenyl) bisglyoxalines, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four-(m-methoxyphenyl) bisglyoxalines, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four-(3, the 4-Dimethoxyphenyl) bisglyoxalines, 2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-four-(4-p-methoxy-phenyl) bisglyoxalines, 2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-four-(3-p-methoxy-phenyl) bisglyoxalines, 2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-four-(3, the 4-Dimethoxyphenyl) bisglyoxalines;

2,2 '-two (2,4 dichloro benzene base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4-dicyano phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4,6-tricyano phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 4-3,5-dimethylphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4, the 6-trimethylphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4-diethyl phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4,6-triethyl phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4-phenylbenzene phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4,6-triphenyl phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2-fluorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (adjacent fluorophenyls)-4,4 ', 5, bisglyoxaline based compounds such as 5 '-tetraphenyl bisglyoxaline etc.

In the above-claimed cpd,, can enumerate 2 as particularly preferred compound, 2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline (B-CIM, hodogaya chemical industry), 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four-(3, the 4-Dimethoxyphenyl) bisglyoxalines (HABI1311, Japanese シ one ベ Le ヘグ Na one), 2,2 '-two (2-aminomethyl phenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline (dark fund changes into).

Solidification compound of the present invention contains (E) and is selected from more than one initiator in oxime series initiators and the triazine series initiators.As the oxime series initiators, can be to be selected from least a in the compound group of following general formula (5) or general formula (6) expression, the polymerization starter that is by the oxime with general formula (5) or (6) expression uses with above-mentioned (B) alkali soluble resins, can improve sensitivity, polyreaction is carried out well, can further improve the controlled of shape and needed thickness thereof.Thus, even at 1500J/m ²Under the following low exposure, also can obtain good sensitivity, adaptation.

In above-mentioned general formula (5), (6), R ¹¹The expression carbonatoms is that 1～20 alkyl, carbonatoms are 3～8 cycloalkyl or phenyl.

R ¹²And R ³Represent independently of one another hydrogen atom, carbonatoms be 1～20 alkyl, carbonatoms be 3～8 cycloalkyl, replace or do not have the phenyl of replacement or carbonatoms be 7～20 ester ring type alkyl (wherein, carbonatoms is except 7～8 the cycloalkyl), the substituting group under the substituted situation of above-mentioned phenyl can be that carbonatoms is that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group, phenyl or halogen atom.Here, these substituent quantity can be 1～5.

R ⁴The expression carbonatoms is that 4～20 oxygen-containing heterocycle, carbonatoms are that 4～20 nitrogen heterocycle or carbonatoms are 4～20 sulfur heterocyclic ring base.

R ⁵Expression hydrogen atom, carbonatoms are that 1～12 alkyl or carbonatoms are 1～12 alkoxyl group.

In addition, q represents 1～5 integer, and p represents 0～5 integer, and r represents 0～6 integer, and p and q satisfy p+q≤5.

In addition, there are a plurality of R ⁴And R ⁵Situation under, mutually can be identical or different respectively.

In above-mentioned general formula (5) and (6), R ¹¹The carbonatoms of expression is that 1～20 alkyl can be a straight chain shape or a catenate alkyl, as its concrete example, for example, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl.Wherein, preferred carbonatoms is 1～10 alkyl, and preferred especially carbonatoms is 1～8 alkyl.

As R ¹¹The carbonatoms of expression is 3～8 cycloalkyl, for example, can enumerate cyclopentyl, cyclohexyl etc.Wherein, be preferably carbonatoms and be 3～6 cycloalkyl, be preferably carbonatoms especially and be 5～6 cycloalkyl.

In the above-mentioned group, as R ¹¹, preference such as methyl, ethyl, n-propyl, sec.-propyl, n-hexyl etc.

As R ¹², R ³The carbonatoms of expression is 1～20 alkyl, can be a straight chain shape or a chain, as its concrete example, for example, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl.Wherein, preferred carbonatoms is 1～10 alkyl, and preferred especially carbonatoms is 1～8 alkyl.

As R ¹², R ³The carbonatoms of expression is 3～8 cycloalkyl, for example, can enumerate cyclopentyl, cyclohexyl etc.Wherein, be preferably carbonatoms and be 3～6 cycloalkyl, be preferably carbonatoms especially and be 5～6 cycloalkyl.

As R ¹², R ³The substituting group of the substituted-phenyl of expression i.e. " carbonatoms is 1～6 alkyl ", can be straight chain shape, chain or cyclic alkyl, as its concrete example, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl etc.Wherein, preferred carbonatoms is 1～6 alkyl, and preferred especially carbonatoms is 1～5 alkyl.

In addition, as R ¹², R ³The substituting group of the substituted-phenyl of expression i.e. " carbonatoms is 1～6 alkoxyl group ", can be straight chain shape, chain or ring-type, as its concrete example, can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy etc.Wherein, preferred carbonatoms is 1～3 alkoxyl group.

As R ¹², R ³The substituting group of the substituted-phenyl of expression is a halogen atom, for example, can enumerate fluorine atom, chlorine atom etc.

As R ¹², R ³The carbonatoms of expression is 7～20 ester ring type alkyl (carbonatoms be 7～8 cycloalkyl except), for example can enumerate di-cycloalkyl, tricyclic alkyl (tricycloalkyl), spiro cycloalkyl group, connection tricyclic alkyl, contain the terpene skeleton group, contain the group of adamantyl skeleton etc.Wherein, preferred carbonatoms is 9～18 ester ring type alkyl, and preferred especially carbonatoms is 9～12.

In the above-mentioned group, as R ¹², preferred di-cycloalkyl, tricyclic alkyl, contain the group of adamantyl skeleton etc., as R ³, preferred tricyclic alkyl, contain the group of adamantyl skeleton etc.

As R ⁴The carbonatoms of expression is 4～20 nitrogen heterocycle, carbonatoms is 4～20 oxygen-containing heterocycle, carbonatoms is 4～20 sulfur heterocyclic ring base, for example can enumerate tetrahydro-thienyl, the azatropylidene base, dihydro azatropylidene base, dioxolanyl, triazinyl, the oxathiane base, thiazolyl oxadiazine base, pepper cyclic group (dioxaindanyl), two thiophene naphthyls (dithianaphthalenyl), furyl, thio-phenyl, pyrryl oxazolyl isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, furan a word used for translation base (furazanyl), pyranyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, pyrrolinyl, morpholinyl, piperazinyl, quinuclidinyl, indyl, pseudoindoyl, benzofuryl, the benzo thio-phenyl, the indolizine base, benzopyranyl, quinolyl, isoquinolyl, purine radicals, quinazolyl, the cinnolines base, phthalazinyl, pteridyl, carbazyl, acridyl, phenanthridinyl, the thioxanthene base, phenazinyl, phenothiazinyl phenoxathiinyl (phenoxathiin) phenoxazinyl, thianthrenyl, tetrahydrofuran base, THP trtrahydropyranyl etc.

Wherein, preferred carbonatoms is 4～20 oxygen-containing heterocycle, preferred especially tetrahydrofuran base, THP trtrahydropyranyl etc.

R ⁵The carbonatoms of expression is that 1～12 alkyl can be straight chain shape, chain or cyclic alkyl, as its concrete example, for example, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, cyclopentyl, cyclohexyl etc.Wherein, preferred carbonatoms is 1～12 alkyl, and preferred especially carbonatoms is 1～8 alkyl.

In addition, as R ⁵The carbonatoms of expression is 1～12 alkoxyl group, can be straight chain shape, chain or cyclic alkoxyl group, as its concrete example, can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy, n-pentyloxy etc.Wherein, preferred carbonatoms is 1～2 alkoxyl group.

Wherein, as above-mentioned R ⁵, special preferable methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, methoxyl group, oxyethyl group.

In above-mentioned general formula (5), (6), q is preferably 1.P is preferably any one in 1,2, is preferably 1 especially, and in addition, r is preferably any one in 0,1,2, is preferably 1 especially.

In the structure of above-mentioned general formula (5) or (6) expression, from obtaining high sensitivity and polymerisation reactivity (curing) and keep fluid preservation and the ageing stability drying regime film forming after under of modulation behind the liquid, improve the shape of pattern of desired formation and controlled, the raising of needed thickness considered with the viewpoint of the adaptation of applied thing, especially preferred R ¹¹Be ethyl, R ¹²Be methyl, R ³Be methyl, R ⁴Be tetrahydrofuran base, R ⁵For methyl, q are 1, p is 1, r is 1 situation.And then, the more preferably structure of general formula (6) expression.

As the concrete example of the compound of above-mentioned general formula (5) or (6) expression, can enumerate ethane, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-benzoyl ethanoyl oxime);

Ethane, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) anisoyl]-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime) etc.

Wherein, preferred especially ethane, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime); Ethane, 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime); Ethane, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime); Ethane, 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl anisoyl)-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime); And ethane, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) anisoyl]-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime).

(E) being selected from oxime is that polymerization starter (oxime series initiators) and triazine are that the polymerization starter more than a kind (initiator) in the polymerization starter (triazine series initiators) is included in the solidification compound of the present invention, but, by using with above-mentioned [A] resin as at least a polymerization starter in the compound group of the following general formula of being selected from of oxime series initiators (5 ') expression, thereby can improve sensitivity, polyreaction is carried out well, can further make the controlled raising of shape and needed thickness.Thus, even 150mJ/cm ²(1500J/m ²) following low exposure, also can obtain good sensitivity, adaptation.

In above-mentioned general formula (5 '), R ¹¹The expression carbonatoms is that 1～20 alkyl, carbonatoms are 3～8 cycloalkyl or phenyl.

R ¹²And R ³Represent independently of one another hydrogen atom, carbonatoms be 1～20 alkyl, carbonatoms be 3～8 cycloalkyl, replace or do not have the phenyl of replacement or carbonatoms be 7～20 ester ring type alkyl (wherein, carbonatoms is except 7～8 the cycloalkyl), the substituting group under the substituted situation of above-mentioned phenyl is that carbonatoms is that 1～6 alkyl, carbonatoms are 1～6 alkoxyl group, phenyl or halogen atom.Here, these substituent quantity can be 1～5.

In addition, p represents 0～5 integer.

In addition, R ⁵Exist under a plurality of situations, can be identical or different mutually.

In above-mentioned general formula (5 '), R ¹¹The carbonatoms of expression is that 1～20 alkyl can be a straight chain shape or a catenate alkyl, as its concrete example, for example, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl.Wherein, preferred carbonatoms is 1～10 alkyl, and preferred especially carbonatoms is 1～8 alkyl.

R ¹¹The carbonatoms of expression is 3～8 cycloalkyl, for example, can enumerate cyclopentyl, cyclohexyl etc.Wherein, be preferably carbonatoms and be 3～6 cycloalkyl, be preferably carbonatoms especially and be 5～6 cycloalkyl.

In the above-mentioned group, as R ¹¹, for example, be preferably methyl, ethyl, n-propyl, sec.-propyl, n-hexyl etc.

R ¹², R ³The carbonatoms of expression is 1～20 alkyl, can be a straight chain shape or a chain, as its concrete example, for example, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl.Wherein, preferred carbonatoms is 1～10 alkyl, and preferred especially carbonatoms is 1～8 alkyl.

In addition, as R ¹², R ³The substituting group of the substituted-phenyl of expression i.e. " carbonatoms is 1～6 alkoxyl group ", can as its concrete example, can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy etc. for straight chain shape, chain or ring-type.Wherein, preferred carbonatoms is 1～3 alkoxyl group.

As R ¹², R ³The carbonatoms of expression is 7～20 ester ring type alkyl (carbonatoms be 7～8 cycloalkyl except), for example can enumerate di-cycloalkyl, tricyclic alkyl, spiro cycloalkyl group, connection tricyclic alkyl, contain the terpene skeleton group, contain the group of adamantyl skeleton etc.Wherein, preferred carbonatoms is 9～18 ester ring type alkyl, and preferred especially carbonatoms is 9～12.

In above-mentioned general formula (5 '), p is preferably any one in 0,1,2, is preferably 0 or 1 especially.

In the structure of above-mentioned general formula (5 ') expression, from obtaining high sensitivity and polymerisation reactivity (curing) and keep fluid preservation and the ageing stability drying regime film forming after under of modulation behind the liquid, improve the shape of pattern of desired formation and controlled, the raising of needed thickness considered with the viewpoint of the adaptation of applied thing, especially preferred R ¹¹Be ethyl, R ¹²Be methyl, R ³Be methyl, R ⁵It for methyl, p 1 situation.

As the concrete example of the compound of above-mentioned general formula (5 ') expression, preferably enumerate following compound (5 '-1)～(5 '-3).In addition, (5 '-1) can be obtained by commercially available product (IRGACUREOXE02).

As triaizine compounds, more preferably, can enumerate the list of at least one, two, or trihalomethyl group is combined on the s-triazine ring and the s-pyrrolotriazine derivatives that obtains, particularly, for example, can enumerate 2,4,6-three (monochloro methyl)-s-triazine, 2,4,6-three (dichloromethyl)-s-triazine, 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-n-propyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(α, α, β-three chloroethyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-phenyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-p-methoxy-phenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(3, the 4-epoxy and phenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-chloro-phenyl-)-4, two (the trichloromethyl)-s-triazines of 6-, 2-[1-(p-p-methoxy-phenyl)-2, the 4-butadienyl]-4, two (the trichloromethyl)-s-triazines of 6-;

2-styryl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-methoxyl-styrene)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-sec.-propyl oxygen base styryl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-tolyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxyl group naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-phenyl sulphur-4, two (the trichloromethyl)-s-triazines of 6-, 2-dibenzylsulfide-4, two (the trichloromethyl)-s-triazines of 6-, 4-(o-bromo-p-N, N-(di ethoxy carbonyl amino)-phenyl)-2,6-two (trichloromethyl)-s-triazine, 2,4,6-three (two brooethyls)-s-triazine, 2,4,6-three (trisbromomethyl)-s-triazine, 2-methyl-4, two (the trisbromomethyl)-s-triazines of 6-, 2-methoxyl group-4, two (the trisbromomethyl)-s-triazines of 6-, 4-(o-bromo-p-N, N-two (ethoxy carbonyl methyl) amino-phenyl)-2,6-two (trichloromethyl)-s-triazine etc.

Wherein preferred triazine series initiators is 2, two (the trichloromethyl)-6-[4 ' of 4--(N, the two ethoxy carbonyl methylaminos of N-)-3 '-bromophenyl]-s-triazine (Wako Pure Chemical Industries, Ltd.'s system), 2-(p-p-methoxy-phenyl)-4, two (the trichloromethyl)-s-triazines of 6-.

In the present invention, consider that from the viewpoint that suppresses the sensitivity inequality (D) content of six aryl bisglyoxaline based compounds is the scope of 2～25 quality % with respect to the total solids composition of solidification compound preferably.In addition, in the present invention, be Photoepolymerizationinitiater initiater and (E) oxime series initiators or triazine series initiators and usefulness with (D) six aryl bisglyoxalines, preferably in its ratio is 1: 0.5～1: 4 scope, more preferably use in 1: 1～1: 3 scope.If use in this scope, then the colourity that is caused by nmp solvent changes, the swelling tolerance is good, and ITO evaporation adaptability is good.

In addition, with respect to the solids component of solidification compound, (D) the six aryl bisglyoxaline based compounds that preferably add 1.0～15 quality % use, and more preferably add 3.0～10.0 quality %.If in this scope, then the colourity that is caused by nmp solvent changes, the swelling tolerance is good, and ITO evaporation adaptability is good.

Can and be Photoepolymerizationinitiater initiater, oxime series initiators also, reach the initiator the triazine series initiators with removing six above-mentioned aryl bisglyoxalines.As these initiators, can use the initiator of enumerating.

For example can enumerate the Lu that puts down in writing in the Japanese kokai publication hei 57-6096 communique for the Jia oxadiazole; United States Patent (USP) No. 4318791 specification sheets, Europe patent application disclose the aromatic carbonyls of putting down in writing in No. 88050 each specification sheets such as specification sheets such as ketal, acetal or benzoin alkylether class; The aromatic ketone compounds of putting down in writing in No. 4199420 specification sheets of United States Patent (USP) such as benzophenone; French Patent is invented (sulfo-) xanthone system or the acridine based compound of putting down in writing in No. 2456741 specification sheets; The coumarin series compounds of putting down in writing in the Te Kaiping 10-62986 communique; The organic boron complex of sulfonium of Te Kaiping 8-015521 communique etc. etc.

As above-mentioned initiator, preferred methyl phenyl ketone system, ketal system, benzophenone series, bitter almond oil camphor system, benzoyl base system, xanthone system, active halogen compound (halogen is for first oxadiazole system, coumarin series), acridine system etc.

As above-mentioned methyl phenyl ketone is Photoepolymerizationinitiater initiater, for example can preferably enumerate 2,2-diethoxy acetophenone, to dimethylamino benzoylformaldoxime, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, to dimethylamino benzoylformaldoxime, 4 '-sec.-propyl-2-hydroxy-2-methyl-Propiophenone, 1-hydroxyl-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2-tolyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholinyl acetone-1 etc.

As above-mentioned ketal is Photoepolymerizationinitiater initiater, for example can preferably enumerate benzyl dimethyl ketal, benzyl-'beta '-methoxy ethyl acetal etc.

As above-mentioned benzophenone series Photoepolymerizationinitiater initiater, for example can preferably enumerate benzophenone, 4,4 '-(two dimethylamino) benzophenone, 4,4 '-(two diethylamino) benzophenone, 4,4 '-dichloro benzophenone etc.

As above-mentioned bitter almond oil camphor system or benzoyl base system Photoepolymerizationinitiater initiater, for example can preferably enumerate bitter almond oil camphor isopropyl ether, bitter almond oil camphor isobutyl ether, benzoin methyl ether, o-benzoyl yl benzoic acid methyl esters etc.

As above-mentioned xanthone is Photoepolymerizationinitiater initiater, for example can preferably enumerate diethyl thioxanthone, di-isopropyl thioxanthone, single isopropyl thioxanthone, clopenthixal ketone etc.

As above-mentioned reactive halogen Photoepolymerizationinitiater initiater (oxadiazole be, coumarin series), for example can excellently repeatedly enumerate 2-trichloromethyl-5-styryl-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(cyano-styrene base)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(naphthalene-1-yl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(4-styryl) styryl-1,3, the 4-oxadiazole, 3-methyl-5-amino-((guanamine-yl) amino)-3-phenyl tonka bean camphor, 3-chloro-5-diethylamino-((guanamine-yl) amino)-3-phenyl tonka bean camphor, 3-butyl-5-dimethylamino-((guanamine-yl) amino)-3-phenyl tonka bean camphor etc.

As above-mentioned acridine is Photoepolymerizationinitiater initiater, for example can preferably enumerate 9-phenylacridine, 1, two (9-acridyl) heptane of 7-etc.

Except that above-mentioned, can enumerate 2,4,6-trimethylphenyl carbonyl-diphenylphosphine acyl group oxide compound, phosphofluoric acid-trialkyl Ben Ji phosphonium salt etc.

Among the present invention, be not limited to above initiator, also can use other known initiators.For example can enumerate United States Patent (USP) the 2nd, 367, poly-ketol aldose (vicinal polyketoaldonyl) compound of the vicinal of putting down in writing in No. 660 specification sheetss; United States Patent (USP) the 2nd, 367, No. 661 and the 2nd, 367, the alpha-carbonyl compound of putting down in writing in No. 670 specification sheetss; The acyloin ether of putting down in writing in the United States Patent (USP) the 2nd, 448, No. 828 specification sheetss; The aromatic series acyloin compound of putting down in writing in the United States Patent (USP) the 2nd, 722, No. 512 specification sheetss that is replaced by α-hydrocarbon; United States Patent (USP) the 3rd, 046, No. 127 and the 2nd, 951, the multinuclear quinoline compound of putting down in writing in No. 758 specification sheetss; The combination of triallyl imidazole dimer/p-aminophenyl ketone of putting down in writing in the United States Patent (USP) the 3rd, 549, No. 367 specification sheetss; The benzothiazole based compound of putting down in writing in the special public clear 51-48516 communique.

Among the present invention, preferably add sensitizing coloring matter as required.By the exposure of the absorbent wavelength of this sensitizing coloring matter, can promote the free radical of above-mentioned polymerization starter composition to react or by the polyreaction of its polymerizable compound that causes.As such sensitizing coloring matter, can enumerate known beam split sensitizing coloring matter or dyestuff or absorb light and with interactional dyestuff of Photoepolymerizationinitiater initiater or pigment.

As the sensitizing coloring matter that can use in the present invention and preferred beam split sensitizing coloring matter or dyestuff for example can be enumerated the polynuclear aromatic same clan (pyrene perylene for example, benzophenanthrene), xanthene class (fluorescein for example, eosin, tetraiodofluorescein, rhodamine B, rose-red), cyanine class (sulphur carbon cyanine (thiacarbocyanine) for example, oxo carbocyanine (oxacarbocyanine)), merocyanine class (merocyanine for example, the carbon merocyanine), thiazides (thionine for example, methylene blue, toluidine blue), acridine (acridine orange for example, chloroflavin, acriflavine), phthalocyanines (phthalocyanine for example, metal phthalocyanine), porphyrin class (tetraphenylporphyrin for example, central metal replaces porphyrin), chlorophyll class (chlorophyll for example, CHLOROPHYLLINE, central metal replaces chlorophyll), metal complex, anthraquinone class (for example anthraquinone), squaric acid inner salt (Squalium) class (for example squaric acid inner salt) etc.

The example of preferred beam split sensitizing coloring matter or dyestuff is as follows.

Can list: the vinylbenzene base system pigment of in the special fair 37-13034 communique of Japan, putting down in writing; The cationic dyestuff of in Japanese kokai publication sho 62-143044 communique, putting down in writing; The quinoxaline salt of in Japanese Patent Publication 59-24147 communique, putting down in writing, open the new methylene blue compound of putting down in writing in the clear 64-33104 communique the spy; Open the anthraquinone class of putting down in writing in the clear 64-56767 communique the spy; Open the benzoxanthene dye of putting down in writing in the flat 2-1714 communique the spy; Open the acridine of putting down in writing in flat 2-226148 communique and the flat 2-226149 communique of Te Kai the spy; The pyrans salt of in the public clear 40-28499 communique of spy, putting down in writing; The cyanine class of in the public clear 46-42363 communique of spy, putting down in writing; Open the cumarone pigment of putting down in writing in the flat 2-63053 communique the spy; Open the conjugation ketone pigment that flat 2-85858 communique, spy are opened flat 2-216154 communique the spy; Open the pigment of putting down in writing in the clear 57-10605 communique the spy; The azo cinnamylidene derivative of in the fair 2-30321 communique of spy, putting down in writing; Open the cyanine class pigment of putting down in writing in the flat 1-287105 communique the spy; Open the spy that clear 62-31844 communique, spy are opened clear 62-31848 communique, the spy opens the xanthene class pigment of putting down in writing in the clear 62-143043 communique; The amino-benzene vinyl ketone of in the public clear 59-28325 communique of spy, putting down in writing; Open the pigment of putting down in writing in the flat 2-179643 communique the spy; Open the merocyanine pigment of putting down in writing in the flat 2-244050 communique the spy; The merocyanine pigment of in the public clear 59-28326 communique of spy, putting down in writing; Open the merocyanine pigment of putting down in writing in the clear 59-89303 communique the spy; Open the merocyanine pigment of putting down in writing in the flat 8-129257 communique the spy; Opening the chromene of putting down in writing in the flat 8-334897 communique the spy is pigment.

(pigment that has maximum absorption wavelength at 350～450nm)

As other preferred configuration of sensitizing coloring matter, can enumerate compound group that belongs to following and the pigment that has maximum absorption wavelength at 350～450nm.

For example, can enumerate salt (for example squaric acid inner salt) in the polynuclear aromatic same clan (for example pyrene, perylene, benzophenanthrene), xanthene class (for example fluorescein, eosin, tetraiodofluorescein, rhodamine B, rose-red), cyanine class (for example thion cyanine, oxo carbocyanine), merocyanine class (for example merocyanine, carbonyl merocyanine), thiazides (for example thionine, methylene blue, toluidine blue), acridine (for example acridine orange, chloroflavin, acriflavine), anthraquinone class (for example anthraquinone), the squaric acid.

(F) 4 officials can above multi-functional epoxy compound

In the present invention, 4 officials can above multi-functional epoxy compound be meant and the compound of the carboxyl heat cross-linking of alkali soluble resins, by heat cross-linking cross-linking density be improved, thereby realize the raising of chemical reagent resistance.

As the multi-functional epoxy compound that can use in the present invention, can be bisphenol A-type, cresols novolak, biphenyl type, alicyclic epoxy compound etc. have 4 above oxirane rings in molecule compound.

As bisphenol A-type, except that can enumerating EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 etc. (above change into manufacturing for Dongdu), DENACOL EX-1101, EX-1102, EX-1103 etc. (above change into manufacturing for Nagase), PLACCEL GL-61, GL-62, G101, G102 (above make for Daicel chemistry), can also enumerate and they similar Bisphenol F types, bisphenol S type.In addition, also can use epoxy acrylate such as Ebecryl 3700,3701,600 (above make for Daicel UCB).

As the cresols novolac-type, can enumerate EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 etc. (above be Dongdu system of changing into), DENACOL EM-125 etc. (above be the Nagase system of changing into); As biphenyl type, can enumerate 3,5,3 ', 5 '-tetramethyl--4,4 '-diglycidyl biphenyl etc.

As the alicyclic epoxy compound, can enumerate セロキサイ De 2021,2081,2083,2085, エ Port リ one De GT-301, GT-302, GT-401, GT-403, EHPE3150 (above be Daicel chemistry system), サ Application ト one ト ST-3000, ST-4000, ST-5080, ST-5100 etc. (above be Dongdu system of changing into) etc.In addition, also can use EPOTOHTOYH-434, YH-434L as amine type Resins, epoxy, in the skeleton of bisphenol A type epoxy resin with dimer acid modified and glycidyl ester etc.

In these multi-functional epoxy compounds, be preferably the phenolic varnish type epoxy compounds of following general formula (I) expression, preferred especially epoxy equivalent (weight) is 200～220.As such raw material, EPICLON N-660, N-665, N-670, N-673, N-680, N-690, N-695, N-685-EXP, N-672-EXP, N-655-EXP-S, N-865, N-865-80M, YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L of Dainippon Ink Chemicals's system etc. be can use, EPICLON N-660, N-665, N-670, N-673, N-680, N-690, N-695, YDCN-704L etc. especially preferably used.

In the formula, 1 be 5～100 integer, R is hydrogen atom or methyl independently of one another.

In composition of the present invention, can contain two or more multi-functional epoxy compounds.

As the content of the multi-functional epoxy compound who the present invention relates in solidification compound, with respect to the total solids composition of removing pigment, be preferably 2～20 quality %, more preferably 3～10 quality %.If this content is in above-mentioned scope, then the solvent resistance of film is good.In addition,,, produce the impaired problem of quality of colour filter,, then produce the problem of anti-NMP variation if content is very few then owing to the yellow coloring after the baking if content is too much.

Pigment dispensing composition of the present invention and solidification compound generally can use solvent suitably to modulate with mentioned component.

As solvent, preferred 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butylacetate, 3-methoxypropionic acid methyl esters, 2-heptanone, pimelinketone, ethyl carbitol acetic ester, acetate of butyl carbitol, methyl proxitol acetate etc.

Solvent can also be used in combination more than 2 kinds except that can using separately.

In solidification compound of the present invention, as required, can contain chain-transfer agent, fluorine series organic compound, thermal polymerization, thermopolymerization composition, thermopolymerization and prevent various additives such as macromolecular compound, tensio-active agent, driving fit promotor, antioxidant, UV light absorber, anti-flocculation agent beyond agent, tinting material, Photoepolymerizationinitiater initiater, other weighting agents, the above-mentioned alkali soluble resins.

As the chain-transfer agent that can in solidification compound of the present invention, add, for example can enumerate N, N such as N-dimethylaminobenzoic acid ethyl ester, N-dialkyl amido phenylformic acid alkyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole etc. have heterocyclic sulfhydryl compound and the multifunctional sulfhydryl compound of aliphatics etc.

Chain-transfer agent can use a kind separately, also can more than 2 kinds and use.

By containing the fluorine series organic compound, can improve the characteristics of liquids (particularly mobile) when making coating fluid, can improve the homogeneity and the joint fluidity of coating thickness.That is,, improved wettability to substrate because the surface tension of substrate and coating fluid is reduced, make the coating on substrate improve, even, be effective in this so when forming film about several μ m, also can form the film of the little uniform thickness of uneven thickness with a spot of liquid measure.

The fluorine containing ratio of fluorine series organic compound is preferably 3～40 quality %, and more preferably 5～30 quality % are preferably 7～25 quality % especially.The fluorine containing ratio is in above-mentioned scope the time, is that effectively the solvability in composition is also good from the viewpoint of coating thickness homogeneity and joint fluidity.

As fluorine is tensio-active agent, the compound that can preferably use endways, at least one position in main chain and the side chain has fluoroalkyl or fluorine alkylidene group.As concrete commercially available product, for example be MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACEF176, MEGAFACE F177, MEGAFACE F183, MEGAFACE 780, MEGAFACE781, MEGAFACE R30, MEGAFACE R08, MEGAFACE F-472SF, MEGAFACE BL20, MEGAFACE R-61, MEGAFACE R-90 (big Japanese ink Co., Ltd. system), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431, Novec FC-4430 (Sumitomo 3M Co., Ltd. system), AashiGuardAG7105,7000,950,7600, SURFLON S-112, SURFLON S-113, SURFLONS-131, SURFLON S-141, SURFLON S-145, SURFLON S-382, SURFLONSC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106 (Asahi Glass Co., Ltd's system), EFTOP EF351, EFTOP 352, EFTOP 801, EFTOP 802 (JEMCO Co., Ltd. system) etc.

Fluorine series organic compound particularly crawling and the uneven thickness when preventing to form thin coating film is effective.In addition, and then, in the slot coated that causes the liquid cutout easily, also be effective.

The addition of fluorine series organic compound is preferably 0.001～2.0 quality % with respect to the total mass of Photocurable composition, more preferably 0.005～1.0 quality %.

Make that to contain thermal polymerization in the solidification compound of the present invention also be effective.As thermal polymerization, for example can enumerate various azo based compounds, superoxide based compound.As above-mentioned azo based compound; can enumerate azo two bases (azobis) based compound; as above-mentioned superoxide based compound, can enumerate ketone peroxide, ketal peroxide, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxy dicarbonate etc.

In the solidification compound of the present invention, the viewpoint from the improvement coating preferably adopts various tensio-active agents to constitute, and except that above-mentioned fluorine is the tensio-active agent, can use nonionic system, positively charged ion system, negatively charged ion is various tensio-active agents.Wherein, preferably using above-mentioned fluorine is that tensio-active agent, nonionic are tensio-active agent.

As nonionic is the preference of tensio-active agent, and nonionics such as for example preferred especially Voranol EP 2001 class, polyoxyethylene alkylaryl ether class, polyxyethylated ester class, sorbitan alkyl esters, monoglyceride alkyl esters are tensio-active agent.Particularly, Voranol EP 2001 classes such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether are arranged; Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether, polystyrene-basedization of polyoxyethylene ether, polyoxyethylene tribenzyl phenyl ether, the polystyrene-based ether of polyoxyethylene-propylene, polyoxyethylene nonylplenyl ether; Polyoxyethylene dialkyls such as polyoxyethylene dilaurate, polyoxyethylene SUNSOFT Q-182S, sorbitan-fatty acid ester, polyoxyethylene sorbitan fatty acid ester class, ethylenediamine polyoxyethylene-nonionics such as polyoxypropylene condenses are tensio-active agent, and they can suitably use by commercially available products such as Kao Corp, NOF Corp, Zhu Ben's Oil Corporation, Asahi Denka Co., Ltd., Sanyo Chemical Industries Co., Ltd..Except that above-mentioned tensio-active agent, can also use above-mentioned dispersion agent.

Except that above-mentioned, can in solidification compound, add various additives.As the concrete example of additive, can enumerate UV light absorber such as 2-(the 3-tertiary butyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone; Anticoalescents such as sodium polyacrylate; Weighting agent such as glass, aluminum oxide; Itaconic acid copolymer, Ba Dousuan multipolymer, maleic acid, partial esterification maleic acid, acid cellulose derivative, in having the polymkeric substance of hydroxyl addition acid anhydrides and the compound that obtains, the nylon that dissolves in alcohol, the alkali-soluble resins such as phenoxy resin that form by dihydroxyphenyl propane and epoxy chloropropane etc.

In addition, promote the alkali dissolution of uncured portion, seeking further to improve under the situation of development of solidification compound, can in solidification compound, add organic carboxyl acid, preferred molecular weight is the lower molecular weight organic carboxyl acid below 1000.Particularly, for example can enumerate formic acid, acetate, propionic acid, butyric acid, valeric acid, PIVALIC ACID CRUDE (25), caproic acid, diethylacetic acid, enanthic acid, aliphatic monocarboxylic acid such as sad; 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; Aliphatic tricarboxylic acids such as tricarballylic acid, equisetic acid, camphoronic acid; Phenylformic acid, toluic acid, isopropyl acid, 2,3, aromatic monocarboxylates such as 5-mesitylenic acid; Aromatic series polycarboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, inclined to one side benzene tetracarboxylic acid, Pyromellitic Acid; Other carboxylic acids such as phenylacetic acid, hydratropic acid, phenylpropionic acid, amygdalic acid, phenyl succsinic acid, atropic acid, styracin, methyl cinnamate, cinnamein, Chinese cassia tree fork acetate, coumaric acid, umbellic acid.

Except that above material, preferably in solidification compound of the present invention, further add hot stopper, for example, quinhydrones, p methoxy phenol, two-Butylated Hydroxytoluene, pyrogallol, tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole etc. are useful.

Solidification compound of the present invention can be modulated via following blending dispersion operation: make and contain alkali soluble resins, optical polymerism compound, and Photoepolymerizationinitiater initiater (preferably with solvent) in the tinting material of having stated, as required it is mixed with additives such as tensio-active agents, use various mixing machines, dispersion machine to carry out blending dispersion.

In addition, the blending dispersion operation is preferably the diffusing operation of handling of the differential that comprises mixing dispersion and carry out subsequently, but also can omit mixing dispersion.

The manufacture method of solidification compound of the present invention one for example shown below.

Use mixing roll limits such as two rollers, three rollers, ball mill, cylinder grinding machine, dispersion machine, kneader, common kneader, refiner, mixing machine, single screw rod or twin screw extruder to give strong shearing force in the mixture of pigment, water-miscible organic solvent and water-soluble inorganic salt, the limit grinds pigment, then, this mixture is put in the water, made pulp-like with stirrer etc.Then, with this slurries filtration, washing, remove water-miscible organic solvent and water-soluble inorganic salt after, drying obtains the pigment of miniaturization.Preferably before miniaturization is handled, add macromolecular compound, pigment is covered.

Pigment, dispersion agent and/or pigment derivative, and solvent in carry out bead and disperse.Main using vertical or horizontal sand mill, pin rod pulverizer, slit pulverizer, ultrasonic dispersing machine etc., is that the bead that is formed by glass, zirconium white etc. of 0.01mm～1mm carries out the diffusing processing of differential with particle diameter, obtains pigment dispensing composition.In addition, also can omit processing with the pigment miniaturization.

In addition, about mixing, dispersive details, be recorded in the T.C.Patton work " Paint Flow and Pigment Dispersion " (John Wiley and Sons society periodical in 1964) etc.

Then, in the above-mentioned pigment dispensing composition that obtains, add optical polymerism compound, polymerization starter and alkali soluble resins etc., obtain solidification compound of the present invention.

Solidification compound of the present invention coating process such as is coated with by rotary coating, slot coated, curtain coating coating, roller coat, rod directly or via other layer to be coated on the substrate, form the coated film of light solidified, mask pattern by regulation exposes, after exposure, uncured development removed with developing solution, can form thus by (3 looks or 4 looks) the of all kinds pattern-like epithelium that pixel forms, obtain colour filter.

The colour filter that colour filter of the present invention is to use the solidification compound of the present invention stated to form on substrates such as glass, preferably make by carrying out following processing successively: with solidification compound of the present invention for example by slot coated directly or across other layers forming on the substrate film after, make this dried coating film, carry out pattern exposure, and use developing solution to carry out development treatment.Thus, can be in technologic difficulty few, high-quality and make the colour filter that is used for liquid crystal display device or solid-state imager at low cost.

As aforesaid substrate, for example, can enumerate non-alkali glass, soda glass, Pyrex (registered trademark) glass, the silica glass that is used for liquid crystal display device etc. and on them, attach the glass of nesa coating or be used for photo-electric conversion element substrate, for example silicon substrate etc. and the plastic base of solid-state imager etc.Usually, formation is provided with transparent resin layer with the black matrix" of each pixel isolation or in order to promote driving fit on these substrates.

For plastic base, preferably have gas-barrier layer and/or solvent resistance layer in its surface.In addition, use on the substrate (hereinafter referred to as " TFT mode liquid crystal drive substrate ") in the driving of disposing thin film transistor (TFT) of thin film transistor (TFT) mode color liquid crystal display arrangement, also can form the pattern-like epithelium that constitutes by Photocurable composition of the present invention, make colour filter.Except being provided for forming the pattern of pixel, can also be provided for forming communicating pores (through hole) or コ font depressed patterns this moment on the photomask that uses.With the substrate in the substrate, for example can enumerate glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc. as TFT mode liquid crystal drive.To these substrates, can implement to utilize suitable pre-treatments such as chemical reagent processing that silane coupling agent etc. carries out, Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum evaporation according to hope.For example can enumerate substrate that is formed with passive films such as silicon nitride film in TFT mode liquid crystal drive with the surface of substrate or on the surface of this driving substrate etc.

Method as solidification compound of the present invention being coated on the substrate is not particularly limited, and preferred slit-rotational method, coating method etc. uses the method (hereinafter referred to as the gap nozzle coating method) of gap nozzle without spin.In the gap nozzle coating method, the condition of slit-method of spin coating and coating method without spin is according to the size of coated substrates and different, for example be coated on the glass substrate (1100mm * when 1250mm) going up in the 5th generation by coating method without spin, spray volume from the solidification compound of gap nozzle was generally for 500～2000 microlitre/seconds, be preferably for 800～1500 microlitre/seconds, in addition, surface covered is generally 50～300mm/ second, is preferably 100～200mm/ second.The solids component of solidification compound is generally 10%～20%, is preferably 13%～18%.On substrate, form by solidification compound of the present invention obtain film the time, as this thickness of filming (prebake conditions is handled the back), be generally 0.3 μ m～5.0 μ m, be preferably 0.5 μ m～4.0 μ m, most preferably be 0.8 μ m～3.0 μ m.

Usually implementing prebake conditions after coating handles.As required, can before prebake conditions, implement vacuum-treat.Vacuum drying condition is as follows, and vacuum tightness is generally 0.1～1.0torr, is preferably about 0.2～0.5torr.

Prebake conditions is handled and can be used hot-plate, baking oven etc. 50 ℃～140 ℃ temperature range, preferably about 70 ℃～110 ℃, carry out under 10 seconds～300 seconds the condition.Also can and with high frequency processing etc.High frequency is handled and also can be used separately.

Then, implement exposure-processed across mask.At this moment, as the radioactive rays that use, ultraviolet rays such as preferred especially g line, h line, i line, i line.The colour filter that liquid crystal indicator is used has preferably mainly used the exposure of h line, i line by proximity printing machine, mirror image projection exposure machine, as exposure, be preferably 5～300mJ/cm ², 10～150mJ/cm more preferably ², 10～100mJ/cm more preferably ²

In development treatment, in developing solution, only make cured portion residual uncured portion stripping after the exposure.As development temperature, be generally 20～30 ℃, as development time, be 20～90 seconds.

As developing solution, so long as dissolve uncured portion light solidified filming of solidification compound and do not dissolve the developing solution of solidified portion, just can use any developing solution.Particularly, can use the combination or the alkaline aqueous solution of various organic solvents.

As above-mentioned organic solvent, can enumerate operable above-mentioned solvent when modulation pigment dispensing composition of the present invention or solidification compound.

As above-mentioned alkaline aqueous solution, for example can enumerate sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, water glass, Starso, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicyclo-[5,4,0]-mode that basic cpds such as 7-hendecene reach 0.001～10 quality %, preferred 0.01～1 quality % with concentration dissolves and the alkaline aqueous solution that obtains.Also can in alkaline aqueous solution, add for example water-miscible organic solvent such as methyl alcohol, ethanol or tensio-active agent etc. in right amount.

Visualization way can be in impregnation method, spray mode, the spray pattern etc. any, also can make up the mode of waving, rotation mode, ultrasonic wave mode etc. in this mode.Before the contact developing solution, also can water in advance etc. soak the face of being developed, it is uneven to prevent to develop.In addition, also can make substrate tilt to develop.

After the development treatment,, after the enforcement drying,, implement heat treated (back baking) in order to make its completely solidified through the drip washing operation that remaining developing solution washing is removed.

The drip washing operation is carried out with pure water usually, but in order to save liquid, can use pure water in final washing, and the washing initial stage is used used pure water, or makes substrate tilt to wash, or and uses ultrasonic irradiation.

Dewater after the drip washing, after the drying, carry out about 200 ℃～250 ℃ heat treated usually.This heat treated (back baking) can be used hot-plate or heater meanses such as convection oven (heated air circulation type drying machine), high frequency heating machine according to above-mentioned condition with the coated film after developing, and carries out with continous way or batch-type.

According to desirable form and aspect number, each color is repeated above operation successively, can make the colour filter of the cured film that is formed with multiple color painted thus.

As the purposes of solidification compound of the present invention, main is that the center is illustrated with the purposes in colour filter, but also goes for and will constitute the formation of the isolated black matrix" of each colored pixels of colour filter.

Above-mentioned black matrix" can form by following operation: by to having used black pigments such as carbon black, titanium be black to expose, develops as the solidification compound of the present invention of pigment, further carry out the back then as required and toast the curing that promotes film.

Embodiment

Below, by embodiment the present invention is made more specific description, still, only otherwise exceed purport of the present invention, just be not limited to following embodiment.In addition, in the absence about specifying, " part " is benchmark with the quality.

＜in chain, have a synthesis example of heterocyclic macromolecular compound 〉

(synthesizing of polymkeric substance 1)

With M-11 (following structure) 27.0g, methyl methacrylate 126.0g, methacrylic acid 27.0g, and 1-methoxyl group-2-propyl alcohol 420.0g import in nitrogen metathetical there-necked flask, by stirrer (new eastern science Co., Ltd.: Three-One Motor) stir, the limit makes nitrogen flow into the flask inner edge to heat, be warmed up to 90 ℃.Add 2 therein, (with the pure medicine of light Co., Ltd. system, V-65) 1.69g was 90 ℃ of following heated and stirred 2 hours for 2-azo two (2, the 4-methyl pentane nitrile).After 2 hours, add the V-65 of 1.69g again, heated and stirred obtained 30 quality % solution of polymkeric substance 1 after 3 hours.By being that the result of the weight-average molecular weight of the gel permeation chromatography (GPC) of the reference material macromolecular compound of measuring gained is 2.0 ten thousand with vinylbenzene.In addition, by using the titration of sodium hydroxide, the acid number that draws the per unit solids component is 98mgKOH/g.

(synthesizing of polymkeric substance 2)

With M-6 (following structure) 27.0g, methyl methacrylate 126.0g, methacrylic acid 27.0g, and 1-methoxyl group-2-propyl alcohol 420.0g import in nitrogen metathetical there-necked flask, by stirrer (new eastern science Co., Ltd.: Three-One Motor) stir, the limit makes nitrogen flow into the flask inner edge to heat, be warmed up to 90 ℃.Add 2 therein, (with the pure medicine of light Co., Ltd. system, V-65) 1.80g was 90 ℃ of following heated and stirred 2 hours for 2-azo two (2, the 4-methyl pentane nitrile).After 2 hours, add the V-65 of 1.80g again, heated and stirred obtained 30 quality % solution of polymkeric substance 2 after 3 hours.By being that the result of the weight-average molecular weight of the gel permeation chromatography (GPC) of the reference material macromolecular compound of measuring gained is 2.1 ten thousand with vinylbenzene.In addition, by using the titration of sodium hydroxide, the acid number that draws the per unit solids component is 99mgKOH/g.

(modulation of coated pigment 1)

The solution 20g and the glycol ether 100g of pigment (C.I. Pigment red 254Ciba Specialty Chemicals corporate system CROMOPHTAL RED BP) 50g, sodium-chlor 500g, above-mentioned polymkeric substance 1 are added in 1 gallon of kneader of stainless steel (aboveground making is made), mixed 9 hours.Then, this mixture is put in about 3 premium on currency, after 1 hour, filtered, wash, remove sodium-chlor and solvent, and carry out drying, make coated pigment 1 with the super mixer stir about.

(modulation of coated pigment 2)

In the modulation of coated pigment 1, use C.I. pigment green 36 (Japanese Le one Block リゾ one Le corporate system Monastral Green 6Y-CL) to replace Pigment red 254, and replace polymkeric substance 1 with polymkeric substance 2, coated pigment 2 is modulated in the modulation of other and coated pigment 1 in the same manner.

(modulation of coated pigment 3)

In the modulation of coated pigment 2, use C.I. pigment Green 7 (the system HELIOGEN Green L8730 of BASF AG) to replace pigment green 36, other modulation with coated pigment 2 are similarly carried out, and modulate coated pigment 3.

(modulation of coated pigment 4)

In the modulation of coated pigment 2, use the C.I. pigment Blue 15: 6 (the system HELIOGEN Blue L6700F of BASF AG) replace pigment green 36, and other modulation with coated pigment 2 are similarly carried out, and modulate coated pigment 4.

(modulation of coated pigment 5)

In the modulation of coated pigment 2, use C.I. pigment Violet 23 (Clariant corporate system HOSTAPERM VIOLET RL-NF) to replace pigment green 36, other modulation with coated pigment 2 are similarly carried out, and modulate coated pigment 5.

(modulation of coated pigment 6,7)

In the modulation of coated pigment 1, the 9 hours time of will mixing changes 7 hours respectively into, 5 hours, modulation coated pigment 6 and coated pigment 7.

(evaluation of the lining degree of pigment)

The pigment 10g that obtains is put among 1-methoxyl group-2-propyl alcohol 100ml, vibrated 3 hours in room temperature with vibrating machine.Use separating centrifuge with 80 afterwards, 000rpm made the pigment sedimentation through 8 hours, and the solids component of supernatant liquor part is obtained by desiccating method.Obtain the amount of free macromolecular compound from pigment, by with handle in the ratio of amount of the macromolecular compound that uses, calculate ionization rate (%).The more little then lining rate to pigment of ionization rate is high more.

The above-mentioned coated pigment that obtains 1～7 all demonstrates the following free amount of 20 quality %, is the pigment that has been covered.

(modulation of dispersible pigment dispersion 1)

Use even matter device that following composition is stirred with rotating speed 3000r.p.m. mixed in 3 hours, the preparation mixing solutions, this composition is with respect to 35 parts of the compositions that is equivalent to pigment of coated pigment 1, ディスパ one エイ De 163 (Sannopco corporate system) as dispersion agent is 7.0 parts, is 200 parts as the methyl proxitol acetate of solvent; Further bead dispersion machine ULTRAAPEX MILL (the longevity industrial's system) dispersion treatment 6 hours of the zirconium white bead by having used 0.1mm φ then.

Equally, the amount of the kind of coated pigment and dispersion agent according to changing shown in the table 1, is obtained dispersible pigment dispersion 2～10.Wherein, the coated pigment 4 in the dispersible pigment dispersion 8 is set at 95: 5 with the ratio of the usage quantity of coated pigment 5, is that 35 parts mode cooperates according to the composition that is equivalent to pigment that adds up to.The high molecular amount of using in dispersion liquid with pigment of lining also is shown in Table 1.

In table 1, dispersible pigment dispersion 10 directly uses Ciba Specialty Chemicals corporate system CROMOPHTAL RED BP to replace using coated pigment.

In addition, dispersible pigment dispersion 15 similarly carries out with the modulation of dispersible pigment dispersion 1 except will change to 18 hours dispersion treatment by homogenizer (rotating speed 5000r.p.m.) by 6 hours dispersion treatment of bead dispersion machine in the modulation of dispersible pigment dispersion 1.

(measure of spread of 1 particle diameter of dispersible pigment dispersion)

The distribution of 1 particle diameter of dispersible pigment dispersion is measured by transmission electron microscope, will be shown in Table 1 by number % less than 0.02 μ m and greater than the shared ratio of particle of the size of particles of 0.08 μ m.

[table 1]

(embodiment 1)

The composition of forming below further adding in the dispersible pigment dispersion 1 of gained mixes back modulation solidification compound of the present invention (colored liquid against corrosion).

(B) alkali soluble resins: multipolymer weight-average molecular weight=30,000 20.8 of benzyl methacrylate and methacrylic acid (=70/30[mol ratio]) part

(C) polymerizable compound: 20 parts of the system DPHA of Nippon Kayaku K. K

(D) polymerization starter: 2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,3 parts of 5 '-tetraphenyl bisglyoxalines

(E) polymerization starter: 4-[o-bromo-p-N, N-two (ethoxy carbonyl) aminophenyl]-2,3 parts of 6-two (trichloromethyl)-s-triazine

(F) multi-functional epoxy compound: 5 parts of the system EPICLON695 of Dainippon Ink Chemicals

0.5 part of diethylamino benzophenone

0.5 part of N-phenyl mercaptobenzimidazole

Tensio-active agent: (following works 1) 1.0 parts

400 parts of solvents (propylene glycol methyl ether acetate/ethoxyl ethyl propionate=8/2)

Works 1

(Mw＝33940，Mw/Mn＝2.55

PO: propylene oxide, EO: oxyethane)

(embodiment 2～16 and comparative example 1～6)

In the composition of the solidification compound of embodiment 1, to the kind of the amount of the amount of the kind of pigment and amount, alkali soluble resins, polymerizable compound, polymerization starter and amount, and multi-functional epoxy compound's amount according to changing the solidification compound of modulation embodiment 2～16 and comparative example 1～6 shown in the table 2.

[table 2]

In table 2, * 1 has been to use the compound identical with embodiment 1.* 2～* 6 is as follows.

* 2:2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four-(3, the 4-Dimethoxyphenyl) bisglyoxalines

* 3:Ciba Specialty Chemicals corporate system oxime series initiators OXE-01 (oxime 1 shown in following)

* 4: oxime 3 (compound of 5 ' of above-mentioned exemplary compounds-2)

* 5: oxime 4 (compound of 5 ' of above-mentioned exemplary compounds-3)

* the functional epoxy compounds of 6:2 Dainippon Ink Chemicals makes EPICLON850-LC

Oxime 1:IRGACURE OXE01

(making of TFT substrate)

Make the TFT substrate according to the method for putting down in writing in No. 3264364 communique of Japanese Patent.That is, on active-matrix substrate, form gate signal line and additional capacity electrode, form gate insulation film thereon, form semiconductor layer and path protection layer, form the source electrode of formation TFT and the n of drain electrode ⁺The Si layer.

Each solidification compound that obtains is spin-coated on the above-mentioned TFT substrate, so that the thickness after the prebake conditions becomes 2.4 μ m, with 90 ℃ oven dryings 60 seconds (prebake conditions).Then, to filming whole with 60mJ/cm ²(illumination 20mW/cm ²) expose, with filming after the exposure with 1% aqueous solution covering of alkaline-based developer CDK-1 (FUJIFILM Electronic Materials Co., Ltd. system), static 60 seconds.After static, pure water is scattered wash-out developer with the shower shape.Then, with above-mentioned such heat treated (back baking) that filming of photocuring processing and development treatment carried out in 220 ℃ baking oven 1 hour of having implemented, on glass substrate, form the pigmentary resin tunicle that the formation colour filter is used, thereby made colored substrate.

(comparative example 7)

Except the dispersible pigment dispersion among the embodiment 11 is changed into the dispersible pigment dispersion 15, modulate solidification compound similarly to Example 1, carry out evaluation similarly to Example 1.The result is as shown in table 3.

(comparative example 8)

Except the dispersible pigment dispersion among the embodiment 11 is changed into the dispersible pigment dispersion 10, modulate solidification compound similarly to Example 1, carry out evaluation similarly to Example 1.The result is as shown in table 3.

(embodiment 33)

In embodiment 1, (F) multi-functional epoxy compound EPICLON695 is altered to EHPE-3150 (DAICEL chemical industrial company system, polyfunctional epoxy resin) modulates solidification compound, carry out evaluation similarly to Example 1.The result is as shown in table 3.

The colored substrate that use obtains is carried out following evaluation, and the result is summarised in the table 3.In addition, in fluid preservation, used solidification compound.Other evaluations are all estimated by the filter substrate of non-TFT.

(NMP tolerance)

[colourity variation]

After the system spectrophotometer MCPD-2000 of Yong Otsuka Electronics Co., Ltd. measures the dichroism of each colored substrate, each test film was flooded 10 minutes in 50 ℃ NMP (N-Methyl pyrrolidone) solution.Then, use pure water drip washing, after under 85 ℃ dry 60 minutes, measure dichroism once more, will make colourity what change by the NMP dipping by Δ E ^*Ab represents.Here, Δ E ^*Ab is meant L ^*a ^*b ^*Aberration in the color specification system.Changes delta E by aberration ^*The value of ab is estimated.

(metewand)

A: Δ E ^*Ab is less than 2

B: Δ E ^*Ab is more than 2 and less than 3

C: Δ E ^*Ab is more than 3 and less than 5

D: Δ E ^*Ab is more than 5

[swell-resistant]

Each colored substrate was flooded 30 minutes down at 60 ℃ in N-Methyl pyrrolidone (solvent), take out and pass through the surfaceness on observation by light microscope colored substrate surface then, estimate according to following metewand.

(metewand)

A: do not change fully.

B: do not change with comparing before the dipping.Solution is painted slightly.

C: some variations are seen on the surface.Solution is painted.

D: the surface becomes coarse shape.Solution is painted.

(ITO evaporation)

(ITO) carries out evaporation (thickness according to ordinary method with indium tin oxide

200 ℃ of evaporation temperature) after, observe in detail with opticmicroscope.

[surface irregularity]

For surfaceness, by the SPA-400AFM mensuration Ra value of atomic force microscope (AFM), Seiko Instruments Co., Ltd. system.Metewand is as described below.

A: less than 3nm

More than the B:3nm and less than 8nm

More than the C:8nm and less than 10nm

More than the D:10nm

[wrinkle]

Observe under 500 times by opticmicroscope.Metewand is as described below.

A: the surface is very level and smooth.

B: level and smooth.

C: can see small concavo-convex.

D: can see concavo-convex.

(fluid preservation stability)

The solidification compound that obtains was preserved 14 days down at 50 ℃, estimated the variation of development time.

(metewand)

The evaluation of development time is the developing photosensitive material that will be coated on the glass substrate, and the time that glass substrate does not have residue to become clean is estimated.

A: development time does not change.

B: the delay of development time was less than 5 seconds.

C: development time postpones more than 5 seconds and less than 10 seconds.

D: development time postpones more than 10 seconds.

(contrast gradient)

On the pigmentary resin tunicle of colored substrate, place polaroid, clamping pigmentary resin tunicle, use the BM-5 of Topcon corporate system to measure the brightness of polaroid when parallel and the brightness when vertical, the brightness when parallel divided by vertically the time brightness and the value that obtains (brightness during=brightness when parallel/vertically) as the index that is used to estimate contrast gradient.

(metewand)

More than the A:8000.

More than the B:6000 and less than 8000.

More than the C:4000 and less than 6000.

D: less than 4000.

(sensitivity)

On substrate, be coated with photosensitive composite, make to estimate and use sensitive layer.In addition, solidification compound uses after transferring liquid at once.Then, by the exposure apparatus that uses in an embodiment, (60mJ/cm exposes with 15 sections stepping wedges (Δ logE=0.15) ²), and develop.Development conditions is identical with embodiment 1.Then, the hop count of all sections (the unchanged hop count of thickness by development) after developing is estimated according to following metewand.

The situation that the A:11 section is above

The situation of B:8～10 section

The situation of C:6～7 section

The situation that the D:5 section is following

(comprehensive evaluation)

With the above-mentioned basis that is evaluated as, be that the level of C, D is judged to be A with the none project.If it is D that 1 project is arranged, then comprehensive evaluation is D, is C with not having D and the level comprehensive evaluation of C is arranged fully.

[table 3]

As known from Table 3, comprise six aryl bisglyoxalines and be polymerization starter and be selected from any one in oxime series initiators or the triazine series initiators and can bring into play effect of the present invention with respect to the solidification compound that the total solids composition comprises the multi-functional epoxy compound that 4 officials can be above, NMP tolerance, ITO evaporation, fluid preservation excellent in stability, contrast gradient is good, the sensitivity height.

Comparative example 5 is results preferably, and still, its pigment concentration is little, is light color, and is impracticable.

(modulation of coated pigment 8)

In the modulation of coated pigment 2, use the yellow ultramarine E4GN GT of LANXESS corporate system to replace pigment green 36, the modulation of other and coated pigment 2 is similarly carried out, and makes coated pigment 8.

The evaluation of the lining degree of coated pigment 8 is carried out according to the method identical with the evaluation of coated pigment 1.Coated pigment 8 demonstrates the following free amount of 20 quality %, is the pigment of lining.

(modulation of dispersible pigment dispersion)

Use even matter device that following composition is stirred with rotating speed 3000r.p.m. mixed in 3 hours, the preparation mixing solutions, this composition is with respect to 35 parts of the compositions that is equivalent to pigment of coated pigment 8, Disperbyk 161 (BYK-Chemie corporate system) as dispersion agent is 7.0 parts, is 200 parts as the methyl proxitol acetate of solvent; Further bead dispersion machine ULTRAAPEX MILL (the longevity industrial's system) dispersion treatment 6 hours of the zirconium white bead by having used 0.1mm φ then.

Equally, the kind of coated pigment and the amount of dispersion agent obtain dispersible pigment dispersion 11,12 according to changing shown in the table 4.Wherein, coated pigment 2 in the dispersible pigment dispersion 11 is set at 83: 17 with the ratio of the usage quantity of coated pigment 8, coated pigment 2 in the dispersible pigment dispersion 12 is set at 63: 37 with the ratio of the usage quantity of coated pigment 8, is that 45 parts mode cooperates by the composition that is equivalent to pigment that adds up to.

The high molecular amount of lining that is used from dispersion liquid with pigment one is also remembered in table 4.

The measure of spread and the dispersible pigment dispersion 1 of 1 particle diameter of dispersible pigment dispersion 11 that obtains and 12 pigment similarly carry out, and the shared ratio of particle that surpasses the size of particles of 0.08 μ m is represented with number % in table 4.

[table 4]

(embodiment 17)

The composition of forming below further adding in the dispersible pigment dispersion 11 or 12 that obtains mixes, and modulates solidification compound of the present invention (colored liquid against corrosion).

(B) alkali soluble resins: 19.09 parts of multipolymer weight-average molecular weight=8,000 (the propylene glycol monomethyl ether solution of 45 quality % concentration) of benzyl methacrylate and methacrylic acid (=70/30[mol ratio])

(C) polymerizable compound: 35.75 parts of the system KAYARAD DPHA of Nippon Kayaku K. K

(D) polymerization starter: (above-mentioned oxime 1,3,4 and following oxime 2: in the table 5, in " kind " hurdle of oxime, be designated as 1～4) 10.88 parts

(E) polymerization starter: 2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,7.25 parts of 5 '-tetraphenyl bisglyoxalines

(F) multi-functional epoxy compound: 6953.75 parts of the system EPICLON of Dainippon Ink Chemicals

2.00 parts of diethylamino benzophenone

1.88 parts of N-phenyl mercaptobenzimidazoles

Tensio-active agent: 0.21 part of the system MEGAFACE F-781F of Dainippon Ink Chemicals

400.0 parts of solvents (propylene glycol methyl ether acetate/ethoxyl ethyl propionate=8/2)

Oxime 2:IRGACURE OXE02

In the composition of the solidification compound of embodiment 17, kind and amount, the amount of alkali soluble resins, the amount of polymerizable compound, the kind that reaches polymerization starter and the amount of pigment are changed the solidification compound of modulation embodiment 18～24 shown in following table 5.In table 5, * 1 is to use the compound identical with embodiment 1.

[table 5]

(making of TFT substrate)

Each solidification compound that obtains is spin-coated on the above-mentioned TFT substrate, so that the thickness after the prebake conditions becomes 2.4 μ m, with 90 ℃ oven dryings 60 seconds (prebake conditions).Then, to filming whole with 60mJ/cm ²(illumination 20mW/cm ²) expose, with filming after the exposure with 1% aqueous solution covering of alkaline-based developer CDK-1 (FUJIFILM Electronic Materials Co., Ltd. system), static 60 seconds.After static, pure water is scattered wash-out developer with the shower shape.Then, with above-mentioned such heat treated (back baking) that filming of photocuring processing and development treatment carried out in 220 ℃ baking oven 1 hour of having implemented, form the pigmentary resin tunicle that the formation colour filter is used, thereby made colored substrate.

The colored substrate that use obtains is carried out the evaluation identical with embodiment 1, and the result is summarised in the table 6.In addition, in fluid preservation stability, used solidification compound.Other evaluations are all estimated by the filter substrate of non-TFT.

[table 6]

As known from Table 6, comprise six aryl bisglyoxalines and be polymerization starter and specific oxime series initiators and can bring into play effect of the present invention with respect to the solidification compound that the total solids composition comprises the multi-functional epoxy compound that (2～20 quality %'s) 4 officials can be above, NMP tolerance, ITO evaporation, fluid preservation excellent in stability, contrast gradient is good, the sensitivity height.

(modulation of coated pigment 9)

In the modulation of coated pigment 2, use Pigment green 58 (DIC corporate system) to replace pigment green 36, other modulation with coated pigment 2 are similarly carried out, and modulate coated pigment 9.

The evaluation of the lining degree of coated pigment 9 is undertaken by the method identical with the evaluation of coated pigment 1.Coated pigment 9 demonstrates the following free amount of 20 quality %, is the pigment of lining as can be known.

(modulation of dispersible pigment dispersion)

Use even matter device that following composition is stirred with rotating speed 3000r.p.m. mixed in 3 hours, the preparation mixing solutions, this composition is with respect to 35 parts of the compositions that is equivalent to pigment of coated pigment 9, Disperbyk 161 (BYK-Chemie corporate system) as dispersion agent is 7.0 parts, is 200 parts as the methyl proxitol acetate of solvent; Further bead dispersion machine ULTRA APEX MILL (the longevity industrial's system) dispersion treatment 6 hours of the zirconium white bead by having used 0.1mm φ then.

Equally, the kind of coated pigment and the amount of dispersion agent obtain dispersible pigment dispersion 13,14 according to changing shown in the table 7.Wherein, coated pigment 9 in the dispersible pigment dispersion 13 is set at 83: 17 with the ratio of the usage quantity of coated pigment 8, coated pigment 9 in the dispersible pigment dispersion 14 is set at 63: 37 with the ratio of the usage quantity of coated pigment 8, is that 45 parts mode cooperates by the composition that is equivalent to pigment that adds up to.

The high molecular amount of lining that is used from dispersion liquid with pigment one is also remembered in table 7.

The measure of spread and the dispersible pigment dispersion 1 of 1 particle diameter of dispersible pigment dispersion 13 that obtains and 14 pigment similarly carry out, and the shared ratio of particle that surpasses the size of particles of 0.08 μ m is represented with number % in table 7.

[table 7]

(embodiment 25)

The composition of forming below further adding in the dispersible pigment dispersion 13,14 that obtains mixes, and modulates solidification compound of the present invention (colored liquid against corrosion).

(D) polymerization starter: above-mentioned oxime 1～4 10.88 parts

(in the table 8, in " kind " hurdle of oxime, being designated as 1～4)

2.00 parts of diethylamino benzophenone

1.88 parts of N-phenyl mercaptobenzimidazoles

In the composition of the solidification compound of embodiment 25, with the amount of the amount of the kind of pigment and amount, alkali soluble resins, polymerizable compound, and the kind of polymerization starter and amount according to changing the solidification compound of modulation embodiment 26～32 shown in the table 8.In table 8, * 1 is to use the compound identical with embodiment 1.

[table 8]

Each solidification compound that obtains is formed the pigmentary resin tunicle that colour filter constitutes usefulness similarly to Example 17 on the TFT substrate, make colored substrate.

The colored substrate that use obtains is carried out the evaluation identical with embodiment 1, and the result is summarised in the table 9.In addition, in fluid preservation stability, used solidification compound.Other evaluations are all estimated by the filter substrate of non-TFT.

[table 9]

As known from Table 9, comprise six aryl bisglyoxalines and be polymerization starter and specific oxime series initiators and can bring into play effect of the present invention with respect to the solidification compound that the total solids composition comprises the multi-functional epoxy compound that (2～20 quality %'s) 4 officials can be above, NMP tolerance, ITO evaporation, fluid preservation excellent in stability, contrast gradient is good, the sensitivity height.

(modulation of dispersible pigment dispersion 16～26)

In the modulation of dispersible pigment dispersion 1～10 and 15, separately dispersion agent is changed to outside the Disperbyk161 (BYK-Chemie corporate system), similarly carry out conditioned pigment dispersion liquid 16～26 with the modulation of dispersible pigment dispersion 1～10 and 15.

(evaluation of dispersible pigment dispersion 16～26)

The dispersible pigment dispersion that obtains 16～26 and dispersible pigment dispersion 1 are similarly estimated less than 0.02 μ m and greater than the shared ratio of particle of the size of particles of 0.08 μ m, and % is shown in Table 10 with number.The pigment usage quantity of dispersible pigment dispersion 16～26, the high molecular amount that is covered, and the amount of dispersion agent also be shown in Table 10.

[table 10]

(modulation of the solidification compound of embodiment 34～49, comparative example 9～14)

In the composition of the solidification compound of embodiment 1, with the kind of the amount of the amount of the kind of pigment and amount, alkali soluble resins, polymerizable compound, polymerization starter and amount, and multi-functional epoxy compound's amount according to changing the solidification compound of modulation embodiment 34～49, comparative example 9～14 shown in the table 11.

[table 11]

In table 11, * 1 is to use the compound identical with embodiment 1.* 2～* 6 be with table 2 in the identical compound of compound that uses.

(modulation of the solidification compound of comparative example 15)

Except the dispersible pigment dispersion among the embodiment 16 16 being altered to dispersible pigment dispersion 26, modulate solidification compound similarly to Example 1.

(comparative example 16)

Except the dispersible pigment dispersion among the embodiment 16 16 being altered to dispersible pigment dispersion 25, modulate solidification compound similarly to Example 1.

(modulation of the solidification compound of embodiment 50)

In embodiment 16, (F) multi-functional epoxy compound EPICLON695 is altered to EHPE-3150 (DAICEL chemical industrial company system, polyfunctional epoxy resin) modulates solidification compound.

(evaluation of embodiment 34～50, comparative example 9～16)

The embodiment 34～50 that use obtains, the solidification compound of comparative example 9～16 carry out following evaluation similarly to Example 1, the results are summarized in the table 12.

[table 12]

As known from Table 12, even use different dispersion agents also can not damage effect of the present invention, it is polymerization starter be selected from any one in oxime series initiators or the triazine series initiators and comprise 4 officials with respect to the total solids composition can above multi-functional epoxy compound that formation of the present invention comprises six aryl bisglyoxalines, NMP tolerance, ITO evaporation, fluid preservation excellent in stability with solidification compound of this formation of the present invention, contrast gradient is good, the sensitivity height.

Claims

1. solidification compound, its comprise (A) tinting material, (B) alkali soluble resins, (C) optical polymerism compound, (D) six aryl bisglyoxalines be polymerization starter, (E) be selected from oxime series initiators and the triazine series initiators more than one, and (F) 4 officials can above multi-functional epoxy compound

With respect to the total solids composition, this (F) multi-functional epoxy compound's content is the scope of 2～20 quality %, and the content of this (A) tinting material is the scope of 25～50 quality %.

2. solidification compound according to claim 1, wherein, described (F) multi-functional epoxy compound is the compound of following general formula (I) expression.

In the general formula (I), 1 is 5～100 integer, and R is hydrogen atom or methyl independently of one another.

3. solidification compound according to claim 1, wherein, described (D) six aryl bisglyoxalines are that Photoepolymerizationinitiater initiater is the polymerization starter of following general formula (II) or general formula (III) expression,

In the general formula (II), X represents that hydrogen atom, halogen atom, cyano group, carbonatoms are that 1～4 alkyl or carbonatoms are 6～9 aryl, A represent independently of one another carbonatoms be 1～12 replacement or the alkoxyl group that does not have replacement or-COO-R ⁹, wherein, R ⁹The expression carbonatoms is that 1～4 alkyl or carbonatoms are 6～9 aryl, and n is 1～3 integer, and m is 1～3 integer,

In the general formula (III), X ¹, X ²And X ³Represent that independently of one another hydrogen atom, halogen atom, cyano group, carbonatoms are that 1～4 alkyl or carbonatoms are 6～9 aryl, wherein, X ¹, X ²And X ³In be not hydrogen atom simultaneously more than 2.

4. solidification compound according to claim 1, wherein, described (A) tinting material is the pigment that is selected from pigment, C.I. pigment green 36 and the C.I. pigment Green 7 of following general formula (IV) expression, and be that the primary particle size is less than 10 quality % and primary particle size are less than 5 quality % greater than the particle of 0.08 μ m pigment less than the particle of 0.02 μ m in the total amount of this pigment

5. solidification compound according to claim 1, wherein, and then, described (A) tinting material is the pigment that comprises C.I. Pigment green 58, and is that the primary particle size is less than 10 quality % and primary particle size are less than 5 quality % greater than the particle of 0.08 μ m pigment less than the particle of 0.02 μ m in the total amount of this pigment.

6. solidification compound according to claim 1, wherein, described (A) tinting material is by resin-coated pigment.

7. colour filter, it directly or across other layers ground is formed with pixel electrode on each colored pixels, described other layers do not comprise liquid crystal layer, described each colored pixels directly or across other layers ground is formed on the TFT substrate, and described each colored pixels is formed by the described solidification compound of claim 1.