CN101959923B

CN101959923B - Curable composition and color filter

Info

Publication number: CN101959923B
Application number: CN200980107350.5A
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: 2013-01-23
Anticipated expiration: 2029-03-02
Also published as: JP2010024434A; CN101959923A; 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 respectively filter substrate and TFT (Thin-Film-Tra nsistor) substrate, the liquid crystal clamping being fitted make.At this moment, filter substrate is used for making the alignment films such as polyimide of liquid crystal aligning in the pigmented layer coating.Therefore, pigmented layer need to 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 sometimes use resin coating ((followingly sometimes be also referred to as " outside cover (overcoat) layer ") is as planarization film on the surface of pigmented layer.For this resin coating, also require equally anti-NMP with pigmented layer.

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

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

In the patent documentation 1, as the photosensitive composite that the colour filter pigmented layer is used, proposed to comprise the composition of six aryl bisglyoxalines.This photosensitive composite is so that sensitivity is good, make solvent resistance be optimized for purpose.But, in this photosensitive composite, have the problem of anti-NMP deficiency 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 anti-NMP and fluid preservation stability, ITO evaporation adaptability and painted both sides all good resin involucra or the anti-corrosion liquid 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 rear discovery, 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 that 5～100, 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 without the alkoxyl group that replaces 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 that the NMP tolerance is high, 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 consist of.The below describes the integrant that each consists of raw material, the best.

(A) tinting material

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

No matter pigment mineral dye or pigment dyestuff, if considering 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 transmissivity is high, colour characteristics good and the high colour filter of contrast gradient is effective for forming.

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 powder pigment 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 powder pigments with transmission electron microscope 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.This operation is carried out to amounting to 3 places in the position that changes powder pigment, with results averaged.

As above-mentioned mineral dye, can enumerate the 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 pigment that 10 quality %s and primary particle size greater than the particle of 0.08 μ m be less than 5 quality %s 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 particularly preferably hydrogen atom, methyl and chlorine atom.

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

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

The usage quantity of water-soluble inorganic salt is preferably 1～50 times of quality of pigment, although more amount grinds effect, considers from the aspect of productivity, and 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, in the situation that the rotating speed that installs as the blade in the operating condition preferred embodiment of kneader is 10～200rpm, in addition, grind effective, therefore preferred in the relatively large situation of the speed ratio of twin shaft.Runtime and dry type grinding 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 for spherical as the preferred grinding particle size of the water-soluble inorganic salt of crushing medium.

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 anthraquione pigmentss, perylene pigments, diketopyrrolopyrrolecocrystals series pigments separately or in them at least a kind, 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, as the diketopyrrolopyrrolecocrystals series pigments, C.I. Pigment red 254 can be enumerated, 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, sometimes is difficult to suppress the transmittance from 400nm to 500nm, can't improve purity of color.In addition, above-mentioned mass ratio is 100: 81 when above, and sometimes colour developing power reduces.Especially, above-mentioned mass ratio is that 100: 10～100: 65 scope is the most desirable.In addition, in the situation that the red pigment combination with one another, mass ratio can be adjusted according to colourity.

In addition, as veridian, can use separately a kind of halogenated phthalocyanines series pigments, 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, transmittance that can establishment 400～450nm, purity of color becomes well, can obtain desirable NTSC target form and aspect.As above-mentioned mass ratio, be particularly preferably 100: 20～100: 150 scope.

In addition, as veridian, can use separately a kind of ZnPc series pigments, 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 ZnPc series pigments 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, transmittance that can establishment 400～450nm, purity of color becomes well, can obtain desirable NTSC target form and aspect.As above-mentioned mass ratio, be particularly preferably 100: 20～100: 150 scope.

As blue pigments, can use separately a kind of phthualocyanine pigment, 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, as tinting material, in the situation that use dyestuff, the Photocurable composition that can be dissolved equably.

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, JP 64-91102 communique, Japanese kokai publication hei 1-94301 communique, Unexamined Patent 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, Unexamined Patent 5-333207 communique, Unexamined Patent 6-35183 communique, Unexamined Patent 6-51115 communique, Unexamined Patent 6-194828 communique, Unexamined Patent 8-211599 communique, Unexamined Patent 4-249549 communique, Unexamined Patent 10-123316 communique, Unexamined Patent 11-302283 communique, Unexamined Patent 7-286107 communique, JP 2001-4823 communique, Unexamined Patent 8-15522 communique, Unexamined Patent 8-29771 communique, Unexamined Patent 8-146215 communique, Unexamined Patent 11-343437 communique, Unexamined Patent 8-62416 communique, JP 2002-14220 communique, JP 2002-14221 communique, JP 2002-14222 communique, JP 2002-14223 communique, Unexamined Patent 8-302224 communique, Unexamined Patent 8-73758 communique, Unexamined Patent 8-179120 communique, the pigment of record in the Unexamined Patent 8-151531 communique etc.

As chemical structure, can enumerate the 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 in depth of shade fully and guarantee that aspect the good colour characteristics be effective.

In the present invention, especially preferably use pigment dyestuff as tinting material, and in the miniaturization operation or dispersion step of pigment, use the material that pigment is obtained with the macromolecular compound coating.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 the dispersiveness that 1 particle state disperses, 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 refers to the pigment that pigment is obtained by macromolecular compound institute's coating.So-called coating refers to, the new interface of the pigment that the surfactivity that produces through miniaturization is high by with the strong electrostatic interaction that has the macromolecular compound of heterocycle at side chain of the present invention, form the firmly coating of this macromolecular compound.Thus, be considered to obtain have the coated pigment of higher dispersion stabilization.That is, in the present invention, even the pigment after coating is processed with the organic solvent washing of solubilized macromolecular compound, the macromolecular compound of coating 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 by iv) have a macromolecular compound institute coating of heterocycle isopolarity group at side chain, part or all that is overlayed on securely the pigment particles surface by this macromolecular compound 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 coating state can be measured to confirm by the free amount (ionization rate) of macromolecular compound that the washing that utilizes organic solvent shown below is obtained.That is, only be adsorbed on macromolecular compound on the pigment through its major part of washing of organic solvent, specifically have and occur 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 coating processing of the present invention with the washing of 1-methoxy-2-propanol, is calculated free amount.The method is that pigment 10g is dropped among the 1-methoxy-2-propanol 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 macromolecular compound free from pigment, by the mass ratio of the macromolecular compound that uses in processing with the initial stage, calculate ionization rate (%).

The ionization rate of the pigment of commercially available grade can be measured by the following method.Namely, with the solvent (such as 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-methoxy-2-propanol 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 less, and is higher to the coating rate of pigment, dispersed, dispersion stabilization is better.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%.

Coating is processed 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 in fact ii) a small amount of water-miscible organic solvent and iv) macromolecular compound, carry out the operation (being called salt grinder order) of mechanically mixing with kneader etc.; This mixture is dropped in water, make the operation of pulp-like with the stirring such as super mixer; And with this slurries filtration, washing, carry out as required dry operation.

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 small amount of iii as wetting agent) water-miscible organic solvent, after mixing with brute forces such as kneaders, this mixture is dropped in water, make pulp-like with the stirring such as super mixer.Then, with this slurries filtration, washing, carry out as required drying, obtain thus the pigment of miniaturization.In addition, in the situation about using in the varnish of colo(u)rant dispersion in oiliness, also can be with the processing pigment (being called filter cake) before dry with the method that be commonly referred to as flash evaporation (flashing), remove in the varnish that the waterside is dispersed in oiliness on the limit.In addition, in the situation that be dispersed in the water system varnish, process pigment and need not drying, filter cake directly can be dispersed in the varnish.

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

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

The macromolecular compound that in the coating of pigment, uses so long as the macromolecular compound that has the adsorptivity group of pigment get final product.Especially preferably be used in that macromolecular compound that side chain has heterocycle carries out that coating is processed and the pigment that obtains.As such macromolecular compound, be preferably the polymkeric substance of the polymerized unit that comprises the monomer that derives from the monomer shown in the following general formula (1) or consisted of by maleimide, maleimide derivatives, be particularly preferably the polymkeric substance that comprises the polymerized unit that derives from the monomer shown in the following general formula (1).

General formula (1)

In the above-mentioned general formula (1), R ¹Expression hydrogen atom or replace or without the alkyl that replaces.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 particularly preferably carbonatoms and is 1～4 alkyl.

R ¹When shown alkyl has substituting group, as this substituting group, for example can enumerate hydroxyl, alkoxyl group (preferred carbonatoms is 1～5, and more preferably carbonatoms is 1～3), such 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 and replace or without the alkylidene group that replaces.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 particularly preferably carbonatoms 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 in the substituent situation, as this substituting group, such as enumerating 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 the group that links with Z.

In the general formula (1), Z represents to have the group of heterocycle structure.As the group with heterocycle structure, for example can enumerate phthalocyanine system, 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, the 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 particularly preferably that to have carbonatoms be more than 6 and the group of 12 following nitrogen heterocyclic ring structures.Be nitrogen heterocyclic ring structure more than 6 as carbonatoms, 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 particularly preferably the structure of following general formula (2), (3) or (4) expression.

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

In the general formula (2), E represent to be selected from singly-bound, alkylidene group (such as 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 in the expression alkyl situation is preferably that carbonatoms is 1～18 alkyl, more preferably carbonatoms is 1～6 alkyl, such as 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 particularly preferably-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 in the situation of expression alkyl is preferably carbonatoms, more preferably carbonatoms is 1～6 alkyl, such as 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 particularly preferably-N=,-NH-and-N (R ^B)-.As Y ¹And Y ²Combination, can enumerate Y ¹And Y ²Middle either party is-N=, the opposing party be-and the 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 independently of one another aromatic nucleus.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 particularly preferably phenyl ring, naphthalene nucleus, pyridine ring.

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, viewpoint from 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 physical property 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 Linear post) TOSOH system

Elutriant: THF

Flow: 1.0ml/min

Temperature: 40 ℃

Testing conditions: RI

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

(acid number)

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

Even in 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 the dispersiveness of pigment.

As dispersion agent, for example suitably known pigment dispersing agent of choice for use or tensio-active agent.

Particularly, can use the compound of numerous species, be tensio-active agent such as enumerating the positively charged ions such as 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), W001 (Yu Business Co., Ltd's system); The 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; The negatively charged ion such as W004, W005, W017 (Yu Business Co., Ltd's system) 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 company system); SOLSPERSE3000,5000,9000,12000,13240,13940,17000,24000,26000, the 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 at 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 forming contrast gradient colour filter high, that the transparency is excellent.

Pigment derivative is specifically take pigment dyestuff as precursor skeleton, 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 the 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 the pigment derivative of record in Japanese kokai publication hei 11-49974 communique, Unexamined Patent 11-189732 communique, Unexamined Patent 10-245501 communique, JP 2006-265528 communique, Unexamined Patent 8-295810 communique, Unexamined Patent 11-199796 communique, JP 2005-234478 communique, JP 2003-240938 communique, the JP 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 %.If this content is in above-mentioned scope, then when viscosity inhibition ground is lower, can disperse well, and can improve dispersion stabilization after disperseing, thereby so that transmissivity increases, excellent colour characteristics can be obtained, when making colour filter, the high-contrast with good colour characteristics can be constituted.

The method of disperseing is such as carrying 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 loose.

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

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

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; examined patent publication 54-34327 number; examined patent publication 58-12577 number; examined patent publication 54-25957 number; JP 59-53836 number; the Sipacril 2739OF of putting down in writing in each communique of JP 59-71048 number; acrylic copolymer; itaconic acid copolymer; the β-crotonic acid multipolymer; maleic acid; partial esterification maleic acid etc.; and the acid cellulose derivative that has carboxylic acid at side chain; addition acid anhydrides in having the polymkeric substance of hydroxyl and polymkeric substance of obtaining etc., and then preferably enumerate the high molecular polymer that has (methyl) acryl at side chain.

Wherein, particularly preferably (methyl) benzyl acrylate/(methyl) acrylic copolymer or the multiple copolymer that consisted of by (methyl) benzyl acrylate/(methyl) vinylformic acid/other monomer.

In addition, as useful polymkeric substance, also can enumerate polymkeric substance that is obtained by the 2-hydroxyethyl methacrylate copolymerization etc.This polymkeric substance can mix to use with any amount.

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

For the concrete Component units of alkali soluble resins, the multipolymer of (methyl) vinylformic acid and other monomer that can follow (methyl) acrylic acid copolymer particularly preferably.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, NVP, methacrylic acid tetrahydro furfuryl ester, Group-capped Polystyrene Macromer, 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 separately the resin that in alkali soluble resins, has polymerizable group; perhaps also can with its with do not have 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.The below shows the example of the polymkeric substance that contains these polymerizable groups, but so long as contain the compound of the caustic solubility group such as COOH base, OH base and carbon-to-carbon unsaturated bond in 1 molecule, just is not subjected to following restriction.

(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 in advance isocyanate group and OH radical reaction and stay next unreacted isocyanate group and contain the compound of at least 1 (methyl) acryl;

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

(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 (1) and (2) particularly preferably.

As concrete example, can use: will by have the OH base such as vinylformic acid 2-hydroxyl ethyl ester, contain the COOH base such as methacrylic acid 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 compound (such as compounds such as the glycidyl acrylates) reaction of the oxirane ring of responding property of OH base and carbon carbon unsaturated link(age) is obtained etc.With the reaction of OH base in, except oxirane ring, can also use the 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 the 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 particularly preferably 3～10 quality %.

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 as above-mentioned ethylenic unsaturated group with at least one addition polymerization, boiling point under the normal pressure being compound more than 100 ℃, such as acrylate or the methacrylic ester that can enumerate the 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 the 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, examined patent publication 50-6034 number, the urethane acrylate class of putting down in writing in the JP 51-37193 communique, JP 48-64183 number, examined patent publication 49-43191 number, the polyester acrylate class of putting down in writing in the examined patent publication 52-30490 communique, Resins, epoxy is polyfunctional acrylate or the methacrylic esters such as Epoxy Acrylates 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 the addition of ethylene oxide in above-mentioned polyfunctional alcohol of putting down in writing as the concrete example of general formula (1) and (2) 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 or examined patent publication 58-49860 number in also preferred Japanese Patent Publication 48-41708 number, JP 51-37193 number, JP 2-32293 number, JP 2-16765 number, examined patent publication 56-17654 number, examined patent publication 62-39417 number, examined patent publication 62-39418 number.And then, by using addition polymerization compounds record in JP 63-277653 number, JP 63-260909 number, Unexamined Patent 1-105238 number, that have amino structure or sulfide structure in the molecule, 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 company system), UA-7200 (Xin Zhong village chemical company system), DPHA-40H (Japanese chemical drug company system), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (common prosperity company system) etc.

In addition, the ethylenically unsaturated compounds class that also preferably has acidic group, as commercially available product, contain such as the conduct that can enumerate Toagosei Co., Ltd's system 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, with respect to 100 parts of the total solids compositions of said composition, be preferably 3～55 parts, more preferably 10～50 parts.If the content of optical polymerism compound is in the above-mentioned scope, then can fully be cured reaction.

Be polymerization starter as (D) six aryl bisglyoxalines, so long as replace and the dimer of the imidazole ring that obtains get final product with 3 aryl, still, the polymerization starter that represents of following general formula (II) or general formula (III) particularly preferably.

In addition, in the situation that have 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-s)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2,4 dichloro benzene base)-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 (2,4,6-trichlorophenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-cyano-phenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-cyano-phenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-aminomethyl phenyl)-4,4 ', 5,5 '-four (4-methoxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-aminomethyl phenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-aminomethyl phenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-ethylphenyl)-4,4 ', 5,5 '-four (4-methoxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-ethylphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-ethylphenyl)-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)-4,4 ', the bisglyoxaline based compounds such as 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) bisglyoxaline, 2,2 '-two (2-chloro-phenyl-)-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-(3,4-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 (2,4-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 (2,4-3,5-dimethylphenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4,6-trimethylphenyls)-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, the bisglyoxaline based compounds such as 5 '-tetraphenyl bisglyoxaline etc.

In the above-claimed cpd, as particularly preferred compound, can enumerate 2,2 '-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-(3,4-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, replacement or without the phenyl that replaces or carbonatoms be 7～20 ester ring type alkyl (wherein, carbonatoms is except 7～8 the cycloalkyl), the substituting group in 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 the alkyl of 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 particularly preferably 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 particularly preferably carbonatoms 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 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 particularly preferably 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 particularly preferably carbonatoms 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 ", it can be the alkyl of straight chain shape, a chain or ring-type, 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 particularly preferably 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 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), such as 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 particularly preferably 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, particularly preferably tetrahydrofuran base, THP trtrahydropyranyl etc.

R ⁵The carbonatoms of expression is that 1～12 alkyl can be the alkyl of straight chain shape, a chain or ring-type, 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 particularly preferably carbonatoms is 1～8 alkyl.

In addition, as R ⁵The carbonatoms of expression is 1～12 alkoxyl group, can be the alkoxyl group of straight chain shape, a chain or ring-type, 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, particularly preferably 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 particularly preferably 1, and in addition, r is preferably any one in 0,1,2, is particularly preferably 1.

In the structure of above-mentioned general formula (5) or (6) expression, from obtaining high sensitivity and polymerisation reactivity (curing) and keeping fluid preservation and the ageing stability drying regime film forming after under of modulation behind the liquid, improve controlled, the raising of the shape of pattern of desired formation and needed thickness and the viewpoint consideration of the adaptation of applied thing, particularly preferably 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-DOX base) anisoyl]-9.H.-carbazole-3-yl]-, 1-(O-ethanoyl oxime) etc.

Wherein, ethane particularly preferably, 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-DOX base) 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, replacement or without the phenyl that replaces or carbonatoms be 7～20 ester ring type alkyl (wherein, carbonatoms is except 7～8 the cycloalkyl), the substituting group in 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 in a plurality of situations, can be mutually identical or different.

In above-mentioned general formula (5 '), R ¹¹The carbonatoms of expression is that 1～20 alkyl can be the alkyl of 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 particularly preferably 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 particularly preferably carbonatoms 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 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 particularly preferably 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 for 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 carbonatoms of expression is 7～20 ester ring type alkyl (carbonatoms be 7～8 cycloalkyl except), such as 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 particularly preferably carbonatoms is 9～12.

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

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

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-(3,4-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 is 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 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, the colourity that is then 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, the colourity that is then caused by nmp solvent changes, the swelling tolerance is good, and ITO evaporation adaptability is good.

Also may be used except six above-mentioned aryl bisglyoxalines be Photoepolymerizationinitiater initiater, oxime series initiators, and the triazine series initiators initiator.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; The aromatic carbonyls such as ketal, acetal or benzoin alkylether class of putting down in writing in No. 4318791 specification sheets of United States Patent (USP), No. 88050 each specification sheets such as specification sheets of Europe Patent Application Publication; The aromatic ketone compounds such as benzophenone of putting down in writing in No. 4199420 specification sheets of United States Patent (USP); 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 Unexamined Patent 10-62986 communique; The sulfonium Organic Bor Complex of Unexamined Patent 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.

Be Photoepolymerizationinitiater initiater as above-mentioned methyl phenyl ketone, 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.

Be Photoepolymerizationinitiater initiater as above-mentioned ketal, such as can preferably enumerating 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, such as can preferably enumerating bitter almond oil camphor isopropyl ether, bitter almond oil camphor isobutyl ether, benzoin methyl ether, o-benzoyl yl benzoic acid methyl esters etc.

Be Photoepolymerizationinitiater initiater as above-mentioned xanthone, such as can preferably enumerating 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-1,3,4-oxadiazole, 3-methyl-5-is 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.

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

Except 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 that is replaced by α-hydrocarbon of putting down in writing in the United States Patent (USP) the 2nd, 722, No. 512 specification sheetss; 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 the triallyl imidazole dimer of putting down in writing in the United States Patent (USP) the 3rd, 549, No. 367 specification sheetss/p-aminophenyl ketone; The benzothiazole based compound of putting down in writing in the examined patent publication 51-48516 communique.

Among the present invention, preferably add as required sensitizing coloring matter.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 light splitting sensitizing coloring matter or dyestuff or absorb light and with the interactional dyestuff of Photoepolymerizationinitiater initiater or pigment.

As the sensitizing coloring matter that can use in the present invention and preferred light splitting 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 (tetraphenylporphyrin for example, central metal replaces porphyrin), chlorophyll class (chlorophyll for example, CHLOROPHYLLINE, central metal replaces chlorophyll), metal complex, Anthraquinones (for example anthraquinone), squaric acid inner salt (Squalium) class (such as the squaric acid inner salt) etc.

The example of preferred light splitting sensitizing coloring matter or dyestuff is as follows.

Can list: the vinylbenzene base system pigment of in Japanese JP 37-13034 communique, 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, the new methylene blue compound of in JP 64-33104 communique, putting down in writing; The Anthraquinones of in JP 64-56767 communique, putting down in writing; The benzoxanthene dye of in Unexamined Patent 2-1714 communique, putting down in writing; The acridine of in Unexamined Patent 2-226148 communique and Unexamined Patent 2-226149 communique, putting down in writing; The pyrans salt of in examined patent publication 40-28499 communique, putting down in writing; The cyanine class of in examined patent publication 46-42363 communique, putting down in writing; The cumarone pigment of in Unexamined Patent 2-63053 communique, putting down in writing; Conjugation ketone pigment at Unexamined Patent 2-85858 communique, Unexamined Patent 2-216154 communique; The pigment of in JP 57-10605 communique, putting down in writing; The azo cinnamylidene derivative of in JP 2-30321 communique, putting down in writing; The anthocyanins of in Unexamined Patent 1-287105 communique, putting down in writing; The xanthene class pigment of in JP 62-31844 communique, JP 62-31848 communique, JP 62-143043 communique, putting down in writing; The amino-benzene vinyl ketone of in examined patent publication 59-28325 communique, putting down in writing; The pigment of in Unexamined Patent 2-179643 communique, putting down in writing; The merocyanine pigment of in Unexamined Patent 2-244050 communique, putting down in writing; The merocyanine pigment of in examined patent publication 59-28326 communique, putting down in writing; The merocyanine pigment of in JP 59-89303 communique, putting down in writing; The merocyanine pigment of in Unexamined Patent 8-129257 communique, putting down in writing; The chromene of putting down in writing in Unexamined Patent 8-334897 communique is pigment.

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

As other preferred configuration of sensitizing coloring matter, can enumerate the 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), Anthraquinones (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 refer to and the compound of the carboxyl heat cross-linking of alkali soluble resins, by heat cross-linking cross-linking density are improved, thereby realize the raising of chemical reagent resistance.

As the multi-functional epoxy compound that can use in the present invention, it 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 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 the 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 change into system for Dongdu), DENACOL EM-125 etc. (above change into system for Nagase); 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 change into system for Dongdu) 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, particularly preferably 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. particularly 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, if content is too much, then owing to the yellow coloring after the baking, produce the impaired problem of quality of colour filter, if content is very few, then produce the problem of anti-NMP variation.

Pigment dispensing composition of the present invention and solidification compound generally can suitably be modulated with solvent 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-methoxy methyl propionate, 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 can using separately.

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

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

Chain-transfer agent can use separately a kind, 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 homogeneity and the joint fluidity of coating thickness.That is, because the surface tension of substrate and coating fluid is reduced, improved the wettability to substrate, so that the coating on substrate improves, even so when forming film about several μ m with a small amount of liquid measure, also can form the film of the little uniform thickness of uneven thickness, be effective in this.

The fluorine containing ratio of fluorine series organic compound is preferably 3～40 quality %, and more preferably 5～30 quality % are particularly preferably 7～25 quality %.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.

Be tensio-active agent as fluorine, 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 (large 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 from forming thin coating film is effective.In addition, and then, in the slot coated that easily causes the liquid cutout, 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 consist of, and except 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.

Being the preference of tensio-active agent as nonionic, is tensio-active agent such as nonionics such as Voranol EP 2001 class, polyoxyethylene alkylaryl ether class, polyxyethylated ester class, sorbitan alkyl esters, monoglyceride alkyl esters particularly preferably.Particularly, the Voranol EP 2001 classes such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether are arranged; The 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; The 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 above-mentioned tensio-active agent, can also use above-mentioned dispersion agent.

Except above-mentioned, can in solidification compound, add various additives.As the concrete example of additive, can enumerate the UV light absorber such as 2-(the 3-tertiary butyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone; The anticoalescents such as sodium polyacrylate; The weighting agent such as glass, aluminum oxide; Itaconic acid copolymer, β-crotonic acid 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 formed by dihydroxyphenyl propane and epoxy chloropropane etc.

In addition, promote the alkali dissolution of uncured section, seeking further to improve in 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, such as enumerating formic acid, acetic acid, propionic acid, butyric acid, valeric acid, PIVALIC ACID CRUDE (25), caproic acid, diethylacetic acid, enanthic acid, the aliphatic monocarboxylic acid such as sad; The aliphatic dicarboxylic acids such as oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane dicarboxylic acid, Methylpropanedioic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl-succsinic acid, citraconic acid; The aliphatic tricarboxylic acids such as tricarballylic acid, equisetic acid, camphoronic acid; Phenylformic acid, toluic acid, isopropyl acid, 2，3-xylic acid, 3, the aromatic monocarboxylates such as 5-mesitylenic acid; The aromatic 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, phenylsuccinic acid, atropic acid, styracin, methyl cinnamate, cinnamein, Chinese cassia tree fork acetic acid, coumaric acid, umbellic acid.

Except 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-butylphenol), 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 loose operation of processing 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 the 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 processed, add macromolecular compound, pigment is carried out coating.

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 differential processing of faling apart with particle diameter, obtains pigment dispensing composition.In addition, also can omit processing with the pigment miniaturization.

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

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

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

Colour filter of the present invention is the colour filter that uses the solidification compound of the present invention stated to form at substrates such as glass, preferably make by being handled as follows successively: with solidification compound of the present invention for example by slot coated directly or across other layers substrate form 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 at low cost the colour filter that is used for liquid crystal display device or solid-state imager.

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

For plastic base, preferably have in its surface gas-barrier layer and/or solvent resistance layer.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 is consisted of 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 the pattern of communicating pores (through hole) or コ font depression this moment on the photomask that uses.As the substrate in the TFT mode liquid crystal drive usefulness substrate, such as enumerating glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc.To these substrates, can implement to utilize according to hope the 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.Such as enumerating substrate that is formed with the 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 in the 5th generation (when 1100mm * 1250mm) is upper 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%.Substrate form by solidification compound of the present invention obtain film the time, as this thickness of filming (prebake conditions process after), 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 processes.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 processed 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 may be used high frequency processing etc.High frequency is processed and also can be used separately.

Then, implement exposure-processed across mask.At this moment, as the radioactive rays that use, the particularly preferably ultraviolet rays such as 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 section 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 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 the 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 in right amount water-miscible organic solvents such as methyl alcohol, ethanol or tensio-active agent etc.

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, prevent from developing uneven.In addition, also can make substrate tilt to develop.

After the development treatment, through the drip washing operation that remaining developing solution washing is removed, after the enforcement drying, solidify fully in order to make it, implement heat treated (rear baking).

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, usually carry out approximately 200 ℃～250 ℃ heat treated.This heat treated (rear baking) can be used hot-plate or the heater meanses such as convection oven (hot 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 thus the colour filter of the cured film that is formed with multiple color painted.

As the purposes of solidification compound of the present invention, mainly centered by the purposes in colour filter, be illustrated, but also go for and to consist of the formation of black matrix" of each colored pixels isolation of colour filter.

Above-mentioned black matrix" can form by following operation: by to having used the black pigments such as carbon black, titanium be black to expose, develop as the solidification compound of the present invention of pigment, then further carry out as required the curing that rear baking 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 take quality as benchmark.

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

(synthesizing of polymkeric substance 1)

With M-11 (following structure) 27.0g, methyl methacrylate 126.0g, methacrylic acid 27.0g, and 1-methoxy-2-propanol 420.0g import in the there-necked flask of nitrogen displacement, 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 ℃.(with the pure medicine of light Co., Ltd. system, V-65) 1.69g was 90 ℃ of lower heated and stirred 2 hours to add therein 2,2-azo two (2,4-methyl pentane nitriles).After 2 hours, add the V-65 of 1.69g, heated and stirred obtained 30 quality % solution of polymkeric substance 1 after 3 hours again.The result of weight-average molecular weight who measures the macromolecular compound of gained by the gel permeation chromatography take vinylbenzene as reference material (GPC) is 2.0 ten thousand.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-methoxy-2-propanol 420.0g import in the there-necked flask of nitrogen displacement, 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 ℃.(with the pure medicine of light Co., Ltd. system, V-65) 1.80g was 90 ℃ of lower heated and stirred 2 hours to add therein 2,2-azo two (2,4-methyl pentane nitriles).After 2 hours, add the V-65 of 1.80g, heated and stirred obtained 30 quality % solution of polymkeric substance 2 after 3 hours again.The result of weight-average molecular weight who measures the macromolecular compound of gained by the gel permeation chromatography take vinylbenzene as reference material (GPC) is 2.1 ten thousand.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)

Solution 20g and the glycol ether 100g of pigment (the C.I. Pigment red 254Ciba Specialty CROMOPHTAL RED processed BP of Chemicals company) 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 into approximately in 3 premium on currency,, filtered, wash after 1 hour with the super mixer stir about, remove sodium-chlor and solvent, and carry out drying, make coated pigment 1.

(modulation of coated pigment 2)

In the modulation of coated pigment 1, use C.I. pigment green 36 (the Japanese Le one Block リゾ Monastral Green processed 6Y-CL of one Le company) replace Pigment red 254, and with polymkeric substance 2 replacement polymkeric substance 1, 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 HELIOGEN Green processed L8730 of BASF AG) to replace pigment green 36, the modulation of other and coated pigment 2 is similarly carried out, and modulates coated pigment 3.

(modulation of coated pigment 4)

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

(modulation of coated pigment 5)

In the modulation of coated pigment 2, use C.I. pigment Violet 23 (the HOSTAPERM VIOLET processed RL-NF of Clariant company) to replace pigment green 36, the modulation of other and coated pigment 2 is similarly carried out, and modulates coated pigment 5.

(coated pigment 6,7 modulation)

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

(evaluation of the coating degree of pigment)

The pigment 10g that obtains is put among the 1-methoxy-2-propanol 100ml, vibrated 3 hours in room temperature with vibrating machine.Use afterwards separating centrifuge with 80,000rpm through 8 hours, make the pigment sedimentation, the solids component of supernatant liquor part is obtained by desiccating method.Obtain from pigment the amount of free macromolecular compound, by with process in the ratio of amount of the macromolecular compound that uses, calculate ionization rate (%).The less then coating rate to pigment of ionization rate is higher.

Coated pigment 1～7 obtained above all demonstrates the following free amount of 20 quality %, the pigment that is coating.

(modulation of dispersible pigment dispersion 1)

Use homogenizer 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 company system) as dispersion agent is 7.0 parts, is 200 parts as the methyl proxitol acetate of solvent; Then 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.

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 as 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 coating of using in dispersion liquid with pigment also is shown in Table 1.

In table 1, dispersible pigment dispersion 10 directly replaces using coated pigment with the CROMOPHTAL RED processed BP of Ciba Specialty Chemicals company.

In addition, dispersible pigment dispersion 15 similarly carries out with the modulation of dispersible pigment dispersion 1 except will change to by 6 hours dispersion treatment of bead dispersion machine 18 hours dispersion treatment by homogenizer (rotating speed 5000r.p.m.) 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 that forms below further adding in the dispersible pigment dispersion 1 of gained mixes rear modulation solidification compound of the present invention (colored anti-corrosion liquid).

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

(C) polymerizable compound: 20 parts of the DPHA processed 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 EPICLON695 processed 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 used the compound identical with embodiment 1.* 2～* 6 is as follows.

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

* the oxime series initiators processed OXE-01 of 3:Ciba Specialty Chemicals company (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)

* 6:2 official can the EPICLON850-LC processed of epoxy compounds Dainippon Ink Chemicals

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, form gate signal line and additional capacity electrode at active-matrix substrate, 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 with 1% aqueous solution covering of alkaline-based developer CDK-1 (FUJIFILM Electronic Materials Co., Ltd. system), static 60 seconds after the exposure.After static, pure water is scattered wash-out developer with the shower shape.Then, with above-mentioned such heat treated (rear 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 at glass substrate, thereby made colored substrate.

(comparative example 7)

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

(comparative example 8)

Except the dispersible pigment dispersion 1 among the embodiment 1 is changed into the dispersible pigment dispersion 10, modulate similarly to Example 1 solidification compound, 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 spectrophotometer MCPD-2000 processed 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 60 minutes, again measure dichroism 85 ℃ of lower dryings, will make colourity what change by Δ E by the NMP dipping ^*Ab represents.Here, Δ E ^*Ab refers to 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 under 60 ℃ in N-Methyl pyrrolidone (solvent), then take out and pass through the surfaceness on observation by light microscope colored substrate surface, estimate according to following metewand.

(metewand)

A: do not change fully.

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

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

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

(ITO evaporation)

Indium tin oxide (ITO) is carried out evaporation (thickness according to ordinary method 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 under 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)

Pigmentary resin tunicle in colored substrate is placed polaroid, clamping pigmentary resin tunicle, use the BM-5 of Topcon company system to measure the brightness of polaroid when parallel and the brightness when vertical, the brightness when parallel when vertical brightness and the value that obtains (brightness during=brightness when parallel/vertical) as the index for the evaluation 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)

Be coated with photosensitive composite at substrate, 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 neither one project.If it is D that 1 project is arranged, then comprehensive evaluation is D, is C with fully not having D and the level comprehensive evaluation of C is arranged.

[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, and sensitivity is high.

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

The evaluation of the coating 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 coating.

(modulation of dispersible pigment dispersion)

Use homogenizer 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 company system) as dispersion agent is 7.0 parts, is 200 parts as the methyl proxitol acetate of solvent; Then 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.

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 as 83: 17 with the ratio of the usage quantity of coated pigment 8, coated pigment 2 in the dispersible pigment dispersion 12 is set as 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 coating that is used from dispersion liquid with pigment one is also remembered in table 4.

Measure of spread and the dispersible pigment dispersion 1 of 1 particle diameter of the 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 represents with number % in table 4.

[table 4]

(embodiment 17)

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

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

(C) polymerizable compound: 35.75 parts of the KAYARAD DPHA processed 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 EPICLON processed 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 MEGAFACE F-781F processed 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 uses 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 with 1% aqueous solution covering of alkaline-based developer CDK-1 (FUJIFILM Electronic Materials Co., Ltd. system), static 60 seconds after the exposure.After static, pure water is scattered wash-out developer with the shower shape.Then, with above-mentioned such heat treated (rear 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, and sensitivity is high.

(modulation of coated pigment 9)

In the modulation of coated pigment 2, use Pigment green 58 (DIC company 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 coating 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 coating as can be known.

(modulation of dispersible pigment dispersion)

Use homogenizer 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 company system) as dispersion agent is 7.0 parts, is 200 parts as the methyl proxitol acetate of solvent; Then 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.

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 as 83: 17 with the ratio of the usage quantity of coated pigment 8, coated pigment 9 in the dispersible pigment dispersion 14 is set as 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 coating that is used from dispersion liquid with pigment one is also remembered in table 7.

Measure of spread and the dispersible pigment dispersion 1 of 1 particle diameter of the 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 represents with number % in table 7.

[table 7]

(embodiment 25)

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

(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 uses the compound identical with embodiment 1.

[table 8]

Each solidification compound that obtains is formed the pigmentary resin tunicle that colour filter consists of usefulness at the TFT substrate similarly to Example 17, 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, and sensitivity is high.

(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 company 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 16～26 that obtains 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 of coating, 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 uses the compound identical with embodiment 1.* 2～* 6 be with table 2 in the Compound Phase that uses with compound.

(modulation of the solidification compound of comparative example 15)

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

(comparative example 16)

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

(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 and be selected from any one in oxime series initiators or the triazine series initiators and comprise the multi-functional epoxy compound that 4 officials can be above with respect to the total solids composition 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, and sensitivity is high.

Claims

1. solidification compound, it comprises oxime series initiators that (A) tinting material, (B) alkali soluble resins, (C) optical polymerism compound, (D) six aryl bisglyoxalines are polymerization starter, (E) following compound (5 '-2) or compound (5 '-3) expression, 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 polymerization starter 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 without the alkoxyl group that replaces 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 solidification compound claimed in claim 1.