CN101535849A

CN101535849A - Color filter, and liquid crystal display device and ccd device each using the color filter

Info

Publication number: CN101535849A
Application number: CNA2007800416886A
Authority: CN
Inventors: 片山晃男; 斋藤直树; 横山裕
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2006-11-08
Filing date: 2007-11-07
Publication date: 2009-09-16
Anticipated expiration: 2027-11-07
Also published as: KR20090081370A; JP2010509619A; TW200831956A; TWI409505B; CN101535849B; WO2008056819A1

Abstract

A color filter having a layer colored in at least one prescribed hue and formed on a substrate, which comprises: a water-insoluble organic pigment (a), a monomer or oligomer having a polymerizable group (b), and a water-soluble polymer (c), in the form of a pigment dispersion, in which the dispersion is solidified by polymerizing the monomer or oligomer so as to form said colored layer, wherein a content of the water-soluble polymer (c) in the colored layer is at least 0.1 mass % of the total solid content.

Description

Color filter and the liquid crystal indicator and the CCD device that use this color filter respectively

Technical field

The present invention relates to have the color filter of high contrast and excellent tone and liquid crystal indicator and the CCD device that uses this color filter respectively.

Background technology

In recent years, along with the raising of the picture quality of liquid crystal indicator (LCD), in numerous terminal applies field, all adopting LCD to replace the display-CRT (Braun tube) that generally uses.Correspondingly, need such product, this product shows the much higher image display performance of quality with regard to color reproduction scope and brightness aspect.In order to meet this requirement, the raising of the performance of color filter is a key factor.This is because the display image that color filter has LCD panel etc. carries out painted function, so it is directly controlling the chromatic characteristic of LCD panel.

As the desired characteristic of color filter, can list high light transmission, excitation, high contrast, low reflectivity etc.Especially, low contrast can cause display screen deepening (due to the decay of light), and causes the difference between the light and shade to become unintelligible.For this reason, need have high comparative.In addition, also wish color reproduction wider range of obtaining by combination B, G and R, and the purity of the color of various gained thus is higher.Yet the contrast that improves color filter causes the reduction of excitation sometimes, and the color reproduction scope is reduced.

Usually, in manufacturing method of color filter, adopted such technology: form dyed layer (JP-A-10-130547 (" JP-A " is meant unexamined Japanese Patent Application Publication), JP-A-10-148712 and JP-A-2000-239554) by the dispersion of using colorant wherein to be dispersed in the organic solvent.This technology all is general to all color filter manufacturing methods that undertaken by coating, printing (transfer printing) and ink-jet.Therefore, as main polymkeric substance, used the material that in organic system, has polymolecularity as spreading agent or cementing agent.Because the factors such as moisture absorption of color filter can be damaged its reliability, therefore except some such as decoration method and the method that is of little use, almost not about the highly-water-soluble polymkeric substance being mixed the report of the technology in the dyed layer.

Summary of the invention

Problem to be solved by this invention provides a kind of have high contrast and excellent colourity and the suitable color filter of making continuously.In addition, another problem to be solved by this invention provides a kind of liquid crystal indicator and CCD device that has used above-mentioned high-quality color filter, and it all demonstrates excellent image display performance.

Realized purpose of the present invention by following means, described means are:

(1) a kind of color filter, it has the tone that is colored as at least a regulation and is formed at dyed layer on the substrate, described dyed layer comprises the pigment dispersion form: water-insoluble organic pigment (a), the monomer with polymerizable group or oligomer (b) and water-soluble polymers (c), wherein, described dispersion is solidified by making described monomer or oligomer polymerization, thereby form described dyed layer

Wherein, in described dyed layer, the content of described water-soluble polymers (c) is at least 0.1 quality % of total solids content.

(2) above-mentioned (1) described color filter, wherein, described pigment dispersion comprises the described organic pigment (a) of particulate form,

Wherein, described particulate is by the organic pigment solution that is dissolved in the organic pigment (a) in the good solvent, with have compatibility with described good solvent and separate out for the solvent of the poor solvent of described organic pigment together.

(3) above-mentioned (2) described color filter, wherein, the number average bead diameter of described pigment particle is in the scope of 0.005 μ m～1 μ m.

(4) above-mentioned (2) described color filter, wherein, the number average bead diameter of described pigment particle is in the scope of 0.005 μ m～0.08 μ m.

(5) above-mentioned (2) described color filter, wherein, the number average bead diameter of described pigment particle is in the scope of 0.005 μ m～0.05 μ m.

(6) any described color filter in above-mentioned (1)～(5), wherein, the number-average molecular weight of described water-soluble polymers is 1,000 or higher.

(7) a kind of liquid crystal indicator, it is equipped with any described color filter in above-mentioned (1)～(6).

(8) a kind of CCD device, it is equipped with any described color filter in above-mentioned (1)～(6).

(9) a kind of pigment dispersion, it contains water-insoluble organic pigment (a) and water-soluble polymers (b),

The liquid water content of wherein said pigment dispersion is 10 quality % or lower, and

The content of wherein said water-soluble polymers (b) is at least 0.1 quality % of organic pigment (a).

(10) above-mentioned (9) described pigment dispersion, it contains the described organic pigment (a) of particulate form,

(11) above-mentioned (10) described pigment dispersion, wherein, the number average bead diameter of described pigment particle is in the scope of 0.005 μ m～1 μ m.

(12) above-mentioned (10) described pigment dispersion, wherein, the number average bead diameter of described pigment particle is in the scope of 0.005 μ m～0.08 μ m.

(13) above-mentioned (10) described pigment dispersion, wherein, the number average bead diameter of described pigment particle is in the scope of 0.005 μ m～0.05 μ m.

(14) any described pigment dispersion in above-mentioned (9)～(13), wherein, the number-average molecular weight of described water-soluble polymers is 1,000 or higher.

By following description, of the present invention other and further feature and advantage will show more fully.

Preferred implementation of the present invention

Below the present invention is described in detail.

Color filter of the present invention has at least one and is formed at dyed layer on the substrate.As described substrate, preferably use transparency carrier, and can use glass plate, have soda-lime glass plate, low-expansion glass and the quartz glass plate of silica coating as its surface.Can be to use the resin molding such as polyethylene terephthalate, Triafol T, polystyrene and polycarbonate for another mode of selecting for use.

There is no particular limitation for the method that forms dyed layer on substrate, gets final product so long as be used to prepare the conventional method of color filter.As described later, can obtain color filter by the following method, described method is: use the device such as spin coater, slit type coater and roll coater that pigment dispersion described later is coated on the substrate, thereby form the coloring phototonus resin bed, expose then and develop.In addition, the such method of also preferred use wherein by at first forming above-mentioned coloring phototonus resin bed on interim support, uses laminating machine that described coloring phototonus resin bed is transferred on the substrate then, then expose and develop, thereby form dyed layer; And/or use such method, wherein use so-called ink-jet system that the drop of pigment dispersion is sprayed on the substrate, thereby form dyed layer.There is no particular limitation to the thickness of described dyed layer, but it is preferably in the scope of 0.5 μ m to 5 μ m, more preferably in the scope of 1 μ m to 3 μ m.There is no particular limitation to the area of described dyed layer.But when forming meticulous pixel, this area is preferably at 400 μ m ²To 90,000 μ m ²Scope in, and more preferably at 1,000 μ m ²To 15,000 μ m ²Scope in.

Above-mentioned dyed layer in the color filter of the present invention is to be formed by the material that polymerization is also solidified, and this material is to obtain by the pigment dispersion polymerization that will comprise water-insoluble organic pigment (a), the monomer with polymerizable group or oligomer (b) and water-soluble polymers (c).Preferably introduce cementing agent (d) and polymerization initiator or polymerization initiator system (e) herein.

(a) water-insoluble organic pigment

As water-insoluble organic pigment, there is no particular limitation to it, as long as this pigment is insoluble in the water.Preferred this pigment is scattered in the dispersion with fine granules of pigments form.When with described pigment miniaturization, preferable methods can be selected from the whole bag of tricks such as vapor phase method, polishing, reprecipitation method and laser ablation method according to the kind of pigment and/or purpose.From obtaining fine size and having that uniform grain sizes distributes and the angle of the granules of pigments of superior dispersion stability is considered, the particulate deposition method that preferred use hereinafter will be described.

Specifically, the example of described water-insoluble organic pigment comprises: perylene compounds pigment perylene ketonic compound class pigment, quinacridone compounds pigment, quinacridone quinone compounds pigment, anthraquinone compounds class pigment, anthanthrene dione compounds class pigment, benzimidazolone compound class pigment, condensation bis-azo compound class pigment, bis-azo compound class pigment, azo-compound class pigment, indanthrone compounds pigment, phthalocyanine compound class pigment, triaryl carbon compound class pigment dioxazine compound class pigment, amino anthraquinones compounds pigment, Diketopyrrolo-pyrrole compounds class pigment, thioindigo compounds pigment, isoindoline compounds class pigment, isoindolinone compounds pigment, pyranthrone compounds pigment or iso-violanthrone compounds pigment, or their potpourri.

More particularly, the example of described water-insoluble organic pigment comprises: perylene compounds pigment, as C.I. paratonere 190 (C.I.No.71140), C.I. paratonere 224 (C.I.No.71127), C.I. pigment violet 29 (C.I.No.71129) etc.; Perylene ketone compounds pigment is as C.I. pigment orange 43 (C.I.No.71105), C.I. paratonere 194 (C.I.No.71100) etc.; Quinacridone compounds pigment is as C.I. pigment violet 19 (C.I.No.73900), C.I. pigment violet 42, C.I. pigment red 122 (C.I.No.73915), C.I. paratonere 192, C.I. paratonere 202 (C.I.Nos.73907), C.I. Pigment Red 207 (C.I.No.73900,73906) or C.I. paratonere 209 (C.I.No.73905) etc.; Quinacridone quinone compounds pigment is as C.I. paratonere 206 (C.I.No.73900/73920), C.I. pigment orange 48 (C.I.No.73900/73920), C.I. pigment orange 49 (C.I.No.73900/73920) etc.; Anthraquinone compounds class pigment is as C.I. pigment yellow 147 (C.I.No.60645) etc.; Anthanthrene dione compounds class pigment is as C.I. paratonere 168 (C.I.No.59300) etc.; Benzimidazolone compound class pigment is as C.I. pigment brown 25 (C.I.No.12510), C.I. pigment violet 32 (C.I.No.12517), C.I. pigment yellow 180 (C.I.No.21290), C.I. pigment yellow 181 (C.I.No.11777), C.I. pigment orange 62 (C.I.No.11775), C.I. paratonere 185 (C.I.No.12516) etc.; Condensation bis-azo compound class pigment is as C.I. pigment yellow 93 (C.I.No.20710), C.I. pigment yellow 94 (C.I.No.20038), C.I. pigment yellow 95 (C.I.No.20034), C.I. pigment Yellow 12 8 (C.I.No.20037), C.I. pigment yellow 166 (C.I.No.20035), C.I. pigment orange 34 (C.I.No.21115), C.I. pigment orange 13 (C.I.No.21110), C.I. pigment orange 31 (C.I.No.20050), C.I. paratonere 144 (C.I.No.20735), C.I. paratonere 166 (C.I.No.20730), C.I. paratonere 220 (C.I.No.20055), C.I. paratonere 221 (C.I.No.20065), C.I. paratonere 242 (C.I.No.20067), C.I. paratonere 248, C.I. paratonere 262, C.I. pigment brown 23 (C.I.No.20060) etc.; Bis-azo compound class pigment is as C.I. pigment yellow 13 (C.I.No.21100), C.I. pigment yellow 83 (C.I.No.21108), C.I. pigment yellow 188 (C.I.No.21094) etc.; Azo-compound class pigment is as C.I. paratonere 187 (C.I.No.12486), C.I. paratonere 170 (C.I.No.12475), C.I. pigment yellow 74 (C.I.No.11714), C.I. pigment yellow 150 (C.I.No.48545), C.I. pigment red 48 (C.I.No.15865), C.I. paratonere 53 (C.I.No.15585), C.I. pigment orange 64 (C.I.No.12760), C.I. paratonere 247 (C.I.No.15915) etc.; Indanthrone compounds pigment is as C.I. pigment blue 60 (C.I.No.69800) etc.; Phthalocyanine compound class pigment is as C.I. pigment Green 7 (C.I.No.74260), C.I. pigment green 36 (C.I.No.74265), naphthol green 37 (C.I.No.74255), pigment blue 16 (C.I.No.74100), C.I. alizarol saphirol 75 (C.I.No.74160:2), C.I. pigment blue 15: 6 (C.I.No.74160), C.I. pigment blue 15: 3 (C.I.No.74160) etc.; Triaryl carbon compound class pigment is as C.I. alizarol saphirol 56 (C.I.No.42800), C.I. pigment Blue-61 (C.I.No.42765:1) etc.; Dioxazine compound class pigment is as C.I. pigment Violet 23 (C.I.No.51319), C.I. pigment violet 37 (C.I.No.51345) etc.; Amino anthraquinones compounds pigment is as C.I. paratonere 177 (C.I.No.65300) etc.; Diketopyrrolo-pyrrole compounds class pigment is as C.I. paratonere 254 (C.I.No.56110), C.I. paratonere 255 (C.I.No.561050), C.I. paratonere 264, C.I. paratonere 272 (C.I.No.561150), C.I. pigment orange 71, C.I. pigment orange 73 etc.; Thioindigo compounds pigment is as C.I. pigment Red 88 (C.I.No.73312) etc.; Isoindoline compounds class pigment is as C.I. pigment yellow 13 9 (C.I.No.56298), C.I. pigment orange 66 (C.I.No.48210) etc.; Isoindolinone compounds pigment is as C.I. pigment yellow 109 (C.I.No.56284), C.I. pigment yellow 185 (C.I.No.56290), C.I. pigment orange 61 (C.I.No.11295) etc.; Pyranthrone compounds pigment is as C.I. pigment orange 40 (C.I.No.59700), C.I. pigment red 21 6 (C.I.No.59710) etc.; Quinoline dai ketone compounds pigment is as C.I. pigment yellow 13 8; Perhaps iso-violanthrone compounds pigment is as C.I. pigment violet 31 (C.I.No.60010) etc.

In color filter of the present invention, also two or more organic pigment or its solid solution can be used in combination.In addition, its dyestuff with routine can also be used.

In color filter of the present invention, based on the total solids content of described dyed layer, the content of described organic pigment is preferably in the scope of 10 quality % to 70 quality %, more preferably in the scope of 30 quality % to 60 quality %.

(b) has the monomer of polymerizable group or have the oligomer of polymerizable group

Be used for the monomer with polymerizable group of color filter of the present invention or oligomer and be preferably monomer or the oligomer that has 2 or more a plurality of ethylenical unsaturated double bonds and can carry out addition polymerization by illumination.This monomer or oligomer can be to have at least one addition polymerization ethylenically unsaturated group and the boiling point under normal pressure is 100 ℃ or higher compound.Its example comprises: monofunctional acrylate and simple function methacrylate, as dipentaerythritol six (methyl) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate and (methyl) phenoxyethyl acrylate; Polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the trimethylolethane trimethacrylate acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane diacrylate, two (methyl) acrylic acid DOPCP, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two (methyl) acrylic acid hexanediol ester, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanuric acid ester, three (acryloxy ethyl) cyanurate, glycerine three (methyl) acrylate; Polyfunctional acrylic ester or multifunctional methacrylate, it can be by carrying out addition with oxirane or epoxypropane and polyfunctional alcohol's (for example trimethylolpropane or glycerine), and this addition product is converted into (methyl) acrylate and obtains.In addition, other preferred examples comprise by oxirane or epoxypropane and polyfunctional alcohol are carried out addition reaction and then carry out those compounds that (methyl) acroleic acid esterification obtains, as described in the general formula among the patent documentation JP-A-10-62986 (1) and (2).At this, expression way herein " (methyl) acrylate " be used for the expression " acrylate " and " methacrylate " these two.

Having the monomer of polymerizable group and the example of oligomer also comprises: the urethane acrylate described in patent documentation JP-B-48-41708 (" JP-B " is meant that the Jap.P. of having examined is open), JP-B-50-6034 and the JP-A-51-37193; Polyester acrylate described in patent documentation JP-A-48-64183, JP-B-49-43191 and the JP-B-52-30490; Polyfunctional acrylic ester or multifunctional methacrylate are as the epoxy acrylate as epoxy resin and (methyl) acrylic acid reaction product.

Wherein, preferred trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate and dipentaerythritol five (methyl) acrylate.

In addition, except that above-mentioned, can also enumerate the preferred example of describing among the patent documentation JP-A-11-133600 of " polymerizable compound B " conduct.

Have these monomers of polymerizable group or the molecular weight of oligomer and be preferably 200 to 1000, and they can use separately, perhaps the potpourri as two or more uses.

In color filter of the present invention, there is no particular limitation to monomer with polymerizable group or the content of oligomer, but be based on the total solids content of described dyed layer, the content of described monomer with polymerizable group or oligomer is usually in the scope of 5 quality % to 50 quality %, preferably in the scope of 10 to 40 quality %.If this content is too much, then is difficult to control development, thereby causes making the problem of adaptability aspect.If this content is very few, the curing power deficiency when then exposing.

(c) water-soluble polymers

In color filter of the present invention, described dyed layer contains water-soluble polymers.Water-soluble polymers is preferably 10 or higher with respect to the solubleness of pure water (25 ℃), and more preferably 50 or higher, be preferably 100 or higher especially.Be neutral polymkeric substance when the state of aqueous solution preferably also, this means that described polymkeric substance is to almost not influence of color filter.For example, preferred such water soluble compound, the pH that the aqueous solution of its 50 quality % demonstrates is 5 to 9, more preferably 6 to 8.Specifically, can use synthetic polymer compound, for example, polyvinyl alcohol (PVA), polyvinylpyrrolidone, polyacrylamide, polyglycol and polyoxyethylene, and the multipolymer of these compounds.In these polymer compounds, preferably polyethylene pyrrolidone especially.These water-soluble polymerss can use separately, perhaps being used in combination with two or more.

There is no particular limitation for the molecular weight of described water-soluble polymers, but its number-average molecular weight (Mn) is preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, be preferably 10,000 to 100,000 especially.

In color filter of the present invention, based on the total solids content of dyed layer, the content of described water-soluble polymers in dyed layer is 0.1 quality % or higher, is preferably 0.5 quality % or higher, more preferably 1 quality % or higher.The content of water-soluble polymers in described dyed layer does not have specific upper limit, but practicality is that based on the total solids content of dyed layer, the content of water-soluble polymers is 5 quality % or lower.

(d) cementing agent

As cementing agent, preferably has the cementing agent of acidic-group.Can when preparation ink-jet ink or preparation photosensitive composition, add this cementing agent.Further preferably, add cementing agent when making paints dispersion or before the dispersion that making paints or when forming pigment particle described later.Cementing agent can be added to organic pigment solution and by to wherein adding organic pigment solution so that pigment particle used poor solvent in the two or in any one when separating out.Can be also preferably when forming pigment particle, to add binder solution separately for another mode of selecting for use.

Cementing agent is preferably the alkali-soluble polymer that has such as carboxylic acid group or carboxylic acid ester groups isopolarity group on side chain.Its example is included in the maleic acid of methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid and the partial esterification described in (for example) patent documentation JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836 and the JP-A-59-71048.Its example also is included in the cellulose derivative that has carboxylic acid group or carboxylic acid ester groups on the side chain.In addition, also preferably use by having the product that the addition cyclic acid anhydride obtains on the polymkeric substance of hydroxyl.In addition, the more preferred example of cementing agent is included in U.S. Patent No. 4, (methyl) benzyl acrylate described in 139,391 and (methyl) acrylic acid multipolymer and the multiple copolymer that forms by (methyl) benzyl acrylate, (methyl) acrylic acid and any other monomers.These binder polymers with polar group all can use separately, also can use with the film forming combination of polymers of routine, make its state with composition use.

Herein " alkali-soluble polymer " is meant such polymkeric substance, when in measuring it, being dissolved with the pH of aqueous solution of this polymkeric substance of 50 quality %, but its acid strength pH be 1 or higher less than 5 scope in.Based on described acid strength, alkali-soluble polymer can be different from the water-soluble polymers of above-mentioned neutrality.

In addition,, can on side chain, have polymerizable group, also can adopt uv-curing type resin and thermoset resin in order to improve cross-linking efficiency.Though below show the example of the polymkeric substance that contains these polymerizable groups, be not limited to following these examples, condition be this polymkeric substance contain such as-COOH base ,-alkali solubility group and carbon-to-carbon unsaturated bond OH base and the ammonium.For example; can use in the following manner the compound that obtains, described mode is: make by having-monomer (as acrylic acid 2-hydroxyl ethyl ester) of OH base, the contain-monomer (as methacrylic acid) of COOH base and multipolymer that can form with the monomer (as acyl compounds or vinyl compound etc.) of these two kinds of monomer generation copolymerization and have epoxide ring (itself and-OH base have reactivity) and the compound (as glycidyl acrylate) of carbon-to-carbon unsaturated bond group reacts.As having reactive compound with-OH, can also use have acyloxy, acid anhydrides and the isocyanate group compound of (replacement epoxide ring).In addition, can also use the reaction product that obtains by by saturated or undersaturated multi-anhydride and the reaction of such compound, wherein said compound is by the reaction of the compound with epoxide ring and unsaturated carboxylic acid (as acrylic acid) and obtain, as patent documentation JP-A-6-102669 and JP-A-6-1938 are disclosed.The example that has the compound of alkali solubility group (as-COOH yl) and carbon-to-carbon unsaturated group simultaneously comprises DIANAL NR series (being produced by Mitsubishi Rayon Co., Ltd.), PHOTOMER 6173 (trade names, contain-the polyurethane acroleic acid oligomer of COOH base, produce by Diamond Shamrock Co., Ltd.), VISCOATR-264, KS RESIST 106 (all be trade names; Produce by Osaka Organic Chemical Industry Co., Ltd.), CYCLOMER P series, PRAXEL CF200 series (be trade name, produce), EBECRYL 3800 (trade name is produced by Daicel-UCB Co., Ltd.) etc. by Daicel chemical industry Co., Ltd..

In addition, as resin glue, can adopt the organic high molecular polymer that on the part of the side chain of polymkeric substance, has water-soluble atomic group.Preferably, resin glue be can be miscible with monomer linear organic high molecular polymer, and it is dissolvable in water in organic solvent and the basic solvent (be preferably can enough weak alkaline aqueous solutions develop).The example of above-mentioned alkali soluble resins is included in the polymkeric substance that has carboxylic acid on the side chain, as the maleic acid of disclosed methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification in (for example) patent documentation JP-A-59-44615, JP-A-54-34327, JP-A-58-12577, JP-A-54-25957, JP-A-59-53836, JP-A-59-71048 etc.Equally, can use the acid cellulose derivant that on side chain, has carboxylic acid.In addition, also can will have the polymkeric substance of hydroxyl (addition has acid anhydrides on it) as above-mentioned alkali soluble resins.In these polymkeric substance, specifically, the multiple copolymer of preferred especially (methyl) benzyl acrylate/(methyl) acrylic copolymer and (methyl) benzyl acrylate/(methyl) acrylic acid/other monomers.As above-mentioned alkali soluble resins, can use at least by (i) be selected from least a sour composition monomer in maleic anhydride (MAA), acrylic acid (AA), methacrylic acid (MA) and the fumaric acid (FA), with (ii) alkyl polyoxyethylene (methyl) acrylate and (iii) (methyl) multipolymer that benzyl acrylate constituted (below be sometimes referred to as " copolymer A ").

As the combination of the composition in the above-mentioned copolymer A, (i) sour composition monomer, (ii) alkyl polyoxyethylene (methyl) acrylate (Acr (EO) _n: CH ₃(OC ₂H ₄) _nOCOC (R)=CH ₂) and (iii) the composition mass ratio of (methyl) benzyl acrylate (Bz (M) A) be preferably 10-25/5-25/50-85,15-20/5-20/60-80 more preferably.In addition, according to GPC, the mean molecular weight (Mw) of above-mentioned multipolymer after by polystyrene conversion is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.

If (i) the composition mass ratio of sour composition monomer is in above-mentioned scope, then alkali solubility and the dissolubility in solvent can reduce hardly.In addition, if (ii) alkyl polyoxyethylene (methyl) acrylate (Acr (EO) _n: CH ₃(OC ₂H ₄) _nOCOC (R)=CH ₂) the composition mass ratio in above-mentioned scope, then the solution of composition launches on substrate easily, and the dispersiveness of colorant can reduce hardly.So, can reach effect of the present invention effectively.If (iii) the composition mass ratio of (methyl) benzyl acrylate (Bz (M) A) is in above-mentioned scope, then the dispersion stabilization of colorant and colorant in composition dispersiveness and the alkaline development adaptability of coated film can reduce hardly.

(ii) alkyl polyoxyethylene (methyl) acrylate (Acr (EO) _n: CH ₃(OC ₂H ₄) _nOCOC (R)=CH ₂) in the repetition number n of polyoxyethylene (EO) n preferably in 2 to 15 scope, more preferably in 2 to 10 scope, in 4 to 10 scope.If repetition number n is in the above-mentioned scope, can produce the development residue hardly after then developing with alkaline developer.The coating non-uniform phenomenon that reduces by flowability when in addition, above-mentioned scope can prevent to produce with composition as coating liquid and cause.Therefore, above-mentioned scope can prevent the homogeneity of coated film thickness and economize fluidity generation deterioration.

These binder polymers with polar group can use separately, perhaps use with the form of the composition that contains binder polymer and conventional film forming polymkeric substance.Based on the pigment particle of 100 mass parts, the addition of binder polymer is generally 10 to 200 mass parts, is preferably 25 to 100 mass parts.

At cementing agent is under the situation of polymer compound, there is no particular limitation to the number of the acidic-group in this polymer compound, but when the number of repeating units that is contained in 1 molecule is set at 100, the number of repeating units that all has acidic-group is preferably 5 to 100, and more preferably 10 to 100.In addition, the polymerization ratio that is derived from the repetitive (1) of the compound with carboxyl and is derived between the repetitive (2) of the compound with carboxylic acid ester groups is as follows: the ratio of repetitive (1) is 5 to 40 moles of %, the ratio of repetitive (2) is 40 to 90 moles of %, and the ratio of other repetitive except repetitive (1) and (2) is 25 moles of % or lower.In addition, the molecular weight with alkali solubility binder polymer compound of acidic-group is preferably 3,000 to 1,000,000, and more preferably 4,000 to 200,000, be preferably 5,000 to 80,000 especially.

About the content of described cementing agent in color filter of the present invention, there is no particular limitation to it.Yet based on the total solids content of dyed layer, the content of cementing agent in dyed layer in the scope of 15～50 quality %, is preferably 20～45 quality % usually.If the amount of cementing agent is too much, then when making described color filter, the viscosity of pigment dispersion is too high, and it can cause making the problem of adaptability aspect.On the other hand, if the amount of described cementing agent is very few, then can have problems aspect the formation coated film.

(e) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system

Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system are (in this article, term " Photoepolymerizationinitiater initiater system " is meant to be combined mutually by multiple compound realizes that photopolymerization causes the polymerization triggering composition of function) example comprise: U.S. Patent No. 2,367, disclosed ortho position idol acyl ketone (vicinal polyketaldonyl) compound in 660, U.S. Patent No. 2,448, acyloin ether compound described in 828, U.S. Patent No. 2,722, aromatic series acyloin compound described in 512 by α-hydrocarbon replacement, U.S. Patent No. 3,046,127 and U.S. Patent No. 2,951, polynucleation quinone compound described in 758, U.S. Patent No. 3,549, triarylimidazoles dipolymer described in 367 and to the combination of amino ketones, benzothiazole compound described in the patent documentation JP-B-51-48516 and trihalomethyl-s-triaizine compounds, U.S. Patent No. 4,239, trihalomethyl-triaizine compounds described in 850, U.S. Patent No. 4, San halogen Jia oxadiazole compound described in 212,976.Preferred especially trihalomethyl-s-triazine, San halogen Jia oxadiazole and triarylimidazoles dipolymer.

In addition; can also enumerate " the polymerization initiator C " described in the patent documentation JP-A-11-133600 as preferred example; as 1-phenyl-1; 2-propanedione-2-(adjacent carbethoxyl group) oxime, O-benzoyl-4 '-(thiophenyl) benzoyl-hexyl-ketoxime, 2; 4,6-trimethylphenyl carbonyl-diphenylphosphine acyloxylation thing and hexafluorophosphoric acid-trialkyl Ben phosphonium salt.

These Photoepolymerizationinitiater initiaters or Photoepolymerizationinitiater initiater system can be used separately.Can be to use two or more the potpourri that is selected from these Photoepolymerizationinitiater initiaters or the Photoepolymerizationinitiater initiater system for another mode of selecting for use.Particularly preferably be, use two or more the potpourri be selected from these Photoepolymerizationinitiater initiaters or the Photoepolymerizationinitiater initiater system.When use is selected from two or more potpourri in these Photoepolymerizationinitiater initiaters or the Photoepolymerizationinitiater initiater system, can improve display characteristic, particularly the homogeneity of Xian Shiing.

About the content of Photoepolymerizationinitiater initiater used in color filter of the present invention or Photoepolymerizationinitiater initiater system, there is no particular limitation to it.But be based on the total solids content of dyed layer, described Photoepolymerizationinitiater initiater or the content of Photoepolymerizationinitiater initiater system in dyed layer in the scope of 0.5～20 quality %, are preferably 1～15 quality % usually.If the amount of initiating agent or initiator system is too much, then exposure sensitivity is too high, and this can cause and be difficult to control.If the amount of initiating agent or initiator system is very few, then exposure sensitivity is low excessively.

Except that mentioned component, in addition can also be with an organic solvent.For organic solvent without any qualification.Described representative examples of organic comprises: ester class, for example ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, the alkyl esters compound, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid butyl ester, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-hydracrylic acid Arrcostab (3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester); 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2 hydroxy propanoic acid methyl esters, the 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid propyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, the 2-beta-hydroxymethyl butyrate, the 2-3-hydroxyethyl butyrate; Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, acetic acid methyl cellosolve, acetate ethyl cellosolve, diethylene glycol monomethyl ether, methyl proxitol acetate; Ketone, for example MEK, methyl isobutyl ketone, cyclohexanone, cyclohexanol, 2-heptanone, 3-heptanone etc.; Arene, for example toluene, dimethylbenzene.In these solvents, as the solvent among the present invention, preferably use 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, acetate ethyl cellosolve, ethyl lactate, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, ethyl carbitol acetic acid esters, acetate of butyl carbitol, methyl proxitol acetate etc.These solvents can use separately or being used in combination with two or more.

In addition, can use boiling point in case of necessity is 180 ℃～250 ℃ solvent.The example of these high boiling solvents comprises: the diethylene glycol single-butyl ether, the TC acetic acid esters, TC, 3,5,5-trimethyl-2-cyclohexene-1-ketone, butyl lactate, the DPGME acetic acid esters, propylene glycol monomethyl ether, propylene-glycol diacetate, the propylene glycol n-propyl ether acetic acid esters, diethylene glycol diethyl ether, 2-ethylhexyl acetic acid esters, 3-methoxyl-3-methyl butyl acetic acid esters, gamma-butyrolacton, tripropylene glycol ethyl methyl acetic acid ester, dipropylene glycol normal-butyl acetic acid esters, propylene glycol phenyl ether acetic acid ester, the 1,3 butylene glycol diacetate esters.

There is no particular limitation for the content of described solvent in color filter of the present invention.But the content of described solvent in pigment dispersion is preferably 10～95 quality %.

Traditional color filter has following problem: in order to realize high excitation, need make each color of pixel enriching, and people recognize and do the membrane thickness unevenness that can make pixel like this and cause color inhomogeneous.Therefore, need to suppress the change of thickness, its film thickness to pixel has a direct impact.

In color filter of the present invention, from obtaining uniform thickness and effectively prevent the uneven angle of the color that is caused by Thickness Variation, the ink-jet ink that color filter is used preferably contains suitable surfactant.

The preferred example of described surfactant is included in disclosed surfactant among patent documentation JP-A-2003-337424 and the JP-A-11-133600.There is no particular limitation to the content of described surfactant in color filter of the present invention.Yet based on the total solids content of dyed layer, the content of described surfactant is preferably 5 quality % or lower.

Preferably contain thermal polymerization inhibitor in the color filter of the present invention.The example of this thermal polymerization inhibitor comprises quinhydrones, Hydroquinone monomethylether, p methoxy phenol, BHT, pyrogallol, tert-butyl catechol, benzoquinones, 4,4 '-sulphur two (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole and phenothiazine.There is no particular limitation to the content of described thermal polymerization inhibitor in color filter of the present invention.But be based on the total solids content of dyed layer, the content of described thermal polymerization inhibitor is preferably 1 quality % or lower.

If desired, can contain ultraviolet light absorber in the color filter of the present invention.The example of ultraviolet light absorber is included in disclosed compound among the patent documentation JP-A-5-72724, salicylate class ultraviolet light absorber, benzophenone ultraviolet light absorber, benzotriazole ultraviolet light absorber, cyanoacrylate ultraviolet light absorber, nickel chelate class ultraviolet light absorber and hindered amines ultraviolet light absorber.

Its concrete example comprises the salicylic acid phenylester, 4-tert-butyl-phenyl salicylate, 2,4-di-tert-butyl-phenyl-3 ', 5 '-di-t-butyl-4 '-hydroxybenzoate, 4-tert-butyl-phenyl salicylate, 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, Octabenzone, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-cyano group-3, the 3-diphenyl-ethyl acrylate, 2,2 '-hydroxyl-4-methoxy benzophenone, nickel dibutyl dithiocarbamate, two (2,2,6,6-tetramethyl-4-pyridine)-sebacate, 4-tert-butyl-phenyl salicylate, the salicylic acid phenylester, 4-hydroxyl-2,2,6,6-tetramethyl piperidine condensation product, succinic acid-two (2,2,6,6-tetramethyl-4-piperidyl)-ester, 2-[2-hydroxyl-3, two (α, the α-Er Jiajibianji) phenyl of 5-]-the 2H-benzotriazole, 7-{[4-chloro-6-(lignocaine)-5-triazine-2-yl] amino }-3-phenyl cumarin.There is no particular limitation for the content of described ultraviolet light absorber in color filter of the present invention.But be based on the total solids content of dyed layer, the content of described ultraviolet light absorber is preferably 5 quality % or lower.

In color filter of the present invention, when the preparation dyed layer, described pigment dispersion can use with the form of ink-jet ink.Thereby preferred control ink temperature makes the amplitude of fluctuation of ink viscosity in ± 5%.Viscosity during injection is preferably 5～25mPas, and more preferably 8～22mPas is preferably 10～20mPas (in this article, if not otherwise specified, viscosity is meant the value in the time of 25 ℃) especially.Except that above-mentioned injection temperation is set, also can regulate viscosity by kind and the addition of controlling the composition that contains in the ink.Above-mentioned viscosity can be by measuring such as the device of routines such as cone-plate type rotational viscosimeter or E type viscosity meter.

From the angle of the flatness (flatness) that improves pixel, the surface tension of ink is preferably 15～40mN/m (in the present invention, if not otherwise specified, surface tension is meant the value in the time of 23 ℃) during injection.Described surface tension is 20～35mN/m more preferably, most preferably is 25～30mN/m.Can be by adding surfactant and selecting the kind of solvent for use to come the reconciliation statement surface tension.Can use that (interface science Co., Ltd. makes by consonance, CBVP-Z), full automatic balance type electron surface tensiometer ESB-V known measuring instruments such as (Co., Ltd. make by the consonance science) measures above-mentioned surface tension according to platinum plate method such as surface tension apparatus.

Injection method as above-mentioned pigment dispersion (it is as ink-jet ink for color filter), can adopt any method in the several different methods, as continuity ground spraying charged ink and utilize method that electric field controls, utilize piezoelectric element intermittently to spray the method for ink and utilize ink is heated and method that the bubble that produces intermittently sprays ink.

About being used to form the ink-jet method of each pixel (pictorial element), can adopt conventional method arbitrarily, as make the ink heat curing method, make the method for ink photocuring and on substrate, form the method for carrying out the ink instillation after the transparent image receiving layer in advance.

As inkjet head (following also abbreviate as sometimes " shower nozzle "), can use shower nozzle commonly used, as continuous injection type shower nozzle and need based jet type (dot-on-demand) shower nozzle.In need based jet type shower nozzle, be that having described in the patent documentation JP-A-9-323420 sprayed those types with movement of valve (movable bulb) preferably as hot shower nozzle (thermal head).As piezo jets, can use the shower nozzle described in (for example) patent documentation EP 277,703 A, EP 278,590 A.Preferably, shower nozzle has temp regulating function, makes it possible to control the temperature of ink.Particularly, preferably set injection temperation so that the viscosity when spraying in 5 to 25mPas scope, and preferably ink temperature is controlled so that spread of viscosity in ± 5%.In addition, preferred sprinkler is carried out work with the driving frequency of 1～500kHz.

After each pixel (pictorial element) forms, the heating steps of heat-treating (so-called oven dry processing) can be set.In heating steps, be placed in the well heater such as electric furnace, drying box and heat having the substrate that photopolymerisable layer takes place by rayed on it, perhaps shine described substrate with infrared lamp.Heat desired temperature and time and depend on the composition of photosensitive coloring composition and the thickness of formed layer.Usually, consider, preferably heated about 10 minutes～about 120 minutes down at about 120 ℃～about 250 ℃ from the angle that can obtain sufficient solvent resistance, alkali resistance and UVA degree.

Be not particularly limited for the pattern form of formed color filter thus.Therefore, it can perhaps can be grid for the bar shaped of general black matrix (black matrix) shape, perhaps is triangle.

Preferably use such manufacture method, wherein, before the step that forms pictorial element with ink-jet ink for color filter, form every rib, then with providing ink to this in the part that rib surrounded.There is no particular limitation every rib to described.Yet, when forming color filter, preferably, use have black matrix function and shaded effect every rib (following also abbreviate " every rib " as every rib) with this.Can adopt with conventional color filter and make this every rib with black matrix identical materials, method.The example of black matrix comprises: the black matrix described in [0012]～[0021] section among [0021]～[0074] section and the patent documentation JP-A-2004-240039 in patent documentation JP-A-2005-3861, and the ink-jet black matrix described in [0009]～[0044] section among [0015]～[0020] section and the patent documentation JP-A-2006-10875 among the patent documentation JP-A-2006-17980.

Above-mentioned pigment dispersion can use with the form of photosensitive composition, to form coated film.Herein " photosensitive composition " is meant the composition that contains described pigment dispersion.The thickness of described coated film can suitably be determined.Yet this thickness is preferably 0.5 μ m～5.0 μ m, more preferably 1.0 μ m～3.0 μ m.In the coated film of using photosensitive composition to form, can form the polymer coated of photosensitive composition by making monomer contained in the composition or oligomer carry out polymerization, thereby make polymer coated color filter (preparation process of color filter will be described below) with formation like this with polymerizable group.Can work by make Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system with illumination, make monomer or oligomer generation polymerization thus with polymerizable group.

Can form above-mentioned coated film by adopting known coating method colored coating photosensitive polymer combination to carry out drying subsequently.Preferably, adopt the slit-shaped nozzle that has slit at the position of discharging coating liquid to come the colored coating photosensitive polymer combination.Specifically, preferably use slit-shaped nozzle and the slot applicator described in patent documentation JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163, the JP-A-2001-310147.

As the method that photosensitive composition is coated on the substrate, from can all even angle that applies the film of 1～3 μ m accurately, whirl coating be excellent.Therefore, this method can obtain extensively general application in color filter is made.Yet, in recent years, be accompanied by the maximization and the batch process of liquid crystal indicator, need further to improve and make efficient and save manufacturing cost.Therefore, in the making of color filter, adopt ratio rotation coating process to be more suitable in the slit coating method that the wide cut large-area substrates is applied.In addition, from saving the angle of coating liquid measure, slit coating is also than rotation coating process excellence, and slit coating can obtain uniform coating with coating liquid measure still less.

Slit coating is a kind of like this coating method, it is characterized in that having following steps: adopting front end to have width is tens of microns slit (gap) and the length applicator head corresponding with the application width of rectangular substrate, and when the spacing (gap) that keeps substrate and applicator head is tens of microns～hundreds of microns, with relative velocity moving substrate and/or the applicator head of determining; And will be coated on the substrate by the coating liquid that slit provides by predetermined discharge capacity.Described slit coating method has the following advantages: (1) compare with whirl coating liquid loss less, (2) owing to do not have coating liquid and do not disperse, (sneaking into again) coated film, (4) can not polluted owing to need not to start the residence time of rotation by the liquid component that disperses in workload when therefore having reduced cleaning treatment, (3), and (tact time), (5) apply large substrate easily therefore to have shortened the productive temp time.Because the slit coating method has these advantages, so the color filter used of its liquid crystal indicator that is suitable for preparing large-scale picture, and the slit coating method also is expected to as the coating method that is used to reduce the liquid coating amount.

Slit coating can form area more than the big coated film of whirl coating.Therefore, when coating liquid is discharged in slit outlet leniently, must make the relative velocity that keeps between applicator and the quilt material that is coated with to a certain degree.Therefore, the coating liquid that uses in the slit coating method requires to have good flowability.In addition, in slit coating, the various conditions that especially require to be provided to the coating liquid on the substrate from the slit of applicator head keep constant at the entire coating width.If such as solution physical property deficiencies such as flowability that applies liquid and viscoelasticity, the uneven problem of coating then takes place easily, thereby be difficult to keep constant applied thickness in the application width direction.Thus, apply the problem that inhomogeneous meeting causes being difficult to obtain uniform coated film.

In view of above situation,, flowability and viscoelastic property that different research improves coating liquid have been carried out in order there not to be the even coated film of non-uniform phenomenon.As mentioned above, proposed such as the molecular weight that reduces polymkeric substance, be chosen in the polymkeric substance of the dissolubility excellence in the solvent, in all kinds of solvents, select and used multiple means such as surfactant in order to control velocity of evaporation.Yet these means all can not fully be improved above-mentioned variety of issue.

Can provide photo-sensitive resin by using above-mentioned photosensitive composition, thus the preparation photosensitive resin transfer material.Described photosensitive resin transfer material preferably uses composite membrane to form, and it is similar to the photosensitive resin transfer material described in the patent documentation JP-A-5-72724.The structure of this composite membrane can be that (for example) is provided with interim stilt, thermoplastic resin, middle layer, photo-sensitive resin and diaphragm and the laminate structures that obtains successively.

Interim stilt must have flexible, even and also can not produce significant deformation, contraction or elongation under the condition of pressurization or heating and pressurizing.The example of this interim stilt comprises: polyethylene terephthalate film, tri cellulose acetate membrane, polystyrene film and polycarbonate membrane.Wherein preferred especially biaxial stretch-formed polyethylene terephthalate film.

The composition that uses in the thermoplastic resin is preferably the organic polymer material described in the patent documentation JP-A-5-72724.Described material is about 80 ℃ or lower organic polymer material by the softening point that dimension block-regulations (specifically, being the method for measuring the polymkeric substance softening point according to U.S. material test method ASTMD1235) records more preferably.Specifically, described material can be organic polymer, and its example comprises: polyolefin, as tygon or polypropylene; Ethylene copolymer is as the multipolymer of ethene and vinyl acetate or its saponification resultant; The multipolymer of ethene and acrylate or its saponification resultant; Polyvinylchloride; Vinyl chloride copolymer is as the multipolymer of vinyl chloride and vinyl acetate or its saponification resultant; Polyvinylidene chloride; Polyvinylidene chloride copolymer; Polystyrene; Styrol copolymer is as the multipolymer of styrene and (methyl) acrylate or its saponification resultant; Polyvinyl toluene; Vinyl toluene copolymer is as the multipolymer of vinyltoluene and (methyl) acrylate or its saponification resultant; Poly-(methyl) acrylate; (methyl) acrylate copolymer is as the multipolymer of (methyl) butyl acrylate and vinyl acetate; And polyamide, as vinyl acetate-nylon copolymer, copolymer nylon, N-alkoxy methyl nylon and N-dimethylamino nylon.

In photosensitive resin transfer material, the middle layer preferably is set, so that prevent the mixing of composition when when applying a plurality of overlay and after coating, preserving.This middle layer is preferably the oxygen Obstruct membrane of describing as " separating layer " among the patent documentation JP-A-5-72724 with the function that intercepts oxygen.By using such oxygen Obstruct membrane, exposure sensitivity can improve, and the time load of exposure machine can reduce, and throughput rate can improve.

It is low and can be dispersed or dissolved in film in water or the alkaline aqueous solution that described oxygen Obstruct membrane is preferably the oxygen permeability.Such film can suitably be selected from known oxygen Obstruct membrane.Wherein, the combination of the special pure and mild polyvinylpyrrolidone of preferably polyethylene.

Thin diaphragm preferably is set, so that the protection photo-sensitive resin is avoided polluting and damage when storing on photo-sensitive resin.Described diaphragm can comprise and the interim identical or materials similar of stilt, but diaphragm should separate with photo-sensitive resin easily.The material of diaphragm can be (for example) organosilicon paper, polyolefin sheets or polytetrafluoroethylsheet sheet.

Described photosensitive resin transfer material can prepare in the following manner: coating wherein is dissolved with also dry this coating liquid of coating liquid (the coating liquid that thermoplastic resin is used) of thermoplastic resin additive therefor to form thermoplastic resin on interim stilt, coating contains the not middle layer of the solvent of heat of solution plastic resin layer coating liquid on thermoplastic resin then, and dry this middle layer is with applying liquid, adopt the photo-sensitive resin that contains the solvent that does not dissolve the middle layer to apply the middle layer then, and dry this photo-sensitive resin is with applying liquid with coating liquid.

Can be for another mode of selecting for use; can prepare described photosensitive resin transfer material in the following manner: prepare the sheet material that wherein above-mentioned interim stilt is provided with thermoplastic resin and middle layer; and wherein diaphragm is provided with the sheet material of photo-sensitive resin; and sheet material is bonding mutually, make middle layer and photo-sensitive resin contact with each other.Also can prepare described photosensitive resin transfer material in the following manner: prepare the sheet material that wherein above-mentioned interim stilt is provided with thermoplastic resin; and wherein diaphragm is provided with the sheet material in photo-sensitive resin and middle layer; and sheet material is bonded to each other, make thermoplastic resin and middle layer contact with each other.

In described photosensitive resin transfer material, the thickness of photo-sensitive resin is preferably 1.0～5.0 μ m, and more preferably 1.0～4.0 μ m are preferably 1.0～3.0 μ m especially.Usually, the thickness of interim stilt is preferably 15～100 μ m, and the thickness of thermoplastic resin is preferably 2～30 μ m, and the thickness in middle layer is preferably 0.5～3.0 μ m, and the thickness of diaphragm is preferably 4～40 μ m.Yet the thickness of each layer is not limited in the above-mentioned scope.

Can utilize known applying device to carry out coat operations in the said method.In the present invention, the preferred employing uses the applying device (slot applicator) of slit-shaped nozzle to carry out coat operations.The preferred example of slot applicator as mentioned above.

According to final use, color filter of the present invention can only have a kind of tone, perhaps has three kinds of different tones such as red, green, blue, perhaps has four kinds of different tones that further comprise black.To dyed layer on substrate pattern and form described method of patterning and be not particularly limited.

Color filter of the present invention can be as the color filter of contrast excellence.For the color filter between two polarization plates, the term of Shi Yonging " contrast " is meant that the ratio of the light transmission capacity when light transmission capacity when polarization axle is parallel is vertical with polarization axle is (referring to for example document The7th Color Optics Conference 1990 in the present invention; Color Filter for 512-color 10.4 "-size TFT-LCDUeki, Koseki, Fukunaga, Yamanaka).

Height difference when the color filter with high-contrast can make this color filter and liquid crystal combination becomes big.Therefore, strengthening LCD to aspect CRT substituting, high-contrast is very important performance.The contrast of color filter of the present invention is preferably 3,000 or higher when monochrome, and more preferably 5,000 or higher, be preferably 7,000 or higher especially.For containing R pixel, G pixel and B pixel and also being provided with the color filter of black matrix as required, contrast is preferably 3,000 or higher, and more preferably 5,000 or higher, be preferably 6,000 or higher especially.The invention is characterized in and to realize above-mentioned high-contrast thus.

When color filter of the present invention is used as the television monitoring color filter, at poor (the Δ E) of the target colourity of the colourity of the redness of measuring under the F10 light source (R) photo-sensitive resin and the redness shown in the following table, be preferably 5 or lower respectively at poor (the Δ E) of the target colourity of the colourity of poor (the Δ E) of the target colourity of the colourity of the green of measuring under the F10 light source (G) photo-sensitive resin and the green shown in the following table and blueness (B) photo-sensitive resin under the F10 light source, measured and the blueness shown in the following table, more preferably 3 or lower, also more preferably 2 or lower.

x y Y

----------------------------

R 0.656 0.336 21.4

G 0.293 0.634 52.1

B 0.146 0.088 6.90

----------------------------

Here, colourity among the present invention utilizes microscope spectrophotometer (to be made by Olympus Optical society, OSP100 or 200) measure, and represent with the xyY value of xyz colour system, wherein said xyY value is to obtain by the result under the condition at F10 light source, 2 degree visual angles is calculated.In addition, the difference of itself and target colourity is with La ^*b ^*The aberration of colour system is represented.

The process that can repeat may further comprise the steps by (for example), make color filter of the present invention until the such method of layer that forms each color, described step is: on substrate, form photo-sensitive resin, and exposure, and photo-sensitive resin is developed.As required, also can introduce the border that black matrix is distinguished described photo-sensitive resin.

In above-mentioned manufacture method, can on substrate, form described photo-sensitive resin by (for example) following method, described method is: (a) adopt known applying device to apply each above-mentioned photosensitive composition, perhaps (b) utilizes above-mentioned photosensitive resin transfer material, thereby adheres to photo-sensitive resin by laminating machine.

When making color filter of the present invention, can adopt any known applying device to apply photosensitive composition.Wherein especially preferably use the slit coating machine.The preferred example of slit coating machine as mentioned above.When by coating when forming photo-sensitive resin, its film thickness is preferably 1.0～3.0 μ m, 1.0～2.5 μ m more preferably, also 1.5～2.5 μ m more preferably.

Utilizing under the situation of photosensitive resin transfer material, can adopt through the roller of heating and/or pressurization or dull and stereotyped by pressing or add hot pressing and adhere on the substrate with forming membranaceous photo-sensitive resin.Specifically, can use laminating machine described in the following patent documentation and laminating method, described patent documentation is: JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836 and JP-A-2002-148794.From suppressing the angle of foreign substance pollution, preferably adopt the method described in the patent documentation JP-A-7-110575.

In color filter of the present invention, when when applying described photosensitive composition and form described photo-sensitive resin, can the oxygen Obstruct membrane be set further on this photo-sensitive resin, can improve its exposure sensitivity thus.As the oxygen Obstruct membrane, can enumerate foregoing film.There is no particular limitation to the thickness of oxygen Obstruct membrane, but it is preferably 0.5～3.0 μ m usually.

The process that can repeat may further comprise the steps by (for example), make color filter of the present invention until the such method of resin bed that forms each color, described step is: be formed at photo-sensitive resin on the substrate above predetermined mask is set, then photo-sensitive resin is exposed to from mask top and sees through under the light in this mask, thermoplastic resin and middle layer, then photo-sensitive resin is developed with developer.

The light source that is used to expose can suitably be selected from the light source that can launch the light (for example 365nm, 405nm etc.) in the wavelength coverage that makes photo-sensitive resin curing.Its object lesson comprises: extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp and metal halide lamp.Exposure is generally about 5～200mJ/cm ², be preferably about 10～100mJ/cm ²

There is no particular limitation to described developer, and can be known developer, the developer described in patent documentation JP-A-5-72724.In addition, described developer is preferably the uncured such developer of photo-sensitive resin of dissolving when developing; For example, preferably contain the developer that when concentration is 0.05～5mol/L pKa is 7～13 compound.Described developer can also contain on a small quantity can be miscible with water organic solvent.

Can comprise with the miscible representative examples of organic of water: methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol, butanols, diacetone alcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzylalcohol, acetone, MEK, cyclohexanone, 6-caprolactone, gamma-butyrolacton, dimethyl formamide, dimethyl acetamide, hexamethyl phosphoramide, ethyl lactate, methyl lactate, epsilon-caprolactams, N-Methyl pyrrolidone.The concentration of this organic solvent is preferably 0.1 quality %～30 quality %.

In described developer, can also add known surfactant.This surfactant concentrations is preferably 0.01 quality %～10 quality %.

The method of developing can be to develop (paddle development), spray development, spray ﹠amp such as stirring; The known method of rotation development or immersion development and so on.

Herein, above-mentioned spray development is described.In spray develops, adopt spray thrower that developer is ejected on the photo-sensitive resin after the exposure, to remove uncured part.Preferably, before development, use the injection alkaline solutions lower such as spray thrower, to remove thermoplastic resin and middle layer to the dissolubility of photo-sensitive resin.After development, preferably, spray detersive etc. with spray thrower, in addition simultaneously with wipe surfaces such as brushes, to remove the development residue.

The fluid temperature of developer is preferably 20 ℃～40 ℃, and the pH of developer is preferably 8～13.

In embodiments of the invention, when making color filter of the present invention, as described in patent documentation JP-A-11-248921 and the Jap.P. No.3255107, the photosensitive composition that forms color filter is stacked to form matrix, on this matrix, form transparency electrode, and projection that division alignment uses is set thereon to form spacer.From the angle that reduces cost, this embodiment is preferred.

When by carrying out coat operations successively with photosensitive composition when stacked, owing to the levelling of coating liquid makes all attenuation of thickness of each overlapping caudacoria.Therefore, preferably that these 4 kinds of colors of K (black), R, G and B are stacked, and the projection of isolating orientation usefulness is set thereon.On the other hand, use when having the transfer materials of thermoplastic resin, preferably pile up 2 or 3 kind of color, constant because its thickness can keep.

In order to prevent that photo-sensitive resin deforms when laminated being undertaken by stacked transfer materials, and make it to keep constant thickness, described matrix to be preferably dimensioned to be 25 μ m * 25 μ m or bigger, be preferably 30 μ m * 30 μ m or bigger especially.

Owing to used the color filter of contrast excellence of the present invention, so liquid crystal indicator of the present invention has excellent sharpness, as the black degree of depth.Liquid crystal indicator of the present invention also is suitable as the liquid crystal indicator of giant-screen, as notebook computer with display and TV monitor.

As mentioned above, the pigment dispersion that uses in the preferred color filter of the present invention contains pigment particle.More preferably, form (separating out) described pigment particle by the following method, described method is: with organic pigment be dissolved in formed organic pigment solution in the good solvent, with having compatibility with good solvent but mix (hereinafter also this method being called " particulate deposition method " sometimes) as the solvent of the poor solvent of organic pigment (hereinafter also this solvent is called " poor solvent of organic pigment " sometimes, or abbreviate as " poor solvent ").In this respect, poor solvent and the good solvent selecting to be used to make up must show sufficient difference in solubility to organic pigment, and must select appropriate solvent according to used pigment.Yet, can adopt solvent combination arbitrarily, as long as they can implement above-mentioned steps.

There is no particular limitation for the poor solvent of organic pigment, if its can with miscible or even mixing of good solvent that is used to dissolve organic pigment.For the poor solvent of organic pigment, the preferred solubleness of organic pigment in this poor solvent is 0.02 quality % or lower, 0.01 quality % or lower more preferably.The solubleness of organic pigment in poor solvent does not have specific lower limit, if but consider normally used organic pigment, then practical is that this solubleness is 0.000001 quality % or higher.This solubleness also can be organic material have acid or alkali in the presence of solubleness when dissolving.In addition, compatibility between good solvent and the poor solvent or even Combination make the meltage of good solvent in poor solvent be preferably 30 quality % or higher, more preferably 50 quality % or higher.The meltage of good solvent in poor solvent do not have specific upper limit, but practical is, these solvents can mix mutually with ratio arbitrarily.

The example of poor solvent comprises that aqueous solvent (for example, water, hydrogeneous alcohol (hydricalcohol), hydrochloric acid and sodium hydrate aqueous solution), alcohol compound solvent, ketone compounds solvent, ether compound solvent, aromatic compound solvent, carbon disulphide solvent, fatty compound solvent, nitrile compounds solvent, halogen-containing compounds solvent, ester type compound solvent, ionic liquid, and their mixed solvent.The preferred example of poor solvent comprises: aqueous solvent, alcohol compound solvent, ketone compounds solvent, ether compound solvent, ester type compound solvent and their mixed solvent; The preferred example of poor solvent comprises aqueous solvent, alcohol compound solvent and ester type compound solvent.

The example of alcohol compound solvent comprises methyl alcohol, ethanol, isopropyl alcohol, n-propanol, 1-methoxyl-2-propyl alcohol etc.The example of ketone compounds solvent comprises acetone, MEK, methylisobutylketone, cyclohexanone etc.The example of ether compound solvent comprises dimethyl ether, diethyl ether, tetrahydrofuran etc.The example of aromatic compound solvent comprises benzene, toluene etc.The example of fatty compound solvent comprises hexane etc.The example of nitrile compounds solvent comprises acetonitrile etc.The example of halogen contained compound solvent comprises methylene chloride, triclene etc.The example of ester type compound solvent comprises ethyl acetate, ethyl lactate, acetate 2-(1-methoxyl) propyl ester etc.The example of ionic solvent comprises 1-butyl-3-methylimidazole and PF ₆ ^-Salt etc.

There is no particular limitation to good solvent, as long as it can dissolve employed organic pigment, and can be miscible with above-mentioned poor solvent or get final product even the mixing.About the solubleness of organic pigment in good solvent, the solubleness of organic pigment is preferably 0.2 quality % or higher, more preferably 0.5 quality % or higher.Do not have the special upper limit for the solubleness of organic pigment in good solvent, but consider the organic material of common employing, practical is that this solubleness is 50 quality % or lower.The solubleness of this solubleness when also can be organic material dissolve under the condition that acid or alkali exist.Compatibility between good solvent and the poor solvent or even blended preferable range are as mentioned above.

The example of good solvent comprises alcohol compound solvent, amides compound solvent, ketone compounds solvent, ether compound solvent, aromatic compound solvent, carbon disulphide solvent, fatty compound solvent, nitrile compounds solvent, sulfoxide compound solvent, halogen-containing compounds solvent, ester type compound solvent, ionic liquid and their mixed solvent etc.Among these solvents, preferred alcohols compounds solvent, ketone compounds solvent, ether compound solvent, sulfoxide compound solvent, ester type compound solvent, amides compound solvent and their mixed solvent; More preferably alcohol compound solvent, ester type compound solvent, sulfoxide compound solvent and amides compound solvent; And preferred especially sulfoxide compound solvent and amides compound solvent.

The example of sulfoxide compound solvent comprises dimethyl sulfoxide (DMSO), diethyl sulfoxide, hexa-methylene sulfoxide and sulfolane.The example of amides compound solvent comprises N, dinethylformamide, 1-Methyl-2-Pyrrolidone, 2-Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 2-Pyrrolidone, epsilon-caprolactams, formamide, N-NMF, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl propanamide and HMPA etc.

In addition, organic pigment is dissolved in the good solvent and the concentration of the organic pigment solution that makes is preferably: the saturation concentration of organic pigment in good solvent is to about 1/100 of this saturation concentration under the condition when dissolving.

There is no particular limitation for the preparation condition of organic pigment solution, and can be selected from from condition of normal pressure to subcritical, super critical condition.In the situation of preparation solution, temperature is preferably-10 ℃～150 ℃ under normal pressure, more preferably-5 ℃～130 ℃, be preferably 0 ℃～100 ℃ especially.

Though it is overlapping that the example of above-mentioned good solvent and the example of poor solvent have, can not select with a kind of solvent simultaneously as good solvent and poor solvent.Can adopt any solvent with the form of combination, as long as the stand-by solubleness of organic material in good solvent is fully greater than its solubleness in poor solvent.Particularly, the difference of the solubleness between them is preferably 0.2 quality % or higher, more preferably 0.5 quality % or higher.The upper limit for the difference of the solubleness between good solvent and poor solvent is not particularly limited.If yet consider normally used organic material, in fact be somebody's turn to do and be limited to 50 quality % or lower.

In above-mentioned particulate deposition method, preferred organic pigment is dissolved in the good solvent equably, and further preferred organic pigment dissolves when acid or alkaline at solvent.Usually, in molecule, have under the situation of organic pigment of the group that can under alkali condition, dissociate, use basic solvent, and in molecule, do not have the group that can under alkali condition, dissociate but have in the molecule under the situation of organic pigment of many nitrogen-atoms (it is easy in conjunction with proton), use acid flux material.For example, quinacridone compounds pigment, Diketopyrrolo-pyrrole compounds class pigment and condensation bis-azo compound class pigment dissolved are in alkali condition, and phthalocyanine compound class pigment dissolved is in acid condition.

The example that is dissolved in spendable alkali under the situation of basic solvent at organic pigment comprises: inorganic base, for example lithium hydroxide, NaOH, potassium hydroxide, calcium hydroxide and baryta hydrate; And organic base, as trialkylamine, diazabicyclo hendecene (DBU) and metal alkoxide.Preferred inorganic base.

Amount to stand-by alkali is not particularly limited, as long as the amount of alkali can make pigment dissolve equably.Under the situation of using inorganic base, for organic pigment, the amount of alkali is preferably 1.0 molar equivalent to 30 molar equivalents, more preferably 1.0 molar equivalent to 25 molar equivalents, more preferably 1 molar equivalent to 20 molar equivalent.Under the situation of using organic base, for organic pigment, the amount of alkali is preferably 1.0 molar equivalent to 100 molar equivalents, more preferably 5.0 molar equivalent to 100 molar equivalents, more preferably 20 molar equivalent to 100 molar equivalents.

The example that is dissolved in the acid of using under the situation of acid flux material at organic pigment comprises: mineral acid, for example sulfuric acid, hydrochloric acid and phosphoric acid; And organic acid, for example acetate, trifluoroacetic acid, oxalic acid, methane-sulforic acid and trifluoromethanesulfonic acid.Wherein, mineral acid is preferred, and sulfuric acid is particularly preferred.

Amount to acid to be used is not particularly limited, as long as the amount of acid can make organic pigment dissolve equably.In many cases, the amount of the acid of use greater than or far above the amount of alkali.No matter the kind of acid is mineral acid or organic acid, for organic pigment, the amount of acid to be used is preferably 3 molar equivalent to 500 molar equivalents, more preferably 10 molar equivalent to 500 molar equivalents, more preferably 30 molar equivalent to 200 molar equivalents.

When alkali or acid mix with organic solvent and use this potpourri as the good solvent of organic pigment, can dissolve fully in order to make alkali or acid, can in organic solvent, add a spot of to alkali or sour solvent (as water or lower alcohol) with highly dissoluble.For the total amount of organic pigment solution, the amount of water or lower alcohol is preferably 50 quality % or lower, perhaps 30 quality % or lower more preferably.Its operable object lesson comprises water, methyl alcohol, ethanol, n-propanol, isopropyl alcohol and butanols.

There is no particular limitation for the used condition of poor solvent when separating out organic pigment, and can select from condition of normal pressure to subcritical, super critical condition.The temperature of separating out organic granular under the normal pressure is preferably-30 ℃～100 ℃, more preferably-10 ℃～60 ℃, be preferably 0～30 ℃ especially.The viscosity that contains the liquid of the pigment particle that is settled out is preferably 0.5～80.0mPas, more preferably 1.0～50.0mPas.

When organic pigment solution is mixed with poor solvent, can be with wherein any one adds among another person and mixes.But, preferably mix, and also preferred poor solvent is in the state that is stirred when mixing by organic pigment solution is joined in the poor solvent.Stirring rate is preferably 100～10,000rpm, and more preferably 150～8,000rpm is preferably 200～6,000rpm especially.Can use during interpolation also and can not use pump etc.As adding method, can adopt the method for in a kind of liquid, adding another kind of liquid, perhaps adopt the method for outside a kind of liquid, adding another kind of liquid, but preferred method of in a kind of liquid, adding another kind of liquid.In the present invention, preferably use pump, by supply pipe one in the liquid is supplied in the another kind of liquid continuously.Preferred 0.1mm～the 200mm of the internal diameter of supply pipe, more preferably 0.2～100mm.The speed of supplying with to another kind of liquid from supply pipe is preferred 1～10,000mL/min, more preferably 5～5,000mL/min.

With regard to volume ratio, the mixing ratio of organic pigment solution and poor solvent (ratio that contains the good solvent/poor solvent in the liquid of the pigment particle that is settled out) is preferably in 1/50～2/3 scope, more preferably in 1/40～1/2 scope, be preferably especially in 1/20～3/8 scope.

There is no particular limitation to the pigment concentration in the liquid that contains the pigment particle that is settled out, as long as can make organic granular, but for every 1000mL dispersion solvent, the amount of organic granular is preferably 10～40, in the scope of 000mg, more preferably 20～30, in the scope of 000mg, be preferably especially 50～25, in the scope of 000mg.

Preparative-scale during for the preparation pigment particle is not particularly limited.Yet preparative-scale is preferably and makes that the amount of poor solvent to be mixed is 10～2,000L, more preferably 50～1,000L.

About the particle diameter of organic granular, can the average-size of one group of particle be quantized by multiple determination method.Parameter commonly used for example for characterize the peaked diameter the most frequently that distributes, corresponding to the median diameter of integration frequencies distribution curve intermediate value and various mean diameter (number average, length is average, area is average, weight average, volume mean diameter etc.) etc.In the present invention, unless otherwise specified, otherwise particle diameter is meant number average diameter.The particle diameter of pigment particle (primary granule) is preferably 1nm～1 μ m, 1～100nm more preferably, and more preferably 5～80nm is preferably 5～50nm especially.Described organic granular can be the potpourri of crystal grain, amorphous granular or these particles, or is in the state of solid solution.Also preferably the organic granular of two or more coexists and forms the situation of potpourri or solid solution and the situation that organic granular has so-called core/shell type structure (wherein, on the surface of described particle, evenly being formed with the layer that is formed by another material).

In addition, unless specialize in the present invention, otherwise use the index of the ratio (Mv/Mn) of volume mean diameter (Mv) and number average diameter (Mn) as the monodispersity (particle size was all once) of expression particle.Single dispersion degree of pigment particle (primary granule) (being Mv/Mn) is preferably 1.0～2.0, and more preferably 1.0～1.8, be preferably 1.0～1.5 especially.

The example of measuring the method for organic granular particle diameter comprises: microscopic method, gravimetric method, light scattering method, light block method, electric-resistivity method, acoustic method and dynamic light scattering method.Wherein, microscopic method and dynamic light scattering method are particularly preferred.The microscopical example that uses in the microscopic method comprises scanning electron microscope and transmission electron microscope.Example according to the particle determinator of dynamic light scattering method comprises Nanotrac UPA-EX150 (trade name) that is produced by NIKKISO Co., Ltd. and the dynamic light scattering photometer DLS-7000 series (trade name) of being produced by OTSUKA ELECTRONICS Co., Ltd..

When the dispersion of preparation pigment particle, preferably to wherein introducing spreading agent.The step of introducing spreading agent is not particularly limited, but preferably to organic pigment solution and poor solvent the two or wherein any one in add spreading agent.In addition, also preferably when the preparation pigment particle, utilize the approach that is independent of above-mentioned two kinds of schemes to add dispersant solution.In addition, also preferred the use carried out the surface-treated pigment particle with spreading agent in advance; Can carry out to promote the surface treatment of dispersant adsorption on granules of pigments to granules of pigments.Spreading agent has following effect: (1) spreading agent is adsorbed on the surface of pigments of separating out fast, and to form fine nano particle, (2) spreading agent prevents that these particles from aggegation taking place once more.

As spreading agent, can use the low-molecular-weight or the polymeric dispersant of anionic, cationic, both sexes, nonionic or pigment derivative type.The molecular weight of used polymeric dispersant can be an arbitrary value, as long as spreading agent can be dissolved in the solution equably, but the molecular weight of polymeric dispersant is preferably 1,000～2,000,000, more preferably 5,000～1,000,000, more preferably 10,000～500,000, be preferably 10,000～100,000 especially.The example of polymeric dispersant comprises polyvinylpyrrolidone, polyvinyl alcohol (PVA), polyvinyl methyl ether, polyethylene oxide, polyglycol, polypropylene glycol, polyacrylamide, vinyl alcohol/vinyl acetate copolymer, the part formalizing thing of polyvinyl alcohol (PVA), the part butyralization thing of polyvinyl alcohol (PVA), vinyl pyrrolidone/vinyl acetate copolymer, the polyethylene oxide/propylene oxide segmented copolymer, polyacrylate, polyvinyl sulfate, poly-(4-vinylpridine) salt, polyamide, PAH salt, the condensation naphthalene sulfonate, cellulose derivative and starch derivative.In addition, can also use natural polymer, the example of natural polymer comprises alginate, gelatin, albumin, casein, Arabic gum, bassora gum and lignosulfonate.Wherein, preferably use any above-mentioned water-soluble polymers, more preferably polyvinyl pyrrolidone.These polymkeric substance can use separately or two kinds or more of being used in combination.These spreading agents can use separately or two kinds or more of being used in combination.The spreading agent that uses during pigment dispersing describes in detail in document " Dispersion Stabilization of pigment and Surface TreatmentTechnique/Evaluation " (Japan internationality chemical corps intelligence association, publish Dec calendar year 2001) 29-46 page or leaf to some extent.

The example of anionic dispersing agent (anionic surface active agent) comprises N-acyl-N-alkyltaurate, soap, alkyl sulfate, alkyl benzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinates, alkylphosphonic, naphthalene sulfonic acids/formalin condensation product and laureth sulfate.The N-acyl-N-alkyltaurate is particularly preferred.As the N-acyl-N-alkyltaurate, those that describe in patent documentation JP-A-3-273067 are preferred.These anionic dispersing agents can use separately or two or more are used in combination.

The example of cationic dispersing agent (cationic surfactant) comprises the diamines of quaternary ammonium salt, alkoxylate polyamines, fatty amine polyglycol ether, fatty amine, derived from aliphatic amine and aliphatic alcohol and polyamines, derived from the imidazoline of fatty acid and the salt of these cationic materials.These cationic dispersing agents can use separately or two kinds or more of being used in combination.

Amphoteric dispersant is to have the cation group spreading agent partly that is contained in the anionic group part that contained in the anionic dispersing agent molecule and the cationic dispersing agent molecule in its molecule.

The example of non-ionic dispersing agent (non-ionics) comprises polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl amine and fatty acid glyceride.Wherein, polyoxyethylene alkylaryl ether is preferred.These non-ionic dispersing agents can use separately or two kinds or more of being used in combination.

Pigment derivative type spreading agent is defined as derived from carrying out the spreading agent that chemical modification prepares as the organic pigment of parent material and by the structure to this fertile material, or forms reaction and the spreading agent of acquisition by the pigment precursors of chemical modification through pigment.The example of pigment derivative type spreading agent comprises: contain sugared pigment derivative type spreading agent, contain piperidyl pigment derivative type spreading agent, the pigment derivative type spreading agent that naphthalene or perylene are derived, has the pigment derivative type spreading agent that is connected the structural functional group of pigment matrix by methylene, carry out the pigment derivative type spreading agent (precursor structure) of chemical modification with polymkeric substance, has sulfonic pigment derivative type spreading agent, pigment derivative type spreading agent with sulfonamido, pigment derivative type spreading agent with ether; And pigment derivative type spreading agent with carboxylic acid group, carboxylic acid ester groups or carboxamide groups.

When preparation is dissolved in the solution of the organic pigment in the good solvent, preferably, contains amino pigment dispersing agent and organic pigment and exist simultaneously.Term as herein described " amino " comprises primary amino radical, secondary amino group and uncle's amino.Amino number can be one or more.Containing amino pigment dispersing agent can be wherein to introduce to contain amino substituent pigment derivative compound in the pigment skeleton, or by containing amino monomer as aggregating into the polymer compound that the branch polymerization forms.The example of these compounds is included in the compound described in patent disclosure JP-A-2000-239554, JP-A-2003-96329, JP-A-2001-31885, JP-A-10-339949 and the JP-B-5-72943.Yet the present invention is not limited to these compounds.

As above-mentioned spreading agent, the preferred at least a compound that uses in the compound that is selected from following general formula (D1), (D3) and formula (D4) expression.

＜1. the compound of general formula (D1) expression 〉

[Chemical formula 1]

General formula (D1)

A—N＝N—X—Y

In general formula (D1), A represents to form with X-Y the composition of azo dyes.Mentioned component A can select arbitrarily, as long as this composition can form azo dyes after carrying out coupling with diazo-compounds.The object lesson of composition A is as follows, but the present invention never is confined to these compounds.

[Chemical formula 2]

Formula 1-1 formula 1-2

Formula 1-3 formula 1-4

Formula 1-5 formula 1-6 formula 1-7

[chemical formula 3]

Formula 1-8 formula 1-9

Formula 1-10 formula 1-11 formula 1-12

In general formula (D1), X represents singly-bound or is selected from following formula (i)～(divalent linker shown in the structural formula v).

[chemical formula 4]

(ii) formula is (iii) for formula (i) formula

(iv) formula is (v) for formula

In general formula (D1), Y represents the group shown in the following general formula (D2).

[chemical formula 5]

General formula (D2)

In general formula (D2), Z represents low-grade alkylidene.In other words, Z can be expressed as-(CH ₂) _b-, b represents 1～5 integer, is preferably 2 or 3.In general formula (D2) ,-NR ₂₁Expression low-grade alkyl amino or contain 5 yuan or 6 yuan of saturated heterocyclyls of nitrogen-atoms.At described-NR ₂₁During the expression low-grade alkyl amino, low-grade alkyl amino can be expressed as-N (C _rH _2r+1) ₂, wherein r represents 1～4 integer, preferably represents 1 or 2.At described-NR ₂₁When expression contained 5 yuan of nitrogen-atoms or 6 yuan of saturated heterocyclyls, this heterocyclic radical was preferably any one heterocyclic radical that following structural formula is represented.

[chemical formula 6]

Pyridine ring piperidine ring morpholine ring

In above-mentioned general formula (D2), Z reaches-NR ₂₁Can randomly have low alkyl group separately or have alkoxy as substituting group.In above-mentioned general formula (D2), a represents 1 or 2, preferably represents 2.

The object lesson of the compound of above-mentioned general formula (D1) expression is as follows, but the present invention never is confined to these object lessons.

[chemical formula 7]

[chemical formula 8]

[chemical formula 9]

[Chemical formula 1 0]

The compound of general formula (D1) expression can be by synthesizing in the method described in (for example) patent documentation JP-A-2000-239554.

＜2. the compound of general formula (D3) expression 〉

[Chemical formula 1 1]

General formula (D3)

In general formula (D3), Q represents to be selected from the residue of the organic dyestuff in anthraquinone compounds dyestuff, azo-compound dyestuff, phthalocyanine compound dyestuff, quinoline a word used for translation ketonic compound dyestuff, dioxazine compound dyestuff, anthracene pyrimidine compound dyestuff, anthanthrone compound dyestuff, indanthrone compound dyestuff, yellow anthrone compound dyestuff, the pyranthrone compound dyestuff, perylene ketonic compound dyestuff, perylene compound dye well thioindigo compound dyestuff.In these organic dyestuff, preferred azo-compound dyestuff is with the dioxazine compound dyestuff.More preferably azo-compound dyestuff.

X ₁Expression-CO-,-CONH-Y ₂-,-SO ₂NH-Y ₂-or-CH ₂NHCOCH ₂NH-Y ₂-.X ₁Be preferably-CO-,-CONH-Y ₂-.

Y ₂Expression can have substituent alkylidene or arlydene separately.In these groups, preferred phenylene, methylene phenyl and hexylidene.More preferably phenylene.

R ₁₁And R ₁₂Expression independently of one another replaces or unsubstituted alkyl, or R ₁₁And R ₁₂Can in conjunction with and form the heterocyclic radical contain nitrogen-atoms at least.In these groups, preferable methyl, ethyl, propyl group or contain the pyridine radicals of nitrogen-atoms.More preferably ethyl.

Y ₁Expression-NH-or-O-.

Z ₁Group shown in expression hydroxyl or the general formula (D3a), condition are to be 1 o'clock at n1, Z ₁Can be-NH-X ₁-Q.M1 represents 1～6 integer, preferred 2～3.N1 represents 1～4 integer, preferred 1 or 2.

[Chemical formula 1 2]

General formula (D3a)

In general formula (D3a), Y ₃Expression-NH-or-O-, and m1, R ₁₁And R ₁₂Identical with its implication in general formula (D3).

The compound of general formula (D3) expression specifically uses (for example) following general formula to represent.

[Chemical formula 1 3]

General formula (D3-1)

General formula (D3-2)

General formula (D3-3)

General formula (D3-4)

General formula (D3-5)

General formula (D3-6)

In general formula (D3-1)～(D3-6), Q, m1, n1, R ₁₁And R ₁₂Identical with its implication in general formula (D3).The object lesson of compound is as follows shown in the general formula (D3), but is not intended that the invention be limited to this.In following example, Cu-Pc represents copper phthalocyanine.

[Chemical formula 1 4]

[Chemical formula 1 5]

The compound of general formula (D3) expression can (for example) obtain by making the reaction of dye composition and intermediate, and wherein said intermediate is to make to have R ₁₁And R ₁₂Amines and have a R ₁₁And R ₁₂Alcoholic compound and halogenation triaizine compounds react and obtain.In addition, the disclosure that can also refer to Patent Document JP-B-5-72943 is synthesized above-claimed cpd.

＜3. contain the pigment dispersing agent of graft copolymer 〉

When preparing above-mentioned pigment particle by deposition method, also preferred the use contained graft copolymer with amino and ether and the spreading agent that also contains other compositions of suitable selection in case of necessity.

Above-mentioned graft copolymer has amino and ether at least, and the monomer that can contain other is as copolymerization units.

The weight-average molecular weight of above-mentioned graft copolymer is preferably 3,000～100, and 000, more preferably 5,000～50,000.If above-mentioned weight-average molecular weight is too small, then be difficult to prevent the aggegation of pigment particle, this causes viscosity to rise sometimes.If above-mentioned weight-average molecular weight is too high, the dissolubility deficiency in organic solvent then, this causes viscosity to rise sometimes.

The polymerizable monomer that preferred above-mentioned graft copolymer contains (i) end at least and has the polyreactive oligomers of ethylenical unsaturated double bonds, (ii) has the monomer of amino and ethylenical unsaturated double bonds and (iii) have ether is as copolymer unit, in case of necessity this graft copolymer also can contain (iv) other monomer as copolymer unit.

The content of each copolymer unit in above-mentioned graft copolymer is as follows: the content of polyreactive oligomers (i) is preferably 15～98 quality %, more preferably 25～90 quality %; Contain amino monomer content (ii) and be preferably 1～40 quality %, more preferably 5～30 quality %; Polymerizable monomer content (iii) with ether is preferably 1～70 quality %, more preferably 5～60 quality %.

If the content of above-mentioned polyreactive oligomers is low excessively, then almost can not obtains the steric repulsion effect that should reach, and be difficult to prevent the aggegation of pigment particle sometimes by spreading agent.If the content of polyreactive oligomers is excessive, the then above-mentioned ratio that contains amino monomers reduces relatively, to such an extent as to the adsorptive power of organic granular is reduced, and dispersiveness becomes not enough sometimes.If the above-mentioned content that contains amino monomers is too small, then, the adsorptive power to organic granular make dispersiveness become not enough sometimes owing to reducing.If it is excessive to contain the content of amino monomers, then the ratio of above-mentioned polyreactive oligomers descends relatively, to such an extent as to almost can not obtain the steric repulsion effect that should reach by spreading agent, and be difficult to fully prevent the aggegation of organic fine particles sometimes.If the content of above-mentioned polymerizable monomer with ether is low excessively, then development adaptability becomes not enough sometimes when making device such as color filter.If have the too high levels of the polymerizable monomer of ether, then the ability as spreading agent descends sometimes.

(i) polyreactive oligomers

Above-mentioned polyreactive oligomers (hereinafter being sometimes referred to as " macromonomer ") comprises the group with ethylenical unsaturated double bonds at two end (end) or an end.In above-mentioned polyreactive oligomers, preferred this oligomer only comprises the group with ethylenical unsaturated double bonds on the end in two end among the present invention.

As above-mentioned oligomer, can enumerate the homopolymer or the multipolymer that form by at least a monomer in the monomer that is selected from (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, styrene, vinyl cyanide, vinyl acetate and butadiene and so on.In these oligomer, homopolymer or the multipolymer and the polystyrene of preferred (methyl) alkyl acrylate.In the present invention, these oligomer can further be substituted.This substituting group is not particularly limited; Can enumerate halogen atom as substituent example.

Above-mentioned example with group of ethylenical unsaturated double bonds comprises (methyl) acryloyl group and vinyl.In these groups, preferred especially (methyl) acryloyl group.

In these used polyreactive oligomerses of the present invention, be preferably the oligomer of following general formula (E6) expression.

[Chemical formula 1 6]

General formula (E6)

In above-mentioned general formula (E6), R ⁶¹And R ⁶³Represent hydroxyl or methyl respectively.R ⁶²The alkylidene that expression has 1～8 carbon atom and can be replaced by alcoholic extract hydroxyl group, and R ⁶²Preferred expression has the alkylidene of 2～4 carbon atoms.Y ⁶The expression phenyl, have phenyl that carbon number is 1～4 alkyl or-COOR ⁶⁴(R ⁶⁴The expression carbon number is 1～6 and the alkyl that can be replaced by alcoholic extract hydroxyl group or halogen atom; Phenyl; Or carbon number is 7～10 aralkyl); And Y ⁶Preferred expression phenyl or-COOR ¹⁶⁴(R ¹⁶⁴The expression carbon number be 1～4 and the alkyl that can be replaced by alcoholic extract hydroxyl group).Q represents the number in 20～200.

The object lesson of above-mentioned polyreactive oligomers comprises the multipolymer of poly-(methyl) acrylic acid 2-hydroxyl ethyl ester, polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, poly-(methyl) isobutyl acrylate and these monomers.In these polymkeric substance, preferably be combined with the polymkeric substance of (methyl) acryloyl group on its molecule end.

Described polyreactive oligomers can be the commercially available product that gets, and perhaps can suitably synthesize to obtain.The example of the commercially available product that gets comprises: single terminal methyl group propylene acidylate polystyrene oligomer (Mn=6000; trade name: AS-6; produce by TOAGOSEI Co., Ltd.); single terminal methyl group propylene acidylate polymethyl methacrylate oligomer (Mn=6000; trade name: AA-6; produce by TOAGOSEI Co., Ltd.); the positive butyl ester oligomer of single terminal methyl group propylene acidylate polyacrylic acid (Mn=6000; trade name: AB-6; produce by TOAGOSEI Co., Ltd.); single terminal methyl group propylene acidylate polymethylmethacrylate/methacrylic acid 2-hydroxyl ethyl ester oligomer (Mn=7000; trade name: AA-714; produce by TOAGOSEI Co., Ltd.); single terminal methyl group propylene acidylate poly-n-butyl methacrylate/methacrylic acid 2-hydroxyl ethyl ester oligomer (Mn=7000; trade name: 707S; produce by TOAGOSEI Co., Ltd.); and single terminal methyl group propylene acidylate polymethylacrylic acid 2-Octyl Nitrite/methacrylic acid 2-hydroxyl ethyl ester oligomer (Mn=7000; trade name: AY-707S or AY-714S are produced by TOAGOSEI Co., Ltd.).

In the present invention; the preferred object lesson of polyreactive oligomers is at least a oligomer in the multipolymer of polymkeric substance, (methyl) alkyl acrylate and polystyrene that is selected from (methyl) alkyl acrylate; the number-average molecular weight of this oligomer is 1; 000 to 20; 000, and end has (methyl) acryloyl group.

(ii) contain amino monomer

As above-mentioned amino monomer, any one in the compound that preferred example is following general formula (E2) expression of containing.

[Chemical formula 1 7]

General formula (E2)

In above-mentioned general formula (E2), R ²¹Expression hydroxyl or methyl.R ²²The expression carbon number is 1～8 alkylidene, and wherein preferred carbon number is 1～6 alkylidene, and preferred especially carbon number is 2～3 alkylidene.

X ²Expression-N (R ²³) (R ²⁴) ,-R ²⁵N (R ²⁶) (R ²⁷), wherein, R ²³And R ²⁴Represent that respectively hydrogen atom, carbon number are 1～6 alkyl or phenyl, and R ²⁵The expression carbon number is 1～6 alkylidene, and R ²⁶And R ²⁷Represent that respectively hydrogen atom, carbon number are 1～6 alkyl or phenyl.

-N (R ²³) (R ²⁴) in R ²³And R ²⁴Be preferably hydrogen atom or carbon number and be 1～4 alkyl or phenyl, and-R ²⁵-N (R ²⁶) (R ²⁷) in R ²⁵Be preferably carbon number and be 2～6 alkylidene; R ²⁶And R ²⁷Be preferably carbon number and be 1～4 alkyl.M2 and n2 represent 1 or 0 respectively.Preferred m2=1 and n2=1, or m2=1 and n2=0 (the gained monomer is corresponding to following general formula (E3) and the monomer (E4) represented).

In the present invention, in the monomer of above-mentioned general formula (E2) expression, preferably be selected from following general formula (E3) and (E4) at least a monomer in the monomer of expression.

[Chemical formula 1 8]

General formula (E3)

In above-mentioned general formula (E3), R ³¹With R ²¹Has identical implication.R ³²With R ²²Has identical implication.X ³With X ²Has identical implication.

[Chemical formula 1 9]

General formula (E4)

In above-mentioned general formula (E4), R ⁴¹And R ²¹Has identical implication.X ⁴With X ²Have identical implication, and X ⁴Be preferably-N (R ⁴³) (R ⁴⁴) (wherein, R ⁴³And R ⁴⁴With R ²³And R ²⁴Have identical implication) or-R ⁴⁵-N (R ⁴⁶) (R ⁴⁷) (wherein, R ⁴⁵, R ⁴⁶And R ⁴⁷Respectively with R ²⁵, R ²⁶And R ²⁷Has identical implication).

The preferred example of the monomer of above-mentioned general formula (E2) expression comprises: (methyl) acrylic amide, as dimethyl (methyl) acrylamide, diethyl (methyl) acrylamide, diisopropyl (methyl) acrylamide, di-n-butyl (methyl) acrylamide, diisobutyl (methyl) acrylamide, morpholinyl (methyl) acrylamide, piperidyl (methyl) acrylamide, N-methyl-2-pyrrolidinyl (methyl) acrylamide and N, N-aminomethyl phenyl (methyl) acrylamide; And aminoalkyl (methyl) acrylic amide, as 2-(N, the N-dimethylamino) ethyl (methyl) acrylamide, 2-(N, the N-diethylamino) ethyl (methyl) acrylamide, 3-(N, the N-diethylamino) propyl group (methyl) acrylamide, 3-(N, N-dimethylamino) propyl group (methyl) acrylamide, 1-(N, N-dimethylamino)-1,1-dimethyl methyl (methyl) acrylamide, 6-(N, N-diethylamino) hexyl (methyl) acrylamide.

The polymerizable monomer that (iii) has ether

As above-mentioned polymerizable monomer, preferably be selected from least a monomer in the monomer of following general formula (E1) expression with ether.

[Chemical formula 2 0]

General formula (E1)

In above-mentioned general formula (E1), R ¹¹Expression hydrogen atom or methyl.R ¹²The expression carbon number is 1～8 alkylidene, is preferably carbon number and is 1～6 alkylidene, and more preferably carbon number is 2～3 alkylidene.X ¹Expression-OR ¹³Or-OCOR ¹⁴, wherein, R ¹³Expression hydrogen atom, carbon number are 1～18 alkyl, phenyl or are the phenyl that 1～18 alkyl replaces by carbon number.R ¹⁴The expression carbon number is 1～18 alkyl.In addition, m3 represents the number in 2～200, is preferably 5～100, is preferably 10～100 especially.

There is no particular limitation to above-mentioned polymerizable monomer with ether, so long as this monomer polymerization and have ether and get final product, and this monomer can suitably be selected from conventional known monomer.Its example comprises: polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polyglycol polypropylene glycol list (methyl) acrylate and poly-1,4-butylene glycol monomethacrylates.These materials can be the commercially available products that gets, and perhaps can be those that suitably synthesize.The example of these commercially available products that get comprises: methoxy polyethylene glycol methacrylate-styrene polymer (trade name: NK ESTER M-40G, M-90G, M-230G (being made by East Asia synthetic chemical industry Co., Ltd.); Trade name: BLENMER-PME-100, PME-200, PME-400, PME-1000, PME-2000 and PME-4000 (making)) by NOF Corp, polyethylene glycol monomethacrylate (trade name: BLENMER-PE-90, PE-200 and PE-350 (making)) by NOF Corp, polypropylene glycol monomethacrylate (trade name: BLENMER-PP-500, PP-800 and PP-1000 (making)) by NOF Corp, polyglycol polypropylene glycol monomethacrylate (trade name: BLENMER-70PEP-370B (making)) by NOF Corp, polyglycol poly-1,4-butylene glycol monomethacrylates (trade name: BLENMER-55PET-800, (making) by NOF Corp) and polypropylene glycol poly-1,4-butylene glycol monomethacrylates (trade name: BLENMER-NHK-5050 (by NOF Corp's manufacturing)).

(iv) other monomer

Above-mentioned graft copolymer can also contain above-mentioned other monomer as copolymer unit.There is no particular limitation to these other monomer, and can suitably select according to purpose.The example of other monomers comprises: aromatic ethenyl compound (for example, styrene, α-Jia Jibenyixi and vinyltoluene), (methyl) alkyl acrylate (for example, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate and (methyl) isobutyl acrylate), (methyl) acrylic acid alkyl aromatic ester (for example, (methyl) benzyl acrylate), (methyl) glycidyl acrylate, vinyl esters of carboxylic acids (for example, vinyl acetate and vinyl propionate base ester), vinyl nitrile (for example, (methyl) vinyl cyanide, α-Lv Daibingxijing), the aliphatics conjugated diolefine (for example, 1,3-butadiene, isoprene) and (methyl) acrylic acid.In these monomers, preferred unsaturated carboxylic acid, (methyl) alkyl acrylate, (methyl) acrylic acid alkyl aromatic ester and vinyl esters of carboxylic acids.

The content of other monomers in the above-mentioned graft copolymer is preferably (for example) 5～70 quality %.If the content of other monomers is low excessively, then be difficult to control the physical property of coated film sometimes.If this too high levels, then graft copolymer is difficult to give full play to the ability as spreading agent sometimes.

The preferred object lesson of above-mentioned graft copolymer comprises:

(11) multipolymer of poly-(methyl) methyl acrylate of 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate,

(12) multipolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate polystyrene,

(13) multipolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/(methyl) methyl acrylate/terminal methyl group propylene acidylate polystyrene,

(14) multipolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate (methyl) methyl acrylate and methacrylic acid 2-hydroxyl ethyl ester,

(17) multipolymer of poly-(methyl) methyl acrylate of 3-(N, N-dimethylamino) propyl group acrylamide/polypropylene glycol list (methyl) acrylate/terminal methyl group propylene acidylate,

(18) multipolymer of poly-(methyl) methyl acrylate of 3-(N, N-dimethylamino) propyl group acrylamide/polyglycol polypropylene glycol list (methyl) acrylate/terminal methyl group propylene acidylate,

(19) 3-(N, N-dimethylamino) propyl group acrylamide/polyglycol gathers 1, the multipolymer of poly-(methyl) methyl acrylate of 4-butylene glycol list (methyl) acrylate/terminal methyl group propylene acidylate,

(20) 3-(N, N-dimethylamino) propyl group acrylamide/polypropylene glycol gathers 1, the multipolymer of poly-(methyl) methyl acrylate of 4-butylene glycol list (methyl) acrylate/terminal methyl group propylene acidylate.

In these multipolymers, preferred (11), (14) and (18).The more preferably compound of following formula (D4) expression.In the formula (D4), Me represents methyl.

[Chemical formula 2 1]

Formula (D4)

A:b:c=15:20:65 (mass ratio)

Can carry out the above-mentioned graft copolymer of the incompatible acquisition of radical polymerization by composition (for example) in solvent to the unit that constitutes above-mentioned multipolymer.This radical polymerization is fashionable carrying out, and can use radical polymerization initiator, in addition, can also use chain-transferring agent (for example, 2 mercapto ethanol and lauryl mercaptan).The instructions that can also refer to Patent Document JP-A-2001-31885 prepares the pigment dispersing agent that contains graft copolymer.

In order further to improve the uniformly dispersed and storage property of pigment particle, based on the pigment of 100 mass parts, the content of spreading agent is preferably 0.1～1000 mass parts, more preferably 1～500 mass parts, more preferably 5～20 mass parts.Crossing the dispersion stabilization that low content causes pigment particle sometimes can not get improving.Spreading agent can use separately, perhaps exercises with being combined into of multiple spreading agent and uses.

In order further to improve the uniformly dispersed and storage property of pigment particle, based on the organic granular of 100 mass parts, the content of spreading agent is preferably 0.1～1000 mass parts, more preferably 1～500 mass parts, more preferably 5～20 mass parts.Crossing the dispersion stabilization that low content causes organic granular sometimes can not get improving.Spreading agent can use separately, perhaps exercises with being combined into of multiple spreading agent and uses.

(concentrating)

Can carry out desalination and concentrated to the pigment particle dispersion, can be suitable for the concentrate of color filter coating liquid or ink-jet ink thus with industrial-scale production.

There is no particular limitation to method for concentration, as long as can concentrate pigment particle liquid by this method.The example of preferred method for concentration comprises: add in the pigment particle dispersion liquid and extract solvent and mixing, with the pigment particle concentration extraction to this extract solvent mutually in, and by this concentrated extracting solutions of filtration such as filtrators, thereby the method for the nano particle liquid that obtains concentrating; The method that the pigment particle sedimentation is concentrated by centrifuging; Carry out the method for desalination and concentration by ultrafiltration; The method that solvent distillation is concentrated by vacuum freeze drying; And under heating or decompression, make solvent seasoning and the method that concentrates.Alternative is that (for example) very preferably uses the combination of two or more these methods.

The concentration of the pigment particle after concentrating is preferably 1～100 quality %, and more preferably 5～100 quality % are preferably 10～100 quality % especially.

There is no particular limitation to the extraction solvent that uses in this concentration extraction process, but be preferably with the dispersion solvent of pigment particle dispersion liquid (for example, aqueous solvent) do not dissolve each other basically (unmixing) solvent (in the present invention, term " does not dissolve each other basically " and is meant that mutual solubility is low, and extract the meltage of solvent in dispersion solvent and be preferably 50 quality % or lower, more preferably 30 quality % or lower; There is not special lower limit though extract the meltage of solvent in dispersion solvent, if but consider dissolubility in conventional solvent, then the amount of this lower limit is actually 1 quality % or higher), and described extraction solvent mix with described dispersion solvent and leave standstill after can form the interface.In addition, this extraction solvent is preferably such solvent, and this solvent makes pigment particle produce redispersible so weak aggegation in extracting solvent.In the present invention, " weak redispersible aggegation " is meant and do not applying under the condition of high shear force by (for example) grinding or high-speed stirred that flocculate is redispersible.This state is preferred, because can be easily and remove apace the dispersion solvent (as water) under this state except filtering by filtrator, can also suppress to make the generation of the strong aggegation that particle diameter changes, and can be with extracting solvent with required pigment particle swelling.As extracting solvent, ester type compound solvent, alcohol compound solvent, aromatic compound solvent and fatty compound solvent are preferred; Ester type compound solvent, aromatic compound solvent and fatty compound solvent are preferred; And the ester type compound solvent is particularly preferred.

The example of ester type compound solvent comprises acetate 2-(1-methoxyl) propyl ester, ethyl acetate, ethyl lactate etc.The example of alcohol compound solvent comprises normal butyl alcohol, isobutyl alcohol etc.The example of aromatic compound solvent comprises benzene,toluene,xylene etc.The example of fatty compound solvent comprises normal hexane, cyclohexane etc.Extracting solvent can be the neat solvent of one of above-mentioned preferred solvent, also can be the mixed solvent that is formed by multiple solvent simultaneously.

The amount of extracting solvent is not particularly limited, as long as this solvent can extract pigment particle, but considers concentration extraction, the amount of extraction solvent is preferably less than the amount of pigment particle dispersion liquid.When representing with volume ratio, if the amount of pigment particle dispersion liquid is 100, the amount of the extraction solvent that is then added is preferably 1 to 100, and more preferably 10 to 90, be preferably 20 to 80 especially.Too much amount can cause concentration time to prolong, and that very few amount can cause extracting is insufficient, and residual in dispersion solvent have a nano particle.

After adding the extraction solvent, fully contact each other with dispersion liquid, preferably fully stir in order to make it.Mix the method that to use any conventional.The temperature of adding in the process of extracting solvent and mixing is not particularly limited, but is preferably 1 ℃ to 100 ℃, more preferably 5 ℃ to 60 ℃.It can use arbitrarily device to add and mix and extract solvent, as long as can implement each step suitably.For example, can use separating funnel shape device.

As the method for ultrafiltration, can use to be used to make silver halide emulsion desalination and concentrated method.The example of this method is at document Research Disclosure, those methods of describing among No.10208 (1972), No.13 122 (1975), the No.16 351 (1977) etc.Pressure differential and flow velocity as the important operation condition, can be by reference at document Haruhiko Oya, " Maku Riyo Gijutsu Handbook (Membrane Utilization TechniqueHandbook) ", Saiwai Shobo publishes (1978), the characteristic curve of describing in the 275th page is selected, but, need find the optimum condition that is used for processing target pigment particle dispersive composition in order to suppress the aggegation of particle.As the method that is used for replenishing because of the solvent that loses through film, can adopt continuously the constant volume method of supplementing solvent or the batch method of adding solvent discontinuously.In the present invention, the constant volume method is preferred, this be because in this method the time of desalting processing shorter relatively.As above-mentioned additional solvent, use the pure water that obtains by ion-exchange or distillation usually.The poor solvent of spreading agent or spreading agent can be blended in the pure water.Alternative another mode is also the poor solvent of spreading agent or spreading agent directly can be joined in the pigment particle dispersion liquid.

As ultra filtration membrane, module such as plate, the screw type of the film of wherein having packed into, cylinder type, macaroni yarn type, hollow fiber type can be available from Asahi Chemical Industry Co., Ltd., Daicel Chemical Industries Co., Ltd., Toray Industries Co., Ltd., NITTO DENKO Co., Ltd. etc.Consider total membrane area, cleaning etc., those macaroni yarn types and screw type are preferred.Molecular cut off as the threshold value index of membrane-permeable material must be determined according to the molecular weight of employed spreading agent.In the present invention, preferably using molecular cut off is those ultra filtration membranes of 5,000 to 50,000, more preferably 5,000 to 15,000.

For concentrated extracting solution is separated from the dispersion solvent of pigment particle dispersion liquid, preferably filter by filtrator.For example, can use the device such as high pressure filtering device to filter the device of usefulness as filtrator.Preferred filtrator comprises nanofilter, ultrafilter etc.Preferably filter and remove residual dispersion solvent, further the pigment particle in the concentrated extracting solution being concentrated, thereby obtain the nano particle liquid that concentrates by filtrator.

Those skilled in the art freeze-drying method are not particularly limited, can adopt any method, as long as can adopt this method.The example of freeze-drying method comprises refrigerant direct expansion method, repeated freezing method, thermal medium round-robin method, triple heat-exchanging method and indirect heating freezing.Wherein, preferably adopt refrigerant direct expansion method or indirect heating freezing, more preferably adopt the indirect heating freezing.In every kind of method, before carrying out freeze drying, preferably carry out precooling.Cryodesiccated condition is not particularly limited, but must makes pending cryodesiccated sample freezing equably.

The example of the device of indirect heating freezing comprises: small frozen dryer, FTS freeze drier, LYOVAC freeze drier, experiment freeze drier, research freeze drier, triple heat interchange vacuum freeze drier, single-cooling type freeze drier and HULL freeze drier.Wherein, preferably use small frozen dryer, experiment freeze drier, study, and more preferably use small frozen dryer or single-cooling type freeze drier with freeze drier or single-cooling type freeze drier.

Cryodesiccated temperature is not particularly limited, and its (for example) is-190 ℃ to-4 ℃ approximately, is preferably-120 ℃ to-20 ℃ approximately, perhaps more preferably makes an appointment with-80 ℃ to-60 ℃.Cryodesiccated pressure also is not particularly limited, and those skilled in the art can carry out suitably this pressure being selected.Suggestion at (for example) about 0.1Pa to 35Pa, be preferably under the pressure of about 1Pa to 15Pa or more preferably about 5Pa to 10Pa and carry out freeze drying.Sublimation drying is (for example) about 2 hours to 48 hours, is preferably about 6 hours to 36 hours, perhaps more preferably about 16 hours to 26 hours.Yet, should be noted in the discussion above that those skilled in the art can suitably select these conditions.About freeze-drying method, can be with reference to (for example) document Pharmaceutical machinery and engineering handbook, JAPAN SOCIETYOF PHARMACEUTICAL MACHINERY AND ENGINEERING, Chijinshokan Co., Ltd., 120-129 page or leaf (in September, 2000), Vacuum handbook, ULVAC, Inc., Ohmsha, Ltd., 328-331 page or leaf (1992) or Freezing and dryingworkshop paper, Koji Ito etc., No.15,82 pages (1965).

The centrifugal separator that uses when concentrating pigment particle by centrifuging can be any device, as long as can make the pigment particle sedimentation in the pigment particle dispersion liquid (or pigment particle concentrated extracting solution).The example of centrifugal separator comprises universal device, has the peeling function system of (suction supernatant layer in system's rotary course is to be discharged into it function system outside) and is used for discharging continuously the continuous centrifugal separator of solid matter.

As the condition of centrifuging, the centrifugal force value of the ratio of acceleration of gravity (centrifugal acceleration that expression applies with) is preferably 50 to 10,000, and more preferably 100 to 8,000, be preferably 150 to 6,000 especially.Temperature during centrifuging is preferably-10 ℃ to 80 ℃, more preferably-5 ℃ to 70 ℃, perhaps is preferably 0 ℃ to 60 ℃ especially, but preferred temperature changes along with the variation of the solvent species of dispersion liquid.

The device that uses when concentrating pigment particle by drying under reduced pressure is not particularly limited, as long as can make the solvent evaporation of pigment particle dispersion liquid (or pigment particle concentrated extracting solution).The example of described device comprises universal vacuum dryer and universal rotary pump, can be while stirring the body at night, under the heating reduced pressure, liquid carried out dry device, thereby and by making liquid be in the device that pipe under heating and the reduced pressure can carry out continuous drying to liquid by inside.

Temperature when carrying out drying under heating and decompression is preferably 30 ℃ to 230 ℃, more preferably 35 ℃ to 200 ℃, perhaps is preferably 40 ℃ to 180 ℃ especially.Pressure during above-mentioned decompression is preferably 100Pa to 100,000Pa, and 300Pa to 90 more preferably, 000Pa perhaps is preferably 500Pa to 80,000Pa especially.

According to above-mentioned method for concentration, can from the pigment particle dispersion liquid, concentrate out pigment particle effectively.About concentration rate, concentration rate (for example) is as follows: in the time will being made as 1 as the concentration of the nano particle in the pigment particle dispersion liquid of raw material, the concentration that the pigment particle after concentrating is stuck with paste can be preferably about 100 to 3,000 times, perhaps more preferably about 500 to 2,000 times.

[fine dispersion]

When pigment particle is in state of aggregation owing to above-mentioned concentrated grade, preferably agglutination body is carried out fine dispersion (in the present invention, term " fine dispersion " is meant such process, and wherein particle is released in the dispersion liquid by state of aggregation, thereby has improved dispersion degree).

Concentrate organic granular contained in the organic granular liquid that forms by above-mentioned extraction solvent, centrifuging and drying etc. and can be in state of aggregation because of concentrating of organic granular usually.In order can to filter fast, and obtain excellent disperse state once more, preferably the form with floccus obtains above-mentioned pigment particle.A little less than being meant each other, floccus gathers the particulate aggregate of the degree (soft aggegation) that can disperse again.By making this pigment particle form floccus, just can from medium, isolate the organic pigment particulate that (for example) separates out apace from aqueous mixture by (for example) filtration.Be scattered in again in the organic solvent that is fit to the manufacturing color filter by the floccus (soft agglutination body) that will separate, thereby can form the pigment dispensing composition (non-aqueous dispersive composition) that is dispersed in the organic solvent effectively.In other words, when the mixed solvent of good solvent and poor solvent is aqueous solvent, can use the 3rd solvent that constitutes by organic solvent to replace aqueous solvent effectively, thereby change dispersion medium (external phase).Mean diameter to floccus is not particularly limited, but considers above-mentioned filtration efficiency, and it is preferably 0.5～500 μ m, more preferably 5～100 μ m.In the present invention, will be referred to as " the 3rd solvent " with good solvent (first solvent) and these two all different solvent of poor solvent (second solvent).

For some particles, can exist the dispersion level deficiency that realizes by conventional process for dispersing so that the situation of fine particlesization, the therefore method that need carry out miniaturization with higher efficient.Even for the organic granular that is in strong state of aggregation, by with number-average molecular weight be 1000 or higher polymer compound introduce method in the organic granular liquid of aggegation and also can make it become wherein organic granular by the dispersion liquid of fine dispersion suitably.(among the present invention, term " aggegation organic granular " is meant that organic granular gathers together and the aggregate that forms under the effect of secondary force, as agglutination body; Under the situation of the primary granule of nano-scale, sometimes also it is called " nano particle of aggegation ") (among the present invention, term " aggegation organic granular liquid " is meant the liquid that contains the aggegation organic granular, and this liquid can be (for example) dispersion liquid, concentrate, paste, slurries, as long as this liquid contains the aggegation organic granular).More particularly, by adding above-mentioned polymer compound, even medium is being changed into the organic solvent that is suitable for color filter, and make after particulate is scattered in the medium again, good fine dispersiveness (producing the characteristic of even and fine particle diameter) that is obtained in the time of also can stably keeping granules of pigments in the mixed liquor of good solvent and poor solvent, to separate out and good dispersion stabilization (characteristic that can keep even and fine particle diameter for a long time), thus high performance color filter obtained.In addition, above-mentioned polymer compound can not make the optical characteristics of color filter and other deterioration in characteristics, and can improve the performance of color filter and liquid crystal indicator by the interaction with the coloring of organic pigment particulate.

As above-mentioned polymer compound, the represented polymer compound of preferred following general formula (1).

[Chemical formula 2 2]

General formula (1)

In above-mentioned general formula (1), A ¹Represent such any monovalent organic radical group, this organic group has that to be selected from by acidic-group, nitrogenous basic group, urea groups, carbamate groups, the group of band coordination oxygen atom, carbon number be group in the group formed of 4 or more alkyl, alkoxysilyl, epoxy radicals, isocyanate group and hydroxyl; Or represent such any monovalent organic radical group, this organic group contains the organic dyestuff structure or the heterocycle that all can further be replaced.If n is 2 or more, then a plurality of A ¹Can be identical or different.

Specifically, to A ¹Be not particularly limited.The example of above-mentioned " any monovalent organic radical group with acidic-group " comprises any monovalent organic radical group that has such as acidic groups such as carboxylic acid group, sulfonic group, sulfate mono ester group, phosphate, phosplate base and boric acid.In addition, the example of above-mentioned " any monovalent organic radical group with nitrogenous basic group " comprises having amino (NH ₂) any monovalent organic radical group, have substituted imine base (NHR ⁸,-NR ⁹R ¹⁰) (wherein, the R of any monovalent organic radical group ⁸, R ⁹And R ¹⁰Represent that independently of one another carbon number is that 1 to 20 alkyl, carbon number are that 6 to 20 aryl or carbon number are 7 to 30 aralkyl), have following general formula (a1) (wherein, in the general formula (a1), R ^A1, R ^A2Represent that independently of one another carbon number is that 1 to 20 alkyl, carbon number are that 6 to 20 aryl or carbon number are 7 to 30 aralkyl) any monovalent organic radical group of the guanidine radicals of expression and have following general formula (a2) (wherein, in the general formula (a2), R ^A3, R ^A4Represent that independently of one another carbon number is that 1 to 20 alkyl, carbon number are that 6 to 20 aryl or carbon number are 7 to 30 aralkyl) any monovalent organic radical group of the amidino groups of expression.

[Chemical formula 2 3]

The example of above-mentioned " any monovalent organic radical group with urea groups " comprises-NHCONHR ¹⁵(wherein, R ¹⁵Expression hydrogen atom, carbon number are that 1 to 20 alkyl, carbon number are that 6 to 20 aryl or carbon number are 7 to 30 aralkyl) etc.

The example of above-mentioned " any monovalent organic radical group with carbamate groups " comprises-NHCOOR ¹⁶,-OCONHR ¹⁷(wherein, R ¹⁶And R ¹⁷Represent that independently of one another carbon number is that 1 to 20 alkyl, carbon number are that 6 to 20 aryl or carbon number are 7 to 30 aralkyl) etc.

The example of above-mentioned " any monovalent organic radical group with the group of oxygen atom ' band coordination ' " comprises having acetylacetone based group, have the group of crown ether etc.

The example of above-mentioned " have carbon number and be 4 or any monovalent organic radical group of more alkyl " comprise carbon number be 4 or higher alkyl (for example, octyl group, dodecyl), carbon number be 6 or higher aryl (for example, phenyl, naphthyl), carbon number is 7 or higher aralkyl (for example, benzyl) etc.The carbon number of these groups does not have specific upper limit, but preferred carbon number is 30 or lower.

The example of above-mentioned " any monovalent organic radical group with alkoxysilyl " comprises the group with trimethoxysilyl or triethoxysilyl.

The example of above-mentioned " any monovalent organic radical group with epoxy radicals " comprises the group with glycidyl.

The example of above-mentioned " any monovalent organic radical group with isocyanate group " comprises 3-isocyanate group propyl group.

The example of above-mentioned " any monovalent organic radical group with hydroxyl " comprises the 3-hydroxypropyl.

By above-mentioned A ¹In these groups of expression, preferably have acidic-group, nitrogenous basic group, urea groups and carbon number and be 4 or higher alkyl in any one any monovalent organic radical group.

Above-mentioned organic dyestuff structure or heterocycle are not particularly limited.But, more particularly, the organic dyestuff example of structure comprises: phthalocyanine compound, insoluble azo-compound, azo lake compound, anthraquinone compounds, quinoline a word used for translation ketonic compound, dioxazine compound, Diketopyrrolo-pyrrole compounds, anthracene pyridine compounds, anthanthrone compound, indanthrone compound, yellow anthrone compound, perylene ketonic compound, perylene compound, thioindigo compound etc.The example of heterocycle comprises thiophene, furans, xanthene, the pyrroles, pyrrolin, pyrrolidine, dioxolanes, pyrazoles, pyrazoline, pyrazolidine, imidazoles oxazole, thiazole oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalimide, naphthalimide, hydantoins, indoles, quinoline, carbazole, acridine, acridone and anthraquinone.

Above-mentioned organic dyestuff structure or heterocycle can have substituting group T.The example of substituting group T comprise carbon number be 1～20 alkyl (for example methyl, ethyl), carbon number be 6～16 aryl (for example phenyl, naphthyl), carbon number be 1～6 acyloxy (for example, acetoxyl group), carbon number be 1～6 alkoxy (for example, methoxyl, ethoxy), halogen atom (for example chlorine, bromine), carbon number be 2～7 alkoxy carbonyl group (for example, methoxycarbonyl group, carbethoxyl group, hexamethylene oxygen carbonyl), cyano group, carbonate group (for example, the carbonic acid tert-butyl ester), hydroxyl, amino, carboxyl, sulfoamido and N-sulfoamido.

In addition, above-mentioned A ¹Can represent with following general formula (4).

[Chemical formula 2 4]

General formula (4)

In above-mentioned general formula (4), B ¹Represent such group, it is the group that 4 or more alkyl, alkoxysilyl, epoxy radicals, isocyanate group and hydroxyl are formed that this group is selected from group, carbon number by acidic-group, nitrogenous basic group, urea groups, carbamate base band coordination oxygen atom; Or expression the organic dyestuff structure or the heterocycle that all can further be replaced.R ¹⁸The expression singly-bound or (a1+1) the organic or inorganic linking group of valency.A1 represents 1～5.At this moment, a1 be 2 or higher situation under, a plurality of B ¹Can be same or different.

The preferred embodiment and the above-mentioned A of the group of general formula (4) expression ¹Identical.

R ¹⁸The expression singly-bound or (a1+1) linking group of valency.A1 represents 1～5.By R ¹⁸The example of linking group of expression comprises: by the group of the atomic building in 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 sulphur atom, it can not be substituted or be substituted base and replace.R ¹⁸Be preferably organic linking group.

R ¹⁸Object lesson comprise following structural unit or the group that constitutes by the combination of following structural unit.In addition, this links radicals R ¹⁸Also can have above-mentioned substituting group T.

[Chemical formula 2 5]

In above-mentioned general formula (1), R ¹The connection base of expression (m+n) valency.M+n is in 3～10 scope.

Above-mentioned R ¹The example of linking group of (m+n) valency of expression comprises that this group can not be substituted or be substituted base and replace by the group of the atomic building in 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 sulphur atom.R ¹Be preferably organic linking group.

R ¹Example comprise the group of above-mentioned (t-1)～(t-34) or the group (it can form ring texture) that constitutes by a plurality of described moiety combinations.Above-mentioned linking group R ¹When having substituting group, this substituent example comprises above-mentioned substituting group T.

R ²Expression singly-bound or divalent linking group.R ²Example comprise that this group can not be substituted or be substituted base and replace by the group of the atomic building in 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 sulphur atom.R ²Object lesson comprise group shown in above-mentioned t-3～t-5, t-7～t-18, t-22～t-26, t-32, the t-34 or the group that constitutes by a plurality of these moiety combinations.R ²Preferably with R ¹The coupling position place have sulphur atom.Above-mentioned R ²When having substituting group, described substituent example comprises above-mentioned substituting group T.

In above-mentioned general formula (1), m represents 1～8.M is preferably 1～5, and more preferably 1～3, be preferably 1～2 especially.

N represents 2～9.N is preferably 2～8, and more preferably 2～7, be preferably 3～6 especially.

In above-mentioned general formula (1), P ¹The expression polymer backbone.This polymer backbone can suitably be selected from conventional polymkeric substance.

In order to form polymer backbone, preferred modified compound or multipolymer (for example, the multipolymer of the multipolymer of polyethers/polyurethane, polyethers/derived from ethylene base polymer of monomers that is selected from by derived from ethylene base polymer of monomers or multipolymer, ester type compound polymkeric substance, ether compound polymkeric substance, polyurethanes compound polymer, amides compound polymkeric substance, epoxy compounds polymkeric substance, organosilicon compound polymkeric substance and these polymkeric substance that use; These multipolymers can be any in random copolymers, segmented copolymer and the graft copolymer) at least a in the group that constitutes; More preferably use and be selected from least a by in the modified compound of derived from ethylene base polymer of monomers or multipolymer, ester type compound polymkeric substance, ether compound polymkeric substance, polyurethanes compound polymer and these polymkeric substance or the group that multipolymer constitutes; Especially preferably use the homopolymer or the multipolymer of derived from ethylene base monomer.

In addition, preferred above-mentioned polymkeric substance dissolves in the organic solvent.If the compatibility of this polymkeric substance and organic solvent is low, then when described polymkeric substance (for example) was used as pigment dispersing agent, the compatibility of this polymkeric substance and dispersion medium died down.Therefore, be difficult to guarantee to be enough to make the adsorbed layer of stably dispersing sometimes.

Preferred P ¹At itself and R ¹The coupling position place sulphur atom is arranged.

In the polymer compound of above-mentioned general formula (1) expression, more preferably by the polymer compound of following general formula (2) expression.

[Chemical formula 2 6]

General formula (2)

In above-mentioned general formula (2), A ²With the A in the above-mentioned general formula (1) ¹Has identical implication.A ²Concrete preferred version also with A ¹Identical.A ²Can also have substituting group, and its example comprises above-mentioned substituting group T.

In above-mentioned general formula (2), R ³The linking group of expression (x+y) valency.R ³With R ¹Has identical implication.R ³Preferable range also with R ¹Identical.At R ³During the linking group of expression (x+y) valency, the value of described x and preferable range thereof are identical with n in the general formula (1).Similarly be that the value of described y and preferable range thereof are identical with m; The value of described x+y and preferable range thereof are identical with m+n.

R ³The linking group of expression is preferably organic linking group.The preferred object lesson of this organic linking group is as follows.Yet the present invention is not limited thereto.

[Chemical formula 2 7]

[Chemical formula 2 8]

Wherein, from acquired, the synthetic easiness of raw material and the deliquescent angle all kinds of solvents, in above-mentioned linking group, preferably above-mentioned (r-1), (r-2), (r-10), (r-11), (r-16) and group (r-17).

At above-mentioned R ³When having substituting group, described substituent example comprises above-mentioned substituting group T.

In above-mentioned general formula (2), R ⁴And R ⁵Represent singly-bound or divalent linking group independently of one another.

As above-mentioned R ⁴, R ⁵" divalent linking group " of expression preferably can randomly substituted straight chain, alkylidene, arlydene or the inferior aralkyl of side chain or ring-type, perhaps-O-,-S-,-C (=O)-,-N (R ¹⁹)-,-SO-,-SO ₂-,-CO ₂-or-N (R ²⁰) SO ₂-, perhaps with two or more these moiety combinations and the divalent group (R that forms ¹⁹And R ²⁰Represent that independently of one another hydrogen atom or carbon number are 1～4 alkyl).The preferred organic linking group of above-mentioned divalent linker.

As above-mentioned R ⁴, the preferably alkylidene of straight or branched or inferior aralkyl, perhaps-O-,-C (=O)-,-N (R ¹⁹)-,-SO ₂-,-CO ₂-or-N (R ²⁰) SO ₂-, perhaps with two or more these moiety combinations and the divalent group that forms.Particularly preferably be the alkylidene or the inferior aralkyl of straight or branched, perhaps-O-,-C (=O)-,-N (R ¹⁹)-or-CO ₂-, perhaps with two or more these moiety combinations and the divalent group that forms.

As above-mentioned R ⁵, preferably singly-bound alkylidene, the inferior aralkyl of straight or branched, perhaps-O-,-C (=O)-,-N (R ¹⁹)-,-SO ₂-,-CO ₂-or-N (R ²⁰) SO ₂-, perhaps with two or more these moiety combinations and the divalent group that forms.Particularly preferably be the alkylidene of straight or branched, inferior aralkyl, perhaps-O-,-C (=O)-,-N (R ¹⁹)-or-CO ₂-, perhaps with two or more these moiety combinations and the divalent group that forms.

At R ⁴Or R ⁵When having substituting group, described substituent example comprises above-mentioned substituting group T.

P in the general formula (2) ²Expression polymer compound residue (polymer backbone), and can suitably be selected from conventional polymkeric substance.P in the preferred version of polymkeric substance and the above-mentioned general formula (1) ¹Identical, and its preferred version also with P ¹Identical.

In the polymer compound of above-mentioned general formula (2) expression, particularly preferably be such polymer compound, wherein R ³Be above-mentioned (r-1), (r-2), (r-10), (r-11), (r-16) or concrete group (r-17); R ⁴Be singly-bound, the alkylidene of straight or branched or inferior aralkyl, perhaps-O-,-C (=O)-,-N (R ¹⁹)-or-CO ₂-, perhaps with two or more these moiety combinations and the divalent group that forms; R ⁵For singly-bound, ethylidene, propylidene or following general formula (s-a) or (s-b) expression linking group; P ²Be the homopolymer of derived from ethylene base monomer or the modified compound of multipolymer, ester type compound polymkeric substance, ether compound polymkeric substance, polyurethanes compound polymer or these polymkeric substance; Y is 1～2; And x is 3～6.In following radicals, R ²¹Expression hydrogen atom or methyl; 1 expression 1 or 2.

[Chemical formula 2 9]

The weight-average molecular weight of above-mentioned polymer compound is at least 1000, is preferably 3000～100,000, more preferably 5000～80000, be preferably 7000～60000 especially.If weight-average molecular weight is in the above-mentioned scope, the a plurality of functional groups that then are incorporated into polymer ends then can give full play to its effect, and polymkeric substance will brought into play excellent performance aspect adsorbability, micella formation performance and the surfactant property of solid surface thus.Therefore, can obtain good dispersiveness and dispersion stabilization.

The object lesson of the compound of general formula (1) expression is as follows.But the present invention is not limited to these object lessons.

As above-mentioned weight-average molecular weight is at least 1000 polymer compound, can use any (hereinafter also this compound being called " polymer compound that contains acidic-group ") in the following polymer compound with acidic-group.As this polymer compound, preferably has the polymer compound of carboxyl.More preferably contain (A) derived from least a repetitive of compound and (B) derived from the copolymer compound of at least a repetitive of compound with carboxylic acid ester groups with carboxyl.

Repetitive (A) derived from the compound with carboxyl is preferably the repetitive that following general formula (I) is represented, the more preferably repetitive of derived from propylene acid or methacrylic acid; Be preferably the repetitive of following general formula (II) expression derived from the repetitive (B) of compound with carboxylic acid ester groups, the repetitive of more preferably following general formula (IV) expression is preferably the repetitive of derived from propylene acid benzyl ester, benzyl methacrylate, phenylethyl, methacrylic acid phenethyl ester, acrylic acid 3-phenylpropyl alcohol ester or methacrylic acid 3-phenyl propyl ester especially.

[chemical formula 48]

General formula (I)

(R ₁Expression hydrogen atom or carbon number are 1～5 alkyl.)

[chemical formula 49]

General formula (II)

(R ₂Expression hydrogen atom or carbon number are 1～5 alkyl.R ₃Represent the group shown in the following general formula (III).)

[chemical formula 50]

General formula (III)

(R ₄Expression hydrogen atom, carbon number are that 1～5 alkyl, hydroxyl, carbon number are that 1～5 hydroxyalkyl or carbon number are 6～20 aryl; R ₅And R ₆Represent that separately hydrogen atom or carbon number are 1～5 alkyl; I represents 1～5 number.)

[chemical formula 51]

General formula (IV)

(R ₇Expression hydrogen atom or carbon number are 1～5 alkyl.R ₈Represent the group shown in the following general formula (V).)

[chemical formula 52]

General formula (V)

(R ₉The expression carbon number is that 2～5 alkyl or carbon number are 6～20 aryl.R ₁₀And R ₁₁Represent that separately hydrogen atom or carbon number are 1～5 alkyl.J represents 1～5 number.)

With regard to derived from the repetitive (A) of compound with derived from regard to the polymerization ratio of the repetitive (B) of compound with carboxylic acid ester groups with carboxyl, the number of repetitive (A) is preferably 3～40 with respect to the ratio (%) of repetitive sum, and more preferably 5～35.

In the present invention, unless otherwise specified, otherwise " molecular weight " of term polymer is meant number-average molecular weight.The example of measuring the method for polymer molecular weight comprises chromatography, viscosimetry, light scattering method and sedimentation velocity method.In the present invention, unless otherwise specified, otherwise all be to use by gel permeation chromatography (carrier: tetrahydrofuran) measure and through the number-average molecular weight of polystyrene conversion.

Polymer compound can be water-soluble or oil-soluble, perhaps can be not only to have water-soluble but also have oil-soluble.

Polymer compound can add with the state that is dissolved in aqueous solvent or the organic solvent, perhaps can add with solid state.In addition, also these adding methods can be used in combination.The example that adds the method for polymer compound with the state in the solvent of being dissolved in comprises: add method in the aggegation organic granular liquid to being in polymer compound under the state that is dissolved in the solvent identical with the solvent of aggegation organic granular liquid; And add method in the aggegation organic granular liquid to being in polymer compound under the state that is dissolved in the solvent miscible but different with the solvent of aggegation organic granular liquid.When adding polymer compound with the state in the solvent of being dissolved in, the concentration of polymer compound is not particularly limited, but it is preferably 1～70 quality %, more preferably 2～65 quality % are preferably 3～60 quality % especially.

Polymer compound can separate out and form in the pigment particle or before or after add, can be in concentrating or before or after add, can concentrate in the organic granular that the back disperses aggegation or before or after add, perhaps can interpolation after these steps finish.Can be to be divided into several parts and add several times by total amount for another mode of selecting for use with polymer compound.In the present invention, can in composition, introduce above-mentioned weight-average molecular weight be 1000 or higher polymer compound as above-mentioned cementing agent.For example, preferably, when carrying out fine dispersion, adds the aggegation organic granular that the pigment particle lye is concentrated the back acquisition polymer compound.

When pigment particle was made as 100 mass parts, the addition of polymer compound was preferably 0.1～1,000 mass parts, and more preferably 5～500 mass parts are preferably 10～300 mass parts especially.

Except above-claimed cpd, the example of described polymer compound also comprises: the part formalizing thing of polyvinyl pyrrolidone, polyvinyl alcohol (PVA), polyvinyl methyl ether, polyethylene oxide, polyglycol, polypropylene glycol, polyacrylamide, vinyl alcohol/vinyl acetate copolymer, polyvinyl alcohol (PVA), part butyralization thing, vinyl pyrrolidone/vinyl acetate copolymer, polyethylene oxide/propylene oxide segmented copolymer, polyamide, cellulose derivative and the starch derivative of polyvinyl alcohol (PVA).In addition, can also use natural polymeric compounds, its example comprises: alginate, gelatin, albumin, casein, Arabic gum, bassora gum, lignosulfonate.

Example with polymer compound of acidic-group comprises poly-sulfuric acid vinyl ester and condensation naphthalene sulfonic acids etc.

Example with polymer compound of carboxyl comprises: polyacrylic acid, polymethylacrylic acid and its any one side chain have the cellulose derivative of carboxyl.The example that contains the multipolymer of at least a repetitive derived from the compound with carboxyl (A) and at least a repetitive derived from the compound with carboxylic acid ester groups (B) comprises: at patent documentation JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, methacrylic acid copolymer described in JP-A-59-53836 and the JP-A-59-71048, acrylic copolymer, itaconic acid copolymer, the crotonic acid multipolymer, the maleic acid of maleic acid and partial esterification.In addition, the more preferred example of described multipolymer comprises U.S. Patent No. 4, acrylic acid/esters multipolymer, methacrylic acid/acrylate copolymer, acrylic acid/methacrylate copolymers, methacrylic acid/methacrylate copolymer described in 139,391 and contain acrylic or methacrylic acid and the multiple copolymer of acrylate or methacrylate and other any vinyl compounds.

The example of vinyl compound comprises the styrene (for example vinyltoluene or vinyl ethylbenzene) of styrene or replacement; The vinyl naphthalene of vinyl naphthalene or replacement; Acrylamide; Methacrylamide; Vinyl cyanide; And methacrylonitrile.Wherein, optimization styrene.

These weight-average molecular weight be 1000 or higher polymer compound can use separately, perhaps with two or more be used in combination, perhaps the compound with molecular weight less than 1000 is used in combination.

Preferably, contain 60 quality % or higher, more preferably 65 quality % or higher organic solvent in the dispersion of pigment particle.There is no particular limitation to this organic solvent, and can suitably be selected from conventional solvent.The example of preferred solvent comprises: ester type compound solvent, alcohol compound solvent, aromatic compound solvent, fatty compound solvent and ketone compounds solvent.Wherein, preferred especially ester type compound solvent and ketone compounds solvent.These solvents can use separately, perhaps being used in combination with two or more.

The example of ester type compound solvent comprises acetate 2-(1-methoxyl) propyl ester, ethyl acetate, ethyl lactate etc.The example of alcohol compound solvent comprises normal butyl alcohol, isobutyl alcohol etc.The example of aromatic compound solvent comprises benzene,toluene,xylene etc.The example of fatty compound solvent comprises normal hexane, cyclohexane etc.The example of ketone compounds solvent comprises MEK, acetone, cyclohexanone etc.

Above-mentioned pigment particle can be scattered in the state in the carrier and uses with (for example).If with coating is example, then carrier is meant the part of the medium that makes pigment dispersing when coating is in liquid condition.Carrier is a liquid condition, and contains and combine with the part (cementing agent) of solidifying coated film with above-mentioned pigment and be used for composition (organic solvent) that this part is dissolved and diluted.In the present invention, the cementing agent that the cementing agent that is adopted when forming nano particle is adopted when decentralized again can be identical, perhaps differs from one another, and also they is called individually the cementing agent of nano particle formation usefulness sometimes and disperses the cementing agent of usefulness again.

Can come suitably to determine to disperse again the concentration of the pigment particle in the pigment particle dispersive composition of back according to application target.Yet based on the total amount of dispersive composition, the concentration of pigment particle is preferably 2～30 quality %, and more preferably 4～20 quality % are preferably 5～15 quality % especially.Under the situation with above-mentioned carrier dispersed color particulate, cementing agent and dissolved dilution can come suitably to determine with the amount of composition according to (for example) organic pigment kind.Yet based on the total amount of dispersive composition, the amount of cementing agent is preferably 1～30 quality %, and more preferably 3～20 quality % are preferably 5～15 quality % especially.Based on the total amount of dispersive composition, dissolved dilution is preferably 5～80 quality % with the amount of composition, more preferably 10～70 quality %.

In the nano particle liquid of concentration extraction, as previously mentioned,, preferably make the pigment particle aggegation above-mentioned by concentrating in order to allow to adopt filtrator to filter fast.Preferably concentrate and make its aggegation by centrifuging or drying.

Can be used for the example that nano particle to this aggegation carries out the method for fine dispersion comprises: adopt hyperacoustic process for dispersing and relate to the method that applies physical energy.

The ultrasonic irradiation device preferably can apply 10kHz or higher hyperacoustic device, and its example comprises ultrasonic homogenizer, supersonic wave cleaning machine etc.In the ultrasonic irradiation process, because raising, fluid temperature cause nano particle generation thermal thermocoagulation (referring to document " Currentpigment Dispersion Technology ＂; Technical Information Institute Co.; Ltd.; 1995; p.166), so fluid temperature preferably remains 1 ℃ to 100 ℃, more preferably remains 5 ℃ to 60 ℃.For example, temperature that can be by regulating dispersion liquid, the temperature of regulating the adjustment layer that be used to control the dispersion liquid temperature wait and control temperature.

Employed dispersion machine when applying physical energy concentrated organic pigment particle is disperseed is not particularly limited, and the example of this dispersion machine comprises kneader, roller mill, masher, high-speed grinder, dissolving machine, homo-mixer and sand mill.In addition, can also enumerate high pressure dispersion method and use method that microballon disperses as method for optimizing.

By above-mentioned manufacture method, can (for example) pigment particle dispersive composition or photosensitive composition in contained pigment particle concentrate and disperse again, (for example 10～100nm) so little nominal particle size also can be like this even it has nano-scale.Therefore, can obtain such color filter when using arbitrary composition in color filter, it shows high optical density (OD), has excellent color filter surface uniformity, produces high contrast, and has the picture noise of minimizing.

In addition, pigment particle contained in pigment particle dispersive composition or the photosensitive composition is disperseed with the graininess of height and the size that evenly reduces.Therefore, even the film that is formed by each above-mentioned composition is than also producing high colorant density under the minimal thickness, thereby the thickness of (for example) color filter is reduced.

In addition, in the time will demonstrating distinct tone and high-strength pigment and be incorporated in pigment particle dispersive composition and the photosensitive composition, each composition all can advantageously be used as manufacturing (for example) color correction device or the used Image forming material of color filter.

And; pigment particle dispersive composition and photosensitive composition all can use the cementing agent that can be dissolved in the alkaline aqueous solution; so that the alkaline developer that makes this cementing agent and be used to expose and develop when forming rendered image is complementary, so above-mentioned composition all can meet the needs of environmental protection.

In addition, can be with organic solvent with appropriate drying property as the solvent (dispersing of pigments medium) that uses in pigment particle dispersive composition, the coloring photosensitive combination, and the composition of gained carries out dry requirement after can satisfying coating.

Color filter of the present invention has high contrast and excellent tone, and is suitable for carrying out on industrialized level continuous a large amount of manufacturings.When color filter of the present invention was used for liquid crystal indicator or CCD device, it can demonstrate excellent display performance.

The present invention will be described in more detail based on example below, but the present invention is not limited to these examples.

Example

(embodiment 1-1)

In 1000ml dimethyl sulfoxide (DMSO) (making) by Wako Pure Chemical Industries Co., Ltd., add the methanol solution (making), 10 of 28% sodium methoxide of 10ml by Wako PureChemical Industries Co., Ltd., 000mg C.I. paratonere 254 (Irgaphor Red BT-CF, make by Ciba Specialty Chemicals company) and 10, the polyvinylpyrrolidone K25 of 000mg (being made by Wako Pure Chemical Industries Co., Ltd.) is with the preparation pigment solution.Except that pigment solution, prepare to contain the ion exchange water 9 of the 1N hydrochloric acid (making) of 100ml in addition by Wako Pure Chemical Industries Co., Ltd., 000ml is as poor solvent.

The pigment solution implantation temperature that to all measure with the flow velocity of 100ml/min with the high capacity flexible hose pump is controlled as in 18 ℃ and the above-mentioned poor solvent that stirs with the rotating speed of 500rpm with the quaterfoil paddle, thereby makes the granules of pigments dispersion that pigment concentration is 0.1 quality %.Under reduced pressure use the PTFE film filter that the pigment dispersion of above preparation is filtered, wash then, being concentrated into pigment concentration again is 20 quality %.Measure by electron microscope, the mean grain size of finding described granules of pigments is 22nm.

Use the condensed pigment of above preparation, preparation has the R pigment dispersion 1-1 of the described composition of table 1.

The composition of table 1 R pigment dispersion 1-1

------------------------------------------------------------

Condensed pigment 52 mass parts

Polymeric dispersant 1 20.8 mass parts

Dispersant A 7 mass parts

Propylene glycol monomethyl ether 15.6 mass parts

------------------------------------------------------------

In table 1, described macromolecule dispersing agent 1 is by benzyl methacrylate and methacrylic acid are carried out the spreading agent that random copolymerization makes with 60/40 mol ratio.Recording its number-average molecular weight (Mn) according to gel permeation chromatography is 32,000.In addition, following compound J1 is used as dispersant A.

[chemical formula 53]

Compound J1

Use above-mentioned R pigment dispersion 1-1, prepare photosensitive composition R1-1 according to the described composition of table 2.

The composition of table 2 photosensitive composition R1-1

------------------------------------------------------------------

R-pigment dispersion 1-1 50 mass parts

Propylene glycol monomethyl ether 8.5 mass parts

MEK 34 mass parts

Cementing agent 0.53 mass parts

DPHA solution 3.42 mass parts

2-trichloromethyl-(to the styryl styryl)-1,3,4-oxadiazole 0.13 mass parts

Polymerization initiator A 0.044 mass parts

Phenothiazine 0.014 mass parts

Surfactant 0.09 mass parts

------------------------------------------------------------------

＜cementing agent 〉

Polymkeric substance (the random copolymers of benzyl methacrylate/methacrylic acid/methyl methacrylate (38/25/37, mol ratio); Mn:40,000): 25 mass parts

Propylene glycol monomethyl ether: 75 mass parts

＜dipentaerythritol acrylate solution (DPHA solution) 〉

Dipentaerythritol acrylate (the polymerization inhibitor MEHQ that contains 500ppm; Make trade name: KAYARAD DPHA): 70 mass parts by Nippon Kayaku Co., Ltd.

Propylene glycol monomethyl ether: 30 mass parts

＜polymerization initiator A 〉

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

＜surfactant 〉

Following structure 1 24 mass parts

MEK 76 mass parts

[chemical formula 54]

Structure 1

(n＝6，x＝55，y＝5，Mw＝33940，Mw/Mn＝2.55，

PO: oxypropylene, EO: the oxidation ethylidene)

Adopt following method to make to have black matrix, the color filter 1-1 of R pixel, G pixel and B pixel.

[making of color filter (adopting the slit-shaped nozzle to make)] by coating

The formation of＜black (K) image 〉

Clean alkali-free glass substrate with the UV cleaning device, wash with clean-out system by hairbrush then, carry out ultrasonic cleaning with ultrapure water again.With this substrate 120 ℃ of following thermal treatments 3 minutes, so that the surface state of substrate is stable.

Be controlled at 23 ℃ with this substrate cooling and with temperature.Use has the glass substrate of slit-shaped nozzle and (is made trade name by F A S Japan Co., Ltd.: MH-1600) will have the photosensitive composition K1 that forms described in the following table 3 and be coated on this substrate with coating machine.Then with VCD (Minton dryer; Make by Tokyo Ohka Kogyo Co., Ltd.) dry 30 seconds to be removing partial solvent, thus make overlay no longer mobile.Then, remove substrate unwanted coating liquid on every side with EBR (trimming machine (edge bead remover)).After 120 ℃ of following preliminary dryings 3 minutes, obtaining film thickness is the photo-sensitive resin K of 2.4 μ m.

The composition of table 3 coloring phototonus resin bed K

-------------------------------------------------------

Carbon black 28 mass parts

Propylene glycol monomethyl ether 8.5 mass parts

MEK 47 mass parts

Cementing agent 10.1 mass parts

Hydroquinone monomethylether 0.002 mass parts

DPHA solution 4.5 mass parts

Polymerization initiator A 0.182 mass parts

Surfactant 0.04 mass parts

--------------------------------------------------------

Have extra-high-pressure mercury vapour lamp near type exposure machine (making) by Hitachi Engineering Co., Ltd. in, substrate and mask (the quartzy exposed mask with picture pattern) are vertically placed, in this state, with the distance setting of exposed mask surface and this photoresist interlayer is 200 μ m, carries out pattern exposure then under the exposure of 300mJ/ square centimeter.

Next, by spraying pure water, make the surface of this photo-sensitive resin K1 evenly wetting with spray spout.Use the KOH class developer (developer that contains KOH and non-ionics then, trade name: CDK-1 is made by Fujiphoto Electronics Materials Co., Ltd) be under the condition of 0.04MPa photo-sensitive resin to be sprayed to develop 80 seconds at 23 ℃, the pressure of flat pattern nozzle.Thus, obtain the image of patterning.Next, under the pressure of 9.8MPa, spray ultrapure water, to remove residue with the UHV (ultra-high voltage) washer jet.Thus, obtain the image K of black (K).Then, with image 220 ℃ of following thermal treatments 30 minutes.

Prepare above-mentioned photosensitive composition K in the following manner, described mode is: at first, take by weighing carbon black, propylene glycol monomethyl ether, under 24 ℃ of temperature (± 2 ℃) they are mixed then, and stirred 10 minutes with the rotating speed of 150rpm.Then, take by weighing MEK, cementing agent, Hydroquinone monomethylether, DPHA solution, polymerization initiator A and surfactant, under 25 ℃ of temperature (± 2 ℃), add, and under 40 ℃ of temperature (± 2 ℃), stirred 30 minutes with the rotating speed of 150rpm potpourri with gained with above-mentioned order.

The formation of＜red (R) pixel 〉

Be formed with thereon on the substrate of above-mentioned image K, use above-mentioned photosensitive composition R1-1, adopt the step identical to form through heat treated pixel R with the step that forms above-mentioned black (K) image.The thickness of the photo-sensitive resin R that obtains like this and the coating amount of pigment are as follows.Prepare photosensitive composition R1-1 by the method identical with the above-mentioned photosensitive composition K of preparation.

Photoresist thickness (μ m) 1.60

Pigment coating amount (g/ square metre) I.00

The coating amount of C.I.P.R.254 (g/ square metre) 0.80

The formation of＜green (G) pixel 〉

Be formed with thereon on the substrate of above-mentioned image K and pixel R, use photosensitive composition G, adopt the step identical to form through heat treated pixel G with the step that forms above-mentioned black (K) image with the composition described in the following table 4.The thickness of the photo-sensitive resin G that obtains like this and the coating amount of pigment are as follows.Prepare photosensitive composition G by the method identical with the above-mentioned photosensitive composition K of preparation.

Photoresist thickness (μ m) 1.60

Pigment coating amount (g/ square metre) 1.92

The coating amount of C.I.P.G.36 (g/ square metre) 1.34

The coating amount of C.I.P.Y.150 (g/ square metre) 0.58

The composition of table 4 photosensitive composition G

-------------------------------------------------------------

G-color compositions (CIPG36) 28.4 mass parts

Y-color compositions (CIPY150) 15.0 mass parts

Propylene glycol monomethyl ether 29.8 mass parts

MEK 25.5 mass parts

Cyclohexanone 1.1 mass parts

Cementing agent 2.0 mass parts

DPHA solution 3.7 mass parts

2-trichloromethyl-(to the styryl styryl)-1,3,4-oxadiazole 0.13 mass parts

Polymerization initiator A 0.054 mass parts

Phenothiazine 0.044 mass parts

Surfactant 0.065 mass parts

---------------------------------------------------------------

＜G-pigment dispersion 〉

C.I.P.G.36 18 mass parts

Polymkeric substance (the random copolymers of benzyl methacrylate/methacrylic acid (72/28, mol ratio); Molecular weight: 38,000): 12 mass parts

Cyclohexanone 35 mass parts

Propylene glycol monomethyl ether: 35 mass parts

＜Y-pigment dispersion 〉

CF Yellow EX3393 (trade name) is made by Mikuni Co., Ltd.

The formation of＜blue (B) pixel 〉

Be formed with thereon on the substrate of above-mentioned image K, pixel R and pixel G, use to have the photosensitive composition B1 that forms described in the following table 5, form through heat treated pixel B according to the step identical with the step that forms above-mentioned black (K) image.Obtain required color filter A by this way.The thickness of the photo-sensitive resin B1 that obtains like this and the coating amount of pigment are as follows.Prepare photosensitive composition B1 by the method identical with the above-mentioned photosensitive composition K of preparation.

Photoresist thickness (μ m) 1.60

Pigment coating amount (g/ square metre) 0.75

The coating amount of C.I.P.B.15:6 (g/ square metre) 0.67

The coating amount of C.I.P.V.23 (g/ square metre) 0.075

The composition of table 5 photosensitive composition B1

----------------------------------------------------------------

B-color compositions (CIPB15:6) 8.5 mass parts

V-color compositions (CIPB15:6+CIPV23) 15.3 mass parts

Propylene glycol monomethyl ether 28.5 mass parts

MEK 24 mass parts

Cementing agent 16.3 mass parts

DPHA solution 4.0 mass parts

2-trichloromethyl-(to the styryl styryl)-1,3,4-oxadiazole 0.133 mass parts

Phenothiazine 0.019 mass parts

Surfactant 0.065 mass parts

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＜B-pigment dispersion 〉

CF Blue EX3357 (trade name) is made by Mikuni Co., Ltd.

＜V-pigment dispersion 〉

CF Blue EX3383 (trade name) is made by Mikuni Co., Ltd.

(embodiment 1-2)

Adopt the method identical to make the color filter 1-2 of R pigment dispersion 1-2, photosensitive composition R1-2 and use photosensitive composition R1-2 with embodiment 1-1, difference is, the consumption of the polyvinylpyrrolidone during with preparation R pigment dispersion 1-1 changes into 20,000mg.Measure by electron microscope, the mean grain size of finding described granules of pigments is 23nm.

(embodiment 1-3)

Adopt the method identical to make the color filter 1-3 of R pigment dispersion 1-3, photosensitive composition R1-3 and use photosensitive composition R1-3 with embodiment 1-1, difference is, the consumption of the polyvinylpyrrolidone during with preparation R pigment dispersion 1-1 changes into 50,000mg.Measure by electron microscope, the mean grain size of finding described granules of pigments is 21nm.

(embodiment 1-4)

Adopt the method identical to make the color filter 1-4 of R pigment dispersion 1-4, photosensitive composition R1-4 and use photosensitive composition R1-4 with embodiment 1-1, difference is, the consumption of the polyvinylpyrrolidone during with preparation R pigment dispersion 1-1 changes into 100,000mg.Measure by electron microscope, the mean grain size of finding described granules of pigments is 20nm.

(embodiment 2)

Adopt the method identical to make the color filter 2 of R pigment dispersion 2, photosensitive composition R2 and use photosensitive composition R2 with embodiment 1-1, difference is, add 50, the polyvinylpyrrolidone K25 that the polyvinylpyrrolidone K90 of 000mg (being made by Wako PureChemical Industries Co., Ltd.) uses when replacing preparing R pigment dispersion 1-1.Measure by electron microscope, the mean grain size of finding described granules of pigments is 20nm.

(embodiment 3)

Adopt the method identical with embodiment 1-4 make paints dispersion and condensed pigment, difference is, is 45 ℃ with the temperature change of poor solvent.Measure by electron microscope, the mean grain size of finding described granules of pigments is 53nm.

By the condensed pigment that obtains more than using, adopt the method identical to make the color filter 3 of R pigment dispersion 3, photosensitive composition R3 and use photosensitive composition R3 with embodiment 1-1.

(comparative example 1)

Adopt the method identical to make the color filter A of R pigment dispersion A, photosensitive composition RA and use photosensitive composition RA with embodiment 1-1, difference is, the polyvinylpyrrolidone that uses when not being added on preparation R pigment dispersion 1-1 when the feed liquid of preparation pigment.Measure by electron microscope, the mean grain size of finding described granules of pigments is 21nm.

(comparative example 2)

At first, with 20,000mg methacrylic acid/benzyl methacrylate multipolymer (mol ratio is 30/70, Mw30, the propylene glycol monomethyl ether solution of 000,40 quality %), 80,000mg sodium chloride and 80,000mg C.I. paratonere 254 mixes.Then, the potpourri that obtains is written in the both arms type kneader (being made by Moriyama Company Co., Ltd.), and descended mixing 10 hours at 80 ℃.After mixing, potpourri is put in the aqueous hydrochloric acid solution of 1 quality % of 500 mass parts, stirred then 1 hour, filter afterwards, with hot wash, drying and grinding.Then, every 1g abrasive material adds the 2.4g propylene glycol monomethyl ether, and mixes.Utilize electronic mill M-50 (making) and use the zirconia microballon of diameter, under the peripheral speed 10m/ condition of second, the color compositions that obtains was disperseed 1 hour as 0.5mm by Eigar Japan Co., Ltd..The above pigment dispersion that obtains is expressed as R-pigment dispersion B.Measure by electron microscope, the mean grain size of finding described granules of pigments is 48nm.

Use R-pigment dispersion B, adopt the method identical to make the color filter B of photosensitive composition RB and use photosensitive composition RB with embodiment 1-1.

Adopt following method to measure each pigment dispersion 1-1 to 1-4,2,3, the A of above preparation and the amount of the polyvinylpyrrolidone among the B.

1. with each pigment dispersion evaporate to dryness under the condition of 100 ℃ and normal pressure.The various solids that grinding obtains.

2. various grinding products are carried out compressing tablet according to the potassium bromide method, with the preparation sample.The Fourier transform infrared spectrometer FTIR-8400S (trade name) that use is made by Shimadzu Corporation measures the amount of the polyvinylpyrrolidone in each sample.

In addition, use the Ka Er-Fei Xiu Moisture Meter MKA-3 that makes by Kyoto Electronic Manufacturing Co., Ltd. to measure the moisture among each pigment dispersion 1-1 to 1-4,2,3, A and the B.

Table 6

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Pigment dispersion polymer content (quality %) ^{(annotating 1)}Moisture (quality %) ^{(annotating 2)}

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1-1 2.97 2.13

1-2 5.22 1.86

1-3 7.51 2.28

1-4 12.89 3.34

2 6.17 2.02

3 3.02 2.11

A is lower than I and measures 2.73

B is lower than I and measures 1.14

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(annotating 1) polyvinylpyrrolidone is with respect to the content (quality %) of pigment

(annotating 2) water is for the content (quality %) of pigment dispersion

For each pigment dispersion 1-1 to 1-4,2,3, the A that estimate above preparation and the performance of B, adopt following method to measure the contrast of coating product.

As backlight assembly, use the three-wavelength cold-cathode tube light source be provided with diffuser plate (FWL18EX-N, trade name is by Toshiba Lighting ﹠amp; Technology Co., Ltd. makes).Each color filter is placed between two polarization plates (HLC2-2518, trade name are made by Sanritz company), measures the light transmission capacity of the polarization axle of the two polarization plates light transmission capacity when parallel when vertical then with polarization axle.With the ratio of these light transmission capacities be defined as contrast (referring to document " Color filter for 512 color disDlay 10.4 "-size TFT-LCD, collaborate The Seventh Color OpticsConference (1990) etc. by Ueki, Koseki, Fukunaga and Yamanaka).Use color briliancy instrument (BM-5, trade name are made by TopconTechno House company) to measure colourity.Place above-mentioned two polarization plates, color filter, color briliancy instrument with following position: polarization plates is placed on the position of distance 13mm backlight.Diameter is that 11mm, length are the position that the cylinder of 20mm is placed on distance 40mm～60mm backlight.Make the rayed that sees through cylinder on the color filter that is arranged at distance 65mm backlight position.The light that sees through is passed be arranged at another polarization plates of distance 100mm backlight position, and measure with the color briliancy instrument that is arranged at apart from 400mm backlight position.The mensuration angle of color briliancy instrument is set at 2 °.Light quantity backlight is set so that when two polarization plates are arranged to the position of parallel Nicol and color filter are not set, its brightness (briliancy) be 1280 candelas/square metre.

Then, adopt following method to measure the amount of the polyvinylpyrrolidone in the dyed layer of above each color filter 1-1 to 1-4,2,3, A for preparing and B.

1. under stereomicrometer, use scraper that a part of dyed layer of each color filter is wiped off, with the preparation sample for analysis.

2. collect each sample of appropriate amount, and it is analyzed according to the pyrolysis gas chromatograph mass spectroscopy.For cracking analysis, use the Curie Point PyrolyzerJHP-5 type cracker of making by JAI company (trade name).The 5973 type devices of being made by Agilent Technologies company (trade name) carry out gaschromatographic mass spectrometric analysis.

3. according to the SIM method polyvinylpyrrolidone is analyzed.Calculate quantitative values according to absolute calibration curve method or standard addition method.

Table 7 shows the content of polymkeric substance (polyvinylpyrrolidone) in contrast under the situation of the described pigment dispersion of coating and the color filter.

Table 7

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The color filter contrast ^{(annotating 1)}Polymer content (quality %) ^{(annotating 2)}

------------------------------------------------------------------

1-1 8,100 0.68

1-2 10,200 1.03

1-3 14,200 2.28

1-4 13,900 5.73

2 11,400 2.67

3 7,300 5.26

A 6,900 is lower than I and measures

B 4,500 is lower than I and measures

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(annotating 1) is according to the contrast of the pigment dispersion of above-mentioned measuring method measurement

Water-soluble polymers (polyvinylpyrrolidone) is with respect to the content of solids content in (annotating 2) color filter

Be appreciated that by The above results the contrast of color filter 1-1 to 1-4,2 and 3 (wherein, dyed layer contains 0.1 quality % or higher polyvinylpyrrolidone (water-soluble polymers)) all is higher than the contrast of color filter A and B.Can estimate, use color filter 1-1 to 1-4,2 and 3 liquid crystal indicator and CCD device will demonstrate augmented performance.

Although color filter 3 contains water-soluble polymers, it demonstrates relatively low contrast.By inference, this possibility of result is to cause owing to the granules of pigments that contains in the color filter 3 has the so big diameter of about 50 nanometers.In this respect, though color filter 3 and color filter B comprise particle diameter granules of pigments much at one, color filter 3 demonstrates the contrast that is better than color filter B, thereby shows owing to introducing the effect that water-soluble polymers produces.

(embodiment 4 and comparative example 3)

Then, adopt following method to make liquid crystal indicator respectively, and estimate its picture quality with above-mentioned color filter.

[manufacturing of liquid crystal indicator]

(formation of ITO electrode)

The glass substrate that is formed with color filter on it is packed in the sputter equipment, and under 100 ℃ with 1300

Thick ITO (tin indium oxide) vacuum moulding machine is on the whole surface of described glass substrate.Then, annealed 90 minutes down at 240 ℃, so that the ITO crystallization.Form ito transparent electrode thus.

(formation of spacer)

Adopt the identical method of spacer formation method described in the embodiment 1 with patent documentation JP-A-2004-240335, on the ito transparent electrode of above-mentioned making, form spacer.

(being used to control the formation of the projection of liquid crystal aligning)

Use following positive-working photosensitive resin layer with coating liquid, be formed with the projection that is formed for controlling liquid crystal aligning on the ito transparent electrode of above-mentioned spacer.

Here, expose in the following ways, development and baking procedure.

To be set near type exposure machine (making) and make that the distance of specific photomask and photoresist laminar surface is 100 μ m by Hitachi High-Tech Electronics Engineering Co., Ltd..Utilize extra-high-pressure mercury vapour lamp to carry out proximity printing through above-mentioned photomask with the exposure of 150mJ/ square centimeter.

Then, reach 30 seconds on the substrate, develop by using down the fountain developing apparatuss that 2.38% tetramethyl ammonium hydroxide solution is ejected at 33 ℃.Thus, by development remove on the photo-sensitive resin do not need the part (exposed portion).Therefore, be formed for controlling the target projection of liquid crystal aligning on a side identical with color filter of substrate, wherein said projection is to make by photo-sensitive resin being patterned as required shape.

Then, the base plate for liquid crystal display device that is formed with the projection that is used to control liquid crystal aligning on it was toasted 30 minutes under 230 ℃ condition.On base plate for liquid crystal display device, form the projection that is used to control liquid crystal aligning of solidifying thus.

＜positive-working photosensitive resin layer the preparation of coating liquid 〉

Eurymeric resist liquid (FH-2413F (trade name) is made by Fujiphoto Electronics Materials Co., Ltd) 53.3 mass parts

MEK 46.7 mass parts

(trade name is by Dainippon Ink ﹠amp for Megafac F-780F; Chemicals Co., Ltd. makes)

0.04 mass parts

(manufacturing of liquid crystal indicator)

The alignment films that is made of polyimide further is set on the base plate for liquid crystal display device of above-mentioned acquisition.Then, will be printed onto the position corresponding to the housing of black matrix by the sealant that epoxy resin is made, wherein said housing is provided so that it surrounds color filter pixel group's periphery.In addition, after the liquid crystal of instillation MVA pattern, aforesaid substrate and opposing substrates are pasted together.Substrate after pasting is heat-treated, thereby make sealant cures.On each surface of the liquid crystal cell that obtains by this way, paste the Polarizer HLC2-2518 that makes by Sanritz company.Then, form and to have three-wavelength cold-cathode tube light source (FWL18EX-N (trade name) is by Toshiba Lighting ﹠amp; Technology Co., Ltd. makes) backlight, and will this rear side that is set in the liquid crystal cell that is provided with above-mentioned Polarizer backlight.Make liquid crystal indicator thus.

About the liquid crystal indicator of above manufacturing, the liquid crystal indicator that will have color filter 1-1 is expressed as liquid crystal indicator 1-1.According to mode same as described above, make liquid crystal indicator 1-2 to 1-4,2,3, A and B respectively.

Estimate the picture quality of each liquid crystal indicator in the following ways.

1. with 8 above-mentioned liquid crystal indicator random arrangement and not labelled, and be shown to the examiner.By the examiner picture quality (the black degree of depth and modulation) of device is graded, its rank is 8 minutes to 1 minute, and wherein 8 minutes rank is best, and 1 minute rank is for the poorest.

2. carry out same evaluation test by 10 examiners.With the above mark addition that obtains, and estimate the picture quality of the liquid crystal indicator of preparation with always assigning to.

Total points be 25 or higher liquid crystal indicator have sufficient Practical Performance.

Gained the results are shown in the table 8.

The evaluation result of the picture quality of the liquid crystal indicator of table 8 preparation

----------------------------------------------------

The total points of liquid crystal indicator image quality evaluation

----------------------------------------------------

1-1 43

1-2 47

1-3 72

1-4 70

2 55

3 29

A 26

B 16

----------------------------------------------------

Be appreciated that by table 8 having the liquid crystal indicator that dyed layer wherein contains the color filter of 0.1 quality % or higher polyvinylpyrrolidone obtains excellent picture quality.In addition, shown in the result of table 7, be appreciated that in the sample that contains granules of pigments (it is as the colorant of color filter, and particle diameter much at one) that picture quality improves along with the content of polypyrrole alkane ketone increases and tends to.

Industrial applicibility

Color filter of the present invention has high contrast and excellent tone, and is suitable for carrying out on industrialized level continuous a large amount of manufacturings.When color filter of the present invention was used for liquid crystal indicator or CCD device, this color filter can demonstrate excellent display performance.

Describe the present invention by embodiment, and short of specifying, just not to be plan be defined in the present invention on any details in the instructions for we, and should be interpreted as widely that the present invention is positioned at the spirit and scope that the claims of enclosing are set forth.

Claims

1. color filter, have the tone that is colored as at least a regulation and be formed at dyed layer on the substrate, described dyed layer comprises the pigment dispersion form: water-insoluble organic pigment (a), the monomer with polymerizable group or oligomer (b) and water-soluble polymers (c), wherein, described dispersion is solidified by making described monomer or oligomer polymerization, thereby form described dyed layer

2. the described color filter of claim 1, wherein, described pigment dispersion comprises the described organic pigment (a) of particulate form,

3. the described color filter of claim 2, wherein, the number average bead diameter of described pigment particle is in the scope of 0.005 μ m～1 μ m.

4. the described color filter of claim 2, wherein, the number average bead diameter of described pigment particle is in the scope of 0.005 μ m～0.08 μ m.

5. the described color filter of claim 2, wherein, the number average bead diameter of described pigment particle is in the scope of 0.005 μ m～0.05 μ m.

6. any described color filter in the claim 1～5, wherein, the number-average molecular weight of described water-soluble polymers is 1,000 or higher.

7. a liquid crystal indicator is equipped with any described color filter in the claim 1～6.

8. a CCD device is equipped with any described color filter in the claim 1～6.

9. a pigment dispersion contains water-insoluble organic pigment (a) and water-soluble polymers (b),

The water cut of wherein said pigment dispersion is 10 quality % or lower, and

The content of wherein said water-soluble polymers (b) is at least 0.1 quality % of described organic pigment (a).

10. the described pigment dispersion of claim 9 contains the described organic pigment (a) of particulate form,

11. the described pigment dispersion of claim 10, wherein, the number average bead diameter of described pigment particle is in the scope of 0.005 μ m～1 μ m.

12. the described pigment dispersion of claim 10, wherein, the number average bead diameter of described pigment particle is in the scope of 0.005 μ m～0.08 μ m.

13. the described pigment dispersion of claim 10, wherein, the number average bead diameter of described pigment particle is in the scope of 0.005 μ m～0.05 μ m.

14. any described pigment dispersion in the claim 9～13, wherein, the number-average molecular weight of described water-soluble polymers is 1,000 or higher.