CN101878440A - Color filter and liquid crystal display device using the same - Google Patents

Color filter and liquid crystal display device using the same Download PDF

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Publication number
CN101878440A
CN101878440A CN2008801181755A CN200880118175A CN101878440A CN 101878440 A CN101878440 A CN 101878440A CN 2008801181755 A CN2008801181755 A CN 2008801181755A CN 200880118175 A CN200880118175 A CN 200880118175A CN 101878440 A CN101878440 A CN 101878440A
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solvent
pigment
color filter
methyl
composition
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Inventor
松本圭右
高桥秀知
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133707—Structures for producing distorted electric fields, e.g. bumps, protrusions, recesses, slits in pixel electrodes

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)

Abstract

The invention provides a color filter and liquid crystal display device using the same. The color filter comprises pixels each containing a pigment dispersion composition and a graft polymer compound. The pigment dispersion composition contains organic pigment particles produced by mixing a solution, which is obtained by dissolving an organic pigment into a good solvent, with a poor solvent for the organic pigment which is compatible with the good solvent.

Description

Color filter and used the liquid crystal indicator of this color filter
Technical field
The present invention relates to color filter and used the liquid crystal indicator of this color filter.
Background technology
In recent years, color filter in liquid crystal display cells (LCD) purposes not only at monitor but also in TV (TV), its purposes also has the tendency of expansion.Along with the expansion of this purposes, require to have the color characteristics of height at aspects such as colourity, contrasts.In addition, in imageing sensor (solid-state imager) purposes, require to have high color characteristics too.At these requirements, need make pigment disperse (good fine dispersiveness) and disperse (good dispersion stabilization) with stable status with finer state.But when with the particle diameter miniaturization of pigment during to nano-scale for example, the surface area of pigment particles increases, so the cohesiveness between pigment particles strengthens, and usually is difficult to take into account above-mentioned fine dispersiveness and dispersion stabilization with high level.
In addition, as pigment dispersing agent, proposed and used the pigment dispersing agent and acid these two kinds of the pigment dispersing agents (with reference to TOHKEMY 2002-296770 communique) of alkalescence.But wherein owing to the pigment dispersing agent of also using alkaline pigment dispersing agent and acidity, so pigment may take place crosslinked.In addition, the fine dispersiveness of pigment, dispersion stabilization can not be said very abundant.In addition, only also disclose at polymer moieties single terminal and imported sulfonic group or sulfate mono ester group and the polymer pigment dispersant (with reference to TOHKEMY 2002-273191 communique) that obtains.But it is importing by high molecular synthetic reaction on this aspect of end group, is in industrial favourable manufacture method efficiently hardly.In addition, whether also unclear fine dispersiveness, dispersion stabilization improve fully.
In addition, also disclose the particle that makes organic pigment and precipitate in the liquid that mixes with liquid phase, and made it contain the method (with reference to international open WO2006/121016 pamphlet, TOHKEMY 2004-043776 communique, TOHKEMY 2007-023169 communique, TOHKEMY 2007-119586 communique) of specific macromolecular compound etc.
Summary of the invention
According to the present invention, provide following technical scheme:
(1) a kind of color filter, it is to form by having the pixel that contains pigment dispensing composition and graft type macromolecular compound, wherein, the solution that described pigment dispensing composition contains by will the dissolving organic pigment forms in good solvent mixes the organic pigment particles that forms with the bad solvent of described organic pigment, and described bad solvent and described good solvent mix.
(2) according to (1) described color filter, wherein, described pigment dispensing composition is not contain the solvent composition in the mixed liquor that forms described organic pigment particles in fact and contain different with it final solvents and form.
(3) according to (1) or (2) described color filter, wherein, the replacement from the solvent composition to described final solvent in the described mixed liquor is to finish by the following operation that repeats more than 1 time: reduce or remove solvent composition the described mixed liquor and the different types of replacement solvent of the solvent composition in interpolation and the described mixed liquor.
According to each described color filter in (1)～(3), it is characterized in that (4) described pigment dispensing composition makes described graft type macromolecular compound coexistence and obtains when described organic pigment particles forms.
(5) according to each described color filter in (1)～(4), it is characterized in that described pigment dispensing composition contains described graft type macromolecular compound and obtains after described organic pigment particles forms.
According to each described color filter in (1)～(5), it is characterized in that (6) described graft type macromolecular compound is the graft type macromolecular compound that has the structural unit of following general formula (5) expression in side chain;
(in the general formula (5), R 74Expression hydrogen atom or carbon number are 1～8 alkyl.Q represent cyano group, carbon number be 6～30 aryl or-COOR 75Wherein, R 75Expression hydrogen atom, carbon number are that 1～22 alkyl or carbon number are 6～30 aryl.)
According to each described color filter in (1)～(6), it is characterized in that (7) number average bead diameter of described organic pigment particles is below the 100 interior rice.
(8) a kind of liquid crystal indicator is characterized in that, it possesses each described color filter in (1)～(7).
(9) according to (8) described liquid crystal indicator, wherein, described liquid crystal indicator is the VA mode.
Above-mentioned and other features of the present invention and advantage can be clearer by following content.
Embodiment
Below, the present invention will be described in detail.
Branch portion (side chain) as if the graft type macromolecular compound that will use in the color filter of the present invention represents with macromolecular compound, then can list polystyrene, polyethylene oxide, polypropyleneoxide, poly-(methyl) acrylate, polycaprolactone etc., preferably in branch portion, have the graft type macromolecular compound of the structural unit of following general formula (5) expression.
Figure GPA00001142255500031
In the general formula (5), R 74Expression hydrogen atom or carbon number are 1～8 alkyl.Q represent cyano group, carbon number be 6～30 aryl or-COOR 75Wherein, R 75Expression hydrogen atom, carbon number are that 1～22 alkyl or carbon number are 6～30 aryl.
Work as R 74When being 1～8 alkyl, be preferably carbon number and be 1～6 alkyl, more preferably methyl for carbon number.R 74Can have substituting group T 1As substituting group T 1, can list halogen atom, carboxyl, alkoxy carbonyl, alkoxy etc.As substituting group T 1During for alkyl,, can list methyl, ethyl, hexyl, octyl group, trifluoromethyl, ethyloic, methoxycarbonyl methyl etc. as concrete example.R 74Especially be preferably hydrogen atom or methyl.
It is 6～20 aryl that Q is preferably carbon number, and more preferably carbon number is 6～12 aryl.When the group of representing as Q is aryl, can have substituting group T 2As substituting group T 2, can list halogen atom, alkyl, alkoxy, alkoxy carbonyl etc.When Q is aryl, as its concrete example, can list phenyl, naphthyl, tolyl, xylyl, propyl group phenyl, butyl phenyl, octyl phenyl, dodecylphenyl, methoxyphenyl, ethoxyl phenenyl, butoxy phenyl, last of the ten Heavenly stems oxygen base phenyl, chlorphenyl, dichlorophenyl, bromophenyl, methoxycarbonyl phenyl, ethoxy carbonyl phenyl, butoxy carbonyl phenyl etc.When Q is aryl, the aryl that does not preferably have substituted aryl or replaced by halogen atom, alkyl or alkoxy.Wherein, the aryl that does not especially preferably have substituted aryl or replaced by alkyl.
Work as R 75When being 1～22 alkyl, be preferably carbon number and be 1～12 alkyl for carbon number, more preferably carbon number is 1～8 alkyl.Q is-COOR 75, as R wherein 75During for alkyl, can also have substituting group T 3As substituting group T 3, can list halogen atom, alkenyl, aryl, hydroxyl, alkoxy, alkoxy carbonyl, amino, amide group, carbamyl etc.Work as R 75During for alkyl; as its concrete example; can list methyl; ethyl; propyl group; butyl; heptyl; hexyl; octyl group; decyl; dodecyl; tridecyl; myristyl; cetyl; octadecyl; the 2-chloroethyl; the 2-bromoethyl; 2-methoxycarbonyl ethyl; the 2-methoxy ethyl; the 2-bromopropyl; the 2-butenyl group; the 2-pentenyl; 3-methyl-2-pentenyl; the 2-hexenyl; 4-methyl-2-hexenyl; benzyl; phenethyl; the 3-phenylpropyl; menaphthyl; 2-naphthalene ethyl; the benzyl chloride base; bromobenzyl; methyl-benzyl; Ethylbenzyl; methoxy-benzyl; dimethyl benzyl; dimethoxy-benzyl; cyclohexyl; 2-cyclohexyl ethyl; 2-cyclopentyl ethyl; dicyclo (3.2.1) suffering-2-base; the 1-adamantyl; dimethylaminopropyl; the acetyl-amino ethyl; N, N-dibutylamino carbamyl ylmethyl etc.In these alkyl, the alkyl that does not preferably have substituted alkyl or replaced by halogen atom, aryl or hydroxyl.Wherein, especially preferably there is not substituted alkyl.
Work as R 75When being 6～30 aryl for carbon number, being preferably carbon number and being 6～20 aryl, being preferably carbon number especially is 6～12 aryl.Work as R 75During for aryl, can also have substituting group T 4As substituting group T 4, can list halogen atom, alkyl, alkenyl, alkoxy, alkoxy carbonyl, amide group etc.As R 75Object lesson during for aryl can list phenyl, naphthyl, tolyl, xylyl, propyl group phenyl, butyl phenyl, octyl phenyl, dodecylphenyl, methoxyphenyl, ethoxyl phenenyl, butoxy phenyl, last of the ten Heavenly stems oxygen base phenyl, chlorphenyl, dichlorophenyl, bromophenyl, methoxycarbonyl phenyl, ethoxy carbonyl phenyl, butoxy carbonyl phenyl, acetamido phenyl, propionamido-phenyl, lauroyl amido phenyl etc.In these aryl, the aryl that does not preferably have substituted aryl or replaced by halogen atom, alkyl or alkoxy.Wherein, the aryl that is especially preferably replaced by alkyl.
As R 75, especially preferred hydrogen atom, carbon number are 1～22 alkyl, preferred especially hydrogen atom, carbon number are 1～12 alkyl.
In branch portion, has the graft type macromolecule of the structural unit of general formula (5) expression about these, if represent the object lesson of its one, then can list poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, poly-(methyl) isobutyl acrylate, poly-((methyl) methyl acrylate-altogether-(methyl) benzyl acrylate), poly-((methyl) methyl acrylate-altogether-styrene), poly-((methyl) methyl acrylate-altogether-(methyl) acrylic acid), poly-((methyl) methyl acrylate-altogether-vinyl cyanide) etc. with polymkeric substance.
The graft polymer that uses among the present invention is not particularly limited, but the position that preferably has a side chain directly or by means of the position, interval by the polymkeric substance of covalent bonds in main chain, but be not limited thereto, for example, can list the multipolymer that constitutes by the polymerism oligomer composition that has the ethylenic unsaturated double-bond endways as copolymer composition, to become the polymkeric substance that the composition at grafting position forms having on (being total to) polymkeric substance of side chain by the high molecular weight reactive addition, thereby the polymkeric substance that will have a side chain carries out polyreaction as starting point and forms polymkeric substance that the grafting position forms etc.Graft polymer among the present invention can use by waiting the polymkeric substance that is synthesized into reference to known high molecular weight reactive or polymerizable monomer and the copolyreaction that has the polymerism oligomer of ethylenic unsaturated double-bond endways.
Synthetic method as the graft type macromolecular compound of the structural unit that in branch portion, has general formula (5) expression at least, particularly, can list the macromonomer and the method that can carry out copolymerization with the ethylenically unsaturated monomers of this macromonomer copolymerization of the polymerism of the structural unit that formation general formula (5) is represented.
In the macromonomer of the polymerism of the structural unit of formation general formula (5) expression, the monomer of preferred following general formula (6) expression.
Figure GPA00001142255500051
In the general formula (6), R 76Expression hydrogen atom or carbon number are 1～8 alkyl.W represents the group of any expression among singly-bound or following (a)～(n).
Figure GPA00001142255500061
Wherein, Z 1, Z 2Expression hydrogen atom, halogen atom, carbon number are 1～6 alkyl, cyano group or hydroxyl.Z 3Expression hydrogen atom, carbon number are that 1～18 alkyl or carbon number are 6～20 aryl.Perhaps, Z 1～Z 3It also can be the linking group that they combine.A represents to constitute the group of Q of the structural unit of described general formula (5) expression with W.As the object lesson of the macromonomer of these general formulas (6) expressions, can list the compound of following formula (6-1)～(6-8) expression.
The definition of A in A and the described general formula (6) is identical.Me represents methyl.As the such macromonomer that can buy with commercially available product, can list the polystyrene oligomer (Mn=6000, trade name: AS-6, East Asia synthetic chemical industry (Co., Ltd.) corporate system) of the positive butyl ester oligomer of polyacrylic acid (Mn=6000, trade name: AB-6, East Asia synthetic chemical industry (Co., Ltd.) corporate system) of the polymethylmethacrylate oligomer (Mn=6000, trade name: AA-6, East Asia synthetic chemical industry (Co., Ltd.) corporate system) of single terminal methyl group propylene acidylate, single terminal methyl group propylene acidylate, single terminal methyl group propylene acidylate.
As the molecular weight of above-mentioned macromonomer, be preferably 1000～20000, more preferably 2000～15000 with the number-average molecular weight (Mn) of polystyrene conversion.When above-mentioned number-average molecular weight is in above-mentioned scope, can more effectively obtain steric repulsion effect as pigment dispersing agent.Need to prove, in the present invention, represent number-average molecular weight when only being called molecular weight, unless otherwise specified, then is the molecular weight of measuring by gel permeation chromatography (carrier is a tetrahydrofuran) with polystyrene conversion.
In order to improve dispersing of pigments, dispersion stabilization, can preferably use " monomer of the block of formation and pigment adsorption " with the ethylenically unsaturated monomers of above-mentioned macromonomer copolymerization.In addition, as other copolymer compositions, can also make " constituting not monomer " copolymerization with the block of pigment adsorption.
About " monomer of the block of formation and pigment adsorption ", can suitably select according to the kind of the pigment that will disperse, they can use separately also and can more than 2 kinds and use.
For example can list have can with the monomer of the functional group of pigment adsorption.Particularly, can list monomer with organic pigment residue or heterocycle structure part, monomer with acidic-group, monomer with basic nitrogen atom, the group, the carbon number that have urea groups, carbamate groups, have a coordination oxygen atom are the monomer of alkyl, alkoxysilyl, ethoxy, isocyanate group or hydroxyl more than 4, or contain monomer of ionic functional group etc.; Wherein, preferably have organic pigment residue or heterocycle structure part monomer, have the monomer of acidic-group or have the monomer of basic nitrogen atom; Especially preferably have the monomer of acidic-group or have the monomer of basic nitrogen atom.
As " constituting not monomer " with the block of pigment adsorption, be not particularly limited, for example can list (methyl) esters of acrylic acid, butenoate class, vinyl ester, maleic acid diester class, dimethyl ester class, itaconic acid diester class, (methyl) acrylic amide, phenylethylene, vinyl ethers, vinyl ketones, olefines, maleimide, (methyl) vinyl cyanide etc.These monomers can use separately also and can more than 2 kinds and use.When being applied to alkaline development and handling needed Photocurable composition, can will have the vinyl monomer of acidic-group and above-mentioned formation not with the monomer of the block of pigment adsorption and use.
As the example of (methyl) esters of acrylic acid, can list (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid pentyl ester, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) acrylic acid tert-butyl group cyclohexyl, (methyl) acrylic acid (2-ethylhexyl) ester, (methyl) acrylic acid uncle monooctyl ester, (methyl) dodecylacrylate, (methyl) acrylic acid stearyl, (methyl) acrylic acid acetate ethyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid (4-hydroxyl butyl) ester, (methyl) acrylic acid (2-methoxy ethyl) ester, (methyl) acrylic acid (2-ethoxyethyl group) ester, (methyl) acrylic acid (2-(2-methoxy ethoxy) ethyl) ester, (methyl) acrylic acid (2-chloroethyl) ester, (methyl) acrylic acid vinyl esters, (methyl) acrylic acid (2-phenyl vinyl) ester, (methyl) acrylic acid (1-propenyl) ester, (methyl) acrylic acid allyl ester, (methyl) acrylic acid (2-allyloxy ethyl) ester, (methyl) acrylic acid propargyl ester, (methyl) benzyl acrylate, diethylene glycol monomethyl ether (methyl) acrylate, diethylene glycol monoethyl ether (methyl) acrylate, triethylene glycol monomethyl ether (methyl) acrylate, Triethylene glycol ethyl ether (methyl) acrylate, poly glycol monomethyl ether (methyl) acrylate, polyethyleneglycol ether (methyl) acrylate, (methyl) acrylic acid (beta-phenoxy ethoxyethyl group) ester, Nonylphenoxy polyglycol (methyl) acrylate, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid trifluoroethyl ester, (methyl) acrylic acid octafluoro amyl group ester, (methyl) acrylic acid perfluoro capryl ethyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid tribromo phenylester, (methyl) acrylic acid tribromo phenyl oxygen base ethyl ester, (methyl) acrylic acid gamma-butyrolacton etc.
As the example of butenoate class, can list butyl crotonate and the own ester of butenoic acid etc.
As the example of vinyl ester, can list vinyl-acetic ester, chloroacetic acid vinyl esters, vinyl propionate base ester, butyric acid vinyl esters, methoxyacetic acid vinyl esters and benzoic acid vinyl esters etc.
As the example of maleic acid diester class, can list dimethyl maleate, diethyl maleate and dibutyl maleate etc.
As the example of dimethyl ester class, can list dimethyl fumarate, DEF and dibutyl fumarate etc.
As the example of itaconic acid diester class, can list dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.
As (methyl) acrylic amide, can list (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-isopropyl (methyl) acrylamide, N-normal-butyl (methyl) acrylamide, the N-tert-butyl group (methyl) acrylamide, N-cyclohexyl (methyl) acrylamide, N-(2-methoxy ethyl) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-phenyl (methyl) acrylamide, N-nitrobenzophenone acrylamide, N-ethyl n-Phenyl Acrylamide, N-benzyl (methyl) acrylamide, (methyl) acryloyl morpholine, diacetone acrylamide, N hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, vinyl (methyl) acrylamide, N, N-diallyl (methyl) acrylamide, N-allyl (methyl) acrylamide etc.
As the example of phenylethylene, can list styrene, methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, cumene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrol, 1-chloro-4-methyl-benzene, by hydroxy styrenes, vinyl benzoic acid methyl esters and the α-Jia Jibenyixi etc. of group that can be by the acidic materials deprotection (for example t-Boc (tertbutyloxycarbonyl) etc.) protection.
As the example of vinyl ethers, can list methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl group vinyl ether, methoxy ethyl vinyl ether and Vinyl phenyl ether etc.
As the example of vinyl ketones, can list methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, phenyl vinyl ketone etc.
As the example of olefines, can list ethene, propylene, isobutylene, butadiene, isoprene etc.
As the example of maleimide, can list maleimide, butyl maleimide, cyclohexyl maleimide, phenyl maleimide etc.
As the example of (methyl) vinyl cyanide, can list methacrylonitrile, vinyl cyanide etc.
Weight-average molecular weight to above-mentioned graft type macromolecular compound is not particularly limited, and is preferably set to 3000～100000 scope, more preferably is set at 5000～50000 scope.When weight-average molecular weight is 3000 when above, can more effectively obtain stabilization effect; When weight-average molecular weight is 100000 when following, can more effectively adsorbs and bring into play good dispersiveness.Need to prove, in the present invention, be meant weight-average molecular weight when only being called molecular weight, unless otherwise specified, then is the molecular weight of measuring by gel permeation chromatography (carrier is a tetrahydrofuran) with polystyrene conversion.
As the commercially available product of described graft type macromolecular compound, can list Lubrizol corporate system " SOLSPERSE 24000,28000,32000,38500,39000,55000 ", BYK Chemie corporate system (being trade name) such as " Disperbyk-111,161,171,174 ".
The graft type macromolecule that uses in the color filter of the present invention to other is not particularly limited, can list communique with Japanese kokai publication sho 54-37082, the compound that the reaction of the poly-alkylene imines of record and petchem obtains in the Japanese kokai publication sho 61-174939 communique etc., the amino of putting down in writing in the Japanese kokai publication hei 9-169821 communique with the side chain of PAH is modified with polyester and the compound that obtains, the polyester polyol of putting down in writing in the Japanese kokai publication sho 60-166318 communique adds generating polyurethane etc., with Japanese kokai publication hei 9-171253 communique or " マ Network ロ モ ノ マ one chemical と industry ", ア イ ピ one シ one publishing department, the graft type macromolecule that those polymerism oligomers (hereinafter referred to as macromonomer) in 1989 etc. are copolymer composition.
In the pigment dispensing composition that uses in color filter of the present invention, the content of above-mentioned graft type macromolecular compound being not particularly limited, is 1～80 quality %, 3～50 quality % more preferably with respect to the total solid composition of pigment dispensing composition preferably.
In the present invention, above-mentioned graft type macromolecular compound can also be used with in addition polymkeric substance or various spreading agent.Be not particularly limited in the present invention,, can list pigment derivative type compound and terminal-modified type macromolecular compound as polymkeric substance that can preferably use or spreading agent.
Pigment derivative type compound (below be also referred to as " pigment derivative type spreading agent ") is meant from deriving as the organic pigment of parent material and by its precursor structure being carried out the pigment derivative type spreading agent that chemical modification is made, or the pigment derivative type spreading agent that obtains by the pigmentation reaction through the pigment precursors of chemical modification.Usually be also referred to as Synergist type spreading agent.
Be not particularly limited, for example, the pigment derivative with acidic-group, the pigment derivative with basic group, the importing of putting down in writing in suitable use TOHKEMY 2007-9096 communique or the Japanese kokai publication hei 7-331182 communique etc. has the pigment derivative of functional groups such as phthalimide methyl etc.
As commercially available product, can list EFKA corporate system " EFKA6745 (trade name, phthalocyanine derivates ", 6750 " trade name, AZO pigments derivant) ", Lubrizol corporate system " SOLSPERSE 5000 (trade name, phthalocyanine derivates), 22000 (trade name, AZO pigments derivant) " etc.
Content to the pigment derivative type compound in the pigment dispensing composition that uses in the color filter of the present invention is not particularly limited, and preferably is 0.01～50 quality %, 0.2～20 quality % more preferably in the total solid composition of described composition.
Method about synthetic above-mentioned end modified version macromolecular compound is not particularly limited, and can list the method for for example following method and their combinations etc.
1. use polymerization initiator that contains functional group and the method for synthesizing by polymerization (for example free radical polymerization, anionic polymerisation, cationic polymerization etc.)
2. use and contain the chain-transferring agent of functional group and by the incompatible method of synthesizing of radical polymerization
Wherein, the functional group of importing can list above-mentioned adsorption site (promptly being selected from the group with organic pigment structure, heterocycle structure, acidic-group, basic nitrogen atom, the group with urea groups, carbamate groups, coordination oxygen atom, carbon number is the position of alkyl, alkoxysilyl, ethoxy, isocyanate group, hydroxyl and ionic functional group more than 4) etc.In addition, also can be the functional group that on these adsorption sites, can derive.
As the chain-transferring agent that functional group can be imported polymer ends; for example can list sulfhydryl compound (mercaptoacetic acid for example; dimercaptosuccinic acid; thiosalicylic acid; 2 mercaptopropionic acid; the 3-mercaptopropionic acid; 3-sulfydryl butyric acid; N-(2-mercapto radical propionyl group) glycocoll; 2-sulfydryl niacin; 3-(N-(2-mercaptoethyl) carbamyl) propionic acid; 3-(N-(2-mercaptoethyl) amino) propionic acid; N-(3-mercapto radical propionyl group) alanine; mistabrom; 3-sulfydryl propane sulfonic acid; 4-sulfydryl fourth sulfonic acid; 2 mercapto ethanol; 3-sulfydryl-1, the 2-propylene glycol; 1-sulfydryl-2-propyl alcohol; 3-sulfydryl-2-butanols; mercapto-phenol; 2-mercaptoethyl amine; the 2-mercaptoimidazole; 2-sulfydryl-3-pyridol; benzenethiol; toluenethiol; the sulfydryl acetophenone; naphthyl mercaptan; naphthalene methyl mercaptan etc.) or as the disulfide of the oxide of these sulfhydryl compounds and halogenide (2-iodo ethyl sulfonic acid for example; 3-iodo propane sulfonic acid etc.).
In addition, as the polymerization initiator that functional group can be imported polymer ends, for example can list 2,2 '-azo two (2-cyano group propyl alcohol), 2,2 '-azo two (2-cyano group amylalcohol), 4,4 '-azo two (4-cyanopentanoic acid), 4,4 '-azo two (4-cyano group valeric chloride), 2,2 '-azo two (2-(5-methyl-2-imidazoline-2-yl) propane), 2,2 '-azo two (2-(2-imidazoline-2-yl) propane), 2,2 '-azo is two, and (2-(3,4,5,6-tetrahydropyrimidine-2-yl) propane), 2,2 '-azo two { 2-(1-(2-hydroxyethyl)-2-imidazoline-2-yl) propane }, 2,2 '-azo two (2-methyl-N-(2-hydroxyethyl)-propionamide) etc. or their derivant etc.
As the monomer that uses in the polymerization,, can use above-mentioned " constituting not monomer " with the block of pigment adsorption for example as free radical polymerization monomer.
As terminal-modified type macromolecule, the end at polymkeric substance that can list for example middle record such as Japanese kokai publication hei 9-77994 communique or TOHKEMY 2002-273191 communique has the macromolecule of functional group.
About the high molecular molecular weight of above-mentioned end modified version, preferable weight-average molecular weight is 1000～50000.When above-mentioned number-average molecular weight is 1000 when above, can more effectively obtain steric repulsion effect as pigment dispersing agent, when being 50000 when following, can more effectively suppress stereoeffect, thereby further shorten time pigment adsorption.
As the high molecular commercially available product of above-mentioned end modified version, can list Lubrizol corporate system " SOLSPERSE 3000,17000,27000 (being trade name) " etc.
Content to the terminal-modified macromolecular compound in the pigment dispensing composition that uses in the color filter of the present invention is not particularly limited, and preferably is 1～80 quality %, 3～50 quality % more preferably in the total solid composition of described composition.
In pigment dispensing composition,, can improve the fine dispersiveness and the dispersion stabilization of pigment by containing above-mentioned grafting polymer compound, preferred above-mentioned pigment derivative type compound and/or the terminal-modified type macromolecular compound of further using.In addition, can keep pigment particles the miniaturization state, can improve colouring power, can also improve application adaptability (being non-aggregation, amorphism, flowability especially).Thus, when constituting color filter of the present invention, can obtain excellent color characteristics and high contrast.
The organic pigment that uses in the color filter of the present invention does not limit aspect tone, can list Li such as perylene compound pigment, purple cyclic ketones compound pigment, quinoline a word used for translation ketonic compound pigment, quinoline a word used for translation ketone naphtoquinone compounds pigment, anthraquinone compounds pigment, anthracene is formed anthrone compound pigment, benzimidazole alkane ketonic compound pigment, disazo condensation compound pigment, bis-azo compound pigment, azo-compound pigment, indanthrone compound pigment, phthalocyanine compound pigment, triaryl carbon compound pigment dioxazine compound pigment, amino anthraquinones compound pigment, diketopyrrolo-pyrrole compound pigment, thioindigo compound pigment, isoindoline compounds pigment, Isoindolone compounds pigment, pyrene anthrone compound pigment, iso-violanthrone compound pigment, their potpourri etc.
Wherein, preferred quinoline a word used for translation ketonic compound pigment, diketopyrrolo-pyrrole compound pigment, dioxazine compound pigment, phthalocyanine compound pigment or azo-compound pigment, more preferably diketopyrrolo-pyrrole compound pigment, phthalocyanine compound pigment Huo dioxazine compound pigment.At this moment, can also be used in combination the organic pigment more than 2 kinds or the solid solution of organic pigment.In addition, can also with combinations such as organic pigment, macromolecule organic material.
In color filter of the present invention, use by organic pigment being dissolved into the organic pigment solution that obtains in the good solvent (the 1st solvent) and having intermiscibility with good solvent and be that the solvent (the 2nd solvent) of bad solvent mixes combination (build up) pigment particles that forms to organic pigment.Wherein, the combination of good solvent and bad solvent need have enough poorly aspect the solubleness of organic pigment, need select preferred combination in conjunction with organic pigment, but so long as the combination that pigment particles is separated out then can select arbitrarily.
As long as good solvent can dissolve employed organic pigment and mix with described bad solvent or mixed uniformly solvent then is not particularly limited.About the dissolubility of organic pigment in good solvent, the solubleness of organic pigment is preferably more than the 0.2 quality %, more preferably more than the 0.5 quality %.The solubleness of organic pigment in good solvent does not have the special upper limit, but when considering used usually organic pigment, is actually below the 50 quality %.This solubleness can be the solubleness when dissolving in the presence of acid or alkali.
As good solvent, for example can list aqueous vehicles (water for example, hydrochloric acid or sodium hydrate aqueous solution), the alcoholic compound solvent, the amide compound solvent, the ketonic compound solvent, the ether compound solvent, the aromatics solvent, the carbon disulphide solvent, the fatty compound solvent, the nitrile compound solvent, the sulfoxide compound solvent, the halogenide solvent, the ester compounds solvent, ionic liquid, their mixed solvent etc., preferred aqueous vehicles, the alcoholic compound solvent, the ketonic compound solvent, the ether compound solvent, the sulfoxide compound solvent, the ester compounds solvent, amide compound solvent or their potpourri, more preferably aqueous vehicles, the alcoholic compound solvent, the ester compounds solvent, sulfoxide compound solvent or amide compound solvent, further preferred aqueous vehicles, sulfoxide compound solvent or amide compound solvent, preferred especially sulfoxide compound solvent or amide compound solvent.
As the sulfoxide compound solvent, can list for example dimethyl sulfoxide (DMSO), diethyl sulfoxide, hexa-methylene sulfoxide, sulfolane etc.As the amide compound solvent, can list for example N, dinethylformamide, 1-Methyl-2-Pyrrolidone (1-methyl-2-pyrrolidone), 2-Pyrrolidone (2-pyrrolidinone), 1,3-dimethyl-2-imidazolone, 2-Pyrrolidone, epsilon-caprolactams, formamide, N-NMF, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl propanamide, HMPA etc.
In addition, about organic pigment being dissolved in the good solvent and the concentration of the organic pigment solution that obtains, about 1/100 scope of saturation concentration～this saturation concentration that preferably be organic pigment under the condition when dissolving in good solvent.
Preparation condition to organic pigment solution is not particularly limited, and can select the scope from normal pressure to subcritical, super critical condition.Preferred normal pressure temperature down be-10～150 ℃, more preferably-5～130 ℃, be preferably 0～100 ℃ especially.
Though common part is arranged as the object lesson of good solvent solvent of enumerating and the solvent of enumerating as bad solvent, but be not with good solvent and identical solvent combination as bad solvent, but be benchmark with pass with each organic pigment that is adopted, as long as the solubleness of organic pigment in good solvent is sufficiently higher than the solubleness in bad solvent, for example the difference of their solubleness is preferably more than the 0.2 quality %, more preferably more than the 0.5 quality %.The difference of the solubleness of organic pigment in good solvent and bad solvent does not have the special upper limit, but considers used organic pigment usually, in fact is generally below the 50 quality %.
When the organic pigment uniform dissolution in good solvent the time, can also be added pigment dissolved promoter such as acid or alkali and dissolved.Usually in molecule, have under the situation of pigment of the group that can dissociate because of alkalescence, preferably add alkali; When not existing because of the group that dissociates of alkalescence and have a plurality of nitrogen-atoms that are easy to the addition proton etc. in molecule, preferably add acid.For example quinoline a word used for translation ketone, diketopyrrolo-pyrrole, disazo condensation compound pigment can dissolve because of alkalescence.Phthalocyanine compound pigment can dissolve because of acid, but the compound that dissolves because of alkalescence is wherein also arranged, because of alkaline mechanism of dissolving and unclear.
As alkali, can list inorganic bases such as lithium hydroxide, NaOH, potassium hydroxide, calcium hydroxide, baryta hydrate, or organic base such as trialkylamine, diazabicyclo hendecene (DBU), metal alkoxide; Wherein preferred trialkylamine, metal alkoxide, more preferably metal alkoxide.Addition to alkali is not particularly limited, and under the situation of inorganic base, is 1.0～30 molar equivalents, more preferably 1.0～25 molar equivalents, preferred especially 1.0～20 molar equivalents with respect to organic pigment preferably.Under the situation of organic base, preferably with respect to organic pigment be 1.0～100 molar equivalents, more preferably 5.0～100 molar equivalents, be preferably 20～100 molar equivalents especially.
As acid, can list mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid, or organic acid such as acetate, trifluoroacetic acid, oxalic acid, methane-sulforic acid, trifluoromethanesulfonic acid; Wherein preferred mineral acid, more preferably sulfuric acid.Addition to acid is not particularly limited, and usually compares with alkali and excessively uses.No matter be mineral acid or organic acid, preferably with respect to organic pigment be 3～500 molar equivalents, more preferably 10～500 molar equivalents, be preferably 30～200 molar equivalents especially.
When with alkali or acid mixes with organic solvent and when using as the good solvent of organic pigment, dissolve fully in order to make alkali or acid, can also in organic solvent, add a little water or lower alcohol etc. have high solubleness in alkali or acid solvent.The amount of water or lower alcohol is below the 50 quality %, more preferably below the 30 quality % with respect to organic pigment solution total amount preferably.Particularly, can make water, methyl alcohol, ethanol, n-propanol, isopropyl alcohol, butanols etc.
When organic pigment was dissolving in good solvent, the organic pigment molecule usually also decomposed.The decomposition of relevant pigment molecule is described below, and preferably suppresses the decomposition of organic pigment when organic pigment solution is contacted with bad solvent.Particularly, when organic pigment dissolved because of the effect of pigment dissolved promoter, the organic pigment molecule also decomposed, and in the case, preferably before making organic pigment solution and bad solvent will soon contact, added pigment dissolved promoter in good solvent.At this moment, for example preferred following manner: organic pigment added to prepare the not consoluet dispersion liquid of organic pigment in the good solvent (for example dimethyl sulfoxide (DMSO)) in advance, add the pigment dissolved promoter formed by above-mentioned acid or alkali then to make pigment solution, immediately pigment solution is mixed with bad solvent afterwards.
The viscosity of organic pigment solution is preferably 0.5～80.0mPas, 1.0～50.0mPas more preferably.
Bad solvent is not particularly limited, and the solubleness of preferred organic pigment is below the 0.02 quality %, more preferably below the 0.01 quality %.The solubleness of organic pigment in bad solvent does not have special lower limit, but considers used organic pigment usually, is actually more than the 0.000001 quality %.This solubleness can be the solubleness when dissolving in the presence of acid or alkali.In addition, about the intermiscibility or the even Combination of good solvent and bad solvent, the preferred good meltage of solvent in bad solvent is more than the 30 quality %, more preferably more than the 50 quality %.The good meltage of solvent in bad solvent do not have the special upper limit, in fact can be with ratio mixing arbitrarily.
As bad solvent, for example can list aqueous vehicles (water for example, hydrochloric acid or sodium hydrate aqueous solution), the alcoholic compound solvent, the ketonic compound solvent, the ether compound solvent, the aromatics solvent, the carbon disulphide solvent, the fatty compound solvent, the nitrile compound solvent, the halogenide solvent, the ester compounds solvent, ionic liquid, their mixed solvent etc., preferred aqueous vehicles, the alcoholic compound solvent, the ketonic compound solvent, the ether compound solvent, ester compounds solvent or their potpourri, more preferably aqueous vehicles, alcoholic compound solvent or ester compounds solvent.
As the alcoholic compound solvent, can list for example methyl alcohol, ethanol, isopropyl alcohol, n-propanol, 1-methoxyl-2-propyl alcohol etc.As the ketonic compound solvent, can list for example acetone, MEK, methyl isobutyl ketone, cyclohexanone.As the ether compound solvent, can list for example dimethyl ether, diethyl ether, tetrahydrofuran etc.As the aromatics solvent, can list for example benzene, toluene etc.As the fatty compound solvent, can list for example hexane etc.As the nitrile compound solvent, can list for example acetonitrile etc.As the halogenide solvent, can list for example methylene chloride, triclene etc.As the ester compounds solvent, can list for example ethyl acetate, ethyl lactate, acetate (2-(1-methoxyl) propyl group) ester etc.As ionic liquid, can list for example 1-butyl-3-methylimidazole and PF 6 -Salt etc.
The condition of the bad solvent when generating organic filler is separated out is not particularly limited, and can select in the scope from normal pressure to subcritical, super critical condition.Temperature under the normal pressure be preferably-30～100 ℃, more preferably-10～60 ℃, be preferably 0～30 ℃ especially.
When organic pigment solution is mixed with bad solvent, can add in the two any and mix, but preferably organic pigment solution jet flow be mixed in bad solvent, at this moment, bad solvent is preferably the state through stirring.Stirring rate be preferably 100～10000rpm, more preferably 150～8000rpm, be preferably 200～6000rpm especially.Can also use pump etc. also can not use during interpolation.In addition, can the interior interpolation of liquid also can add outward by liquid, but more preferably add in the liquid.In addition, preferably by supply pipe and utilize pump to supply in the liquid continuously.The internal diameter of supply pipe is preferably 0.1～200mm, 0.2～100mm more preferably.The speed of supplying with in liquid from supply pipe is preferably 1～10000ml/min, 5～5000ml/min more preferably.
When organic pigment solution is mixed with bad solvent,, can control the particle diameter of the organic nano particle of separating out generation by regulating Reynolds number.Wherein, Reynolds number is the dimensionless group of the flow state of expression fluid, and it is represented with following formula.
Re=ρ UL/ μ mathematical expression (1)
In the mathematical expression (1), Re represents that Reynolds number, ρ represent the density [kg/m of organic pigment solution 3], relative velocity [m/s], L when U represents that organic pigment solution and the 2nd solvent meet represent the stream of the part that organic pigment solution and the 2nd solvent meet or the equivalent diameter [m] of supply port, the coefficient of viscosity [Pas] that μ represents organic pigment solution.
Equivalent diameter L is when the pipe arrangement with the arbitrary section shape is assumed to be pipe with its opening diameter or stream equivalence, the diameter of this equivalence pipe.When the sectional area with pipe arrangement be A, when being p with the periphery of the infiltration length (girth) of pipe arrangement or stream, equivalent diameter L represents with following mathematical expression (2).
L=4A/p mathematical expression (2)
Preferred organic pigment solution is injected in the bad solvent to form particle by pipe arrangement, and when using pipe as pipe arrangement, equivalent diameter is consistent with the diameter of pipe.For example can regulate equivalent diameter by the opening diameter that changes liquid supply port.Value to equivalent diameter L is not particularly limited, and is for example identical with the definition of the preferred internal diameter of above-mentioned supply port.
Relative velocity U when organic pigment solution is met with bad solvent is defined as the relative velocity of the direction vertical with the face of the two part of meeting.That is, for example in the time will injecting organic pigment solution in static bad solvent and mix, the speed of injecting from supply port equates with relative velocity U.Value to relative velocity U is not particularly limited, and preference is as being set at 0.5～100m/s, more preferably being set at 1.0～50m/s.
The density p of organic pigment solution is the value by the kind decision of selected material, in the scope of the preferred material that uses, in fact for example is 0.8～2.0kg/m in manufacture method of the present invention 3In addition, the coefficient of viscosity μ of organic pigment solution also is that its preferable range is identical with the definition of the preferred viscosity of above-mentioned organic pigment solution by the value of decisions such as used material and environment temperature.
The more little then easy more formation laminar flow of the value of Reynolds number (Re), big more then easy more formation turbulent flow.For example by Reynolds number is adjusted to more than 60, can control the particle diameter of organic nano particle, Reynolds number (Re) is preferably set to more than 100, more preferably is set at more than 150.Reynolds number does not have the special upper limit, for example by regulating to control, can controlledly obtain good organic nano particle in the scope below 100000, and is therefore preferred.Perhaps, for the mean grain size that makes the nano particle that obtains reaches below the 60nm, also Reynolds number can be set in conditions of higher.At this moment, in above-mentioned scope, by improving Reynolds number, can controlledly obtain the littler organic nano particle of particle diameter usually.
The mixing ratio of organic pigment solution and bad solvent is preferably 1/50～2/3, more preferably 1/40～1/2, is preferably 1/20～3/8 especially in volume ratio.
Nano particle concentration when organic fine particles is separated out in the liquid is not particularly limited, preferably with respect to solvent 1000ml organic filler be the scope of 10～40000mg, more preferably 20～30000mg scope, be preferably the scope of 50～25000mg especially.
In addition, the preparative-scale when the pigment nano particle is generated is not particularly limited, and the combined amount of preferred bad solvent is the preparative-scale of 10～2000L, the preparative-scale of 50～1000L more preferably.
About the particle diameter of organic filler, the method that has the measuring method utilized to quantize, also represent with the mean size of colony; Particle diameter as frequent use, the peaked mode particle diameter that expression distributes, the median particle diameter that is equivalent to the intermediate value of integral distribution curve, various mean grain size (number is average, length is average, area is average, quality is average, volume averaging etc.) etc. are arranged, in the present invention, unless otherwise specified, then mean grain size is meant number average bead diameter.The mean grain size of pigment particle (primary particle) is a nano-scale, and preference is as being below the 100nm.In addition, this mean grain size be preferably 1nm～1 μ m, more preferably 1～200nm, more preferably 2～100nm, be preferably 5～80nm especially.Need to prove that in manufacture method of the present invention, the particle of formation can be that the crystalline particle also can be the noncrystalline particle, perhaps also can be their potpourri.
In addition, as the index of the monodispersity of representing particle, in the present invention, unless otherwise specified, use the ratio (Mv/Mn) of volume average particle size (Mv) and number average bead diameter (Mn).The monodispersity of pigment particle (primary particle) is that Mv/Mn is preferably 1.0～2.0, more preferably 1.0～1.8, is preferably 1.0～1.5 especially.
Assay method as the particle diameter of organic filler can list microscopic method, mass method, light scattering method, light shield method, electric-resistivity method, acoustic method, dynamic light scattering method, preferred especially microscopic method, dynamic light scattering method.As spendable microscope in the microscopic method, can list for example scanning electron microscope, transmission electron microscope etc.As the particle assay device that utilizes dynamic light scattering method, for example can list day machine dress corporate system Nano Trak UPA-EX150, Da mound electronics corporation's braking attitude light scattering photometer DLS-7000 series (being trade name) etc.
In the present invention,, preferably make in pigment solution and the bad solvent at least one contain spreading agent, preferably make pigment solution contain spreading agent at least when pigment particle is separated out with preparation during dispersion liquid.In addition, when above-mentioned pigment particles is separated out, can also make described grafting polymer compound coexistence.
Also preferred the use carried out the surface-treated pigment particles with spreading agent in advance, can carry out promoting the surface treatment of spreading agent to the absorption of pigment particles.Spreading agent has following effects: (1) is adsorbed onto the surface of pigments of separating out rapidly and forms fine nano particle; And (2) prevent that these particles from condensing again.As spreading agent, can use for example macromolecule dispersing agent of anionic property, cationic, zwitter-ion, nonionic or pigment derivative.In addition, as this spreading agent, can also use above-mentioned graft type macromolecular compound.
As macromolecule dispersing agent, its weight-average molecular weight is preferably 1000～500000, more preferably 10000～500000, is preferably 10000～100000 especially.Particularly, can list polyvinylpyrrolidone, polyvinyl alcohol (PVA), polyvinyl methyl ether, polyglycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl-acetic ester multipolymer, polyvinyl alcohol (PVA)-part dimethoxym ethane thing, polyvinyl alcohol (PVA)-part butyral thing, vinylpyrrolidone-vinyl-acetic ester multipolymer, polyethylene oxide/propylene oxide segmented copolymer, polyacrylate, polyvinyl sulfuric acid salt, poly-(4-vinylpridine) salt, polyamide, PAH salt, condensation naphthalene sulfonate, cellulose derivative, starch derivative etc.In addition, can also use natural polymer subclasses such as alginates, gelatin, albumin, casein, Arabic gum, tragacanth gum, lignosulfonate.Wherein, preferably polyethylene pyrrolidone.These macromolecular compounds can a kind use separately or are used in combination more than 2 kinds, in addition, can also be used in combination low-molecular-weight spreading agent.About being used for the spreading agent of pigment dispersing, " be documented in 29～46 pages of " pigment dispersing stabilization と surface treatment skill Intraoperative Evaluation value " (chemical feelings Reported Association meeting, Dec calendar year 2001 development capable).
As anionic property spreading agent (anionic surfactant), can list N-acyl-N-alkyltaurate, soap, alkyl sulfate salt, alkyl benzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinate succinate, alkyl phosphate salt, naphthalene sulfonic acid-formaldehyde condensation product, polyxyethylated sulfuric acid etc.Wherein, preferred N-acyl-N-alkyltaurate.As the N-acyl-N-alkyltaurate, the compound of putting down in writing in the preferred Japanese kokai publication hei 3-273067 instructions.These anionic property spreading agents can use separately also and can be used in combination more than 2 kinds.
Diamines that cationic spreading agent (cationic surfactant) comprises quaternary ammonium salt, alkoxylate polyamines, fatty amine polyoxyethylene ether, fatty amine, derived by fatty amine and aliphatic alcohol and polyamines, by the imidazoline of fatty acid derived and the salt of their cationic material.These cationic spreading agents can use separately also and can be used in combination more than 2 kinds.
The zwitter-ion spreading agent is to have the cation group spreading agent partly that anionic group part that described anionic property spreading agent has in molecule and cationic spreading agent have in molecule in molecule simultaneously.
As nonionic spreading agent (nonionic surfactant), can list polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl amine, fatty acid glyceride etc.Wherein, preferred polyoxyethylene alkylaryl ether.These nonionic spreading agents can use separately also and can be used in combination more than 2 kinds.
As pigment derivative type spreading agent, can list previously described pigment derivative type compound.
As spreading agent, the preferred use contained amino pigment dispersing agent.Wherein, amino comprises primary amino radical, secondary amino group, uncle's amino, and it also can be a plurality of that amino number can be one.Can be to import to have the pigment derivative compound that amino substituting group forms on the pigment skeleton, also can be to have the polymer compound that amino monomer obtains as the polymerization composition.As their example, can list the compound put down in writing in TOHKEMY 2000-239554 communique for example, 2003-96329 communique, 2001-31885 communique, Japanese kokai publication hei 10-339949 communique, the special fair 5-72943 communique of Japan, the international paragraph 0018～0033 that discloses the WO2006/121017 pamphlet, the Japanese Patent Application 2006-129714 instructions etc., but be not limited to these.
In order further to improve the uniformly dispersed and storage stability of pigment nano particle, the content of spreading agent is preferably the scope of 0.1～1000 mass parts, more preferably scope, the scope of 5～20 mass parts more preferably of 1～500 mass parts with respect to pigment 100 mass parts.If the content of spreading agent is too small, be difficult to sometimes then see that the dispersion stabilization of pigment nano particle improves.In addition, spreading agent can use separately also and can a plurality ofly be used in combination.
In the present invention, preferably after being separated out, the organic pigment particulate reduces or removes the solvent composition (following also abbreviate as this operation concentrated sometimes) of the dispersion liquid that contains this precipitation particles.Thus, can obtain to be suitable for nano particle concentrate or the organic pigment fine-particle powder of making the color filter coating fluid.
In the present invention, for concentrating of solvent, can be used alone or in combination common device.For example, the dryer as using hot blast preferably uses posture dryer, band drier, stirring drier, fluidized bed dryer, spray dryer, pneumatic drier etc.; As utilizing heat conducting dryer, preferably use heated drum, multiple pipe dryer, drum drier etc.In addition, form, can also use freeze drier or infrared drier according to solvent.
In these means, from being suitable for obtaining the viewpoint of the organic pigment fine-particle powder of convection drying, especially preferably use spray dryer (for example Ohkawara Kakohki Co., Ltd.'s system COC-12), fluidized bed dryer (for example Nara Machinery Co., Ltd.'s system MSD-100) by dispersion liquid.In addition,, also can be used in combination multiple dry means, for example can use and to obtain technologies such as fine-particle powder with the pigment dispersing thing that drum drier concentrates in advance with the heated drum bone dry in order to obtain the few organic pigment fine-particle powder of residual solvent amount.
About drying condition,, then do not restrict especially so long as can make solvent evaporate and not make the scope of material generation modifications such as pigment and spreading agent.Take place under the situation of modification under than the low temperature of this temperature at other spreading agents etc., it be natural needing further to reduce temperature.But, owing to consider that according to employed solvent kind difference, admissible temperature range inner drying speed is slack-off, therefore this moment is in order to accelerate rate of drying, according to the kind of dryer can make up decompression, mix, means such as multipolarity.
The amount that reduces or remove the solvent composition is not particularly limited, and in the mode that reduces the solvent composition, the 50 quality % that preferably remove total solvent composition are above, more preferably remove more than the 75 quality %.Become to assign to obtain in the mode of organic pigment fine-particle powder removing solvent, the 80 quality % that preferably remove total solvent composition are above, more preferably remove more than the 90 quality %.
When by reducing or when removing solvent and becoming to assign to make the solvent composition to reduce, the water cut in the residual dispersion thing being not particularly limited, be preferably set to 0.01～3 quality %, more preferably be set at 0.01～1 quality %.At this moment, preferably remove solvent by for example above-mentioned seasoning etc. and become to assign to obtain the organic pigment fine-particle powder, the content of solid constituent was preferably set to 50～100 quality %, more preferably was set at 70～100 quality % this moment.
Can carry out repeatedly enrichment process, preference is as before described interpolation the 3rd solvent later and/or carry out afterwards.
In the present invention, preferably as above through concentrating or powdered and add different types of solvent in the material that obtains, the solvent that carries out more than 1 time is replaced.At this moment, the organic filler that preferably will be in state of aggregation disperses again.Contained organic filler may condense because of its enrichment or powdered usually in the above-mentioned organic filler solution by being concentrated such as extraction solvent, centrifuging, dryings.To this, filtrator filters though can carry out faster, in order to obtain good disperse state once more, preferably makes the form of the floc unit of cohesion with the degree that can disperse again.
In addition, in the pigment dispensing composition that in color filter of the present invention, uses,, can controlledly form the soft condensed matter of wherein contained organic pigment particulate by predetermined process, operation.Wherein, soft cohesion is meant the weak state of aggregation of the degree that can disperse again as required as described above, should be called floc unit especially by soft condensed matter sometimes.Thus, the organic pigment particulate of for example separating out can be formed floc unit and separate in the dispersive composition of water system by filtering fast etc.And then, separated floc unit can be distributed to again and be suitable for making in the organic solvent of color filter, thereby make the dispersive composition of organic solvent system efficiently.That is, when the mixed solvent of good solvent (the 1st solvent) and bad solvent (the 2nd solvent) is the solvent of water system, it can be replaced to efficiently the 3rd solvent of forming by organic solvent, thereby switch dispersion medium (external phase).
For the particle that makes above-mentioned soft state of aggregation disperses again, use common decentralized method not enough sometimes.The formation that described graft type macromolecular compound can act on so soft condensed matter (floc unit) disperses with it again, makes temporary transient soft cohesion of soft condensed matter (floc unit) or dispersion more apace, thereby can obtain good disperse state.Therefore, good fine dispersiveness (obtaining the characteristic of nominal particle size equably) when particle is separated out in the mixed liquor of good solvent and bad solvent and dispersion stabilization (characteristic of long term maintenance fine particle size equably) be even switching to medium the final solvent that is suitable for color filter and also be maintained after the dispersion, thereby can realize the high-performance of color filter.And above-mentioned grafting polymer compound can not hinder the optical characteristics of color filter etc., thereby can realize the high-performance of color filter and liquid crystal indicator.
In the present invention, preferably after pigment particle is separated out, replace the solvent composition as described above, and make it contain replacement, also can make it become the final solvent of pigment dispensing composition with solvent (the 3rd solvent).In the present invention, " final solvent " is meant main solvent in the pigment dispensing composition when carrying out solidification and making color filter (preferably accounting for the solvent more than the 50 quality % of pigment dispensing composition).In addition, preferably in dispersive composition, do not contain the solvent that is replaced by final solvent, is removed or reduces (for example making the solvent composition of the mixed liquor that above-mentioned organic pigment particulate separates out) in fact.At this moment, do not contain in fact be meant its content can not produce the performance (contrast etc.) of the regulation of color filter in essence effect or this below degree, for example preferred in above-mentioned dispersive composition contained amount be below the 10 quality %.
Kind to the 3rd solvent is not particularly limited, be preferably organic solvent, for example preferred ester compounds solvent, alcoholic compound solvent, aromatics solvent, fatty compound solvent, ketonic compound solvent, preferred especially ester compounds solvent, ketonic compound solvent.
As the ester compounds solvent, can list for example acetate (2-(1-methoxyl) propyl group) ester, ethyl acetate, ethyl lactate etc.As the alcoholic compound solvent, can list for example normal butyl alcohol, isobutyl alcohol etc.As the aromatics solvent, can list for example benzene,toluene,xylene etc.As the fatty compound solvent, can list for example normal hexane, cyclohexane etc.As the ketonic compound solvent, can list for example MEK, acetone, cyclohexanone etc.
Wherein, preferred ethyl lactate, ethyl acetate, acetone, ethanol, more preferably ethyl lactate.These solvents can also can more than 2 kinds and be used in a kind of independent use.Wherein, the 3rd solvent is and good solvent (the 1st solvent) or the different solvent of bad solvent (the 2nd solvent).Need to prove, in the present invention, will become sometimes composition medium, be referred to as " the 3rd solvent " with described good solvent and described bad solvent solvent all inequality.Other compositions that can contain above-mentioned solvent and then contain as required.
Add to replace with period of solvent so long as after pigment particle is separated out, then be not particularly limited, but preferably after aforesaidly concentrating, removing operation, add.That is, the solvent composition of being made up of good solvent (the 1st solvent) and bad solvent (the 2nd solvent) in the mixed liquor after preferably organic nano particle being separated out replaces with and replaces with solvent (the 3rd solvent).
In addition, when preparation pigment dispensing composition described later, preferably through the 1st time concentrate, remove operation (the 1st concentrate) after, add the 3rd solvent and carry out the solvent replacement, utilize the 2nd time the operation (the 2nd concentrates) that concentrates, removes that the solvent composition is reduced to obtain concentrate or to remove the solvent composition to obtain powder again.And, add bonding agent and/or solvent afterwards, thereby can obtain desired pigment dispensing composition.
The addition of replacing with solvent is not particularly limited, and is 100～300000 mass parts, 500～10000 mass parts more preferably with respect to pigment particle 100 mass parts preferably.
Pigment particle can use with the state that disperses in for example excipient (vehicle).If described excipient is with coating, then refer to make when being in liquid condition the part of the medium of pigment dispersing, it is included as liquid and by combining the part (bonding agent) that makes curing of coating with described pigment and with the composition (organic solvent) of its dissolved dilution.Wherein, in the present invention, the bonding agent that nano particle used when forming with decentralized again in the bonding agent of use can be identical also can be different.
In the present invention, the concentration of the pigment particles in the pigment dispensing composition can suitably be determined according to purpose, preferably with respect to the total amount of dispersive composition, pigment particles be preferably 2～30 quality %, more preferably 4～20 quality %, be preferably 5～15 quality % especially.In the time of in being distributed to aforesaid excipient, the amount of bonding agent and dissolved dilution composition can wait suitably according to the kind of organic pigment to be determined, with respect to the total amount of dispersive composition, bonding agent be preferably 1～30 quality %, more preferably 3～20 quality %, be preferably 5～15 quality % especially.The dissolved dilution composition is preferably 5～80 quality %, 10～70 quality % more preferably.
In having reduced the concentrated nano particle liquid of solvent composition, as mentioned before, nano particle condenses sometimes.As the method that such cohesion nano particle is disperseed again, can use the method for for example utilizing hyperacoustic process for dispersing or applying physical energy.Employed ultrasonic irradiation device preferably has can apply the above hyperacoustic function of 10kHz, for example ultrasonic equal pulp grinder, ultrasonic washer etc.Because when fluid temperature rose in ultrasonic irradiation, heat-coagulation (with reference to non-patent literature 1) can take place nano particle, therefore preferably fluid temperature is set at 1～100 ℃, more preferably is set at 5～60 ℃.The temperature controlling method can be by dispersion liquid temperature controlling, temperature control dispersion liquid the temperature control of adjustment layer wait and carry out.
Apply the dispersion machine that uses when physical energy concentrates the pigment nano particle dispersion that obtains as making, be not particularly limited, can list for example dispersion machines such as kneader, roller mill, masher, super mill (Supermill), dissolver, homogenizer, sand mill.In addition, as suitable process for dispersing, also can list the process for dispersing of high pressure dispersion method, use fine particle bead.
Photosensitive composition comprises dispersion thing, bonding agent, monomer or oligomer and the Photoepolymerizationinitiater initiater or the Photoepolymerizationinitiater initiater system of described organic pigment nano particle.Below each composition of photosensitive composition is described.
About the organic pigment particulate of making nano-scale and the method for its dispersion liquid are at length narrated.The content of pigment particle is preferably 3～90 quality %, more preferably 20～80 quality %, 25～60 quality % more preferably with respect to the total solid composition in the photosensitive composition (in the present invention, the total solid composition is meant the total of the composition except organic solvent).Measure when too much when this, the viscosity of dispersion liquid rises, and is making existing problems aspect the adaptability sometimes.Measure when very few when this, colouring power is abundant inadequately sometimes.About the pigment nano particle (pigment particle) of performance colorant effect, preferable particle size is that following, the special preferable particle size of 0.1 μ m is below the 0.08 μ m.In addition, in order to mix colours, can also use with common pigment combinations.Pigment can use pigment mentioned above.
As monomer or oligomer, the polyfunctional monomer that preferably has 2 above ethylenic unsaturated double-bonds and carry out addition polymerization by the irradiation of light.As such monomer and oligomer, can list in molecule, have at least 1 can addition polymerization ethylenic unsaturated group and boiling point under the normal pressure be compound more than 100 ℃.
Monomer or oligomer can use separately also can mix use more than 2 kinds, with respect to the total solid composition of photosensitive composition, its content is generally 5～50 quality %, is preferably 10～40 quality %.When this is measured when too much, it is difficult that the control of development becomes, and making existing problems aspect the adaptability sometimes; Measure when very few when this, the curing power when exposing sometimes is insufficient.
As bonding agent, preferably have the bonding agent of acidic-group, can add during with the preparation of jetted ink or photosensitive composition at color filter, but preferably when making above-mentioned pigment dispensing composition or the pigment nano particle add when forming.Can also and be used at organic pigment solution adding organic pigment solution to add bonding agent in the bad solvent the two or one of them that generates the pigment nano particle.Also preferably binder solution is added when the pigment nano particle forms by other system in addition.
As bonding agent, preferably has the polymkeric substance of the alkali-soluble of carboxylic acid group or carboxylate group isopolarity group at side chain.
Bonding agent can use separately or use with the state with the composition of the polymkeric substance of common film forming and usefulness, is generally 10～200 mass parts, is preferably 25～100 mass parts with respect to the addition of pigment particle 100 mass parts.
As Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system (in the present invention, the Photoepolymerizationinitiater initiater system is meant the potpourri of bringing into play the function of photopolymerization initiation with a plurality of combination of compounds), can use the compound that uses in the common photopolymerisable initiation.
Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system can be used separately also can mix use more than 2 kinds, preferred especially use more than 2 kinds.When using at least 2 kinds of Photoepolymerizationinitiater initiaters, the inequality that display characteristic particularly shows can reduce.
With respect to the total solid composition of photosensitive composition, the content of Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system is generally 0.5～20 quality %, is preferably 1～15 quality %.When this is measured when too much, sensitivity is too high and become and be difficult to control sometimes; Measure when very few when this, the sensitivity of exposing sometimes is low excessively.
In photosensitive composition, except mentioned component, can also further use resin combination preparation organic solvent (the 4th solvent), also can be with it as final solvent.Example as the 4th solvent is not particularly limited, and can enumerate ester output class, ethers, ketone.In these solvents, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, acetate ethyl card must esters, acetate butyl card must ester, propylene glycol methyl ether acetate etc. can be used as solvent and preferably uses.These solvents can use separately also and can be used in combination more than 2 kinds.In addition, as the 4th solvent, can use above-mentioned high boiling organic solvent, for example can use boiling point as required is 180 ℃～250 ℃ solvent.The content of the 4th solvent is preferably 10～95 quality % with respect to the resin combination total amount.
In addition, in photosensitive composition, can also contain surfactant, thermal polymerization and prevent agent, colorant (dyestuff, pigment), ultraviolet light absorber, adhesion auxiliary agent, other adjuvant etc.
Photosensitive composition can be made the color filter jetted ink by suitably its composition being regulated.When making color filter and use jetted ink, preferably contain above-mentioned pigment particles, above-mentioned monomer or oligomer and above-mentioned bonding agent, preferably do not use above-mentioned Photoepolymerizationinitiater initiater system.At this moment, preferably control ink temperature so that the amplitude of fluctuation of ink viscosity is in ± 5%.Viscosity during ejaculation be preferably 5～25mPas, more preferably 8～22mPas, be preferably 10～20mPas (value when in the present invention, viscosity then is meant 25 ℃ unless otherwise specified) especially.Except setting above-mentioned ejaculation temperature,, also can regulate viscosity by regulating the kind and the addition of ingredient in the printing ink.Described viscosity for example can utilize common device such as cone-plate type rotational viscosimeter or E type viscosity meter to measure.
In addition, from the viewpoint of the flatness that improves pixel, the surface tension of the printing ink when preferably penetrating be 15～40mN/m (in the present invention, surface tension unless otherwise specified, the value when then being meant 23 ℃).More preferably 20～35mN/m, most preferably be 25～30mN/m.Surface tension can be regulated by interpolation surfactant, solvent types.Described surface tension for example can use surface tension apparatus (consonance interface science Co., Ltd. system, CBVP-Z) or full automatic balance type electricity to cause surface tensiometer ESB-V analyzers such as (consonance scientific company systems), measure by the platinized platinum method.
Attached as color filter with blowing of jetted ink, can adopt and spray charged printing ink continuously and utilize method that electric field controls, use piezoelectric element method, the heating printing ink of ink jet and the whole bag of tricks such as method that utilize it to foam and spray off and on off and on.
In addition, about in order to form the employed ink ejecting method of each pixel, can use, on substrate, form the usual ways such as method that transparent image receiving layer is beaten droplet then in advance the method for the method of printing ink heat curing, photocuring.
In the present invention, before using color filter to form pixel, preferably make the next door in advance, apply printing ink to the part of being surrounded by this next door with jetted ink.This next door can be any next door, under the situation of making color filter, the next door with light-proofness (following also abbreviate as " next door ") of band black matrix" function is arranged preferably.This next door can use with common color filter with the same material of black matrix", make by same method.
Above-mentioned photosensitive composition can be coated with by common coating process, can form coated film by being dried then.About coating process, can list the coating that for example utilizes the slit-shaped nozzle, spin coating etc.
Photosensitive transfer printing material has the photo-sensitive resin that contains above-mentioned photosensitive composition, concrete formation is not particularly limited, but is preferably the photosensitive transfer printing material that for example uses integrated film to form.Example as the formation of one-body molded film can list interim supporter/thermoplastic resin/middle layer/photo-sensitive resin/protective film and stack gradually the formation that forms.
In photosensitive transfer printing material, even interim supporter need have flexible and under pressurization or pressurization and heating remarkable distortion, contraction or elongation do not take place yet.As the example of so interim supporter, can list pet film, cellulose triacetate film, plasticon, polycarbonate film etc., wherein, preferred especially biaxial stretch-formed pet film.
As the composition that uses in the thermoplastic resin, the organic polymer material of putting down in writing in the preferred Japanese kokai publication hei 5-72724 communique, being preferably selected from the softening point of measuring by dimension card Vicat method (particularly for utilizing the polymkeric substance softening point measurement method of U.S. material test method(s) ASTMD1235) especially is about organic polymer material below 80 ℃.Particularly, can list tygon, polyolefin such as polypropylene, ethene and vinyl-acetic ester or its saponified various ethylene copolymers, ethene and acrylate or its are saponified, Polyvinylchloride, vinyl chloride and vinyl-acetic ester and saponified various vinyl chloride copolymers thereof, Vingon, metachloroethylene copolymer, polystyrene, styrene and (methyl) acrylate or its saponified various styrol copolymers, polyvinyl toluene, vinyltoluene and (methyl) acrylate or its saponified various vinyl toluene copolymers, poly-(methyl) acrylate, (methyl) acrylate copolymer of (methyl) butyl acrylate and vinyl-acetic ester etc., vinyl-acetic ester multipolymer nylon, copolymer nylon, N-alkoxy methyl nylon, the organic polymers such as various polyamides of N-dimethylamino nylon.
In photosensitive transfer printing material, for prevent when the coating multiple coating layer and the coating back when preserving composition mix, the middle layer preferably is set.As this middle layer, preferably use conduct " separating layer " oxygen barrier film record, that have the oxygen block function in the Japanese kokai publication hei 5-72724 communique, in the case, time load minimizing, the throughput rate raising of sensitivity raising, exposure machine during exposure.
As this oxygen barrier film, preferably show low oxygen permeability and can be dispersed or dissolved in oxygen barrier film in water or the aqueous alkali, can from normally used oxygen barrier film, suitably select.Wherein, the combination of special preferably polyethylene alcohol and polyvinylpyrrolidone.
For fear of contaminated when preserving or damage, thin protective film is set on photo-sensitive resin preferably.Protective film can be formed by or materials similar identical with interim supporter, but should be difficult to separate from photo-sensitive resin.As the protective film material, preference such as organosilicon paper, polyolefin or polytetrafluoroethylsheet sheet.
Photosensitive transfer printing material can followingly be made: coating on interim supporter, the dry coating fluid (thermoplastic resin coating fluid) that dissolves the adjuvant of thermoplastic resin and obtain are to be provided with thermoplastic resin, the solution of coating on thermoplastic resin afterwards, dry intermediate layer material by the solvent composition that does not make the thermoplastic resin dissolving is provided with photo-sensitive resin with the solvent application, the drying that do not make the middle layer dissolving afterwards.
In addition, also can followingly make: prepare on above-mentioned interim supporter, to be provided with thermoplastic resin and middle layer and the sheet material that obtains and on protective film, photo-sensitive resin is set and the sheet material that obtains, and fit mutually so that the middle layer contacts with photo-sensitive resin; Perhaps, prepare on above-mentioned interim supporter, thermoplastic resin to be set and the sheet material that obtains and photo-sensitive resin is set and middle layer and the sheet material that obtains on protective film, and fit so that thermoplastic resin contacts with the middle layer mutually.
In photosensitive transfer printing material, the thickness of photo-sensitive resin be preferably 1.0～5.0 μ m, more preferably 1.0～4.0 μ m, be preferably 1.0～3.0 μ m especially.In addition, be not to limit especially, preferred thickness of each layer about other, preferred usually interim supporter is that 15～100 μ m, thermoplastic resin are that 2～30 μ m, middle layer are that 0.5～3.0 μ m, protective film are 4～40 μ m.
Color filter of the present invention has the pixel that contains above-mentioned pigment dispensing composition and above-mentioned grafting polymer compound.At this moment, pixel preferably is made of 3 looks (R pixel, G pixel, B pixel), and is that next door, each pixel are divided and are provided on the substrate by the next door with above-mentioned black matrix" preferably.
Color filter of the present invention is excellence aspect contrast.In the present invention, contrast be illustrated between 2 polaroids, when polarization axle is parallel light transmission capacity when vertical ratio (with reference to " and nineteen ninety the 7th the color reversion glory learn コ Application Off ア レ Application ス, 512 colour specifications 10.4 " サ イ ズ TFT-LCD with カ ラ one Off イ Le タ, plant wooden, Xiao Seki, good fortune forever, in the mountain " etc.).
The contrast height of color filter means that the difference of the light and shade when making up with liquid crystal can be bigger, and this is very important performance concerning LCD replaces CRT.
Color filter of the present invention is being used for the TV time spent, the value of each monochromatic colourity that the redness (R) that preferred F10 light source sends, green (G) and blueness (B) are whole and following table record is (in the present invention following, be called " target colourity ") poor (Δ E) 5 with interior scope in, more preferably 3 with interior, particularly preferably in 2 in.
x????????y????????Y
---------------------------
R????0.656????0.336????21.4
G????0.293????0.634????52.1
B????0.146????0.088????6.90
---------------------------
In the present invention, colourity utilizes microspectrophotometer (Olympus Optical Co Ltd.'s system, OSP100 or 200) to measure, and the result who spends as the F10 light source visual field 2 calculates, with the xyY value representation of xyz chromatic diagram.In addition, with the difference La of target colourity *b *The aberration of chromatic diagram is represented.
Contrast of LCD degree height, the dense degree of black that possesses color filter of the present invention etc. described the power excellence, is preferably the VA mode especially.Applicable this computer of taking notes is with the liquid crystal indicator of big picture such as display or TV monitor etc.In addition, color filter of the present invention is preferred for the CCD device, and the excellent performance of performance.
According to the present invention, the color filter that color characteristics is good and contrast is high of the dispersive composition making of using the pigment particle with fine dispersiveness and dispersion stabilization can be provided, and use liquid crystal indicator this color filter, that show excellent display characteristic.
Color filter of the present invention is to use the dispersive composition of the pigment particle with fine dispersiveness and dispersion stabilization to make, show that high color describes power and suppress the unequal good color characteristics of color and high contrast, used the liquid crystal indicator of this color filter to bring into play to suppress and prevent that it from burning the display characteristic of the excellence of sticking (the Japanese original text is " the baked I is paid I ").
Embodiment
Below based on embodiment the present invention is described in further detail, but the present invention not Application Example carry out determinate explanation.In addition, in the present embodiment, " part " and " % " is quality criteria unless otherwise specified.
(embodiment, comparative example)
＜pigment dispensing composition A 〉
In dimethyl sulfoxide (DMSO) (with the pure medicine corporate system of light) 1500ml, add 28% methanol solution 75.0ml, pigment C.I. paratonere 254 (Irgaphor Red BT-CF, trade name, CibaSpecialty Chemicals (Co., Ltd.) corporate system) 50g and polyvinylpyrrolidone (the pure medicine corporate system of K-30, trade name and the light) 90.0g of sodium methoxide, thereby (density is 1.0kg/m to preparation pigment solution A 2).Use Viscometer VM-10A-L (trade name, CBC materials corporate system) to measure the viscosity of this pigment solution A, the viscosity of pigment solution A when fluid temperature is 25.0 ℃ is 18.0mPas as a result.Prepare the different therewith water 2000ml that contains 1mol/l hydrochloric acid (with the pure medicine corporate system of light) 20ml as bad solvent.
At this, pigment solution A is injected into temperature with NP-KX-500 type high capacity pulse-free pump (non-pulsationpump) (trade name, Japanese precision chemical corporate system) is controlled to be 25 ℃, and has carried out with 500rpm with GK-0222-10 type ラ モ Application De ス タ one ラ one (trade name, Fujisawa Pharmaceutical's system) among the water 2000ml of bad solvent of stirring.With the stream diameter of the liquor charging pipe arrangement of pigment solution A with supply with bore and be set at 0.8mm, this supply port is submerged in the bad solvent, 100ml/min injects with flow velocity, forms organic pigment particles, thus preparation dispersible pigment dispersion A.For the pigment nano particle among this dispersible pigment dispersion A, use Nano Trak UPA-EX150 (trade name, day machine dress corporate system) to measure number average bead diameter Mn, the result is 22nm.
To concentrate 90 minutes with the Kokusan of Co., Ltd. corporate system H-112 type filter centrifugal and Shikishima Canvas (Co., Ltd.) corporate system P89C type filter cloth with 5000rpm according to the dispersible pigment dispersion A of said process preparation, and reclaim the pigment nano particle that obtains and concentrate pastel.Use the pigment content of Agilent corporate system 8453 type spectrophotometric determination pastel, the result is 17.2 quality %.
Then, (mol ratio is 28/72 to be added in pigment dispersing agent A 0.1g, the methacrylic acid/benzyl methacrylate multipolymer that interpolation is synthesized according to TOHKEMY 2000-239554 communique among the ethyl lactate 50.0cc in the concentrated pastel 13.8g of above-mentioned pigment nano particle, weight-average molecular weight is 30,000,40% acetate (1-methoxyl-2-propyl group) ester solution) 5.94g and the solution that obtains; Stirred 60 minutes with 1500rpm with dissolver.Afterwards, add ethyl acetate 25.0cc, and then make dispersion liquid with the 500rpm stirring after 10 minutes with dissolver.
The dispersion liquid that obtains is filtered with Sumitomo electric fine polymer corporate system FP-010 type filter, thereby obtain the concentrated pigment liquid A (nano dye concentration is 33.4 quality %) of pasty state.
Use above-mentioned pastel, prepare the pigment dispensing composition A of following composition.
The concentrated pigment liquid A 19.3g of above-mentioned pasty state
Acetate (1-methoxyl-2-propyl group) ester 45.1g
The potpourri of above-mentioned composition uses the zirconium dioxide bead of diameter as 0.65mm with motor-driven mill M-50 (ア イ ガ one ジ ヤ パ Application corporate system), is that 9m/s disperseed 1 hour with the peripheral speed, makes pigment dispensing composition A.
(formation of black (K) image)
After the washing of alkali-free glass substrate usefulness UV wash mill, wash with washing agent, and then carry out supersound washing with ultrapure water.To this substrate carry out under 120 ℃, 3 minutes thermal treatment, make the surface state stabilization.
With after this substrate cooling temperature adjustment to 23 ℃, with glass substrate with slit-shaped nozzle with coating machine (FAS Technologies corporate system, trade name: MH-1600) be coated with by what following table 1-1 was put down in writing and form the photosensitive composition K1 that constitutes.Then with dry 30 seconds of VCD (Minton dryer, Tokyo are answered chemical industry (Co., Ltd.) corporate system), make the part of solvent dry, after coating layer lost flowability, 120 ℃ of following prebake 3 minutes, obtaining thickness was the photo-sensitive resin K1 of 2.4 μ m.
Table 1-1
K pigment dispersing thing 1 (carbon black) 25 mass parts
Propylene glycol methyl ether acetate 8.0 mass parts
MEK 53 mass parts
K pigment dispersing thing 1 (carbon black) 25 mass parts
Bonding agent 2 9.1 mass parts
The hydroquinone monomethyl ether 0.002 mass parts
DPHA liquid 4.2 mass parts
Polymerization initiator A 0.16 mass parts
Surfactant 1 0.044 mass parts
In having the type that closely the connects exposure machine of ultrahigh pressure mercury lamp (the High-Tech ElectronicsEngineering of Hitachi (Co., Ltd.) corporate system), make substrate and mask (quartzy exposed mask) state for standing vertically with picture pattern, with the distance setting between exposed mask face and this photo-sensitive resin is 200 μ m, uses 300mJ/cm 2Exposure carry out pattern exposure.
Then, with the shower nozzle pure water of spraying, after the surface of this photo-sensitive resin K1 is evenly moistening, with KOH is that developer solution (contains KOH, non-ionic surfactant, commodity are called 100 times of dilutions of CDK-1, Fujifilm Electronic Materials corporate system) be that 0.04MPa carries out shower and developed 80 seconds at 23 ℃ down and with flat burner pressure, obtain the Butut image.Then, with the pressure injection ultrapure water of UHV (ultra-high voltage) Washing spray nozzle,, obtain the image K of black (K) to remove residue with 9.8MPa.Then, heat is located 30 minutes under 220 ℃.
Photosensitive composition K1 is following to be obtained: at first, measure K pigment dispersing thing 1, propylene glycol methyl ether acetate, in temperature is that 24 ℃ (± 2 ℃) mix down, stirred 10 minutes with 150rpm, then, measure MEK, bonding agent 2, the hydroquinone monomethyl ether, DPHA liquid, polymerization initiator A (2, two (the trichloromethyl)-6-[4 ' of 4--(N, the two ethoxy carbonyl methyl of N-) amino-3 '-bromophenyl]-the s-triazine), surfactant 1, in temperature is to add successively under 25 ℃ (± 2 ℃), is to obtain in 30 minutes with the 150rpm stirring under 40 ℃ (± 2 ℃) in temperature again.
＜K pigment dispersing thing 1 〉
Carbon black 13.1 mass parts
(trade name: Nipex 35, Degussa Japan (Co., Ltd.) corporate system)
Pigment dispersing agent A 0.65 mass parts
Polymkeric substance 6.72 mass parts
(random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight are 3.7 ten thousand)
Propylene glycol methyl ether acetate 79.53 mass parts
Figure GPA00001142255500321
＜bonding agent 2 〉
Polymkeric substance 27 mass parts
(random copolymers of benzyl methacrylate/methacrylic acid=78/22 mol ratio, molecular weight 3.8 ten thousand)
Propylene glycol methyl ether acetate 73 mass parts
＜DPHA liquid 〉
Dipentaerythritol acrylate 76 mass parts
(contain polymerization inhibitor MEHQ 500ppm, Japanese chemical drug (Co., Ltd.) corporate system, trade name: KAYARAD DPHA)
Propylene glycol methyl ether acetate 24 mass parts
＜surfactant 1 〉
MEGAFACE F-780-F 30 mass parts
(big Japanese ink chemical industry (Co., Ltd.) corporate system): composed as follows
C 6F 13CH 2CH 2OCOCH=CH 240 mass parts,
H (OCH (CH 3) CH 2) 7OCOCH=CH 255 mass parts, with
H (OCH 2CH 2) 7OCOCH=CH 2The multipolymer of 5 mass parts (molecular weight is 30,000)
MEK 70 mass parts
(formation of red (R) pixel)
On the substrate that has formed above-mentioned image K, use by the photosensitive composition R1 that constitutes that forms that puts down in writing among the following table 1-2, with the same operation of formation of above-mentioned black (K) image, form the pixel R after the thermal treatment.The thickness of this photo-sensitive resin R1 and the coating weight of pigment are as follows.In addition, the preparation process of photosensitive composition R1 is identical with above-mentioned photosensitive composition K1.
Photoresist thickness (μ m) 1.60
Pigment application amount (g/m 2) 1.00
C.I.P.R.254 coating weight (g/m 2) 0.80
C.I.P.R.177 coating weight (g/m 2) 0.20
Table 1-2
Pigment dispensing composition A (CIPR254) 40 mass parts
R pigment dispersing thing 2 (CIPR177) 4.5 mass parts
Propylene glycol methyl ether acetate 7.6 mass parts
MEK 37 mass parts
Bonding agent 1 0.7 mass parts
DPHA liquid 3.8 mass parts
Polymerization initiator B 0.12 mass parts
Polymerization initiator A 0.05 mass parts
Phenothiazine 0.01 mass parts
Pigment dispensing composition A (CIPR254) 40 mass parts
Surfactant 1 0.06 mass parts
＜R pigment dispersing thing 2 〉
C.I.P.R.177 18 mass parts
(trade name: Cromophtal Red A2B, Ciba Specialty Chemicals (Co., Ltd.) corporate system)
Polymkeric substance 12 mass parts
(random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight are 30,000)
Propylene glycol methyl ether acetate 70 mass parts
＜bonding agent 1 〉
Polymkeric substance 27 mass parts
(random copolymers of benzyl methacrylate/methacrylic acid=78/22 mol ratio, molecular weight are 40,000)
Propylene glycol methyl ether acetate 73 mass parts
＜polymerization initiator B 〉
2-trichloromethyl-(right-the styryl styryl) 1,3, the 4-oxadiazole
(formation of green (G) pixel)
On the substrate that has formed above-mentioned image K and pixel R, use by the photosensitive composition G1 that constitutes that forms that puts down in writing among the following table 1-3, according to forming pixel G after the thermal treatment with the same operation of the formation of above-mentioned black (K) image.The thickness of this photo-sensitive resin G1 and the coating weight of pigment are as follows.In addition, the preparation process of photosensitive composition G1 is identical with above-mentioned photosensitive composition K1.
Photoresist thickness (μ m) 1.60
Pigment application amount (g/m 2) 1.92
C.I.P.G.36 coating weight (g/m 2) 1.34
C.I.P.Y.150 coating weight (g/m 2) 0.58
Table 1-3
G pigment dispersing thing 1 (CIPG36) 28 mass parts
Y pigment dispersing thing 1 (CIPY150) 15 mass parts
Propylene glycol methyl ether acetate 29 mass parts
MEK 26 mass parts
Cyclohexanone 1.3 mass parts
Bonding agent 2 2.5 mass parts
DPHA liquid 3.5 mass parts
G pigment dispersing thing 1 (CIPG36) 28 mass parts
Polymerization initiator B 0.12 mass parts
Polymerization initiator A 0.05 mass parts
Phenothiazine 0.01 mass parts
Surfactant 1 0.07 mass parts
＜G pigment dispersing thing 1 〉
Fujifilm Electronic Materials (Co., Ltd.) corporate system " trade name: GT-2 "
＜Y pigment dispersing thing 1 〉
Mikuni color (Co., Ltd.) corporate system " trade name: CF yellow-EX3393 "
(formation of blue (B) pixel)
On the substrate that has formed above-mentioned image K, pixel R and pixel G, use is by the photosensitive composition B1 that constitutes that forms that puts down in writing among the following table 1-4, according to form the same operation of described black (K) image, form the pixel B after the thermal treatment, obtain color filter A1.The thickness of this photo-sensitive resin B1 and the coating weight of pigment are as follows.In addition, the preparation process of photosensitive composition B1 is identical with above-mentioned photosensitive composition K1.
Photoresist thickness (μ m) 1.60
Pigment application amount (g/m 2) 0.75
C.I.P.B.15:6 coating weight (g/m 2) 0.705
C.I.P.V.23 coating weight (g/m 2) 0.045
Table 1-4
B pigment dispersing thing 1 (CIPB15:6) 8.6 mass parts
B pigment dispersing thing 2 (CIPB15:6+CIPV23) 15 mass parts
Propylene glycol methyl ether acetate 28 mass parts
MEK 26 mass parts
Bonding agent 3 17 mass parts
DPHA liquid 4.0 mass parts
Polymerization initiator B 0.17 mass parts
Phenothiazine 0.02 mass parts
B pigment dispersing thing 1 (CIPB15:6) 8.6 mass parts
Surfactant 0.06 mass parts
＜B pigment dispersing thing 1 〉
Mikuni color (Co., Ltd.) corporate system " trade name: CF blue-EX3357 "
＜B pigment dispersing thing 2 〉
Mikuni color (Co., Ltd.) corporate system " trade name: CF blue-EX3383 "
＜bonding agent 3 〉
Polymkeric substance 27 mass parts
(random copolymers of benzyl methacrylate/methacrylic acid/methyl methacrylate=36/22/42 mol ratio, molecular weight are 3.8 ten thousand)
Propylene glycol methyl ether acetate 73 mass parts
[making of liquid crystal indicator]
Use color filter A1 to make liquid crystal indicator A1, and display characteristic is estimated.
The glass substrate that will be formed with color filter is put into sputter equipment, 100 ℃ of following whole vacuum evaporations 1300
Figure GPA00001142255500361
Behind the ITO of thickness (indium tin oxide), annealed 90 minutes down, make the ITO crystallization, thereby form ito transparent electrode at 240 ℃.According to " embodiment 1 " of TOHKEMY 2004-240335 communique in the same method of sept formation method of record, on the ito transparent electrode of above-mentioned making, form sept.Use following positive-working photosensitive resin layer coating fluid, be formed with formation liquid crystal aligning control projection on the ito transparent electrode of described sept.But, expose, develop and cure operation and use following method.Configuration closely connects exposure machine (the High-Tech ElectronicsEngineering of Hitachi strain formula meeting corporate system) and so that the distance on the surface of the photomask of regulation and photo-sensitive resin is 100 μ m, utilizes ultrahigh pressure mercury lamp with 150mJ/cm by this photomask 2Irradiation energy closely connect exposure.
Eurymeric resist liquid: 53.3 mass parts
(Fujifilm Electronic Materials (Co., Ltd.) corporate system FH-2413F)
MEK: 46.7 mass parts
MEGAFACE F-780F 0.04 mass parts
(big Japanese ink chemical industry (Co., Ltd.) corporate system)
Then, 2.38% tetramethylammonium hydroxide aqueous solution is sprayed to substrate last 30 second under 33 ℃, develops simultaneously with the shower type developing apparatus.Thus, developing and to remove the unwanted part (exposure portion) of photo-sensitive resin, is the base plate for liquid crystal display device of the liquid crystal aligning control that constitutes of the photo-sensitive resin of the shape of expectation with projection thereby obtain being formed with on color filter side group plate by Butut.Then, this is formed with liquid crystal aligning control under 230 ℃, cured 30 minutes, control and use projection thereby on base plate for liquid crystal display device, form liquid crystal aligning through solidifying with the base plate for liquid crystal display device of projection.
The alignment films that is made of polyimide further is set on the above-mentioned base plate for liquid crystal display device that obtains.Afterwards, according to the mode of the pixel groups of surrounding color filter with the sealant of the position printing epoxy resin of the black matrix" housing that is equivalent to be provided with around, and drip MVA pattern liquid crystal simultaneously, after fitting with counter substrate, the substrate that applying forms is heat-treated, make sealant cures.On two faces of the liquid crystal cells that so obtains, attach the polaroid HLC2-2518 of the SANRITZ of Co., Ltd. corporate system.Then, constitute 3 wavelength cold-cathode tube light source (Toshiba Lighting﹠amp; Technology (Co., Ltd.) corporate system FWL18EX-N) backlight, and be configured in the side at the back side that becomes the liquid crystal cells that is provided with described polaroid, thus make liquid crystal indicator A1.
[mensuration of the contrast of color filter]
Measure the contrast of the red pixel of the above-mentioned color filter A1 that obtains by following assay method.Locate to be provided with diffuser plate at cold-cathode tube light source (using among the SHARP corporate system LCD TV LC-22GD3) and make back light unit, between 2 polaroids (the polaroid POLAX-15N of the Le ケ オ of Co., Ltd. corporate system), color filter is set, the Y value of the colourity of the light that the Y value of the colourity of the light that sees through when by using polaroid being arranged on parallel Nicol sees through when being arranged to cross Nicols is obtained contrast.The mensuration of colourity is used chroma-luminance meter (Topcon of Co., Ltd. corporate system BM-5A).2 polaroids, color filter, chroma-luminance meter the following mensuration in position is set: at next-door neighbour's backlight rear polaroid and working sample are set, the light of transmission is seen through from the polaroid that is arranged on chroma-luminance meter the place ahead, measure with the chroma-luminance meter of the position that is arranged at 500mm.The mensuration angle of chroma-luminance meter is set at 2 °.Light quantity setting backlight is maximum.In said method, owing to measure the independent contrast of red pixel, therefore in said method, in the chroma-luminance meter, increase attachment lens (Topcon of Co., Ltd. corporate system AL-11), to measure regional centralized to 60～70 μ m, the chroma-luminance meter that only makes light through the R pixel in the color filter enter the position that is arranged at 50mm carries out.The results are shown in down in the Table A.
[evaluation of the sticking fault of the burning of liquid crystal indicator]
For liquid crystal indicator A1,, measure the remnant DC voltages that occurs in the liquid crystal cells, as the index of burning sticking fault by obtaining the method that the flicker of putting down in writing among Fig. 4 B that makes TOHKEMY 2000-275645 communique reaches minimum the suitableeest utility voltage.Wherein, the measured value of remnant DC voltages is more little, more can inhibition of sintering the generation of sticking fault.At this, the average evaluation that remnant DC voltages is lower than 80mV is that average evaluation more than the 100mV is " burning sticky hair gives birth to " for " burn sticking take place ", the average evaluation that will be lower than 100mV for " burning the sticking generation that has slightly ", with remnant DC voltages.The results are shown in down in the Table A.
[evaluation of the display characteristic of liquid crystal indicator]
Adopt the display characteristic (red describe, the color inequality of the redness during monochromatic the demonstration have or not) of 10 people's group assessment liquid crystal indicator A1.Adopt following grade evaluation on average being shown in the Table A with 10 people.
Red describes
5: the red excellence of describing
4: red describe no problem (well)
3: red describing has deficiency (common) slightly
2: the red deficiency (poor slightly) of describing
1: red reproduction poor (non-constant)
Red color inequality
5: red color inequality is not seen fully
4: red color inequality no problem (well)
3: red color inequality can be felt (common) slightly
2: red color inequality can be known identification (poor slightly)
1: red color uneven significantly visible (non-constant)
Polymkeric substance that uses when the polymkeric substance that uses when pigment particles is formed and the preparation of pigment dispensing composition and spreading agent replace, similarly make color filter A2～A14 and liquid crystal indicator A2～A14 respectively with the manufacturing process of color filter A1 and liquid crystal indicator A1 shown in Table A.
In addition, except the pigment dispensing composition A that uses following pigment dispersing thing B replacement use, all fully similarly make color filter A15 and liquid crystal indicator A15 with the making of color filter A1 and liquid crystal indicator A1.
* pigment dispensing composition B
The embodiment 2 same methods of employing and TOHKEMY 2002-296770 communique are made the following pigment dispersing thing B that forms.
C.I. paratonere 254 6.4g
Disperbyk161 (trade name, BYK Chemie corporate system) 16.64g
Acetate (1-methoxyl-2-propyl group) ester 38.16g
They are mixed, fully disperse with sand mill.In the liquid that obtains, add single terminal carboxyl group polybenzyl methacrylate (material of record among the embodiment 2 of TOHKEMY 2002-296770 communique) 3.2g, mix, make pigment dispensing composition B by Break down legal system.
In addition, same, except the pigment dispensing composition A that replaces using with following pigment dispersing thing C, fully similarly make color filter A16 and liquid crystal indicator A16 with the making of color filter A1 and liquid crystal indicator A1.
* pigment dispensing composition C
Same composition, the method for dispersible pigment dispersion G-1 among the embodiment (paragraph 0089) of employing and TOHKEMY 2002-273191 communique, and replace with C.I. pigment green 36, C.I. pigment yellow 13 8 respectively with weight such as C.I. paratonere 254 ground, in addition, fully similarly make pigment dispensing composition C with dispersible pigment dispersion G-1 by Break down legal system.
Contrast, burning to each test body is sticking, display characteristic is estimated, and the results are shown in down in the Table A.
Table A
Figure GPA00001142255500401
Graft type 1: graft type macromolecular compound, SOLSPERSE 24000GR (trade name, Lubrizol corporate system)
Graft type 2: graft type macromolecular compound, SOLSPERSE 28000 (trade name, Lubrizol corporate system)
Graft type 3: graft type macromolecular compound, SOLSPERSE 32000 (trade name, Lubrizol corporate system)
Graft type 4: graft type macromolecular compound, Disperbyk-161 (trade name, BYK Chemie corporate system)
Pigment derivative type 1:EFKA6750 (trade name, EFKA corporate system)
Pigment derivative type 2:SOLSPERSE 5000 (trade name, Lubrizol corporate system)
Terminal-modified type 1:SOLSPERSE 3000 (trade name, Lubrizol corporate system)
D-1: contain single terminal sulfonic polymethylmethacrylate
From The above results as can be known, by using the graft type macromolecular compound, not only can obtain the color filter of high-contrast, and can improve the various performances of the color filter in the liquid crystal indicator.The detailed mechanism of action it be unclear that, but think because the graft type macromolecule to by the absorption affinity height of pigment solution with the surface of mixing the pigment particle of separating out of the bad solvent of pigment, when making color filter and even liquid crystal indicator, in the decentralized environment of above-mentioned pigment particle, show distinctive effect, thereby keep good fine dispersiveness and dispersion stabilization.
The high color of color filter demonstration of the present invention is described power and is suppressed unequal good color characteristics of color and high contrast, can be applicable to liquid crystal indicator.In addition, liquid crystal indicator of the present invention has inhibition, prevents that it from burning the display characteristic of sticking excellence.
Though the present invention and embodiment thereof are illustrated together, but short of specifying, then be that what kind of detailed description all is not that we are invented the qualification of being done, as long as, then should do the explanation of wide region without prejudice to the spirit and scope of the represented invention of the scope of appended claim.
The application advocates the right of priority at the patented claim Japanese Patent Application 2007-311472 of Japan's proposition on November 30th, 2007, and its content is incorporated herein by the part of the record of this instructions as reference.

Claims (9)

1. color filter, it is to form by having the pixel that contains pigment dispensing composition and graft type macromolecular compound, wherein, the solution that described pigment dispensing composition contains by will the dissolving organic pigment forms in good solvent mixes the organic pigment particles that forms with the bad solvent of described organic pigment, and described bad solvent and described good solvent mix.
2. color filter according to claim 1, wherein, described pigment dispensing composition is not contain the solvent composition in the mixed liquor that forms described organic pigment particles in fact and contain different with it final solvents to form.
3. color filter according to claim 1 and 2, wherein, the replacement from the solvent composition to described final solvent in the described mixed liquor is to finish by the following operation that repeats more than 1 time: reduce or remove solvent composition the described mixed liquor and the different types of replacement solvent of the solvent composition in interpolation and the described mixed liquor.
4. according to each described color filter in the claim 1～3, it is characterized in that described pigment dispensing composition makes described graft type macromolecular compound coexistence and obtains when described organic pigment particles forms.
5. according to each described color filter in the claim 1～4, it is characterized in that described pigment dispensing composition contains described graft type macromolecular compound and obtains after described organic pigment particles forms.
6. according to each described color filter in the claim 1～5, it is characterized in that described graft type macromolecular compound is the graft type macromolecular compound that has the structural unit of following general formula (5) expression in side chain;
Figure FPA00001142255400011
In the general formula (5), R 74Expression hydrogen atom or carbon number are 1～8 alkyl, Q represent cyano group, carbon number be 6～30 aryl or-COOR 75, wherein, R 75Expression hydrogen atom, carbon number are that 1～22 alkyl or carbon number are 6～30 aryl.
7. according to each described color filter in the claim 1～6, it is characterized in that the number average bead diameter of described organic pigment particles is below 100 nanometers.
8. a liquid crystal indicator is characterized in that, it possesses each described color filter in the claim 1～7.
9. according to 8 described liquid crystal indicators, wherein, described liquid crystal indicator is the VA mode.
CN2008801181755A 2007-11-30 2008-11-26 Color filter and liquid crystal display device using the same Pending CN101878440A (en)

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