CN102279526B - Color composition for color filter and color filter - Google Patents

Color composition for color filter and color filter Download PDF

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Publication number
CN102279526B
CN102279526B CN201110184450.7A CN201110184450A CN102279526B CN 102279526 B CN102279526 B CN 102279526B CN 201110184450 A CN201110184450 A CN 201110184450A CN 102279526 B CN102279526 B CN 102279526B
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resin
methyl
color filter
acid
parts
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CN102279526A (en
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斋藤悠生
北村健一
小久保奈津子
山本昌幸
佐佐木正博
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Toyocolor Co Ltd
Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
Toyocolor Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

The invention provides a color composition for a color filter. The color composition comprises a coloring agent, a binder resin and an organic solvent. The coloring agent comprises blue pigment and crude salt product. The crude salt product is formed from a xanthenes-based acidic dye and a compound having a cationic group. The compound having a cationic group comprises one selected from the group consisting of quaternary ammonium compound, amine, and a resin having the cationic group at a side chain.

Description

Color composition for color filter and color filter
Technical field
The present invention relates to the color composition for color filter using in the manufacture of color filter and the color filter with the filter section that uses its formation, this color filter is for color liquid crystal display arrangement, colour pick-up tube element etc.
Background technology
In recent years, liquid crystal indicator, because it is slim, is therefore be evaluated as and has saving spatiality, lightweight and save electric power etc., recently, in TV purposes, is popularized rapidly.In TV purposes, require further to improve the performances such as brightness and contrast, as forming in the color filter of parts of color liquid crystal device, also expect further to improve transmissivity, improve contrast etc.
As the method for making of color filter, known have a following method: utilizing photoresist to form after pattern, by the decoration method of pattern-dyed; Be pre-formed the transparency electrode of predetermined pattern, by applying voltage, the resin ionization that contains pigment of dissolving, disperse formed to the electrodeposition process of pattern in solvent; The ink that use contains heat reactive resin or ultraviolet curable resin for example carries out the print process of hectographic printing; Use is dispersed in the colorants such as pigment the Pigments method of the colored anticorrosive additive material forming in photo anti-corrosion agent material etc.Recently, Pigments method becomes main flow.But, there is confusion by the polarized light degree of liquid crystal control in the light scattering that use pigment produces due to pigment particles as the color filter of colorant etc., consequently, has the problem of the brightness or the contrast reduction that easily cause color liquid crystal display arrangement.
As the technology addressing this problem, propose to contain the colored anticorrosive additive material of dyestuff as colorant.But, for the dyestuff using in color filter, require heat-resisting and photostability and with form the compatibility of resin of color filter and the dissolubility in the organic solvent that dissolves this resin.For example, Japanese kokai publication hei discloses the colored anticorrosive additive material that mixed dye forms in hardening resin composition for No. 6-75375.But this colour anticorrosive additive material, due to baking after can carrying out at lower temperature, is therefore the material that has used the dyestuff that thermotolerance is low, it not the material that the thermotolerance etc. of dyestuff self is improved.
Therefore,, in order to increase dissolubility and to improve thermotolerance and photostability, proposed to use the salt of anionic property dyestuff and cationic compound as the color filter of colorant.For example, in No. 5-333207, TOHKEMY, disclose the one-tenth salt dyestuff that alkylammonium, alkanol ammonium or cyclohexyl ammonium for anionic dye is formed to salt and obtain, in No. 2004-307391, TOHKEMY, disclose the one-tenth salt dyestuff that anionic dye naphthyl ammonium formation salt is obtained.But, these become salt dyestuff to the dissolubility of the solvent using in the time making color filter not enough, also poor with the compatibility of adhesive resin, be therefore difficult to provide the firmly adaptation between the transparency carrier such as long-term storing stability and film and glass of color composition for color filter.
In addition, the crystallinity water-based coloured material that anionic dye cationic polymer is formed to salt and obtain is for example disclosed in No. 2005-350648, TOHKEMY.But this crystallinity water-based coloured material, in order to use and to be used with particle state, aspect the color filter purposes that requires to use under dissolved state, does not carry out detailed research.
On the other hand, for example in No. 2000-352819, TOHKEMY, proposed will add the colored resin composition that anionic property dyestuff forms in the copolymer solution that there is the monomer copolymerization of amide structure and obtain.It,, by making amide structure as working with the colored spots of anionic property dyestuff, can make the dyestuff stabilization in film, improves tolerance.But in disclosed method, multipolymer mixes in organic solvent with anionic dye therein, therefore exist the dyestuff that polarity is high cannot fully dissolve and produce the such problem of foreign matter.
Summary of the invention
Invent problem to be solved
The object of this invention is to provide a kind of color composition for color filter of excellent storage stability and can not produce foreign matter and and the transparency carrier such as glass between there is the firmly color filter of adaptation.
For solving the means of problem
People of the present invention have carried out meticulous research to achieve these goals, the color composition for color filter that found that the salt (salify product) that the salt-forming reaction that contains the resin by have cationic group at side chain and anionic property dyestuff obtains has high storage stability, and can on this film, not produce foreign matter, adaptation excellence, based on this discovery, thereby complete the present invention.
; according to an aspect of the present invention, provide a kind of color composition for color filter, it is characterized in that; contain colorant, adhesive resin and organic solvent, above-mentioned colorant contains at side chain and has the resin of cationic group and the salify product of anionic property dyestuff.
In one or more mode of the present invention, the above-mentioned resin that has a cationic group at side chain is the vinyl resin that contains the structural unit that following general formula (1) represents.
(in general formula (1), R 1represent hydrogen atom or replacement or unsubstituted alkyl.R 2～R 4represent independently of one another hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted thiazolinyl or replacement or unsubstituted aryl, R 2～R 4in two also can interosculate and form ring.Q represents alkylidene, arlydene ,-CONH-R 5-or-COO-R 5-, R 5represent alkylidene.Y -represent inorganic or organic negative ion.)
In addition,, in one or more mode of the present invention, the ammonium salt value of the vinyl resin of the structural unit that contains above-mentioned general formula (1) expression is 10～200mgKOH/g.
In addition, in one or more mode of the present invention, above-mentioned salify product is to have the resin of cationic group and anionic property dyestuff mixes by above-mentioned at side chain in aqueous solution, and the salt that the counter cation of the counter anion by the above-mentioned resin at side chain with cationic group and anionic dye is formed is removed and the product that makes.
In addition,, in one or more mode of the present invention, above-mentioned organic solvent contains the a kind of above organic solvent being selected from ethyl glycol acetate class, aromatic series alcohols and ketone.
In addition,, in one or more mode of the present invention, above-mentioned colorant also contains pigment.
In addition,, in one or more mode of the present invention, above-mentioned color composition for color filter also contains photopolymerization monomer and/or Photoepolymerizationinitiater initiater.
In addition, according to a further aspect in the invention, provide a kind of color filter that utilizes color composition for color filter of the present invention to form.
Invention effect
In the present invention, contain the color composition for color filter at side chain with the resin of cationic group and the salify product of anionic property dyestuff by use, can obtain the color filter that there is high storage stability, can not produce foreign matter and adaptation excellence in the time that film forms.
Embodiment
Below, the present invention is described in detail.
Color composition for color filter of the present invention is in the colorant carrier that contains adhesive resin and organic solvent, to contain the color composition for color filter at side chain with the resin of cationic group and the salify product of anionic property dyestuff.
< salify product >
There is the resin of cationic group at side chain
As thering is the resin of cationic group for what obtain salify product of the present invention at side chain, as long as there is the resin of at least 1 salt groups at side chain, just have no particular limits, as preferred salt, from the viewpoint such as acquired, preferably ammonium salt, salt compounded of iodine, sulfonium salt, diazo salt He phosphonium salt, if consider storage stability (thermal stability), more preferably ammonium salt, salt compounded of iodine and sulfonium salt.More preferably ammonium salt.
In order to modulate the color composition for color filter that contains salify product of the present invention, embody as the characteristic of color filter, the resin that has a cationic group at side chain preferably has and the resin matrix (part except the cationic group of side chain) of adhesive resin identical type that forms color composition for color filter.In the present invention, as adhesive resin, preferably use acrylic resin, therefore, as the resin at side chain with cationic group, be preferably vinyl resin, be particularly preferably acrylic resin.
As this vinyl resin at side chain with cationic group, preferably use the vinyl resin of the structural unit that contains following general formula (1) expression, particularly preferably use acrylic resin.
In general formula (1), R 1represent hydrogen atom or replacement or unsubstituted alkyl.As R 1the alkyl representing, for example, can enumerate methyl, ethyl, propyl group, normal-butyl, isobutyl, the tert-butyl group, n-hexyl, cyclohexyl.As this alkyl, the alkyl that preferably carbon number is 1～12, the alkyl that more preferably carbon number is 1～8, the alkyl that particularly preferably carbon number is 1～4.
Have in substituent situation at these alkyl, as this substituting group, for example, can enumerate hydroxyl, alkoxy etc.
As R 1, most preferably hydrogen atom or methyl.
In general formula (1), R 2～R 4represent independently of one another hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted thiazolinyl or replacement or unsubstituted aryl.
Wherein, as R 2～R 4the alkyl representing, for example can enumerate straight chained alkyl (methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-octyl, positive decyl, dodecyl, n-tetradecane base, n-hexadecyl and n-octadecane base etc.), branched alkyl (isopropyl, isobutyl, sec-butyl, the tert-butyl group, isopentyl, neopentyl, tertiary pentyl, isohesyl, 2-ethylhexyl and 1,1,3,3-tetramethyl butyl etc.), naphthenic base (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl etc.) and crosslinked ring type alkyl (norborneol alkyl, adamantyl and pinane base etc.).As alkyl, the alkyl that preferably carbon number is 1～18, the alkyl that further preferably carbon number is 1～8.
As R 2～R 4the thiazolinyl representing, for example, can enumerate thiazolinyl (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-1-propylene base, 1-methyl-2-propenyl, 2-methyl-1-propylene base and 2-methyl 2-propenyl etc.), the cycloalkenyl group (2-cyclohexenyl group and 3-cyclohexenyl group etc.) of straight or branched.As thiazolinyl, the thiazolinyl that preferably carbon number is 2～18, the thiazolinyl that further preferably carbon number is 2～8.
As R 2～R 4the aryl representing, for example, can enumerate monocyclic aryl (phenyl etc.), condensation polycyclic formula aryl (naphthyl, anthryl, phenanthryl, anthraquinonyl, fluorenyl and naphthoquinones base etc.) and heteroaromatic alkyl (thienyl (group being derived by thiophene)), furyl (group being derived by furans), pyranose (group being derived by pyrans), pyridine radicals (by pyridine derived group), 9-xanthene ketone group (group being derived by xanthone) and 9-thioxanthene ketone group (group being derived by thioxanthones) etc.
For R 2～R 4, have in substituent situation at abovementioned alkyl, thiazolinyl, aryl, as this substituting group, for example, can enumerate the substituting group being selected from halogen atom, hydroxyl, alkoxy, aryloxy group, thiazolinyl, acyl group, alkoxy carbonyl, carboxyl and phenyl etc.As substituting group, particularly preferably halogen atom, hydroxyl, alkoxy, phenyl.
As R 2～R 4, from the viewpoint of stability, preferably replace or unsubstituted alkyl, more preferably unsubstituted alkyl.
In addition R, 2～R 4in two also can interosculate and form ring.
In general formula (1), the Q that connects propenyl position and ammonium salt base represents alkylidene, arlydene ,-CONH-R 5-or-COO-R 5-, R 5represent alkylidene.Wherein, the polymerism of the monomer of the acrylic resin of the structural unit that comprises general formula (1) expression from generation, acquired reason, be preferably-CONH-R of Q 5-,-COO-R 5-.In addition R, 5more preferably methylene, ethylidene, propylidene or butylidene, be particularly preferably ethylidene.
Y in general formula (1) -(counter anion) is inorganic or organic negative ion.As counter anion, can use known negative ion, specifically, can enumerate hydroxide ion; The halogen ions such as chlorion, bromide ion, iodide ion; The carboxylic acid ion such as formate ion, acetate ion; The inorganic acid radical ions such as carbanion, bicarbonate ion, nitrate ion, sulfate ion, sulfite ion, chromate ion, dichromate ion, phosphate anion, high manganese ion; Cyanide ion; And, the complex ions that six cyano group high ferro (III) acid ions are such etc.Consider from the viewpoint of synthetic adaptability and stability, preferably halogen ion and carboxylic acid ion, most preferably halogen ion.In the time of the counter anion organic acid ion such as be carboxylic acid ion, organic acid ion can with resin matrix covalent bonding, this organic acid ion can form molecule inner salt with the cationic group of side chain.
The vinyl resin of structural unit that general formula (1) represents that contains as optimal way of the present invention is generally copolymer resins.In order to obtain this copolymer resins, not only can be by thering is the ethylenically unsaturated monomers of ammonium salt base and the method for copolymerization monomer copolymerization obtains, can also be by thering is amino ethylenically unsaturated monomers and copolymerization monomer copolymerization, and make that copolymerization obtains there is amino copolymer resins and salinization reagent reacting and the method for carrying out ammonium salt obtains.
Below, the concrete example that can be used for obtaining as the ethylenically unsaturated monomers of the vinyl resin, the especially acrylic resin that contain the structural unit that general formula (1) represents of optimal way of the present invention is shown.In addition, in this manual, will represent that any one of " acrylic acid, methacrylic acid " or both situations are recited as " (methyl) acrylic acid ".Equally, will represent that any one of " acryloyl group, methacryl " or both situations are recited as " (methyl) acryloyl group ".
As the ethylenically unsaturated monomers with quaternary ammonium salt base, for example can enumerate (methyl) acryloxy ethyl-trimethyl salmiac, (methyl) acryloxy ethyl triethyl ammonium chloride, (methyl) acryloxy ethyl dimethyl benzyl ammonium chloride, (methyl) alkyl acrylates such as (methyl) acryloxy ethyl-methyl morpholinyl ammonium chloride are quaternary ammonium salt, (methyl) acryloyl group aminopropyl trimethyl ammonium chloride, (methyl) acryloyl group amino-ethyl triethyl ammonium chloride, alkyl (methyl) the acrylamide quaternary ammonium salts such as (methyl) acryloyl group amino-ethyl dimethyl benzyl ammonium chloride, dimethyldiallylammonium Methylsulfate, trimethyl-ethylene base Phenyl chloride etc.
As thering is amino ethylenically unsaturated monomers, for example, can enumerate (methyl) acrylic acid dimethyl aminoethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid dipropyl amino-ethyl ester, (methyl) acrylic acid diisopropylaminoethyl ethyl ester, (methyl) acrylic acid dibutylamino ethyl ester, (methyl) acrylic acid diisobutyl amino-ethyl ester, (methyl) acrylic acid di-t-butyl amino-ethyl ester, dimethylaminopropyl (methyl) acrylamide, diethylamino propyl group (methyl) acrylamide, dipropyl aminopropyl (methyl) acrylamide, diisopropylaminoethyl propyl group (methyl) acrylamide, dibutylamino propyl group (methyl) acrylamide, diisobutyl aminopropyl (methyl) acrylamide, di-t-butyl aminopropyl (methyl) acrylamide etc. has (methyl) acrylate or (methyl) acrylamide of dialkyl amido, can enumerate dimethylamino styrene, dimethylaminomethyl styrene etc. has the phenylethylene of dialkyl amido, diallyl methyl amine, the diallyl amines such as diallylamine, N-ethenyl pyrrolidone, NVP, N-vinylcarbazole etc. contains amino aromatic vinyl base system monomer.
As salting agent, for example, can enumerate alkyl bromide or benzyl chloride or the benzyl bromide a-bromotoluenes etc. such as alkyl chloride, methyl bromide, bromic ether, propyl bromide or n-octyl bromide such as the sulphonic acid esters such as alkyl sodium sulfate ester, methyl tosylate or methyl benzene sulfonate such as dimethyl suflfate, dithyl sulfate or dipropyl sulfate, methyl chloride, ethyl chloride, propyl chloride or octyl group chlorine.
Have amino ethylenically unsaturated monomers and salting agent react normally by with respect to amino for waiting mole following salting agent to drip and carry out to having in amino ethylenically unsaturated monomers solution.The temperature in ammonium saltization when reaction is 90 ℃ below left and right, especially, by vinyl monomer ammonium salt in the situation that, is preferably 30 ℃ below left and right, and the reaction time is about 1～4 hour.
In addition,, as salting agent, can also use alkoxy carbonyl alkyl halogenide.Alkoxy carbonyl alkyl halogenide can represent with following general formula (2).
Z-R 6-COOR 7general formula (2)
(in general formula (2), Z is the halogens such as chlorine, bromine, is preferably bromine, R 6for carbon number is 1～6, is preferably 1～5, more preferably 1～3 alkylidene, R 7for carbon number is 1～6, is preferably 1～3 low alkyl group.)
Having amino ethylenically unsaturated monomers is by waiting mole following alkoxy carbonyl alkyl halogenide similarly to react with above-mentioned salting agent by being, then making-COOR with respect to amino with halid reaction of alkoxy carbonyl alkyl 7hydrolysis, is converted into carboxylic acid ion (COO -) and obtain.Thus, can obtain the ethylenically unsaturated monomers that there is carboxybetaine structure and there is ammonium salt group.
In addition, as mentioned above, by method same as described above, make to react with salting agent by thering is the amino copolymer resins that has that amino ethylenically unsaturated monomers obtains with copolymerization monomer copolymerization, thereby can obtain the copolymer resins with quaternary ammonium salt base.
As above-mentioned comonomer, can use ethylenically unsaturated monomers.As this ethylenically unsaturated monomers, for example the ester class of preferred (methyl) esters of acrylic acid, crotonates class, vinyl ester, maleic acid diester class, dimethyl ester class, itaconic acid diester class, (methyl) acrylic amide, vinyl ethers, vinyl alcohol, phenylethylene, (methyl) vinyl cyanide etc.
As the concrete example of this vinyl monomer (comonomer), for example, can enumerate following compound.
As the example of (methyl) esters of acrylic acid, can enumerate (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, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) acrylic acid tert-butylcyclohexyl ester, (methyl) acrylic acid 2-ethyl cyclohexyl ester, the tertiary monooctyl ester of (methyl) acrylic acid, (methyl) dodecylacrylate, (methyl) acrylic acid stearyl, (methyl) acrylic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) acrylic acid 3-phenoxy group-2-hydroxy propyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid diethylene glycol monomethyl ether, (methyl) acrylic acid diethylene glycol monoethyl ether, (methyl) acrylic acid triethylene glycol monomethyl ether, (methyl) acrylic acid triethylene glycol list ether, (methyl) polyalkylene glycol acrylate monomethyl ether, (methyl) polyalkylene glycol acrylate list ether, (methyl) acrylic acid beta-phenoxy ethoxy ethyl ester, (methyl) acrylic acid Nonylphenoxy macrogol ester, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid perfluoro capryl ethyl ester, (methyl) acrylic acid two encircles pentyl ester, (methyl) tribromophenyl acrylate, (methyl) acrylic acid tribromo phenyl oxygen base ethyl ester etc.
As the example of crotonates class, can enumerate butyl crotonate and the own ester of crotonic acid etc.
As the example of vinyl ester, can enumerate vinyl acetate, propionate, vinyl butyrate, methoxyacetic acid vinyl acetate and vinyl benzoate etc.As the example of maleic acid diester class, can enumerate dimethyl maleate, diethyl maleate and dibutyl maleate etc.
As the ion of dimethyl ester class, can enumerate dimethyl fumarate, DEF and dibutyl fumarate etc.
As the example of itaconic acid diester class, can enumerate dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.
As the example of (methyl) acrylic amide, can enumerate (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-benzyl (methyl) acrylamide, (methyl) acryloyl morpholine, diacetone acrylamide etc.
As the example of vinyl ethers, can enumerate methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether and methoxy ethyl vinyl ether etc.As the example of phenylethylene, can enumerate styrene, methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, cumene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chlorostyrene, dichlorobenzene ethene, bromostyrene, chloro methyl styrene, by can such as, by hydroxy styrenes, vinyl benzoic acid methyl esters and the α-methyl styrene etc. of the group of acidic materials deprotection (t-Boc etc.) protection.
In addition, can there is acidic group as the ethylenically unsaturated monomers of comonomer.As the ethylenically unsaturated monomers with acidic group, can enumerate the unsaturated monocarboxylic classes such as acrylic acid, methacrylic acid, crotonic acid, α-chloro-acrylicacid, cinnamic acid; Unsaturated dicarboxylic or its anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; 3 yuan of above unsaturated polybasic carboxylic acid or its anhydrides; List [(methyl) acryloxyalkyl] the ester class of the polybasic carboxylic acid more than binary such as mono succinate (2-acryloxy ethyl) ester, mono succinate (2-methacryloxyethyl) ester, phthalic acid list (2-acryloxy ethyl) ester, phthalic acid list (2-methacryloxyethyl) ester; List (methyl) esters of acrylic acid of the polymkeric substance that two ends such as ω-carboxyl-polycaprolactone single-acrylate, ω-carboxyl-polycaprolactone monomethacrylates are carboxyl etc.
The method that preferably contains the vinyl resin of the structural unit of general formula (1) expression as acquisition the present invention, can be used the known methods such as anionic polymerisation, active anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization and active free radical polymerization.Wherein, preferred free radical polymerization or active free radical polymerization.
The in the situation that of radical polymerization, preferably use polymerization initiator.As polymerization initiator, can use for example azo based compound and organic peroxide.As the example of azo based compound, can enumerate 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (cyclohexane 1-nitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2,4-dimethyl-4-methoxyl valeronitrile), dimethyl 2,2 '-azo two (2 Methylpropionic acid ester), 4,4 '-azo two (4-cyanopentanoic acid), 2,2 '-azo two (2-hydroxymethyl propionitrile), 2,2 '-azo two [2-(2-imidazoline-2-yl) propane] etc.As the example of organic peroxide; can enumerate benzoyl peroxide, benzoyl peroxide formic acid tertiary butyl ester, cumene hydroperoxide, diisopropyl peroxydicarbonate, diη-propyl peroxy dicarbonate, two (2-ethoxyethyl group) peroxy dicarbonate, tert-butyl hydroperoxide neodecanoic acid ester, t-butylperoxy pivarate, (3; 5,5-trimethyl acetyl base) superoxide, dipropyl acyl peroxide, diacetyl peroxide etc.These polymerization initiators may be used alone, or two or more kinds may be used in combination.Polymeric reaction temperature is preferably 40～150 ℃, and more preferably 50～110 ℃, polymerization reaction time is preferably 3～30 hours, more preferably 5～20 hours.
Living radical polymerization is due to the subsidiary reaction that can suppress to be produced by common free radical polymerization, and can carry out equably aggregation growth, therefore the uniform resin of block polymer synthesis and molecular weight more easily.
Wherein, Transfer Radical Polymerization take organohalogen compounds or halogenation sulfonyl compound as initiating agent, take transition metal complex as catalyzer; from being adapted to the aspect of monomer widely and can adopting the aspect of the polymerization temperature that can adapt with existing equipment, be preferred.Transfer Radical Polymerization can be carried out according to the method for recording in following list of references 1～8 grade.
(list of references 1) Fukuda etc., Prog.Polym.Sci.2004,29,329
(list of references 2) Matyjaszewski etc., Chem.Rev.2001,101,2921
(list of references 3) Matyjaszewski etc., J.Am.Chem.Soc.1995,117,5614
(list of references 4) Macromolecules 1995,28,7901, Science, 1996,272,866
(list of references 5) WO96/030421
(list of references 6) WO97/018247
(list of references 7) Japanese kokai publication hei 9-208616 communique
(list of references 8) Japanese kokai publication hei 8-41117 communique
In above-mentioned polymerization preferably with an organic solvent.As organic solvent, there is no particular limitation, for example, can use ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, dimethylbenzene, acetone, hexane, MEK, cyclohexanone, propylene glycol methyl ether acetate, DPE acetic acid esters, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters or diethylene glycol monobutyl ether acetic acid esters etc.These polymer solvents can also mix two or more to use.
The present invention preferably contains the amount of the ammonium salt base existing in the vinyl resin of structural unit that general formula (1) represents, and there is no particular limitation, and the ammonium salt value of preferred resin is 10～200mgKOH/g, more preferably 20～130mgKOH/g.If ammonium salt value is less than 10mgKOH/g, the ratio of the anionic property dyestuff of reaction is less, and therefore colouring power reduces, and needs more salify product in anticorrosive additive material.Therefore, originally add the minimizing such as adhesive resin or curable resin in anticorrosive additive material to, can cause that the glass adaptation deterioration of resist film and the film tolerance of resist film worsen.On the other hand, if more than 200mgKOH/g, the solvent solubility of salify product worsens, and can in anticorrosive additive material, the form with impurity separate out.
In addition, ammonium salt value is the term that is equivalent to so-called total base status, the alkali (cationic group) existing in the vinyl resin of the structural unit that comprises general formula (1) expression is only ammonium salt base, therefore in this manual, uses the such statement of ammonium salt value.In the present invention, ammonium salt value by with the whole ammonium salt bases that 1g comprised in the vinyl resin of structural unit that general formula (1) represents in and the milligram number of the potassium hydroxide (KOH) of needed silver nitrate equivalent represent.
There is no particular limitation for the molecular weight of the vinyl resin of the structural unit that comprises general formula (1) expression using in the present invention, be preferably 1000～500000, more preferably 3000～15000 by the conversion weight-average molecular weight that gel permeation chromatography (GPC) is measured.
In addition, in the present invention, preferably comprise the vinyl resin of structural unit that general formula (1) represents and preferably there is the characteristic being dissolved in the solvent being widely used in color composition for color filter.Thus, can obtain the film that can not produce foreign matter.Especially be more preferably dissolved in propylene glycol methyl ether acetate.
In side chain, have in the resin of cationic group, there is no particular limitation for the total content of the structural unit that above-mentioned general formula (1) is represented, in side chain, having entire infrastructure unit contained in the resin of cationic group is 100 quality %, from the solvent solubility of salify product and the aspect of colouring power, more than the total content of the structural unit that above-mentioned general formula (1) represents is preferably 5 quality %, more preferably 10～50 quality %.
Anionic property dyestuff
As the anionic property dyestuff for obtaining salify product of the present invention, as long as with the above-mentioned coloring compound at side chain with the resin ionic bonding (salify) of cationic group.As this coloring compound, as long as there is the compound of carboxylic acid group, sulfonic group, phenol hydroxyl, phosphate or their slaine etc. in molecule, there is no particular limitation, can consider dissolubility to organic solvent or developer solution, becomes salt, absorbance, suitably select with the required all properties of the interaction, photostability, thermotolerance etc. of other compositions in this composition.
As anionic property dyestuff, for example, can enumerate anthraquinone series anion dyestuff, monoazo series anion dyestuff, bisdiazo series anion dyestuff, oxazine series anion dyestuff, amino ketones series anion dyestuff, xanthene series anion dyestuff, quinoline series anion dyestuff, triphenyl methane series anion dyestuff etc.Below, represent to be used for the concrete example of the synthetic anionic property dyestuff of salify product by color index number.
As red colour system dyestuff, can enumerate C.I. azogeramine, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76:1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 etc.
In addition, can also use C.I. direct red 1, 2, 2:1, 4, 5, 6, 7, 8, 10, 10:1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26:1, 28, 29, 31, 33, 33:1, 34, 35, 36, 37, 39, 42, 43, 43:1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67:1, 68, 72, 72:1, 73, 74, 75, 77, 78, 79, 81, 81:1, 85, 86, 88, 89, 90, 97, 100, 101, 101:1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122:1, 124, 125, 127, 127:1, 127:2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238 grades are as red colour system dyestuff.
As yellow based dye, can enumerate C.I. Indian yellow 2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17:1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 etc.
In addition, can also use C.I. directly yellow 1,2,4,5,12,13,15,20,24,25,26,32,33,34,35,41,42,44,44:1,45,46,48,49,50,51,61,66,67,69,70,71,72,73,74,81,84,86,90,91,92,95,107,110,117,118,119,120,121,126,127,129,132,133,134 etc. as weld.
As Yellow Red dyestuff, can enumerate C.I. acid orange 1,1:1,4,5,6,7,8,9,10,12,14,16,17,18,19,20,20:1,22,23,24,24:1,25,27,28,28:1,30,31,33,35,36,37,38,41,45,49,50,51,54,55,56,59,79,83,94,95,102,106,116,117,119,128,131,132,134,136,138 etc.
In addition, can also use C.I. direct orange 1,2,3,4,5,6,7,8,10,13,17,19,20,21,24,25,26,29,29:1,30,31,32,33,43,49,51,56,59,69,72,73,74,75,76,79,80,83,84,85,87,88,90,91,92,95,96,97,98,101,102,102:1,104,108,112,114 etc. as Yellow Red dyestuff.
As blue dyes, can enumerate C.I. Blue VRS, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41:1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62:1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 84, 85, 86, 88, 89, 90, 90:1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127:1, 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 etc.
In addition, can also use directly indigo plant 1 of C.I., 2, 3, 4, 6, 7, 8, 8:1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21:1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98:1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129, 130, 130:1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158:1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260, 263 grades are as blue dyes.
As cudbear, can enumerate C.I. acid violet 1,2,3,4,5,5:1,6,7,7:1,9,11,12,13,14,15,16,17,19,20,21,23,24,25,27,29,30,31,33,34,36,38,39,41,42,43,47,49,51,63,67,72,76,96,97,102,103,109 etc.
In addition, can also use C.I. directly purple 1,3,4,5,6,7,8,9,10,11,12,13,14,16,17,18,21,22,25,26,27,28,29,30,31,32,34,35,36,37,38,39,40,41,42,43,45,51,52,54,57,58,61,62,63,64,71,72,77,78,79,80,81,82,83,85,86,87,88,93,97 etc. as cudbear.
As green colouring material, can enumerate C.I. acid green 2,3,5,6,7,8,9,10,11,13,14,15,16,17,18,19,20,22,25,25:1,27,34,36,37,38,40,41,42,44,54,55,59,66,69,70,71,81,84,94,95 etc.
In addition, can also use C.I. direct green 11,13,14,24,30,34,38,42,49,55,56,57,60,78,79,80 etc. as green colouring material.
Salify
Salify product of the present invention by by dissolved side chain have that the resin of cationic group and the aqueous solution of anionic property dyestuff stir or vibration or the aqueous solution of resin at side chain with cationic group is being stirred with the aqueous solution of anionic property dyestuff or vibrate under mix, thereby can easily obtain.In aqueous solution, the anionic property group ionization of the cationic group of resin and dyestuff, there is ionic bonding and form salt in them, and this salt is water-insoluble, therefore separates out.On the contrary, the salt being formed by the counter anion of resin and the counter cation of anionic property dyestuff is water miscible, therefore can be waited and be removed by washing.The resin and the anionic property dyestuff that have a cationic group at side chain that use can only use respectively single kind, also can use the multiple kind that structure is different.
As the aqueous solution using when the salify, for resin and the anionic property dyestuff at side chain with cationic group are dissolved, can make the mixed solution of water and water-miscible organic solvent.As water-miscible organic solvent, can enumerate methyl alcohol, ethanol, n-propanol, isopropyl alcohol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, normal butyl alcohol, isobutyl alcohol, 2-(methoxymethoxy) ethanol, butoxy ethanol, (2-isoamoxy) ethanol, 2-(own oxygen base) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diglycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol methyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, DPE, triethylene glycol, triethylene glycol monomethyl ether, polyglycol, glycerine, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, MEK, DMF, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), diox, 2-Pyrrolidone, 2-methyl pyrrolidone, METHYLPYRROLIDONE, 1,2-hexanediol, 2,4,6-hexanetriol, four furfuryl alcohol, 4-methoxyl-4-methylheptanone etc.These water-miscible organic solvents, take the general assembly (TW) of aqueous solution as benchmark, preferably use with the ratio of 5～50 % by weight, most preferably use with the ratio of 5～20 % by weight.
There is the resin of cationic group and the ratio of anionic property dyestuff as long as in the scope of the mol ratio of whole cationic structural units of resin and whole anionic property groups of anionic property dyestuff 10/1～1/4 at side chain, just can suitably modulate salify product of the present invention, this mol ratio is more preferably in 2/1～1/2 scope.
< pigment >
Color composition for color filter of the present invention can also contain pigment.
As pigment, organic or inorganic pigment can be used separately or two or more is mixed and is used.The preferred color emissivity of pigment is high and thermotolerance is high pigment, the high pigment of heat-resisting decomposability particularly preferably, use organic pigment conventionally.Below, represent the concrete example of the organic pigment that can use in color composition for color filter with color index number.
In the red colored composition that is used to form red filter joint, for example can use C.I. paratonere 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 122, 123, 146, 150, 166, 168, 169, 176, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 268, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, the red pigments such as 286 or 287.In addition, in red colored composition, all right coupling C.I. pigment orange 36, 38, 43, orange pigment and/or the C.I. pigment yellows 1 such as 71 or 73, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, the yellow uitramarines such as 220 or 221.
In the green coloring composition that is used to form green filter joint, for example, can use C.I. pigment Green 7,10,36,37, the viridine greens such as 58.In addition, in green coloring composition, can coupling C.I. pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, the yellow uitramarines such as 220 or 221.
In the blue colored composition that is used to form blue electric-wave filter joint, for example, can use C.I. pigment blue 1,1:2,1:3,2,2:1,2:2,3,8,9,10,10:1,11,12,15,15:1,15:2,15:3,15:4,15:6,16,18,19,22,24,24:1,53,56,56:1,57,58,59,60,61,62, the blue pigments such as 64.In addition, in blue colored composition, can also coupling C.I. pigment violet 1, the violet pigments such as 19,23,27,29,30,32,37,40,42,50.
In the cyan coloured composition that is used to form cyan filter section, for example can be by C.I. pigment blue 15: 1,15:2,15:4,15:3,15:6,16, the blue pigments such as 81 use separately or mix and use.
In the magenta coloured composition that is used to form magenta filter section, for example can be by the violet pigments such as C.I. pigment violet 1,19, C.I. paratonere 144,146,177,169,81 and red pigment use or mixing use separately.Can also coupling yellow uitramarine in magenta composition.
In addition, as inorganic pigment, can enumerate titanium dioxide, barium sulphate, zinc white, lead sulfate, chrome yellow, zinc yellow, colcother (red iron oxide (III)), cadmium red, ultramarine, Prussian blue, chrome oxide green, cobalt green, umber, synthetic iron black etc.In order to obtain the balance of colored degree and lightness and to guarantee good coating, sensitivity, developability etc., inorganic pigment can also be used in combination with organic pigment.
In the present invention, in the situation that using pigment, from the viewpoint of lightness and stability, with respect to 100 weight portion pigment, preferably salify product is in the scope of 1～800 weight portion.
The miniaturization of pigment
As the pigment adding in coloured composition of the present invention, for corresponding with high-transmission rate and high-contrast, preferably grind to process to wait by salt and realize miniaturization.From the finely disseminated aspect colorant carrier, more than the primary particle size of pigment is preferably 10nm.In addition, from forming the aspect of the filter section that contrast is high, be preferably below 80nm.Particularly preferred scope is the scope of 20～60nm.
It is to use the mixing rolls such as kneader, 2 roller mills, 3 roller mills, bowl mill, masher, sand mill by the potpourri limit heating edge mechanically milling of pigment and water-soluble inorganic salt and water-miscible organic solvent that so-called salt mill is processed, and then removes the processing of water-soluble inorganic salt and water-miscible organic solvent by washing.Water-soluble inorganic salt plays the effect of grinding aid, in the time that salt mill is processed, utilizes the high rigidity of inorganic salts that pigment is pulverized.By making that pigment is carried out to the constrained optimization while processing of salt mill, can obtain that primary particle size is very fine and the dispersion of distribution is narrow, there is the pigment of narrow size-grade distribution.
As water-soluble inorganic salt, can use sodium chloride, barium chloride, potassium chloride, sodium sulphate etc., from price, preferably use sodium chloride (salt).From treatment effeciency and production efficiency, water-soluble inorganic salt, with respect to 100 weight portion pigment, preferably uses with the ratio of 50～2000 weight portions, most preferably uses with the ratio of 300～1000 parts.
Water-miscible organic solvent has the effect of moistening pigment and water-soluble inorganic salt, as long as can dissolve (mixing) in water, and can not dissolve in fact inorganic salts used, and just there is no particular limitation.Wherein, while mill due to salt, temperature improves, and forms solvent and holds evaporable state, and therefore, from the viewpoint of security, preferably boiling point is 120 ℃ of above high boiling solvents.For example can use 2-methyl cellosolve, butoxy ethanol, 2-(isoamoxy) ethanol, 2-(own oxygen base) ethanol, diglycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, aqueous polyglycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, dipropylene glycol, dipropylene glycol monomethyl ether, DPE, aqueous polypropylene glycol etc.Water-miscible organic solvent, with respect to 100 weight portion pigment, preferably uses with the ratio of 5～1000 weight portions, most preferably uses with the ratio of 50～500 weight portions.
In the time pigment being carried out to the processing of salt mill, as required, can also add resin.There is no particular limitation for the kind of the resin using, and can use natural resin, modified natural resin, synthetic resin, with synthetic resin of the modifications such as natural resin etc.Resin used is at room temperature preferably solid and for water-insoluble, and more preferably in above-mentioned organic solvent part solvable.The use amount of resin, with respect to 100 weight portion pigment, is preferably used with the ratio of 5～200 weight portions.
< adhesive resin >
Adhesive resin is for the toner that is scattered here and there, especially disperses the material of salify product and pigment, or material for making the dyeing of salify product, soaking into, comprises thermoplastic resin.
As adhesive resin, preferably in whole wavelength region may of 400～700nm of visible region spectral-transmission favtor be preferably more than 80%, more preferably more than 95% resin.In addition,, in the case of using in the mode of the painted anticorrosive additive material of alkali developable, preferably use the alkali-soluble vinyl resin that the ethylenically unsaturated monomers copolymerization that contains acidic-group is formed.In addition,, in order further to improve photo sensitivity, can also use the energy ray-curable resin with the unsaturated activity double key of ethylenic.
Thermoplastic resin
As thermoplastic resin, for example can enumerate acryl resin, butyral resin, styrene-maleic acid, haloflex, chlorinated polypropylene, Polyvinylchloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane series resin, vibrin, vinyl resin, alkyd resin, polystyrene resin, polyamide, rubber series resin, thermoprene is resin, cellulose family, tygon (HDPE, LDPE), polybutadiene and polyimide resin etc.
Alkali-soluble vinyl resin
As the alkali-soluble vinyl resin that the ethylenically unsaturated monomers copolymerization that contains acidic-group is formed, for example, can enumerate the resin with the acidic-group such as carboxyl, sulfo group.As alkali soluble resin, specifically, can enumerate acryl resin, alpha-olefin/maleic acid (acid anhydride) multipolymer, styrene/Styrene Sulfonic Acid Copolymer, ethene/(methyl) acrylic copolymer or isobutylene/maleic acid (acid anhydride) multipolymer etc. with acidic-group.Wherein, the acryl resin that be selected from least a kind of resin in acryl resin and the styrene/Styrene Sulfonic Acid Copolymer with acidic-group, especially has acidic-group, because thermotolerance, the transparency are higher, therefore preferably uses.
As the energy ray-curable resin with the unsaturated activity double key of ethylenic; can use following resin; this resin be by making to there is hydroxyl, carboxyl, the substituent macromolecule of amino isoreactivity with there is isocyanate group, aldehyde radical, substituent (methyl) acyclic compound of epoxy radicals isoreactivity or cinnamic acid and react, in this macromolecule, import the resin that the photocrosslinking reaction groups such as (methyl) acryloyl group, styryl form.(methyl) acyclic compound that in addition, can also use macromolecule utilization (methyl) acrylic acid hydroxyalkyl acrylate that styrene-copolymer-maleic anhydride or alpha-olefin-copolymer-maleic anhydride etc. are contained to acid anhydrides etc. to have hydroxyl carries out half esterification and the resin that obtains.
As thermoplastic resin, the resin simultaneously with alkali-soluble energy and energy line curing performance is also preferred for color composition for color filter.
There is no particular limitation for the molecular weight of the adhesive resin using in the present invention, and the conversion weight-average molecular weight of measuring by gel permeation chromatography (GPC) is preferably 5000～100000, and more preferably 7000～50000.The conversion weight-average molecular weight of adhesive resin if 5000～100000 is difficult to produce film and reduces in the time developing, and in addition, in the time developing, has the good tendency of deciduous of non-pixel portion, is preferred.
From film forming and the good aspect of various tolerance, adhesive resin is with respect to the total amount of 100 weight portion colorants, preferably use with amounts more than 30 weight portions, high from colorant concentration, also to embody good color characteristics aspect, is preferably used with the amount below 500 weight portions.
< heat-curable compounds >
In the present invention, preferably also comprise and the thermoset resin of the thermoplastic resin coupling as adhesive resin.In the time using color composition for color filter of the present invention to make color filter, by comprising heat-curable compounds, thereby reaction in the time of the burning till of filter section, improve the cross-linking density of film, the thermotolerance that therefore can obtain filter section improves, suppression filter saves while burning till pigment cohesion, contrast improve such effect.
As heat-curable compounds, for example can enumerate epoxy compound and/or resin, benzoguanamine compound and/or resin, Abietyl modified maleinization compound and/or resin, Abietyl modified fumaric acid compound and/or resin, melamine compound and/or resin, urea compounds and/or resin and oxybenzene compound and/or resin, but the present invention is not limited thereto.In color composition for color filter of the present invention, preferably use epoxy compound and/or resin.
Epoxy compound can be low molecular compound, can be also the high-molecular weight compounds as resin.
As the example of this epoxy compound, can enumerate bisphenols (bisphenol-A, Bisphenol F, bisphenol S, biphenyl, biphenyl AD etc.), phenol (phenol, alkyl substituted phenol, aromatic series fortified phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy benzenes, alkyl replaces dihydroxy benzenes, dihydroxy naphthlene etc.) and various aldehyde (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl substituted benzene formaldehyde, hydroxy benzaldehyde, naphthaldehyde, glutaraldehyde, o-phthalaldehyde(OPA), crotonaldehyde, cinnamic acid etc.) condensed polymer, phenol and various diolefin compound (bicyclopentadiene, terpene, vinyl cyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, divinyl biphenyl, diisopropenyl biphenyl, butadiene, isoprene etc.) polymkeric substance, phenol and ketone (acetone, MEK, methyl isobutyl ketone, acetophenone, benzophenone etc.) condensed polymer, phenol and aromatic series diformazan alcohols (benzene dimethanol, α, α, α ', α '-benzene dimethanol, biphenyl dimethanol, α, α, α ', α '-biphenyl dimethanol etc.) condensed polymer, phenol and aromatic series dichloromethane base class (α, α '-xylene dichloride, dichloride methyl biphenyl etc.) condensed polymer, the condensed polymer of bisphenols and various aldehyde, the glycidyl ether that the glycidyls such as alcohols are formed is epoxy resin, alicyclic epoxy resin, glycidyl group amine is epoxy resin, ethylene oxidic ester is epoxy resin etc., as long as normally used epoxy compound, is just not limited to these.They can use separately, also can use two or more.
As commercially available product, for example, can enumerate Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (is trade name above; Oiling SHELL EPOXY Co., Ltd. manufactures), Epicoat 1004, Epicoat 1256 (be trade name above; JAPAN EPOXY RESINS Co., Ltd. manufacture), TECHMORE VG3101L (trade name; Mitsui Chemicals, Inc manufactures), EPPN-501H, 502H (trade name; Nippon Kayaku K. K manufacture), JER 1032H60 (trade name; JAPAN EPOXY RESINS Co., Ltd. manufactures), JER 157S65,157S70 (trade name; JAPAN EPOXY RESINS Co., Ltd. manufacture), EPPN-201 (trade name; Nippon Kayaku K. K manufactures), JER152, JER154 (be trade name above; JAPAN EPOXY RESINS Co., Ltd. manufactures), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (be trade name above; Nippon Kayaku K. K manufactures), CELLOXIDE 2021, EHPE-3150 (be trade name above; DAICEL chemical industry Co., Ltd. manufactures), DENACOL EX-810, EX-830, EX-851, EX-512, EX-421, EX-313, EX-201, EX-111 (be trade name above; Nagasechemtex Co., Ltd. manufactures) etc., but be not limited to these.
The combined amount of epoxy compound, with respect to 100 weight portion colorants, is preferably 0.5～300 weight portion, more preferably 1.0～50 weight portions.In the situation of less than 0.5 weight portion, improved heat resistance effect is little, if more than 300 weight portions,, in the time saving by photoetching shaping filter, produces sometimes unfavorable condition.
In addition,, in color composition for color filter of the present invention, for solidifying of auxiliary heat-curable compounds, as required, can also contain hardening agent, curing accelerator.As hardening agent, amine compound, acid anhydrides, active ester, carboxylic acid based compound, sulfonic acid based compound etc. are effectively, but are not defined in especially these, as long as the material that can react with heat-curable compounds, just can use hardening agent arbitrarily.As above-mentioned curing accelerator, for example, can use amines (for example dicyandiamide, benzyl dimethyl amine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, N-dimethyl benzyl amine etc.), quarternary ammonium salt compound (such as triethyl benzyl ammonia chloride etc.), block isocyanate compound (such as dimethylamine etc.), imdazole derivatives two ring type amidine compounds and salt (for example imidazoles thereof, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole etc.), phosphorus compound (such as triphenylphosphine etc.), S-pyrrolotriazine derivatives (for example 2,4-diamido-6-methacryloxyethyl-S-triazine, 2-vinyl-2,4-diamido-S-triazine, 2-vinyl-4,6-diamido-S-triazine isocyanuric acid addition product, 2,4-diamido-6-methacryloxyethyl-S-triazine isocyanuric acid addition product etc.).These materials can use separately a kind, also can be by two or more coupling.As the content of above-mentioned curing accelerator, with respect to 100 weight portion heat-curable compounds, be preferably 0.01～15 weight portion.
< organic solvent >
The shaping filter joint easily for the mode that makes colorant fully disperse, soak in colorant carrier and to become 0.2～5 μ m with dry film thickness on the substrates such as glass substrate is coated with contains organic solvent in coloured composition of the present invention.
As organic solvent, for example, can enumerate ethyl lactate, benzylalcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-BDO, 1,3-BDO diacetate esters, Isosorbide-5-Nitrae-dioxs, 2-enanthol, 2-methyl isophthalic acid, ammediol, Isophorone, 3,3,5-trimethylcyclohexanone, 3-ethoxyl ethyl propionate, 3-methyl isophthalic acid, 3-butylene glycol, MMB, 3-methoxyl-3-methyl butyl acetic acid esters, 3-methoxybutanol, 3-methoxyl butylacetic acid ester, 4-heptanone, m-xylene, NSC 62102, m-dichlorobenzene, DMA, DMF, normal butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, ortho-chlorotolu'ene, adjacent diethylbenzene, o-dichlorobenzene, parachlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl benzene, gamma-butyrolacton, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, butyl cellosolve, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol list tertbutyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol ether, ethylene glycol ether, glycol monoethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethyl carbitol, diethylene glycol dimethyl ether, diglycol monotertiary isopropyl ether, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetic acid esters, diethylene glycol monomethyl ether, cyclohexanol, adnoral acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetic acid esters, DPE, Dipropylene glycol mono-n-butyl Ether, dipropylene glycol list propyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, glycerol triacetate, Tri(propylene glycol)butyl ether,mixture of isomers, Tripropylene glycol monomethyl Ether, propylene-glycol diacetate, propylene glycol phenyl ether, dihydroxypropane single-ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether propionate, benzylalcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester etc.
Wherein, from the dispersion of pigment of the present invention, salify product, dissolve good aspect, preferably use the aromatic series alcohols such as dibasic alcohol acetate esters, benzylalcohol such as ethyl lactate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or cyclohexanone etc. ketone.Especially from the viewpoint of safety and sanitation aspect and lowering viscousity, more preferably propylene glycol methyl ether acetate.
These organic solvents can use separately a kind, or two or more is mixed and is used.In the situation that being mixed solvent of more than two kinds, above-mentioned preferred organic solvent preferably contains 65～95 % by weight.
In addition, from coloured composition being adjusted to suitable viscosity, form the aspect of filter section of the homogeneous film thickness of target, organic solvent, with respect to the colorant that amounts to 100 weight portions, preferably uses with the amount of 800～4000 weight portions.
< disperses >
Coloured composition of the present invention can by above-mentioned salify product and the above-mentioned colorant carrier that comprises adhesive resin and solvent so that containing pigment in the situation that preferably together with the dispersing aid such as pigment derivative, use the various dispersing apparatus such as triple-roller mill, two roller mill, sand mill, kneader or masher carry out fine dispersion and manufacture.In addition, coloured composition of the present invention also can mix to manufacture by making pigment, salify product, other colorant philosophies be distributed to the material forming in colorant carrier.
Dispersing aid
Be scattered here and there toner in colorant carrier time, can suitably use the dispersing aiies such as pigment derivative, resin type spreading agent, surfactant.Dispersing aid is of value to the dispersion of colorant, and prevent disperse after colorant again cohesion effective, therefore using the coloured composition that by dispersing aid, colorant is disperseed in colorant carrier to form, can obtain the color filter that spectral-transmission favtor is high.
In the present invention, also expect that salify product has the effect as pigment dispersion aids.
As pigment derivative, can enumerate and in organic pigment, anthraquinone, acridine or triazine, import alkali subtituent, acidic substituent and maybe can there is the compound that substituent benzene diimide methyl forms, for example, can use the compound of recording in Japanese kokai publication sho 63-305173 communique, Japanese Patent Publication 57-15620 communique, Japanese Patent Publication 59-40172 communique, Japanese Patent Publication 63-17102 communique, Japanese Patent Publication 5-9469 communique etc., they may be used alone, can also be 2 or more kinds in combination.
From improving the dispersed viewpoint of adding pigment, the combined amount of pigment derivative, with respect to the interpolation pigment that amounts to 100 weight portions, more than being preferably 0.5 weight portion, more preferably more than 1 weight portion, most preferably is ratios more than 3 weight portions.In addition,, from thermotolerance, sunproof viewpoint, the combined amount of pigment derivative, with respect to the interpolation pigment that amounts to 100 weight portions, is preferably 40 weight portions, more preferably the ratio below 35 weight portions.
Resin type spreading agent comprises to have and is adsorbed in the pigment compatibility position of the character of adding pigment and has the position of compatibility with colorant carrier, plays the effect of adding pigment and make its stable dispersion in colorant carrier that is adsorbed in.As resin type spreading agent, specifically, can use polyurethane, the polycarboxylates such as polyacrylate, unsaturated polyester acid amides, poly carboxylic acid, poly carboxylic acid (part) amine salt, poly carboxylic acid ammonium salt, poly carboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, the polycarboxylate that contains hydroxyl, their modifier, the oiliness spreading agent such as acid amides or its salt that poly-(low-grade alkylidene imines) forms with having the pet reaction of free carboxy, (methyl) acrylic acid-styrol copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid, polyvinyl alcohol (PVA), the water soluble resins such as polyvinyl pyrrolidone or water-soluble high-molecular compound, polyester system, modified polyacrylate system, ethylene oxide/propylene oxide additive compound, phosphate system etc., they can use separately, also two or more can be mixed and uses.
As commercially available resin type spreading agent, can enumerate the Disperbyk-101 that BYK ChemieJapan company makes, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen etc., the SOLSPERSE-3000 that Lubrizol company of Japan manufactures, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500 etc., the EFKA-46 that CibaJapan company manufactures, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503 etc., the Ajisper PA111 that Ajinomoto Fine-Techno company manufactures, PB711, PB821, PB822, PB824 etc.
As surfactant, can enumerate alkali salt, odium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl base ether sodium disulfonate, lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, Texapon Special, the stearic acid monoethanolamine of NaLS, polyoxyethylene alkyl ether sulfate salt, neopelex, styrene-acrylic copolymer, the anionic surfactant such as monoethanolamine, polyoxyethylene alkyl ether phosphate of styrene-acrylic copolymer; The nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylplenyl ether, polyoxyethylene alkyl ether phosphate, Tween-60, polyethylene glycol monolaurate; The cationic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adduct; The amphoteric surfactantes such as alkyl betaine, alkyl imidazoline such as alkyl dimethyl oxyneurine, they may be used alone, can also be 2 or more kinds in combination.
Add combined amount in resin type spreading agent, surfactant situation with respect to the interpolation pigment that amounts to 100 weight portions, be preferably 0.1～55 weight portion, the ratio of 0.1～45 weight portion more preferably.In the combined amount of resin type spreading agent, surfactant with respect to amounting to interpolation pigment less than 0.1 weight portion of 100 weight portions, be difficult to obtain the effect of adding, if combined amount is more than 55 weight portions, excessive spreading agent can be on disperseing to produce bad impact.
< photopolymerization monomer >
Coloured composition of the present invention can also contain photopolymerization monomer and/or Photoepolymerizationinitiater initiater.
In photopolymerization monomer, to contain by ultraviolet ray or hot etc. and solidify the monomer or the oligomer that generate transparent resin, they may be used alone, can also be 2 or more kinds in combination.The combined amount of monomer, with respect to the colorant that amounts to 100 weight portions, is preferably the ratio of 5～400 weight portions, from the viewpoint of photo-curable and developability, and the more preferably ratio of 10～300 weight portions.
As solidifying by ultraviolet ray or hot etc. the monomer or the oligomer that generate transparent resin, for example, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) cyclohexyl acrylate, (methyl) propenoic acid beta-carboxyl ethyl ester, polyglycol two (methyl) acrylate, two (methyl) acrylic acid 1,6-hexanediol ester, two (methyl) acrylic acid triethyleneglycol ester, two (methyl) acrylic acid tripropylene glycol ester, three (methyl) acrylic acid trihydroxy methyl propyl ester, three (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, 1,6-hexanediol diglycidyl ether two (methyl) acrylate, bisphenol-A diglycidyl ether two (methyl) acrylate, neopentyl glycol diglycidyl ether two (methyl) acrylate, six (methyl) acrylic acid dipentaerythritol ester, five (methyl) acrylic acid dipentaerythritol ester, (methyl) acrylic acid three encircles decyl ester, ester acrylate, (methyl) acrylate of methylolation melamine, epoxy (methyl) acrylate, the various acrylate such as urethane acrylate and methacrylate, (methyl) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol bisthioglycolate vinyl ether, pentaerythrite trivinyl ether, (methyl) acrylamide, N-hydroxymethyl (methyl) acrylamide, N-vinyl formamide, vinyl cyanide etc., but be not limited to these.
< Photoepolymerizationinitiater initiater >
Color composition for color filter of the present invention is in the situation that making this painted said composition solidify and save by photoetching process shaping filter by ultraviolet ray, can add Photoepolymerizationinitiater initiater etc., make in the mode of solvent develop type or the painted anticorrosive additive material of alkali developable.Combined amount while using Photoepolymerizationinitiater initiater, based on all coloring agent, is preferably 5～200 % by weight, from the viewpoint of photo-curable and developability, and more preferably 10～150 % by weight.
As Photoepolymerizationinitiater initiater, can use 4-phenoxy group dichloroacetophenone, 4-tert-butyl group dichloroacetophenone, diethoxy acetophenone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl sulfenyl) phenyl]-2-morpholino propane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholine) phenyl]-1-butanone or 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-acetophenone based compounds such as butane-1-ketone, the benzoin based compounds such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin isopropyl ether or benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, benzoyl methyl benzoate, 4-phenyl benzophenone, dihydroxy benaophenonel, propylene acidifying benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide or 3,3 ', the benzophenone based compounds such as 4,4 '-tetra-(tert-butyl hydroperoxide carbonyl) benzophenone, thioxanthones, CTX, 2-methyl thioxanthones, isopropyl thioxanthone, 2, the thioxanthones based compounds such as 4-diisopropyl thioxanthones or 2,4-diethyl thioxanthone, 2, 4, the chloro-s-triazine of 6-tri-, 2-phenyl-4, 6-bis-(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4, 6-bis-(trichloromethyl)-s-triazine, 2-(p-methylphenyl)-4, 6-bis-(trichloromethyl)-s-triazine, 2-piperonyl-4, 6-bis-(trichloromethyl)-s-triazine, 2, 4-bis-(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalene-1-yl)-4, 6-bis-(trichloromethyl)-s-triazine, 2-(4-methoxyl-naphthalene-1-yl)-4, 6-bis-(trichloromethyl)-s-triazine, 2, 4-trichloromethyl-(piperonyl)-s-triazine, or 2, the triazine based compounds such as 4-trichloromethyl-(4 '-methoxyl-styrene)-6-triazine, 1,2-octane diketone, 1-[4-(phenyl sulfenyl)-, 2-(O-benzoyl oximes)] or the oxime ester based compound such as O-(acetyl group)-N-(1-phenyl-2-oxo-2-(4 '-methoxyl-naphthyl) ethylidene) hydramine, the phosphine based compounds such as two (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, the quinone based compounds such as 9,10-phenanthrenequione, camphorquinone, EAQ, borate-based compound, carbazole based compound, imidazole compound, or two luxuriant titanium sub-group compound etc.
These Photoepolymerizationinitiater initiaters can use a kind, or as required, with ratio arbitrarily, two or more are mixed and are used.These Photoepolymerizationinitiater initiaters, with respect to the colorant in the color composition for color filter of total 100 weight portions, are preferably the ratio of 5～200 weight portions, from the viewpoint of photo-curable and developability, and the more preferably ratio of 10～150 weight portions.
< sensitizer >
And then, in color composition for color filter of the present invention, can contain sensitizer.
As sensitizer, can enumerate the unsaturated ketone take chalcone derivative and two benzylideneacetones etc. as representative, take benzil and camphorquinone etc. as representative 1,2-derovatives, benzoin derivatives, fluorene derivative, naphthoquinone derivatives, anthraquinone derivative, xanthene derivant, thioxanthene derivative, xanthone derivant, thioxanthone derivates, coumarin derivative, coumarin ketone derivates, cyanine derivant, Merocyanine derivatives, the polymethine pigments such as oxonols derivant, acridine derivatives, azine derivatives, thiazine derivative, oxazine derivatives, indoline derivative thing, azulene derivatives, azulene derivatives, derivant in squaric acid, derivatives of porphyrin, Tetraphenyl porphyrin derivative, triarylmethane derivatives, Tetrabenzoporphyrin derivant, four pyrazines porphyrazine derivant, phthalocyanine derivates, four azepine porphyrazine derivants, four quinoxalines porphyrazine derivant, naphthalene cyanine derivant, sub-phthalocyanine derivates, pyrans (pyrylium) derivant, thiapyran (thiopyrylium) derivant, Tetraphylline (tetraphylline) derivant, wheel ene derivative, spiropyran derivatives, spiro oxazone derivative, sulfo-spiropyran derivatives, metal arene complex compound, organic ruthenium complex compound, or Michler's keton derivant, alpha-acyloxy ester, acylphosphine oxide, methyl benzoylformate, benzil, 9,10-phenanthrenequione, camphorquinone, EAQ, 4, the different phthalophenone of 4 '-diethyl (isophthalophenone), 3,3 '-or 4,4 '-tetra-(tert-butyl hydroperoxide carbonyl) benzophenone, 4,4 '-diethylamino benzophenone etc.
More particularly, can enumerate the volumes such as volume, " pigment Ha Application De Block Star Network " (1986; Talk Talk society), the former letters in great river such as the former letter in great river, " Machine energy property pigment chemistry " (1981 years, シ-エ system シ-), gloomy loyal three youths in pond etc. compile and " Te Shu Machine can material " (1986, シ-エ system シ-) the middle sensitizer of recording, but be not limited thereto.In addition, can also contain the sensitizer that ultraviolet is illustrated to absorption to the light display of near infrared region.
As required, sensitizer can use two or more with ratio arbitrarily.Combined amount while using sensitizer amounts to 100 weight portions with respect to Photoepolymerizationinitiater initiater contained in coloured composition, is preferably the ratio of 3～60 weight portions, from the viewpoint of photo-curable, developability, and the more preferably ratio of 5～50 parts.
< amine compound >
In addition,, in coloured composition of the present invention, can contain the amine compound having the function of the hydrogen reduction of dissolving.
As this amine compound, can enumerate triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethyl amine methyl benzoate, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite and N, N-dimethyl-p-toluidine etc.
< levelling agent >
In coloured composition of the present invention, in order to make on transparency carrier the levelability of composition good, preferably add levelling agent.As levelling agent, preferably on main chain, there is the dimethyl siloxane of polyether structure or polyester construction.As the concrete example of dimethyl siloxane on main chain with polyether structure, can enumerate FZ-2122, the BYK-333 that BYK Chemie company manufactures etc. that Dong Li Dow Corning Corporation manufactures.As the concrete example of dimethyl siloxane on main chain with polyester construction, can enumerate BYK-310, BYK-370 etc. that BYK Chemie company manufactures.Can also will on main chain, there is the dimethyl siloxane of polyether structure and on main chain, there is the dimethyl siloxane coupling of polyester construction.The content of levelling agent is the total weight based on coloured composition conventionally, preferably uses 0.003～0.5 % by weight.
As the material that is particularly preferably used as levelling agent, it can be the one in molecule with the so-called surfactant of hydrophobic group and hydrophilic group, although and it is still little with respect to the dissolubility of water to have hydrophilic group, in the situation that adding in coloured composition, there is the feature that its surface tension reduction effectiveness is low, in addition, but although surface tension reduction effectiveness low be useful to the good material of the wetting state of glass plate, and can preferably use under the addition that there will not be the paint film defect being caused by foaming the fully electrical material of inhibition zone.As the levelling agent with this preferred characteristics, can preferably use the dimethyl polysiloxane with polyoxyalkylene unit.As polyoxyalkylene unit, have polyoxyethylene units, PPOX unit, and dimethyl polysiloxane also can have polyoxyethylene units and PPOX unit simultaneously.
In addition, the bonding mode of polyoxyalkylene unit and dimethyl polysiloxane can be the pendant type of polyoxyalkylene unit bonding in the repetitive of dimethyl polysiloxane, in the terminal-modified type of the end bonding of dimethyl polysiloxane, alternately repeat any in the straight chain shape segmented copolymer type of bonding with dimethyl polysiloxane.The dimethyl polysiloxane with polyoxyalkylene unit can be buied by Dong Li DOW CORNING Co., Ltd., for example, can enumerate FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2207, but be not limited to these.
In levelling agent, can also assist the surfactant that adds anionic property, cationic, nonionic or both sexes.Surfactant can mix two or more to use.
As the auxiliary anionic surfactant who adds in levelling agent, can enumerate alkali salt, sodium alkyl naphthalene sulfonate, alkyl diphenyl base ether sodium disulfonate, lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, Texapon Special, stearic acid monoethanolamine, odium stearate, the NaLS of polyoxyethylene alkyl ether sulfate salt, neopelex, styrene-acrylic copolymer, monoethanolamine, the polyoxyethylene alkyl ether phosphate etc. of styrene-acrylic copolymer.
As the auxiliary cationic surfactant adding in levelling agent, can enumerate alkyl quaternary ammonium salts or their ethylene oxide adduct.As the auxiliary nonionic surfactant adding in levelling agent, can enumerate polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylplenyl ether, polyoxyethylene alkyl ether phosphate, Tween-60, polyethyleneglycol lauryl etc.; The amphoteric surfactantes such as alkyl betaine, alkyl imidazoline such as alkyl dimethyl oxyneurine and fluorine system or silicone-based surfactant.
Other additive component of < >
In coloured composition of the present invention, for make composition through time viscosity stabilization, can contain storage-stable agent.In addition,, in order to improve and the adaptation of transparency carrier, can also contain the closely sealed improving agents such as silane coupling agent.
As storage-stable agent, for example, can enumerate organic phosphine, the phosphites etc. such as the organic acids such as the quaternary ammonium salt such as benzyl trimethyl chloride, diethyl hydramine chloride, lactic acid, oxalic acid and methyl ether thereof, tert-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl phosphine.Storage-stable agent, with respect to the colorant that amounts to 100 weight portions, can be used the amount of 0.1～10 weight portion.
As closely sealed improving agent, can enumerate vinyl three ('beta '-methoxy ethoxy) silane, vinyl Ethoxysilane, the vinyl silanes classes such as vinyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane etc. (methyl) acryloyl group silanes, β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, β-(3,4-epoxy radicals cyclohexyl) methyltrimethoxy silane, β-(3,4-epoxy radicals cyclohexyl) ethyl triethoxysilane, β-(3,4-epoxy radicals cyclohexyl) methyl triethoxysilane, γ-glycidoxypropyltrime,hoxysilane, the epoxy radicals silicone hydride classes such as γ-glycidoxy propyl-triethoxysilicane, N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl) γ aminopropyltriethoxy silane, N-β (amino-ethyl) gamma-amino propyl group methyldiethoxysilane, γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, N-phenyl-gamma-amino propyl trimethoxy silicane, the amino silane classes such as N-phenyl-γ aminopropyltriethoxy silane, γ mercaptopropyitrimethoxy silane, the silane coupling agents such as Thiosilicane class such as γ-sulfydryl propyl-triethoxysilicane.Closely sealed improving agent amounts to 100 weight portions with respect to the colorant in coloured composition, can use 0.01～10 weight portion, preferably uses the amount of 0.05～5 weight portion.
< oversize grain remove >
Coloured composition of the present invention is preferably by means such as centrifuging, sintered filter, membrane filters, by oversize grains more than 5 μ m, preferably oversize grain more than 1 μ m, more preferably oversize grain more than 0.5 μ m and the dust of sneaking into are removed.This coloured composition does not preferably contain in fact particle more than 0.5 μ m.More preferably below 0.3 μ m.
< color filter >
Then, color filter of the present invention is described.Color filter of the present invention has the filter section that uses color composition for color filter of the present invention to form.As color filter, can enumerate and there is the color filter that red filter saves, green filter saves and blue electric-wave filter saves, or there is the color filter of magenta filter section, cyan filter section and yellow filter joint.
As transparency carrier, can use the resin plates such as the glass plates such as soda-lime glass (soda-lime glass), low alkali pyrex, alkali-free aluminium pyrex or polycarbonate, polymethylmethacrylate, polyethylene terephthalate.In addition,, in order to realize the liquid crystal drive after panelization, also can be formed with on the surface of glass plate or resin plate the transparency electrode being formed by indium oxide, tin oxide etc.
The manufacture method of color filter
Color filter of the present invention can pass through print process or photoetching process manufacture.
Owing to needing only the printing of the coloured composition by being repeatedly modulated into printing-ink and being dried, just can carry out patterning by print process shaping filter joint, therefore as the manufacture method of color filter, be cheaply, and production excellence.In addition,, along with the development of printing technology, can also there is the printing of the fine pattern of high dimensional accuracy and smoothness.In order to print, be preferably formed as form that ink can not be dried, curing composition in galley or blanket (blanket) is upper.In addition, the mobility of controlling the ink on printing machine is also important, can also adjust ink viscosity by spreading agent or extender pigment.
In the situation that saving by photoetching process shaping filter, by coating processes such as spraying process, spin-coating method, slot coated method, rolling methods, the coloured composition that is modulated to above-mentioned solvent develop type or the painted anticorrosive additive material of alkali developable is coated on transparency carrier, and making dry film thickness is 0.2～5 μ m.As required to dry film by carrying out ultraviolet exposure with the mask with predetermined pattern contacting with this film or contactless state arranges.Then, by flooding in solvent or alkaline developer or by sprayer etc., developer solution being sprayed, uncured portion is removed, form the pattern of expecting, then, also repeat same operation for other color, thereby can produce color filter.And then, in order to promote the polymerization of painted anticorrosive additive material, can also heat as required.According to photoetching process, can manufacture than the higher color filter of above-mentioned print process precision.
In the time developing, as alkaline developer, can use the aqueous solution such as sodium carbonate, potassium hydroxide, can also use the organic base such as dimethyl benzyl amine, triethanolamine.In addition,, in developer solution, can also add defoamer or surfactant.In addition, in order to improve ultraviolet exposure sensitivity, can be after above-mentioned painted anticorrosive additive material be coated with and be dried, be coated with water-soluble or buck soluble resin, such as polyvinyl alcohol (PVA) or water soluble acrylic resin etc. dry, thereby form the film that prevents the polymerization obstruction being caused by oxygen, carry out afterwards ultraviolet exposure.
Color filter of the present invention, except said method, can be manufactured by electrodeposition process, transfer printing etc., and coloured composition of the present invention can use method arbitrarily.In addition, electrodeposition process is to utilize the nesa coating forming on substrate, by the electrophoresis of colloidal particle, forms filter section of all kinds at nesa coating substrates, thereby manufactures the method for color filter.In addition, transfer printing is to be pre-formed filter section on the surface of the transfer printing substrate of fissility, and this filter section is transferred to the method on the substrate of expectation.
On transparency carrier or reflection substrate, form before filter section of all kinds, can be pre-formed black matrix".As black matrix", can use the inoranic membrane such as multilayer film, titanium nitride of chromium or chromium/chromium oxide or disperse the resin molding of opacifier, but be not limited thereto.In addition, can on above-mentioned transparency carrier or reflection substrate, form in advance film diode (TFT), then form filter section of all kinds.In addition,, on color filter of the present invention, as required, can form outer overlay film or transparent electrolemma etc.
Embodiment
Below, based on embodiment, the present invention will be described, but the present invention is not limited thereto.In addition, unless otherwise specified, " part " refers to " weight portion ".
First, by the adhesive resin using in embodiment and comparative example, miniaturization pigment, there is the resin of cationic group at side chain, the manufacture of salify product describes.
The modulation > of < adhesive resin
The modulation of binder resin solution 1
Add 70.0 parts of cyclohexanone to having in detachable 4 mouthfuls of flasks of thermometer, cooling tube, nitrogen ingress pipe, stirring apparatus, minim pipette, be warming up to 80 ℃, nitrogen displacement will be carried out in flask, then by within for minim pipette 2 hours, dripping 13.3 parts of n-BMAs, 4.6 parts of 2-hydroxyethyl methacrylates, 4.3 parts of methacrylic acids, 7.4 parts to cumyl phenol ethylene oxide modification acrylate (" ARONIX M110 " that East Asia synthetic Zhu Shihui company manufactures), 0.4 part 2, the potpourri of 2 '-azoisobutyronitrile.After dropping finishes, then continue reaction 3 hours, the solution of the acryl resin that acquisition weight-average molecular weight is 26000.This solution is cooled to after room temperature, take out about 2g resin solution as sample, heat drying 20 minutes at 180 ℃, measure nonvolatile component, based on this measured value, add methoxy propyl yl acetate to the mode that becomes 20 % by weight by nonvolatile component in synthetic before resin solution, thus modulating adhesive resin solution 1.
Here, the weight-average molecular weight of adhesive resin (Mw) is to measure by the gel permeation chromatography take polystyrene as standard substance (GPC).
The manufacture > of < miniaturization pigment
Blue miniaturization pigment (P-1)
In 1 gallon of kneader (aboveground making manufacturing) of stainless steel, adding 100 parts of phthalocyanines is blue pigment C.I. pigment blue 15: salt and 100 portions of diglycols of 6 (Toyo Ink manufacturing companies manufacture " LIONOL BLUE ES "), 800 parts of pulverizing, at 70 ℃ mixing 12 hours.This potpourri is joined in 3000 parts of warm water, and limit is heated to approximately 70 ℃ of limits super mixer stir about 1 hour, forms slurries shape, repeatedly filter, wash, remove after salt and solvent, at 80 ℃, be dried 24 hours, obtain 98 parts of blue miniaturization pigment (P-1).The average primary particle diameter of gained pigment is 28.3nm.
Here, the average primary particle diameter of pigment uses transmission electron microscope (NEC company manufactures " JEM-1200EX "), and in the observation sample under measuring 50,000 times, the primary particle size of whole pigment particles, uses its mean value.In addition, be not spherical in the situation that, measure major diameter and minor axis in shape of particle, the value that will be obtained by (major diameter+minor axis)/2 is as particle diameter.
Purple miniaturization pigment (P-2)
In 1 gallon of kneader (aboveground making manufacturing) of stainless steel, adding 120 parts of dioxs is salt and 100 portions of diglycols of violet pigment C.I. pigment Violet 23 (Clariant company manufacture " Fast Violet RL "), 1600 parts of pulverizing, at 90 ℃ mixing 18 hours.This potpourri is joined in 5000 parts of warm water, and limit is heated to approximately 70 ℃ of limits super mixer stir about 1 hour, forms slurries shape, repeatedly filter, wash, remove after salt and solvent, at 80 ℃, be dried 24 hours, obtain 118 parts of purple miniaturization pigment (P-2).The average primary particle diameter of gained pigment is 26.4nm.
Red miniaturization pigment (P-3)
In 1 gallon of kneader (aboveground making manufacturing) of stainless steel, adding 120 parts of diketopyrrolopyrrolecocrystals is salt and 120 portions of diglycols of red pigment C.I. paratonere 254 (CibaJapan company manufacture " IRGAZINRED 2030 "), 1000 parts of pulverizing, at 60 ℃ mixing 10 hours.This potpourri is joined in 2000 parts of warm water, and limit is heated to approximately 80 ℃ of limits super mixer stir about 1 hour, forms slurries shape, repeatedly filter, wash, remove after salt and solvent, at 80 ℃, be dried 24 hours, obtain 115 parts of red miniaturization pigment (P-3).The average primary particle diameter of gained pigment is 24.8nm.
Yellow miniaturization pigment (P-4)
In 1 gallon of kneader (aboveground making manufacturing) of stainless steel, adding 100 parts of nickel complexes is yellow uitramarine C.I. pigment yellow 150 (Lanxess company manufacture " E-4GN "), 700 parts of sodium chloride and 180 portions of diglycols, at 80 ℃ mixing 6 hours.This potpourri is joined in 2000 parts of warm water, and limit is heated to approximately 80 ℃ of limits super mixer stir about 1 hour, forms slurries shape, repeatedly filter, wash, remove after salt and solvent, at 80 ℃, be dried 24 hours, obtain 95 parts of yellow miniaturization pigment (P-4).The average primary particle diameter of gained pigment is 39.2nm.
Green miniaturization pigment (P-5)
In 1 gallon of kneader (aboveground making manufacturing) of stainless steel, adding 120 parts of phthalocyanines is viridine green C.I. pigment green 36 (Toyo Ink manufacturing company manufacture " LIONOL GREEN 6YK "), 1600 parts of sodium chloride and 270 portions of diglycols, at 70 ℃ mixing 12 hours.This potpourri is joined in 5000 parts of warm water, and limit is heated to approximately 70 ℃ of limits super mixer stir about 1 hour, forms slurries shape, repeatedly filter, wash, remove after salt and solvent, at 80 ℃, be dried 24 hours, obtain 117 parts of red miniaturization pigment (P-5).The average primary particle diameter of gained pigment is 32.6nm.
< has the modulation > of the resin of cationic group at side chain
There is the modulation of the resin 1 of cationic group at side chain
Having in 4 mouthfuls of detachable flasks of thermometer, stirring machine, distillation cascade, refrigeratory, add 67.3 parts of MEKs, flow down and be warming up to 75 ℃ at nitrogen.In addition, by 34.0 parts of methyl methacrylates, 28.0 parts of n-BMAs, 28.0 parts of 2-Ethylhexyl Methacrylates, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 part 2,2 '-azo two (2,4-methyl pentane nitrile) and after 25.1 parts of MEKs evenly mix, the potpourri of gained is joined in tap funnel, this tap funnel is arranged on above-mentioned 4 mouthfuls of detachable flasks, with within 2 hours, dripping this potpourri.Finish after 2 hours dripping, confirm that by solid constituent polymerization yield is more than 98%, weight-average molecular weight (Mw) is 6830, be cooled to 50 ℃.In this cooling reaction mixture, then add 3.2 parts of chloromethanes, 22.0 parts of ethanol, at 50 ℃, react 2 hours, be then warming up to 80 ℃ with 1 hour, then react 2 hours.Thus, obtain resinous principle be 47 % by weight there is the resin 1 of cationic group at side chain.The ammonium salt value of gained resin is 34mgKOH/g.
Here the weight-average molecular weight (Mw) that has a resin of cationic group at side chain, is to be measured and obtained by the gel permeation chromatography take polystyrene as standard substance (GPC).In addition, the ammonium salt value at side chain with the resin of cationic group is take 5% potassium chromate aqueous solution as indicator, with the silver nitrate aqueous solution titration of 0.1N, obtains in ammonium salt base and after needed silver nitrate amount, be converted into the value of the equivalent of potassium hydroxide, be expressed as the ammonium salt value of solid constituent.
There is the modulation of the resin 2 of cationic group at side chain
Having in 4 mouthfuls of detachable flasks of thermometer, stirring machine, distillation cascade, refrigeratory, add 62.4 parts of isopropyl alcohols, flow down and be warming up to 75 ℃ at nitrogen.In addition; by 32.1 parts of β-dimethyl-aminoethylmethacrylates, 25.1 parts of n propyl methacrylates, 25.1 parts of methacrylic acid Lauryl Ester, 17.7 parts of methacryl aminopropyl trimethyl ammonium chlorides, 5.7 part 2; 2 '-azo two (2; 4-methyl pentane nitrile) and after 15.6 parts of MEKs evenly mix; the potpourri of gained is joined in tap funnel; this tap funnel is arranged on above-mentioned 4 mouthfuls of detachable flasks, with within 2 hours, dripping this potpourri.Finish after 2 hours dripping, confirm that by solid constituent polymerization yield is more than 98%, weight-average molecular weight (Mw) is 7420, be cooled to 50 ℃.In this cooling reaction mixture, add 72 parts of isopropyl alcohols, what obtain resinous principle and be 40 % by weight has the resin 2 of cationic group at side chain.The ammonium salt value of gained resin is 45mgKOH/g.
There is the modulation of the resin 3 of cationic group at side chain
Having in 4 mouthfuls of detachable flasks of thermometer, stirring machine, distillation cascade, refrigeratory, add 67.3 parts of MEKs, flow down and be warming up to 75 ℃ at nitrogen.In addition, by 27.5 parts of isopropyl methacrylates, 25.0 parts of benzyl methacrylates, 27.5 parts of 2-Ethylhexyl Methacrylates, 20.0 parts of N, N-dimethylaminomethyl styrene, 6.7 part 2,2 '-azo two (2,4-methyl pentane nitrile) and after 25.1 parts of MEKs evenly mix, join in tap funnel, this tap funnel is arranged on 4 mouthfuls of detachable flasks, with dropping in 2 hours.Finish after 2 hours dripping, confirm that by solid constituent polymerization yield is more than 98%, weight-average molecular weight (Mw) is 6770, be cooled to 50 ℃.In this cooling reaction mixture, then add 15.7 parts of benzyl chlorides, 22.0 parts of ethanol, at 50 ℃, react 2 hours, be then warming up to 80 ℃ with 1 hour, then react 2 hours.Thus, obtain resinous principle be 50 % by weight there is the resin 3 of cationic group at side chain.The ammonium salt value of gained resin is 60mgKOH/g.
There is the modulation of the resin 4 of cationic group at side chain
Having in 4 mouthfuls of detachable flasks of thermometer, stirring machine, distillation cascade, refrigeratory, add 62.4 parts of isopropyl alcohols, flow down and be warming up to 75 ℃ at nitrogen.In addition, by 25.0 parts of methyl methacrylates, 25.0 parts of methacrylic acid stearyl esters, 20.0 parts of cyclohexyl methacrylates, 15.0 parts of BlenmerPE90 (You company manufactures, diglycol monotertiary methacrylate), 20.0 parts of NVPs, 4.7 part 2,2 '-azo two (2,4-methyl pentane nitrile) and after 15.6 parts of isopropyl alcohols evenly mix, the potpourri obtaining is joined in tap funnel, this tap funnel is arranged on above-mentioned 4 mouthfuls of detachable flasks, with within 2 hours, dripping this potpourri.Finish after 2 hours dripping, confirm that by solid constituent polymerization yield is more than 98%, weight-average molecular weight (Mw) is 7550, be cooled to 50 ℃.In this cooling reaction mixture, then add 9.0 parts of chloromethanes, 22.0 parts of isopropyl alcohols, at 50 ℃, react 2 hours, be then warming up to 80 ℃ with 1 hour, then react 2 hours.Then, add 50 parts of isopropyl alcohols, what obtain resinous principle and be 44 % by weight has the resin 4 of cationic group at side chain.The ammonium salt value of gained resin is 92mgKOH/g.
There is the modulation of the resin 5 of cationic group at side chain
Having in 4 mouthfuls of detachable flasks of thermometer, stirring machine, distillation cascade, refrigeratory, add 82.0 parts of MEKs, flow down and be warming up to 75 ℃ at nitrogen.In addition, by 23.5 parts of β-dimethyl-aminoethylmethacrylates, 26.0 part Tert-butyl Methacrylate, 25.0 parts of methacrylic acid Lauryl Ester, (Japanese chemical drug company manufactures for 10.0 parts of KayamerPM-21, the phosphate of the 2-hydroxyethyl methacrylate of addition 1mol 6-caprolactone), 17.5 parts of diethylamino propyl methyl acid esters, 6.0 part 2, 2 '-azo two (2, 4-methyl pentane nitrile) and after 25.6 parts of MEKs evenly mix, the potpourri of gained is joined in tap funnel, this tap funnel is arranged on above-mentioned 4 mouthfuls of detachable flasks, with within 2 hours, dripping this potpourri.Finish after 2 hours dripping, confirm that by solid constituent polymerization yield is more than 98%, weight-average molecular weight (Mw) is 7010, be cooled to 50 ℃.Thus, obtain resinous principle be 48 % by weight there is the resin 5 of cationic group at side chain.The ammonium salt value of gained resin is 49mgKOH/g.
There is the modulation of the resin 6 of cationic group at side chain
Having in 4 mouthfuls of detachable flasks of thermometer, stirring machine, distillation cascade, refrigeratory, add 62.4 parts of isopropyl alcohols, flow down and be warming up to 75 ℃ at nitrogen.In addition; by 32.1 parts of methyl acrylates, 30.1 parts of n propyl methacrylates, 32.1 parts of methacrylic acid Lauryl Ester, 5.7 parts of methacryl amino-ethyl trimethyl ammonium chlorides, 6 part 2; 2 '-azo two (2; 4-methyl pentane nitrile) and after 25.0 parts of MEKs evenly mix; the potpourri of gained is joined in tap funnel; this tap funnel is arranged on above-mentioned 4 mouthfuls of detachable flasks, with within 2 hours, dripping this potpourri.Finish after 2 hours dripping, confirm that by solid constituent polymerization yield is more than 98%, weight-average molecular weight (Mw) is 7000, be cooled to 50 ℃.Then add 65 parts of isopropyl alcohols, what obtain resinous principle and be 40 % by weight has the resin 6 of cationic group at side chain.The ammonium salt value of gained resin is 15mgKOH/g.
There is the modulation of the resin 7 of cationic group at side chain
Having in 4 mouthfuls of detachable flasks of thermometer, stirring machine, distillation cascade, refrigeratory, add 62.4 parts of isopropyl alcohols, flow down and be warming up to 75 ℃ at nitrogen.In addition; by 17.0 parts of butyl methacrylates, 16.0 parts of n propyl methacrylates, 16.0 parts of styrene, 51.0 parts of methacryl amino-ethyl trimethyl ammonium chlorides, 6 part 2; 2 '-azo two (2; 4-methyl pentane nitrile) and after 25.0 parts of MEKs evenly mix; the potpourri of gained is joined in tap funnel; this tap funnel is arranged on above-mentioned 4 mouthfuls of detachable flasks, with within 2 hours, dripping this potpourri.Finish after 2 hours dripping, confirm that by solid constituent polymerization yield is more than 98%, weight-average molecular weight (Mw) is 7050, be cooled to 50 ℃.Then in this cooling reaction mixture, add 65 parts of isopropyl alcohols, what obtain resinous principle and be 40 % by weight has the resin 7 of cationic group at side chain.The ammonium salt value of gained resin is 138mgKOH/g.
Here, the amine value at side chain with the resin of cationic group is to obtain by potential difference titration after the amount of the required hydrochloric acid of neutralization at the aqueous hydrochloric acid solution that uses 0.1N, is converted into the equivalent of potassium hydroxide.
The manufacture > of < salify product
Salify product (A-1)
According to following order, manufacture the salify product (A-1) being formed by C.I. acid red 289 and the resin 1 at side chain with cationic group.
In 2000 parts of water, add 51 parts of resins 1 at side chain with cationic group, be fully uniformly mixed, then the resin solution of gained is heated to 60 ℃.The aqueous solution of having dissolved 10 parts of C.I. acid reds 289 in 90 parts of water is slowly dripped in above-mentioned resin solution.After dropping, at 60 ℃, stir 120 minutes, fully react.As the confirmation of reaction end, to filter paper dropwise reaction liquid, while disappearance to permeate, as terminal, judgement obtains salify product.The reaction mixture of gained is stirred on limit, limit lets cool to room temperature, then carry out suction filtration, washing, afterwards the salify product dryer remaining on filter paper removed to moisture and is dried, obtaining 32 parts of salify products (A-1) that formed by C.I. acid red 289 and the resin 1 at side chain with cationic group.
Salify product (A-2)
According to following order, manufacture the salify product (A-2) being formed by C.I. Blue VRS 12 and the resin 2 at side chain with cationic group.
In the methanol aqueous solution of 2000 part 10%, add 88 parts of resins 2 at side chain with cationic group, be fully uniformly mixed, then the resin solution of gained is heated to 60 ℃.The aqueous solution of having dissolved 10 parts of C.I. Blue VRSs 12 in 90 parts of water is slowly dripped in above-mentioned resin solution.After dropping, at 60 ℃, stir 120 minutes, fully react.As the confirmation of reaction end, to filter paper dropwise reaction liquid, while disappearance to permeate, as terminal, judgement obtains salify product.The reaction mixture limit that gained is stirred on limit lets cool to room temperature, then carry out suction filtration, washing, afterwards the salify product dryer remaining on filter paper removed to moisture and is dried, obtaining 43 parts of salify products (A-2) that formed by C.I. Blue VRS 12 and the resin 2 at side chain with cationic group.
Salify product (A-3)
According to following order, manufacture the salify product (A-3) being formed by C.I. acid blue 93 and the resin 3 at side chain with cationic group.
In the DMF aqueous solution of 2000 part 10%, add 46.7 parts of resins 3 at side chain with cationic group, be fully uniformly mixed, then the resin solution of gained is heated to 70 ℃.The aqueous solution of having dissolved 10 parts of C.I. acid blue 9s 3 in 90 parts of water is slowly dripped in above-mentioned resin solution.After dropping, at 70 ℃, stir 120 minutes, fully react.As the confirmation of reaction end, to filter paper dropwise reaction liquid, while disappearance to permeate, as terminal, judgement obtains salify product.The reaction mixture limit that gained is stirred on limit lets cool to room temperature, then carry out suction filtration, washing, afterwards the salify product dryer remaining on filter paper removed to moisture and is dried, obtaining 29 parts of salify products (A-3) that formed by C.I. acid red 93 and the resin 3 at side chain with cationic group.
Salify product (A-4)
According to following order, manufacture the salify product (A-4) being formed by the acid derivant of C.I. pigment yellow 13 8 and the resin 4 at side chain with cationic group.
In the sulfuric acid of 100 part 101%, add 10 parts of C.I. pigment yellow 13s 8, be heated to 60 ℃ and carry out sulfonation.Then, this reaction solution is injected to a large amount of frozen water, evolution reaction product (sulfonic acid), filters it with pressure filter, washing.The water pastel of the sulfonic acid of gained is disperseed in the water of 2000 parts again, use sodium hydrate aqueous solution that pH is adjusted into alkalescent.Slowly drip in the aqueous dispersions of the above-mentioned sulfonic acid of having adjusted pH dissolved 20.0 parts of solution that there is the resin 4 of cationic group at side chain in 190 parts of water.After dropping, at 60 ℃, stir 120 minutes, fully react.As the confirmation of reaction end, to filter paper dropwise reaction liquid, while disappearance to permeate, as terminal, judgement obtains salify product.The reaction mixture limit that gained is stirred on limit lets cool to room temperature, then carry out suction filtration, washing, afterwards the salify product dryer remaining on filter paper removed to moisture and is dried, obtaining 19 parts of salify products (A-4) that formed by the acid derivant of C.I. pigment yellow 13 8 and the resin 4 at side chain with cationic group.
Salify product (A-5)
According to following order, manufacture the salify product (A-5) being formed by C.I. Acid Red 249 and the resin 5 at side chain with cationic group.
In the acetic acid of 2000 part 20%, add 63.2 parts of resins 5 at side chain with cationic group, be fully uniformly mixed, be then heated to 60 ℃, carry out the ammonium salt of the tertiary amino of side chain.The aqueous solution of having dissolved 10 parts of C.I. Acid Red 249s in 90 parts of water is slowly dripped in the resin solution of above-mentioned ammonium salt.After dropping, at 60 ℃, stir 120 minutes, fully react.As the confirmation of reaction end, to filter paper dropwise reaction liquid, while disappearance to permeate, as terminal, judgement obtains salify product.The reaction mixture limit that gained is stirred on limit lets cool to room temperature, then carry out suction filtration, washing, afterwards the salify product dryer remaining on filter paper removed to moisture and is dried, obtaining 38 parts of salify products (A-5) that formed by C.I. Acid Red 249 and the resin 5 at side chain with cationic group.
Salify product (A-6)
According to following order, manufacture the salify product (A-6) being formed by C.I. direct blue 86 and Disperbyk-2000 (BYKChemieJapan company manufactures, modified acroleic acid based block copolymer, ammonium salt value 61mgKOH/g).
In 2000 parts of water, add 50.9 parts of Disperbyk-2000, be fully uniformly mixed, then the resin solution of gained is heated to 60 ℃.Slowly drip in above-mentioned resin solution dissolved 10 parts of direct aqueous solution of blue 86 of C.I. in 90 parts of water.After dropping, at 60 ℃, stir 120 minutes, fully react.As the confirmation of reaction end, to filter paper dropwise reaction liquid, while disappearance to permeate, as terminal, judgement obtains salify product.The reaction mixture limit that gained is stirred on limit lets cool to room temperature, then carry out suction filtration, washing, removes the salify product dryer remaining on filter paper moisture and is dried afterwards, obtains 31 parts of salify products (A-6) that formed by C.I. direct blue 86 and Disperbyk-2000.
Salify product (A-7)
According to following order, manufacture the salify product (A-7) being formed by C.I. acid blue 93 and the resin 6 at side chain with cationic group.
In the DMF aqueous solution of 2000 part 10%, add 186.8 parts of resins 6 at side chain with cationic group, be fully uniformly mixed, then the resin solution of gained is heated to 70 ℃.The aqueous solution of having dissolved 10 parts of C.I. acid blue 9s 3 in 90 parts of water is slowly dripped in above-mentioned resin solution.After dropping, at 70 ℃, stir 120 minutes, fully react.As the confirmation of reaction end, to filter paper dropwise reaction liquid, while disappearance to permeate, as terminal, judgement obtains salify product.The reaction mixture limit that gained is stirred on limit lets cool to room temperature, then carry out suction filtration, washing, afterwards the salify product dryer remaining on filter paper removed to moisture and is dried, obtaining 75 parts of salify products (A-7) that formed by C.I. acid red 93 and the resin 6 at side chain with cationic group.
Salify product (A-8)
According to following order, manufacture the salify product (A-8) being formed by C.I. acid blue 93 and the resin 1 at side chain with cationic group.
In the DMF aqueous solution of 2000 part 10%, add 93.4 parts of resins 1 at side chain with cationic group, be fully uniformly mixed, then the resin solution of gained is heated to 70 ℃.The aqueous solution of having dissolved 10 parts of C.I. acid blue 9s 3 in 90 parts of water is slowly dripped in above-mentioned resin solution.After dropping, at 70 ℃, stir 120 minutes, fully react.As the confirmation of reaction end, to filter paper dropwise reaction liquid, while disappearance to permeate, as terminal, judgement obtains salify product.The reaction mixture limit that gained is stirred on limit lets cool to room temperature, then carry out suction filtration, washing, afterwards the salify product dryer remaining on filter paper removed to moisture and is dried, obtaining 48 parts of salify products (A-8) that formed by C.I. acid red 93 and the resin 1 at side chain with cationic group.
Salify product (A-9)
According to following order, manufacture the salify product (A-9) being formed by C.I. acid blue 93 and the resin 4 at side chain with cationic group.
In the DMF aqueous solution of 2000 part 10%, add 31.1 parts of resins 4 at side chain with cationic group, be fully uniformly mixed, then the resin solution of gained is heated to 70 ℃.The aqueous solution of having dissolved 10 parts of C.I. acid blue 9s 3 in 90 parts of water is slowly dripped in above-mentioned resin solution.After dropping, at 70 ℃, stir 120 minutes, fully react.As the confirmation of reaction end, to filter paper dropwise reaction liquid, while disappearance to permeate, as terminal, judgement obtains salify product.The reaction mixture limit that gained is stirred on limit lets cool to room temperature, then carry out suction filtration, washing, afterwards the salify product dryer remaining on filter paper removed to moisture and is dried, obtaining 22 parts of salify products (A-9) that formed by C.I. acid red 93 and the resin 4 at side chain with cationic group.
Salify product (A-10)
According to following order, manufacture the salify product (A-10) being formed by C.I. acid blue 93 and the resin 7 at side chain with cationic group.
In the DMF aqueous solution of 2000 part 10%, add 23.2 parts of resins 7 at side chain with cationic group, be fully uniformly mixed, then the resin solution of gained is heated to 70 ℃.The aqueous solution of having dissolved 10 parts of C.I. acid blue 9s 3 in 90 parts of water is slowly dripped in above-mentioned resin solution.After dropping, at 70 ℃, stir 120 minutes, fully react.As the confirmation of reaction end, to filter paper dropwise reaction liquid, while disappearance to permeate, as terminal, judgement obtains salify product.The reaction mixture limit that gained is stirred on limit lets cool to room temperature, then carry out suction filtration, washing, afterwards the salify product dryer remaining on filter paper removed to moisture and is dried, obtaining 19 parts of salify products (A-10) that formed by C.I. acid red 93 and the resin 7 at side chain with cationic group.
Salify product (C-1)
According to following order, manufacture the salify product (C-1) being formed by C.I. acid red 289 and VARISOFT TA100 (QUARTAMIN D86P).
In the sodium hydrate aqueous solution of 2000 part 10%, add 11.5 parts of QUARTAMIN D86P, be fully uniformly mixed, then the solution of gained is heated to 60 ℃.The aqueous solution of having dissolved 10 parts of C.I. acid reds 289 in 90 parts of water is slowly dripped in above-mentioned solution.After dropping, at 60 ℃, stir 120 minutes, fully react.As the confirmation of reaction end, to filter paper dropwise reaction liquid, while disappearance to permeate, as terminal, judgement obtains salify product.The reaction mixture limit that gained is stirred on limit lets cool to room temperature, then carry out suction filtration, washing, removes the salify product dryer remaining on filter paper moisture and is dried afterwards, obtains 17 parts of salify products (C-1) that formed by C.I. acid red 289 and QUARTAMIN D86P.
Salify product (C-2)
According to following order, manufacture the salify product (C-2) being formed by C.I. Blue VRS 12 and single lauryl trimethyl ammonium chloride (QUARTAMIN 24P).
In the sodium hydrate aqueous solution of 2000 part 7%, add 8.1 parts of QUARTAMIN 24P, be fully uniformly mixed, then the solution of gained is heated to 50 ℃.The aqueous solution of having dissolved 10 parts of C.I. Blue VRSs 12 in 90 parts of water is slowly dripped in above-mentioned solution.After dropping, at 50 ℃, stir 120 minutes, fully react.As the confirmation of reaction end, to filter paper dropwise reaction liquid, while disappearance to permeate, as terminal, judgement obtains salify product.The reaction mixture limit that gained is stirred on limit lets cool to room temperature, then carry out suction filtration, washing, removes the salify product dryer remaining on filter paper moisture and is dried afterwards, obtains 16 parts of salify products (C-2) that formed by C.I. Blue VRS 12 and QUARTAMIN 24P.
< solvent solubility test method >
Salify product obtained above is evaluated to solvent solubility.Evaluation is that the solution state of observing the salify product solution of the concentration that is adjusted to 5wt% carries out.Solvent uses cyclohexanone and propylene glycol methyl ether acetate (PGMAC).Each salify product solution is adjusted into after 5% concentration, stirs with mixer, then leave standstill 1 hour, set it as evaluation solution.Dissolved state is evaluated according to the standard of 4 levels shown below.
◎: dissolve completely; Zero: substantially dissolve; △: be partly dissolved; ×: do not dissolve
Result is shown in following table 1.
Table 1:
Salify product Cyclohexanone PGMAC
A-1 ◎ ◎
A-2 ◎ ○
A-3 ◎ ○
A-4 ◎ ◎
A-5 ◎ ◎
A-6 ◎ ○
A-7 ◎ ○
A-8 ◎ ○
A-9 ◎ ○
A-10 ○ △
C-1 ○ △
C-2 △ ×
Embodiment 1: the making of coloured composition (DB-1)
After composition shown in lower Table A is uniformly mixed, use the zirconium oxide bead that diameter is 0.5mm, disperse after 5 hours with Ai Geer (Eiger) grinding machine (Eiger Japan company manufacture " Mini model M-250MKII "), with the filtrator filtration of 5.0 μ m, make pigment dispersion (DB-1).
Table A:
Embodiment 2～8,17～20, comparative example 1～3: the making of coloured composition (DB-2～15)
Except salify product, miniaturization pigment are changed into the composition shown in table 2, make similarly to Example 1 coloured composition (DB-2～15).
The evaluation > of < coloured composition
Coloured composition (DB-1～15) to gained, relates to the test of storage stability and film foreign matter by the following method.In the result of test shown in table 2.
Storage stability test method
Use E type viscosity meter (the TUE-20L type that Dong Ji industry company manufactures), measure the viscosity of the coloured composition of making at 25 ℃ with rotating speed 20rpm.By the initial stage viscosity on making same day of coloured composition and the constant temperature enclosure at 40 ℃ preserve promotion after 7 days through time viscosity, calculate viscosity rate of change, according to following standard evaluation storage stability.
◎: be less than 1 one-tenth; Zero: 1 one-tenth above and be less than 2 one-tenth; △: 2 one-tenth above and be less than 5 one-tenth; ×: more than 5 one-tenth
Result is shown in following table 2.
Film foreign matter test method
Make test substrate with the coloured composition of firm modulation, evaluate by calculating population.First, on transparency carrier, be coated with coloured composition, make dry film thickness be about 2.0 μ m, in baking oven, at 230 ℃, heat 20 minutes, obtain test substrate.Then, use the metallurgical microscopes " BX60 " that Olympus-systems company manufactures to observe surface (multiplying power is 500 times), calculate the population that can observe in 5 visuals field of meaning in office by transmission, evaluate according to following standard.In evaluation result, ◎ and zero is that foreign matter number is less, good, and △ is the more but not in-problem level on using of foreign matter number, × be equivalent to the state that cannot use because there is the coating irregular (spot) that caused by foreign matter.
◎: 5 of less thaies;
Zero: 5 above and be less than 20;
△: 20 above and be less than 100;
×: more than 100
Result is shown in following table 2.
Table 2
Contain that to be included in the coloured composition result that side chain has the salify product (A-1～10) of the resin of cationic group be overall excellent storage stability, film can not produce foreign matter substantially yet.On the other hand, the coloured composition that comprises the cationic salify product (C-1,2) that uses alkyl amine system, aspect film foreign matter, finds also to have fallen into the scope of allowing, but generally storage stability worsen, by through time preserve coloured composition be difficult to make film.
Embodiment 9～16,21～24, comparative example 4～6
Embodiment 9; Anticorrosive additive material (R-1)
Uniform stirring mixes the composition shown in following table B, then filters with the filtrator of 1.0 μ m, makes alkali developable anticorrosive additive material R-1.
Table B:
Embodiment 10～16,21～24, comparative example 4～6; Anticorrosive additive material (R-2～15)
Except coloured composition (DB-1) is changed into the coloured composition shown in table 3, similarly to Example 9, make alkali developable anticorrosive additive material (R-2～15).
The evaluation > of < anticorrosive additive material
Anticorrosive additive material (R-1～15) to gained, relates to the test of film foreign matter and glass adaptation by the following method.
Film foreign matter test method
The rotating speed that the anticorrosive additive material of gained in embodiment 9～16,21～24, comparative example 4～6 is become to 2.5 μ m with dried thickness is spin-coated on the glass substrate that 100mm～100mm, 1.1mm are thick, dry after 20 minutes at 70 ℃, by thering is the photomask that width is the strip open part of 100 μ m, use ultrahigh pressure mercury lamp, with accumulative total light quantity 150mJ/cm 2carry out ultraviolet exposure, unexposed portion is rinsed with 5% aqueous sodium carbonate, then, at 230 ℃, with hot-air oven baking 20 minutes, thereby on substrate, form the strip pattern that width is 100 μ m.Then, the metallurgical microscopes " BX60 " that uses Olympus-systems company to manufacture to this making substrate carries out surface observation (500 times of multiplying powers), calculate the population that can observe in 5 visuals field of meaning in office by transmission, evaluate according to following standard.In evaluation result, ◎ and zero is that foreign matter number is less, good, and △ is the more but not in-problem level on using of foreign matter number, × be equivalent to the state that cannot use because there is the coating irregular (spot) that caused by foreign matter.
◎: 5 of less thaies;
20 of zero: 5 above and less thaies;
△: 100 of 20 above and less thaies;
×: more than 100
Result is shown in following table 3.
Glass fitness test method
As the fitness test about on glass, form film according to testing identical order with above-mentioned film foreign matter, the chemical reagent resistance of the film by confirming gained is evaluated.As test method, in 5% sodium hydrate aqueous solution, at 25 ℃, flood 30 minutes, the adaptation to glass before and after visualization dipping, point 3 levels are evaluated.
Zero: confirm not peel off completely; △: confirm to peel off a little; ×: confirm to peel off
Result is shown in table 3.
Table 3
Anticorrosive additive material Coloured composition Film foreign matter Glass adaptation
Embodiment 9 R-1 DB-1 ◎ ○
Embodiment 10 R-2 DB-2 ○ ○
Embodiment 11 R-3 DB-3 ◎ ○
Embodiment 12 R-4 DB-4 ○ △
Embodiment 13 R-5 DB-5 ◎ ○
Embodiment 14 R-6 DB-6 ○ ○
Embodiment 15 R-7 DB-7 ○ ○
Embodiment 16 R-8 DB-8 ○ ○
Embodiment 21 R-12 DB-12 ◎ △
Embodiment 22 R-13 DB-13 ◎ ○
Embodiment 23 R-14 DB-14 ○ ○
Embodiment 24 R-15 DB-15 △ ○
Comparative example 4 R-9 DB-9 ○ ×
Comparative example 5 R-10 DB-10 △ ×
Comparative example 6 R-11 DB-11 × ×
The film foreign matter of the anticorrosive additive material (R-1～15) of embodiment 9～16,21～24 is in the scope that can be used as color filter, and glass adaptation is also good result.On the other hand, the glass adaptation of the anticorrosive additive material of comparative example 4,5 (R-9,10) is poor, and the anticorrosive additive material (R-11) of comparative example 6 produces more foreign matter, therefore cannot reach the quality that can be used as color filter.Thus, find to contain and use the coloured composition that there is the salify product of the resin of cationic group at side chain to provide to there is good painting membrane stage and the excellent color filter of glass adaptation simultaneously.
Embodiment 25: anticorrosive additive material (R-16)
After composition shown in following table C is uniformly mixed, with the filtrator filtration of 1.0 μ m, make alkali developable anticorrosive additive material R-16.
Table C:
Embodiment 26: anticorrosive additive material (R-17)
Except the epoxy compound solution 1 of embodiment 25 (alkali developable anticorrosive additive material R-1) being replaced with to epoxy compound 2 (the PGMA solution of " EX-201 " 20% that Nagasechemtex company manufactures), similarly obtain alkali developable anticorrosive additive material (R-17) with anticorrosive additive material R-1.
Embodiment 27: anticorrosive additive material (R-18)
Except the epoxy compound solution 1 of embodiment 25 (alkali developable anticorrosive additive material R-1) being replaced with to epoxy compound 3 (the PGMA solution of " Epicoat 825 " 20% that oiling SHELL EPOXY company manufactures), similarly obtain alkali developable anticorrosive additive material (R-18) with anticorrosive additive material R-1.
The evaluation > of < contrast
To become x=0.150 in illuminant-C, the thickness of the mode of y=0.060 is painting erosion resistant agent material on glass substrate, and this substrate is heated 20 minutes at 230 ℃, measures by the following method the contrast of the substrate of gained, and result is shown in table 4.
The assay method of the contrast of film
The glass substrate of the dry coating that is provided with anticorrosive additive material is clamped between the 1st polaroid and the 2nd polaroid, uses back light for liquid crystal display device unit light irradiation from the 1st polaroid side.From the light of back light unit from the 1st polaroid by partially, then, pass through from dry coating and the glass substrate of anticorrosive additive material, arrive the 2nd polaroid.As long as the polarization axle of the 1st polaroid and the 2nd polaroid is parallel to each other, luminous energy sees through the 2nd polaroid, but in the mutually perpendicular situation of polarization axle of two polaroids, light is blocked by the 2nd polaroid.But, play inclined to one side light when the substrate by being coated with anticorrosive additive material by the 1st polaroid, be offset in a part for plane of polarization if there is the scattering that caused by coloring agent component etc., in the time that the polarization axle of two polaroids is parallel, the light quantity that sees through the 2nd polaroid reduces, in the time that the polarization axle of two polaroids is vertical, a part of light can see through the 2nd polaroid.Utilize nitometer on the 2nd polaroid to measure the brightness of this transmitted light, brightness when brightness when parallel the polarization axle of two polaroids when parallel (brightness) is vertical with respect to the polarization axle of two polaroids when vertical (brightness) be compared to contrast., contrast is calculated and is obtained by following formula.
Contrast=when parallel (brightness)/when vertical (brightness)
Therefore, if because the colorant in anticorrosive additive material film causes scattering, when parallel, brightness reduces, and brightness increases when vertical, and therefore contrast reduces.
In addition, as nitometer, use chroma-luminance meter (" BM-5A " that TOPCON company manufactures), as polaroid, " NPF-G1220RU " polaroid that uses Dong electrician society to manufacture.In addition, in the time measuring, in order to cover unwanted light, in mensuration part, lay the black mask that has the square hole of 1cm.
Table 4
Anticorrosive additive material Coloured composition Heat-curable compounds Contrast
Embodiment 9 R-1 DB-1 - 9500
Embodiment 25 R-16 DB-1 Epoxy compound solution 1 10500
Embodiment 26 R-17 DB-1 Epoxy compound solution 2 10200
Embodiment 27 R1-18 DB-1 Epoxy compound solution 3 10300
The anticorrosive additive material (R-16～18) that contains epoxy compound has high contrast, and more excellent color filter can be provided.

Claims (7)

1. a color composition for color filter, is characterized in that, it comprises colorant, adhesive resin and organic solvent, and described colorant contains that the resin that makes to have a cationic group at side chain reacts with anionic property dyestuff and the salify product that obtains,
The described resin that has a cationic group at side chain is the vinyl resin that contains the structural unit that following general formula (1) represents,
general formula (1)
In general formula (1), R 1represent hydrogen atom or replacement or unsubstituted alkyl, R 2～R 4represent independently of one another hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted thiazolinyl or replacement or unsubstituted aryl, R 2～R 4in two also can interosculate and form ring, Q represent alkylidene, arlydene or-COO-R 5-, R 5represent alkylidene, Y-represents inorganic or organic negative ion,
Described vinyl resin is that the conversion weight-average molecular weight that GPC measures is 1000～500000 with gel permeation chromatography.
2. color composition for color filter according to claim 1, is characterized in that, the ammonium salt value of the vinyl resin of the structural unit that contains described general formula (1) expression is 10～200mgKOH/g.
3. color composition for color filter according to claim 1 and 2, it is characterized in that, described salify product is to have the resin of cationic group and anionic property dyestuff mixes by described at side chain in aqueous solution, and the salt that the counter cation of the counter anion by the described resin at side chain with cationic group and anionic dye is formed is removed and the compound that makes.
4. color composition for color filter according to claim 1 and 2, is characterized in that, described organic solvent contains the a kind of above organic solvent being selected from ethyl glycol acetate class, aromatic series alcohols and ketone.
5. color composition for color filter according to claim 1 and 2, is characterized in that, described colorant also contains pigment.
6. color composition for color filter according to claim 1 and 2, is characterized in that, described color composition for color filter also contains photopolymerization monomer and/or Photoepolymerizationinitiater initiater.
7. a color filter, it is to utilize the color filter that in claim 1～6, the color composition for color filter described in any one forms.
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