CN101673052A - Coloring radioactive composition, colorant dispersion liquid, a color filter and a colorful LCD device - Google Patents

Coloring radioactive composition, colorant dispersion liquid, a color filter and a colorful LCD device Download PDF

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Publication number
CN101673052A
CN101673052A CN200910165932A CN200910165932A CN101673052A CN 101673052 A CN101673052 A CN 101673052A CN 200910165932 A CN200910165932 A CN 200910165932A CN 200910165932 A CN200910165932 A CN 200910165932A CN 101673052 A CN101673052 A CN 101673052A
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methyl
solvent
radiation sensitive
colorant
mass parts
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CN101673052B (en
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荒井雅史
高见朋宏
大喜多健三
吉泽英彻
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JSR Corp
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JSR Corp
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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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F5/00—Screening processes; Screens therefor
    • G03F5/20—Screening processes; Screens therefor using screens for gravure printing
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/20—Exposure; Apparatus therefor

Abstract

The invention relates to a coloring radioactive composition, a colorant fluid dispersion, a color filter and a colorful LCD component. The invention provides green pixel that can form high ration between lightness and contrast, and the contrast will not drop down following pass of time. The coloring radioactive composition comprises a colorant (A), a alkalis soluble resin (B), a polyfunctional monomer (C) and a coloring radioactive initiator of polymerization (D) and a solvent (E), characterized in that the colorant (A) contains C.I. everbright fast pigment green 58, and the solvent (E) contains two acetoxyl groups.

Description

Coloring radiation sensitive composition, colorant dispersion, color filter and color liquid crystal display device
Technical field
The present invention relates to coloring radiation sensitive composition, colorant dispersion, color filter and color liquid crystal display device, more particularly, the formation that relates in the color filter used in transmission-type or Reflexible color LCD, colour pick-up tube element, organic EL display element, the Electronic Paper etc. the dyed layer that is suitable for radiation-sensitive linear composition, have the color filter of the dyed layer that adopts this radiation-sensitive linear composition formation and a color liquid crystal display device with this color filter.
Background technology
As adopting coloring radiation sensitive composition to form the method for color filter, known on the substrate or be pre-formed on the substrate of required pattern-like light shield layer, the formation coloring radiation sensitive composition is filmed, by the photomask useful to irradiation of rays with predetermined pattern (hereinafter referred to as " exposure "), and develop and to remove unexposed portion with dissolving, cure after carrying out then and obtain the method (reference example such as patent documentation 1, patent documentation 2) of each color pixel.
Liquid crystal display cells with this color filter needs high brightnessization and enlarges the color reproduction scope, thereby for color filter, also requires to have high transmittance and high excitation in recent years day by day.
For green pixel, as the material of the color filter that brightness height and color reproduction wide ranges can be provided, the known noticeable color compositions (reference example such as patent documentation 3) that contains many halos zinc phthalocyanine color that has.Yet, contain the color compositions of many halos zinc phthalocyanine color, if will improve contrast, exist contrast in time and the problem that descends.
Because above background, can form the high green pixel of brightness and contrast and not exist contrast in time and the radiation-sensitive linear composition that descends so press for exploitation.
[prior art]
[patent documentation]
[patent documentation 1] Japanese kokai publication hei 2-144502 communique
[patent documentation 2] Japanese kokai publication hei 3-53201 communique
[patent documentation 3] TOHKEMY 2007-284589 communique
Summary of the invention
The objective of the invention is, the radiation-sensitive linear composition that can form the high green pixel of brightness and contrast and not exist contrast to descend in time is provided.
Purpose of the present invention in addition also comprises the color filter with the green pixel that is formed by above-mentioned radiation-sensitive linear composition is provided, and the color liquid crystal display device with this color filter.
In light of this situation, present inventors attentively study, and are surprised to find that, disperse by many halos zinc phthalocyanine color C.I. naphthol green 58 and specific group of solvents are merged, and can address the above problem, thereby finish the present invention.
Promptly, the invention provides a kind of coloring radiation sensitive composition, be to contain (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer, (D) radiation sensitive linear polymerization initiator and (E) coloring radiation sensitive composition of solvent, it is characterized in that, as (A) colorant, contain C.I. naphthol green 58, and, as (E) solvent, contain solvent with 2 acetoxyl groups.
So-called among the present invention " ray " is meant the implication of the ray that contains luminous ray, ultraviolet ray, far ultraviolet, electron beam, X ray etc.
In addition, the invention provides a kind of coloring radiation sensitive composition, be to contain (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer, (D) radiation sensitive linear polymerization initiator and (E) coloring radiation sensitive composition of solvent, it is characterized in that, as (A) colorant, contain bromo chloro zinc phthalocyanine, and, as (E) solvent, contain solvent with 2 acetoxyl groups.
In addition, the invention provides a kind of colorant dispersion, the solvent that it is characterized in that containing C.I. naphthol green 58 and have 2 acetoxyl groups.
In addition, the present invention also provides the color filter with the green pixel that forms with this coloring radiation sensitive composition, and the color liquid crystal display device with this color filter.
Coloring radiation sensitive composition of the present invention can form the high green pixel of brightness and contrast, and contrast can not descend in time.
Therefore, color filter with the green pixel that forms with coloring radiation sensitive composition of the present invention for example is suitable for transmission-type or reflection-type color liquid crystal display element, colour pick-up tube element, color sensor, organic EL display element, Electronic Paper etc. very much.
Embodiment
In coloring radiation sensitive composition of the present invention (following also abbreviate as " radiation-sensitive linear composition "), (A) colorant contains C.I. naphthol green 58.C.I. naphthol green 58 is bromo chloro zinc phthalocyanines, is preferably the structure of following formula (1) expression.
Figure G2009101659320D00031
(in the formula (1), X represents hydrogen atom, chlorine atom or bromine atoms independently of each other, and all among the X, 10～15 is bromine atoms, and 1～6 is the chlorine atom).
Radiation-sensitive linear composition of the present invention can further contain other colorants beyond the C.I. naphthol green 58.As other colorants, have no particular limits, pigment, dyestuff and natural colouring matter are any all can be used, and because color filter requires to have the color development and the thermotolerance of high-purity high light transmittance, so preferred organic pigment.
In the present invention, the content ratio of C.I. naphthol green 58 on the meaning that obtains the high green pixel of brightness, is preferably 20～100 quality % in all coloring agent, be preferably 35～75 quality % especially.
As above-mentioned other colorants, can enumerate the compound that is divided into pigment class in the pigment index for example, specifically, can enumerate the pigment that has following pigment index (C.I.) name.
C.I. pigment Green 7, C.I. pigment green 36;
C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 17, C.I. pigment yellow 20, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 55, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 166, C.I. pigment yellow 168, C.I. pigment yellow 180, C.I. pigment yellow 211, C.I. pigment yellow 219;
C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 61, C.I. pigment orange 64, C.I. pigment orange 68, C.I. pigment orange 70, C.I. pigment orange 71, C.I. pigment orange 72, C.I. pigment orange 73, C.I. pigment orange 74;
C.I. paratonere 1, C.I. paratonere 2, C.I. paratonere 5, C.I. paratonere 17, C.I. pigment red 31, C.I. pigment red 32, C.I. pigment red 41, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 149, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 170, C.I. paratonere 171, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 178, C.I. paratonere 179, C.I. paratonere 180, C.I. paratonere 185, C.I. paratonere 187, C.I. paratonere 202, C.I. paratonere 206, C.I. Pigment Red 207, C.I. paratonere 209, C.I. pigment red 21 4, C.I. paratonere 220, C.I. paratonere 221, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 243, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 262, C.I. paratonere 264, C.I. paratonere 272;
These other colorants can use in independent or two or more mixing.
In these other colorants, when forming green pixel, preferred C.I. pigment Green 7, C.I. pigment green 36, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180, C.I. pigment yellow 219 etc.
In the present invention, C.I. naphthol green 58 and other colorants as required, re-use after can adopting recrystallization method, reprecipitation method, solvent wash method, sublimed method, vaccum heating method or their combination etc. to make with extra care.In addition, C.I. naphthol green 58 and other colorants as required, can also re-use its particle surface after with polymer modification.As the polymkeric substance on modified pigment particles surface, can enumerate the polymkeric substance of putting down in writing in the Japanese kokai publication hei 8-259876 communique for example, perhaps commercially available various pigment dispersing are with polymkeric substance or oligomer etc.
In the present invention, (A) content ratio of colorant on the meaning that forms the high green pixel of brightness and excitation, in all solids composition, is preferably 5～70 quality %, is preferably 5～60 quality % especially.Here, solid constituent is meant following solvent composition in addition.
Contained (B) alkali soluble resin in the radiation-sensitive linear composition of the present invention, so long as have solubility for used alkaline developer in the development treatment operation when dyed layer forms, then it is had no particular limits, be generally have carboxyl, the polymkeric substance of acid functional groups such as phenol hydroxyl.Wherein, the alkali soluble resin that preferably contains polymkeric substance with carboxyl, especially preferably have 1 above carboxyl ethylene unsaturated monomer (below be also referred to as " containing the carboxyl unsaturated monomer ") but with the multipolymer of the ethylene unsaturated monomer of other copolymerization (below be also referred to as " copolymerization unsaturated monomer ") (below be also referred to as " carboxy-containing copolymer ").
As containing the carboxyl unsaturated monomer, can for example enumerate
Unsaturated monocarboxylics such as (methyl) acrylic acid, crotonic acid, α-Lv Bingxisuan, cinnamic acid;
Unsaturated diacid acid such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or its acid anhydrides;
List [(methyl) acryloxyalkyl] ester of the polybasic carboxylic acid that binary such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester are above;
ω-two ends such as carboxyl polycaprolactone list (methyl) acrylate have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl etc.
The above-mentioned carboxyl unsaturated monomer that contains can use in independent or two or more mixing.
In the present invention, as containing the carboxyl unsaturated monomer, preferred (methyl) acrylic acid, mono succinate [2-(methyl) acryloxy ethyl] ester, ω-carboxyl polycaprolactone list (methyl) acrylate etc., preferred especially (methyl) acrylic acid.
These contain the carboxyl unsaturated monomer and can independent or two or more mixing use.
In carboxy-containing copolymer, the copolymerization ratio that contains the carboxyl unsaturated monomer is preferably 5～50 quality %, more preferably 10～40 quality %.At this moment, if this copolymerization ratio is very few, then exist the gained radiation-sensitive linear composition for the little tendency of the dissolubility of alkaline developer, on the other hand, if too much, then exist for the dissolubility of alkaline developer excessively, when developing, cause pixel to come off and pixel surface produces the tendency of film be full of cracks easily from substrate with alkaline developer.
In addition, as the copolymerization unsaturated monomer, can for example enumerate
Maleimide:
N-phenylmaleimide, N-o-hydroxy-phenyl maleimide, hydroxy phenyl maleimide between N-, N-p-hydroxybenzene maleimide, N-benzyl maleimide, N-cyclohexyl maleimide, N-succinimido-3-dimaleoyl imino benzoic ether, N-succinimido-4-dimaleoyl imino butyric ester, N-succinimido-6-dimaleoyl imino capronate, N-succinimido-3-dimaleoyl imino propionic ester, the maleimide that N-positions such as N-(acridinyl) maleimide replace;
Styrene, α-Jia Jibenyixi, adjacent vinyltoluene, between vinyltoluene, to vinyltoluene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, adjacent vinylphenol, between vinylphenol, to vinylphenol, to hydroxyl-α-Jia Jibenyixi, adjacent vinyl benzyl methyl ether, between the vinyl benzyl methyl ether, to the vinyl benzyl methyl ether, adjacent vinyl benzyl glycidyl ether, between the vinyl benzyl glycidyl ether, to aromatic ethenyl compounds such as vinyl benzyl glycidyl ethers;
Indenes classes such as indenes, 1-methyl indenes;
(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) acrylic acid 2-hydroxyethyl ester, (methyl) acrylic acid 2-hydroxy-propyl ester, (methyl) acrylic acid 3-hydroxy-propyl ester, (methyl) acrylic acid 2-hydroxybutyl ester, (methyl) acrylic acid 3-hydroxybutyl ester, (methyl) acrylic acid 4-hydroxybutyl ester, (methyl) acrylic acid allyl ester, (methyl) acrylic acid benzyl ester, (methyl) acrylic acid cyclohexyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid 2-methoxy ethyl ester, (methyl) acrylic acid 2-phenoxy group ethyl ester, (methyl) acrylic acid methoxyl diglycol ester, (methyl) acrylic acid methoxyl triethyleneglycol ester, (methyl) acrylic acid MPEG ester, (methyl) acrylic acid methoxyl dipropylene glycol ester, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy propyl ester, glycerine list (methyl) acrylate, (methyl) acrylic acid 4-hydroxy phenyl ester, to the esters of unsaturated carboxylic acids such as (methyl) acrylate of the oxirane modification of cumyl phenol;
Unsaturated carboxylic acid glycidyl esters such as (methyl) acrylic acid glycidyl esters;
Vinyl carboxylates such as vinyl acetate, propionate, vinyl butyrate, benzoic acid vinyl acetate;
Unsaturated ethers such as vinyl methyl ether, EVE, allyl glycidyl ether;
Vinyl cyanide compounds such as (methyl) vinyl cyanide, α-Lv Bingxijing, vinylidene dinitrile;
Unsaturated amides such as (methyl) acrylamide, α-chloropropene acid amides, N-2-hydroxyethyl (methyl) acrylamide;
Aliphatics conjugated diolefines such as 1,3-butadiene, isoprene, chloro pentadiene;
Polymer molecule chain ends such as polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane have the macromonomer of list (methyl) acryloyl group etc.
These copolymerization unsaturated monomers can use in independent or two or more mixing.
In the present invention; as the copolymerization unsaturated monomer; preferably contain and be selected from the maleimide that the N-position replaces; aromatic ethenyl compound; esters of unsaturated carboxylic acids; the polymer molecule chain end has at least a monomer in the group that the macromonomer of list (methyl) acryloyl group constitutes, and more preferably contains to be selected from N-phenylmaleimide; N-cyclohexyl maleimide; styrene; α-Jia Jibenyixi; to hydroxyl-α-Jia Jibenyixi; (methyl) methyl acrylate; (methyl) n-butyl acrylate; (methyl) 2-ethylhexyl acrylate; (methyl) acrylic acid 2-hydroxyethyl ester; (methyl) acrylic acid allyl ester; (methyl) acrylic acid benzyl ester; glycerine list (methyl) acrylate; (methyl) acrylic acid 4-hydroxy phenyl ester; (methyl) acrylate to the oxirane modification of cumyl phenol; the polystyrene macromolecular monomer; at least a monomer in the group that the polymethylmethacrylate macromonomer constitutes.
In addition; in the present invention, the carboxy-containing copolymer that has polymerism unsaturated links such as (methyl) acryloyl group on the disclosed side chain in for example Japanese kokai publication hei 5-19467 communique, Japanese kokai publication hei 6-230212 communique, the TOHKEMY 2008-181095 communique etc. can also be used as alkali soluble resin.
Alkali soluble resin among the present invention by gel permeation chromatography (GPC, eluting solvent: the weight-average molecular weight of the polystyrene conversion of Ce Dinging (below be also referred to as " Mw ") tetrahydrofuran), be generally 1000～45000, be preferably 3000～20000.If Mw is too small, then exist the residual film ratio of gained overlay film to descend, infringement pattern form, thermotolerance, and the possibility of electric property variation; On the other hand,, then exist resolution to descend, damage pattern form, and when adopting the gap nozzle mode to apply, be easy to generate the danger of dry foreign matter if excessive.
In addition, the Mw of the alkali soluble resin among the present invention with by gel permeation chromatography (GPC, eluting solvent: the ratio (Mw/Mn) of the number-average molecular weight of the polystyrene conversion of Ce Dinging (hereinafter referred to as " Mn ") tetrahydrofuran) is preferably 1.0～5.0, more preferably 1.0～3.0.
Alkali soluble resin among the present invention can be by for example making unsaturated monomers such as (methyl) acrylic acid in appropriate solvent, 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2, carry out polymerization under the existence of 2 '-azo two radical polymerization initiators such as (4-methoxyl-2,4-methyl pentane nitriles) and prepare.
Alkali soluble resin among the present invention can be after carrying out free radical polymerization with unsaturated monomer as mentioned above, makes with extra care by the reprecipitation method that adopts the different organic solvent of two or more polarity to prepare.Promptly, with the solution in the good solvent after the polymerization, after removing insoluble impurity by filter or centrifuging etc. as required, put in the precipitation agent (poor solvent) of a large amount of (being generally 5～10 times amount of polymer solution volume), multipolymer is precipitated again and make with extra care.At this moment, in the polymer solution in the remaining impurities, the impurity that dissolves in precipitation agent remains in liquid phase and separates from refining alkali soluble resin.
As the combination of the good solvent/precipitation agent that uses in this reprecipitation method, can enumerate for example diethylene glycol monomethyl ether acetic acid esters/normal hexane, methyl ethyl ketone/normal hexane, diethylene glycol monomethyl ether acetic acid esters/normal heptane, methyl ethyl ketone/normal heptane etc.
In addition; alkali soluble resin among the present invention; can also pass through 2 each unsaturated monomer of its copolymer composition; 2 '-azoisobutyronitrile; 2; 2 '-azo two (2; the 4-methyl pentane nitrile); 2; 2 '-azo two (4-methoxyl-2; the 4-methyl pentane nitrile) radical polymerization initiator and pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl ester such as; pyrazoles-1-carbodithioic acid benzyl ester; Thiuram disulfide; two (pyrazol-1-yl thiocarbonyl) disulfide; two (3-methyl-pyrazol-1-yl thiocarbonyl) disulfide; two (4-methyl-pyrazol-1-yl thiocarbonyl) disulfide; two (5-methyl-pyrazol-1-yl thiocarbonyl) disulfide; two (3; 4; 5-trimethyl-pyrazol-1-yl thiocarbonyl) disulfide; two (pyrroles-1-base thiocarbonyl) disulfide; two thiobenzoyl disulfide etc. play under the existence of molecular weight regulator of iniferter agent (Iniferter) effect; in inert solvent; usually making temperature of reaction is 0～150 ℃; preferred 50～120 ℃, carry out active free radical polymerization and prepare.
In addition, alkali soluble resin among the present invention, can also by with each unsaturated monomer of its copolymer composition above-mentioned radical polymerization initiator and play the chain-transferring agent effect the multi-thiol compound in the presence of, in appropriate solvent, carry out free radical polymerization and prepare.Here, so-called multi-thiol compound, be meant the compound that has 2 above sulfydryls in 1 molecule, can enumerate for example trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptopropionic acid ester), tetraethylene glycol two (3-mercaptopropionic acid ester), dipentaerythritol six (3-mercaptopropionic acid ester), pentaerythrite four (sulfo-glycolate), 1,4-two (3-sulfydryl butyryl acyloxy) butane, pentaerythrite four (3-sulfydryl butyric ester), 1,3,5-three (3-sulfydryl butoxyethyl group)-1,3,5-triazine-2,4,6-(1H, 3H, 5H) triketone etc.
In the present invention, (B) content of alkali soluble resin with respect to 100 mass parts (A) colorant, is generally 10～1000 mass parts, is preferably 20～500 mass parts.At this moment, if the content of alkali soluble resin is very few, for example have then that alkali-developable descends, on the substrate of unexposed portion or produce the possibility of residue and scum on the light shield layer; On the other hand,, then exist, be difficult to reach the possibility of aim colour concentration as film because colorant concentration is relatively low if too much.
(C) multi-functional monomer among the present invention is the monomer with 2 above polymerism unsaturated links.
As this multi-functional monomer, can for example enumerate
Two (methyl) acrylate of alkylene glycol such as ethylene glycol, propylene glycol;
Two (methyl) acrylate of ployalkylene glycol such as polyglycol, polypropylene glycol;
Many (methyl) acrylate of the polyvalent alcohol that ternarys such as glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol are above or their dicarboxylic acid modifier;
Oligomer (methyl) acrylate such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Two terminal hydroxyls are poly--two (methyl) acrylate of two terminal hydroxyl polymkeric substance such as 1,3-butadiene, two terminal hydroxyl polyisoprene, two terminal hydroxyl polycaprolactones;
The triacrylate of three [2-(methyl) acryloxy ethyl] phosphate, the modification of isocyanuric acid oxirane, have the urethane structure many (methyl) acrylate, have many (methyl) acrylate of caprolactone structure etc.
In these multi-functional monomers, many (methyl) esters of acrylic acids and the dicarboxylic acid modifier thereof of the polyvalent alcohol that preferred ternary is above, many (methyl) acrylate that has many (methyl) acrylate of urethane structure and have the caprolactone structure.Many (methyl) esters of acrylic acids and dicarboxylic acid modifier thereof as the polyvalent alcohol more than the ternary, preferred trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, the mono-esterification thing of pentaerythritol triacrylate and succinic acid, the mono-esterification thing of pentaerythritol acrylate trimethyl and succinic acid, the mono-esterification thing of dipentaerythritol five acrylate and succinic acid, the mono-esterification thing of dipentaerythritol pentamethyl acrylate and succinic acid etc., big from the intensity of dyed layer, the surface smoothing of dyed layer is good, and be difficult to produce scum on the unexposed portion substrate He on the light shield layer, aspects such as residual film are considered, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, the mono-esterification thing of the mono-esterification thing of pentaerythritol triacrylate and succinic acid and dipentaerythritol five acrylate and succinic acid.
The content of (C) the multi-functional monomer among the present invention with respect to 100 mass parts (B) alkali soluble resin, is preferably 20～500 mass parts, is preferably 100～300 mass parts especially.At this moment, if the content of multi-functional monomer is very few, then there are the intensity of pixel and the tendency that surface smoothing, solvent resistance descend, on the other hand, if too much, for example have then that alkali-developable descends, on the unexposed portion substrate or be easy to generate the tendency of scum, residual film etc. on the light shield layer.
In addition, in the present invention, the part of multi-functional monomer can also replace with the simple function monomer with 1 polymerism unsaturated link.
As above-mentioned simple function monomer, can enumerate for example list [(methyl) acryloxyalkyl] ester of the polybasic carboxylic acid more than the binary such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester; Two ends of ω-carboxyl polycaprolactone list (methyl) acrylate have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl; N-(methyl) acryloyl morpholine, N-vinyl pyrrolidone, N-vinyl-epsilon-caprolactams in addition, as commercially available product, can be enumerated M-5600 (trade name ， East Asia synthetic (strain) produces) etc.
These simple function monomers can use in independent or two or more mixing.
The content of the simple function monomer among the present invention with respect to the total amount of multi-functional monomer and simple function monomer, is preferably below the 90 quality %, more preferably below the 50 quality %.At this moment, if the usage rate of simple function monomer is too much, then there are the intensity of pixel and the tendency of surface smoothing decline.
(D) radiation sensitive linear polymerization initiator that uses among the present invention, be to expose, can produce the compound of spike of the polymerization of the simple function monomer that can cause above-mentioned (C) multi-functional monomer and use as required by the ray that employing contains luminous ray, ultraviolet ray, far ultraviolet, electron beam, X ray etc.
As this radiation sensitive linear polymerization initiator, can enumerate for example thioxanthones compounds, acetophenone compounds, diimidazole compounds, compound in triazine class, O-acyl group oxime compound, salt compounds, benzoin compounds, Benzophenones compound, α-cyclohexadione compounds, multinuclear quinones, diazonium compounds, acid imide sulphonic acid ester (imide sulfonate) compounds etc.
In the present invention; the radiation sensitive linear polymerization initiator can use in independent or two or more mixing; as the radiation sensitive linear polymerization initiator, be preferably selected from least a in the group that thioxanthones compounds, acetophenone compounds, diimidazole compounds, compound in triazine class, O-acyl group oxime compound constitute.In addition, contain the radiation-sensitive linear composition of C.I. naphthol green 58, be easy to generate the cohesion foreign matter of this pigment, on the meaning that reduces the cohesion foreign matter, preferably contain the thioxanthones compounds.
In the present invention, more preferably above-mentioned thioxanthones compounds and other radiation sensitive linear polymerization initiators are used in combination.In this case, the content ratio of thioxanthones compounds in whole radiation sensitive linear polymerization initiators, is preferably 1～75 quality %, is preferably 5～50 quality % especially.By using this radiation sensitive linear polymerization initiator, can obtain to have high sensitive and the good radiation-sensitive linear composition of dispersion stabilization.
Among the present invention in the preferred radiation sensitive linear polymerization initiator, object lesson as the thioxanthones compounds, can enumerate thioxanthones, 2-methyl thioxanthones, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2-dodecyl thioxanthones, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones, 2-clopenthixal ketone etc.
In these thioxanthones compounds, preferred 2-methyl thioxanthones, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone.
Above-mentioned thioxanthones compounds can use in independent or two or more mixing.
In addition, object lesson as above-mentioned acetophenone compounds, can enumerate 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholinyl phenyl) butane-1-ketone, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone etc.
In these acetophenone compounds, preferred 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholinyl phenyl) butane-1-ketone.
Above-mentioned acetophenone compounds can use in independent or two or more mixing.
In addition, as the object lesson of above-mentioned diimidazole compounds, can enumerate 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole etc.
In these diimidazole compounds, preferred 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole etc.
Above-mentioned diimidazole compounds can use in independent or two or more mixing.
In addition, when using the diimidazole compounds, consider preferred coupling hydrogen donor from the angle that can improve susceptibility as the radiation sensitive linear polymerization initiator.Here so-called " hydrogen donor " is meant the compound that hydrogen atom can be provided to the free radical that the diimidazole compounds produces by exposure.As hydrogen donor, can enumerate for example thio-alcohol hydrogen donor, 4 such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, amine hydrogen donors such as 4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone.In the present invention, hydrogen donor can use in independent or two or more mixing, preferably uses the thio-alcohol hydrogen donor.
In the present invention, when with hydrogen donor and the coupling of diimidazole compounds, the content of hydrogen donor with respect to 100 mass parts diimidazole compounds, is preferably 1～300 mass parts, is preferably 5～200 mass parts especially, more preferably 10～150 mass parts.At this moment,, then there is the tendency that effect descends of improving of susceptibility if the content of hydrogen donor is very few, on the other hand, if too much, the tendency that then exists formed dyed layer when developing, to come off from substrate easily.
In addition, object lesson as above-mentioned compound in triazine class, can enumerate 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4,6-two (trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-[2-(furans-2-yl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-[2-(4-lignocaine-2-aminomethyl phenyl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-two (trichloromethyl)-s-triazine, 2-(4-ethoxybenzene vinyl)-4,6-two (trichloromethyl)-s-triazine, 2-(4-n-butoxy phenyl)-4,6-two (trichloromethyl)-s-triazine etc. has the compound in triazine class of halogenated methyl.
Above-mentioned compound in triazine class can use in independent or two or more mixing.
In addition; object lesson as above-mentioned O-acyl group oxime compound; can enumerate 1; the 2-heptadione; 1-[4-(thiophenyl) phenyl]-; 2-(O-benzoyl oximes); 1; the 2-acetyl caproyl; 1-[4-(thiophenyl) phenyl]-; 2-(O-benzoyl oximes); 1; the 2-acetyl caproyl; 1-[4-(benzoyl) phenyl]-; 2-(O-benzoyl oximes); ethyl ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime); ethyl ketone; 1-[9-ethyl-6-(3-methyl benzoyl)-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime); ethyl ketone; 1-(9-ethyl-6-benzoyl-9H-carbazole-3-yl)-; 1-(O-acetyl group oxime); ethyl ketone; 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl)-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime); ethyl ketone; 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl benzoyl)-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime); ethyl ketone; 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base benzoyl)-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime); ethyl ketone; 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl benzoyl)-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime); ethyl ketone; 1-[9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1; the 3-dioxolanyl) benzoyl }-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime); ethyl ketone; 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime); ethyl ketone; 1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime); ethyl ketone; 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime); ethyl ketone; 1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime); ethyl ketone; 1-[9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1; the 3-dioxolanyl) methoxybenzoyl base }-9H-carbazole-3-yl]-, 1-(O-acetyl group oxime) etc.
In these O-acyl group oxime compounds; preferred 1; the 2-acetyl caproyl; 1-[4-(thiophenyl) phenyl]-; 2-(O-benzoyl oximes), ethyl ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime), ethyl ketone; 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9H-carbazole-3-yl]-; 1-(O-acetyl group oxime), ethyl ketone, and 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1; the 3-dioxolanyl) methoxybenzoyl base }-9H-carbazole-3-yl]-, 1-(O-acetyl group oxime).
Above-mentioned O-acyl group oxime compound can use in independent or two or more mixing.
In the present invention, the content of radiation sensitive linear polymerization initiator with respect to the multi-functional monomer of 100 mass parts (C), is generally 0.01～120 mass parts, is preferably 1～100 mass parts, more preferably 1～70 mass parts.At this moment, if the content of radiation sensitive linear polymerization initiator is very few, it is insufficient then to exist exposure to solidify, be difficult to obtain the danger of pattern of pixels according to the color filter of predetermined layout setting, on the other hand, if too much, the tendency that then exists formed pattern of pixels when developing, to come off from substrate easily.
(E) solvent that uses among the present invention contains the solvent with 2 acetoxyl groups.As the object lesson of solvent, can enumerate propylene-glycol diacetate, 1,3 butylene glycol diacetate esters, 1,6-hexanediol diacetate esters etc. with 2 acetoxyl groups.
Above-mentioned solvent with 2 acetoxyl groups can use in independent or two or more mixing.
In the present invention, other solvents can be used with the solvent with 2 acetoxyl groups.As this other solvents, can for example enumerate
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diglycol monotertiary positive propyl ether, the diglycol monotertiary n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol list ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, the propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, the single ether of dipropylene glycol, the single positive propyl ether of dipropylene glycol, the dipropylene glycol mono-n-butyl ether, the tripropylene glycol monomethyl ether, (gathering) alkylene glycol monoalky lethers such as tripropylene glycol list ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-(gathering) alkylene glycol monoalky lether acetic acid esters such as 3-methoxyl butyl propionic ester;
Ethers such as diethylene glycol dimethyl ether, diglycol methyl ethyl ether, diethyl carbitol, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Lactic acid alkyl ester such as methyl lactate, ethyl lactate;
2-hydroxy-2-methyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other ester classes such as 2-ketobutyric acid ethyl ester;
Aromatic hydrocarbon such as toluene, dimethylbenzene;
N, acid amides such as dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or lactams etc.
In these other solvents, from dissolubility, the screening characteristics equal angles of pigment-dispersing, pigment composition in addition, preferred propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butyl propionic ester.
Above-mentioned other solvents can use in independent or two or more mixing.
The solvent that uses among the present invention is preferably the solvent with 2 acetoxyl groups and the potpourri of other solvents, has the content ratio of the solvent of 2 acetoxyl groups, all being preferably 1～60 quality % in the solvents, is preferably 1～45 quality % especially.At this moment, very few as if the content ratio of solvent with 2 acetoxyl groups, then there is the danger that can not obtain Expected Results, on the other hand,, then exist solvent composition to be difficult to evaporation, the danger that makes the formation of filming become difficult if too much.
The content of solvent, have no particular limits, from the screening characteristics of gained radiation-sensitive linear composition, stable equal angles, preferably making the total concentration that desolventizes each composition in addition of said composition is the amount of 5～50 quality %, especially preferably is the amount of 10～40 quality %.
In the present invention, radiation-sensitive linear composition can adopt the modulation of suitable method, for example, can modulate by (A)～(E) composition and following adjuvant are mixed together.Modulator approach as preferred radiation-sensitive linear composition, can enumerate and to contain the colorant of C.I. naphthol green 58, in the solvent that contains solvent with 2 acetoxyl groups, at (F) spreading agent and the dispersing aid that adds as required in the presence of, according to circumstances with a part (B) composition, for example adopting bowl mill, rolls etc. to pulverize simultaneously mixes, disperses, make colorant dispersion, in this colorant dispersion, add (B)～(D) composition and the solvent that further appends as required and adjuvant and mixing again and the method for modulation.
At this moment, in the whole solvents that in the modulation of colorant dispersion, use, have the content ratio of the solvent of 2 acetoxyl groups, be preferably more than the 2 quality %, be preferably especially more than the 5 quality %.
(F) spreading agent that uses in the modulation as above-mentioned colorant dispersion can use suitable spreading agents such as cationic, anionic species, nonionic class or both sexes, the preferred polymers spreading agent.The especially preferred segmented copolymer that constitutes by the block that does not have the pigment adsorption group on block that has the pigment adsorption group on the side chain and the side chain (below be also referred to as " segmented copolymer type spreading agent ").
As the pigment adsorption group in the segmented copolymer type spreading agent, can enumerate for example basic group, carboxyl, phosphono, quaternary ammonium root, carbonate, phosphate radical etc. such as amino.The block that has the pigment adsorption group on the side chain is made of the repetitive that for example derives from (methyl) acrylate with these pigment adsorption groups.
In addition, do not have the block of pigment adsorption group on the side chain, preferably on its side chain, have chain or cyclic alkyl, aryl, aralkyl, polycaprolactone structure, polyether structure etc.The block that does not have the pigment adsorption group on the side chain is made of the repetitive that for example derives from (methyl) acrylate with these functional groups or structure.
This segmented copolymer type spreading agent can commerce be buied, and for example, can enumerate Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (being produced by PVC Star Network ケ ミ one (BYK) society) etc.
Above-mentioned segmented copolymer spreading agent can use in independent or two or more mixing.
In the present invention, other spreading agents can be used with segmented copolymer type spreading agent.As this other spreading agents, particularly, can enumerate polyurethane, polyester, cationic graft polymer etc.Here, kation sex comb type graft polymer, be meant to have and have on the trunk polymer of a plurality of basic groups (cationic functional group) at 1 molecule, the polymkeric substance of the structure of the above branch polymer of scion grafting 2 molecules can be enumerated the polymkeric substance that the part of trunk polymer for example constitutes for the ring-opening polymerization polymer of 6-caprolactone for polyethyleneimine, branch polymer part.
This spreading agent can commerce be buied, for example, as polyurethane, can enumerate Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (production of above PVC Star Network ケ ミ one (BYK) society), ソ Le ス パ one ス 76500 (producing) by Le one Block リ ゾ one Le (strain) society, as the cationic graft polymer, can enumerate ソ Le ス パ one ス 24000 (producing) by Le one Block リ ゾ one Le (strain) society, ア ジ ス パ one PB821, ア ジ ス パ one PB822, ア ジ ス パ one PB823, ア ジ ス パ one PB824, ア ジ ス パ one PB827 (producing) etc. by monosodium glutamate Off ア イ Application テ Network ノ Co., Ltd..
These spreading agents can use in independent or two or more mixing.
The content of spreading agent with respect to 100 mass parts (A) colorant, is generally below 100 mass parts, is preferably 0.5～100 mass parts, and more preferably 1～70 mass parts is preferably 10～50 mass parts especially.At this moment, if the content of spreading agent surpasses 100 mass parts, then there is the danger of infringement development.
Radiation-sensitive linear composition of the present invention contains above-mentioned (A)～(E) composition, and as required, can also further contain adjuvant.
Here as adjuvant, can enumerate for example filling agent such as glass, alumina; Macromolecular compounds such as polyvinyl alcohol (PVA), poly-(fluoro-alkyl acrylate) class; Surfactants such as nonionic class surfactant, cationic surfactant, anionic species surfactant; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, adhesion promotors such as 3-sulfydryl propyl trimethoxy silicane; 2, antioxidants such as 2-sulphur two (4-methyl-6-tert butyl phenol), 2,6 di t butyl phenol; Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy Benzophenones; Anti-coagulants such as sodium polyacrylate; Development residue improvers such as malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid etc.
Color filter of the present invention has the green pixel that is formed by radiation-sensitive linear composition of the present invention.
Below, the method that forms color filter of the present invention is described.
At first, on substrate surface, as required, formation marks off the light shield layer that will form pixel portion, again on this substrate, apply the fluid composition of the radiation-sensitive linear composition that has disperseed viridine green of the present invention after, carry out prebake and make solvent evaporation, formation is filmed.Then, by photomask to this film expose after, develop with alkaline developer, remove the unexposed portion of filming with dissolving, cure after carrying out then, form the pel array that the green pixel pattern is provided with by predetermined layout.
Then, employing has disperseed the fluid composition of each radiation-sensitive linear composition of redness or blue pigment, with the above-mentioned coating of similarly carrying out each fluid composition, prebake, exposure, development and after cure, on same substrate, form red pixel array and blue pixel array successively, make the color filter that on substrate, is provided with redness, green and blue trichromatic pel array.But, in the present invention, the formation of each color pixel order is not limited to said sequence.
Used substrate when forming pixel can be enumerated for example glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc.
In addition, on these substrates, as required, can also carry out suitable pre-treatments such as chemical reagent processing, plasma treatment, ion plating, sputter, gas-phase reaction method, vacuum evaporation such as silane coupling agent in advance.
When the fluid composition with radiation-sensitive linear composition is coated on the substrate, can adopt spraying process, rolling method, whirl coating (spin-coating method), slit die coating process, rod to be coated with suitable coating methods such as method, ink-jet method, preferred especially spin-coating method, slit die coating process.
Applied thickness as dried thickness, is generally 0.1～10 μ m, is preferably 0.2～8.0 μ m, is preferably 0.2～6.0 μ m especially.
The ray that uses during as the formation pixel can use for example luminous ray, ultraviolet ray, far ultraviolet, electron beam, X ray etc., and optimal wavelength is the ray of 190～450nm scope.
The exposure of ray is preferably 10～10000J/m usually 2
In addition, as above-mentioned alkaline developer, preference such as sodium carbonate, NaOH, potassium hydroxide, tetramethyl ammonium hydroxide, choline, 1,8-diazabicylo [5.4.0]-7-undecylene, 1, the aqueous solution of 5-diazabicylo [4.3.0]-5-nonene etc.
Can also add for example water-miscible organic solvent such as amount of methanol, ethanol and surfactant etc. in the above-mentioned alkaline developer.In addition, alkali is washed after developing usually.
As the development treatment method, can adopt flushing development method, hydro-peening development method, immersion (dipping) development method, pasting (パ De Le/liquid is contained the り method) development method etc.Development conditions is preferably under the normal temperature developed 5～300 seconds.
The color filter of the present invention that so makes is because brightness and contrast's height is therefore very suitable in color liquid crystal display device, colour pick-up tube element, color sensor, organic EL display element, Electronic Paper etc.
[embodiment]
Below, enumerate embodiment embodiments of the present invention are carried out more specific description.But the present invention is not limited to following embodiment.
The modulation of colorant dispersion
Modulation example 1
Will be by as potpourri 40 mass parts of the C.I. naphthol green 58 (productions of DIC society) of (A) colorant and 60/40 (mass ratio) of C.I. pigment yellow 150, as Disperbyk-2001 (PVC Star Network ケ ミ one (BYK) the society production of spreading agent, solids content concn is 45.1 quality %) 24 mass parts and as propylene glycol methyl ether acetate 116 mass parts, 1 of solvent, the mixed liquor that 3-butylene glycol diacetate esters 20 mass parts are formed, mix, disperseed 12 hours with bowl mill, modulate dispersible pigment dispersion (A-1).
Modulation example 2
Will be by as potpourri 40 mass parts of the C.I. naphthol green 58 (productions of DIC society) of (A) colorant and 60/40 (mass ratio) of C.I. pigment yellow 150, as Disperbyk-2001 (PVC Star Network ケ ミ one (BYK) the society production of spreading agent, solids content concn is 45.1 quality %) 24 mass parts and the mixed liquor formed as propylene glycol methyl ether acetate 116 mass parts of solvent, propylene-glycol diacetate 20 mass parts, mix, disperseed 12 hours with bowl mill, modulate dispersible pigment dispersion (A-2).
Modulation example 3
Will be by as potpourri 40 mass parts of the C.I. naphthol green 58 (productions of DIC society) of (A) colorant and 60/40 (mass ratio) of C.I. pigment yellow 150, as Disperbyk-2001 (PVC Star Network ケ ミ one (BYK) the society production of spreading agent, solids content concn is 45.1 quality %) 24 mass parts and as propylene glycol methyl ether acetate 96 mass parts, 1 of solvent, the mixed liquor that 3-butylene glycol diacetate esters 40 mass parts are formed, mix, disperseed 12 hours with bowl mill, modulate dispersible pigment dispersion (A-3).
Modulation example 4
Will be by as potpourri 40 mass parts of the C.I. naphthol green 58 (productions of DIC society) of (A) colorant and 60/40 (mass ratio) of C.I. pigment yellow 150, as Disperbyk-2001 (PVC Star Network ケ ミ one (BYK) the society production of spreading agent, solids content concn is 45.1 quality %) 24 mass parts and as 3-ethoxyl ethyl propionate 76 mass parts, 1 of solvent, the mixed liquor that 3-butylene glycol diacetate esters 60 mass parts are formed, mix, disperseed 12 hours with bowl mill, modulate dispersible pigment dispersion (A-4).
Modulation example 5
Will be by as potpourri 40 mass parts of the C.I. naphthol green 58 (productions of DIC society) of (A) colorant and 60/40 (mass ratio) of C.I. pigment yellow 150, as Disperbyk-2001 (PVC Star Network ケ ミ one (BYK) the society production of spreading agent, solids content concn is 45.1 quality %) 24 mass parts and as 3-methoxyl butylacetic acid ester 76 mass parts, 1 of solvent, the mixed liquor that 3-butylene glycol diacetate esters 60 mass parts are formed, mix, disperseed 12 hours with bowl mill, modulate dispersible pigment dispersion (A-5).
Modulation example 6
Will be by as potpourri 40 mass parts of the C.I. naphthol green 58 (productions of DIC society) of (A) colorant and 60/40 (mass ratio) of C.I. pigment yellow 150, as Disperbyk-2001 (PVC Star Network ケ ミ one (BYK) the society production of spreading agent, solids content concn is 45.1 quality %) 24 mass parts and as 1 of solvent, the mixed liquor that 3-butylene glycol diacetate esters 136 mass parts are formed, mix dispersion 12 hours with bowl mill, modulate dispersible pigment dispersion (A-6).
Relatively modulate example 1
Will be by as potpourri 40 mass parts of the C.I. naphthol green 58 (productions of DIC society) of (A) colorant and 60/40 (mass ratio) of C.I. pigment yellow 150, as Disperbyk-2001 (PVC Star Network ケ ミ one (BYK) the society production of spreading agent, solids content concn is 45.1 quality %) 24 mass parts and the mixed liquor formed as propylene glycol methyl ether acetate 136 mass parts of solvent, mix, disperseed 12 hours with bowl mill, modulate dispersible pigment dispersion (a-1).
Relatively modulate example 2
Will be by as potpourri 40 mass parts of the C.I. naphthol green 58 (productions of DIC society) of (A) colorant and 60/40 (mass ratio) of C.I. pigment yellow 150, as Disperbyk-2001 (PVC Star Network ケ ミ one (BYK) the society production of spreading agent, solids content concn is 45.1 quality %) 24 mass parts and the mixed liquor formed as glycerol triacetate (solvent) 136 mass parts of solvent with 3 acetoxyl groups, mix, disperseed 12 hours with bowl mill, modulate dispersible pigment dispersion (a-2).
Relatively modulate example 3
Will be by as potpourri 40 mass parts of the C.I. naphthol green 58 (productions of DIC society) of (A) colorant and 60/40 (mass ratio) of C.I. pigment yellow 150, as Disperbyk-2001 (PVC Star Network ケ ミ one (BYK) the society production of spreading agent, solids content concn is 45.1 quality %) 24 mass parts and the mixed liquor formed as propylene glycol methyl ether acetate 116 mass parts of solvent, cyclohexanone 20 mass parts, mix, disperseed 12 hours with bowl mill, modulate dispersible pigment dispersion (a-3).
Relatively modulate example 4
Will be by as potpourri 40 mass parts of the C.I. naphthol green 58 (productions of DIC society) of (A) colorant and 60/40 (mass ratio) of C.I. pigment yellow 150, as Disperbyk-2001 (PVC Star Network ケ ミ one (BYK) the society production of spreading agent, solids content concn is 45.1 quality %) 24 mass parts and the mixed liquor formed as propylene glycol methyl ether acetate 116 mass parts of solvent, propylene glycol monomethyl ether 20 mass parts, mix, disperseed 12 hours with bowl mill, modulate dispersible pigment dispersion (a-4).
Relatively modulate example 5
Will be by as potpourri 40 mass parts of the C.I. pigment green 36 of (A) colorant and 53/47 (mass ratio) of C.I. pigment yellow 150, as Disperbyk-2001 (PVC Star Network ケ ミ one (BYK) the society production of spreading agent, solids content concn is 45.1 quality %) 24 mass parts and the mixed liquor formed as propylene glycol methyl ether acetate 116 mass parts of solvent, cyclohexanone 20 mass parts, mix, disperseed 12 hours with bowl mill, modulate dispersible pigment dispersion (a-5).
(B) alkali soluble resin is synthetic
Synthesis example 1
To condenser pipe is housed, in the flask of stirrer, add 2,2 '-azo two (2, the 4-methyl pentane nitrile) 2.5 mass parts and ethylene glycol monomethyl ether acetate 200 mass parts, continue to add methacrylic acid 15 mass parts, ω-carboxyl two caprolactone mono acrylic esters 10 mass parts, N-phenylmaleimide 15 mass parts, methacrylic acid 2-ethylhexyl 33 mass parts, styrene 12 mass parts, glycerin monomethyl acrylic ester 15 mass parts and α-Jia Jibenyixierjuwu (chain-transferring agent) 5.0 mass parts, after the nitrogen ventilation, under slowly stirring, make reaction solution be warming up to 80 ℃, keep this temperature to carry out polymerization in 3 hours.Then, reaction solution is warming up to 100 ℃, appends 0.5 mass parts 2,2 '-azo two (2, the 4-methyl pentane nitrile) continued polymerization 1 hour again, obtained resin solution (solids content concn=30 quality %).Gained resin M w=14000, Mn=5700.This resin solution is as " resin solution (B-1) ".
Embodiment 1
The modulation of radiation-sensitive linear composition
With dispersible pigment dispersion (A-1) 400 mass parts; resin solution (B-1) 200 mass parts as (B) alkali soluble resin; dipentaerythritol acrylate 60 mass parts as (C) multi-functional monomer; as 2 of (D) radiation sensitive linear polymerization initiator; 4-diethyl thioxanthone 6 mass parts; ethyl ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-; (チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ society produces 1-(O-acetyl group oxime); trade name IRGACURE OX02) 5 mass parts; 2; 2 '-two (2-chlorphenyls)-4; 4 '; 5; 5 '-tetraphenyl-1; 2 '-diimidazole, 2 mass parts and 2-mercaptobenzothiazole 2 mass parts; and mix as the propylene glycol methyl ether acetate of solvent; making its solids content concn is 20.0%, modulates fluid composition (G1).
Liquid towards composition (G1) is estimated according to following order.Evaluation result is listed in table 1.
The evaluation of colorimetric properties and contrast
On the same day of modulating, adopt spin coater, be variable with the rotational speed, fluid composition (G1) is coated on 3 surfaces has formed the SiO that prevents the sodion stripping 2After on the soda-lime glass substrate of film, on 90 ℃ heating plate, carry out 4 minutes prebake, form different 3 of thickness and film.
Then, these substrates are cooled to room temperature after, adopt high-pressure sodium lamp, to filming with 400J/m 2Exposure contain the exposure of the ray of 365nm, 405nm and each wavelength of 436nm.Then, to these substrates with 1kgf/cm 2Development pressure (nozzle diameter 1nm) spray the developer solution that 23 ℃ the potassium hydroxide aqueous solution by 0.04 quality % is formed, carry out flushing development in 1 minute.Then, this substrate with after the ultrapure water washing, drying, is carried out curing after 30 minutes in 220 ℃ cleaning oven again, form to estimate and use cured film.
To 3 cured film of gained, adopt color analysis instrument (by greatly
Figure G2009101659320D00271
The MCPD 2000 that Electricity (strain) makes), by illuminant-C under the 2 degree visuals field, measure chromaticity coordinate value in the CIE color specification system (x, y) and values (Y).Chromaticity coordinate value x when obtaining chromaticity coordinate value y=0.600, values (Y) by measurement result.
In addition, to 3 cured film of gained, adopt the mensuration of contrast meter (Pot Ban Electricity Machine She System CT-1, Block ラ Application Network 5000) degree of comparing, the contrast when obtaining chromaticity coordinate value y=0.600.
(G1) at room temperature preserved 1 month with fluid composition, similarly carried out the mensuration of chroma characteristic and contrast, the chromaticity coordinate value x when obtaining chromaticity coordinate value y=0.600, values (Y) and contrast.Evaluation result is listed in table 1.
Embodiment 2～6 and comparative example 1～5
In embodiment 1, except the kind with dispersible pigment dispersion replace with as shown in table 1, modulate fluid composition (G2)～(G11) similarly to Example 1.
Then, except using the alternative fluid composition (G1) of fluid composition (G2)～(G11) respectively, estimate similarly to Example 1.Evaluation result is listed in table 1.
Table 1
As shown in Table 1, contain C.I. naphthol green 58 and radiation-sensitive linear composition, can form the high green pixel of brightness and contrast, and contrast can not descend in time with solvent of 2 acetoxyl groups.On the contrary, when use has the solvent of 1 acetoxyl group (comparative example 1) and when using the solvent with 3 acetoxyl groups (comparative example 2), compare when having the solvent of 2 acetoxyl groups with use, contrast is low.

Claims (8)

1, a kind of coloring radiation sensitive composition, be to contain (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer, (D) radiation sensitive linear polymerization initiator and (E) coloring radiation sensitive composition of solvent, it is characterized in that, as (A) colorant, contain C.I. naphthol green 58, and,, contain solvent with 2 acetoxyl groups as (E) solvent.
2, a kind of coloring radiation sensitive composition, be to contain (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer, (D) radiation sensitive linear polymerization initiator and (E) coloring radiation sensitive composition of solvent, it is characterized in that, as (A) colorant, contain bromo chloro zinc phthalocyanine, and,, contain solvent with 2 acetoxyl groups as (E) solvent.
3, claim 1 or 2 described coloring radiation sensitive compositions, wherein (E) solvent is to have the solvent of 2 acetoxyl groups and the potpourri of other solvents, and the content ratio with solvent of 2 acetoxyl groups is 1～60 quality % in whole solvents.
4, the described coloring radiation sensitive composition of claim 3 wherein further contains (F) spreading agent.
5, the described coloring radiation sensitive composition of claim 4 wherein as (F) spreading agent, comprises the segmented copolymer that is made of the block that does not have the pigment adsorption group on block that has the pigment adsorption group on the side chain and the side chain.
6, a kind of colorant dispersion is characterized in that containing: C.I. naphthol green 58, have the solvent of 2 acetoxyl groups and the segmented copolymer that is made of the block that does not have the pigment adsorption group on block that has the pigment adsorption group on the side chain and the side chain.
7, a kind of color filter, it has the green pixel that adopts claim 1 or 2 described coloring radiation sensitive compositions to form.
8, a kind of color liquid crystal display device, it has the described color filter of claim 7.
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