CN1677138A - Radiation-ray sensitive composition for colour-filtering piece, colour filtering piece and colour liquid crystal display device - Google Patents

Radiation-ray sensitive composition for colour-filtering piece, colour filtering piece and colour liquid crystal display device Download PDF

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Publication number
CN1677138A
CN1677138A CNA2005100627042A CN200510062704A CN1677138A CN 1677138 A CN1677138 A CN 1677138A CN A2005100627042 A CNA2005100627042 A CN A2005100627042A CN 200510062704 A CN200510062704 A CN 200510062704A CN 1677138 A CN1677138 A CN 1677138A
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methyl
acrylate
acid
pigment
radiation
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CN100376905C (en
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沼田淳
小林和博
森下聪
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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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

Abstract

The present invention provides a radiation sensitive composition for a color filter comprising (A) a pigment, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photopolymerization initiator and (F) a solvent, wherein the dispersant (B) comprises an acrylic copolymer obtained through living anionic polymerization and having an amine value (unit; mgKOH/g) and an acid value (unit; mgKOH/g) each greater than 0.

Description

Color filter radiation-ray sensitive composition, color filter and color liquid crystal display arrangement
Technical field
The present invention relates to color filter radiation-ray sensitive composition, color filter and color liquid crystal display arrangement.Particularly, color filter that the color filter that the present invention relates to be used to make color filter forms with radiation-ray sensitive composition, by said composition and the color liquid crystal display arrangement with this color filter, wherein said color filter is used for transmission-type or Reflexible color LCD, colour pick-up tube element etc.
Background technology
Known when making color filter with colored radiation-sensitive composition, usually at substrate or be pre-formed on the substrate of light shield layer of required pattern, form the tunicle of colored radiation-sensitive composition, and by having the photomask irradiation radioactive ray (hereinafter referred to as " exposure ") of required pattern form, develop then and dissolve and remove unexposed part, cure after then carrying out, form the method (opening flat 2-144502 communique and the flat 3-53201 communique of Te Kai) of versicolor pixel pattern thus with reference to the spy with Network リ-Application オ-Block Application or hot plate.Yet, in said method, particularly when pigment concentration contained in the painted radiation-ray sensitive composition is high, producing residue or scum on the substrate of unexposed portion or on the light shield layer sometimes during development.
The ejection pressure that improves developer solution to avoid producing above-mentioned residue or scum effective, exist again but then and the disadvantage that pattern is damaged or peel off occurs, the colored radiation-sensitive composition that pattern is damaged or peel off does not take place yet even therefore remain to be developed a kind of ejection pressure with the good raising of tack substrate developer solution.
In addition, in recent years, along with the maximization of liquid crystal indicator, the substrate that has formed color filter also increases gradually.Therefore, in the exposure process when forming color filter, adopt and divide what is called " multiple exposure " method of exposure for several times, but the T.T. of exposing required increases.Therefore, consider, even need the short colored radiation-sensitive composition that also can form pixel pattern of time shutter from improving the productive capacity aspect.
Yet existing colored radiation-sensitive composition occurs the damaged of pattern sometimes or comes off when forming pixel pattern with short exposure time (promptly low exposure) during development, and differing meets the demands surely.In addition, under the situation of low exposure, the tunicle that is made of colored radiation-sensitive composition solidifies insufficient, and the surface smoothing of pattern is obviously impaired, and the result has problems such as the liquid crystal aligning of causing is bad.And, existing colored radiation-sensitive composition generally have through the time tackify tendency, exist can not be long time stored after the preparation problem.
Therefore, a kind of and substrate adherence are good also has also good color filter radiation-ray sensitive composition of enough developments and patterned surfaces flatness and bin stability under the situation of low exposure even demand urgently developing.
Summary of the invention
A kind of and substrate adherence are good also to have an also good color filter radiation-ray sensitive composition such as enough developments and patterned surfaces flatness and bin stability etc. under the situation of low exposure even problem of the present invention provides.
Another problem of the present invention provides the color filter that is formed by above-mentioned composition of the present invention.
Another problem of the present invention provides the liquid crystal indicator with color filter of the present invention.
Other problem of the present invention and advantage will be come clear and definite by the following description.
The first, according to the present invention, above-mentioned problem of the present invention solves with radiation-ray sensitive composition by following color filter, it is characterized in that said composition comprises: (A) pigment; (B) spreading agent; (C) alkali soluble resin, it comprises (c1) and contains (methyl) acrylic acid carboxyl unsaturated monomer that contains, (c2) maleimide of N-position replacement, and (c3) be selected from styrene, α-Jia Jibenyixi, to hydroxyl-α-Jia Jibenyixi, (methyl) methyl acrylate, (methyl) n-butyl acrylate, 2-ethylhexyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, allyl (methyl) acrylate, benzyl (methyl) acrylate, glycerine list (methyl) acrylate, at least a kind multipolymer in polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer; (D) multi-functional monomer; (E) Photoepolymerizationinitiater initiater and (F) solvent, wherein said (B) spreading agent contains acrylic copolymer, and this acrylic copolymer obtains through active anionic polymerization, and its amine value (the mg KOH/g of unit) and acid number (the mg KOH/g of unit) are all greater than 0.
The second, according to the present invention, above-mentioned problem of the present invention solves with radiation-ray sensitive composition by following color filter, it is characterized in that said composition comprises: (A) pigment; (B) spreading agent; (C) alkali soluble resin; (D) multi-functional monomer; (E) Photoepolymerizationinitiater initiater and (F) solvent, and said composition comprises (B) spreading agent, (C) alkali soluble resin and (F) prepares in the medium of solvent by (A) pigment is dispersed in advance, wherein said (B) spreading agent contains acrylic copolymer, this acrylic copolymer obtains through active anionic polymerization, and its amine value (the mg KOH/g of unit) and acid number (the mg KOH/g of unit) are all greater than 0.
The 3rd, according to the present invention, above-mentioned problem of the present invention can be by being solved with the color filter that radiation-ray sensitive composition forms by above-mentioned each color filter.
The 4th, according to the present invention, above-mentioned problem of the present invention can solve by the liquid crystal indicator that comprises above-mentioned color filter.
Color filter of the present invention is good with the adherence of substrate with radiation-ray sensitive composition, even also have enough developments and patterned surfaces flatness under the situation of hanging down exposure, and bin stability etc. is also fine.
Therefore, to be suitable for forming in the electronics industry with the color liquid crystal display arrangement color filter with the radiation-ray sensitive composition utmost point be the various color filters of representative to color filter of the present invention.
Embodiment
Below describe the present invention in detail.
The color filter radiation-ray sensitive composition
-(A) pigment-
Pigment among the present invention is not had particular restriction, can be any in organic pigment, the inorganic pigment.Wherein, under high-purity, consider especially preferred organic pigment aspect high radioparent colour developing and the thermotolerance from pursuing color filter.
Above-mentioned organic pigment comprises for example Colour Index (C.I.; The distribution of The Society of Dyersand Colourists society) is sorted in the compound in the pigment in, specifically can enumerates the material of following Colour Index (C.I.) numbering.
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 211;
C.I. pigment orange 36, C.I. pigment orange 43, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 71;
C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. pigment red 122, C.I. pigment red 123, C.I. pigment red 149, C.I. paratonere 168, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 180, C.I. paratonere 185, C.I. Pigment Red 207, C.I. paratonere 208, C.I. paratonere 209, C.I. pigment red 21 5, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 243, C.I. paratonere 254;
C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29;
C.I. pigment blue 15, C.I. pigment blue 60, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6;
C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 136, C.I. naphthol green 210;
C.I. pigment brown 23, C.I. pigment brown 25.
These organic pigments can use separately, and perhaps two or more mix use.
Among the present invention, organic pigment can pass through the refining back of combination of recrystallization method, reprecipitation method, solvent wash method, sublimed method, vaccum heating method or these methods to be used.
Above-mentioned inorganic pigment for example can enumerate titanium dioxide, barium sulphate, lime carbonate, zinc paste, lead sulfate, yellow lead, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine, dark blue, chrome oxide green, cobalt green, umber, titanium black, synthesize iron oxide black, carbon black etc.
These inorganic pigments can use separately, and perhaps two or more mix use.
And, in the present invention, according to circumstances, can also and use above-mentioned pigment and one or more dyestuffs or natural colouring matter.
Among the present invention, as required, can carry out modification to the pigment particles surface and use with polymkeric substance.The polymkeric substance of pigment particles surface modification for example can be enumerated the special polymkeric substance put down in writing in the flat 8-259876 communique or the commercially available various pigment dispersing opened with polymkeric substance or oligomer etc.
-(B)-spreading agent
Spreading agent among the present invention contains acrylic copolymer (hereinafter referred to as " acrylic dispersants (B1) ", this acrylic copolymer obtains through active anionic polymerization, and its amine value (the mg KOH/g of unit, as follows) and acid number (the mg KOH/g of unit, as follows) are all greater than 0.
The amine value of acrylic dispersants (B1) is preferably 10～100, and more preferably 15～50.The acid number of acrylic dispersants (B1) is preferred 5～50, and more preferably 10～30.At this moment, if the amine value of acrylic dispersants (B1) is 0, then the composition of gained has the tendency that bin stability reduces, and the acid number of acrylic dispersants (B1) is 0 o'clock, with the adherence of substrate the tendency of reduction is arranged.
The commercially available product of acrylic dispersants (B1) can be enumerated Disperbyk-2001 (amine value=29, acid number=19, BYK company) etc.
Among the present invention, acrylic dispersants (B1) can be separately or two or more mix and use.
Among the present invention, can be with acrylic dispersants (B1) and other spreading agent and usefulness.
Described other spreading agent comprises for example polyethylene oxide alkyl ethers such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether; Polyethylene oxide alkyl phenyl ethers such as polyethylene oxide n-octyl phenyl ether, polyethylene oxide n-nonyl phenyl ether; Polyethylene glycol di such as polyethylene glycol dilaurate, polyglycol distearate; Sorbitan fatty acid esters; Fatty acid modified polyester; The tertiary amine modified polyurethane; The polyethyleneimine: amine; The material that comprises following trade name in addition, KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Port リ Off ロ-(common prosperity society chemistry (strain) system), エ Off ト Star プ (ト-ケ system プ ロ ダ Network Star society system), メ ガ Off ア Star Network (big Japanese イ Application キ chemical industry (strain) system), Off ロ ラ-De (Sumitomo ス リ-エ system (strain) system), ア サ ヒ ガ-De, サ-Off ロ Application (above material is rising sun whistle (strain) system), Disperbyk-101, Disperbyk-103, Disperbyk-107, Disperbyk-110, Disperbyk-111, Disperbyk-115, Disperbyk-130, Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-165, Disperbyk-166, Disperbyk-170, Disperbyk-180, Disperbyk-182, Disperbyk-2000 (above material is PVC Star Network ケ ミ-ジ ヤ パ Application (strain) system), ソ Le ス パ-ス S5000, ソ Le ス パ-ス S12000, ソ Le ス パ-ス S13240, ソ Le ス パ-ス S13940, ソ Le ス パ-ス S17000, ソ Le ス パ-ス S20000, ソ Le ス パ-ス S22000, ソ Le ス パ-ス S24000, ソ Le ス パ-ス S24000GR, ソ Le ス パ-ス S26000, ソ Le ス パ-ス S27000, ソ Le ス パ-ス S28000 (above material is ア PVC シ ア (strain) system), EFKA46, EFKA47, EFKA48, EFKA745, EFKA4540, EFKA4550, EFKA6750, EFKA LP4008, EFKA LP4009, EFKA LP4010, EFKA LP4015, EFKA LP4050, EFKA LP4055, EFKA LP4560, EFKA LP4800, EFKA Polymer400, EFKA Polymer 401, EFKA Polymer 402, EFKA Polymer 403, EFKA Polymer 450, EFKA Polymer 451, EFKA Polymer 453 (above material is エ Off カ ケ ミ カ Le ズ (strain) system); ア ジ ス パ-PB-822 (aginomoto Off ア イ Application テ Network ノ (strain) system) etc.
Above-mentioned other spreading agent can be separately or two or more mix and use.
With respect to the total amount of acrylic dispersants (B1) and other spreading agent, the usage ratio of other spreading agent is preferably 0～75 weight %, more preferably 0～50 weight %.When the usage ratio of other spreading agent surpasses 75 weight %, may not guarantee the well balanced of development property, surface smoothing and bin stability.
Among the present invention, with respect to (A) pigment 100 weight portions, the consumption of acrylic dispersants (B1) (converting with solid constituent) is preferably 1～50 weight portion, more preferably 3～30 weight portions.If the consumption of acrylic dispersants (B1) is lower than 1 weight portion, then resulting composition has the tendency that bin stability reduces; On the other hand, if the consumption of acrylic dispersants (B1) is higher than 50 weight portions, the tendency that produces residue easily on substrate is arranged.
-(C) alkali soluble resin-
Alkali soluble resin among the present invention is so long as play bonding agent to (A) pigment, and to the used developer solution of the development step in the color filter manufacturing, the material that especially preferably alkaline-based developer had solubility, then do not have particular determination.Wherein, the alkali soluble resin that preferably has carboxyl, more preferably have in the molecule one or more carboxyls ethylenically unsaturated monomers (hereinafter referred to as " containing the carboxyl unsaturated monomer ") but with the multipolymer (hereinafter referred to as " carboxy-containing copolymer ") of the ethylenically unsaturated monomers (hereinafter referred to as " copolymerization unsaturated monomer ") of other copolymerization.
Containing the carboxyl unsaturated monomer for example comprises:
Unsaturated monocarboxylic acids such as (methyl) acrylic acid, crotonic acid, α-Lv Bingxisuan, cinnamic acid;
Unsaturated dicarboxylic or its acid anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid;
Unsaturated polybasic carboxylic acid or its acid anhydrides that ternary or ternary are above;
List [(methyl) acryloxyalkyl] ester of binary such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester or the above polybasic carboxylic acid of binary;
ω-two ends such as carboxyl polycaprolactone list (methyl) acrylate have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl etc.
These contain in the carboxyl unsaturated monomer, and phthalic acid list [2-acryloxy ethyl] ester has commercially available with trade name M-5400 (East Asia synthetic (strain) system).
Above-mentioned contain the carboxyl unsaturated monomer can be separately or two or more mix and use.
In addition, the copolymerization unsaturated monomer for example comprises:
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 (ス Network シ Application イ ミ ジ Le)-3-maleimide benzoate, N-succinimido-4-maleimide butyrate, N-succinimido-6-maleimide caproate, N-succinimido-3-maleimide propionate, the maleimide that N-positions such as N-(acridinyl) maleimide replace;
Styrene, α-Jia Jibenyixi, neighbour-vinyltoluene, between-vinyltoluene, right-vinyltoluene, right-chlorostyrene, neighbour-methoxy styrene, between-methoxy styrene, p-methoxystyrene, right-hydroxyl-α-Jia Jibenyixi, neighbour-vinyl benzyl methyl ether, between-the vinyl benzyl methyl ether, right-the vinyl benzyl methyl ether, neighbour-vinyl benzyl glycidyl ether, between-the vinyl benzyl glycidyl ether, right-aromatic ethenyl compounds such as vinyl benzyl glycidyl ether;
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, 2-ethylhexyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, 2-hydroxybutyl (methyl) acrylate, 3-hydroxybutyl (methyl) acrylate, 4-hydroxybutyl (methyl) acrylate, allyl (methyl) acrylate, benzyl (methyl) acrylate, cyclohexyl (methyl) acrylate, phenyl (methyl) acrylate, 2-methoxy ethyl (methyl) acrylate, 2-phenoxy group ethyl (methyl) acrylate, methoxyl diglycol (methyl) acrylate, methoxyl triethylene glycol (methyl) acrylate, MPEG (methyl) acrylate, methoxyl dipropylene glycol (methyl) acrylate, isobornyl (methyl) acrylate, three ring [5.2.1.0 2,6] last of the ten Heavenly stems-esters of unsaturated carboxylic acids such as 8-base (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, glycerine list (methyl) acrylate;
Unsaturated carboxylic acid aminoalkyl esters such as 2-amino-ethyl (methyl) acrylate, 2-dimethylaminoethyl (methyl) acrylate, 2-aminopropyl (methyl) acrylate, 2-dimethylamino-propyl (methyl) acrylate, 3-aminopropyl (methyl) acrylate, 3-dimethylamino-propyl (methyl) acrylate;
Unsaturated carboxylic acid ethylene oxidic esters such as glycidyl (methyl) acrylate;
Vinyl carboxylates such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, EVE, allyl glycidyl ether;
Vinyl cyanide compounds such as (methyl) vinyl cyanide, α-Lv Daibingxijing, vinylidene dinitrile;
Unsaturated amides such as (methyl) acrylamide, alpha-chloro acrylamide, N-2-hydroxyethyl (methyl) acrylamide;
Aliphatics conjugated diolefines such as 1,3-butadiene, isoprene, chlorbutadiene;
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 be separately or two or more mix and use.
As neccessary composition, what according to circumstances contain single (methyl) acrylate of mono succinate [2-(methyl) acryloxy ethyl] ester and/or ω-carboxyl polycaprolactone (カ Network ロ ラ Network ト Application) contains the carboxyl unsaturated monomer to carboxy-containing copolymer among the present invention preferred (c1) with (methyl) acrylic acid; (c2) maleimide of N-position replacement; And (c3) be selected from styrene, α-Jia Jibenyixi, to hydroxyl-α-Jia Jibenyixi, (methyl) methyl acrylate, (methyl) n-butyl acrylate, 2-ethylhexyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, glycerine list (methyl) acrylate, at least a kind multipolymer in other copolymerization unsaturated monomer of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer (hereinafter referred to as " carboxy-containing copolymer (C1) ").
The preferred object lesson of carboxy-containing copolymer (C1) for example comprises:
(methyl) acrylic acid/N-phenylmaleimide/styrene/benzyl (methyl) acrylate copolymer;
Between (methyl) acrylic acid/N--hydroxy phenyl maleimide/styrene/benzyl (methyl) acrylate copolymer;
(methyl) acrylic acid/N-is right-hydroxy phenyl maleimide/styrene/benzyl (methyl) acrylate copolymer;
(methyl) acrylic acid/N-cyclohexyl maleimide/styrene/benzyl (methyl) acrylate copolymer;
(methyl) acrylic acid/N-phenylmaleimide/α-Jia Jibenyixi/benzyl (methyl) acrylate copolymer;
(methyl) acrylic acid/N-phenylmaleimide/styrene/normal-butyl (methyl) acrylate copolymer;
(methyl) acrylic acid/N-phenylmaleimide/styrene/2-ethylhexyl (methyl) acrylate copolymer;
(methyl) acrylic acid/N-phenylmaleimide/right-hydroxyl-α-Jia Jibenyixi/benzyl (methyl) acrylate copolymer;
(methyl) acrylic acid/N-phenylmaleimide/styrene/normal-butyl (methyl) acrylate copolymer;
(methyl) acrylic acid/N-phenylmaleimide/styrene/2-ethylhexyl (methyl) acrylate copolymer;
(methyl) acrylic acid/N-phenylmaleimide/styrene/2-hydroxyethyl (methyl) acrylate/benzyl (methyl) acrylate copolymer;
(methyl) acrylic acid/N-phenylmaleimide/styrene/benzyl (methyl) acrylate/glycerine list (methyl) acrylate copolymer;
(methyl) acrylic acid/N-is right-hydroxy phenyl maleimide/styrene/benzyl (methyl) acrylate/glycerine list (methyl) acrylate copolymer;
(methyl) acrylic acid/N-phenylmaleimide/styrene/phenyl (methyl) acrylate/2-hydroxyethyl (methyl) acrylate/polystyrene macromolecular monomer copolymer;
(methyl) acrylic acid/N-phenylmaleimide/styrene/phenyl (methyl) acrylate/2-hydroxyethyl (methyl) acrylate/polymethylmethacrylate macromonomer multipolymer;
(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-phenylmaleimide/styrene/benzyl (methyl) acrylate copolymer;
(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-is right-hydroxy phenyl maleimide/styrene/benzyl (methyl) acrylate copolymer;
(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-phenylmaleimide/styrene/allyl (methyl) acrylate copolymer;
(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-cyclohexyl maleimide/styrene/allyl (methyl) acrylate copolymer;
(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-cyclohexyl maleimide/styrene/benzyl (methyl) acrylate copolymer;
Between (methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/N--hydroxy phenyl maleimide/styrene/benzyl (methyl) acrylate copolymer;
(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/N-is right-hydroxy phenyl maleimide/styrene/benzyl (methyl) acrylate copolymer;
(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/N-phenylmaleimide/styrene/benzyl (methyl) acrylate/glycerine list (methyl) acrylate copolymer;
(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/N-is right-hydroxy phenyl maleimide/styrene/benzyl (methyl) acrylate/glycerine list (methyl) acrylate copolymer etc.
In addition, carboxy-containing copolymer (C1) carboxy-containing copolymer in addition for example comprises:
(methyl) acrylic acid/(methyl) methyl acrylate copolymer;
(methyl) acrylic acid/benzyl (methyl) acrylate copolymer;
(methyl) acrylic acid/2-hydroxyethyl (methyl) acrylate/benzyl (methyl) acrylate copolymer;
(methyl) acrylic acid/(methyl) methyl acrylate/polystyrene macromolecular monomer copolymer;
(methyl) acrylic acid/(methyl) methyl acrylate/polymethylmethacrylate macromonomer multipolymer;
(methyl) acrylic acid/benzyl (methyl) acrylate/polystyrene macromolecular monomer copolymer;
(methyl) acrylic acid/benzyl (methyl) acrylate/polymethylmethacrylate macromonomer multipolymer;
(methyl) acrylic acid/2-hydroxyethyl (methyl) acrylate/benzyl (methyl) acrylate/polystyrene macromolecular monomer copolymer;
(methyl) acrylic acid/2-hydroxyethyl (methyl) acrylate/benzyl (methyl) acrylate/polymethylmethacrylate macromonomer multipolymer etc.
In the carboxy-containing copolymer, the copolymerization ratio that contains the carboxyl unsaturated monomer is preferably 5～50 weight %, more preferably 10～40 weight %.When this polymerization ratio is lower than 5 weight %, the gained radiation-ray sensitive composition has the tendency of reduction to the dissolubility of alkaline developer, and when being higher than 50 weight %, dissolubility to alkaline developer is excessive, when developing, exist to cause pixel easily from substrate comes off or the pixel surface film splits tendency with alkaline-based developer.
By gel permeation chromatography (GPC, eluting solvent: the alkali soluble resin Mw that tetrahydrofuran) records is preferably 3,000～300,000, more preferably 5,000～100,000.
In addition, by gel permeation chromatography (GPC, eluting solvent: the alkali soluble resin Mn that tetrahydrofuran) records is preferably 3,000～60,000, more preferably 5,000～25,000.
The Mw of alkali soluble resin is preferably 1～5 with the ratio (Mw/Mn) of Mn, and more preferably 1～4.
The present invention has the alkali soluble resin of above-mentioned particular range Mw and Mn by use, can obtain the good radiation-ray sensitive composition of development property, can form the pixel pattern of sharp image border thus, and be difficult to when developing on the substrate of unexposed portion and light shield layer, form residue, scum and residual film etc.
Among the present invention, alkali soluble resin can be separately or two or more mix and use.
Among the present invention, with respect to (A) pigment 100 weight portions, the consumption of alkali soluble resin is preferably 10～1,000 weight portion, more preferably 20～500 weight portions.If the consumption of alkali soluble resin is lower than 10 weight portions, may occurs then that alkali-developable for example reduces or on the substrate of unexposed portion or light shield layer, produce scum or residual film.On the other hand, if the consumption of alkali soluble resin is higher than 1,000 weight portion, then pigment concentration reduces relatively, therefore may inaccessible aim colour density as film.
-(D) multi-functional monomer-
Multi-functional monomer of the present invention is the monomer with two or more polymerism unsaturated links.
Multi-functional monomer for example comprises:
Two (methyl) acrylate of aklylene glycol such as ethylene glycol, propylene glycol;
Two (methyl) acrylate of poly alkylene glycol such as polyglycol, polypropylene glycol;
Poly-(methyl) acrylate or its dicarboxylic acid modifier of the polyvalent alcohol that ternary such as glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol or ternary are above;
Oligomeric (methyl) acrylate such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Two ends are the poly-1,3-butadiene of hydroxyl, and two ends are that polyisoprene, two ends of hydroxyl are two (methyl) acrylate of the two terminal hydroxyl fluidized polymers such as polycaprolactone of hydroxyl, or
Three [2-(methyl) acryloxy ethyl] phosphate etc.
In the above-mentioned multi-functional monomer, poly-(methyl) acrylate or its dicarboxylic acid modifier of the polyvalent alcohol that preferred ternary or ternary are above are specially trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.Good from pixel intensity and surface smoothing, and be difficult on the substrate of unexposed portion and light shield layer, form aspects such as scum, residual film and consider, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol acrylate.
Above-mentioned multi-functional monomer can be separately or two or more mix and use.
Among the present invention, with respect to (C) alkali soluble resin 100 weight portions, the consumption of multi-functional monomer is preferably 5～500 weight portions, more preferably 20～300 weight portions.If the consumption of multi-functional monomer is lower than 5 weight portions, the tendency that pixel intensity and surface smoothing reduction are then arranged, and the consumption of multi-functional monomer is when being higher than 500 weight portions, exists alkali-developable for example to reduce or be easy to generate the tendency of scum or residual film etc. on the substrate of unexposed portion or light shield layer.
Among the present invention, can replace the part of multi-functional monomer with the simple function monomer that has 1 polymerism unsaturated link.
As above-mentioned simple function monomer; except for example with (C) alkali soluble resin in enumerate contain the identical monomer of carboxyl unsaturated monomer or copolymerization unsaturated monomer or N-(methyl) acryloyl morpholine, N-vinyl pyrrolidone, the N-vinyl-epsilon-caprolactams; can also enumerate M-5600 (trade name, East Asia synthetic (strain) system) etc.
Above-mentioned simple function monomer can be separately or two or more mix and use.
Among the present invention, with respect to the total amount of multi-functional monomer and simple function monomer, the usage ratio of simple function monomer preferably is less than or equal to 90 weight %, more preferably less than or equal 50 weight %.If the usage ratio of simple function monomer is higher than 90 weight %, pixel intensity or surface smoothing just might be not enough.
Among the present invention, with respect to (C) alkali soluble resin 100 weight portions, the total use amount of multi-functional monomer and simple function monomer is preferably 5～500 weight portions, more preferably 20～300 weight portions.If this total use amount is lower than 5 weight portions, the tendency of pixel intensity and surface smoothing reduction is then arranged, and when being higher than 500 weight portions, exist alkali-developable for example to reduce or on the substrate of unexposed portion or light shield layer, be easy to generate the tendency of scum or residual film etc.
-(E) Photoepolymerizationinitiater initiater-
Among the present invention, Photoepolymerizationinitiater initiater is the exposure that can pass through visible light, ultraviolet ray, far ultraviolet, electron ray, X ray isoradial, and generation can make the simple function monomer of above-mentioned (D) multi-functional monomer and use according to circumstances begin the compound of the spike of polymerization.
Described Photoepolymerizationinitiater initiater comprises for example acetophenone compounds, bisglyoxaline compounds, compound in triazine class, benzoin compounds, Benzophenones compound, α-cyclohexadione compounds, multinuclear quinones, xanthone compounds, diazonium compounds etc.
Among the present invention, Photoepolymerizationinitiater initiater can be separately or two or more mix and use.Photoepolymerizationinitiater initiater among the present invention is preferably selected from least a in acetophenone compounds, bisglyoxaline compounds and the compound in triazine class.
In the preferred Photoepolymerizationinitiater initiater of the present invention, the object lesson of acetophenone compounds comprises 2-hydroxy-2-methyl-1-phenylacetone-1,2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butanone-1,1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenyl ethyl ketone-1 etc.
In the above-mentioned acetophenone compounds, preferred especially 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butanone-1 etc.
Above-mentioned acetophenone compounds can be separately or two or more mix and use.
Among the present invention, during as Photoepolymerizationinitiater initiater, with respect to total weight 100 weight portions of (D) multi-functional monomer and simple function monomer, its use amount is preferably 0.01～100 weight portion with the acetophenone compounds, more preferably 1～80 weight portion, further preferred 5～60 weight portions.If the consumption of acetophenone compounds is lower than 0.01 weight portion, then may be insufficient by the curing that exposure is carried out, be difficult to obtain the dyed layer of pixel pattern according to the predetermined arrangement configuration.On the other hand, if this consumption is higher than 100 weight portions, then formed pixel has when developing and is easy to the tendency that comes off from substrate.
In addition, the object lesson of above-mentioned bisglyoxaline compounds comprises for example 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyls)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.
In the above-mentioned bisglyoxaline compounds, more preferably 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.Preferred especially 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
The dissolubility of above-mentioned bisglyoxaline compounds in solvent is good, can not produce foreign matters such as insolubles, precipitate, and it is highly sensitive, by low-energy exposure curing reaction is fully carried out, and can be at unexposed portion generation curing reaction, therefore, the tunicle after the exposure clearly is divided into cured portion that is insoluble to developer solution and the uncured portion that has highly dissoluble in developer solution.The high meticulous dyed layer that the pixel pattern that can form does not thus have undercut disposes according to predetermined arrangement.
Above-mentioned bisglyoxaline compounds can be separately or two or more mix and use.
Among the present invention, during as Photoepolymerizationinitiater initiater, with respect to total weight 100 weight portions of (D) multi-functional monomer and simple function monomer, its use amount is preferably 0.01～40 weight portion with the bisglyoxaline compounds, more preferably 1～30 weight portion, further preferred 1～20 weight portion.If the consumption of bisglyoxaline compounds is lower than 0.01 weight portion, then may be insufficient by the curing that exposure is carried out, be difficult to obtain the dyed layer of pixel pattern according to the predetermined arrangement configuration.On the other hand, if this consumption is higher than 40 weight portions, then formed pixel has when developing and is easy to the tendency that comes off from substrate.
-hydrogen donor-
Among the present invention, when using the bisglyoxaline compounds,, therefore preferred with following hydrogen donor and with can further improving sensitivity as Photoepolymerizationinitiater initiater.
So-called " hydrogen donor " is meant the compound that hydrogen atom can be provided the free radical that is produced by the bisglyoxaline compounds by exposure.
The sulfur alcohol compound of the preferred following definitions of hydrogen donor among the present invention and aminated compounds etc.
Described sulfur alcohol compound comprises that with phenyl ring or heterocycle be parent nucleus, and contain one or more, preferred 1～3, the more preferably compound (hereinafter referred to as " thio-alcohol hydrogen donor ") of 1～2 sulfydryl that directly combines with this parent nucleus.
Described aminated compounds comprises that with phenyl ring or heterocycle be parent nucleus, and contain one or more, preferred 1～3, the more preferably compound (hereinafter referred to as " amine hydrogen donor ") of 1～2 amino that directly links to each other with this parent nucleus.
In addition, these hydrogen donors also can have sulfydryl and amino simultaneously.
Below be described more specifically these hydrogen donors.
The thio-alcohol hydrogen donor can comprise phenyl ring or heterocycle respectively more than 1 or 1, also can comprise phenyl ring and heterocycle.When containing two or more described ring, can form or not form condensed ring.
In addition, when the thio-alcohol hydrogen donor has two or more sulfydryl, if residual at least 1 free sulfhydryl groups, one or more can the replacement in all the other sulfydryls by alkyl, aralkyl or aryl.And as long as residual at least 1 free sulfhydryl groups, can have the structural unit of two sulphur atoms, or two sulphur atoms are with the structural unit of the form combination of disulfide by divalent organic group combinations such as alkylidenes.
And the thio-alcohol hydrogen donor can be in sulfydryl place in addition by replacements such as carboxyl, alkoxy carbonyl, substituted alkoxy carbonyl, phenyloxycarbonyl, substituent phenoxy carbonyl and nitrile (ニ ト リ Le) bases.
The object lesson of described thio-alcohol hydrogen donor comprises 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-2,5-dimethyl aminopyridine etc.
In the above-mentioned thio-alcohol hydrogen donor, preferred 2-mercaptobenzothiazole, 2-mercaptobenzoxazole etc., preferred especially 2-mercaptobenzothiazole.
Secondly, the amine hydrogen donor can comprise phenyl ring or heterocycle respectively more than 1 or 1, also can comprise phenyl ring and heterocycle.When containing two or more described ring, can form or not form condensed ring.
In addition, the amine hydrogen donor can have one or more amino to be replaced by alkyl or substituted alkyl, and can be in amino place in addition by replacements such as carboxyl, alkoxy carbonyl, substituted alkoxy carbonyl, phenyloxycarbonyl, substituent phenoxy carbonyl and itrile groups.
The object lesson of described amine hydrogen donor comprises 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (lignocaine) benzophenone, 4-lignocaine acetophenone, 4-Dimethylaminobenzene methyl ethyl ketone methyl ketone, ethyl-4-dimethylaminobenzoic acid ester, 4-dimethylaminobenzoic acid, 4-dimethylamino benzonitrile etc.
In the above-mentioned amine hydrogen donor, preferred 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (lignocaine) benzophenone etc., preferred especially 4,4 '-two (lignocaine) benzophenone.
In addition, during the Photoepolymerizationinitiater initiater of amine hydrogen donor beyond using the bisglyoxaline compounds, the effect of sensitizer is arranged.
Among the present invention, hydrogen donor can be separately or two or more mix and use.From formed pixel when developing, be difficult for from substrate come off and the intensity of pixel and highly sensitive aspect consider that preferred compositions is used a kind or multiple thio-alcohol hydrogen donor and a kind or various kinds of amine class hydrogen donor.
The concrete preferred example of thio-alcohol hydrogen donor and the combination of amine hydrogen donor comprises 2-mercaptobenzothiazole/4,4 '-two (dimethylamino) benzophenone, 2-mercaptobenzothiazole/4,4 '-two (lignocaine) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (dimethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (lignocaine) benzophenone etc.Preferred combination comprises 2-mercaptobenzothiazole/4,4 '-two (lignocaine) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (lignocaine) benzophenone etc., particularly preferred combination is 2-mercaptobenzothiazole/4,4 '-two (lignocaine) benzophenone.
In the combination of thio-alcohol hydrogen donor and amine hydrogen donor, the weight ratio of thio-alcohol hydrogen donor and amine hydrogen donor is preferably 1: 1～and 1: 4, more preferably 1: 1～1: 3.
Among the present invention, with hydrogen donor and bisglyoxaline compounds and time spent, with respect to total weight 100 weight portions of (D) multi-functional monomer and simple function monomer, the consumption of hydrogen donor is preferably 0.01～40 weight portion, more preferably 1～30 weight portion, further preferred 1～20 weight portion.If the consumption of hydrogen donor is lower than 0.01 weight portion, then the effect of improving of sensitivity has and reduces tendency, and this consumption is when being higher than 40 weight portions, and formed pixel has when developing and is easy to the tendency that comes off from substrate.
In addition, the object lesson of above-mentioned compound in triazine class comprises 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-dimethoxy phenyl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-(the 4-methoxyphenyl]-4,6-two (trichloromethyl)-s-triazine, 2-(4-ethoxybenzene vinyl]-4,6-two (trichloromethyl)-s-triazine and 2-(4-n-butoxy phenyl]-4,6-two (trichloromethyl)-s-triazine etc. has the compound in triazine class of halogenated methyl.
In the above-mentioned compound in triazine class, preferred especially 2-[2-(3, the 4-dimethoxy phenyl) vinyl]-4,6-two (trichloromethyl)-s-triazine.
Above-mentioned compound in triazine class can be separately or two or more mix and use.
Among the present invention, during as Photoepolymerizationinitiater initiater, with respect to total weight 100 weight portions of (D) multi-functional monomer and simple function monomer, the consumption of compound in triazine class is preferably 0.01～40 weight portion with compound in triazine class, more preferably 1～30 weight portion, further preferred 1～20 weight portion.If the consumption of compound in triazine class is lower than 0.01 weight portion, then the curing of probably being undertaken by exposure is insufficient, be difficult to obtain the dyed layer of pixel pattern according to the predetermined arrangement configuration, and this consumption is when being higher than 40 weight portions, formed pixel has when developing and is easy to the tendency that comes off from substrate.
-additive component-
Color filter of the present invention can also comprise various additive components as required with in the radiation-ray sensitive composition.
As above-mentioned additive component, can enumerate and have the further dissolubility and further suppress of radiation-ray sensitive composition in alkaline developer the develop organic acid of the residual effect of back insolubles etc. or the organic amino compounds (except that above-mentioned hydrogen donor) etc. of improving.
The aliphatic carboxylic acid of one or more carboxyls is arranged in the preferred molecule of above-mentioned organic acid or contain the phenyl carboxylic acid.
Described aliphatic carboxylic acid for example comprises:
Formic acid, acetate, propionic acid, butyric acid, valeric acid, trimethylace tonitric, caproic acid, diethacetic acid, enanthic acid, aliphatic monocarboxylic acid such as sad;
Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, the acid of Block ラ シ Le, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoronic acid etc.
In addition, the above-mentioned compound that compound that the phenyl carboxylic acid can comprise that carboxyl for example directly links to each other with phenyl or carboxyl link to each other with phenyl by the divalence carbochain etc. that contains.
Containing the phenyl carboxylic acid for example comprises:
Benzoic acid, toluic acid, cumfrey, 2,3-mesitylenic acid, 3, aromatic monocarboxylates such as 5-mesitylenic acid;
Aromatic dicarboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid (TPA);
Ternary or the above aromatic series polybasic carboxylic acids of ternary such as trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid; Or
Phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, the acid of シ Application Na ミ リ デ Application, the acid of Network マ Le, umbellic acid etc.
In the above-mentioned organic acid, consider from aspects such as alkali dissolution, the dissolubility the aftermentioned solvent, the substrate that prevents unexposed portion and scum on the light shield layer or residual films, aliphatic carboxylic acid preferred aliphat dicarboxylic acid, preferred especially malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid and mesaconic acid etc., contain phenyl carboxylic acid optimization aromatic dicarboxylic acid, and preferred especially phthalic acid.
Above-mentioned organic acid can be separately or two or more mix and use.
With respect to total weight 100 weight portions of (A)～(E) composition and additive component, the organic acid consumption preferably is less than or equal to 15 weight portions, more preferably less than or equal 10 weight portions.If the organic acid consumption is lower than 15 weight portions, the adherence of then formed pixel and substrate has the tendency of reduction.
In addition, in the preferred molecule of above-mentioned organic amino compounds the fatty amine of one or more amino is arranged or contain phenyl amine.
Described fatty amine for example comprises:
Single (ring) alkyl amine such as n-propylamine, isopropylamine, n-butylamine, isobutyl amine, sec-butylamine, tert-butylamine, n-amylamine, n-hexylamine;
Two (ring) alkyl amines such as Methylethyl amine, diethylamide, methyl n-pro-pyl amine, ethyl n-pro-pyl amine, di-n-propyl amine, diisopropylamine, di-n-butyl amine, diisobutyl amine, two sec-butylamine, di-t-butyl amine;
Dimethyl. ethylamine, methyl diethylamide, triethylamine, dimethyl n propyl group amine, diethyl. three (ring) alkyl amines such as n-pro-pyl amine, methyl di-n-propyl amine, ethyl di-n-propyl amine, three n-pro-pyl amine, triisopropylamine, tri-n-butyl amine, triisobutyl amine, three sec-butylamine, tri-tert amine;
The 2-ethylaminoethanol, single (ring) alkanolamine such as 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 4-amino-1-butanols;
Two (ring) alkanolamines such as diethanolamine, two n-propanol amine, diisopropanolamine, two normal butyl alcohol amine, two isobutyl hydramine;
Three (ring) alkanolamines such as triethanolamine, three n-propanol amine, triisopropanolamine, three normal butyl alcohol amine, three isobutyl hydramine;
3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1,2-butylene glycol, 4-amino-1,3-butylene glycol, 3-dimethylamino-1,2-propylene glycol, 3-lignocaine-1,2-propylene glycol, 2-dimethylamino-1, ammediol, 2-lignocaine-1, amino (ring) alkane glycol such as ammediol;
Amino carboxylic acids such as Beta-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid etc.
Contain phenyl amine and for example comprise that compound, amino amino and that phenyl directly links to each other pass through the compound that the divalence carbochain links to each other with phenyl etc.
Containing phenyl amine for example comprises:
Aniline, neighbour-methylaniline ,-methylaniline, right-methylaniline, right-ethylaniline, naphthalidine, 2-naphthylamines, N, accelerine, N, N-diethylaniline, right-methyl-N, aromatic amines such as accelerine;
Neighbour-aminobenzyl alcohol ,-aminobenzyl alcohol, right-aminobenzyl alcohol, right-dimethylamino benzylalcohol, right-aminobenzyl alcohol classes such as lignocaine benzylalcohol;
O-aminophenol ,-amino-phenol, para-aminophenol, right-dimethyl p-aminophenol, right-aminophenols such as diethylaminophenol;
Aminobenzoic acids such as m-anthranilic acid, Para-Aminobenzoic, right-dimethylaminobenzoic acid, right-lignocaine benzoic acid etc.
In the above-mentioned organic amino compounds, consider from aspects such as the dissolubility the aftermentioned solvent, the substrate that prevents unexposed portion and scum on the light shield layer or residual films, preferred single (ring) alkanolamine of fatty amine and amino (ring) alkane glycol, preferred especially 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1,2-butylene glycol etc.Contain the preferred aminophenols of phenyl amine, preferred especially O-aminophenol ,-amino-phenol, para-aminophenol etc.
Above-mentioned organic amino compounds can be separately or two or more mix and use.
With respect to total weight 100 weight portions of (A)～(E) composition and additive component, the consumption of organic amino compounds preferably is less than or equal to 15 weight portions, more preferably less than or equal 10 weight portions.If the consumption of organic amino compounds surpasses 15 weight portions, the adherence of then formed pixel and substrate has the tendency of reduction.
In addition, above-mentioned additive component in addition for example comprises:
Blue pigment derivative such as copper phthalocyanine derivative thing or yellow pigment derivant etc. disperse auxiliary agent;
Filling agent such as glass, aluminium oxide;
Polyvinyl alcohol (PVA), polyalkylene glycol monoalkyl ether, poly-macromolecular compounds such as (fluoro-alkyl acrylate);
Surfactants such as nonionic class, cationic, anionic species;
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, adherence promoter such as 3-sulfydryl propyl trimethoxy silicane;
2, antioxidant such as 2-thiobis (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 benzophenone class;
Anti-coagulants such as sodium polyacrylate;
1,1 '-azo two (hexamethylene-1-nitrile), 2-phenylazos-4-methoxyl-2, hot radical propellants such as 4-methyl pentane nitrile etc.
(F) solvent
Solvent among the present invention can suitably select to use disperse or dissolve (A)～(E) composition that constitutes radiation-ray sensitive composition and adjuvant and with these compositions reactions, have appropriate volatile solvent.
Described solvent for example comprises:
Alcohols such as methyl alcohol, ethanol, benzylalcohol;
The glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl n-propyl ether, the glycol monomethyl n-butyl ether, the diglycol monotertiary methyl ether, carbiphene, the diglycol monotertiary n-propyl ether, the diglycol monotertiary n-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether, DPGME, dihydroxypropane single-ethyl ether, the single n-propyl ether of dipropylene glycol, the single n-butyl ether of dipropylene glycol, the tripropylene glycol monomethyl ether, (gathering) alkylene glycol monoalkyl ethers such as tripropylene glycol list ethylether;
(gathering) alkylene glycol monoalkyl ethers acetic acid esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol monomethyl n-propyl ether acetic acid esters, glycol monomethyl n-butyl ether acetic acid esters, diglycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diglycol monotertiary n-propyl ether acetic acid esters, diglycol monotertiary n-butyl ether acetic acid esters, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, 3-methoxyl butylacetic acid ester;
Ethers such as diethylene glycol dimethyl ether, diglycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methyl penta-2-ketone), 4-hydroxy-4-methyl oneself-ketones such as 2-ketone;
Lactic acid alkyl ester such as methyl lactate, ethyl lactate;
Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, 3-methyl-3-methoxyl butylacetic acid ester, n-butyl propionate, 3-methyl-3-methoxyl butyl propionic ester, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, hydroxyl ethyl acetate, ethoxy ethyl acetate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-hydroxy-2-methyl ethyl propionate, 2-hydroxy-3-methyl methyl butyrate, ester classes such as 2-ketobutyric acid ethyl ester;
Aromatic hydrocarbons such as toluene, dimethylbenzene;
N-Methyl pyrrolidone, N, amide-types such as dinethylformamide, N,N-dimethylacetamide etc.
In the above-mentioned solvent, from dissolubility, pigment-dispersing, aspects such as coating are considered, preferred benzylalcohol, the glycol monomethyl n-butyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, the ethylene glycol monomethyl ether acetate, glycol monomethyl n-butyl ether acetic acid esters, diglycol monotertiary n-butyl ether acetic acid esters, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, diethylene glycol dimethyl ether, the diglycol methyl ethyl ether, cyclohexanone, the 2-heptanone, the 3-heptanone, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, 3-methoxyl butylacetic acid ester, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-methyl-3-methoxyl butyl propionic ester, ethyl pyruvate etc.
Above-mentioned solvent can be separately or two or more mix and use.
In addition, above-mentioned solvent can also and be used with high boiling solvent such as benzylisoeugenol, hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, glycol monomethyl phenyl ether acetic acid esters.
Above-mentioned high boiling solvent can be separately or two or more mix and use.
Consumption to solvent does not have particular restriction, but consider from aspects such as the coating of gained radiation-ray sensitive composition, bin stabilities, the total concentration of other each composition the solvent in said composition is preferably 5～50 weight %, more preferably 10～40 weight %.
The preparation method of-color filter usefulness radiation-ray sensitive composition-
Color filter of the present invention is not had particular restriction with the preparation method of radiation-ray sensitive composition, but preferably through make in advance (A) pigment dispersing comprise (B) spreading agent, (C) alkali soluble resin and (F) step in the medium of solvent be prepared.
Below will make the step of (A) pigment dispersing in above-mentioned medium be called " preparation dispersion steps " in advance, and make the dispersion liquid of (A) pigment dispersing gained in above-mentioned medium be called " preparation dispersion liquid " in advance.
The relative color filter of consumption of (C) alkali soluble resin is preferably 5～100 weight %, more preferably 10～50 weight % with (C) alkali soluble resin consumption in the radiation-ray sensitive composition in the preparation dispersion steps.At this moment, if (C) consumption of alkali soluble resin is lower than 5 weight %, then there is the bin stability of resulting composition to reduce or the easy tendency that on substrate, produces residue.
The preparation dispersion steps can for example assign to carry out by using mixing arrangements such as dissolver, ball mill, rod mill to mix above-mentioned each one-tenth.
In the preparation dispersion liquid that obtains like this, (A) mean grain size of pigment is preferably 50～400nm, more preferably 50～150nm.
After the preparation dispersion steps, preparation dispersion liquid and (D) multi-functional monomer and (E) Photoepolymerizationinitiater initiater and according to circumstances also have (C) alkali soluble resin and (F) solvent, with its-rise by conventional method and mix, can obtain color filter radiation-ray sensitive composition of the present invention thus.
The formation method of color filter
The following describes the method for using color filter of the present invention to form color filter of the present invention with radiation-ray sensitive composition (being designated hereinafter simply as " radiation-ray sensitive composition ").
The formation method of color filter of the present invention comprises the step of following (1)～(4) at least.
(1) step of formation radiation-ray sensitive composition tunicle of the present invention on substrate;
(2) with at least a portion step of exposing of radioactive ray with above-mentioned tunicle;
(3) the described tunicle step of developing after will exposing;
(4) step of curing behind the described tunicle after will developing.
Next coming in order explanation above-mentioned steps.
-(1) step-
At first, form light shield layer in the mode of dividing the part that forms pixel as required on the surface of substrate, coating radiation-ray sensitive composition of the present invention carries out prebake then on this substrate, makes solvent evaporation, thereby forms tunicle.
The substrate that uses in this step comprises for example glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide and polyester sulfone, also has the ring-opening polymerization polymer of cyclic olefin or its hydrogenation products etc. in addition.
In addition, these substrates can also adopt the suitable pre-service such as medicine processing, plasma treatment, ion plating, sputter, gas-phase reaction method and vacuum evaporation of silane coupling agent etc. as required.
When being coated on radiation-ray sensitive composition on the substrate, can adopt suitable rubbing methods such as spin coating, curtain coating coating, roller coat, wherein preferably adopt the rubbing method of spinner or slit die spreader.
The condition optimization temperature of prebake is that 70～110 ℃, time are about 2～4 minutes.
Coating thickness is preferably 0.1～8.0 μ m with dried film thickness gauge, more preferably 0.2～6.0 μ m, further preferred 0.2～4.0 μ m.
-(2) step-
Then, make formed tunicle at least a portion exposure with radioactive ray.In this step, when making the part exposure of tunicle, preferably expose by photomask with predetermined pattern.
The used radioactive ray that expose can suitably be selected for example visible light, ultraviolet ray, far ultraviolet, electron ray and X ray isoradial, the radioactive ray of optimal wavelength in 190～450nm scope for use.
The radioactive ray exposure is preferably 10～10,000J/m 2About.
-(3) step-
Then, the tunicle after the exposure with developer solution, preferred bases developing liquid developing, is dissolved the unexposed portion of removing tunicle, form predetermined pattern thus.
Described alkaline developer preference such as sodium carbonate, NaOH, potassium hydroxide, tetramethyl ammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecylene and 1, the aqueous solution of 5-diazabicyclo-[4.3.0]-5-nonene etc.
Also can add for example water-miscible organic solvent such as methyl alcohol, ethanol or surfactant etc. in right amount in the above-mentioned alkaline developer.In addition, alkali is preferably washed after developing.
The development treatment method can be used spray (シ ヤ ワ-) development method, spray development method, immersion development method and パ De Le development method etc.
The preferred temperature of development conditions is that normal temperature, time are about 5～300 seconds.
-(4) step-
Then, will cure behind the tunicle after developing, can obtain the substrate of pixel pattern thus with the predetermined arrangement configuration.
After the treatment conditions preference that cures such as temperature be that 180～240 ℃, time are about 15～90 minutes.Preferred 0.1～6.0 μ m of the thickness of the pixel of Xing Chenging, more preferably 0.5～3.0 μ m like this.
By repeating above-mentioned (1)～(4) step with each radiation-ray sensitive composition that has disperseed redness, green or blue pigment, on same substrate, form redness, green and blue picture element pattern, can on substrate, form dyed layer red, green and that blue trichromatic pixel pattern disposes with predetermined arrangement thus.
In addition, can select the formation order of pixel pattern of all kinds among the present invention arbitrarily.
Color filter
Color filter of the present invention forms with radiation-ray sensitive composition with color filter of the present invention.
Except transmission-type or Reflexible color LCD, color filter of the present invention is very useful in colour pick-up tube element, color sensor.
Color liquid crystal display arrangement
Color liquid crystal display arrangement of the present invention has color filter of the present invention.
Color liquid crystal display arrangement of the present invention can adopt suitable structure.For example, can adopt following structure: the driving that color filter is formed at disposed thin film transistor (TFT) (TFT) is with on the substrate beyond the substrate, drives that to pass through liquid crystal layer with substrate and the substrate that has formed color filter relative.Also can adopt following structure: form color filter in the driving of having disposed thin film transistor (TFT) (TFT) on substrate surface, this substrate is relative by liquid crystal layer with the substrate of ITO (indium oxide of doped tin) electrode.Back one structure can significantly improve the aperture ratio, and the advantage that can access bright and high meticulous liquid crystal indicator is arranged.
Embodiment
Be described more specifically embodiment of the present invention by the following examples, but the invention is not restricted to following examples.
Embodiment 1
Will be as potpourri 15 weight portions of the C.I. paratonere 254/C.I. paratonere 177=80/20 (weight ratio) of (A) pigment, Disperbyk-2001 (solid component concentration 45.1 weight %) 5 weight portions as (B) spreading agent (are pressed the solid constituent conversion, about 2.26 weight portions), methacrylic acid/N-phenylmaleimide/styrene/benzyl methacrylate copolymer (copolymerization weight ratio=20/30/20/30 as (C) alkali soluble resin, Mw=9,500, Mn=5,000) propylene glycol monomethyl ether 37 weight portions and 3-ethoxyl ethyl propionate 37 weight portions of 6 weight portions and conduct (F) solvent, handle preparation preparation dispersion liquid (R1) with ball mill.
Then, mix preparation dispersion liquid (R1) 100 weight portions, methacrylic acid/mono succinate (2-methacryloxyethyl) ester/N-phenylmaleimide/styrene/benzyl methacrylate copolymer (copolymerization weight ratio=25/10/30/20/15 as (C) alkali soluble resin, Mw=12,000, Mn=6,500) 5 weight portions, dipentaerythritol acrylate 10 weight portions as (D) multi-functional monomer, as 2-methyl-(4-methyl mercapto phenyl)-2-morpholino-1-acetone-15 weight portion of (E) Photoepolymerizationinitiater initiater and 3-methoxyl butylacetic acid ester 70 weight portions of conduct (F) solvent, preparation radiation-ray sensitive composition.
Embodiment 2
Will be as potpourri 15 weight portions of the C.I. pigment green 36/C.I. pigment yellow 13 8/C.I. pigment yellow 150=50/40/10 (weight ratio) of (A) pigment, Disperbyk-2001 7.5 weight portions as (B) spreading agent (are pressed the solid constituent conversion, about 3.38 weight portions), methacrylic acid/ω-carboxyl two caprolactone mono acrylic ester/N-phenylmaleimides/styrene/benzyl methacrylate/glycerin monomethyl acrylic ester multipolymer (copolymerization weight ratio=15/10/20/10/35/10 as (C) alkali soluble resin, Mw=6,000, Mn=3,000) propylene glycol monomethyl ether 73.5 weight portions of 4 weight portions and conduct (F) solvent, handle preparation preparation dispersion liquid (G1) with method with embodiment 1.
Then, mix preparation dispersion liquid (G1) 100 weight portions, methacrylic acid/N-phenylmaleimide/styrene/benzyl methacrylate/glycerin monomethyl acrylic ester multipolymer (copolymerization weight ratio=15/25/15/35/10 as (C) alkali soluble resin, Mw=13,500, Mn=6,000) 5 weight portions, dipentaerythritol acrylate 10 weight portions as (D) multi-functional monomer, as 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butanone-15 weight portion of (E) Photoepolymerizationinitiater initiater and 3-ethoxyl ethyl propionate 70 weight portions of conduct (F) solvent, preparation radiation-ray sensitive composition.
Embodiment 3
Will be as potpourri 15 weight portions of C.I. pigment blue 15/C.I. pigment Violet 23=90/10 (weight ratio) of (A) pigment, Disperbyk-2001 10 weight portions as (B) spreading agent (are pressed the solid constituent conversion, 4.51 weight portion), acrylic acid/N-phenylmaleimide/styrene/phenyl methyl acrylate/2-hydroxyethyl meth acrylate/polymethylmethacrylate macromonomer multipolymer (copolymerization weight ratio=15/20/10/35/10/10 as (C) alkali soluble resin, Mw=23,000, Mn=11,000) propylene glycol monomethyl ether 63 weight portions and propylene glycol monomethyl ether 10 weight portions of 2 weight portions and conduct (F) solvent, handle preparation preparation dispersion liquid (B1) with method with embodiment 1.
Then, mix preparation dispersion liquid (B1) 100 weight portions, methacrylic acid/N-phenylmaleimide/α-Jia Jibenyixi/benzyl methacrylate copolymer (copolymerization weight ratio=20/25/25/30 as (C) alkali soluble resin, Mw=43,000, Mn=21,000) 10 weight portions, dipentaerythritol acrylate 20 weight portions as (D) multi-functional monomer, as 2-methyl-(4-methyl mercapto phenyl)-2-morpholino-1-acetone-15 weight portion of (E) Photoepolymerizationinitiater initiater and 3-methyl-3-methoxyl butylacetic acid ester 30 weight portions and the propylene glycol list ethylether acetic acid esters 80 of conduct (F) solvent, preparation radiation-ray sensitive composition.
Embodiment 4
In the preparation dispersion steps, with methacrylic acid/N-phenylmaleimide/styrene/normal-butyl methacrylate copolymer (copolymerization weight ratio=20/30/20/30, Mw=8,000, Mn=4,000) 6 weight portions replace (C) alkali soluble resin 6 weight portions among the embodiment 1; With preparation dispersion liquid (R1) step of mixing in, with methacrylic acid/N-phenylmaleimide/styrene/2-ethylhexyl methacrylate copolymer (copolymerization weight ratio=20/30/20/30, Mw=14,000, Mn=6,500) 5 weight portions replace (C) alkali soluble resin 5 weight portions among the embodiment 1, and other is identical with embodiment 1, the preparation radiation-ray sensitive composition.
Comparative example 1
With (B) spreading agent Disperbyk-2001 5 weight portions that prepare dispersion liquid (R1) among ソ Le ス パ-ス S24000 (amine value=50, acid number=25) 2.5 weight portions replacement embodiment 1, other is identical with embodiment 1, the preparation radiation-ray sensitive composition.
Comparative example 2
With methacrylic acid/benzyl methacrylate copolymer (copolymerization weight ratio=25/75, Mw=13,000, Mn=6,500) replace preparing among the embodiment 1 methacrylic acid/N-phenylmaleimide/styrene/benzyl the methacrylate copolymer of (C) alkali soluble resin of dispersion liquid (R1).In addition, with methacrylic acid/2-hydroxyethyl meth acrylate/benzyl methacrylate copolymer (copolymerization weight ratio=15/15/70, Mw=16,000, Mn=7,500) (C) alkali soluble resin methacrylic acid/mono succinate (2-methacryloxyethyl) ester/N-phenylmaleimide/styrene/benzyl methacrylate copolymer among the replacement embodiment 1, other is identical with embodiment 1, the preparation radiation-ray sensitive composition.
Comparative example 3
With Disperbyk-182 (amine value=14, acid number=0, solid component concentration 44.6 weight %) 7.5 weight portions (by solid constituent about 3.35 weight portions that convert) replace preparing among the embodiment 2 (B) spreading agent Disperbyk-2001 7.5 weight portions of dispersion liquid (G1), other is identical with embodiment 2, the preparation radiation-ray sensitive composition.
Comparative example 4
With methacrylic acid/ω-carboxyl polycaprolactone single-acrylate/styrene/benzyl methacrylate/glycerin monomethyl acrylic ester multipolymer (copolymerization weight ratio=15/15/20/35/15, Mw=15,500, Mn=6,500) replace preparing among the embodiment 2 (C) alkali soluble resin methacrylic acid/ω-carboxyl two caprolactone mono acrylic ester/N-phenylmaleimides/styrene/benzyl methacrylate/glycerin monomethyl acrylic ester multipolymer of dispersion liquid (G1).In addition, with methacrylic acid/benzyl methacrylate copolymer (copolymerization weight ratio=25/75, Mw=22,000, Mn=10,000) (C) alkali soluble resin methacrylic acid/N-phenylmaleimide/styrene/benzyl methacrylate/glycerin monomethyl acrylic ester multipolymer among the replacement embodiment 2, other is identical with embodiment 2, the preparation radiation-ray sensitive composition.
Comparative example 5
With (B) spreading agent Disperbyk-2001 10 weight portions that prepare dispersion liquid (B1) among ア ジ ス パ-PB-822 (amine value=13, acid number=16) 4.5 weight portions replacement embodiment 3, other is identical with embodiment 3, the preparation radiation-ray sensitive composition.
The radiation-ray sensitive composition that obtains in the various embodiments described above and the comparative example is carried out following evaluation, and evaluation result is as shown in table 1.
Adherence is estimated
2 of the #1737 glass substrates of preparation コ-ニ Application グ company are coated on above-mentioned each radiation-ray sensitive composition on each substrate surface with spin coater, carry out 3 minutes prebake at 70 ℃ then, and forming film thickness is the tunicle of 2.5 μ m.Then each substrate is cooled to room temperature, with high-pressure mercury-vapor lamp (illumination 250W/m 2) by photomask with comprising the ultraviolet exposure of 365nm, 405nm and each wavelength of 436nm, wherein the tunicle exposure on substrate is 1,000J/m 2, the tunicle exposure on another piece substrate is 500J/m 2Then with the tunicle on each substrate with 23 ℃ of developer solution CD150CR (containing potassium hydroxide 0.04 weight %) of JSR (strain) company as developer solution, press 0.3MPa (nozzle diameter 1.0mm) spray to develop 1 minute with the developer solution ejection, wash with ultrapure water, after 200 ℃, cured 30 minutes then, on each substrate, form line/empty pattern (ラ イ Application ア Application De ス ペ-ス パ -Application) striated pixel pattern of 90/210 μ m.
With the pixel pattern of observation by light microscope gained, do not find that pixel pattern is damaged and peel off be evaluated as " zero ", find damaged or peel off be evaluated as " * ".
The surface smoothing evaluation
With the upper face roughness of each pixel pattern of gained in the above-mentioned adherence evaluation of the atomic force microscope evaluation of measuring of デ ジ Le イ Application ス Star Le メ Application Star company, it is good to be considered as surface smoothing when usually surfaceness is not higher than 60 .
The development evaluation
With spin coater above-mentioned each radiation-ray sensitive composition is coated on the #1737 glass baseplate surface of コ-ニ Application グ company, carries out 3 minutes prebake at 90 ℃ then, forming film thickness is the tunicle of 2.5 μ m.Then substrate is cooled to room temperature, with high-pressure mercury-vapor lamp (illumination 250W/m 2) by photomask, with the ultraviolet ray that comprises 365nm, 405nm and each wavelength of 436nm, with 1,000J/m 2Exposure this tunicle that exposes.Then with tunicle with the developer solution CD150CR (containing potassium hydroxide 0.04 weight %) of JSR (strain) company as developer solution, pressed 0.1MPa (nozzle diameter 0.3mm) spray development tunicle 1 minute with the developer solution ejection, wash with ultrapure water, after 200 ℃, cured 30 minutes then, on substrate, form line/empty pattern striated pixel pattern of 90/210 μ m.
With the pixel pattern of observation by light microscope gained, on the substrate of unexposed portion, do not find be evaluated as " zero " of residue and scum, find be evaluated as " * " of residue or scum.
Bin stability is estimated
Initial viscosity with each radiation-ray sensitive composition of E type viscometer determining of Tokyo gauge company.Each radiation-ray sensitive composition 50g is packed in the lucifuge glass container, left standstill 14 days at 23 ℃, the viscosity after leaving standstill with the E type viscometer determining of Tokyo gauge company then with air-tight state.Viscosity after calculating is left standstill is with respect to the rate of change of initial viscosity, and rate of change is less than being evaluated as " zero " at 5% o'clock, rate of change be evaluated as in 5%～＜10% o'clock " △ ", rate of change is 10% or 10% to be evaluated as " * " when above.
Table 1
Adherence Surfaceness () Development Bin stability
Exposure Exposure
??1000J/m 2 ??500J/m 2 ?1000J/m 2 ??500J/m 2
Embodiment 1 ????○ ????○ ????38 ????50 ????○ ????○
Embodiment 2 ????○ ????○ ????31 ????42 ????○ ????○
Embodiment 3 ????○ ????○ ????22 ????33 ????○ ????○
Embodiment 4 ????○ ????○ ????25 ????36 ????○ ????○
Comparative example 1 ????○ ????× ????65 ????88 ????× ????×
Comparative example 2 ????× ????× ????78 ????106 ????× ????×
Comparative example 3 ????○ ????× ????67 ????92 ????× ????△
Comparative example 4 ????× ????× ????70 ????97 ????× ????×
Comparative example 5 ????× ????× ????45 ????64 ????× ????×

Claims (4)

1, the color filter radiation-ray sensitive composition is characterized in that, said composition comprises: (A) pigment; (B) spreading agent; (C) alkali soluble resin, it comprises (c1) and contains (methyl) acrylic acid carboxyl unsaturated monomer that contains, (c2) maleimide of N-position replacement, and (c3) be selected from styrene, α-Jia Jibenyixi, to hydroxyl-α-Jia Jibenyixi, (methyl) methyl acrylate, (methyl) n-butyl acrylate, 2-ethylhexyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, allyl (methyl) acrylate, benzyl (methyl) acrylate, glycerine list (methyl) acrylate, at least a kind multipolymer in polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer; (D) multi-functional monomer; (E) Photoepolymerizationinitiater initiater and (F) solvent, wherein said (B) spreading agent contains acrylic copolymer, and this acrylic copolymer obtains through active anionic polymerization, and its amine value (the mg KOH/g of unit) and acid number (mgKOH/g of unit) are all greater than 0.
2, the color filter radiation-ray sensitive composition is characterized in that, said composition comprises: (A) pigment; (B) spreading agent; (C) alkali soluble resin; (D) multi-functional monomer; (E) Photoepolymerizationinitiater initiater and (F) solvent, and said composition comprises (B) spreading agent, (C) alkali soluble resin and (F) prepares in the medium of solvent by above-mentioned (A) pigment is dispersed in advance, wherein said (B) spreading agent contains acrylic copolymer, this acrylic copolymer obtains through active anionic polymerization, and its amine value (the mg KOH/g of unit) and acid number (the mg KOH/g of unit) are all greater than 0.
3, a kind of color filter, it is formed with radiation-ray sensitive composition by claim 1 or 2 described color filters.
4, a kind of liquid crystal indicator, it comprises the described color filter of claim 3.
CNB2005100627042A 2004-03-30 2005-03-30 Radiation-ray sensitive composition for colour-filtering piece, colour filtering piece and colour liquid crystal display device Expired - Fee Related CN100376905C (en)

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