CN100351656C - Coloration-photosensitive resin composition - Google Patents

Coloration-photosensitive resin composition Download PDF

Info

Publication number
CN100351656C
CN100351656C CNB2003101204544A CN200310120454A CN100351656C CN 100351656 C CN100351656 C CN 100351656C CN B2003101204544 A CNB2003101204544 A CN B2003101204544A CN 200310120454 A CN200310120454 A CN 200310120454A CN 100351656 C CN100351656 C CN 100351656C
Authority
CN
China
Prior art keywords
acid
methyl
photosensitive composition
pigment
ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CNB2003101204544A
Other languages
Chinese (zh)
Other versions
CN1504777A (en
Inventor
天辰佳正
市川幸司
武部和男
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of CN1504777A publication Critical patent/CN1504777A/en
Application granted granted Critical
Publication of CN100351656C publication Critical patent/CN100351656C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • 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

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)

Abstract

Provided is a colored photosensitive resin composition having good stability over aging. The colored photosensitive resin composition contains: a coloring agent (A); a binder polymer (B); a photopolymerizable compound (C); a photopolymerization initiator (D); and a solvent (E). The solvent (E) contains propyleneglycolmonomethylether acetate and 4-hydroxy-4-methyl-2-pentanone. The colored photosensitive resin composition is preferably used for formation of a color filter.

Description

Photosensitive composition
Technical field
The present invention relates to photosensitive composition.
Background technology
Photosensitive composition is the photosensitive polymer combination that contains colorant, as using for the material that forms the colored pattern that constitutes colored filter.Herein, so-called colored filter (カ ラ-Off ィ Le ) is the display image colorize that can be used for liquid crystal indicator, or is used for the optical element of the image colorization of will take by solid-state imager.So-called colored pattern for example, is color pixel, black matrix"s (プ ラ Star Network マ ト リ Star Network ス) etc. such as red, green, blue, have wire, also the mosaic shape arranged.
In recent years, along with the increase of colored filter turnout, the production of the photosensitive composition that uses in it is made also increases simultaneously.But, if produce photosensitive composition in a large number, in fact very long until the inventory time of the manufacturing that is used for colored filter, the coloring agent component generation sedimentation of photosensitive composition at this moment etc., if its former state is used for the manufacturing of colored filter, the problem that exists so-called yield rate to reduce.Therefore, proposed to improve dispersing of pigments by pigment is handled with fatty alcohol and fatty amine, improve the method (with reference to Japanese documentation 1) that colored filter forms the ageing stability (storage stability) of material simultaneously, but not talkative its is that ageing stability is good.
Japanese documentation 1
Te Kaiping 9-178923 communique.
Summary of the invention
The object of the present invention is to provide the good photosensitive composition of ageing stability.
Present inventors, for the photosensitive composition of finding to address the above problem, carried out deep repeatedly research, found that, by solvent as photosensitive composition, use contains the solvent of propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2 pentanone, can improve the ageing stability of photosensitive composition, thereby has finished the present invention.
Promptly, the invention provides photosensitive composition, it is characterized in that solvent (E) contains propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2 pentanone in the photosensitive polymer combination that contains colorant (A), binder polymer (B), optical polymerism compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E).
In addition, the invention provides the formation method of pattern, it is characterized in that above-mentioned composition is coated on the substrate, remove volatile ingredient and form dyed layer, this dyed layer is exposed, and carry out video picture by photomask.
Embodiment
Photosensitive composition of the present invention contains colorant (A), binder polymer (B), optical polymerism compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E), and solvent (E) contains propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2 pentanone.
The colorant that uses among the present invention (A) is preferably pigment, as pigment, can enumerate organic pigment, inorganic pigment.
As pigment, particularly, can enumerate the compound that is sorted in the pigment index (The Society of Dyers and Colourists publication) in the pigment (Pigment).Particularly, can enumerate for example C.I. pigment yellow 1, C.I. pigment yellow 3, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 15, C.I. pigment yellow 16, C.I. pigment yellow 17, C.I. pigment yellow 20, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 53, C.I. pigment yellow 83, C.I. pigment yellow 86, C.I. pigment yellow 93, C.I. pigment yellow 94, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 117, C.I. pigment Yellow 12 5, C.I. pigment Yellow 12 8, C.I. pigment yellow 13 7, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 147, C.I. pigment Yellow 14 8, C.I. pigment yellow 150, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 166, C.I. pigment yellow 17 3, C.I. pigment yellow 194, CI. pigment yellow 214 yellow uitramarines such as grade;
C.I. pigment orange 13, C.I. pigment orange 31, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 42, C.I. pigment orange 43, C.I. pigment orange 51, C.I. pigment orange 55, C.I. pigment orange 59, C.I. pigment orange 61, C.I. pigment orange 64, C.I. pigment orange 65, C.I. pigment orange 71, C.I. pigment orange 73 orange pigments such as grade;
C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. paratonere 105, 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 176, C.I. paratonere 177, C.I. paratonere 180, C.I. paratonere 192, C.I. paratonere 209, C.I. pigment red 21 5, C.I. pigment red 21 6, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264, red pigments such as C.I. paratonere 265;
C.I. pigment blue 15, the C.I. pigment blue 15: 3, the C.I. pigment blue 15: 4, the C.I. pigment blue 15: 6, blue pigments such as C.I. pigment blue 60;
C.I. pigment violet 1, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29, C.I. pigment violet 32, C.I. pigment violet 36, C.I. pigment violet 38 violet pigments such as grade;
C.I. pigment Green 7, viridine greens such as C.I. pigment green 36;
C.I. pigment brown 23, C.I. pigment brown 25 browns such as grade;
C.I. pigment black 1, C.I. pigment black 7 black pigments such as grade etc., preferably contain and be selected from C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. paratonere 177, C.I. paratonere 209, C.I. paratonere 254, the C.I. pigment Violet 23, the C.I. pigment blue 15: 6 and the C.I. pigment green 36 at least a pigment.
These pigment may be used alone, can also be two or more kinds in combination.
For example, red pixel be form, C.I. paratonere 209 and C.I. pigment yellow 13 9 preferably contained; Form green pixel, preferably contain the CI. pigment green 36 and be selected from C.I. pigment yellow 150 and C.I. pigment yellow 13 8 at least a; Form blue picture element, preferably contain the C.I. pigment blue 15: 6.
Wherein, owing to thermotolerance, color emissivity excellence, preferably use organic pigment.
Organic pigment in the above-mentioned pigment; as required; can implement rosin handles; the surface treatment of the pigment derivative of use importing acidic-group or basic group etc.; employing macromolecular compound etc. is handled in the grafting of surface of pigments; adopt micronize such as sulfuric acid micronize method to handle, and the carrying out washing treatment that is used to remove the organic solvent of impurity and water etc., ionic impurity is removed processing etc. by ion exchange process etc.
The content of the colorant in the solid constituent of photosensitive composition (A) is preferably below the above 60 quality % of 25 quality %, more preferably below the above 55 quality % of 27 quality %, further below the above 50 quality % of preferred 30 quality %.
Colorant (A) if content below 60 quality % more than the 25 quality %, colour saturation during as colored filter is abundant, and, can form the sufficient pattern of physical strength owing to can contain binder polymer measuring in the composition, be preferred therefore.
Herein, the solid constituent of so-called photosensitive composition is meant and removes the residual part in (E) back of desolvating from photosensitive composition.
Colorant (A) is preferably uniform particle diameter.Colorant (A) is under the situation of pigment, by containing pigment dispersing agent and carrying out dispersion treatment, can obtain the dispersible pigment dispersion of the state that pigment disperses equably in solution.
As above-mentioned pigment dispersing agent, can enumerate for example kation system, negative ion system, nonionic system, both sexes, polyester system, surfactants such as polyamine system etc. can also can make up separately more than 2 kinds and use.
The use amount of pigment dispersing agent, per 1 mass parts colorant (A) is preferably below 1 mass parts, more preferably below above 0.5 mass parts of 0.05 mass parts.If the use amount of above-mentioned pigment dispersing agent is below per 1 mass parts colorant, 1 mass parts,, be preferred therefore because the tendency of the pigment that can obtain homogeneously dispersed state is arranged.
As the binder polymer that uses among the present invention (B), but can enumerate the monomer that for example contains carboxyl and with acrylic acid series copolymer of multipolymer of other monomers of this monomer copolymerization etc. etc.
As the monomer that contains carboxyl, can enumerate the unsaturated carboxylic acid that for example in the molecule of unsaturated polybasic carboxylic acids such as unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated tricarboxylic acids etc., has at least one carboxyl.
As unsaturated monocarboxylic, can enumerate for example acrylic acid, methacrylic acid, crotonic acid, α-Lv Bingxisuan, cinnamic acid etc. herein.As unsaturated dicarboxylic, can enumerate for example maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc.
Unsaturated polybasic carboxylic acid can be acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride.In addition, unsaturated polybasic carboxylic acid, it can be its single (2-methacryloxy alkyl) ester, mono succinate (2-acryloxy ethyl) ester for example, mono succinate (2-methacryloxyethyl) ester, phthalic acid list (2-acryloxy ethyl) ester, phthalic acid list (2-methacryloxyethyl) ester etc.Unsaturated polybasic carboxylic acid can be list (methyl) acrylate of the dicarboxyl polymkeric substance of its two end, for example can enumerate (ω-carboxyl polycaprolactone single-acrylate, ω-carboxyl polycaprolactone monomethacrylates etc.These contain the monomer of carboxyl, can also can mix use more than 2 kinds separately.
But as above-mentioned and other monomers monomer copolymerization that contains carboxyl, can enumerate for example styrene, α-Jia Jibenyixi, neighbour-vinyltoluene, between-vinyltoluene, right-vinyltoluene, right-chlorostyrene, neighbour-methoxy styrene, between-methoxy styrene, p-methoxystyrene, neighbour-vinyl benzyl methyl ether, between-the vinyl benzyl methyl ether, right-the vinyl benzyl methyl ether, neighbour-vinyl benzyl glycidyl ether ,-the vinyl benzyl glycidyl ether, right-the vinyl benzyl glycidyl ether, aromatic ethenyl compounds such as indenes; Methyl acrylate, methyl methacrylate, ethyl acrylate, Jia Jibingxisuanyizhi, the acrylic acid n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, the secondary butyl ester of methacrylic acid, tert-butyl acrylate, the metering system tert-butyl acrylate, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester, acrylic acid 3-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester, acrylic acid 2-hydroxyl butyl ester, methacrylic acid 2-hydroxyl butyl ester, acrylic acid 3-hydroxyl butyl ester, methacrylic acid 3-hydroxyl butyl ester, acrylic acid 4-hydroxyl butyl ester, methacrylic acid 4-hydroxyl butyl ester, allyl acrylate, allyl methacrylate, acrylic acid benzyl ester, methacrylic acid benzyl ester, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, acrylic acid 2-methoxyl ethyl ester, methacrylic acid 2-methoxyl ethyl ester, acrylic acid 2-phenoxy ethyl, methacrylic acid 2-phenoxy ethyl, acrylic acid methoxyl diglycol ester, methacrylic acid methoxy base diglycol ester, acrylic acid methoxyl triethyleneglycol ester, methacrylic acid methoxy base triethyleneglycol ester, acrylic acid MPEG ester, methacrylic acid methoxy base propylene glycol ester, acrylic acid methoxyl dipropylene glycol ester, methacrylic acid methoxy base dipropylene glycol ester, isobornyl acrylate, IBOMA, acrylic acid two pentadiene esters, methacrylic acid two pentadiene esters, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, methacrylic acid 2-hydroxyl-3-phenoxy group propyl ester, glycerine mono acrylic ester, unsaturated carboxylate types such as glycerin monomethyl acrylic ester;
Acrylic acid 2-amino ethyl ester, methacrylic acid 2-amino ethyl ester, acrylic acid 2-dimethylamino ethyl ester, methacrylic acid 2-dimethylamino ethyl ester, the amino propyl ester of acrylic acid 2-, the amino propyl ester of methacrylic acid 2-, acrylic acid 2-dimethylamino propyl ester, methacrylic acid 2-dimethylamino propyl ester, the amino propyl ester of acrylic acid 3-, the amino propyl ester of methacrylic acid 3-, acrylic acid 3-dimethylamino propyl ester, unsaturated carboxylic acid aminoalkyl ester classes such as methacrylic acid 3-dimethylamino propyl ester;
Glycidyl acrylate, unsaturated carboxylic acid ethylene oxidic ester classes such as glycidyl methacrylate;
Vinyl acetate, propionate, vinyl butyrate, vinyl carboxylates classes such as vinyl benzoate;
Vinyl methyl ether, EVE, unsaturated ethers such as allyl glycidyl ether;
Vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, vinyl cyanide based compounds such as vinyl cyanide fork;
Acrylamide, Methacrylamide, α-chloropropene acid amides, N-2-hydroxyethyl acrylamide,
Unsaturated acyl amines such as N-2-hydroxyethyl Methacrylamide;
Maleic amide, N-phenyl maleimide, unsaturated acyl amines such as N-cyclohexyl maleic amide;
1,3-butadiene, isoprene, aliphatics conjugated dienes such as chlorbutadiene;
At polystyrene, polymethyl acrylate, polymethylmethacrylate, the positive butyl ester of polyacrylic acid, Vinalac 5920, the polymer molecule chain end of polysiloxane has the macromonomer class of single acryloyl group or monomethyl acryloyl group etc.
These monomers can also can mix use separately more than 2 kinds.
The content of the monomeric unit that contains carboxyl of above-mentioned copolymerization species is preferably 10～50 quality %, more preferably 15～40 quality %, more preferably 25～40 quality %.The above-mentioned content that contains the monomeric unit of carboxyl if be 10～50 quality %, for the imaging liquid favorable solubility, has the tendency that correctly forms image during video picture, be preferred therefore.
As aforesaid propylene acid based copolymer, can enumerate for example (methyl) acrylic acid/(methyl) methyl acrylate copolymer, (methyl) acrylic acid/(methyl) acrylic acid benzyl ester multipolymer, (methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) acrylic acid benzyl ester multipolymer, (methyl) acrylic acid/(methyl) methyl acrylate/polystyrene macromolecular monomer copolymer, (methyl) acrylic acid/(methyl) methyl acrylate/poly-(methyl) methyl acrylate macromonomer multipolymer, (methyl) acrylic acid/(methyl) acrylic acid benzyl ester/polystyrene macromolecular monomer copolymer, (methyl) acrylic acid/(methyl) acrylic acid benzyl ester/poly-(methyl) methyl acrylate macromonomer multipolymer, (methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) acrylic acid benzyl ester/polystyrene macromolecular monomer copolymer, (methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) acrylic acid benzyl ester/poly-(methyl) methyl acrylate macromonomer multipolymer, (methyl) acrylic acid/styrene/(methyl) acrylic acid benzyl ester/N-phenyl maleimide multipolymer, (methyl) acrylic acid/mono succinate (2-acryloxy ethyl) ester/styrene/(methyl) acrylic acid benzyl ester/N-phenyl maleimide multipolymer, (methyl) acrylic acid/mono succinate (2-acryloxy ethyl) ester/styrene/(methyl) allyl acrylate/N-phenyl maleimide multipolymer, (methyl) acrylic acid/(methyl) acrylic acid benzyl ester/N-phenyl maleimide/styrene/glycerine list (methyl) acrylate copolymer etc.In addition, so-called (methyl) acrylate, expression acrylate or methacrylate.
Wherein, preferred (methyl) acrylic acid/(methyl) acrylic acid benzyl ester multipolymer that uses, (methyl) acrylic acid/(methyl) acrylic acid benzyl ester/styrol copolymer, (methyl) acrylic acid/(methyl) methyl acrylate copolymer, (methyl) acrylic acid/(methyl) methyl acrylate/styrol copolymer.
Aforesaid propylene acid based copolymer, the weight average molecular weight of its polystyrene conversion is 3,000～400,000, more preferably 5,000～100,000, further be preferably 10,000～40,000.If molecular weight is 3,000～400,000, because hardness of film improves, residual film ratio is also high, and unexposed portion is to the favorable solubility of imaging liquid, and therefore the tendency that exists sharpness to improve is preferred.
In addition, the acid number of aforesaid propylene acid based copolymer is preferably 30～250, and more preferably 60～180, more preferably 80～160.Above-mentioned acid number if be 30～250, improves and unexposed portion dissolves easily the dissolubility of imaging liquid, and the pattern of exposed portion is residual when ISOization and video picture in addition, and therefore the tendency that exists residual film ratio to improve is preferred.Herein, acid number be with in and the value measured of amount (mg) form of the necessary potassium hydroxide of 1g acrylate copolymer, usually can be by obtaining with the potassium hydroxide aqueous solution titration.
The content of binder polymer in the solid constituent of photosensitive composition (B) is preferably below the above 90 quality % of 5 quality %, more preferably below the above 80 quality % of 10 quality %, below the above 70 quality % of further preferred 20 quality %.If content is not easy to mix depression in the pattern below 90 quality % more than the 5 quality %, there is the good tendency of cohesive, therefore the tendency that exists sharpness and residual film ratio to improve in addition is preferred.
The optical polymerism compound (C) that uses among the present invention is by polymeric compounds such as the living radical that produces from Photoepolymerizationinitiater initiater (D) by irradiates light, acid, can enumerate the compound that for example has the polymerism carbon-to-carbon unsaturated bond etc.
Above-mentioned optical polymerism compound (C) is preferably the polyfunctional optical polymerism compound that has more than 3 functional groups.As 3 polyfunctional optical polymerism compounds more than the functional group, can enumerate for example tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate etc.Above-mentioned optical polymerism compound (C) can also can make up separately more than 2 kinds and use.
The content of the optical polymerism compound (C) in the solid constituent of photosensitive composition, be preferably below the above 90 quality % of 5 quality %, more preferably below the above 80 quality % of 10 quality %,, below the above 70 quality % of further preferred 20 quality %.The content of above-mentioned optical polymerism compound (C) if below 90 quality % more than the 5 quality %, takes place to solidify and the residual film ratio raising fully, is difficult to mix depression in the pattern, has the good tendency of cohesive, is preferred therefore.
The Photoepolymerizationinitiater initiater that uses among the present invention (D) preferably contains at least a acetophenone based compound.
As the acetophenone based compound, can enumerate for example diethoxy acetophenone, 2-methyl-2-morpholino-1-(4-methyl thio-phenyl) propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, the 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-oligomer such as l-ketone etc., preferred 2-methyl-2-is ridiculed generation-1-(4-methyl thio-phenyl) propane-1-ketone etc.In addition, a plurality of acetophenone systems and other Photoepolymerizationinitiater initiater can be used in combination.As the Photoepolymerizationinitiater initiater beyond the acetophenone system, can enumerate the living radical generation agent that produces living radical by irradiates light, acid producing agent etc.
As the living radical initiating agent, can enumerate for example benzoin based compound, benzophenone based compound, thioxanthones based compound, three
Figure C20031012045400091
Based compound etc.
As the benzoin based compound, can enumerate for example benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether etc.
As the benzophenone based compound, can enumerate for example benzophenone, neighbour-benzoyl methyl benzoate, 4-phenyl benzophenone; 4-benzoyl-4 '-methyldiphenyl base sulphite, 3,3 ', 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6-tri-methyl benzophenone etc.
As the thioxanthones based compound, can enumerate for example 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
As the triazine based compound, for example can enumerate 2, two (the trichloromethyl)-6-(4-methoxyphenyl) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1,3 of 4-, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3,5-triazine, 2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl of 4-]-1,3,5-triazines, 2, two (trichloromethyl)-6-[2-(furans-2-yl) vinyl of 4-]-1,3, the 5-triazine, 2,4-pair ((trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl of 4-]-1,3,5-triazine etc.
Produce agent as living radical, for example can use 2,4; 6-trimethylbenzoyl diphenyl phosphine oxide, 2,2 '-two (neighbour-chlorphenyl)-4; 4 ', 5,5 '-tetraphenyl-1; 2 '-diimidazole, 10-butyl-2-chloro-acridine ketone, 2-EAQ; benzyl, 9, the 10-phenanthrenequione; camphorquinone, phenyl glyoxalic acid methylester, two luxuriant titaniums (チ ノ セ Application) compound etc.
As acid producing agent, can enumerate for example 4-hydroxy phenyl dimethyl sulfonium p-toluenesulfonic esters, 4-hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium p-toluenesulfonic esters, 4-acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, the triphenylsulfonium p-toluenesulfonic esters, the triphenylsulfonium hexafluoro antimonate, diphenyl iodine (ヨ-De ニ ウ system) p-toluenesulfonic esters, salts such as diphenyl iodine hexafluoro antimonate, or nitrobenzyl toluene sulfonate (class of ト シ レ-ト), benzoin toluenesulfonic acid salt etc.
In addition, producing as living radical in the above-claimed cpd of agent, also can be the compound that produces living radical and acid simultaneously, and for example, triazine is a Photoepolymerizationinitiater initiater, also can be used as acid producing agent and uses.
The content of photopolymer initiating agent (D) with respect to total amount 100 mass parts of binder polymer (B) and optical polymerism compound (C), is preferably below above 20 mass parts of 0.1 mass parts, more preferably below above 15 mass parts of 1 mass parts.The content of Photoepolymerizationinitiater initiater is if be that high sensitizationization and time shutter shorten throughput rate and improve, and on the other hand, exist light sensitivity to cross the tendency of the constant difference of high definition, are preferred therefore below above 20 mass parts of 0.1 mass parts.
In the photosensitive composition of the present invention, can further contain photopolymerization and cause auxiliary agent (G).Photopolymerization causes auxiliary agent (G), normally can unite with Photoepolymerizationinitiater initiater (D) and to use and to begin the compound that the polymerization of the optical polymerism compound of polymerization is used in order promoting by Photoepolymerizationinitiater initiater.
As Photoepolymerizationinitiater initiater auxiliary agent (G), can enumerate amine compound, alkoxy anthracene based compound, thioxanthones based compound etc.
As aminated compounds, can enumerate for example triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N, N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) diformazan benzophenone (being commonly called as Meath Le Shi ketone), 4,4 '-two (diethylamino) benzophenone, 4,4 '-two (ethylmethylamino) benzophenone etc., wherein, preferred 4,4 '-two (diethylamino) benzophenone.
As the alkoxy anthracene based compound, for example can enumerate 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.
As the thioxanthones based compound, can enumerate for example 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
Photopolymerization causes auxiliary agent (G), can use more than 2 kinds alone or in combination.In addition, cause auxiliary agent (G), can use commercially availablely, cause auxiliary agent (G), for example can enumerate commodity " EAB-F " (hodogaya chemical industry (strain) system) by name etc. as commercially available photopolymerization as photopolymerization.
Combination as Photoepolymerizationinitiater initiater in the photosensitive composition of the present invention (D) and photopolymerization initiation auxiliary agent (G), can enumerate for example diethoxy acetophenone/4,4 '-two (diethylamino) diformazan benzophenone, 2-methyl-2-morpholino-1-(4-methyl thio-phenyl) propane-1-ketone/4,4 '-two (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone/4,4 '-two (diethylamino) benzophenone, benzyl dimethyl ketal/4,4 '-two (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone/4,4 '-two (diethylamino) benzophenone, 1-hydroxycyclohexylphenylketone/4,4 '-two (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligomer/4 of propane-1-ketone, 4 '-two (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone/4,4 '-two (diethylamino) benzophenone etc., preferably can enumerate 2-methyl-2-morpholino-1-(4-methyl thio-phenyl) propane-1-ketone/4,4 '-two (diethylamino) benzophenone etc.
When using these photopolymerization to cause auxiliary agents (G), its use amount, per 1 mole of Photoepolymerizationinitiater initiater (D) is generally below 10 moles, is preferably more than 0.01 mole below 5 moles.
As the solvent that uses among the present invention (E), can enumerate the solvent that contains propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2 pentanone.In the solvent (E), can contain other solvents except that above-mentioned 2 kinds.As other solvents, can enumerate for example above-mentioned ethers in addition, the ketone beyond the arene, above-mentioned ketone, alcohols, ester class, amide-type, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) etc.
As ethers, can enumerate for example tetrahydrofuran, oxinane, 1,4-two  alkane, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ethers, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, methylcellosolve acetate, ethyl cellosolve acetate, the ethyl carbitol acetic acid esters, acetate of butyl carbitol, methyl proxitol acetate, methoxyl butylacetic acid ester, methoxyl amyl group acetic acid esters, anisole, phenetol, methyl anisole etc.
As aromatic hydrocarbon based, can enumerate benzene, toluene, dimethylbenzene, sym-trimethyl benzene etc.
As ketone, can enumerate for example acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-heptanone, cycloheptanone, cyclohexanone etc.
As alcohols, can enumerate for example methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine etc.
As the ester class, can enumerate for example ethyl acetate, acetate-positive butyl ester, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, the glycolic methyl esters, the glycolic ethyl ester, glycolic butyl ester, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the 3-hydroxy methyl propionate, 3-oxygen base ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid propyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, gamma-butyrolacton etc.
As amide-type, can enumerate for example N, dinethylformamide, N,N-dimethylacetamide etc.
Wherein, preferably unite use 3-ethoxyl ethyl propionate.
Above-mentioned solvent can also can make up separately more than 2 kinds and use.
The content of the solvent (E) in the photosensitive composition (total amount) is preferably below the above 95 quality % of 70 quality %, more preferably below the above 90 quality % of 75 quality %.If the content of solvent is below 95 quality % more than the 70 quality %, the flatness during coating is good, and in addition, colour saturation can be sufficient during owing to the formation colored filter, has the good tendency of display characteristic, is preferred therefore.
The content of the 4-hydroxy-4-methyl-2 pentanone in the solvent (E) is preferably below the above 40 quality % of 3 quality %, more preferably below the above 30 quality % of 5 quality, below the above 20 quality % of further preferred 8 quality %.Solvent (E) preferably is made of propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2 pentanone basically.
In the photosensitive composition of the present invention, can also contain surfactant (F).As surfactant (F), can enumerate being selected from the silicone-based surfactant, fluorine is surfactant and has at least a in the silicone-based surfactant of fluorine atom.
As the silicone-based surfactant, can enumerate surfactant that for example has siloxane bond etc., particularly, can enumerate for example ト-レ silicone DC3PA, same SH7PA, same DC11PA, same SH21PA, same SH28PA, same 29SHPA, same SH30PA, polyether-modified silicone oil SH8400 (trade name: ト-レ silicone (strain) system), KP321, KP322, KP323, KP24, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's silicone system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (ジ-ィ-Toshiba's silicone (strain) system) etc.
As fluorine is surfactant, can enumerate surfactant with fluorocarbon chain etc.Particularly, can enumerate Off ロ リ Na-ト (registered trademark) FC430, same FC431 (Sumitomo ス リ-エ system (strain) system), メ ガ Off ァ Star Network (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same R30 (big Japanese ink chemical industry (strain) system), エ Off ト ッ プ (registered trademark) EF301, same EF303, same EF351, same EF352 (new autumn fields changes into (strain) system), サ-Off ロ Application (registered trademark) S381, same S382, same SC101, same SC105 (Asahi Glass (strain) system), E5844 (strain) ダ ィ キ Application Off ァ ィ Application ケ ミ カ Le institute system), BM-1000, (trade name is BM-1100: BM Chemie society system) etc.
As silicone-based surfactant, can enumerate surfactant with siloxane bond and fluorocarbon chain etc. with fluorine atom.Particularly, can enumerate for example メ カ Off ァ Star Network (registered trademark) R08, same BL20, same F475, same F477, same F443 (big Japanese ink chemical industry (strain) system) etc.
These surfactants can also can make up separately more than 2 kinds and use.
The content of surfactant (F) is preferably below above 0.6 mass parts of 0.0005 mass parts with respect to 100 mass parts photosensitive compositions (total amount of (A)～(E)), more preferably above 0.5 mass parts of 0.001 mass parts.Surfactant (F) if content below 0.6 mass parts more than 0.0005 mass parts owing to there is a good tendency of flatness, be preferred therefore.
In the photosensitive composition of the present invention, can also contain filling agent, the macromolecular compound beyond the binder polymer, adhesion promoter, antioxidant, ultraviolet light absorber, coagulation-prevention agent, organic acid, organic amino compounds, adjuvants such as hardening agent.
As filling agent, can enumerate for example glass, particulates such as aluminium oxide.
As the macromolecular compound beyond the binder polymer, can enumerate for example polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, polyacrylic acid chlorine Arrcostab etc.
As adhesion promoter, can enumerate for example 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 methyl dimethoxysilane, 2-(3,4-ethoxy cyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methylpropenyl oxygen base propyl trimethoxy silicane, 3-sulfydryl propyl trimethoxy silicane etc.
As antioxidant, for example can enumerate 4,4 '-sulfo-two (the 6-tert-butyl group-3-methylphenol), 2,6-two-tert-butyl group-4-methylphenol etc.
As ultraviolet light absorber, can enumerate for example 2-(the 2-hydroxyl-3-tert-butyl group-5-aminomethyl phenyl)-benzotriazoles such as 5-chlorobenzotriazole system;
2-hydroxyl-benzophenone series such as 4-octyl group oxygen benzophenone;
2,4-two-tert-butyl-phenyl-3, benzoic ethers such as 5-two-tertiary butyl-4-hydroxy benzoic ether system;
2-(4,6-diphenyl-1,3,5-triazines-2-yl)-triazines such as 5-hexyl oxo phenol system.
As coagulation-prevention agent, can enumerate for example sodium polyacrylate etc.As organic acid, can enumerate for example formic acid, acetate, propionic acid, butyric acid, valeric acid, neopentanoic acid, caproic acid, diethacetic acid, enanthic acid, the sad aliphatic monocarboxylic acid class that waits;
Oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, tridecandioic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, the cyclohexyl dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, aliphatic dicarboxylic acid classes such as mesaconic acid;
The third three acid, aconitic acid, aliphatic tricarboxylic acids classes such as camphoronic acid;
Benzoic acid, toluic acid, cumic acid, mesitylenic acid, 3, aromatic monocarboxylate's classes such as 5-mesitylenic acid;
Phthalic acid, m-phthalic acid, aromatic dicarboxylic acid classes such as terephthalic acid (TPA);
Trimellitic acid, trimesic acid, mellophanic acid, aromatic multi-carboxy acid's classes such as pyromellitic acid etc.
As organic amino compounds, can enumerate for example n-propylamine, isopropylamine, n-butylamine, isobutyl amine, sec-butylamine, tert-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive undecylamine, monoalkyl amines such as positive lauryl amine;
Cyclohexylamine, 2-methyl cyclohexylamine, 3-methyl cyclohexylamine, monocycle alkyl amines such as 4-methyl cyclohexylamine;
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, two n-pentyl amine, dialkyl amines such as di-n-hexyl amine;
Methyl cyclohexylamine, monoalkyl monocycle alkyl amines such as ethyl cyclohexylamine;
Bicyclic alkyl amines such as dicyclohexyl amine;
Dimethylethyl amine, methyl diethylamide, triethylamine, dimethyl n propylamine, diethyl n-propylamine, the methyl di-n-propylamine, ethyl di-n-propylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, triisobutylamine, tri sec-butylamine, three tert-butylamines, tri-n-amyl amine, trialkyl amines such as three n-hexylamines;
Dimethyl cyclohexyl amine, dialkyl group monocycle alkyl amines such as diethyl cyclohexylamine;
The methyl bicyclic hexylamine, ethyl dicyclohexyl amine, monoalkyl bicyclic alkyl amines such as thricyclohexyl amine;
Diamido ethanol, 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 6-amino-strand alkanol amines such as 1-hexanol;
4-amino-mononaphthene alcaminess such as 1-cyclohexanol;
Diethanolamine, two n-propanol amine, diisopropanolamine, two normal butyl alcohol amine, two isobutyl hydramine, two n-amyl alcohol amine, two alkanolamine such as two hexanol amine;
Two cyclic alkanol amines such as two (4-cyclohexanol) amine;
Triethanolamine, three n-propanol amine, triisopropanolamine, three normal butyl alcohol amine, three isobutyl hydramine, three n-amyl alcohol amine, trialkanolamine classes such as three n-hexyl alcohol amine;
Three cyclic alkanol amines such as three (4-cyclohexanol) amine;
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, the 2-propylene glycol, 3-diethylamino-1,2-propylene glycol, 2-dimethylamino-1, ammediol, 2-diethylamino-1, amino-alkane glycolss such as ammediol;
4-amino-1,2-cyclohexanediol, 4-amino-1, amino cycloalkanes glycolss such as 3-cyclohexanediol;
1-amino cyclopentyl ketone methyl alcohol, 4-amino cyclopentyl ketone methyl alcohol etc. contain amino cyclanone methyl alcohol class;
The amino cyclohexanone methyl alcohol of 1-, the amino cyclohexanone methyl alcohol of 4-, 4-dimethylamino cyclopentanone methyl alcohol, 4-diethylamino cyclopentanone methyl alcohol, 4-dimethylamino cyclohexanone methyl alcohol, 4-diethylamino cyclohexanone methyl alcohol etc. contain amino cyclanone methyl alcohol class;
Beta-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaprolc acid, the amino cyclopropionate of 1-, the amino cyclohexane carboxylic of 1-, aminocarboxylic acids such as the amino cyclohexane carboxylic of 4-;
Aniline, neighbour-methylaniline.Between-methylaniline, right-methylaniline, right-ethylaniline, right-n-pro-pyl aniline, cumidine, right-n-butyl aniline, right-tert-butyl group aniline, 1-naphthylamine, 2-naphthylamine, N, accelerine, N, the N-diethylaniline, right-methyl-N, aromatic amines such as accelerine;
Neighbour-aminobenzyl alcohol ,-aminobenzyl alcohol, right-aminobenzyl alcohol, right-the dimethylamino benzyl alcohol, right-aminobenzyl alkanols such as diethylamino benzyl alcohol;
O-aminophenol ,-amino-phenol, para-aminophenol, right-dimethylamino phenol, right-amino phenols such as diethylamino phenol etc.;
M-anthranilic acid, Para-Aminobenzoic, right-dimethylaminobenzoic acid, right-aminobenzoic acids such as diethyl amino yl benzoic acid.
As hardening agent, for example can enumerate, by the carboxyl reaction in heating and the binder polymer and can make the crosslinked compound of binder polymer, polymerization and make the compound etc. of colored pattern curing separately.As above-claimed cpd, can enumerate for example epoxy compound, oxetane compounds etc. preferably use oxetane compound.
Herein, as epoxy compound, for example can enumerating, bisphenol-A is an epoxy resin, hydrogenated bisphenol A is an epoxy resin, Bisphenol F is an epoxy resin, A Hydrogenated Bisphenol A F is an epoxy resin, phenolic resin varnish type epoxy resin, other fragrant family epoxy resin, alicyclic ring family epoxy resin, hetero ring type epoxy resin, ethylene oxidic ester are resin, and glycidyl amine is a resin, epoxidation wet goods epoxy resin, with the brominated derivative of these epoxy resin, the aliphatics beyond epoxy resin and its brominated derivative, alicyclic or aromatic epoxy compound, the epoxide of butadiene (being total to) polymkeric substance, the epoxide of (being total to) polymers of isoprene, (being total to) polymkeric substance of glycidyl (methyl) acrylate, triglycidyl group chlorinated isocyanurates etc.
As oxetane compound, can enumerate for example carbonic ester dioxetane, xylylene dioxetane, adipate dioxetane, terephthalate dioxetane, cyclohexane dicarboxylic acid dioxetane etc.
Photosensitive composition of the present invention, contain as hardening agent under the situation of epoxy compound, oxetane compound etc., can contain the epoxy radicals that can make epoxy compound, the compound of oxetane compound oxetanes skeleton ring-opening polymerization.As this compound, can enumerate for example polybasic carboxylic acid class, polybasic acid anhydride class etc.
As the polybasic carboxylic acid class, can enumerate for example phthalic acid, 3,4-dimethyl benzene dioctyl phthalate, m-phthalic acid, terephthalic acid (TPA), Pyromellitic Acid, trimellitic acid, 1,4,5,8-naphthalene tetracid, 3,3 ', 4, aromatic series polybasic carboxylic acid classes such as 4 '-benzophenone tetrabasic carboxylic acid;
Succinic acid, glutaric acid, hexane diacid, 1,2,3,4-butyl tetrabasic carboxylic acid, maleic acid, fumaric acid, aliphatics polybasic carboxylic acid classes such as itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyl tetrahydro phthalic acid, six hydrogen m-phthalic acids, six hydrogen terephthalic acid (TPA)s, 1,2,4-cyclopentane tricarboxylic acids, 1,2,4-hexamethylene tricarboxylic acids encircles penta tetrabasic carboxylic acid, and 1,2,4, alicyclic polybasic carboxylic acid classes such as 5-hexamethylene tetrabasic carboxylic acid etc.
As the polybasic acid anhydride class, can enumerate for example phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, 3,3 ', 4, aromatic series polybasic acid anhydride classes such as 4 '-benzophenone tetracarboxylic dianhydride;
Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic acid acid anhydride, maleic anhydride, 1,2,3, aliphatics polybasic acid anhydride classes such as 4-butyl tetracarboxylic dianhydride;
Hexahydrophthalic anhydride, 3,4-dimethyl tetrahydro phthalic anhydride, 1,2,4-encircles penta tricarboxylic acid anhydride, 1,2,4-hexamethylene tricarboxylic acid anhydride encircles penta tetracarboxylic dianhydride, 1,2,4,5-hexamethylene tetracarboxylic dianhydride, Ha イ ミ Star Network acid anhydrides, alicyclic polybasic acid anhydride classes such as Na ヅ Application acid anhydrides;
Ethylene glycol bis trimellitate (ト リ メ リ テ ィ ト) acid, glycerine three trimellitate acid anhydrides etc. contain the carboxyanhydrides of ester group etc.
As above-mentioned carboxyanhydrides, can use commercially available as epoxy curing agent.As above-mentioned epoxy curing agent, can enumerate for example trade name " ァ デ カ Ha-De Na-EH-700 " (rising sun electrochemical industry (strain) system), trade name " リ カ シ Star De HH " (new Japanese physics and chemistry (strain) system), trade name " MH-700 " (new Japanese physics and chemistry (strain) system) etc.
Above-mentioned hardening agent can also can be used in combination of two or more separately
Method as preparation photosensitive composition of the present invention, for example can enumerate, make in the solvent (E) and deposit pigment dispersing agent and colorant (A) such as pigment is disperseed, colorant (A) dispersion liquid of preparation uniform grading, further, make the binder polymer (B) that is dissolved in the solvent, optical polymerism compound (C), Photoepolymerizationinitiater initiater (D) and other dissolvings such as adjuvant as required, (A) mixes with dispersion liquid with above-mentioned colorant, further adds the method for solvent etc. as required.
The photosensitive composition that so obtains is through transporting and take care of the manufacturing that offers color filter.In above-mentioned transportation, during the keeping (for example 5 ℃), usually, to preserve at a certain temperature, its temperature is generally 0～25 ℃, is preferably 5～10 ℃.Offer the manufacturing (for example 23 ℃) of color filter from being formulated into of photosensitive composition, short more good more during this, photosensitive composition, during at least 3 months of its preparation beginning, preferably keep forming and preparing the performance of the color filter of same quality at that time.
In addition, during the exploitation of photosensitive composition, in it estimates in advance,, just elongated during the exploitation if confirm ageing stability during above-mentioned 3 months.Therefore, what carry out is to estimate the temperature of the temperature of ageing stability from above-mentioned routine, brings up to for example 40 ℃～60 ℃, quicken through the time change, shorten the method that the holding time estimates.
Therefore, for example can enumerate the viscosity rate of change of photosensitive composition as the method for index as the evaluation method of above-mentioned ageing stability etc.The viscosity rate of change can be obtained with following formula 1.
Figure C20031012045400181
(in the formula, η 0Be illustrated in the viscosity of measuring before beginning to preserve, η represents to preserve at a certain temperature surmising of measuring behind the certain hour.)
In order to calculate above-mentioned viscosity rate of change, measure viscosity.Viscosity can for example be used E type viscosity meter コ-Application プ レ-ト under certain liquid temperature (for example 23 ℃), at certain revolution (50rpm for example.) measure down.
The viscosity rate of change is preferably below 3%.If below 3%, owing to can be preferred therefore just to have prepared the identical performance in back, good, the no foreign matter of flatness ground formation color filter with photosensitive composition.
In addition, photosensitive composition of the present invention is enclosed it in container usually, offers transportation, keeping.
As using photosensitive composition of the present invention to form the method for color filter patterns, for example can enumerate, photosensitive composition of the present invention (for example red) is applied on the substrate, removing desolvates waits volatile ingredient to form dyed layer, by photomask make that this dyed layer exposes, the method for video picture etc.
,, can enumerate for example glass substrate herein, silicon substrate, polycarbonate substrate, polyester substrate, aromatic polyamide substrate, polyamide-imide substrate, polyimide substrate, Al substrate, the substrate of surface smoothings such as GaAs substrate etc. as substrate.
On these substrates, can implement to handle by the medicine of chemicals such as silane coupling agent, plasma treatment, ion plating is handled, sputter process, gas-phase reaction is handled, pre-treatments such as vacuum evaporation processing.
In addition, on these substrates, can form other colored pattern.
Use as substrate under the situation of silicon substrate, on the surface of silicon substrate etc., can form charge bonded element (CCD), thin film transistor (TFT) (TFT) etc.
In order to go up the coating photosensitive composition at aforesaid substrate (comprising the substrate that forms other colored pattern), preferably, use the coating of existing rotary coating and aneroid, especially use rotary coating to be applied on the substrate etc., make volatile ingredient volatilizations such as solvent then by heating.Heating about 40 ℃～120 ℃, is carried out about 1～5 minute usually.
Like this, at substrate or formed the dyed layer that solid formation that flatness on the substrate of other colored pattern forms photosensitive composition well divides.
The dyed layer that forms is by also exposure, video picture of photomask.
I line (wavelength 365nm), h line, g line etc. are used in exposure, but preferably use i line (wavelength 365nm).I line (wavelength 365nm) light source preferably uses extra-high-pressure mercury vapour lamp (ウ シ オ motor (strain) society system; HB-75105AA OP1) lamp, the irradiation light quantity is generally 50～400mJ/cm 2About.
Video picture is implemented by flooding in imaging liquid usually.As imaging liquid, for example, can enumerate NaOH, potassium hydroxide, sodium carbonate, sodium butylnaphthalenesulfonate, tetramethyl ammonium hydroxide (TMAH) etc.
Especially, the preferred imaging liquid that contains 0.05% NaOH, 0.2% sodium butylnaphthalenesulfonate in quality ratio that uses.
After the video picture, as required, with washings such as pure water, then, can be 180 ℃～240 ℃ heat treated of carrying out about 10～60 minutes.
Like this, form colored pattern (1) (for example red).
Then, on colored pattern (1), use photosensitive composition (for example green),, form colored pattern (2) (for example green) with similarly above-mentioned.And, on colored pattern (2), use photosensitive composition (for example blue), with similarly above-mentioned, form colored pattern (3) (for example blue).Like this, can the manufacturing purpose colored filter.
By on the colored filter that obtains as mentioned above, will be through ITO, oriented film, bonding through the substrate and the TFT substrate of friction process by dividing plate, and inject liquid crystal and can make liquid crystal indicator.
Embodiment
Above-mentioned embodiments of the present invention are illustrated, but above-mentioned disclosed embodiments of the present invention, illustration just eventually, scope of the present invention is not limited to these embodiments.The scope of the invention comprises, and is represented by the scope of claim, and implication that is equal to the record of claim scope and all changes in the scope.Below, illustrate in greater detail the present invention by embodiment, but the present invention is not limited because of these embodiment.
The composition that uses in the present embodiment is as follows, is below to omit expression.
(A-1) colorant: C.I. paratonere 254
(B) binder polymer: [ratio of methacrylic acid monomer and methacrylic acid benzyl ester monomer is mass ratio (mol ratio) 30: 70 for methacrylic acid and methacrylic acid benzyl ester multipolymer, acid number 113, the weight average molecular weight of polystyrene conversion is 30,000]
(C) optical polymerism compound: dipentaerythritol acrylate
(D-1) Photoepolymerizationinitiater initiater: 2-methyl-2-morpholino-1-(4-methyl thio-phenyl) propane-1-ketone
(D-2) Photoepolymerizationinitiater initiater: 2, two (the trichloromethyl)-6-piperonyl-1,3,5-triazines of 4-
(G-1) photopolymerization causes auxiliary agent: 2, and the 4-diethyl thioxanthone
(E-1) solvent: propylene glycol monomethyl ether
(E-2) solvent: 4-hydroxy-4-methyl-2 pentanone
Embodiment 1
[preparation of photosensitive composition 1]
The following compositions mixing is obtained photosensitive composition 1.
(A-1) 7.98 mass parts
Polyester series pigments spreading agent 2.39 mass parts
(B) 5.40 mass parts
(C) 3.60 mass parts
(D-1) 0.54 mass parts
(D-2) 0.54 mass parts
(G-1) 0.54 mass parts
(E-1) 76.54 mass parts
(E-2) 2.37 mass parts
[viscosity rate of change]
The viscosity rate of change of photosensitive composition 1 is shown in Table 1.
[dry foreign matter]
The photosensitive composition 1 of enclosing 20mL in the spiral brown bottle of 30mL is also airtight, after the fierce up and down vibration, above-mentioned brown bottle is preserved 1 month at 23 ℃.With above-mentioned brown bottle Kaifeng, in photosensitive composition, can't see the sedimentation of dry foreign matter.Do not see dry foreign matter at the spiral part of bottle in addition yet.
Embodiment 2
[preparation of photosensitive composition 2]
The following compositions mixing is obtained photosensitive composition 2.
(A-1) 7.98 mass parts
Polyester series pigments spreading agent 2.39 mass parts
(B) 5.40 mass parts
(C) 3.60 mass parts
(D-1) 0.54 mass parts
(D-2) 0.54 mass parts
(G-1) 0.54 mass parts
(E-1) 71.01 mass parts
(E-2) 7.90 mass parts
[viscosity rate of change]
The viscosity rate of change of photosensitive composition 2 is shown in Table 1.
[dry foreign matter]
Except replacing estimating similarly to Example 1 the photosensitive composition 1 with photosensitive composition 2.In photosensitive composition, do not see the sedimentation of dry foreign matter, confirm not see dry foreign matter at the bottle spiral part in addition yet.
Embodiment 3
[preparation of photosensitive composition 3]
The following compositions mixing is obtained photosensitive composition 3.
(A-1) 7.98 mass parts
Polyester series pigments spreading agent 2.39 mass parts
(B) 5.40 mass parts
(C) 3.60 mass parts
(D-1) 0.54 mass parts
(D-2) 0.54 mass parts
(G-1) 0.54 mass parts
(E-1) 63.11 mass parts
(E-2) 15.80 mass parts
[viscosity rate of change]
The viscosity rate of change of photosensitive composition 3 is shown in Table 1.
[dry foreign matter]
Except replacing estimating similarly to Example 1 the photosensitive composition 1 with photosensitive composition 3.In photosensitive composition, do not see the sedimentation of dry foreign matter, do not see dry foreign matter at the spiral part of bottle in addition yet.
Embodiment 4
[preparation of photosensitive composition 4]
The following compositions mixing is obtained photosensitive composition 4.
(A-1) 7.98 mass parts
Polyester series pigments spreading agent 2.39 mass parts
(B) 5.40 mass parts
(C) 3.60 mass parts
(D-1) 0.54 mass parts
(D-2) 0.54 mass parts
(G-1) 0.54 mass parts
(E-1) 47.31 mass parts
(E-2) 31.60 mass parts
[viscosity rate of change]
The viscosity rate of change of photosensitive composition 4 is shown in Table 1.
[dry foreign matter]
Except replacing estimating similarly to Example 1 the photosensitive composition 1 with photosensitive composition 4.In photosensitive composition, do not see the sedimentation of dry foreign matter, confirm not see dry foreign matter at the spiral part of bottle in addition yet.
Comparative example 1
[preparation of photosensitive composition 5]
The following compositions mixing is obtained photosensitive composition 4.
(A-1) 7.98 mass parts
Polyester series pigments spreading agent 2.39 mass parts
(B) 5.40 mass parts
(C) 3.60 mass parts
(D-1) 0.54 mass parts
(D-2) 0.54 mass parts
(G-1) 0.54 mass parts
(E-1) 78.91 mass parts
[viscosity rate of change]
The viscosity rate of change of photosensitive composition 5 is shown in Table 1.
[dry foreign matter]
Except replacing estimating similarly to Example 1 the photosensitive composition 1 with photosensitive composition 5.In photosensitive composition, do not see the sedimentation of dry foreign matter, but see that at the spiral part of bottle dry foreign matter is arranged.
Comparative example 2
[preparation of photosensitive composition 6]
Similarly to Example 1, obtain photosensitive composition 6 except replacing the propylene glycol monomethyl ether with 4-hydroxy-4-methyl-2 pentanone.
[viscosity rate of change]
The viscosity rate of change of photosensitive composition 6 is shown in Table 1.
[dry foreign matter]
Except replacing estimating similarly to Example 1 the photosensitive composition 1 with photosensitive composition 6.In photosensitive composition, do not see the sedimentation of dry foreign matter, but see that at the spiral part of bottle dry foreign matter is arranged.
Table 1
Viscosity rate of change (%) Dry foreign matter
40 ℃ * 1 week 23 ℃ * 1 month
Embodiment 1 2.0 2.0 Do not have
Embodiment 2 2.8 2.5 Do not have
Embodiment 3 2.5 2.1 Do not have
Embodiment 4 2.9 2.5 Do not have
Comparative example 1 2.8 3.2 Have
Comparative example 2 10.4 6.2 Have
Industrial utilizability
According to the present invention, can provide ageing stability good painted photosensitive polymer combination. Painted photosensitive polymer combination of the present invention because ageing stability is excellent, if be used for slot coated, can obtain good the filming of flatness.

Claims (4)

1, photosensitive composition, it is characterized in that in the photosensitive composition that contains colorant (A), binder polymer (B), optical polymerism compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E) solvent (E) contains propylene glycol monomethyl ether and content is the following 4-hydroxy-4-methyl-2 pentanones of the above 40 quality % of 3 quality %.
2, the composition of claim 1 record, wherein the content of the solvent in the photosensitive composition (E) is below the above 95 quality % of 70 quality %.
3, the composition of claim 1 or 2 records, wherein solvent (E) is made of propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2 pentanone basically.
4, the formation method of pattern is characterized in that the composition of any record in the claim 1～3 is applied on the substrate, removes volatile ingredient and forms dyed layer, by photomask and with this dyed layer exposure, video picture.
CNB2003101204544A 2002-12-02 2003-11-30 Coloration-photosensitive resin composition Expired - Lifetime CN100351656C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2002349501 2002-12-02
JP349501/02 2002-12-02
JP349501/2002 2002-12-02

Publications (2)

Publication Number Publication Date
CN1504777A CN1504777A (en) 2004-06-16
CN100351656C true CN100351656C (en) 2007-11-28

Family

ID=34260210

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2003101204544A Expired - Lifetime CN100351656C (en) 2002-12-02 2003-11-30 Coloration-photosensitive resin composition

Country Status (3)

Country Link
KR (1) KR101046889B1 (en)
CN (1) CN100351656C (en)
TW (1) TWI326296B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4631808B2 (en) * 2006-06-08 2011-02-16 住友化学株式会社 Colored photosensitive resin composition
JP5420527B2 (en) * 2009-12-22 2014-02-19 エルジー・ケム・リミテッド Crosslinkable compound and photosensitive composition containing the same
JP5978670B2 (en) * 2012-03-15 2016-08-24 住友化学株式会社 Colored curable resin composition
JP2015041104A (en) * 2013-08-22 2015-03-02 東友ファインケム株式会社 Colored photosensitive resin composition, and color filter and display device including the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1038525A (en) * 1988-05-26 1990-01-03 赫希斯特人造丝公司 The colour filter system of LCD
CN1128362A (en) * 1994-11-15 1996-08-07 赫司特日本有限公司 Photosensitive resin composition
JP2000095992A (en) * 1998-09-22 2000-04-04 Dainippon Printing Co Ltd Pigment dispersing agent and photosensitive coloring composition
US6255034B1 (en) * 1997-09-09 2001-07-03 Jsr Corporation Radiation sensitive composition
CN1334469A (en) * 2000-07-11 2002-02-06 新日铁化学株式会社 Method for making color filter and coloring photosensitive resin composition
JP2002296778A (en) * 2001-01-24 2002-10-09 Sumitomo Chem Co Ltd Color photosensitive composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002049149A (en) * 2000-08-01 2002-02-15 Fuji Photo Film Co Ltd Negative type resist composition for electron beam or x-ray
JP4608796B2 (en) * 2001-03-28 2011-01-12 住友化学株式会社 Colored photosensitive resin composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1038525A (en) * 1988-05-26 1990-01-03 赫希斯特人造丝公司 The colour filter system of LCD
CN1128362A (en) * 1994-11-15 1996-08-07 赫司特日本有限公司 Photosensitive resin composition
US6255034B1 (en) * 1997-09-09 2001-07-03 Jsr Corporation Radiation sensitive composition
JP2000095992A (en) * 1998-09-22 2000-04-04 Dainippon Printing Co Ltd Pigment dispersing agent and photosensitive coloring composition
CN1334469A (en) * 2000-07-11 2002-02-06 新日铁化学株式会社 Method for making color filter and coloring photosensitive resin composition
JP2002296778A (en) * 2001-01-24 2002-10-09 Sumitomo Chem Co Ltd Color photosensitive composition

Also Published As

Publication number Publication date
TWI326296B (en) 2010-06-21
KR20040048306A (en) 2004-06-07
TW200422354A (en) 2004-11-01
KR101046889B1 (en) 2011-07-07
CN1504777A (en) 2004-06-16

Similar Documents

Publication Publication Date Title
CN1770012A (en) Staining light-sensitive resin composition
CN1143143C (en) Ink jet colour filter resin composition, colour filter and manufacturing method thereof
CN1079547C (en) Photosensitive resin composition
CN1782748A (en) Radiation sensitive composition for color filters, method for the preparation of the same and color liquid crystal display device
CN100350281C (en) Radioactive-ray sensitive composition for colour optical filter, colouring-layer for mation method and use
CN1991584A (en) Light solidification pigmentation composition and color filter, and liquid crystal display device
CN1690735A (en) Dyed layer forming radiation linear combination, colour filter and liquid crystal display screen
CN1677138A (en) Radiation-ray sensitive composition for colour-filtering piece, colour filtering piece and colour liquid crystal display device
CN1881081A (en) Radiation sensitive composition and color filter for forming coloration layer
CN1950751A (en) Radiation-sensitive resin composition, spacer, and method of forming the same
CN1683943A (en) Radioactive ray sensitive composition for forming coloring layer, color filter and color liquid crystal display plate
CN1532566A (en) Radiation sensitive composition for color filter
CN101046630A (en) Radiation sensibility composition for forming staining layer, color filter and color liquid crystal display element
CN1673780A (en) Radiation sensitive composition for repairing a color filter defect and method of repairing a color filter defect
CN101067723A (en) Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device
CN1707358A (en) Photosensitive resin composition
CN1821877A (en) Radiation sensitive resin composition for forming spacer, spacer, method for forming same and liquid crystal display element
CN1834164A (en) Pigmentation combination
CN1904735A (en) Painted photosensitive resin composition
CN1867640A (en) Pigment dispersion liquid, process for producing the same, colored resin composition, color filter and liquid crystal display
CN1696830A (en) Colored photosensitive resin composition
CN1916762A (en) Photosensitive resin composition, cushion for display panel and display panel
CN1577089A (en) Tinted photosensitive resin composition
CN1612042A (en) Colouring photosensitive resin composition
CN100351656C (en) Coloration-photosensitive resin composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20071128