CN101526739A - Radioactive ray sensitive composition, color filter and colourful liquid crystal display device for forming green pixel - Google Patents
Radioactive ray sensitive composition, color filter and colourful liquid crystal display device for forming green pixel Download PDFInfo
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- CN101526739A CN101526739A CN200910006742A CN200910006742A CN101526739A CN 101526739 A CN101526739 A CN 101526739A CN 200910006742 A CN200910006742 A CN 200910006742A CN 200910006742 A CN200910006742 A CN 200910006742A CN 101526739 A CN101526739 A CN 101526739A
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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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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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
Abstract
The invention provides a radioactive ray sensitive composition, a color filter and a colourful liquid crystal display device which can form green pixel with high brightness, good dispersion stability and sensitivity. The radioactive ray sensitive composition for forming the green pixel comprises A colorant, B alkaline solubility resin, C polyfunctional monomer and D radioactive ray sensitive polymerization initiator. The colorant A comprises C.I. everbright fast pigment green 58. The radioactive ray sensitive polymerization initiator D comprises a compound shown in formula (1), wherein R1-R4 are interdependent, respectively representing hydrogen atom, alkoxyl group with 1-18 carbon atoms or alkoxyl group with 1-18 carbon atoms.
Description
Technical field
The present invention relates to be used to form radiation-ray sensitive composition, color filter and the color liquid crystal display arrangement of green pixel, more particularly, relate to for the useful radiation-ray sensitive composition of manufacturing that is used in the color filter in transmission-type or reflection color liquid crystal device, the colour pick-up tube element etc.; The color filter that forms by this radiation-ray sensitive composition; And the color liquid crystal display device that possesses this color filter.
Background technology
As using colored radiation-sensitive composition to form the method for color filter, known have a following method: on the substrate or be pre-formed on the substrate of light shield layer of required pattern and form filming of colored radiation-sensitive composition, via photomask irradiation radioactive ray (hereinafter referred to as " exposure ") with predetermined pattern, develop, unexposed portion is removed in dissolving, carry out the back baking then, obtain each color pixel (for example with reference to patent documentation 1, patent documentation 2) thus.
The liquid crystal display cells that possesses above-mentioned color filter requires the expansion in high brightness and color rendition zone, therefore, also requires color filter to have the excitation of higher transmittance and Geng Gao in recent years.
About green pixel, as the material that the wide color filter in high brightness and color rendition zone can be provided, known have a color compositions that contains poly-zinc halide phthalocyanine color, is subjected to people's attention (for example with reference to patent documentation 3).But the dispersion stabilization that contains the color compositions that gathers the zinc halide phthalocyanine color is poor, therefore is easy to generate foreign matter, is difficult to be applied to volume production.
On the other hand, in the color filter technique field in recent years, employed substrate size maximizes day by day in the formation of color filter, meanwhile, reduction exposure, shortening productive temp time become main flow, therefore, when requiring colored radiation-sensitive composition to develop the damaged of pattern not taken place yet or peel off, promptly requires high sensitivity under low exposure.
Based on above background, press for exploitation and can form the also excellent and highly sensitive radiation-ray sensitive composition of the high green pixel of brightness, dispersion stabilization.
Patent documentation 1: Japanese kokai publication hei 2-144502 communique
Patent documentation 2: Japanese kokai publication hei 3-53201 communique
Patent documentation 3: TOHKEMY 2007-284589 communique
Summary of the invention
The object of the present invention is to provide and to form the high green pixel of brightness, dispersion stabilization radiation-ray sensitive composition also excellent and highly sensitive, that be used to form green pixel.
Another purpose of the present invention is to provide color filter that possesses the pixel that is formed by the above-mentioned radiation-ray sensitive composition that is used to form green pixel and the color liquid crystal display device that possesses this color filter.
In view of the foregoing, the inventor has carried out deep research, the unexpected discovery: by make poly-zinc halide phthalocyanine color C.I. naphthol green 58 with specific radiation-sensitive polymerization initiator combination, be contained in the radiation-ray sensitive composition, can solve above-mentioned problem, thereby finish the present invention.
Promptly, the invention provides the radiation-ray sensitive composition that is used to form green pixel, said composition contains (A) colorant, (B) alkali soluble resins, (C) multi-functional monomer and (D) radiation-sensitive polymerization initiator, wherein, (A) colorant contains C.I. naphthol green 58, and (D) the radiation-sensitive polymerization initiator contains the compound shown in the following formula (1):
(in the formula, R
1-R
4Independent separately, expression hydrogen atom, the alkyl of carbon number 1-18 or the alkoxy of carbon number 1-18).
The present invention also provides the color filter that possesses the pixel of using this radiation-ray sensitive composition to form and form, the color liquid crystal display device that possesses this color filter.
The radiation-ray sensitive composition of the application of the invention has the green pixel that does not produce foreign matter on high brightness, the pixel and also the damaged of pattern can not be taken place or peel off when developing even can form under low exposure.
Color filter of the present invention is for example extremely useful for transmission-type or reflection color liquid crystal display, colour pick-up tube element, color sensor etc.
Embodiment
In the radiation-ray sensitive composition (following abbreviate as sometimes " radiation-ray sensitive composition ") that is used to form green pixel of the present invention, (A) colorant contains C.I. naphthol green 58.In this case, the content of C.I. naphthol green 58 is preferred 20-100 quality % in all coloring agent, preferred especially 35-75 quality %.By using above-mentioned colorant, can obtain to have the green pixel of high brightness.
Radiation-ray sensitive composition of the present invention can further contain other colorant beyond the C.I. naphthol green 58.Other colorant is not particularly limited, because color filter requires the colour developing and the thermotolerance of high-purity, high light transmittance, and therefore preferred organic pigment.
Other organic pigment for example has the compound that is categorized as pigment in the colorant index, and the compound of following band colorant index (C.I.) numbering is specifically arranged.
C.I. pigment Green 7, C.I. pigment green 36;
C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 17, C.I. pigment yellow 20, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 55, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 166, C.I. pigment yellow 168, C.I. pigment yellow 211, C.I. pigment yellow 119;
C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 61, C.I. pigment orange 64, C.I. pigment orange 68, C.I. pigment orange 70, C.I. pigment orange 71, C.I. pigment orange 72, C.I. pigment orange 73, C.I. pigment orange 74;
C.I. paratonere 1, C.I. paratonere 2, C.I. paratonere 5, C.I. paratonere 17, C.I. pigment red 31, C.I. pigment red 32, C.I. pigment red 41, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 149, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 170, C.I. paratonere 171, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 178, C.I. paratonere 179, C.I. paratonere 180, C.I. paratonere 185, C.I. paratonere 187, C.I. paratonere 202, C.I. paratonere 206, C.I. Pigment Red 207, C.I. paratonere 209, C.I. pigment red 21 4, C.I. paratonere 220, C.I. paratonere 221, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 243, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 262, C.I. paratonere 264, C.I. paratonere 272;
These other organic pigments can be used alone or two or more kinds mixed.
In these other organic pigments, consider preferred C.I. pigment Green 7, C.I. pigment green 36, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 219 etc. from the angle that forms green pixel.
Among the present invention, C.I. naphthol green 58 and other pigment can be as required, by using behind recrystallization method, reprecipitation method, solvent wash method, sublimed method, vaccum heating method or their purifying such as combination.C.I. naphthol green 58 and other pigment can carry out using after the modification to its particle surface with polymkeric substance as required.The polymkeric substance of granules of pigments surface modification for example there are polymkeric substance that polymkeric substance described in the Japanese kokai publication hei 8-259876 communique or commercially available various pigment dispersing use or oligomer etc.
Among the present invention, consider that from the angle of the green pixel that forms high brightness (A) colorant preferably accounts for all solid 5-70 quality % that form in dividing, and especially preferably accounts for 5-60 quality %.Here, Gu the formation branch is the composition beyond the aftermentioned solvent.
About (B) alkali soluble resins contained in the radiation-ray sensitive composition of the present invention, as long as it has solubility to the alkaline developer that uses in the development treatment step when forming dyed layer, be not particularly limited, normally have the polymkeric substance of acidic functionalities such as carboxyl, phenolic hydroxyl.Wherein, the polymkeric substance that preferably contains the tool carboxyl, especially preferably have an above carboxyl ethylenically unsaturated monomers (hereinafter referred to as " containing the carboxyl unsaturated monomer ") but and the multipolymer (hereinafter referred to as " carboxy-containing copolymer ") of the ethylenically unsaturated monomers of other copolymerization (hereinafter referred to as " copolymerization unsaturated monomer ").
Containing the carboxyl unsaturated monomer for example has:
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;
One [(methyl) acryloxyalkyl] ester of the polybasic carboxylic acid that binary such as succinic acid one [2-(methyl) acryloxy ethyl] ester, phthalic acid one [2-(methyl) acryloxy ethyl] ester are above;
Two ends such as ω-carboxyl polycaprolactone one (methyl) acrylate have one (methyl) acrylate etc. of the polymkeric substance of carboxyl and hydroxyl.
Above-mentioned carboxylic unsaturated monomer can use separately or use mixing more than 2 kinds.
Among the present invention, contain preferred (methyl) acrylic acid of carboxyl unsaturated monomer, succinic acid one [2-(methyl) acryloxy ethyl] ester, ω-carboxyl polycaprolactone one (methyl) acrylate etc., preferred especially (methyl) acrylic acid.
These carboxylic unsaturated monomers can use separately or use mixing more than 2 kinds.
In the carboxy-containing copolymer, the copolymerization ratio that contains the carboxyl unsaturated monomer is preferably 5-50 quality %, further preferred 10-40 quality %.At this moment, this copolymerization ratio is lower than 5 quality %, then the gained radiation-ray sensitive composition has the tendency of reduction to the dissolubility of alkaline developer, and above 50 quality %, then excessive to the dissolubility of alkaline developer, when developing, have to cause pixel to come off or the coarse tendency of film on pixel surface easily from substrate with alkaline developer.
The copolymerization unsaturated monomer for example has:
Maleimide;
N-phenylmaleimide, N-o-hydroxy-phenyl maleimide, hydroxy phenyl maleimide between N-, N-p-hydroxybenzene maleimide, N-benzyl maleimide, N-cyclohexyl maleimide, N-succinimido-3-dimaleoyl imino benzoic ether, N-succinimido-4-dimaleoyl imino butyric ester, N-succinimido-6-dimaleoyl imino capronate, N-succinimido-3-dimaleoyl imino propionic ester, N-substituted maleimide amine such as N-(acridinyl) maleimide;
Styrene, α-Jia Jibenyixi, adjacent vinyltoluene, between vinyltoluene, to vinyltoluene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, adjacent vinylphenol, between vinylphenol, to vinylphenol, to hydroxyl-α-Jia Jibenyixi, adjacent vinyl benzyl methyl ether, between the vinyl benzyl methyl ether, to the vinyl benzyl methyl ether, adjacent vinyl benzyl glycidyl ether, between the vinyl benzyl glycidyl ether, to aromatic vinyl compounds such as vinyl benzyl glycidyl ethers;
Indenes classes such as indenes, 1-methyl indenes;
(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid 3-hydroxyl butyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) allyl acrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-phenoxy ethyl, (methyl) acrylic acid methoxyl diglycol ester, (methyl) acrylic acid methoxyl triethyleneglycol ester, (methyl) acrylic acid MPEG ester, (methyl) acrylic acid methoxyl dipropylene glycol ester, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring [5.2.1.0
2.6] decane-8-base ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, one (methyl) acrylic acid glyceride, (methyl) acrylic acid 4-hydroxylphenyl ester, to the esters of unsaturated carboxylic acids such as oxirane modification (methyl) acrylate of cumylphenol;
Unsaturated carboxylic acid ethylene oxidic esters such as (methyl) glycidyl acrylate;
Vinyl carboxylates such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate;
Other unsaturated ethers such as vinyl methyl ether, EVE, allyl glycidyl ether;
Vinyl cyanide based compounds such as (methyl) vinyl cyanide, α-Lv Bingxijing, vinylidene dinitrile;
Unsaturated amides such as (methyl) acrylamide, α-chloropropene acid amides, N-2-hydroxyethyl (methyl) acrylamide;
Aliphatic conjugated diene such as 1,3-butadiene, isoprene, chlorbutadiene;
The end of polymer molecular chains such as polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane has the macromonomer of one (methyl) acryloyl group etc.
These copolymerization unsaturated monomers can use separately or be use mixing two or more.
Among the present invention; the copolymerization unsaturated monomer preferably contains and is selected from N-substituted maleimide amine; aromatic vinyl compound; esters of unsaturated carboxylic acids; the end of polymer molecular chain has macromonomer at least a of one (methyl) acryloyl group; further preferably contain and be selected from N-phenylmaleimide; N-cyclohexyl maleimide; styrene; α-Jia Jibenyixi; to hydroxyl-α-Jia Jibenyixi; (methyl) methyl acrylate; (methyl) n-butyl acrylate; (methyl) 2-EHA; (methyl) acrylic acid 2-hydroxy methacrylate; (methyl) allyl acrylate; (methyl) benzyl acrylate; one (methyl) acrylic acid glyceride; (methyl) acrylic acid 4-hydroxylphenyl ester; oxirane modification (methyl) acrylate to cumylphenol; the polystyrene macromolecular monomer; polymethylmethacrylate macromonomer at least a especially preferably contains and is selected from N-phenylmaleimide; N-cyclohexyl maleimide; styrene; α-Jia Jibenyixi; (methyl) 2-EHA; one (methyl) acrylic acid glyceride at least a.
Among the present invention, for example the alkali soluble resins reaction that obtains by the copolymerization unsaturated monomer copolymerization that makes unsaturated isocyanate compound such as 2-(methyl) acryloxy ethyl isocyanate and (methyl) acrylic acid 2-hydroxyethyl ester etc. have hydroxyl can import the polymerism unsaturated link in the side chain of alkali soluble resins.
Alkali soluble resins among the present invention by gel permeation chromatography (GPC, eluting solvent: tetrahydrofuran) measure, be generally 1 through the weight-average molecular weight of polystyrene conversion (below be also referred to as " Mw "), 000-45,000, preferred 3,000-20,000.Mw is lower than 1,000, and the reductions such as residual film ratio of gained tunicle are then arranged, and pattern form, thermotolerance etc. are impaired, the possibility of electric properties deteriorate in addition, and surpass 45,000, then there is resolution to reduce, pattern form is impaired, in addition, is easy to generate the possibility of dry foreign matter when being coated with by the gap nozzle mode.
Alkali soluble resins of the present invention by gel permeation chromatography (GPC, eluting solvent: tetrahydrofuran) measure, be generally 1 through the number-average molecular weight of polystyrene conversion (below be also referred to as " Mn "), 000-45,000, preferred 3,000-20,000.
The ratio (Mw/Mn) of the Mw of alkali soluble resins of the present invention and Mn preferred 1.0-5.0, more preferably 1.0-3.0.
Alkali soluble resins of the present invention for example can be in appropriate solvent, 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-unsaturated monomer copolymerization such as (methyl) acrylic acid are prepared under the existence of azo two radical polymerization initiators such as (4-methoxyl-2,4-methyl pentane nitriles).
In addition; alkali soluble resins of the present invention for example can be 2; 2 '-azoisobutyronitrile; 2; 2 '-azo two (2; the 4-methyl pentane nitrile); 2; 2 '-azo two (4-methoxyl-2; the 4-methyl pentane nitrile) radical polymerization initiator such as; and pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters; pyrazoles-1-carbodithioic acid benzyl ester; Thiuram disulfide; two (pyrazol-1-yl thiocarbonyl) disulfide; two (3-methyl-pyrazol-1-yl thiocarbonyl) disulfide; two (4-methyl-pyrazol-1-yl thiocarbonyl) disulfide; two (5-methyl-pyrazol-1-yl thiocarbonyl) disulfide; two (3; 4; 5-trimethyl-pyrazol-1-yl thiocarbonyl) disulfide; two (pyrroles-1-base thiocarbonyl) disulfide; under the existence of the molecular weight regulator of performance such as two thiobenzoyl disulfide iniferter effect; in inert solvent; be generally 0-150 ℃; under preferred 50-120 ℃ the temperature of reaction, prepare by carrying out active free radical polymerization as each unsaturated compound of its constituent.
Alkali soluble resins of the present invention can also pass through will carry out the incompatible preparation of radical polymerization as each unsaturated monomer of its constituent in appropriate solvent in the presence of the multi-thiol compound of above-mentioned radical polymerization initiator and the effect of performance chain-transferring agent.Here, the multi-thiol compound is meant the compound that has 2 above mercaptos in 1 molecule, for example have: trimethylolpropane tris (3-mercaptopropionic acid ester), four (3-mercaptopropionic acid) pentaerythritol ester, two (3-mercaptopropionic acid) tetraethylene glycol ester, six (3-mercaptopropionic acid) dipentaerythritol ester, four (mercaptoacetic acid) pentaerythritol ester, 1, two (3-sulfydryl butyryl acyloxy) butane, four (the 3-sulfydryl butyric acid) pentaerythritol esters, 1 of 4-, 3,5-three (3-sulfydryl butyl oxygen base ethyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone etc.
Alkali soluble resins of the present invention can carry out purifying via the reprecipitation method that uses the organic solvent that polarity is different more than 2 kinds after as mentioned above polymerizable unsaturated compound being carried out free radical polymerization.That is, the solution in the good solvent after the polymerization is removed insoluble foreign matter by filter or centrifuging etc. as required, be injected into then in the precipitation agent (lean solvent) of a large amount of (5-10 that is generally the polymer solution volume doubly measures), make multipolymer precipitate purifying again.At this moment, remain in the foreign matter in the polymer solution, the soluble foreign matter of precipitation agent is remained in the liquid phase, separated in the alkali soluble resins by purifying.
The combination of the good solvent/precipitation agent that uses in this reprecipitation method for example has diethylene glycol monomethyl ether acetic acid esters/normal hexane, methyl ethyl ketone/normal hexane, diethylene glycol monomethyl ether acetic acid esters/normal heptane, methyl ethyl ketone/normal heptane etc.
Among the present invention, (B) content of alkali soluble resins is with respect to the common preferred 10-1 of 100 mass parts (A) colorant, 000 mass parts, preferred especially 20-500 mass parts.At this moment, the content of alkali soluble resins is lower than 10 mass parts, then for example there is alkali-developable to reduce, in the possibility that produces residue or scumming on the substrate of unexposed portion or on the light shield layer, and surpass 1,000 mass parts then has colorant concentration to reduce relatively, and film is difficult to realize the possibility of aim colour concentration.
(C) of the present invention multi-functional monomer is the monomer with 2 above polymerism unsaturated links.
Above-mentioned multi-functional monomer for example has:
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 their the dicarboxylic acid modifier of the polyvalent alcohol that ternarys such as glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol are above;
Oligomeric (methyl) acrylate such as polyester, epoxy resin, carbamate resins, alkyd resin, organic siliconresin, spirane resin;
Two terminal for hydroxyl poly--1,3-butadiene, two end be that hydroxyl polyisoprene, two ends are that two ends such as hydroxyl polycaprolactone are two (methyl) acrylate of hydroxy polymer;
Tricresyl phosphate [2-(methyl) acryloxy ethyl] ester or
Cyamelide oxirane modification triacrylate etc.
In these multi-functional monomers, poly-(methyl) esters of acrylic acid or their the dicarboxylic acid modifier of the polyvalent alcohol that preferred ternary is above.Specifically, preferred trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetracrylate, pentaerythritol tetramethacrylate, five acrylic acid dipentaerythritol ester, pentamethyl acrylic acid dipentaerythritol ester, six acrylic acid dipentaerythritol ester, hexamethyl acrylic acid dipentaerythritol ester, one carboxylate of pentaerythritol triacrylate and succinic acid, one carboxylate of trimethyl acrylic acid pentaerythritol ester and succinic acid, one carboxylate of five acrylic acid dipentaerythritol ester and succinic acid, one carboxylate of pentamethyl acrylic acid dipentaerythritol ester and succinic acid etc., intensity height from dyed layer, the surface smoothing excellence of dyed layer, and be difficult to produce scumming on the substrate of unexposed portion He on the light shield layer, the angle of the residual grade of film is considered, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate, five acrylic acid dipentaerythritol ester, six acrylic acid dipentaerythritol ester, one carboxylate of pentaerythritol triacrylate and succinic acid, an and carboxylate of five acrylic acid dipentaerythritol ester and succinic acids.
Above-mentioned multi-functional monomer can use separately or use mixing more than 2 kinds.
Among the present invention, (C) content of multi-functional monomer is with respect to 100 mass parts (B) alkali soluble resins, usually preferred 5-500 mass parts, preferred especially 20-300 mass parts.In this case, the content of multi-functional monomer is lower than 5 mass parts, and the intensity of pixel or the tendency of surface smoothing reduction are then arranged, and surpasses 500 mass parts, for example then there is alkali-developable reduce, producing residual etc. the tendency of scumming, film on the substrate of unexposed portion or on the light shield layer easily.
Among the present invention, also the part of multi-functional monomer can be replaced into simple function monomer with 1 polymerism unsaturated link.
Above-mentioned simple function monomer for example has: succinic acid one [2-(methyl) acryloxy ethyl ester]; one [(methyl) acryloxyalkyl] ester of the polybasic carboxylic acid that phthalic acid one binary such as [2-(methyl) acryloxy ethyl esters] is above; ω-two ends such as carboxyl polycaprolactone one (methyl) acrylate have one (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl; or N-(methyl) acryloyl morpholine; the N-vinyl pyrrolidone; N-vinyl-epsilon-caprolactams; in addition also has M-5600 (trade name, East Asia synthetic (strain) preparation) as the commercial goods etc.
These simple function monomers can use separately or use mixing more than 2 kinds.
The proportional total amount with respect to multi-functional monomer and simple function monomer that contains of simple function monomer of the present invention is preferably below the 90 quality %, more preferably below the 50 quality %.At this moment, the usage ratio of simple function monomer surpasses 90 quality %, and then pixel intensity or surface smoothing have the tendency of reduction.
(D) radiation-sensitive polymerization initiator that uses among the present invention is the exposure by visible light, ultraviolet ray, far ultraviolet, electron ray, X ray isoradial, and generation can cause above-mentioned (C) multi-functional monomer and the compound of the spike of the polymerization of the simple function monomer that uses according to situation.
Among the present invention,, can obtain radiation-ray sensitive composition highly sensitive and the dispersion stabilization excellence by containing the compound (D) shown in the above-mentioned formula (1) as the radiation-sensitive polymerization initiator.
Promptly, (diamido) benzophenone cpd isoradial susceptibility polymerization initiator has a plurality of amino usually mostly in molecule, the inventor considers that these a plurality of amino and C.I. naphthol green 58 interact, destroy disperse state, can produce foreign matter, carried out deep research for this reason, found that: the compound shown in the following formula (1) is the most suitable to be made up with C.I. naphthol green 58.
In the following formula (1), R
1And R
3Be preferably hydrogen atom, R
2And R
4Be preferably the alkyl of hydrogen atom or carbon number 1-12, R
2And R
4The alkyl of hydrogen atom or carbon number 1-6 more preferably.
The object lesson of the thioxanthones compounds shown in the following formula (1) has: thioxanthones, 2-methyl thioxanthones, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2-dodecyl thioxanthones, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones etc.
In these thioxanthones compounds, preferred 2-methyl thioxanthones, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones.
Among the present invention, the thioxanthones compounds can use separately or use mixing more than 2 kinds.
Among the present invention, preferably other radiation-sensitive polymerization initiator is used with above-mentioned thioxanthones compounds.In this case, consider that from the angle of dispersion stabilization the content of thioxanthones compounds is preferably 1-75 quality %, more preferably 5-50 quality % in the radiation-sensitive polymerization initiator.By using above-mentioned radiation-sensitive polymerization initiator, can obtain radiation-ray sensitive composition highly sensitive and the dispersion stabilization excellence.
Other radiation-sensitive polymerization initiator for example has: acetophenone compounds, bisglyoxaline compounds, compound in triazine class, O-acyl oxime compound, salt compounds, benzoin compounds, benzophenone compound, α-cyclohexadione compounds, polycyclic quinone compound, xanthone compounds, diazonium compounds, imino group sulfonates compounds etc.
Among the present invention, other radiation-sensitive polymerization initiator can use separately or use mixing more than 2 kinds, and other radiation-sensitive polymerization initiator of the present invention is preferably and is selected from least a of acetophenone compounds, bisglyoxaline compounds and O-acyl oxime compound.
In preferred other radiation-sensitive polymerization initiator of the present invention, the object lesson of acetophenone compounds has: 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 1,2-octane diketone etc.
In these acetophenone compounds, preferred especially 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone, 1,2-acetyl caproyl etc.
Above-mentioned acetophenone compounds can use separately or use mixing more than 2 kinds.
The object lesson of above-mentioned bisglyoxaline compounds has: 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-chlorphenyls)-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 these bisglyoxaline compounds, preferred 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-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
Above-mentioned bisglyoxaline compounds can use separately or use mixing more than 2 kinds.
Among the present invention, when using the bisglyoxaline compounds, consider, preferably be used in combination with following hydrogen donor from the angle that can further improve sensitivity as other radiation-sensitive polymerization initiator.
" hydrogen donor " described here is meant compound from hydrogen atom to the free radical that is produced by the bisglyoxaline compounds by exposure that can supply with.
The sulfur alcohol compound of the preferred following definitions of hydrogen donor of the present invention.
Above-mentioned sulfur alcohol compound comprises with phenyl ring or heterocycle as parent nucleus, has more than 1, preferred 1-3, the compound of further preferred 1-2 sulfydryl that directly combines with this parent nucleus.
Sulfur alcohol compound can have each phenyl ring or heterocycle more than 1, also can have phenyl ring and heterocycle.Have when these encircle more than 2, can form or not form fused rings.
When sulfur alcohol compound has 2 above sulfydryls, as long as residual at least one free sulfhydryl groups, promptly can being replaced more than 1 of remaining sulfydryl by alkyl, aralkyl or aryl, and then, as long as residual have at least one free sulfhydryl groups, promptly can have the structural unit of 2 sulphur atoms combination or 2 sulphur atoms structural unit with the form combination of disulfide by divalent organic group such as alkylidene.
The position of sulfur alcohol compound beyond sulfydryl can be further by replacements such as carboxyl, alkoxy carbonyl, substituted alkoxy carbonyl, phenyloxycarbonyl, substituent phenoxy carbonyl, itrile groups.
The object lesson of above-mentioned sulfur alcohol compound has: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-2,5-dimethyl aminopyridine etc.
In these sulfur alcohol compounds, preferred 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, preferred especially 2-mercaptobenzothiazole.
Among the present invention, sulfur alcohol compound can use separately or use mixing more than 2 kinds.
Among the present invention, when sulfur alcohol compound was used in combination with the bisglyoxaline compounds, the content of sulfur alcohol compound was with respect to below the preferred 1-300 mass parts of 100 mass parts bisglyoxaline compounds, below the preferred especially 5-200 mass parts, and further preferred 10-150.At this moment, the content of hydrogen donor is lower than 1 mass parts, and then the improved effect of sensitivity has the tendency of reduction, and surpasses 300 mass parts, and then formed dyed layer has the tendency that comes off from substrate easily when developing.
Above-mentioned O-acyl oxime compound is to have oxime ester structure (〉 C=N-O-CO-) compound.Its object lesson for example has: 1; 2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime); 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl]-nonane-1; 2-nonane-2-oxime-O-benzoic ether; 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl]-nonane-1; 2-nonane-2-oxime-O-acetic acid esters; 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl]-pentane-1; 2-pentane-2-oxime-O-acetic acid esters; 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl]-octane-1-ketoxime-O-acetic acid esters; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-ethyl-6-(1; 3; the 5-trimethylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-butyl-6-(2-ethylamino benzonitrile acyl group)-9H-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl group) ethyl ketone oxime; 1-[9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1,3-two oxa-s penta cyclic group) the methoxybenzoyl base]-9H-carbazole-3-yl]-1-(O-acetyl group) ethyl ketone oxime etc.
In these O-acyl oxime compounds; preferred especially 1; 2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl group) ethyl ketone oxime, 1-[9-ethyl-6-(2-methyl-4-(2; 2-dimethyl-1,3-two oxa-s penta cyclic group) the methoxybenzoyl base)-9H-carbazole-3-yl]-1-(O-acetyl group) ethyl ketone oxime etc.
Above-mentioned O-acyl oxime compound can use separately or use mixing more than 2 kinds.
Among the present invention, (D) content of radiation-sensitive polymerization initiator is with respect to the common preferred 0.01-120 mass parts of the multi-functional monomer of 100 mass parts (C), preferred especially 1-100 mass parts, further preferred 1-70 mass parts.In this case, the content of radiation-sensitive polymerization initiator is lower than 0.01 mass parts, the curing deficiency that then has exposure to cause, be difficult to obtain the pattern of pixels possibility of the color filter that forms of alignment arrangements according to the rules, and surpass 120 mass parts, the tendency that then has the pattern of pixels of formation when developing, to come off from substrate easily.
Radiation-ray sensitive composition of the present invention contains above-mentioned (A)-(D) composition, can also further contain other adjuvant as required.
Here, other adjuvant for example has filling agents such as glass, aluminium oxide; Macromolecular compounds such as polyvinyl alcohol (PVA), poly-(acrylic acid fluoroalkyl ester) class; Surfactants such as non-ionic surfactant, cationic surfactant, anionic surfactant; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, applying promoter such as 3-sulfydryl propyl trimethoxy silicane; 2, antioxidants 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; Alkali solubility improvers such as malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid etc.
Among the present invention, radiation-ray sensitive composition can be according to suitable method preparation, for example (A) composition and above-mentioned (B)-(D) composition and solvent described later or adjuvant can be mixed together and prepare, preferably in solvent, at spreading agent and the dispersing aid that adds as required in the presence of, according to circumstances, with the part of (A) colorant with (B) composition, for example use ball mill, pulverizing such as roller mill, mix simultaneously and disperse, make dispersible pigment dispersion, this dispersion liquid and (B)-(D) composition and the solvent that further appends as required or adjuvant are mixed prepare.
The spreading agent that uses in the preparation of above-mentioned dispersible pigment dispersion for example can use suitable spreading agents such as cationic, anionic species, nonionic class or both sexes, preferred polymers spreading agent.Alkylammonium salt or phosphate ester salt, kation sex comb type graft polymer etc. that modified acroleic acid analog copolymer, acrylic copolymer, polyurethane, polyester, high-molecular copolymer are arranged specifically.Here, kation sex comb type graft polymer is meant the polymkeric substance that has the structure that grafting on the trunk polymkeric substance of a plurality of basic groups (cationic functional group) forms in conjunction with the branch polymkeric substance more than 2 molecules at 1 molecule, for example has: by the trunk polymer moieties is that polyethyleneimine, branch polymer moieties are the polymkeric substance that the ring-opening polymerization polymer of 6-caprolactone constitutes.In these spreading agents, preferred modified acroleic acid analog copolymer, polyurethane, kation sex comb type graft polymer.
Above-mentioned spreading agent can obtain through commercial approach, for example the modified acroleic acid analog copolymer has: Disperbyk-2000, Disperbyk-2001, BYK-LPN 21116, BYK-LPN21324 (above) by BYK Chemie (BYK) preparation, polyurethane has: Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above) by BYK Chemie (BYK) preparation, Solsperse 76500 (Lubrizol (strain) preparation), kation sex comb type graft polymer has: Solsperse 24000 (Lubrizol (strain) preparation), AJISPER PB821, AJISPER PB822, AJISPER PB823, AJISPERPB824, AJISPER PB827 (preparation of aginomoto Fine-techno Co., Ltd.) etc.
These spreading agents can use separately or use mixing more than 2 kinds.The content of spreading agent is generally below 100 mass parts with respect to 100 mass parts (A) colorant, preferred 0.5-100 mass parts, further preferred 1-70 mass parts, preferred especially 10-50 mass parts.At this moment, the content of spreading agent surpasses 100 mass parts, and then development property etc. may be impaired.
The radiation-ray sensitive composition that is used to form dyed layer of the present invention is essential composition with above-mentioned (A)-(D) composition, contains above-mentioned additive component as required, also can cooperate solvent, makes liquid composition.
As long as above-mentioned solvent can with constitute (A)-(D) composition of radiation-ray sensitive composition or additive component disperses or dissolves and not with these compositions reactions, have the volatility of appropriateness, can suitably select use.
Above-mentioned solvent can exemplify following:
Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol one n-propyl ether, ethylene glycol one n-butyl ether, diethylene glycol monomethyl ether, carbitol, diglycol one n-propyl ether, diglycol one n-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol one ether, the propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol one positive propyl ether, propylene glycol one n-butyl ether, the dipropylene glycol monomethyl ether, dipropylene glycol one ether, dipropylene glycol one n-propyl ether, dipropylene glycol one n-butyl ether, the tripropylene glycol monomethyl ether, (gathering) aklylene glycol one alkyl ethers such as tripropylene glycol one ether;
Methyl glycol acetate, ethoxyethyl acetate(EA), diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetic acid esters, ethoxy propyl acetate, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-(gathering) aklylene glycol one alkyl ether acetic acid esters such as 3-methoxyl butyl propionic ester;
Ethers such as diethylene glycol dimethyl ether, diglycol MEE, diethyl carbitol, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Propylene glycol diacetate, oxalic acid 1,3 butylene glycol ester, oxalic acid 1, diacetate esters classes such as 6-hexanediol ester;
Lactic acid alkyl ester such as methyl lactate, ethyl lactate;
2-hydroxy-2-methyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl, the acetate isopentyl, n-butyl propionate, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other ester classes such as 2-ketobutyric acid ethyl ester;
Aromatic hydrocarbon such as toluene, dimethylbenzene;
N, acid amides or lactams such as dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone.
In these solvents, from pigment-dispersing, the dissolubility of the composition beyond the pigment, the coating equal angles is considered, preferred propylene glycol monomethyl ether, methyl glycol acetate, propylene glycol monomethyl ether acetic acid esters, ethoxy propyl acetate, diethylene glycol dimethyl ether, the diglycol methyl ethyl ether, cyclohexanone, the 2-heptanone, the 3-heptanone, propylene glycol diacetate, oxalic acid 1, the 3-butanediol ester, oxalic acid 1,6-hexanediol ester, ethyl lactate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, acetate 3-methoxyl butyl ester, propionic acid 3-methyl-3-methoxyl butyl ester, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate.
Above-mentioned solvent can use separately or use mixing more than 2 kinds.
Also can be used in combination high boiling solvents such as benzyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol one phenyl ether acetic acid esters with above-mentioned solvent.
Above-mentioned high boiling solvent can use separately or use mixing more than 2 kinds.
The content of solvent is not particularly limited, consider from the coating of gained radiation-ray sensitive composition, stable equal angles, the content of preferred solvent make removing of said composition the total concentration of each composition outside the solvent be generally 5-50 quality %, particularly 10-40 quality %.
Color filter of the present invention possesses the green pixel that is formed by radiation-ray sensitive composition of the present invention.
Below describe for the method that forms color filter of the present invention.
At first, on the surface of substrate, form light shield layer as required, form the part of pixel with zoning, coating is dispersed with the liquid composition of the radiation-ray sensitive composition of viridine green of the present invention on this substrate, carry out preliminary drying then, make solvent evaporation, formation is filmed.Then, via photomask this is filmed and to expose, use alkaline developer to develop then, the unexposed portion of filming is removed in dissolving, forms the pel array of green pattern of pixels alignment arrangements in accordance with regulations then by the back baking.
Then, use is dispersed with the liquid composition of each radiation-ray sensitive composition of redness or blue pigment, with above-mentioned coating, preliminary drying, exposure, development and the back baking of similarly carrying out each liquid composition, on same substrate, form red pel array and blue pixels array successively, obtain the color filter that redness, green and blue trichromatic pel array dispose on substrate.But, among the present invention, the order that forms each color pixel is not limited to above-mentioned.
Employed substrate for example can be glass, silicon, polycarbonate, polyester, aromatic poly amide, polyamidoimide, polyimide etc. when forming pixel.
Also can be as required these substrates be implemented to use the suitable pre-treatments such as agent treated, Cement Composite Treated by Plasma, ion plating processing, sputter, gas-phase reaction method, vacuum evaporation of silane coupling agents etc.
When being coated on the liquid composition of radiation-ray sensitive composition on the substrate, can adopt spraying process, rolling method, spin-coating method, seam pattern rubbing method, rod to be coated with suitable rubbing methods such as method, ink-jet method, preferred especially spin-coating method, seam pattern rubbing method.
Coating thickness is generally 0.1-10 μ m according to dried thickness, preferred 0.2-8.0 μ m, preferred especially 0.2-6.0 μ m.
The radioactive ray that use when forming pixel for example can use visible light, ultraviolet ray, far ultraviolet, electron ray, X ray etc., and optimal wavelength is at the radioactive ray of 190-450nm scope.
The usually preferred 10-10 of the exposure of radioactive ray, 000J/m
2Even radiation-ray sensitive composition of the present invention is at 400J/m
2Under the following exposure, the pattern of pixels in the time of also can not developing damaged or peel off.
The for example preferred sodium carbonate of above-mentioned alkaline developer, NaOH, potassium hydroxide, Tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecylene, 1, the aqueous solution of 5-diazabicyclo-[4.3.0]-5-nonene etc.
Also can suitably add for example water-miscible organic solvent such as methyl alcohol, ethanol or surfactant etc. in the above-mentioned alkaline developer.Alkali is washed after developing usually.
Developing method can adopt spray development method, spray development method, immersion development method, puddle formula development method etc.Development conditions preferably is 5-300 second at normal temperatures.
Above-mentioned color filter brightness height of the present invention and the range of color reproduction that obtains is wide, and be therefore extremely useful in color liquid crystal display device, colour pick-up tube element, color sensor etc.
Color liquid crystal display device of the present invention possesses color filter of the present invention.
An embodiment as color liquid crystal display device of the present invention, the radiation-ray sensitive composition that is used to form dyed layer of the application of the invention, on the thin film transistor base plate array, form pixel as mentioned above, can prepare the color liquid crystal display device that brightness is high especially and range of color reproduction is wide.
Embodiment
Below provide embodiment, further specify embodiment of the present invention, but the present invention is not limited to following embodiment.
The preparation of dispersible pigment dispersion
Preparation example 1
To contain 40 mass parts as Disperbyk-2001 (BYK Chemie (BYK) preparation of the potpourri of 60/40 (mass ratio) of the C.I. naphthol green 58 of (A) colorant and C.I. pigment yellow 150,24 mass parts as spreading agent, Gu form to divide concentration 45.1 quality %) and 136 mass parts mix with ball mill as the mixed liquor of the propylene glycol monomethyl ether acetic acid esters of solvent and disperseed preparation dispersible pigment dispersion (A-1) 12 hours.
Preparation example 2
To contain 40 mass parts as Disperbyk-2001 (BYK Chemie (BYK) preparation of the potpourri of 40/60 (mass ratio) of the C.I. naphthol green 58 of (A) colorant and C.I. pigment yellow 13 8,24 mass parts as spreading agent, Gu form to divide concentration 45.1 quality %) and 136 mass parts mix with ball mill as the mixed liquor of the propylene glycol monomethyl ether acetic acid esters of solvent and disperseed preparation dispersible pigment dispersion (A-2) 12 hours.
Preparation example 3
To contain 40 mass parts as Disperbyk-2001 (BYK Chemie (BYK) preparation of the potpourri of 19/41/40 (mass ratio) of C.I. naphthol green 58, C.I. pigment green 36 and the C.I. pigment yellow 150 of (A) colorant, 24 mass parts as spreading agent, Gu form to divide concentration 45.1 quality %) and 136 mass parts mix with ball mill as the mixed liquor of the propylene glycol monomethyl ether acetic acid esters of solvent and disperseed preparation dispersible pigment dispersion (A-3) 12 hours.
Preparation example 4
To contain 40 mass parts as Disperbyk-2001 (BYK Chemie (BYK) preparation of the potpourri of 55/45 (mass ratio) of the C.I. pigment green 36 of (A) colorant and C.I. pigment yellow 150,24 mass parts as spreading agent, Gu form to divide concentration 45.1 quality %) and 136 mass parts mix with ball mill as the mixed liquor of the propylene glycol monomethyl ether acetic acid esters of solvent and disperseed preparation dispersible pigment dispersion (A-4) 12 hours.
Synthesis example 1
(B) alkali soluble resins is synthetic
To possessing condenser pipe, add 2.5 mass parts 2 in the flask of stirring machine, 2 '-azo two (2, the 4-methyl pentane nitrile) and 200 mass parts methyl glycol acetates, then add 15 mass parts methacrylic acids, 10 mass parts ω-carboxyls, two caprolactones, one acrylate, 15 mass parts N-phenylmaleimides, 33 mass parts methacrylic acid 2-ethylhexyls, 12 mass parts styrene, 15 mass parts monomethyl acrylic acid glyceride and 5.0 mass parts α-Jia Jibenyixi dimers (chain-transferring agent), carry out the nitrogen displacement, slowly stir then, reaction solution is warming up to 80 ℃, keeps this temperature polyase 13 hour.Reaction solution is warming up to 100 ℃ then, appends 0.5 mass parts 2,2 '-azo two (2, the 4-methyl pentane nitrile) continued polymerization 1 hour again, obtained resin solution (Gu forming branch concentration=30 quality %).The Mw=14 of gained resin, 000, Mn=5,700.This resin solution is called " resin solution (B-1) ".
Embodiment 1
The preparation of liquid composition
Use 400 mass parts dispersible pigment dispersions (A-1); 200 mass parts resin solutions (B-1) as (B) alkali soluble resins; 60 mass parts, six acrylic acid dipentaerythritol ester as (C) multi-functional monomer; 6 mass parts 2 as (D) radiation-sensitive polymerization initiator; the 4-diethyl thioxanthone; 5 mass parts 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yls]-(the Ciba Specialty Chemicals preparation of 1-(O-acetyl group) ethyl ketone oxime; trade name IRGACUREOX02); 2 mass parts 2; 2 '-two (2-chlorphenyls)-4; 5; 4 '; 5 '-tetraphenyl-1; 2 '-bisglyoxaline and 2 mass parts 2-mercaptobenzothiazoles; and mix as the propylene glycol monomethyl ether acetic acid esters of solvent; make solid formation branch concentration reach 20.0%, preparation liquid composition (G1).
In the following order liquid composition (G1) is estimated, evaluation result is shown in Table 2.
The evaluation of foreign matter and sensitivity
Use the spin coating instrument that liquid composition (G1) is coated on the soda-lime glass substrate and (be formed with the SiO that prevents surperficial stripping sodion on this substrate
2Film), uses 90 ℃ hot plate preliminary drying 100 seconds then, form filming of thickness 2.5 μ m.
Then, this substrate is cooled to room temperature, uses high-pressure sodium lamp then, via photomask (slit width 90 μ m), with contain the radioactive ray of 365nm, 405nm and each wavelength of 436nm, with 400J/m
2Exposure expose to filming, then with development pressure 110kPa, 1.2L/ minute condition of developer solution flow, contained 23 ℃, 30 ℃ developer solution of 0.04 quality % potassium hydroxide aqueous solution to this substrate ejection, spray development thus with 90 seconds.Then that this substrate is also air-dry with the ultrapure water washing, further in 220 ℃ cleaning oven, carry out 30 minutes back baking, on substrate, form green striated pattern of pixels and arrange the pel array that forms.
By the pattern of pixels on the observation by light microscope gained substrate, on pattern of pixels, do not see foreign matter, pattern edge is not seen damaged.
Chromaticity evaluation
Use spin coating instrument changes revolution, liquid composition (G1) is coated on the soda-lime glass substrate (be formed with the SiO that prevents surperficial stripping sodion on this substrate
2Film), is coated with 3 plate bases, uses 90 ℃ hot plate preliminary drying 4 minutes then, form different 3 of thickness and film.
Then, these substrates are cooled to room temperature, use high-pressure sodium lamp then, via photomask, with contain the radioactive ray of 365nm, 405nm and each wavelength of 436nm, with 400J/m
2Exposure expose to filming, then with development pressure 1kgf/cm
2(nozzle diameter 1mm) contains 23 ℃, the developer solution of 0.04 quality % potassium hydroxide aqueous solution to the ejection of these substrates, sprays development thus.Then that this substrate is also air-dry with the ultrapure water washing, further in 220 ℃ cleaning oven, carry out 30 minutes back baking, on substrate, form the dot pattern of 200 * 200 μ m.
For the gained dot pattern, use color analysis instrument (Da mound electronics (strain) system, MCPD2000), with illuminant-C, the 2 degree visuals field measure the CIE color specification systems chromaticity coordinate value (x, y) and values (Y).Obtain chromaticity coordinate value x, values (Y) under certain chromaticity coordinate value y by measurement result.Evaluation result is as shown in table 2.The Y value is big more represents that then transmittance (brightness) is high more.
Embodiment 2-6 and comparative example 1-8
With the kind and the amount change as shown in table 2 of the constituent among the embodiment 1, in addition carry out preparation liquid composition (G2)-(G14) similarly to Example 1.
Then, use liquid composition (G2)-(G14) to replace liquid composition (G1) respectively, in addition estimate similarly to Example 1.The result is as shown in table 2.
C-1: six acrylic acid dipentaerythritol ester
D-1:2, the 4-diethyl thioxanthone
The potpourri of D-2:2-isopropyl thioxanthone and 4-isopropyl thioxanthone (trade name DAROCUREIDX, Ciba Specialty Chemicals preparation)
D-3:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl group) ethyl ketone oxime (trade name IRGACURE OX02, Ciba Specialty Chemicals preparation)
D-4:2,2 '-two (2-chlorphenyl)-4,5,4 ', 5 '-tetraphenyl-1,2 '-bisglyoxaline
The D-5:2-mercaptobenzothiazoler
D-6:2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone (trade name IRUGACURE369, Ciba Specialty Chemicals preparation)
D-7: benzophenone
D-8:2,4-diethylamino benzophenone
D-9:2,4-dimethylamino benzophenone
Table 2
| Liquid composition | Foreign matter | Pattern is damaged | Colourity x | Chromaticity y | The Y value | |
| Embodiment 1 | G1 | Do not have | Do not have | 0.292 | 0.600 | 57.8 |
| Embodiment 2 | G2 | Do not have | Do not have | 0.292 | 0.600 | 57.5 |
| Embodiment 3 | G3 | Do not have | Do not have | 0.332 | 0.540 | 74.0 |
| Embodiment 4 | G4 | Do not have | Do not have | 0.292 | 0.600 | 55.6 |
| Embodiment 5 | G5 | Do not have | Do not have | 0.292 | 0.600 | 57.7 |
| Embodiment 6 | G6 | Do not have | Have | 0.292 | 0.600 | 57.6 |
| Comparative example 1 | G7 | Have | Do not have | 0.292 | 0.600 | 57.6 |
| Comparative example 2 | G8 | Have | Do not have | 0.292 | 0.600 | 57.5 |
| Comparative example 3 | G9 | Do not have | Have | 0.292 | 0.600 | 57.9 |
| Comparative example 4 | G10 | Have | Do not have | 0.332 | 0.540 | 74.2 |
| Comparative example 5 | G11 | Do not have | Do not have | 0.292 | 0.600 | 54.6 |
| Comparative example 6 | G12 | Have | Do not have | 0.292 | 0.600 | 55.8 |
| Comparative example 7 | G13 | Do not have | Have | 0.292 | 0.600 | 57.6 |
| Comparative example 8 | G14 | Have | Have | 0.292 | 0.600 | 57.5 |
By table 1 and table 2 as can be known, use C.I. naphthol green 58,, and do not have the foreign matter generation on the pixel, do not see the damaged of pattern as (Y value) height of the transmittance of luminance index as colorant, when using the thioxanthones compounds as polymerization initiator.
Claims (4)
1. be used to form the radiation-ray sensitive composition of green pixel, said composition contains (A) colorant, (B) alkali soluble resins, (C) multi-functional monomer and (D) radiation-sensitive polymerization initiator, (A) colorant contains C.I. naphthol green 58, and (D) the radiation-sensitive polymerization initiator contains the compound shown in the following formula (1):
In the formula, R
1-R
4Separate, expression hydrogen atom, the alkyl of carbon number 1-18 or the alkoxy of carbon number 1-18.
2. the described radiation-ray sensitive composition of claim 1, wherein, (D) the radiation-sensitive polymerization initiator further contains at least a compound that is selected from acetophenone compounds, bisglyoxaline compounds and O-acyl group oxime compound.
3. color filter, this color filter possess the pixel of using claim 1 or 2 described radiation-ray sensitive compositions to form.
4. liquid crystal display cells, this liquid crystal display cells possesses the described color filter of claim 3.
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| JP (2) | JP5527965B2 (en) |
| KR (1) | KR20090091016A (en) |
| CN (2) | CN101526739A (en) |
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| KR101422851B1 (en) * | 2008-04-10 | 2014-08-14 | 동우 화인켐 주식회사 | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
| JP5546801B2 (en) * | 2008-06-10 | 2014-07-09 | 富士フイルム株式会社 | Photosensitive resin composition for ultraviolet light laser exposure, pattern forming method, color filter produced using the method, method for producing color filter, and liquid crystal display device |
| JP5720670B2 (en) * | 2010-02-24 | 2015-05-20 | Jsr株式会社 | Color filter and color liquid crystal display element |
| TWI477904B (en) * | 2010-03-26 | 2015-03-21 | Sumitomo Chemical Co | Photosensitive resin composition |
| JP5726462B2 (en) * | 2010-09-01 | 2015-06-03 | 富士フイルム株式会社 | Colored photosensitive composition, method for producing color filter, color filter, and liquid crystal display device |
| JP2012203361A (en) * | 2011-03-28 | 2012-10-22 | Mitsubishi Chemicals Corp | Coloring resin composition, color filter, liquid crystal display device, and organic el display device |
| JP2013011867A (en) * | 2011-05-31 | 2013-01-17 | Sumitomo Chemical Co Ltd | Colored photosensitive resin composition |
| JP6503156B2 (en) * | 2014-03-10 | 2019-04-17 | 東洋インキＳｃホールディングス株式会社 | Colored composition for solid-state imaging device and color filter |
| KR102371945B1 (en) * | 2017-11-03 | 2022-03-08 | 동우 화인켐 주식회사 | Colored Photosensitive Resin Composition, Color Filter and Display Device |
| CN111752096B (en) * | 2019-03-29 | 2022-10-14 | 常州正洁智造科技有限公司 | Photosensitive resin composition for color filter and color filter |
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| JP2812583B2 (en) * | 1991-05-31 | 1998-10-22 | 日本化薬株式会社 | Photopolymer composition for color filter |
| JPH1055064A (en) * | 1996-08-08 | 1998-02-24 | Mitsubishi Chem Corp | Color resist composition and color filter |
| JP3940547B2 (en) * | 2000-06-14 | 2007-07-04 | Ｊｓｒ株式会社 | Color filter |
| KR100839573B1 (en) * | 2001-02-23 | 2008-06-19 | 디아이씨 가부시끼가이샤 | Color filter |
| WO2003072614A2 (en) * | 2002-02-28 | 2003-09-04 | Showa Denko K.K. | Thiol compound, photopolymerization initiator composition and photosensitive composition |
| KR101075686B1 (en) * | 2006-01-13 | 2011-10-21 | 토요잉크Sc홀딩스주식회사 | Diketooxime ester compound and use thereof |
| JP5275548B2 (en) * | 2006-03-30 | 2013-08-28 | 三菱化学株式会社 | Green pigment dispersion, colored resin composition, color filter, and liquid crystal display device |
| JP5141939B2 (en) * | 2006-04-18 | 2013-02-13 | Ｄｉｃ株式会社 | Polyhalogenated zinc phthalocyanine pigment composition and color filter |
| JP4631808B2 (en) * | 2006-06-08 | 2011-02-16 | 住友化学株式会社 | Colored photosensitive resin composition |
| JP2007333885A (en) * | 2006-06-13 | 2007-12-27 | Toyo Ink Mfg Co Ltd | Photosensitive colored composition and color filter formable from the same |
| WO2008156148A1 (en) * | 2007-06-21 | 2008-12-24 | Mitsubishi Chemical Corporation | Pigment dispersion, coloring composition for color filter, color filter, liquid crystal display and organic el display |
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| JP5527965B2 (en) | 2014-06-25 |
| TWI454846B (en) | 2014-10-01 |
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| TW200941139A (en) | 2009-10-01 |
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