CN100443931C - Radiation sensitive composition and method for the preparation of the same - Google Patents

Radiation sensitive composition and method for the preparation of the same Download PDF

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Publication number
CN100443931C
CN100443931C CNB2005100844237A CN200510084423A CN100443931C CN 100443931 C CN100443931 C CN 100443931C CN B2005100844237 A CNB2005100844237 A CN B2005100844237A CN 200510084423 A CN200510084423 A CN 200510084423A CN 100443931 C CN100443931 C CN 100443931C
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pigment
methyl
paratonere
acrylate
radiation sensitive
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CN1758077A (en
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绫部真嗣
河本达庆
长塚富雄
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JSR Corp
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Abstract

A radiation-sensitive composition for the color filter contains (A) a pigment, (B) an alkali soluble resin, (C) a polyfunctional monomer, and (D) a radiation-sensitive radical generating agent. (A) The pigment contains 5 wt% or greater of a C.I. pigment yellow 219, and an average particle radius r (unit nm) of (A) the pigment is more than or equal to 50 and less than or equal to 300.

Description

Radiation sensitive compositions and modulation method thereof
Technical field
The present invention relates to radiation sensitive compositions and modulation method thereof, colored filter and color liquid crystal display device.In more detail, the color liquid crystal display device that relate to the employed radiation sensitive compositions of manufacturing of the colored filter that uses in transmission-type or reflection-type color liquid crystal device, the colour development tube elements etc. and modulation method thereof, has the colored filter of the pixel that forms by this radiation sensitive compositions and possess this colored filter.
Background technology
The colored filter that forms as using painted radiation sensitive compositions, known method (opening flat 2-144502 communique and the spy opens flat 3-53201 communique with reference to the spy) is: on the substrate or be pre-formed on the substrate of light shield layer of pattern of expectation, form filming of painted radiation composition, photomask irradiation radioactive ray by having predetermined pattern (below be called " exposure ", unexposed portion is removed in development and dissolving, back baking afterwards obtains each color pixel thus.
The liquid crystal display cells that possesses this colored filter is just being sought its high briliancyization, for this reason,, also more and more requiring its high transmission rate in recent years for colored filter.
In addition, in recent years, along with popularizing of Digital Video and high definition television etc., color liquid crystal display device is also more and more higher to showing as the requirement of the high color density of the redness as the mazarine as the seawater in winter and the pure red setting sun.And when showing this high color density, because black display portion " deceive " can't clearly show and soft edge does not have the picture of level, in high color density, requirement has high-contrast.Therefore, seek just strongly in recent years to develop and satisfy radiation-ray sensitive composition for colour-filtering piece high transmission rate and contrast, that can form redness and green pixel.
Generally, contain yellow uitramarine in redness and the green pixel, known this can influence transmittance and contrast greatly.In the past, the main C.I. pigment yellow 83 that uses in the yellow uitramarine, the transmittance and the contrast of the pixel that is obtained by the painted radiation sensitive compositions that contains the C.I. pigment yellow 83 do not reach enough levels, more images with high image quality also can't be satisfactory if want to provide.
Summary of the invention
The objective of the invention is to, provide to form the high red pixel of transmittance and contrast and the radiation-ray sensitive composition for colour-filtering piece of green pixel.
Other purposes of the present invention are, the modulation method of above-mentioned radiation-ray sensitive composition for colour-filtering piece is provided.
Other purposes of the present invention also are, colored filter with the pixel that is formed by above-mentioned radiation-ray sensitive composition for colour-filtering piece and the color liquid crystal display device that possesses this colored filter are provided.
Can know clearly other purposes of the present invention and advantage by the following description.
Utilize the present invention, above-mentioned purpose of the present invention and advantage, first, reach by a kind of sense radioactivity composition, it contains (A) pigment, (B) alkali soluble resin, (C) multi-functional monomer and (D) radioactivity-sensitive free radical generating agent, it is characterized in that (A) pigment contains the C.I. pigment yellow 219 of 35～75 weight %, and (A) the mean grain size r of pigment (nm of unit) is 50≤r≤300, and is used for the manufacturing of colored filter.
In preferred embodiments, above-mentioned (A) pigment also contains the C.I. pigment green 36, is used to form green pixel.
In another embodiment preferred, above-mentioned (A) pigment also contains the pigment of at least a C.I. of being selected from paratonere 177, C.I. paratonere 242 and C.I. paratonere 254, is used to form red pixel.
" radioactive ray " among the present invention comprise visible light, ultraviolet ray, far ultraviolet, electron ray, X ray etc.
Utilize the present invention, above-mentioned purpose of the present invention and advantage, second, reach by a kind of modulation method of feeling the radioactivity composition, it is characterized in that, with dispersible pigment dispersion and (B) alkali soluble resin, (C) multi-functional monomer and (D) the radioactivity-sensitive free radical generating agent mix mutually and generate radiation-ray sensitive composition for colour-filtering piece, described dispersible pigment dispersion is to contain the C.I. pigment yellow 219 of 35～75 weight %, (A) pigment that mean grain size surpasses 300nm mixes dispersion while pulverizing and obtains in solvent, wherein the mean grain size r of (A) pigment (nm of unit) is the dispersible pigment dispersion of 50≤r≤300.
In preferred embodiments, above-mentioned (A) pigment also contains the C.I. pigment green 36, is used to form green pixel.
In another embodiment preferred, above-mentioned (A) pigment also contains the pigment of at least a C.I. of being selected from paratonere 177, C.I. paratonere 242 and C.I. paratonere 254, is used to form red pixel.Utilize the present invention, above-mentioned purpose of the present invention and advantage, the 3rd, to reach by a kind of colored filter, it has red pixel and/or the green pixel that is formed by above-mentioned radiation sensitive compositions.
Utilize the present invention, above-mentioned purpose of the present invention and advantage, the 4th, to reach by a kind of color liquid crystal display arrangement, it possesses above-mentioned colored filter.
Embodiment
Below, be elaborated for the present invention.
Radiation-ray sensitive composition for colour-filtering piece
(A) pigment
Pigment among the present invention contains Colour Index (C.I.; The Society of Dyers andColourists company publishes.Down together.) in C.I. pigment yellow 219.
Pigment among the present invention according to circumstances can also contain other pigment.
Other pigment as above-mentioned are not particularly limited, but consider and require colored filter to have the color development and the thermotolerance of high-purity, high light transmittance, preferred organic pigment.
As other organic pigments, the compound that is classified as pigment in Colour Index is for example arranged, can list the material that is composed of following Colour Index (C.I.) number particularly.
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 Green 7, C.I. pigment green 36;
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.
In these other organic pigments, other organic pigments during as the formation red pixel, preference such as C.I. paratonere 177, C.I. paratonere 242, C.I. paratonere 254 etc., and other organic pigments when forming green pixel, preference such as C.I. pigment yellow 13 8, C.I. pigment yellow 150, C.I. pigment green 36 etc.
Above-mentioned other organic pigments, can separately or mix 2 kinds with on use.
In the pigment of the present invention, the content of C.I. pigment yellow 219 is more than the 5 weight %, is preferably 20～90 weight %, is preferably 35～75 weight % especially.By using this pigment, can obtain showing good development, high-contrast, and the redness and the green pixel of high transmission rate, no foreign matter.
Among the present invention, C.I. pigment yellow 219 and other pigment as required, can utilize recrystallization method, reprecipitation method, solvent wash method, sublimed method, vaccum heating method or their combination etc. to make with extra care and use.
The mean grain size r of the pigment that uses among the present invention (nm of unit) wishes can satisfy 50≤r≤300, preferred 100≤r≤300, preferred especially 50≤r≤200.By using the pigment of this mean grain size r, can obtain high-contrast, and the red and green pixel of high transmission rate.At this, " mean grain size " is meant the mean grain size of the offspring that primary particle (single crystallite) set of pigment forms.
In addition, the size distribution of the offspring of pigment used in the present invention (below abbreviate " size distribution " as.) for the offspring that meets (mean grain size ± 100) nm is more than all 70 weight %, be preferably more than the 80 weight %.
With commercially available C.I. pigment yellow 219 (mean grain size surpasses 300nm usually), with other pigment that use as required (mean grain size surpasses 300nm usually), preferably as the pigment mixed liquor that forms with spreading agent and solvent, for example use comminutors such as ball mill, roller mill, modulate pigment with above-mentioned mean grain size and size distribution by in solvent, mixing dispersion while pulverizing.The pigment that obtains thus is generally the form of dispersible pigment dispersion.
As the employed spreading agent of dispersible pigment dispersion, for example can list suitable spreading agents such as cationic, anionic species, both sexes and nonionic class, preferably contain compound with ammonia ester bond (below be sometimes referred to as " ammonia ester class spreading agent ".) spreading agent.
Above-mentioned ammonia ester bond can be present in preferred formula R-NH-COO-R ', and (at this, R and R ' are the organic group of aliphatics, alicyclic or aromatic 1 valency or multivalence, and the organic group of this multivalence further has group or other group bondings of ammonia ester bond with other.) in the lipophilicity group and/or hydrophilic radical in the represented ammonia ester class spreading agent, maybe can be present in the main chain and/or side chain of ammonia ester class spreading agent, also can in ammonia ester class spreading agent, exist more than 1.There are 2 in ammonia ester bond when above in ammonia ester class spreading agent, each ammonia ester bond can be the same or different.
As this ammonia ester class spreading agent, for example, can list diisocyanate and/or triisocyanate and have the polyester of hydroxyl and/or have the reaction product of the polyester of hydroxyl at two ends at an end.
As above-mentioned diisocyanate, can list, for example, benzene-1,3-diisocyanate, benzene-1, phenylene diisocyanates such as 4-diisocyanate; Toluene-2,4-diisocyanate, 4-diisocyanate, Toluene-2,4-diisocyanate, 5-diisocyanate, Toluene-2,4-diisocyanate, 6-diisocyanate, Toluene-3,4-dithiol, toluene diisocyanates such as 5-diisocyanate; 1,2-dimethylbenzene-3,5-diisocyanate, 1,2-dimethylbenzene-3,6-diisocyanate, 1,3-dimethylbenzene-2,4-diisocyanate, 1,3-dimethylbenzene-2,5-diisocyanate, 1,3-dimethylbenzene-4,6-diisocyanate, 1,4-dimethylbenzene-2,5-diisocyanate, 1,4-dimethylbenzene-2, other aromatic diisocyanates such as Xylene Diisocyanate such as 6-diisocyanate.
In addition,, can list as above-mentioned triisocyanate, for example, benzene-1,2,4-triisocyanate, benzene-1,2,5-triisocyanate, benzene-1,3, benzene triisocyanates such as 5-triisocyanate; Toluene-2,4-diisocyanate, 3,5-triisocyanate, Toluene-2,4-diisocyanate, 3,6-triisocyanate, Toluene-2,4-diisocyanate, 4,5-triisocyanate, Toluene-2,4-diisocyanate, 4, toluene triisocyanates such as 6-triisocyanate; 1,2-dimethylbenzene-3,4,5-triisocyanate, 1,2-dimethylbenzene-3,4,6-triisocyanate, 1,3-dimethylbenzene-2,4,5-triisocyanate, 1,3-dimethylbenzene-2,4,6-triisocyanate, 1,3-dimethylbenzene-4,5,6-triisocyanate, 1,4-dimethylbenzene-2,3,5-triisocyanate, 1,4-dimethylbenzene-2,3, other aromatic series triisocyanates such as dimethylbenzene triisocyanate such as 6-triisocyanate.
These diisocyanate and triisocyanate can distinguish separately or mix 2 kinds with on use.
Have the polyester of hydroxyl and have the polyester of hydroxyl at an end as above-mentioned at two ends, can list, for example, terminal or two ends have hydroxyl polycaprolactone, have the poly-valerolactone of hydroxyl at terminal or two ends, the poly-propiolactone etc. that has hydroxyl at terminal or two ends has hydroxyl at terminal or two ends polylactone; The polybutylene terephthalate etc. that have the polyethylene terephthalate of hydroxyl at terminal or two ends, has a hydroxyl at terminal or two ends has the polycondensation polyester of hydroxyl etc. at terminal or two ends.
These an end have hydroxyl polyester and the polyester that two ends have a hydroxyl can distinguish separately or mix 2 kinds with on use.
As the ammonia ester class spreading agent among the present invention, the preferred fragrance (cyclo) aliphatic diisocyanates with have the polylactone of hydroxyl and/or have the reaction product of the polylactone of hydroxyl at an end at two ends, preferred especially toluene diisocyanate with have the polycaprolactone of hydroxyl and/or have the reaction product of the polycaprolactone of hydroxyl at two ends at an end.
Object lesson as this ammonia ester class spreading agent, can list, for example, commodity EFKA (manufacturing of エ Off カ one ケ ミ カ Le ズ PVC one Block イ (EFKA) company), the Disperbyk by name (series of products of the manufacturing of BYK CHEMIE (BYK) company, デ イ ス パ ロ Application (nanmu originally changes into (strain) and makes) etc.
The polystyrene conversion weight-average molecular weight of measuring through gel permeation chromatography (GPC) of the ammonia ester class spreading agent among the present invention is preferably 5,000～50, and 000, more preferably 7,000～20,000.
Above-mentioned ammonia ester class spreading agent can separately or mix 2 kinds with on use.
The consumption of the ammonia ester class spreading agent during the conditioned pigment dispersion liquid with respect to pigment 100 weight portions, is preferably below 100 weight portions, 0.5～100 weight portion more preferably, and more preferably 1～70 weight portion is preferably 10～50 weight portions especially.At this moment, the consumption of ammonia ester class spreading agent might damage development etc. if surpass 100 weight portions.
The solvent that uses during as the conditioned pigment dispersion liquid can list, for example, and for the solvent identical of radiation-ray sensitive composition for colour-filtering piece among the present invention with the aftermentioned solvent.
The consumption of the solvent during the conditioned pigment dispersion liquid with respect to pigment 100 weight portions, is preferably 500～1,000 weight portion.
When using ball mill conditioned pigment dispersion liquid, for example, can use diameter is glass microballoon about 0.5～10mm or titanium microballon etc., preferably mixes, disperses with the equilateral cooling pigment of chilled water mixed liquor limit.
At this moment, the filling rate of microballon is preferably 50～80% of grinding machine capacity, and the injection rate IR of pigment mixed liquor is preferably about 20～50% of grinding machine capacity.Processing time is preferably 2～50 hours, more preferably 2～25 hours.
When using roller mill conditioned pigment dispersion liquid, for example, can use three-roll mill or two roller mills etc., preferably handle with the equilateral cooling pigment of chilled water mixed liquor limit.
At this moment, preferred roller is spaced apart below the 10 μ m, and shearing force is preferably 10 8Dyn/ is about second.Processing time is preferably 2～50 hours, more preferably 2～25 hours.
So the mean grain size and the size distribution of the pigment in the dispersible pigment dispersion of modulation can utilize dynamic light scattering method to measure.
(B) alkali soluble resin
As the alkali soluble resin among the present invention, so long as (A) pigment is played the effect of bonding agent, and the developer solution that uses in the developing procedure when making colored filter, the material that preferred alkaline-based developer has solubility get final product, and is not particularly limited.Can list, for example, but have the polymerism unsaturated monomer of acidic functionalities such as carboxyl, phenol hydroxyl, sulfonic acid and the unsaturated monomer of other copolymerization (below be called " copolymerization unsaturated monomer ".) interpolymer.
As the polymerism unsaturated monomer with carboxyl (below be called " unsaturated monomer that contains carboxyl ".), can list, for example,
Unsaturated single carbonic acid such as (methyl) acrylic acid, crotonic acid, α-Lv Bingxisuan, cinnamic acid;
Unsaturated dicarboxylic and their acid anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid;
Unsaturated polybasic carboxylic acid or its acid anhydrides that ternary is above;
List [(methyl) acryloxyalkyl] ester of the polybasic carboxylic acids more than 2 yuan such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester;
ω-carboxyl polycaprolactone list (methyl) acrylate etc. have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl etc. at two ends.
These contain in the unsaturated monomer of carboxyl, preferred especially (methyl) acrylic acid, mono succinate [2-(methyl) acryloxy ethyl] ester, ω-carboxyl polycaprolactone list (methyl) acrylate.
The above-mentioned unsaturated monomer that contains carboxyl, can separately or mix 2 kinds with on use.
As polymerism unsaturated monomer with phenol hydroxyl, can list, for example, o-hydroxy ethene, a hydroxy styrenes, para hydroxybenzene ethene, adjacent hydroxyl-α-Jia Jibenyixi, hydroxyl-α-Jia Jibenyixi, to hydroxyl-α-Jia Jibenyixi, N-salicyl maleimide, N-resorcyl maleimide, N-to hydroxyphenyl maleimide etc.
These have the polymerism unsaturated monomer of phenol hydroxyl, can separately or mix 2 kinds with on use.
As having sulfonic polymerism unsaturated monomer, can list, for example, different propene sulfonic acid, p styrene sulfonic acid etc.
These have sulfonic polymerism unsaturated monomer, can separately or mix 2 kinds with on use.
As the copolymerization unsaturated monomer, can list, for example,
Polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane etc. an end of the strand of polymkeric substance have (methyl) acryloyl group macromonomer (below abbreviate " macromonomer " as.)；
N-phenylmaleimide, N-salicyl maleimide, N-resorcyl maleimide, N-be to N-(replacement) aryl maleimides such as aminomethyl phenyl maleimide, N-p-methylphenyl maleimide, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, N-p-methoxyphenyl maleimide between hydroxyphenyl maleimide, N-o-methyl-phenyl-maleimide, N-, or N-position substituted maleimide amine such as N-cyclohexyl maleimide;
Styrene, α-Jia Jibenyixi, adjacent vinyltoluene, a vinyltoluene, to vinyltoluene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to aromatic ethenyl compounds such as vinyl benzyl glycidol 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) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 3-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) acrylic acid 3-hydroxy butyl ester, (methyl) acrylic acid 4-hydroxy 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, methoxyl diethylene glycol (methyl) acrylate, methoxyl triethylene glycol (methyl) acrylate, MPEG (methyl) acrylate, methoxyl dipropylene glycol (methyl) acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid bicyclopentadiene ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, esters of unsaturated carboxylic acids such as (methyl) acrylic acid glyceride;
Unsaturated carboxylic acid aminoalkyl esters such as (methyl) acrylic acid 2-amino ethyl ester, (methyl) acrylic acid 2-methylamino ethyl ester, the amino propyl ester of (methyl) acrylic acid 2-, (methyl) acrylic acid 2-dimethylamino propyl ester, the amino propyl ester of (methyl) acrylic acid 3-, (methyl) acrylic acid 3-dimethylamino propyl ester;
Unsaturated carboxylic acid ethylene oxidic esters such as (methyl) glycidyl acrylate; Vinyl carboxylates such as vinyl acetate, propionate, vinyl butyrate, benzoic acid vinyl acetate;
Other unsaturated ethers such as methoxy ethylene, ethyl vinyl ether, allyl glycidyl ether;
Vinyl cyanide based compounds such as (methyl) vinyl cyanide, α-Lv Daibingxijing, vinyl cyanide fork;
Unsaturated amides such as (methyl) acrylamide, alpha-chloro acrylamide, N-2-hydroxyethyl (methyl) acrylamide;
1,3-butadiene, isoprene, chlorbutadiene etc.
These copolymerization unsaturated monomers can use separately also can mix more than 2 kinds and use.
In the above-mentioned copolymerization unsaturated monomer, preferred macromonomer, N-position substituted maleimide amine, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid glyceride.In addition, in the macromonomer, preferred especially polystyrene macromolecular monomer, poly-(methyl) methyl acrylate macromonomer, preferred especially N-phenylmaleimide, N-cyclohexyl maleimide in the substituted maleimide amine of N-position.
As preferred alkali soluble resin among the present invention, can list the unsaturated monomer that contains carboxyl and copolymerization unsaturated monomer multipolymer (below be called " multipolymer that contains carboxyl ".)。
As the multipolymer that contains carboxyl, preferably contain the unsaturated monomer that (a) contains carboxyl, (b) be selected from polystyrene macromolecular monomer, poly-(methyl) methyl acrylate macromonomer, N-phenylmaleimide, N-cyclohexyl maleimide, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid glyceride at least a kind, according to circumstances, the multipolymer of preferred monomer mixture (below be called " multipolymer (I) that contains carboxyl ".) further contain (c) and be selected from least a in styrene, (methyl) methyl acrylate, (methyl) allyl acrylate and (methyl) phenyl acrylate.
The multipolymer of particularly preferred monomer mixture (below be called " multipolymer (II) that contains carboxyl ".), containing (a) is neccessary composition with (methyl) acrylic acid, according to circumstances, further contain the unsaturated monomer composition that contains carboxyl that is selected from mono succinate [2-(methyl) acryloxy ethyl] ester and/or ω-carboxyl polycaprolactone list (methyl) acrylate and (b) be selected from polystyrene macromolecular monomer, poly-(methyl) methyl acrylate macromonomer, N-phenylmaleimide, N-cyclohexyl maleimide, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) benzyl acrylate and (methyl) acrylic acid glyceride at least a kind; According to circumstances, further contain (c) and be selected from least a in styrene, (methyl) methyl acrylate, (methyl) allyl acrylate and (methyl) phenyl acrylate.
Multipolymer (II) object lesson that contains carboxyl for example has:
(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride multipolymer,
(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-phenylmaleimide/styrene/(methyl) allyl acrylate multipolymer,
(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-phenylmaleimide/(methyl) benzyl acrylate/styrol copolymer,
(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-cyclohexyl maleimide/styrene/(methyl) allyl acrylate multipolymer,
(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-cyclohexyl maleimide/(methyl) benzyl acrylate/styrol copolymer,
(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-phenylmaleimide/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride/styrol copolymer,
(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/N-phenylmaleimide/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride/styrol copolymer,
(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate multipolymer,
(methyl) acrylic acid/polystyrene macromolecular monomer/(methyl) benzyl acrylate multipolymer,
(methyl) acrylic acid/poly-(methyl) methyl acrylate macromonomer/(methyl) benzyl acrylate multipolymer,
(methyl) acrylic acid/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride multipolymer,
(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxyl ethyl ester/(methyl) benzyl acrylate multipolymer,
(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxyl ethyl ester/(methyl) phenyl acrylate multipolymer,
(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxyl ethyl ester/styrol copolymer, (methyl) acrylic acid/N-cyclohexyl maleimide/(methyl) benzyl acrylate/styrol copolymer,
(methyl) acrylic acid/polystyrene macromolecular monomer/(methyl) acrylic acid 2-hydroxyl ethyl ester/(methyl) benzyl acrylate multipolymer,
(methyl) acrylic acid/poly-(methyl) methyl acrylate macromonomer/(methyl) acrylic acid 2-hydroxyl ethyl ester/(methyl) benzyl acrylate multipolymer,
(methyl) acrylic acid/N-phenylmaleimide/(methyl) benzyl acrylate/styrol copolymer,
(methyl) acrylic acid/N-phenylmaleimide/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride/styrol copolymer etc.
Contain preferred 5～50 weight % of copolymerization ratio of the unsaturated monomer that contains carboxyl in the multipolymer of carboxyl, more preferably 10～40 weight %.At this moment, if contain the copolymerization ratio less than 5 weight % of the unsaturated monomer of carboxyl, the sense radioactivity resin combination that obtains tends to lowly the dissolubility of alkaline-based developer, on the other hand, when surpassing 50 weight %, dissolubility to alkaline-based developer is excessive, and when utilizing alkaline-based developer to develop, pixel is easy to be come off or be easy to cause that the film on pixel surface is coarse by substrate.
In the present invention, alkali soluble resin adopt gel permeation chromatography (GPC, eluting solvent: tetrahydrofuran) the polystyrene conversion weight-average molecular weight of Ce Dinging (below be called " Mw ") is preferred 3,000～300,000, more preferably 5,000～100,000.
In addition, alkali soluble resin among the present invention adopt gel permeation chromatography (GPC, eluting solvent: tetrahydrofuran) the polystyrene conversion number-average molecular weight of Ce Dinging (below be called " Mn ") is preferred 3,000～60,000, more preferably 5,000～25,000.
By using this have specific Mw or the alkali soluble resin of Mn, can obtain the good radiation sensitive compositions of development property, when can form the pixel of sharp keen pattern edge thus, be difficult to during development residue, scum, residual film etc. are taking place on the substrate of unexposed portion or on the light shield layer.
In addition, the ratio (Mw/Mn) of the Mw of the alkali soluble resin among the present invention and Mn is preferred 1～5, and more preferably 1～4.
Among the present invention, alkali soluble resin can use separately also can mix more than 2 kinds and use.
The consumption of the alkali soluble resin among the present invention is preferred 10～1,000 weight portion of (A) pigment 100 weight portions, more preferably 20～500 weight portions relatively.At this moment, if usefulness quantity not sufficient 10 weight portions of alkali soluble resin, for example, might descend by alkali-developable, or on the substrate of unexposed portion or on the light shield layer scum or residual film take place, opposite, when surpassing 1, during 000 weight portion,, may be difficult to reach aim colour concentration as film because pigment concentration is low relatively.
(C) multi-functional monomer
Multi-functional monomer among the present invention has the polymerism unsaturated link more than 2 in molecule.
Multi-functional monomer so for example has: two (methyl) acrylate of alkane glycol such as ethylene glycol, propylene glycol;
Two (methyl) acrylate of the poly-alkane glycol of polypropylene glycols such as dipropylene glycol that the polyglycol such as diethylene glycol that the above ethylene glycol condensation of 2 molecules forms, the above propylene glycol condensation of 2 molecules form and so on;
Poly-(methyl) acrylate or its dicarboxylic acid modifier of the polyvalent alcohols more than 3 yuan such as glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol;
Oligomeric (methyl) acrylate such as polyester, epoxy resin, urethane resin, alkyd resin, organic siliconresin, spirane resin;
Two ends have hydroxyl poly--1,3-butadiene, have the polyisoprene of hydroxyl at two ends, the polycaprolactone etc. that has hydroxyl at two ends has the polymkeric substance of hydroxyl at two ends two (methyl) acrylate and three [2-(methyl) acryloxy ethyl] phosphate etc.
In these multi-functional monomers, poly-(methyl) acrylate and the dicarboxylic acid modifier thereof of the polyvalent alcohol that preferred ternary is above for example have: trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate particularly.Because the pixel concentration height, the flatness on pixel surface is good, and be difficult to take place scum on the substrate of unexposed portion and the light shield layer, residual film, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol acrylate.Above-mentioned multi-functional monomer can separately or mix use more than 2 kinds.
The consumption of the multi-functional monomer among the present invention is (B) alkali soluble resin 100 weight portions relatively, are preferably 5～500 weight portions, more preferably 20～300 weight portions.At this moment, if it is the consumption of multi-functional monomer has the tendency of pixel intensity or surface smoothing reduction less than 5 weight portions, opposite, when surpassing 500 weight portions, for example have alkali-developable to reduce or the substrate of unexposed portion on or be easy to take place tendencies such as scum, residual film on the light shield layer.
Among the present invention, also can and use simple function monomer with multi-functional monomer with 1 polymerism unsaturated link.
Above-mentioned simple function monomer, can list, for example, to the illustrative unsaturated monomer that contains carboxyl of above-mentioned (B) alkali soluble resin, copolymerization unsaturation monomer and N-vinyl succinimide, the N-vinyl pyrrolidone, N-vinyl phthalimide, N-vinyl-2-Pyrrolidone, N-vinyl-epsilon-caprolactams, the N-vinyl pyrrole, the N-ethenyl pyrrolidone, the N-vinyl imidazole, N-vinyl imidazole alkane, N-vinyl indoles, N-vinyl indoline, N-vinyl benzo imidazoles, the N-vinylcarbazole, N-vinyl piperidines, N-vinyl piperazine, N-vinyl morpholine, N-vinyl nitrogen-containing heterocycle compounds such as N-vinyl phenoxazine; N-(methyl) acryloyl morpholine, in addition, commercially available product has M-5300, M-5400, M-5600 (trade name, East Asia synthetic (strain) system) etc.
These simple function monomers can separately or mix use more than 2 kinds.
The total amount of multi-functional relatively monomer of the usage rate of simple function monomer and simple function monomer is preferably below the 90 weight %, more preferably below the 50 weight %.At this moment, if the usage rate of simple function monomer surpasses 90 weight %, the intensity of pixel or surface smoothing have the tendency of reduction.
(D) radioactivity-sensitive free radical generating agent
Radioactivity-sensitive free radical generating agent among the present invention (being designated hereinafter simply as " free radical generating agent ") is a kind of exposure that utilizes visible light, ultraviolet ray, far ultraviolet, electronics line, X ray etc., and generation can cause above-mentioned (C) multi-functional monomer and according to circumstances mix the compound of the free radical of the simple function monomer generation polymerization of using.
This free radical generating agent for example has: acetophenone based compound, bisglyoxaline based compound, triazine based compound, styrax based compound, benzoin based compound, α-diketone based compound, multinuclear quinone based compound, xanthone based compound, diazonium based compound.
Among the present invention, free radical generating agent can separately or mix use more than 2 kinds.Free radical generating agent among the present invention preferably uses and is selected from least a in acetophenone based compound, bisglyoxaline based compound and the triazine based compound.
Among the present invention, the consumption of free radical generating agent is 100 weight portions with respect to the summation of (C) multi-functional monomer 100 weight portions or itself and simple function monomer, preferred 0.01～80 weight portion, more preferably 1～60 weight portion.At this moment, if usefulness quantity not sufficient 0.01 weight portion of optical free radical initiating agent, the curing that exposure causes is insufficient, may be difficult to obtain the colored filter that pattern of pixels sequence configuration according to the rules forms, on the other hand, when surpassing 80 weight portions, the pixel of formation has when developing and is easy to the tendency that comes off from substrate.
Among the present invention in the preferred free radical generating agent, the object lesson of acetophenone based compound for example has: 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-methyl isophthalic acid-(4-methyl sulfo-) phenyl]-2-morpholinyl acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone-1,1-hydroxyl cyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 1,2-acetyl caproyl, 1-[4-(phenyl sulfo-) phenyl]-2-(o-benzoyl oxime) etc.
Preferred especially 2-methyl isophthalic acid-(4-(methyl sulfo-) phenyl)-2-morpholinyl acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone-1,1 in these acetophenone based compounds, 2-acetyl caproyl, 1-[4-(phenyl sulfo-) phenyl]-2-(o-benzoyl oxime).
Above-mentioned acetophenone based compound can separately or mix use more than 2 kinds.
Among the present invention, when free radical generating agent uses the acetophenone based compound, its consumption is total 100 weight portions (with simple function monomer and time spent) of (C) multi-functional monomer 100 weight portions or itself and simple function monomer relatively, be preferably 0.01～80 weight portion, more preferably 1～60 weight portion, further preferred 1～30 weight portion.At this moment, if usefulness quantity not sufficient 0.01 weight portion of acetophenone based compound, the curing that exposure causes is not enough, may be difficult to obtain the colored filter that pattern of pixels sequence configuration according to the rules forms, on the other hand, when surpassing 80 weight portions, the pixel of formation has when developing and is easy to the tendency that comes off from substrate.
In addition, the object lesson of above-mentioned bisglyoxaline based compound for example 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-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline; 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline; 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline; 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline; 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline; 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.
In these bisglyoxaline based 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-trichloro-benzenes)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc., preferred especially 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
These bisglyoxaline based compounds are good to the dissolubility of solvent, do not produce not foreign matter such as dissolved matter, precipitate, and, highly sensitive, utilize a spot of energy to expose just can to make fully it that curing reaction takes place, simultaneously at unexposed portion curing reaction does not take place, therefore, filming after the exposure divided into the insoluble cured portion of developer solution clearly and developer solution had the uncured portion of highly dissoluble, thus, can form the pattern of pixels sequence according to the rules of not having cave in (undercut) and dispose the high meticulous colored filter that forms.
Above-mentioned bisglyoxaline based compound can separately or mix use more than 2 kinds.
Among the present invention, when free radical generating agent uses the bisglyoxaline based compound, its consumption is the total amount of (C) multi-functional monomer 100 weight portions or itself and simple function monomer (with the simple function monomer and use time) 100 weight portions relatively, be preferably 0.01～40 weight portion, more preferably 1～30 weight portion, more preferably 1～20 weight portion.At this moment, if usefulness quantity not sufficient 0.01 weight portion of bisglyoxaline based compound, the curing that exposure causes is insufficient, may be difficult to obtain the colored filter that pattern of pixels sequence configuration according to the rules forms, on the other hand, when surpassing 40 weight portions, the pixel of formation has when developing and is easy to come off or be easy to cause the coarse tendency of film on pixel surface from the substrate of the pixel that forms.
Hydrogen donor
Among the present invention, when free radical generating agent uses the bisglyoxaline based compound, consider the further sensitivity that improves, the preferred mixing used following hydrogen donor.
" hydrogen donor " described here is meant the free radical by exposing and being produced by the bisglyoxaline based compound relatively, can give the compound of hydrogen atom.
Mercaptan based compound, the amine compound of the preferred following definitions of hydrogen donor among the present invention.
Above-mentioned mercaptan based compound is made of following compound, that is, described compound is a parent nucleus with phenyl ring or heterocycle, have more than one, preferred 1～3, more preferably 1～2 be bonded directly to sulfydryl on this parent nucleus (below be called " mercaptan is hydrogen donor ").
Above-mentioned amine compound is made of following compound, that is, described compound is a parent nucleus with phenyl ring or heterocycle, has more than one, preferred 1～3, more preferably 1～2 the amino that is bonded directly to this parent nucleus (below be called " ammonia is hydrogen donor ").
In addition, these hydrogen donors also can have sulfydryl and amino simultaneously.
Below, these hydrogen donors are carried out further specific description.
Mercaptan is that hydrogen donor can have phenyl ring or the heterocycle more than 1 respectively, can have two kinds of phenyl ring and heterocycles in addition.When having ring such more than two, can form also and can not form condensed ring.
In addition, mercaptan be hydrogen donor when the sulfydryl that has more than 2, as long as residual at least one free sulfydryl, remaining sulfydryl more than 1 also can use alkyl, aralkyl or aryl replacement.And as long as residual at least one free sulfydryl just can have following structural unit, that is, two sulphur atoms are by the structural unit of divalent organic group bondings such as alkylidene; Perhaps two sulphur atoms are by the structural unit of the form bonding of disulfide.
And mercaptan is that hydrogen donor also can be in sulfydryl position in addition, by for example replacements such as carboxyl, alkoxy carbonyl, substituted alkoxy carbonyl, phenyloxycarbonyl, substituent phenoxy carbonyl, nitro.
These mercaptan are that the object lesson of hydrogen donor for example has: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-2,5-dimethyl aminopyridine etc.
These mercaptan are in the hydrogen donor, preferred 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, preferred especially 2-mercaptobenzothiazole.
In addition, amine is that hydrogen donor can have more than one phenyl ring or heterocycle respectively, can have two kinds of phenyl ring and heterocycles in addition.Having plural these whens ring, can form also and can not form condensed ring.
Amine is that hydrogen donor also can be replaced more than one amino by alkyl or substituted alkyl.In addition, the position beyond amino also can be by replacements such as carboxyl, alkoxy carbonyl group, substituted alkoxycarbonyl, carbobenzoxy, substituted benzene oxygen carbonyl, nitros.
These amine are that the object lesson of hydrogen donor for example has: 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, ethyl-4-dimethylaminobenzoic acid ester, 4-dimethylamino benzoic acid, 4-dimethylaminophenyl cyanogen etc.
These amine are preferred 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone in the hydrogen donor; Preferred especially 4,4 '-two (diethylamino) benzophenone.
During free radical generating agent that amine is hydrogen donor beyond using the bisglyoxaline based compound, also has the effect of sensitizer.
Hydrogen donor can use separately among the present invention, also can mix more than 2 kinds and use.But the pixel of considering formation comes off on being difficult to by substrate when developing, or pixel intensity and highly sensitive, and the mercaptan that preferably is used more than one is that hydrogen donor and more than one amine are hydrogen donor.
Mercaptan is that hydrogen donor and amine are that the object lesson that hydrogen donor makes up for example has: 2-mercaptobenzothiazole/4,4 '-two (dimethylamino) benzophenone; 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone; 2-mercaptobenzoxazole/4,4 '-two (diethylamino) benzophenone; 2-mercaptobenzoxazole/4,4 '-two (diethylamino) benzophenone etc.Particularly preferred 2-mercaptobenzothiazole/4 that are combined as, 4 '-two (diethylamino) benzophenone; 2-mercaptobenzoxazole/4,4 '-two (diethylamino) benzophenone, particularly preferred 2-mercaptobenzothiazole/4 that are combined as, 4 '-two (diethylamino) benzophenone.
Mercaptan is that hydrogen donor and amine are in the combination of hydrogen donor, and mercaptan is that hydrogen donor and amine are preferred 1: 1～1: 4 of the weight ratio of hydrogen donor, more preferably 1: 1～1: 3.
Among the present invention, when hydrogen donor being mixed use with the bisglyoxaline based compound, its consumption is total amount (with simple function monomer and time spent) 100 weight portions of (C) multi-functional monomer 100 weight or itself and simple function monomer relatively, be preferably 0.01～40 weight portion, more preferably 1～30 weight portion, further preferred 1～20 weight portion.At this moment, if usefulness quantity not sufficient 0.01 weight portion of hydrogen donor, the sensitivity improving effect is tended to lowly.On the contrary, when surpassing 40 weight portions, the pixel of formation comes off on being easy to by substrate when developing.
In addition, above-mentioned triazine based compound object lesson for example has: 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(5-methylfuran-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(furans-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[4-methoxyphenyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-ethoxybenzene vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-n-butoxy phenyl)-4, two (the trichloromethyl)-s-triazine etc. of 6-have the triazine based compound of halogenated methyl.
In these triazine based compounds, preferred especially 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-.
Above-mentioned triazine based compound can use separately also can mix two or more uses.
Among the present invention, when using the triazine based compound as free radical generating agent, its consumption is the total amount of (C) multi-functional monomer 100 weight or itself and simple function monomer (under the situation of simple function monomer and usefulness) 100 weight portions relatively, be preferably 0.01～40 weight portion, more preferably 1～30 weight portion, further preferred 1～20 weight portion.When usefulness quantity not sufficient 0.01 weight portion of triazine based compound, the curing deficiency that exposure causes, may be difficult to obtain the colored filter that pattern of pixels sequence configuration according to the rules forms, on the other hand, when surpassing 40 weight portions, the pixel of formation has when developing and is easy to the tendency that comes off from substrate.
Other adjuvants
Colored filter radiation-sensitive resin composition of the present invention contains above-mentioned (A)～(D) composition, also can contain other adjuvants as required.
Other adjuvants for example have: filling agents such as glass, aluminium oxide; Polyvinyl alcohol (PVA), poly-macromolecular compounds such as (fluoroalkyl acrylate); Nonionic system, kation system, negative ion are surfactants such as 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, driving fit promoter such as 3-sulfydryl propyl trimethoxy silicane; 2,2-thiobis (4-methyl-6-tert butyl phenol), 2, antioxidant such as 6-di-tert-butylphenol; Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone; Anti-coagulants such as sodium polyacrylate etc.
Solvent
Radiation-ray sensitive composition for colour-filtering piece of the present invention, other adjuvants that contain above-mentioned (A)～(D) composition and add arbitrarily.The preferred solvent that cooperates is modulated as liquid composition.
As long as above-mentioned solvent can make (A)～(D) composition or other additive components that constitute radiation-sensitive resin composition disperse or dissolve, and do not react with these compositions, the volatility with appropriateness gets final product, and can suitably select to use.
These solvents for example have:
Alcohol such as methyl alcohol, ethanol, benzylalcohol;
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, the diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol monomethyl ether, the single ether of dipropylene glycol, the single positive propyl ether of dipropylene glycol, the dipropylene glycol mono-n-butyl ether, the tripropylene glycol monomethyl ether, (gathering) alkane glycol monoalkyl ethers such as tripropylene glycol list ether;
(gathering) alkane glycol monoalkyl ether acetic acid esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, glycol monomethyl n-propyl ether acetic acid esters, glycol monomethyl n-butyl ether acetic acid esters, diethylene glycol monomethyl ether acetic acid esters, TC acetic acid esters, diethylene glycol list n-propyl ether acetic acid esters, diethylene glycol list n-butyl ether acetic acid esters, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, acetate 3-methoxyl butyl ester;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol MEE, diethylene glycol diethyl ether, tetrahydrofuran;
Ketone such as MEK, cyclohexanone, 2-heptanone, 3-heptanone, 2-Ketol (4-hydroxy-4-methyl pentane-2-ketone), 4-hydroxy-4-methyl hexane-2-one;
Lactic acid alkyl ester such as methyl lactate, ethyl lactate;
Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, 3-methyl-3-methoxyl butylacetic acid ester, n-butyl propionate, 3-methyl-3-methoxyl butyl propionic ester, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, hydroxyl ethyl acetate, ethoxy ethyl acetate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, powder acid methyl esters, the powder acetoacetic ester, powder acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-hydroxy-2-methyl ethyl propionate, 2-hydroxy-3-methyl methyl butyrate, other esters such as 2-ketobutyric acid ethyl ester;
Aromatic hydrocarbon such as toluene, dimethylbenzene;
N-Methyl pyrrolidone, N, acid amides such as dinethylformamide, N,N-dimethylacetamide etc.
Wherein, consider dissolubility, pigment-dispersing, coating etc., preferred benzylalcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, ethylene glycol monomethyl ether acetate, the ethylene glycol mono-n-butyl ether acetic acid esters, diethylene glycol mono-n-butyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, the diethylene glycol MEE, cyclohexanone, the 2-heptanone, the 3-heptanone, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, acetate 3-methoxyl butyl ester, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-methyl-3-methoxyl butyl propionic ester, powder acetoacetic ester etc.
Above-mentioned solvent can separately or mix use more than 2 kinds.
Further, can be with above-mentioned solvent and with high boiling solvents such as benzyl ether, two n-hexyl ethers, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, carbonic allyl ester, ethyleneglycol monophenylether acetic acid esters.
These high boiling solvents can be used alone or in mixture of two or more.
The consumption of solvent is not particularly limited, and considers the coating, storage stability of the radiation sensitive compositions that obtains etc., and the total concentration of each composition of removing the solvent of said composition is preferably 5～50 weight %, further preferred 10～40 weight %.
The formation method of colored filter
Below, use sense radioactivity composition of the present invention, describe for the method that forms colored filter of the present invention.
Form the method for colored filter, preferably contain according to following order operations that implement, following at least (1)～(4).
(1) on substrate, forms filming of radiation sensitive compositions of the present invention.
(2) operation of on above-mentioned at least a portion of filming, exposing.
(3) operation of filming after the development exposure.
(4) operation of filming after the back baking is developed.
Below, these operations are described successively.
(1) operation
At first, on substrate surface, in requisition for forming light shield layer, to distinguish the part that forms pixel, on this substrate, for example, after the common radiation sensitive compositions of the present invention that contains (A) pigment with green was coated with as liquid composition, the preliminary drying evaporation removes desolvated, and forms thus and films.
As the substrate that in this operation, uses, can list, for example, glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide-imide, polyimide, polyethersulfone, the ring-opening polymerization polymer of cycloolefin and its hydrogenation products etc. in addition.
In addition, on these substrates, as requested, can implement suitable pre-treatments such as medicine processing, plasma treatment, ion plating, sputter, gas-phase reaction method, vacuum evaporation such as silane coupling agent in advance.
Coating is during liquid composition on substrate, can adopt spin-coating method, flow coat method, rolling method, use the suitable rubbing methods such as rubbing method of slit dyestuff groove, preferred spin-coating method, used the rubbing method of slit dyestuff groove.
The condition optimization of preliminary drying is for to carry out about 2～4 minutes under 70～110 ℃.
Coating thickness, the thickness as removing after desolvating is preferably 1.0～10 μ m, and more preferably 1.0～6.0 μ m are preferably 1.0～4.0 μ m especially.
(2) operation
Afterwards, at least a portion of filming that forms, expose.At this moment, on a part of filming, expose, preferably by having the photomask exposure of predetermined pattern.
The radioactive ray that exposure is used can use, for example visible light, ultraviolet ray, far ultraviolet, electron ray, X ray etc., and optimal wavelength is positioned at the radioactive ray of 190～450nm scope.
The exposure of radioactive ray is preferably 10～10,000J/m 2
(3) operation
Afterwards, use developer solution, preferred alkaline-based developer, the unexposed portion of filming is removed in dissolving.
Above-mentioned alkaline-based developer, preference such as sodium carbonate, NaOH, potassium hydroxide, tetramethyl-ammonium oxyhydroxide, choline, 1, two [the 5.4.0]-7-undecylenes, 1 of 8-diazacyclo, the aqueous solution of two [the 4.3.0]-5-nonenes of 5-diazacyclo etc.
Can in above-mentioned alkaline developer, add for example water-miscible organic solvent such as methyl alcohol, ethanol and surfactant etc. in right amount.Need to prove that alkali is washed after developing usually.
The applicable shower development method of development treatment method, spray development method, immersion development method, (paddle) development method etc. of striking.
Development conditions is preferably at normal temperatures about 10～300 seconds.
(4) operation
Afterwards, filming after developing by back baking can obtain the substrate that green pixel pattern sequence configuration according to the rules that the solidfied material by radiation sensitive compositions constitutes forms.
Back baking condition optimization descended about 20～40 minutes at 180～230 ℃.
The thickness of the pixel of Xing Chenging is preferably 0.5～5.0 μ m like this, more preferably 1.5～3.0 μ m.
In addition, by using the red radiation sensitive compositions of the present invention that contains (A) pigment, repeat above-mentioned (1)～(4) operation, on same substrate, form red pattern of pixels, the of the present invention blue radiation sensitive compositions that contains blue pigment by use, repeat above-mentioned (1)～(4) operation, on same substrate, form the blue pixels pattern, thus, can on substrate, form the pel array that the sequence configuration according to the rules of green, red and blue trichromatic pattern of pixels forms.But, also can use painted radiation sensitive compositions beyond the radiation sensitive compositions of the present invention (below be called " other painted radiation sensitive compositions ") to form the either party of above-mentioned green pixel pattern and red pixel pattern, and, among the present invention, can select the formation order of pattern of pixels of all kinds arbitrarily.
Need to prove, contain blue radiation sensitive compositions and other painted radiation sensitive compositions of blue pigment, be not particularly limited, can list, for example, the composition that the pigment beyond (A) composition among the present invention and (B)～(D) composition among the present invention are mixed.The mean grain size r (nm of unit) of pigment wishes to be 50≤r≤300 in these other painted radiation sensitive compositions, preferred 100≤r≤300, the scope of preferred especially 50≤r≤200.In addition, pigment particle size distributes and wishes that also the secondary example in (mean grain size ± 100) nm scope accounts for more than the 70 all weight %, is preferably more than the 80 weight %.Pigment with this mean grain size r and size distribution, can utilize with modulate the invention described above in the identical method of the dispersible pigment dispersion of (A) pigment obtain.
Colored filter
Colored filter of the present invention has red pixel and/or the green pixel that is formed by radiation sensitive compositions of the present invention.
Colored filter of the present invention, for example, exceedingly useful to the color liquid crystal display arrangement of transmission-type or reflection-type, colorful visualization tube elements, color sensor etc.
Color liquid crystal display device
Color liquid crystal display device of the present invention possesses colored filter of the present invention.
Color liquid crystal display device of the present invention can adopt suitable structure.For example, can adopt following structure: form colored filter in the driving of disposing thin film transistor (TFT) (TFT) on other substrate outside the substrate, drive that to pass through liquid crystal layer with substrate and the substrate that is formed with colored filter relative; Dispose the substrate that is formed with the substrate of colored filter on the surface of driving with substrate of thin film transistor (TFT) (TFT) and is formed with ITO (indium oxide of doped tin) electrode, relative by liquid crystal layer.The latter's structure can greatly improve numerical aperture, has to obtain the advantage bright and liquid crystal display cells that height is meticulous.
Radiation sensitive compositions of the present invention can form high red pixel of transmittance and contrast and green pixel.
Embodiment
Below, further specifically describe embodiments of the present invention by embodiment.But the present invention is not limited to following embodiment.
Synthesis example 1
In the flask that is provided with condenser pipe, stirrer, add 2,2 '-azo two (2, the 4-methyl pentane nitrile) 1 weight portion and diethylene glycol monomethyl ether acetic acid esters 200 weight portions, then, add methacrylic acid 15 weight portions, N-phenylmaleimide 25 weight portions, benzyl methacrylate 35 weight portions, glycerine monomethacrylates 10 weight portions, styrene 15 weight portions and α-Jia Jibenyixierjuwu (chain-transferring agent) 2.5 weight portions, be replaced into after the nitrogen, stir lentamente, make reaction solution be warming up to 80 ℃, keep this temperature, polyase 13 hour.Reactant liquor is warming up to 100 ℃ afterwards, adds 2 of 0.5 weight portion, 2 '-azo two (2, the 4-methyl pentane nitrile) continued polymerization 1 hour again, thus, obtained resin solution (solid component concentration=30 weight %).The Mw=30 of the resin that obtains, 000, Mn=10,000.With this resin solution as " resin solution (B-1) ".
Embodiment 1
The modulation of dispersible pigment dispersion
With (A) pigment: 30/70 (weight ratio) potpourri, 40 weight portions of C.I pigment green 36 and C.I. pigment yellow 219, spreading agent: BYK 2001 (Disperbyk:BYK CHEMIE (BYK) corporate system, solid component concentration 45.1 weight %) 10 weight portions (being converted into about 4.51 weight portions of solid constituent) and solvent: the mixed liquor that is made of 150 weight portion 3-ethoxyl ethyl propionates utilizes ball mill to mix dispersion 12 hours, is modulated into dispersible pigment dispersion (P1).
For dispersible pigment dispersion (P1), utilize the mean grain size of dynamic light scattering determination pigment, the result is 250nm.
The modulation of liquid composition
With dispersible pigment dispersion (P1) 600 weight portions, (B) alkali soluble resin: resin solution (B-1) 200 weight portions, (C) multi-functional monomer: dipentaerythritol acrylate 60 weight portions, (D) free radical generating agent: 40 weight portion 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone-1 and solvent: propylene glycol methyl ether acetate 1,000 weight portion mixes, and is modulated into liquid composition (G1).
The formation of pattern of pixels
Be formed with SiO in order to prevent at surperficial stripping sodion 2On the soda-lime glass substrate of film, behind the use spinner coating liquid composition (G1), preliminary drying is 10 minutes in 90 ℃ cleaning oven, forms filming of thickness 3.2 μ m.
Then, cool off this substrate to room temperature, use high-pressure mercury-vapor lamp, by photomask, with the radioactive ray of each wavelength that contains 365nm, 405nm and 436nm with 5,000J/m 2Exposure exposure film.Afterwards, 1 minute this substrate of dipping in the developer solution that is made of 23 ℃ 0.04 weight % potassium hydroxide aqueous solution after the development, with ultrapure water washing, air-dry, carries out 30 minutes back baking under 250 ℃ again, forms green striated pattern of pixels on substrate.The thickness of this pixel is 2.50 μ m.
The evaluation of colourity
With the colourity of color analyzer TC-1800M (Tokyo electricity look (strain) system) evaluation pixels, the result be (x, y, Y)=(0.288,0.600,52.3).
The evaluation of contrast
Clamp the substrate that obtains with 2 Polarizers, (wavelength coverage 380～780nm) is rotated the Polarizer of front face side while shine with fluorescent light by rear side, utilize brightness photometer LS-100 (MINOLTA (strain) system) to measure maximal value and minimum value, maximal value spent as a comparison divided by the value of minimum value estimate, the result is 1,080.
Comparative example 1
The modulation of dispersible pigment dispersion
Use (A) pigment: 80/20 (weight ratio) potpourri, 30 weight portions of C.I pigment green 36 and C.I. pigment yellow 83, spreading agent: BYK 2001 (Disperbyk:BYK CHEMIE (BYK) corporate system, solid component concentration 45.1 weight %) 10 weight portions (being converted into about 4.51 weight portions of solid constituent) and solvent: 160 weight portion 3-ethoxyl ethyl propionates, in addition operate equally with embodiment, be modulated into dispersible pigment dispersion (p1).
For dispersible pigment dispersion (p1), utilize the mean grain size of dynamic light scattering determination pigment, the result is 300nm.
The modulation of liquid composition
With dispersible pigment dispersion (p1) 200 weight portions, (B) alkali soluble resin: resin solution (B-1) 200 weight portions, (C) multi-functional monomer: dipentaerythritol acrylate 60 weight portions, (D) free radical generating agent: 40 weight portion 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone-1 and solvent: propylene glycol methyl ether acetate 1,000 weight portion mixes, and is modulated into liquid composition (g1).
The formation of pattern of pixels and evaluation
Operate similarly to Example 1 the liquid composition (G1) except that replacing with liquid composition (g1), having formed thickness on substrate is the green color stripe shape pattern of pixels of 2.50 μ m, estimates.
As a result, the colourity of pixel is that (Y)=(0.288,0.600,48.5), contrast is 450 for x, y.
Embodiment 2
The modulation of dispersible pigment dispersion
With (A) pigment: 40/15/45 (weight ratio) potpourri, 30 weight portions of C.I pigment green 36 and C.I. pigment yellow 150 and C.I. pigment yellow 219, spreading agent: BYK 2001 (Disperbyk:BYK CHEMIE (BYK) corporate system, solid component concentration 45.1 weight %) 10 weight portions (being converted into about 4.51 weight portions of solid constituent) and solvent: the mixed liquor that is made of 160 weight portion 3-ethoxyl ethyl propionates utilizes ball mill to mix dispersion 12 hours, is modulated into dispersible pigment dispersion (P2).
For dispersible pigment dispersion (P2), utilize the mean grain size of dynamic light scattering determination pigment, the result is 200nm.
The modulation of liquid composition
With dispersible pigment dispersion (P2) 400 weight portions, (B) alkali soluble resin: resin solution (B-1) 200 weight portions, (C) multi-functional monomer: dipentaerythritol acrylate 60 weight portions, (D) free radical generating agent: 40 weight portion 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone-1 and solvent: propylene glycol methyl ether acetate 1,000 weight portion mixes, and is modulated into liquid composition (G2).
The formation of pattern of pixels and evaluation
Operate similarly to Example 1 the liquid composition (G1) except that replacing with liquid composition (G2), having formed thickness on substrate is the green color stripe shape pattern of pixels of 2.50 μ m, estimates.
As a result, the colourity of pixel is that (Y)=(0.300,0.570,61.1) contrast is 1,200 for x, y.
Comparative example 2
The modulation of dispersible pigment dispersion
Except that 50/10/40 (weight ratio) potpourri, 30 weight portions that use C.I pigment green 36 and C.I. pigment yellow 150 and C.I. pigment yellow 13 8, operation is modulated into dispersible pigment dispersion (p2) similarly to Example 2.
For dispersible pigment dispersion (p2), utilize the mean grain size of dynamic light scattering determination pigment, the result is 250nm.
The modulation of liquid composition
Except that using dispersible pigment dispersion (p2) to replace the dispersible pigment dispersion (P2), operation is modulated into liquid composition (g2) similarly to Example 2.
The formation of pattern of pixels and evaluation
Operate similarly to Example 1 the liquid composition (G1) except that replacing with liquid composition (g2), having formed thickness on substrate is the green color stripe shape pattern of pixels of 2.50 μ m, estimates.
As a result, the colourity of pixel is that (Y)=(0.300,0.570,60.5), contrast is 900 for x, y.

Claims (8)

1. radiation sensitive compositions, it contains (A) pigment, (B) alkali soluble resin, (C) multi-functional monomer and (D) radioactivity-sensitive free radical generating agent, it is characterized in that, (A) pigment contains the C.I. pigment yellow 219 of 35～75 weight %, and (A) the mean grain size r of pigment is 50nm≤r≤300nm, and is used for the manufacturing of colored filter.
2. the described radiation sensitive compositions of claim 1, wherein (A) pigment also contains the C.I. pigment green 36, is used to form green pixel.
3. the described radiation sensitive compositions of claim 1, wherein (A) pigment also contains the pigment of at least a C.I. of being selected from paratonere 177, C.I. paratonere 242 and C.I. paratonere 254, is used to form red pixel.
4. the modulation method of a radiation sensitive compositions, wherein, with dispersible pigment dispersion and (B) alkali soluble resin, (C) multi-functional monomer and (D) the radioactivity-sensitive free radical generating agent mix mutually and generate radiation-ray sensitive composition for colour-filtering piece, described dispersible pigment dispersion surpasses 300nm (A) pigment and mixes dispersion while pulverizing obtain in solvent containing 35～75 weight %C.I. pigment yellows 219, mean grain size, and wherein the mean grain size r of (A) pigment is 50nm≤r≤300nm.
5. the modulation method of the described radiation sensitive compositions of claim 4, wherein (A) pigment also contains the C.I. pigment green 36, is used to form green pixel.
6. the modulation method of the described radiation sensitive compositions of claim 4, wherein (A) pigment also contains the pigment of at least a C.I. of being selected from paratonere 177, C.I. paratonere 242 and C.I. paratonere 254, is used to form red pixel.
7. colored filter, it has red pixel and/or the green pixel that is formed by the described radiation sensitive compositions of claim 1.
8. color liquid crystal display device, it possesses the described colored filter of claim 7.
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