CN100578266C - Radiation sensitive composition for color filters, method for the preparation of the same, color filter and color liquid crystal display device - Google Patents

Radiation sensitive composition for color filters, method for the preparation of the same, color filter and color liquid crystal display device Download PDF

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Publication number
CN100578266C
CN100578266C CN200510103807A CN200510103807A CN100578266C CN 100578266 C CN100578266 C CN 100578266C CN 200510103807 A CN200510103807 A CN 200510103807A CN 200510103807 A CN200510103807 A CN 200510103807A CN 100578266 C CN100578266 C CN 100578266C
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methyl
pigment
acid
radiation
color filter
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CN1782748A (en
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槙平勇
成濑真吾
长塚富雄
M·吉原
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JSR Corp
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Abstract

To provide a radiation-sensitive composition for a color filter with which a red pixel having high transmittance and a contrast ratio can be formed, the composition having rheological characteristics suitable for coating a large substrate. The radiation-sensitive composition contains: (A) a pigment; (B) a dispersant; (C) a copolymer of (c1) a carboxyl group-containing unsaturated monomer comprising an (meth)acrylic acid, (c2) N-site substituted maleimide, and (c3) at least one kind of copolymerizable unsaturated monomer selected from a group consisting of polystyrene macromonomers and polymethylmethacrylate macromonomers; (D) a polyfunctional monomer; (E) a radiation-sensitive radical generating agent; and (f) a solvent. The pigment (A) contains C.I.Pigment Red 242 by >=20 wt.% and the average particle size r (nm) of the pigment (A) is in the range of 50<=r<=200.

Description

The radiation-sensitive composition that is used for color filter, its preparation method, color filter and color liquid crystal display arrangement
Technical field
The present invention relates to be used for the radiation-sensitive composition of color filter, its preparation method, color filter and color liquid crystal display arrangement.More specifically, relate to the radiation-sensitive composition that is used for color filter, said composition can be used for being manufactured on employed color filter in transmission-type and Reflexible color LCD and the coloured image camera head, also relate to its preparation method, have the color filter of the red pixel of forming by the radiation-sensitive composition that is used for color filter, and the color liquid crystal display arrangement with this color filter.
Background technology
As the method for making color filter with colored radiation-sensitive composition, known method is, in substrate or comprising the coating that forms colored radiation-sensitive composition in the substrate of light shield layer with desired pattern, carry out radiation (being referred to as " exposure " hereinafter) by mask with desired pattern, utilize alkaline developer to develop, so that dissolving is also disposed unexposed portion, and in clean baking oven or after on the heating plate, cure, thereby obtain colour element (with reference to JP-A2-144502 and JP-A3-53201) (term as used herein " JP-A " is " unexamined; disclosed Japanese patent application ").
Therefore because expectation comprises that the liquid crystal indicator of color filter has high brightness, the demand to color filter with high-transmission rate increases.In order to satisfy this demand,, be known that the combination with C.I. paratonere 254 and C.I. paratonere 242 is effective especially as the pigment that is used to form red pixel as disclosed in JP-A 2002-372618.
Along with the immediate development of digital camera and high-definition television, to can show heavy colour for example the needs of the color liquid crystal display arrangement of mazarine sea in winter or the cerise setting sun increase.If " blackness " of black display part do not clearly illustrate out, then will obtain unsharp blurred picture.The pixel or the color layer that therefore, need have high colouring intensity and hard contrast ratio.
Along with liquid crystal indicator is done increasingly dimensionally, the substrate of glass that is used to make color filter is also done increasingly dimensionally.Be known that when substrate being done dimensionally when big, be difficult on the whole surface of substrate and form uniform coat film.The typical coating technique that is used for the radiation-sensitive composition of color filter comprises center drippage cladding process, slit spin coating method and slot coated method.Have been found that when utilizing these coating techniques the rheology of coating solution self can influence coating efficiency greatly.Though with regard to coating efficiency, the expectation rheology of solution is newton's solution, when the dispersion efficiency of pigment dispersion hanged down, the dispersion that obtains trended towards becoming non newtonian solution.In this case, utilize the coating technique of control film thickness by rotation, for example cladding process and slit spin coating method are dripped in the center, will have the difference of film thickness between the core of substrate and end portion.Even utilize the slot coated technology that does not have rotation, also can make transmission and homogenize characteristic become even worse, cause breakdown of coating thus, for example inhomogeneous the or formation striped on the film thickness.Thus, wish that the radiation-sensitive composition that is used for color filter has the rheological properties that approaches newton's solution.
Summary of the invention
An object of the present invention is to provide a kind of radiation-sensitive composition that is used for color filter, this radiation-sensitive composition provides the red pixel with high-transmission rate and hard contrast ratio, and has the rheological properties that is suitable for the large-sized substrates application.
Another object of the present invention provides a kind of preparation method who is used for the radiation-sensitive composition of color filter of the present invention.
Another purpose of the present invention provides a kind of color filter relevant with the preparation method of the radiation-sensitive composition that is used for color filter of the present invention and the color liquid crystal display arrangement with this color filter.
Other purposes of the present invention and advantage will display by following description.
At first, realize above-mentioned purpose of the present invention and advantage by the radiation-sensitive composition that is used for color filter, said composition comprises (A) pigment, (B) spreading agent, (C) alkali soluble resins, this alkali soluble resins comprises (c1), (c2) and multipolymer (c3), wherein (c1) comprises (methyl) acrylic acid unsaturated monomer that contains carboxyl, (c2) be N-substituted maleimide amine, (c3) for being selected from styrene, α-Jia Jibenyixi is to hydroxyl-α-Jia Jibenyixi, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and polymethylmethacrylate macromonomer at least a, (D) polyfunctional monomer, (E) radiosensitive free-radical generating agent and (F) solvent, wherein pigment (A) comprises 20wt% or more C.I. paratonere 242, and mean grain size " r " is 50 to 200 (nm).
Term as used herein " radiation " comprises visible radiation, ultraviolet radiation, far-ultraviolet radiation, electron irradiation and x-ray radiation.
Secondly, the preparation method of the above-mentioned radiation-sensitive composition by being used for color filter realizes above-mentioned purpose of the present invention and advantage, and this method may further comprise the steps:
Disperse (A) pigment in the medium that comprises (B) spreading agent, at least a portion (C) alkali soluble resins and at least a portion (F) solvent, this pigment comprises 20wt% or more C.I. paratonere 242, and mean grain size is greater than 200nm; With
With the dispersion of gained and (D) polyfunctional monomer, (E) radiosensitive free-radical generating agent, and if optional (C) alkali soluble resins that exists mix mutually with (F) solvent.
The 3rd, realize above-mentioned purpose of the present invention and advantage by the color filter that forms by the above-mentioned above-mentioned radiation-sensitive composition that is used for color filter with red pixel.
The 4th, realize above-mentioned purpose of the present invention and advantage by color liquid crystal display arrangement with above-mentioned color filter.
Embodiment
Describe the present invention hereinafter.
(A) pigment
According to Colour Index (C.I.: issued by dyer author and colourist association (The Society of Dyersand Colourists), suitable equally hereinafter), the pigment among the present invention comprises C.I. paratonere 242.
Pigment among the present invention also can comprise the pigment that other depend on the circumstances.
Though above-mentioned other pigment are not subjected to any concrete restriction, organic pigment preferably is because color filter needs the development and the thermotolerance of high-purity, high Transparent color.
The example of above-mentioned other organic pigments is the compounds that are categorized as a pigment group according to Colour Index, particularly is the compound with following Colour Index (C.I.) number:
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 and C.I. pigment yellow 211;
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 51, 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 and C.I. pigment orange 74; With
C.I. paratonere 1, C.I. paratonere 2, C.I. paratonere 5, C.I. Pigment Red 9, C.I. paratonere 17, C.I. pigment red 31, C.I. pigment red 32, C.I. pigment red 41, C.I. Pigment Red 97, 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 208, C.I. paratonere 209, C.I. pigment red 21 4, C.I. pigment red 21 5, C.I. paratonere 220, C.I. paratonere 221, C.I. paratonere 224, C.I. paratonere 243, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 262, C.I. paratonere 264 and C.I. paratonere 272.
In these other organic pigments, be preferably selected from C.I. pigment yellow 13 9, C.I. pigment orange 38, C.I. paratonere 177 and C.I. paratonere 254 at least a, and preferred especially C.I. paratonere 254.
Above-mentioned other organic pigments can use separately, and perhaps two or more are used in combination.
The content of C.I. paratonere 242 is 20wt% or more in pigment of the present invention, promptly 20 to 100wt%, preferred 30 arrives 100wt%, preferred especially 50 to 100wt%.By using this pigment, can obtain to have hard contrast than and the red pixel of high-transmission rate, and can obtain to have the radiation-sensitive composition that is used for color filter of the rheological properties of the large-sized substrates of being applicable to.
In the present invention, can precipitate again before use as required by recrystallization, solvent cleaning, distillation, heating in vacuum or their combination come C.I. paratonere 242 and other pigment are carried out purifying.
The mean grain size " r " of the pigment that uses is 50 to 200nm in the present invention, preferably 50 arrives 150nm.Have the pigment of above-mentioned mean grain size " r " by utilization, can obtain to have hard contrast than and the red pixel of high-transmission rate.The mean grain size of employed here term " mean grain size " expression secondary particle, this secondary particle is the agglomerate of the primary particle (fine monocrystalline) of pigment.
About the size-grade distribution (abbreviating " size-grade distribution " hereinafter as) of the secondary particle of the pigment that uses among the present invention, particle diameter preferably accounts for overall 80wt% or more for the secondary particle of (mean grain size ± 100) nm accounts for overall 70wt% or more.
Can be by commercially available C.I. paratonere 242 (its mean grain size is usually greater than 300nm) and optional other pigment (its mean grain size is usually greater than 300nm) being mixed and being distributed to (B) spreading agent, (C) in alkali soluble resins and the solvent, utilize the muller of ball mill (bead mill) for example or roller mill simultaneously, resulting pigment mixed solution is ground, prepare pigment with above-mentioned mean grain size and size-grade distribution.Usually the pigment of gained is used as pigment dispersion thus.
(B) spreading agent
In the present invention, the example of spreading agent comprises polyoxyethylene alkyl ether, polyoxyethylene lauryl ether for example, polyoxyethylene octadecyl ether and polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ether, for example polyoxyethylene n-octyl phenyl ether and polyoxyethylene n-nonyl phenyl ether; Polyethylene glycol di, for example polyethylene glycol dilaurate and polyglycol distearate; Sorbitan fatty acid esters; Fatty acid modified polyester; The polyurethane of tertiary amine modification; And polyethyleneimine.Can on market, buy these spreading agents: KP (Shin-Etsu chemistry company limited), Polyflow (Kyoeisha Kagaku company limited), FTop (Tokem Products Co., Ltd) with following trade name, Megafac (Dainippon printing ink and chemical company), Florade (Sumitomo 3M company limited), Asahi Guard and Surflon (Asahi Glass Co., Ltd.), Disperbyk-101 ,-103 ,-107,-110 ,-111 ,-115,-130 ,-160 ,-161,-162 ,-163 ,-164,-165 ,-166 ,-170,-180 ,-182 ,-2000 and-2001 (the Japanese company limiteds of BYK chemistry), Solsperse S5000,12000,13240,13940,17000,20000,22000,24000,24000GR, 26000,27000 and 28000 (Avicia company limiteds), EFKA 46,47,48,745,4540,4550,6750, EFKA LP4008,4009,4010,4015,4050,4055,4560,4800, EFKA polymkeric substance 400,401,402,403,450,451 and 453 (EFKA chemistry company limited) and AdisparPB-821 and 822 (Ajinomoto Fine Techno technology company limited).
These spreading agents can use separately, but perhaps two or more are used in combination.
Based on the pigment (A) of 100 weight portions, the quantity of spreading agent (according to solids content) 1 to 50 weight portion preferably is more preferably 3 to 30 weight portions among the present invention.When the quantity of spreading agent during less than 1 weight portion, the storage stability of resulting composition can reduce, and when the quantity of spreading agent during greater than 50 weight portions, will produce residue in substrate.
It is identical with the solvent of the radiation-sensitive composition that is used for color filter of the present invention that will illustrate hereinafter to be used to prepare the solvent of pigment dispersion.
Based on the pigment of 100 weight portions, the amount of solvents that is used to prepare pigment dispersion is 500 to 1000 weight portions preferably, are more preferably 700 to 900 weight portions.
In order to utilize ball mill to prepare pigment dispersion, preferably be about 0.5 to 10mm beaded glass or titania pearl and the solution that has mixed pigment is mixed and disperse with diameter, with chilled water etc. it is cooled off simultaneously.
The filling rate of pearl preferably the muller capacity 50 to 80%, and the solution that is mixed with pigment that injects is 20 to 50% of muller capacity approximately.In preferably 2 to 50 hours processing time, be more preferably 2 to 25 hours.
In order to utilize roller mill to prepare pigment dispersion, preferably utilize three-roll grinder or two roller mills to mix the solution of hybrid pigment, with chilled water etc. it is cooled off simultaneously.
Spacing between roller is 10 μ m or still less preferably, and shearing force preferably is 10 approximately 8Dyne/second.In preferably 2 to 50 hours processing time, be more preferably 2 to 25 hours.
Can utilize the dynamic light scattering method, the mean grain size and the size-grade distribution that are included in the pigment in the pigment dispersion of so preparing are measured.
(C) alkali soluble resins
In the present invention, alkali soluble resins is as the bonding agent of pigment (A), and the dissolubility that has in developer, special preferably employed alkaline developer in the development step of color filter manufacturing process.Though it is not subjected to special qualification, but the alkali soluble resins that preferably has carboxyl, preferably have especially at least one carboxyl ethylenically unsaturated monomers (being referred to as " comprising the unsaturated monomer of carboxyl " hereinafter) but with the multipolymer (being referred to as " comprising the multipolymer of carboxyl " hereinafter) of the ethylenically unsaturated monomers (being referred to as " but unsaturated monomer of copolymerization " hereinafter) of other copolymerization.
The example that comprises the unsaturated monomer of carboxyl comprises unsaturated monocarboxylic acid, (methyl) acrylic acid for example, crotonic acid, α-Lv Bingxisuan and cinnamic acid; Unsaturated dicarboxylic acid and acid anhydrides thereof, maleic acid for example, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; Unsaturated polybasic carboxylic acid and acid anhydrides thereof with three and more a plurality of carboxyls; List [(methyl) acryloxyalkyl] ester with polybasic carboxylic acid of two or more carboxyls, for example single [2-(methyl) acryloxy ethyl] succinate and single [2-(methyl) acryloxy ethyl] phthalic ester; With list (methyl) acrylate that has the polymkeric substance of carboxyl and hydroxyl at two ends, ω-carboxyl polycaprolactone list (methyl) acrylate for example.
Among above-mentioned these comprise the unsaturated monomer of carboxyl, single (2-acryloxy ethyl) succinate and single (2-acryloxy ethyl) phthalic ester can buy on market, and its trade name is respectively (Toagosei chemical industry company limited) M-5300 and M-5400.
The above-mentioned unsaturated monomer that comprises carboxyl can use separately, but perhaps two or more are used in combination.
But the example of copolymerization unsaturated monomer comprises maleimide; N-substituted maleimide amine, N-phenylmaleimide for example, N-salicyl maleimide, N-resorcyl maleimide, N-is to the hydroxyphenyl maleimide, N-benzyl maleimide, N-cyclohexyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester and N-(acridinyl) maleimide; Aromatic vinyl compound, styrene for example, α-Jia Jibenyixi, adjacent vinyltoluene, a vinyltoluene is to vinyltoluene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, 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 glycidol ether, between vinyl benzyl glycidol ether and to the vinyl benzyl glycidol ether; Indenes, for example indenes and 1-methyl indenes; Esters of unsaturated carboxylic acids, (methyl) methyl acrylate for example, (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-Hydroxy ethyl acrylate, (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 dipropyl glycol ester, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester and single (methyl) acrylic acid glyceride; The unsaturated carboxylic acid aminoalkyl ester, (methyl) acrylic acid 2-amino ethyl ester for example, (methyl) acrylic acid 2-dimethylaminoethyl, 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-and (methyl) acrylic acid 3-dimethylamino propyl ester; Unsaturated carboxylic acid ethylene oxidic ester, for example (methyl) glycidyl acrylate; Vinyl carboxylates, vinyl acetate for example, propionate, vinyl butyrate and vinyl benzoate; The unsaturated ethers of other types, vinyl methyl ether for example, EVE and allyl glycidyl ether; Vinyl cyanide compound, (methyl) vinyl cyanide for example, α-Lv Daibingxijing and vinylidene cyanide; Unsaturated amides, (methyl) acrylamide for example, alpha-chloro acrylamide and N-2-hydroxyethyl (methyl) acrylamide; The aliphatics conjugated diolefine, 1,3-butadiene for example, isoprene and chlorbutadiene; And has the macromonomer of list (methyl) acryloyl group at the polymer molecule end of the chain, polystyrene for example, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate and polysiloxane.
But above-mentioned these copolymerization unsaturated monomers can use separately, but perhaps two or more are used in combination.
In the present invention, comprise the multipolymer (being referred to as " comprising the multipolymer (C1) of carboxyl " hereinafter) that the multipolymer of carboxyl preferably is grouped into by following three kinds of one-tenth, promptly (c1) comprises and contains the carboxyl unsaturated monomer as (methyl) acrylic acid of basis and optional list [2-(methyl) acryloxy ethyl] succinate and/or ω-carboxyl polycaprolactone list (methyl) acrylate, (c2) N-substituted maleimide amine and (c3) be selected from styrene, α-Jia Jibenyixi, to hydroxyl-α-Jia Jibenyixi, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) allyl acrylate, (methyl) benzyl acrylate, monomethyl) acrylic acid glyceride, but at least a other copolymerization unsaturated monomers of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer.
The preferred embodiment that comprises the multipolymer (C1) of carboxyl comprises (methyl) acrylic acid, N-phenylmaleimide, the multipolymer of styrene and (methyl) benzyl acrylate, (methyl) acrylic acid, N-resorcyl maleimide, the multipolymer of styrene and (methyl) benzyl acrylate, (methyl) acrylic acid, N-is to the hydroxyphenyl maleimide, the multipolymer of styrene and (methyl) benzyl acrylate, (methyl) acrylic acid, N-cyclohexyl maleimide, the multipolymer of styrene and (methyl) benzyl acrylate, (methyl) acrylic acid, N-phenylmaleimide, the multipolymer of α-Jia Jibenyixi and (methyl) benzyl acrylate, (methyl) acrylic acid, N-phenylmaleimide, multipolymer to hydroxyl-α-Jia Jibenyixi and (methyl) benzyl acrylate, (methyl) acrylic acid, N-phenylmaleimide, styrene, the multipolymer of (methyl) acrylic acid 2-hydroxyl ethyl ester and (methyl) benzyl acrylate, (methyl) acrylic acid, N-phenylmaleimide, styrene, the multipolymer of (methyl) benzyl acrylate and single (methyl) acrylic acid glyceride, (methyl) acrylic acid, N-is to the hydroxyphenyl maleimide, styrene, the multipolymer of (methyl) benzyl acrylate and single (methyl) acrylic acid glyceride, (methyl) acrylic acid, N-phenylmaleimide, styrene, (methyl) phenyl acrylate, the multipolymer of (methyl) acrylic acid 2-hydroxyl ethyl ester and polystyrene macromolecular monomer, (methyl) acrylic acid, N-phenylmaleimide, styrene, (methyl) phenyl acrylate, the multipolymer of (methyl) acrylic acid 2-hydroxyl ethyl ester and polymethylmethacrylate macromonomer, (methyl) acrylic acid, single [2-(methyl) acryloxy ethyl] succinate, N-phenylmaleimide, the multipolymer of styrene and (methyl) benzyl acrylate, (methyl) acrylic acid, single [2-(methyl) acryloxy ethyl] succinate, N-is to the hydroxyphenyl maleimide, the multipolymer of styrene and (methyl) benzyl acrylate, (methyl) acrylic acid, single [2-(methyl) acryloxy ethyl] succinate, N-phenylmaleimide, the multipolymer of styrene and (methyl) allyl acrylate, (methyl) acrylic acid, single [2-(methyl) acryloxy ethyl] succinate, N-cyclohexyl maleimide, the multipolymer of styrene and (methyl) allyl acrylate, (methyl) acrylic acid, single [2-(methyl) acryloxy ethyl] succinate, N-cyclohexyl maleimide, the multipolymer of styrene and (methyl) benzyl acrylate, (methyl) acrylic acid, ω-carboxyl polycaprolactone list (methyl) acrylate, N-resorcyl maleimide, the multipolymer of styrene and (methyl) benzyl acrylate, (methyl) acrylic acid, ω-carboxyl polycaprolactone list (methyl) acrylate, N-is to the hydroxyphenyl maleimide, the multipolymer of styrene and (methyl) benzyl acrylate, (methyl) acrylic acid, ω-carboxyl polycaprolactone list (methyl) acrylate, N-phenylmaleimide, styrene, multipolymer and (methyl) acrylic acid of (methyl) benzyl acrylate and single (methyl) acrylic acid glyceride, ω-carboxyl polycaprolactone list (methyl) acrylate, N-is to the hydroxyphenyl maleimide, styrene, the multipolymer of (methyl) benzyl acrylate and single (methyl) acrylic acid glyceride.
Except the multipolymer (C1) that comprises carboxyl, the example that comprises the multipolymer of carboxyl also comprises the multipolymer of (methyl) acrylic acid and (methyl) methyl acrylate, the multipolymer of (methyl) acrylic acid and (methyl) benzyl acrylate, (methyl) acrylic acid, the multipolymer of (methyl) acrylic acid 2-hydroxyl ethyl ester and (methyl) benzyl acrylate, (methyl) acrylic acid, the multipolymer of (methyl) methyl acrylate and polystyrene macromolecular monomer, (methyl) acrylic acid, the multipolymer of (methyl) methyl acrylate and polymethylmethacrylate macromonomer, (methyl) acrylic acid, the multipolymer of (methyl) benzyl acrylate and polystyrene macromolecular monomer, (methyl) acrylic acid, the multipolymer of (methyl) benzyl acrylate and polymethylmethacrylate macromonomer, (methyl) acrylic acid, (methyl) acrylic acid 2-hydroxyl ethyl ester, the multipolymer of (methyl) benzyl acrylate and polystyrene macromolecular monomer and (methyl) acrylic acid, (methyl) acrylic acid 2-hydroxyl ethyl ester, the multipolymer of (methyl) benzyl acrylate and polymethylmethacrylate macromonomer.
In comprising the multipolymer of carboxyl, the content that comprises the unsaturated monomer of carboxyl preferably 5 arrives 50wt%, is more preferably 10 to 40wt%.When the content of the unsaturated monomer that comprises carboxyl was less than 5wt%, the solubleness of gained radiation-sensitive composition in alkaline developer can reduce, and when its content during more than 50wt%, the solubleness of radiation-sensitive composition in alkaline developer can become too high.The result is that when utilizing alkaline developer that composition is developed, pixel may may become coarse from the film surface of substrate disengaging and pixel.
In comprising the multipolymer of carboxyl (C1), the content that comprises the unsaturated monomer of carboxyl preferably 5 arrives 50wt%, is more preferably 10 to 40wt%.When the content of the unsaturated monomer that comprises carboxyl was less than 5wt%, the solubleness of gained radiation-sensitive composition in alkaline developer can reduce, and when its content during more than 50wt%, the solubleness of radiation-sensitive composition in alkaline developer can become too high.The result is that when utilizing alkaline developer that composition is developed, pixel may break away from from substrate.
The content of N-substituted maleimide amine preferably 5 arrives 40wt%, is more preferably 10 to 30wt%.When the content of N-substituted maleimide amine is less than 5wt%, during developing, may produce residue, and when its content during more than 40wt%, pixel may variation to the adhesion of substrate.
In addition, but the content of other copolymerization unsaturated monomers preferably 30 arrives 90wt%, is more preferably 40 and arrives 80wt%.When but the content of other copolymerization unsaturated monomers was less than 30wt%, pixel may variation to the adhesion of substrate, and when content during more than 90wt%, the solubleness in alkaline developer may reduce.
(GPC, eluting solvent: tetrahydrofuran) weight-average molecular weight of measured alkali soluble resins (Mw) preferably 3000 to 300000, are more preferably 5000 to 100000 to utilize gel permeation chromatography.
(GPC, eluting solvent: tetrahydrofuran) number-average molecular weight of measured alkali soluble resins (Mn) preferably 3000 to 60000, are more preferably 5000 to 25000 to utilize gel permeation chromatography.
In the present invention, the Mw/Mn of alkali soluble resins is more preferably 1 to 4 than preferably 1 to 5.
In the present invention, the alkali soluble resins that has specific Mw and Mn by utilization, obtain to have the radiation-sensitive composition of fabulous development, and can form pattern of pixels thus with clear pattern edge, and during developing, on the light shield layer of substrate and unexposed portion, be difficult to produce residue, stain or thin film residue.
In the present invention, above-mentioned alkali soluble resins can use separately, but perhaps two or more are used in combination.
In the present invention, based on the pigment (A) of 100 weight portions, the quantity of alkali soluble resins is 10 to 1000 weight portions preferably, are more preferably 20 to 500 parts.When the quantity of alkali soluble resins was less than 10 weight portions, alkalescence development property may reduce, and perhaps may produce stain or thin film residue on the light shield layer of substrate and unexposed portion.When its quantity during more than 1000 weight portions, it is low relatively that the concentration of pigment becomes, thereby may be difficult to obtain the object color component intensity of film.
(D) polyfunctional monomer
In the present invention, polyfunctional monomer is the monomer with two or more polymerizable unsaturated bonds.
The example of polyfunctional monomer comprises two (methyl) acrylate of aklylene glycol such as ethylene glycol and propylene glycol; Two (methyl) acrylate of poly alkylene glycol such as polyglycol and polypropylene glycol; Polyvalent alcohol such as glycerine with 3 or more a plurality of hydroxyls, trimethylolpropane, poly-(methyl) acrylate and its dicarboxylic acids modified product of pentaerythrite and dipentaerythritol; (methyl) acrylate oligomer, polyester for example, epoxy resin, urethane resin, alkyd resin, silicones and spirane resin; Two (methyl) acrylate that has the polymkeric substance of hydroxyl at two ends for example has the poly-1,3-butadiene of hydroxyl at two ends, have the polyisoprene of hydroxyl at two ends and have the polycaprolactone of hydroxyl at two ends; With three [2-(methyl) acryloxy ethyl] phosphate.
Among above-mentioned these polyfunctional monomers, poly-(methyl) acrylate and the dicarboxylic acids modified product thereof that preferably have the polyvalent alcohol of 3 or more a plurality of hydroxyls, trimethylolpropane tris (methyl) acrylate for example, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, with dipentaerythritol six (methyl) acrylate, preferred especially trimethylolpropane triacrylate among these, pentaerythritol triacrylate and dipentaerythritol acrylate, because they provide the pixel with excellent in strength and surface flatness, and on the light shield layer of substrate and unexposed portion, be difficult to produce stain or thin film residue.
Above-mentioned polyfunctional monomer can use separately, but perhaps two or more are used in combination.
In the present invention, based on the alkali soluble resins (C) of 100 weight portions, the quantity of polyfunctional monomer is 5 to 500 weight portions preferably, are more preferably 20 to 300 weight portions.When the quantity of polyfunctional monomer is less than 5 weight portions, the intensity of pixel and surface flatness may variation, and when its quantity during more than 500 weight portions, alkalescence development property may reduce, and perhaps can produce stain and thin film residue on the light shield layer of substrate and unexposed portion.
In the present invention, the monofunctional monomer with a polymerizable unsaturated bond can be used in combination with polyfunctional monomer.
The example of above-mentioned monofunctional monomer is included as above-mentioned alkali soluble resins (C) but the cited above-mentioned unsaturated monomer of carboxyl and the unsaturated monomer of copolymerization of comprising; N-(methyl) acryloyl morpholine; the N-vinyl pyrrolidone, N-vinyl epsilon-caprolactams and commercially available M-5600 (Toagosei chemical industry company limited).
Above-mentioned monofunctional monomer can use separately, but perhaps two or more are used in combination.
In the present invention, based on the general assembly (TW) of polyfunctional monomer and monofunctional monomer, the quantity of monofunctional monomer is 90wt% or still less preferably, more preferably 50wt% or still less.When the quantity of monofunctional monomer during more than 90wt%, it is unsatisfactory that the intensity of pixel and surface flatness can become.
In the present invention, based on the alkali soluble resins (C) of 100 weight portions, the total quantity of polyfunctional monomer and monofunctional monomer is 5 to 500 weight portions preferably, are more preferably 20 to 300 weight portions.When above-mentioned total quantity is less than 5 weight portions, the intensity of pixel and surface flatness may variation, and when its quantity during more than 500 weight portions, alkalescence development property may reduce, and perhaps may produce stain and thin film residue on the opacifier layer of substrate and unexposed portion.
(E) radiosensitive free-radical generating agent
In the present invention, radiosensitive free-radical generating agent is a kind of like this compound, it can form active specy when exposing under radiation, this active specy can cause above-mentioned polyfunctional monomer (D) and the optional monofunctional monomer polymerization of using, and described radiation is for example visible radiation, ultraviolet radiation, far-ultraviolet radiation, electron irradiation or x-ray radiation.
The example of radiosensitive free-radical generating agent comprises the acetophenone based compound, bisglyoxaline based compound, triazine-based compound, the benzoin based compound, benzophenone based compound, α-diketone based compound, the quinone based compound, photosensitive article thing of many rings, xanthone based compound and diazo compound.
In the present invention, above-mentioned radiosensitive free-radical generating agent can be used separately, but perhaps two or more are used in combination.In the present invention, radiosensitive free-radical generating agent preferably is selected from the acetophenone based compound, bisglyoxaline based compound and triazine-based compound at least a.
In the present invention, the example of acetophenone based compound comprises 2-hydroxyl 2-methyl 1-phenylacetone-1 in preferred radiosensitive free-radical generating agent, 2-methyl 1-(4-methyl mercapto phenyl)-2-morpholino acetone-1,2-benzyl 2-dimethylamino-1-(4-morpholino phenyl) butanone-1,1-hydroxycyclohexylphenylketone and 2,2-dimethoxy 1,2-diphenyl ethyl ketone-1.
In above-mentioned these acetophenone based compounds, preferred especially 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino acetone-1 and 2-benzyl-2-dimethylamino 1-(4-morpholino phenyl) butanone-1.
Above-mentioned acetophenone based compound can use separately, but perhaps two or more are used in combination.
In the present invention, when the acetophenone based compound is used as radiosensitive free-radical generating agent, based on the polyfunctional monomer (D) of 100 weight portions and the total amount of monofunctional monomer, the quantity of acetophenone based compound is 0.01 to 100 weight portion preferably, be more preferably 1 to 80 weight portion, especially preferably 5 to 60 weight portions.When the quantity of acetophenone based compound is less than 0.01 weight portion,, may be difficult to obtain having the dyed layer of intended pixel pattern because the curing that exposure is caused is incomplete.When the quantity of acetophenone based compound during more than 100 weight portions, the pixel that forms may break away from from substrate during developing.
The example of above-mentioned bisglyoxaline based compound comprises 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 and 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl 1,2 '-bisglyoxaline.
In above-mentioned these bisglyoxaline based composition and use thereof in packaging, 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 and 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl 1,2 '-bisglyoxaline is preferred, and 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl 1,2 '-bisglyoxaline are particularly preferred.
Above-mentioned bisglyoxaline based compound has fabulous solubleness in solvent, do not produce for example insoluble matter and sedimentary impurity, have high sensitivity, just can fully promote curing reaction, and do not make unexposed portion generation curing reaction by the exposure that utilizes less energy.Thus, the coat film that is obtained after the exposure clearly is divided into cured portion that is insoluble to developer and the uncured portion that has high-dissolvability in developer, might form thus to have the high-resolution dyed layer intended pixel pattern and that do not cave in.
Above-mentioned bisglyoxaline based compound can use separately, but perhaps two or more are used in combination.
In the present invention, when the bisglyoxaline based compound is used as radiosensitive free-radical generating agent, polyfunctional monomer (D) and monofunctional monomer total amount based on 100 weight portions, the quantity of bisglyoxaline based compound is 0.01 to 40 weight portion preferably, be more preferably 1 to 30 weight portion, especially preferably 1 to 20 weight portion.When the quantity of bisglyoxaline based compound is less than 0.01 weight portion,, may be difficult to obtain having the dyed layer of intended pixel pattern because the curing that exposure is caused is incomplete.When the quantity of bisglyoxaline based compound during more than 40 weight portions, the pixel that forms may break away from from substrate during developing.
-hydrogen donor-
In the present invention, when with the bisglyoxaline based compound during, preferably be used in combination, so that further improve sensitivity with following hydrogen donor as radiosensitive free-radical generating agent.
Here employed term " hydrogen donor " expression can provide the compound of hydrogen atom to the free radical that is formed by the bisglyoxaline based compound by exposure.
In the present invention, preferred hydrogen donor is the mercapto compound or the amino-compound of following defined.
Described mercapto compound is phenyl ring or the heterocycle that has as female ring, and 1 or more, preferred 1 to 3, and the more preferably compound (being referred to as " mercapto hydrogen donor " hereinafter) of the sulfydryl that directly closes with female loops of 1 or 2.
Described amino-compound is phenyl ring or the heterocycle that has as female ring, and 1 or more, preferred 1 to 3, and the more preferably compound (being referred to as " amino hydrogen donor " hereinafter) of the amino that directly closes with female loops of 1 or 2.
These hydrogen donors can have sulfydryl and amino simultaneously.
To provide detailed description subsequently about these hydrogen donors.
The mercapto hydrogen donor can have at least one phenyl ring or heterocycle, or has the two simultaneously.When it has two or more above-mentioned rings, can form condensed ring, also can not form condensed ring.
When the mercapto hydrogen donor has two or more sulfydryls, as long as keep at least one free sulfydryl, can use alkyl, aralkyl or aryl replace at least one other sulfydryl.In addition, as long as keep at least one free sulfydryl, the mercapto hydrogen donor can have a kind of like this structural unit, for example wherein utilizing, the divalent organic base of alkylidene combines two sulphur atoms, or have another kind of structural unit, wherein the form with disulfide combines two sulphur atoms.
In addition, can utilize carboxyl, alkoxy carbonyl group, substituted alkoxycarbonyl, carbobenzoxy, substituted benzene oxygen carbonyl or itrile group come the substituted thiol group hydrogen donor on the position except the sulfydryl position.
The example of mercapto hydrogen donor comprises 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto 1,3,4-thiadiazoles and 2-sulfydryl-2,5-dimethylamino naphthyridine.
In above-mentioned these mercapto hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferred, and 2-mercaptobenzothiazole is particularly preferred.
Amino hydrogen donor can have at least one phenyl ring or heterocycle, or has the two simultaneously.When it has two or more above-mentioned rings, can form condensed ring, also can not form condensed ring.
Can utilize alkyl or substituted alkyl to come at least one amino in the substituted-amino hydrogen donor.Can utilize carboxyl, alkoxy carbonyl, the substituted alkoxy carbonyl, phenyloxycarbonyl, substituted benzene oxygen carbonyl or itrile group come the substituted-amino hydrogen donor on the position except amino position.
The example of above-mentioned amino hydrogen donor comprises 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (lignocaine) benzophenone, 4-lignocaine acetophenone, 4-dimethylamino propiophenone, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid and 4-dimethylamino phenyl cyanogen.
In these amino hydrogen donors, 4,4 '-two (dimethylamino) benzophenone and 4,4 '-two (lignocaine) benzophenone are preferred, and 4,4 '-two (dimethylamino) benzophenone is particularly preferred.
Even when the radiosensitive free-radical generating agent used except the bisglyoxaline based compound, also can be with amino hydrogen donor as sensitizer.
In the present invention, above-mentioned hydrogen donor can use separately, but perhaps two or more are used in combination.Preferably use the composition of at least a mercapto hydrogen donor and at least a amino hydrogen donor,, and have high strength and sensitivity during developing because formed pixel can not break away from from substrate.
The mercapto hydrogen donor comprises with the preferred embodiment that amino hydrogen donor combines, 2-mercaptobenzothiazole and 4, the composition of 4 '-two (dimethylamino) benzophenone, 2-mercaptobenzothiazole and 4, the composition of 4 '-two (diethylamino sulfydryl) benzophenone, 2-mercaptobenzoxazole and 4, the composition of 4 '-two (dimethylamino) benzophenone, 2-mercaptan mercaptobenzoxazole and 4, the composition of 4 '-two (lignocaine) benzophenone.In these compositions, 2-mercaptan mercaptobenzothiazoler and 4, the composition of 4 '-two (lignocaine) benzophenone, with 2-mercaptobenzoxazole and 4, the composition of 4 '-two (lignocaine) benzophenone is preferred, and 2-mercaptobenzothiazole and 4, the composition of 4 '-two (lignocaine) benzophenone is particularly preferred.
In the composition of mercapto hydrogen donor and amino hydrogen donor, the weight ratio of mercapto hydrogen donor and amino hydrogen donor preferably 1: 1 to 1: 4 is more preferably 1: 1 to 1: 3.
In the present invention, when hydrogen donor was used in combination with the bisglyoxaline based compound, based on the total amount of polyfunctional monomer (D) monofunctional monomer of 100 weight portions, the quantity of hydrogen donor is 0.01 to 40 weight portion preferably, be more preferably 1 to 30 weight portion, especially preferably 1 to 20 weight portion.When the quantity of hydrogen donor was less than 0.01 weight portion, its effect that improves sensitivity may descend.When the quantity of hydrogen donor during more than 40 weight portions, the pixel that forms may break away from from substrate during developing.
The example of above-mentioned triazine-based compound comprises the triazine-based compound with halomethyl, for example 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4,6-two (trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-[2-(furans-2-yl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-[2-(4-lignocaine-2-aminomethyl phenyl) alkene ethyl]-4,6-two (trichloromethyl)-s-triazine, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-two (trichloromethyl)-s-triazine, 2-(4-ethoxybenzene vinyl)-4,6-two (trichloromethyl)-s-triazine and 2-(4-n-butoxy phenyl)-4,6-two (trichloromethyl)-s-triazine.
In these triazine-based compounds, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4,6-two (trichloromethyl)-s-triazine is particularly preferred.
Above-mentioned triazine-based compound can use separately, but perhaps two or more are used in combination.
In the present invention, when triazine-based compound is used as radiosensitive free-radical generating agent, total amount based on the polyfunctional monomer and the monofunctional monomer of 100 weight portions, the quantity of triazine-based compound is 0.01 to 40 weight portion preferably, be more preferably 1 to 30 weight portion, especially preferably 1 to 20 weight portion.When the quantity of triazine-based compound is less than 0.01 weight portion,, may be difficult to obtain having the dyed layer of intended pixel pattern because the curing that exposure is caused is incomplete.When the quantity of triazine-based compound during more than 40 weight portions, the pixel that forms may break away from from substrate during developing.
-adjuvant-
The radiation-sensitive composition that is used for color filter among the present invention can comprise various adjuvants on demand.
Above-mentioned adjuvant comprises organic acid or organic amino compounds (not comprising above-mentioned hydrogen donor), improves in the solubleness of radiation-sensitive composition in alkaline developer as further, and suppress the not existence of lysate residue after development.
Above-mentioned organic acid is aliphatic carboxylic acid or comprise the carboxylic acid of phenyl preferably, has at least one carboxyl in molecule.
The example of aliphatic carboxylic acid comprises the aliphatics monocarboxylic acid, formic acid for example, acetate, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethacetic acid, acetate and sad; Aliphatic dicarboxylic acid, ethane diacid for example, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, tridecandioic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, dimethyl succinic acid, tetramethyl-succinic acid, cyclohexane dicarboxylic acid, methylene-succinic acid, methyl-maleic acid, maleic acid, fumaric acid and mesaconic acid; And aliphatic tricarboxylic acids, tricarballylic acid for example, aconitic acid and camphoronic acid.
The above-mentioned carboxylic acid that comprises phenyl for example is the compound with the carboxyl that directly combines with phenyl, or has the compound of the carboxyl that combines with phenyl by the divalence carbochain.
The example that comprises the carboxylic acid of phenyl comprises the one dollar aromatic carboxylic acid, benzoic acid for example, toluic acid, cumfrey, 2, the 3-mesitylenic acid and
Figure C20051010380700181
Woods acid; Aromatic dicarboxylic acid, phthalic acid for example, isophthalic acid and terephthalic acids; Aromatic multi-carboxy acid with 3 or more a plurality of carboxyls, trihemellitic acid for example, trimesic acid, mellophanic acid and pyromellitic acid; And phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, inferior cinnamic acid, coumaric acid and 2,4 dihydroxycinnamic acids.
In these organic acids, preferably aliphatic dicarboxylic acid is used as aliphatic carboxylic acid, and the solubleness from alkali solubility, the solvent that will be described below and prevent substrate and and the light shield layer of unexposed portion produce the viewpoint of stain or thin film residue, preferred especially malonic acid, hexane diacid, methylene-succinic acid, methyl-maleic acid, fumaric acid and mesaconic acid.Preferably aromatic dicarboxylic acid is used as the carboxylic acid that comprises phenyl, and preferred especially phthalic acid.
Above-mentioned organic acid can use separately, but perhaps two or more are used in combination.
Based on total amount be (A) of 100 weight portions to (E) composition and adjuvant, organic acid quantity is 15 weight portions or still less preferably, are more preferably 10 weight portions or still less.When organic acid quantity during greater than 15 weight portions, the adhesion of formed pixel and substrate may reduce.
Above-mentioned organic amino compounds is aliphatic amine or comprise the amine of phenyl preferably, has at least one amino in molecule.
The example of above-mentioned aliphatic amine comprises one (ring) alkyl amine, n-propylamine for example, isopropylamine, n-butylamine, isobutyl amine, sec-butylamine, tert-butylamine, n-amylamine and n-hexylamine; Two (ring) alkyl amine, Methylethyl amine for example, diethylamine, methyl n-pro-pyl amine, ethyl n-pro-pyl amine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-iso-butylmanice, di-sec-butylamine and two tert-butylamines; Three (ring) alkyl amine, dimethylethyl amine for example, methyl diethylamide, triethylamine, dimethyl n propyl group amine, diethyl n-pro-pyl amine, methyl di-n-propyl amine, ethyl di-n-propyl amine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, triisobutylamine, tri sec-butylamine and three tert-butylamines; One (ring) alkanolamine, 2-ethylaminoethanol for example, the amino 1-propyl alcohol of 3-, the amino 1-butanols of 1-amino-2-propyl alcohol and 4-; Two (ring) alkanolamine, diethanolamine for example, two n-propanol amine, diisopropanolamine, two normal butyl alcohol amine and two isobutyl hydramine; Three (ring) alkanolamine, triethanolamine for example, three n-propanol amine, triisopropanolamine, three normal butyl alcohol amine and three isobutyl hydramine; Amino (ring) alkane glycol, 3-amino-1 for example, 2-propylene glycol, 2-amino-1, ammediol, 4-amino-1, the 2-butylene glycol, 4-amino-1,3 butylene glycol, 3-dimethylamino-1,2-propylene glycol, 3-lignocaine-1, the 2-propylene glycol, 2-dimethylamino-1, ammediol and 2-lignocaine-1, ammediol; And amino carboxylic acid, for example Beta-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid and 3-aminoisobutyric acid.
The above-mentioned amino that comprises phenyl for example is to have the compound of the amino that directly combines with phenyl, or have the compound of the amino that combines with phenyl by the divalence carbochain.
The example that comprises the amine of phenyl comprises, aromatic amine, and aniline for example, o-toluidine, a methylaniline, to methylaniline, to ethylaniline, naphthalidine, 2-naphthylamines, N, accelerine, N, N-diethylaniline and, accelerine to methyl-N; Aminobenzyl alcohol, for example adjacent aminobenzyl alcohol, an aminobenzyl alcohol is to aminobenzyl alcohol, to dimethylamino benzylalcohol with to diethylamino benzylalcohol; Amino-phenol, o-aminophenol for example, m-aminophenol, para-aminophenol is to dimethylamino phenol with to diethylamino phenol; And aminobenzoic acid, gavaculine for example, p-aminobenzoic acid, ESCAROL 507 and to the diethyl amino yl benzoic acid.
In these organic amino compounds, preferably with (ring) alkanolamine and amino (ring) alkane glycol as aliphatic amine, and the solubleness from the solvent that will be described below and prevent substrate and and the light shield layer of unexposed portion produce the viewpoint of stain or thin film residue, preferred especially 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino 1,2-propylene glycol, 2-amino-1, ammediol and 4-amino-1, the 2-butylene glycol.Preferably with amino-phenol as the amino that comprises phenyl, and preferred especially o-aminophenol, m-aminophenol and para-aminophenol.
Above-mentioned organic amino compounds can use separately, but perhaps two or more are used in combination.
Based on (A) of the 100 weight portions total amount to (E) composition and adjuvant, the quantity of organic amino compounds is 15 weight portions or still less preferably, are more preferably 10 weight portions or still less.When the quantity of organic amino-compound during greater than 15 weight portions, the adhesion of formed pixel and substrate may reduce.
Except above-mentioned adjuvant, adjuvant also comprises dispersing aid, for example blue pigment derivant or yellow uitramarine derivant, for example copper phthalocyanine derivative thing; Filler, for example glass or aluminium oxide; Polymer compound, polyvinyl alcohol (PVA) for example, polyalkylene glycol monoalkyl ether or poly-(acrylic acid fluoroalkyl ester); Nonionic, kation or anionic surfactant; Adhesion promotor, vinyltrimethoxy silane for example, 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-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane or 3-sulfydryl propyl trimethoxy silicane; Antioxidant, for example 2,2-thiobis (4-methyl-6-tert butyl phenol) or 2,6 di t butyl phenol; Ultraviolet light absorber, for example 2-(the 3-tert-butyl group-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxy benzophenone; Adherence inhibitor, for example sodium polyacrylate; Produce agent with hot radical, for example 1,1 '-azo two (cyclohexane-1-nitrile) or 2-phenylazo-4-methoxyl 2,4-methyl pentane nitrile.
(F) solvent
As solvent of the present invention, if this solvent disperse or dissolve constitute radiation-sensitive composition (A) to (E) composition and adjuvant, and can not catch up with and state composition and react and have suitable volatility, just can use.
The example of solvent comprises alcohol, methyl alcohol for example, ethanol and phenmethylol; (gathering) alkylene glycol monoalkyl ethers, glycol monomethyl methyl ether for example, ethylene glycol monomethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diglycol monotertiary methyl ether, carbiphene, the diglycol monotertiary positive propyl ether, diglycol monotertiary n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether, dipropyl glycol monomethyl ether, dipropyl glycol list ethylether, dipropyl glycol list positive propyl ether, dipropyl glycol mono-n-butyl ether, 3 third glycol monomethyl ether and 3 third glycol list ethylethers; (gathering) alkylene glycol monoalkyl ethers acetate, ethylene glycol monomethyl ether acetate for example, ethylene glycol monomethyl ether acetate, ethylene glycol propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, the diglycol monomethyl ether acetate, the carbiphene acetate, diglycol monotertiary positive propyl ether acetate, diglycol monotertiary n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol list ethylether acetate and 3-methoxy butylacetic acid ester; Other types ether, diethylene glycol dimethyl ether for example, diglycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketone, methyl ethyl ketone for example, cyclohexanone, the 2-heptanone, the 3-heptanone, diacetone alcohol (4-hydroxy-4-methyl penta-2-ketone) and 4-hydroxy-4-methyl oneself-2-ketone; Lactic acid alkyl ester, for example methyl lactate and ethyl lactate; The other types ester, ethyl acetate for example, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl formate, acetate 3-methyl-3-methoxy butyl ester, n-butyl propionate, propionic acid 3-methyl-3-methoxy butyl ester, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, hydroxyl ethyl acetate, ethoxy ethyl acetate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-hydroxyl 2 Methylpropionic acid ethyl ester, 2-hydroxy-3-methyl methyl butyrate and 2-ketobutyric acid ethyl ester; Aromatic hydrocarbon, for example toluene and dimethylbenzene; And acid amides, N-Methyl pyrrolidone for example, N, dinethylformamide and N,N-dimethylacetamide.
Among these solvents, from solubleness, the angle of pigment-dispersing and coating performance, phenmethylol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, ethylene glycol monomethyl ether acetate, glycol monomethyl n-butyl ether acetate, diglycol monotertiary n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol list ethylether acetate, diethylene glycol dimethyl ether, diglycol methyl ethyl ether, cyclohexanone, the 2-heptanone, the 3-heptanone, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl formate, 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, 3-ethoxy-Ji ethyl propionate propionic acid 3-methyl 3-methoxy butyl ester and ethyl pyruvate are particularly preferred.
Above-mentioned solvent can use separately, but perhaps two or more are used in combination.
In addition, high boiling solvent, for example benzylisoeugenol, two hexyl ethers, acetonyl acetone, isophorone, caproic acid, sad, the 1-octanol, 1 nonyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate or glycol monomethyl phenyl ether acetate can be used in combination with above-mentioned solvent.
These high boiling solvents can use separately, but perhaps two or more are used in combination.
The quantity of solvent is not subjected to special qualification, but from the coating performance of gained radiation-sensitive composition and the viewpoint of storage stability, the numerical value of expectation is, except the solvent of composition, the total amount of guaranteeing all the components preferably 5 arrives 50wt%, especially preferably 10 arrives 40wt%.
-preparation be used for color filter radiation-sensitive composition method-
Do not do special restriction though the present invention is used for the method for the radiation-sensitive composition of color filter to preparation, preferably pigment (A) is dispersed in advance in the medium that has comprised spreading agent (B), alkali soluble resins (C) and solvent (F).
To in above-mentioned medium, the step of dispersed color (A) be referred to as " pre-dispersed step ", and will in above-mentioned medium, the dispersion of dispersed color (A) gained be referred to as " predispersion ".
In pre-dispersed step, based on the content at the radiation-sensitive composition alkali soluble resins (C) that is used for color filter, the quantity of alkali soluble resins (C) preferably 5 arrives 100wt%, is more preferably 10 to 50wt%.When the quantity of alkali soluble resins (C) was less than 5wt%, the storage stability of resulting composition may reduce, and perhaps may produce residue in substrate.
Can implement pre-dispersed step by mentioned component being mixed with for example mixer of dissolver, ball mill or roller mill.
Method according to the routine use, after pre-dispersed step, by predispersion is mixed mutually with polyfunctional monomer (D), radiosensitive free-radical generating agent (E) and all the other alkali soluble resinss (C) and optional solvent (F), obtain being used among the present invention the radiation-sensitive composition of color filter.
Form the method for color filter
Below, will method that utilize the radiation-sensitive composition (hereinafter it being abbreviated as " radiation-sensitive composition ") that is used for color filter among the present invention to form color filter be described.
The step of (1) to (4) below the method for formation color filter of the present invention comprises at least:
(1) coat film of formation radiation-sensitive composition of the present invention in substrate;
(2) make to the coat film of small part and under radiation, expose;
(3) after exposure, coat film is developed; With
(4) after developing, bake after coat film carried out.
Below will describe above-mentioned each step.
-step (1)-
At first, on substrate surface, form light shield layer as required, be used to be identified for forming the part of pixel, then, the radiation-sensitive composition among the present invention is coated in the substrate, and carry out the prebake conditions solvent evaporated, thereby form coat film.
Employed substrate is by glass in this step, silicon, and polycarbonate, polyester, aromatic poly amide, polyamidoimide, polyimide, polyethersulfone, the ring-opening polymerization polymer of cycloolefin or its hydrogenated products are made.
Randomly can carry out known pre-service, for example utilize chemical treatment, Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction or the vacuum deposition of silane coupling reagent this substrate.
In order in substrate, to apply radiation-sensitive composition, can utilize known coating technique, spin-coating method for example, curtain coating rubbing method or rolling method.Preferably use rotary coating equipment or built-up pattern coating apparatus.
For the prebake conditions condition, preferably 70 to 110 ℃ of following radiation-sensitive composition heating 2 to 4 minutes.
The thickness of coat film, its thickness 0.1 to 8.0 μ m preferably is more preferably 0.2 to 6.0 μ m, especially preferably 0.2 to 4.0 μ m after drying.
-step (2)-
Then, make to the coat film of small part and under radiation, expose.In this step,, preferably utilize photomask with predetermined pattern in order to make the exposure of part coat film.
The radiation that is used to expose is from visible radiation, ultraviolet radiation, and far-ultraviolet radiation is suitably selected in electron irradiation and the X-radiation.Preferably have 190 radiation to the 450nm wavelength.
The dosage of radiation preferably 10 arrives 10000J/m 2
-step (3)-
Afterwards, utilize developer that the coat film after the exposure is developed, alkaline developer preferably with dissolving and dispose the unexposed portion of coat film, makes to form predetermined pattern.
Above-mentioned alkaline developer is sodium carbonate, NaOH, potassium hydroxide, tetramethyl ammonium hydroxide, choline, 1 preferably, 8-diazabicylo-[5.4.0]-7-undecylene, 1, the aqueous solution of 5-diazabicylo-[4.3.0]-5-nonene.
Can be with water-miscible organic solvent right quantity, for example methyl alcohol or ethanol, perhaps surfactant adds in the above-mentioned alkaline developer.Preferably water washes coat film after alkaline development.
Can utilize spray to develop, spray developing is contaminated (dipping) and is developed or the puddle development.
For development conditions, preferably will film and carry out about 5 to 300 seconds development at normal temperatures.
-step (4)-
By the coat film that has developed being carried out the molten baking in back, can obtain to have the substrate of intended pixel pattern.
For after the condition that bakes, preferably under 180 to 240 ℃ to coat film heating 15 to 90 minutes.
The film thickness of the pixel that forms is 0.1 to 6.0 μ m preferably, is more preferably 0.5 to 3.0 μ m.
In view of the above, repeat above-mentioned steps (1) to (4) by each radiation-sensitive composition that the present invention is comprised redness, green and blue pigment and be formed on same suprabasil redness, green and blue pixel pattern, make it might in substrate, form the color layer of being formed by predetermined redness, green and blue pixel pattern thus.
In the present invention, the order of above-mentioned these pattern of pixels of formation is arbitrarily.
Color filter
Color filter among the present invention is to be formed by the radiation-sensitive composition that is used for color filter among the present invention.
Color filter among the present invention is specially adapted to transmission-type and Reflexible color LCD, coloured image imaging device, color sensor or the like.
Color liquid crystal display arrangement
Color liquid crystal display arrangement of the present invention comprises color filter of the present invention.
Color liquid crystal display arrangement among the present invention can have suitable structure.For example, it can have such structure, forms color filter in the substrate that is separated with the driving substrate with thin film transistor (TFT) (TFT), and drives substrate and have a substrate of color filter positioned opposite to each other, is inserted with liquid crystal layer between them.Replacedly, this color liquid crystal display arrangement also can be had such structure, make substrate by in driving substrate, forming color filter with thin film transistor (TFT) (TFT), in another substrate, has ITO (indium oxide of tin dope) electrode, two substrates are positioned opposite to each other, are inserted with liquid crystal layer between them.The structure of back can improve numerical aperture significantly, thus make it to obtain to become clear, the high-resolution liquid crystal display device.
The radiation-sensitive composition that is used for color filter among the present invention has the rheological properties that is suitable for the large-sized substrates application, and the red pixel with high-transmission rate and hard contrast ratio can be provided.
Thus, in electronics industry, the radiation-sensitive composition that is used for color filter among the present invention can be advantageously used in and form the color filter that comprises the color filter that is used for color liquid crystal display arrangement.
Embodiment
Provide following examples for further specifying purpose of the present invention, but never with it as limitation of the invention.
Synthetic embodiment 1
With 2 of 2.7 weight portions, 2 '-azo two (2, the 4-methyl pentane nitrile) and the diglycol monomethyl ether acetate of 200 weight portions be transported in the flask with cooling tube and stirrer, then with the methacrylic acid of 15 weight portions, the N-phenylmaleimide of 25 weight portions, the benzyl methacrylate of 45 weight portions, the α-Jia Jibenyixi dimer (chain-transferring agent) of the styrene of 15 weight portions and 5 weight portions is transported in this flask, replace with nitrogen in this flask, and reaction solution is heated with 80 ℃, and kept this temperature 3 hours, make its polymerization thereby accompany by simultaneously to stir lenitively.Afterwards, further reaction solution is heated, add 2 of 0.5 weight portion with 100 ℃, 2 '-azo two (2, the 4-methyl pentane nitrile), and continue again to carry out 1 hour polymerization, thereby obtain resin solution (solids content of 33.1wt%).The gained resin has 15000 Mw and 7000 Mn.With this resin called after resin (B-1).
Synthetic embodiment 2
With 2 of 1.5 weight portions, 2 '-azo two (2, the 4-methyl pentane nitrile) and the diglycol monomethyl ether acetate of 200 weight portions be transported in the flask with cooling tube and stirrer, then with the methacrylic acid of 20 weight portions, the N-phenylmaleimide of 25 weight portions, the benzyl methacrylate of 30 weight portions, the monomethyl acrylic acid glyceride of 10 weight portions, the α-Jia Jibenyixi dimer (chain-transferring agent) of the styrene of 15 weight portions and 2.5 weight portions is transported in this flask, replace with nitrogen in this flask, and reaction solution is heated with 80 ℃, and kept this temperature 3 hours, make its polymerization thereby accompany by simultaneously to stir lenitively.Afterwards, further reaction solution is heated, add 2 of 0.3 weight portion with 100 ℃, 2 '-azo two (2, the 4-methyl pentane nitrile), and continue again to carry out 1 hour polymerization, thereby obtain resin solution (solids content of 33.0wt%).The gained resin has 20000 Mw and 9000 Mn.With this resin called after resin (B-2).
Synthetic embodiment 3
With 2 of 2.7 weight portions, 2 '-azo two (2, the 4-methyl pentane nitrile) and the diglycol monomethyl ether acetate of 200 weight portions be transported in the flask with cooling tube and stirrer, then with the methacrylic acid of 25 weight portions, the α-Jia Jibenyixi dimer (chain-transferring agent) of the benzyl methacrylate of 75 weight portions and 5 weight portions is transported in this flask, replace with nitrogen in this flask, and reaction solution is heated with 80 ℃, and kept this temperature 3 hours, make its polymerization thereby accompany by simultaneously to stir lenitively.Afterwards, further reaction solution is heated, add 2 of 0.3 weight portion with 100 ℃, 2 '-azo two (2, the 4-methyl pentane nitrile), and continue again to carry out 1 hour polymerization, thereby obtain resin solution (solids content of 33.2wt%).The gained resin has 17000 Mw and 8600 Mn.With this resin called after resin (B-3).
Embodiment 1
The solution that has mixed comprises, 30 weight portions are as pigment (A), with the C.I. paratonere 242 of 70/30 weight ratio mixing and the potpourri of C.I. paratonere 254,10 weight portions (is 100.0wt% according to solids content), Adisper PB821 as developer (B), 10 weight portions, resin (B-1) as alkali soluble resins (C), and 100 weight portion, 3-ethoxyl ethyl propionate as solvent, with above-mentioned soln using Diamond Fine Mill (trade name of having mixed, the ball mill of Mitsubishi Material company limited, the pearl diameter is 1.0mm) mix and disperseed 5 hours, thus prepare pigment dispersion.
When utilizing the dynamic light scattering method, when the average pigment particle size of gained pigment dispersion was measured, its diameter was 140nm.
Under the condition hereinafter, utilize the dynamic light scattering method, the average pigment particle size of gained pigment dispersion is measured.
Device name: the FPAR-1000 of Otsuka Denshi company limited (optical fiber particle analyzer).
Test condition: dilute pigment dispersion with propylene glycol monomethyl ether acetate, make pigment content account for 5% of gained solution, so that measure mean grain size.
Computing method: utilize accumulation method to calculate.
Afterwards, this pigment dispersion with 400 weight portions, 200 weight portions, as the resin (B-2) of alkali soluble resins (C), 60 weight portions, as the dipentaerythritol acrylate of polyfunctional monomer (D), 40 weight portions, as 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butanone-1 of free-radical generating agent (E), and 1000 weight portion, together mix as the propylene glycol monomethyl ether acetate of solvent, thereby prepare fluid composition (R1).
The assessment of rheological properties
Under 23 ℃, utilize ARES100FRT viscoelasticity measurement instrument (production of TA Instr Ltd.), with the shear rate of 0.5 to 500 (l/s), continuously the viscosity of gained fluid composition (R1) is measured (rheology measurement method).From the measurement result of gained, calculate rheological parameters (={ viscosity when 1.0 (l/s) shear rate }/{ viscosity when 100 (l/s) shear rate }).
When rheological parameters was very big, poor between substrate core and the marginal portion on film thickness that is to say that the film thickness between the part of low shear rate and the part of high-rate of shear is poor, and the trend that becomes big is arranged, and caused the result of breakdown of coating.
When rheological parameters was assessed, it was 1.25.Accountable is that rheological properties is gratifying when rheological parameters is in 1.0 to 1.5 the scope.
The assessment of storage stability
The ELD viscosity meter that utilizes Tokyo Keiki company limited to be produced is measured the viscosity of the fluid composition (R1) of gained.To measuring in the viscosity of the composition of placing for 1 week under 40 ℃ and the viscosity of under 23 ℃, having placed 1 month composition.The result is, the viscosity of the composition of just having prepared is 7.5mPas, and the viscosity of the composition after placing for 1 week under 40 ℃ is 8.0mPas, and the viscosity of the composition after having placed 1 month under 23 ℃ is 7.8mPas.Accountable is to compare its viscosity to be changed to 20% or still less the time, storage stability is gratifying when with firm preparation.
Afterwards, fluid composition (R1) is coated in two with the rotary coating machine and has the SiO that is used to prevent lip-deep sodion wash-out 2In the 15cm of film * 15cm soda-lime glass substrate, and in dustless baking box with 90 ℃ to its prebake conditions 10 minutes, so that form the coat film of 1.8 μ m thickness.
Then, substrate is cooled to room temperature, and utilizes high-pressure sodium lamp, make one of them substrate see through photomask, at 5000J/m 2, radiation with 365nm, 405nm and 436nm wavelength exposure down.After this this substrate is immersed in 23 ℃ potassium hydroxide 0.04wt% aqueous solution and made its development in 1 minute, it is washed and in air, make its drying with ultrapure water.After this, under 230 ℃ this substrate carried out 30 minutes after bake, thereby in substrate, form the flammulation pattern of pixels.The film thickness of pixel is 1.50 μ m.This substrate is used as assessment impurity, colourity and Δ Eab *The substrate of characteristic.
In addition, utilize high-pressure sodium lamp, the unfavorable photomask of using makes another substrate at 5000J/m 2, radiation with 365nm, 405nm and 436nm wavelength exposure down.Afterwards under 230 ℃ this substrate carried out 30 minutes after bake, thereby in substrate, form the red film of solid.The film thickness of pixel is 1.50 μ m.With the substrate of this substrate as the assessment contrast ratio.
The assessment of impurity and colourity
When utilizing optical microscope that formed pattern of pixels is observed, on pixel, do not see impurity.
When with MCPD2000 color analyzer (Otsuka Denshi company limited), when the colourity of pixel is assessed, its colourity be (x, y, Y)=(0.598,0.354,31.2).
The assessment of contrast ratio
The substrate of gained is clipped between two depolarization plates, and, when from behind the depolarization plate in the front side being shone, it is rotated, so that measure the maximal value and the minimum value of transmitted intensity with LS-100 nitometer (Minolta company limited) with fluorescent light (380 to 780nm wavelength).When with maximal value divided by the numerical value of minimum value gained during as contrast ratio, contrast ratio is 700.We can say when contrast ratio greater than 600 the time, contrast ratio is gratifying.
Δ Eab *The assessment of characteristic
Utilize color analyzer, substrate core and distance center part 5.5cm are measured the colourity of the part of angular direction, thereby calculate colour difference Δ Eab between two parts *, wherein have the flammulation pattern of pixels in this substrate.
As assessment Δ Eab *The time, it is 1.75.Accountable is Δ Eab *Be 3 or more hour, Δ Eab *Characteristic is gratifying.
Embodiment 2
Except the C.I. paratonere 242 that mixes with 30 weight portions, with 50/50 weight ratio and C.I. paratonere 254 as the pigment (A), prepare fluid composition (R2) in the mode identical with embodiment 1.
When utilizing the dynamic light scattering method, when the mean grain size of gained pigment dispersion was measured, its diameter was 130nm.Its rheological parameters is 1.21, and its viscosity is 6.5mPas when just preparing, and having placed 1 its viscosity of all backs under 40 ℃ is 6.9mPas, and its viscosity is 6.7mPas after having placed 1 month under 23 ℃.
Forming film thickness in substrate is the flammulation pattern of pixels of 1.50 μ m, and except being to utilize the fluid composition (R2), assesses in the mode identical with embodiment 1.
The result is not see impurity on pixel.The colourity of pixel is that (Y)=(0.598,0.346,29.2), contrast ratio is 850, Δ Eab for x, y *Be 2.10.
Comparative example 1
Except being replaces PB821 to be used as spreading agent (B) with 10 weight portion Solsperse S28000 (solids content is 100.0wt%), and replace resin (B-1) to be used as outside the alkali soluble resins (C) with resin (B-3), prepare fluid composition (r1) in the mode identical with embodiment 1.
When utilizing the dynamic light scattering method that the pigment mean grain size of gained pigment dispersion is measured, it is 250nm.The rheological parameters of pigment dispersion is 6.23, and its viscosity is 13.0mPas when just preparing, and having placed 1 its viscosity of all backs under 40 ℃ is 25.0mPas, and its viscosity is 20.0mPas after having placed 1 month under 23 ℃.
Forming film thickness in substrate is the flammulation pattern of pixels of 1.50 μ m, and except being to utilize the fluid composition (r1), assesses in the mode identical with embodiment 1.
The result is not see impurity on pixel.The colourity of pixel is that (Y)=(0.598,0.353,30.0), contrast ratio is 350, Δ Eab for x, y *Be 8.05.
Comparative example 2
Except being replaces resin (B-1) to be used as the alkali soluble resins (C) with resin (B-3), prepare fluid composition (r2) in the mode identical with embodiment 1.
When utilizing the dynamic light scattering method that the pigment mean grain size of gained pigment dispersion is measured, it is 180nm.The rheological parameters of pigment dispersion is 2.01, and its viscosity is 9.5mPas when just preparing, and having placed 1 its viscosity of all backs under 40 ℃ is 14.0mPas, and its viscosity is 12.5mPas after having placed 1 month under 23 ℃.
Forming film thickness in substrate is the flammulation pattern of pixels of 1.50 μ m, and except being to utilize the fluid composition (r2), assesses in the mode identical with embodiment 1.
The result is not see impurity on pixel.The colourity of pixel is that (Y)=(0.598,0.354,30.5), contrast ratio is 500, Δ Eab for x, y *Be 3.01.

Claims (6)

1, a kind of radiation-sensitive composition that is used for color filter, it comprises (A) pigment, (B) spreading agent,
(C) alkali soluble resins, this alkali soluble resins comprises (c1), (c2) and multipolymer (c3), wherein (c1) comprises (methyl) acrylic acid unsaturated monomer that contains carboxyl, (c2) be N-substituted maleimide amine, (c3) for being selected from styrene, α-Jia Jibenyixi, to hydroxyl-α-Jia Jibenyixi, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and polymethylmethacrylate macromonomer at least a, (D) polyfunctional monomer, (E) radiosensitive free-radical generating agent and (F) solvent, wherein
Pigment (A) comprises 20wt% or more C.I. paratonere 242, and mean grain size " r " is 50 to 200nm;
Described radiosensitive free-radical generating agent is a kind of like this compound, and it can form active specy when exposing under radiation, and this active specy can cause above-mentioned polyfunctional monomer (D) and the optional monofunctional monomer polymerization of using; And
Described polyfunctional monomer is the monomer with two or more energy polymerization unsaturated links.
2, the radiation-sensitive composition that is used for color filter of claim 1, wherein the content of C.I. paratonere 242 is 50 to 100wt% in (A) pigment.
3, a kind of method for preparing the radiation-sensitive composition that is used for color filter of claim 1 or 2 may further comprise the steps:
Containing (B) spreading agent, (C) alkali soluble resins and (F) disperseing (A) pigment in the medium of solvent, this pigment comprises 20wt% or more C.I. paratonere 242, and the mean grain size of this pigment is greater than 200nm; With
With the dispersion of gained and (D) polyfunctional monomer, (E) radiosensitive free-radical generating agent and optional (C) alkali soluble resins reach (F) that solvent mixes mutually.
4, the method for claim 3, wherein the content of C.I. paratonere 242 is 50 to 100wt% in (A) pigment.
5, a kind of color filter that forms by the radiation-sensitive composition that is used for color filter of claim 1 or 2.
6, a kind of liquid crystal indicator that includes the color filter of claim 5.
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TWI257527B (en) * 2001-12-18 2006-07-01 Jsr Corp Radiation sensitive composition for color filter, method to form color filter, color filter and color liquid crystal display device
JP3900078B2 (en) * 2001-12-18 2007-04-04 Ｊｓｒ株式会社 Radiation sensitive composition for color filter, color filter, and color liquid crystal display device
JP4428911B2 (en) * 2002-07-05 2010-03-10 Ｊｓｒ株式会社 Radiation sensitive composition for color filter, color filter and color liquid crystal display element

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