CN1529206A - Light-sensitive resin composition for colour filter film - Google Patents
Light-sensitive resin composition for colour filter film Download PDFInfo
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- CN1529206A CN1529206A CNA031601359A CN03160135A CN1529206A CN 1529206 A CN1529206 A CN 1529206A CN A031601359 A CNA031601359 A CN A031601359A CN 03160135 A CN03160135 A CN 03160135A CN 1529206 A CN1529206 A CN 1529206A
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Abstract
The composition contains alkali-solubility resin (A), compound (B) of unsaturation group containing ethane like, optical initializing agent (C), organic solvent (D), and paint (E). The alkali-solubility resin is polymerized by monomer and other monomer possible to be copolymerized. The said monomer includes at least an aromatic functional group and dipole moment lower than 1.5D. Content of oligomer of alkali-solubility resin with molecular weight less than 1000 is less than 0.6 % weight of solid ingredient of light-sensitive resin composition. With composition being coated, exposed and developed, less level of residue is in unexposed part and black matrix on base plate. After developing, and baking, pixels possess good thermo stability and alkali resistivity. Clear electrode layer of the liquid crystal display has small value of impedance.
Description
Technical field
The present invention relates to the photosensitive resin composition on a kind of colored filter that is applied in LCD.Particularly provide a kind of via after exposure, developing, level of residue on unexposed part and light shield layer on the substrate (black matrix) is few, and after bake development, back, thermotolerance, the alkali resistance of picture element are good, the ITO of LCD (transparent electrode layer) resistance value is little, and the photosensitive resin composition for colour filter that can alkaline-based developer develops.
Background technology
In the technical field of LCD (LCD), general system coats photosensitive resin composition on the substrate and carries out drying (pre-roasting), see through light shield and implement ultraviolet exposure, sclerosis, after the mat alkaline-based developer develops the formation pattern again, again this is heat-treated (back is roasting).Particularly, as cured films such as red, blue, the green picture element (pixel) in the colored filter, resin black matrix (black matrix), diaphragm or interlayer dielectrics, all be to utilize this processing procedure to be finished.
But the cured film of above-mentioned various uses, its forming process or form after processing, cured film generally all must be exposed to the environment of high temperature more than 220 ℃ or highly basic, strong acid, so this cured film all need possess characteristics such as preferable high temperature resistant, acid and alkali resistance.For example at present when making red, blue, the green picture element (pixel) of colored filter, when forming ito transparent electrode on the picture element, must be in high temperature (230 ℃), secondly, carry out also must imposing 230 ℃ to 260 ℃ pyroprocessing in the flow process of Low ESRization of transparency electrode.
At above-mentioned requirement, with methacrylic acid monomer as major component institute's copolymerization and the relevant report of vinyl copolymer employed alkali soluble resin when being used as forming the picture element pattern, disclosed.The spy of patent of this type such as day disclosure special permission opens flat 1-152449 communique, the spy opens flat 9-311210 communique.But employed multipolymer is after 220 ℃ thermal treatment in this type patent, and the ester functional group that side chain easily takes place decomposes evapotranspires, and then the shortcoming that has the ITO resistance value to increase exists.
In addition in the method for making of red, blue, the green picture element (pixel) of aforementioned colored filter, be based on decoration method in the past, its method is with possible resin (as natural gelatin, the casein etc.) pattern picture in advance that dyes, and gets red, blue, green picture element and then with dyeing.
But,, generally all have the not good really good problem of thermotolerance because of the restriction of material with the prepared picture element of decoration method.
Recently, for improving this stable on heating problem, be to change to use the photosensitive material of pigment dispersing method.The pigment dispersing method has advantages such as method for making is simple, the life-span is long.
But in the manufacture process because of red, blue, green picture element, need repeat to implement steps such as exposure, development.After often red, blue, green picture element formed, the photoresist of unexposed portion failed to remove fully, and the residual problem of residue will be arranged on the substrate.
Therefore, after the development, still need to do clean work, so, easily make the manufacturing process of colored filter complicated with the water of thin developer solution or high pressure.
Summary of the invention
The object of the present invention is to provide a kind of photosensitive resin composition for colour filter of LCD.
The technical solution used in the present invention is, this constituent comprises: alkali soluble resin (A), the compound (B) that contains the ethene unsaturated group, light initiator (C), organic solvent (D) and pigment (E), and wherein this alkali soluble resin (A) comprises and contains a kind of tool aromatic series (aromatic) functional group at least and following monomer and other the copolymerizable monomer polymerization of dipole moment 1.5D forms; And the molecular weight of this alkali soluble resin (A) accounts for below the 0.6 weight % of the solid shape branch of photosensitive resin composition at the content of the oligomer below 1000.
The beneficial effect of constituent of the present invention is, after exposure, developing, level of residue on unexposed part and light shield layer on the substrate (black matrix) is few, and after bake development, back, thermotolerance, the alkali resistance of picture element are good, the ITO of LCD (transparent electrode layer) resistance value is little, and can develop by alkaline-based developer.
Embodiment
Below the present invention is described in detail: (A) alkali soluble resin
Alkali soluble resin of the present invention (A) comprises the monomer and other the copolymerizable monomer polymerization that contain at least below a kind of tool aromatic series functional group and the dipole moment 1.5D and forms.The instantiation of the monomer that above-mentioned tool aromatic series functional group and dipole moment 1.5D are following is as follows:
Compound (1)
Compound (2)
Compound (3)
Compound (5)
And styrene (styrene), α-Jia Jibenyixi (α-methyl styrene), adjacent ethene methylbenzene (o-vinyl toluene), to ethene methylbenzene (p-vinyl toluene), an ethene methylbenzene (m-vinyl toluene) etc.
Wherein the person of exemplifying is preferable with compound (2), compound (6) and styrene.These contain unsaturated monomer can separately or mix the use of plural number kind.
But measure the method for method system mat dielectric constant of dipole moment or mat molecular ray method etc., then use the measuring method of microwave spectrum among the present invention.This method system spreads to obtain dipole moment by Stark (Stark) division that effect caused of microwave absorbing spectrum.
For aforementioned other copolymerizable monomer, so long as can with have aromatic series functional group and the dipole moment monomer copolymerizable person below 1.5D and get final product, unrestricted in the use, wherein closing monomer (being designated hereinafter simply as the unsaturated monomer that contains carboxyl) with the ethene insatiable hunger of carboxyl with one or more especially is good with the monomer mixture that other copolymerizable ethylene unsaturated monomer (being designated hereinafter simply as other unsaturated monomer) is constituted.
The above-mentioned unsaturated monomer that contains carboxyl is for example: unsaturated monocarboxylic acid classes such as acrylic acid, methacrylic acid, butenoic acid, α-Lv Bingxisuan, ethylacrylic acid and cinnamic acid; Unsaturated dicarboxylic acid (acid anhydride) classes such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride; Unsaturated polyvalent carboxylic acid (acid anhydride) class that 3 valencys are above or the like.
Wherein cited person is to be preferable with acrylic acid, methacrylic acid.These unsaturated monomers that contain carboxyl can separately or mix plural number and plant use.
Aforementioned other unsaturated monomer for example is: methyl acrylate, methyl methacrylate, ethyl acrylate, Jia Jibingxisuanyizhi, the acrylic acid n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, isobutyl methacrylate, acrylic acid second butyl ester, methacrylic acid second butyl ester, tert-butyl acrylate, the metering system tert-butyl acrylate, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester, acrylic acid 3-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester, acrylic acid 2-hydroxyl butyl ester, methacrylic acid 2-hydroxyl butyl ester, acrylic acid 3-hydroxyl butyl ester, methacrylic acid 3-hydroxyl butyl ester, acrylic acid 4-hydroxyl butyl ester, methacrylic acid 4-hydroxyl butyl ester, allyl acrylate, allyl methacrylate, the acrylic acid benzene methyl, the methacrylic acid benzene methyl, phenyl acrylate, phenyl methacrylate, acrylic acid triethylene glycol methoxyethoxy ester (methoxy triethylene glycolacrylate), methacrylic acid triethylene glycol methoxyethoxy ester (methoxy triethylene glycolmethacrylate), lauryl methacrylate (lauryl methacrylate), methacrylic acid myristyl ester (tertadecyl methacrylate), methacrylic acid cetyl ester (cetyl methacrylate), methacrylic acid stearyl (octadecyl methacrylate), methacrylic acid eicosyl ester (eicosylmethacrylate), the unsaturated carboxylate type of methacrylic acid docosyl ester (docosyl methacrylate) etc.; Unsaturated carboxylic acid ammonia alkane ester classes such as acrylic acid 2-ammonia ethyl ester, methacrylic acid 2-ammonia ethyl ester, acrylic acid 2-ammonia propyl ester, methacrylic acid 2-ammonia propyl ester, acrylic acid 3-ammonia propyl ester, methacrylic acid 3-ammonia propyl ester; Unsaturated carboxylic acid glycidyl ester classes such as acrylic acid epoxy propyl diester, methacrylic acid glycidyl ester; The vinyl carboxylates class of vinyl acetate, propionate, vinyl butyrate, benzoic acid vinyl acetate etc.; Unsaturated ethers such as methoxy ethylene, ethyl vinyl ether, allyl glycidyl ethers, methylallyl glycidyl ethers; The vinyl cyanide based compound of vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, the inferior ethene of cyaniding etc.; The unsaturated vinegar amine of acrylamide, metering system vinegar amine, α-chloropropene vinegar amine, N-hydroxyethyl acrylamide, N-hydroxyethyl metering system vinegar amine etc.; The aliphatics conjugated diene of 1,3-butadiene, different propylene, chloropropene etc.
Wherein cited person is preferable with methyl acrylate, methyl methacrylate, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid benzene methyl, methacrylic acid benzene methyl.Above-mentioned other unsaturated monomer can use separately, perhaps mixes two or more and usefulness.
Alkali soluble resin of the present invention (A), the consumption (raw material benchmark) of its copolymerization usefulness monomer as shown below.
The consumption of the monomer that tool aromatic series functional group and dipole moment 1.5D are following is preferably 1～35 weight portion, is more preferred from 2～30 weight portions, and the best is 3～25 weight portions.
The consumption of other copolymerizable monomer is preferably 99～65 weight portions, is more preferred from 98～70 weight portions, and the best is 97～75 weight portions.
When other copolymerizable monomer means the unsaturated monomer that contains carboxyl and other unsaturated monomer, and during the scope that the consumption of the monomer that tool aromatic series functional group and dipole moment 1.5D are following is as above remembered, the consumption that then contains the carboxyl unsaturated monomer is preferably 2～40 weight portions, be more preferred from 5～35 weight portions, the best is 8～30 weight portions; The consumption of other unsaturated monomer is preferably 25～97 weight portions, is more preferred from 40～93 weight portions, and the best is 50～89 weight portions.
In the composition of alkali soluble resin of the present invention (A), if do not contain any aforementioned tool aromatic series functional group and the following monomer polymerization structure of dipole moment 1.5D, then photosensitive resin composition for colour filter is via after coating, exposure, developing, part and light shield layer (black matrix) level of residue upward unexposed on the substrate are many, develop, the back roasting after, the thermotolerance of picture element, alkali resistance is relatively poor and the ITO of LCD (transparent electrode layer) resistance value is higher.
During alkali soluble resin of the present invention (A) polymerization, use the following monomer of aforementioned tool aromatic series functional group and dipole moment 1.5D, the content of the oligomer of alkali soluble resin (A) is increased.The consumption of the monomer that this tool aromatic series functional group and dipole moment 1.5D are following is in the preferable scope that ties up to note.
Alkali soluble resin of the present invention (A) comprises and contains the following monomer of a kind of tool aromatic series functional group and dipole moment (dipolemoment) 1.5D and other copolymerizable monomer polymerization at least and get.
The employed during fabrication solvent of alkali soluble resin of the present invention (A) is an ethylene glycol monomethyl ether than the dust head generally, ethylene glycol ethyl ether, diethylene glycol methyl ether, DGDE, the diglycol positive propyl ether, the diglycol n-butyl ether, the triethylene glycol methyl ether, the triethylene glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, the dipropylene glycol methyl ether, the dipropylene glycol ether, the dipropylene glycol positive propyl ether, the dipropylene glycol n-butyl ether, tripropylene glycol methyl ether (tripropyleneglycol mono methyl ether), tripropylene glycol ether (tripropylene glycol mono ethylether) waits its (gathering) alkylene glycol mono alkane ethers; (gathering) alkylene glycol mono alkane ether acetate classes such as glycol methyl ether acetate, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetate; Other ethers such as diethylene glycol dimethyl ether, diglycol ethyl methyl ether, diethyl carbitol, tetrahydrofuran; Ketones such as MEK, cyclohexanone, 2-heptanone, 3-heptanone; Lactic acid alkane ester classes such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester; 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butyl propionic ester, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other ester classes such as 2-oxygen base ethyl butyrate; Aromatic hydrocarbons such as toluene, dimethylbenzene class; N-Methyl pyrrolidone, N, carboxylic acyloxy amines such as dinethylformamide, N,N-dimethylacetamide or the like.This equal solvent can use separately, also can mix more than 2 kinds and use.Be preferable in the aforementioned solvents with 1-Methoxy-2-propyl acetate, 3-ethoxyl ethyl propionate.
The initiator that alkali soluble resin (A) is used when making, be generally free radical shape polymerization initiator, for example 2,2 '-azobis isobutyronitrile (2,2 '-azobisisobutyronitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile) [2,2 '-azobis-(2,4-dimethylvaleronitrile)], 2, two (the 4-methoxyls-2 of 2 '-azo, the 4-methyl pentane nitrile) [2,2 '-azobis-(4-methoxy-2,4-dimethylvaleronitrile)], 2,2 '-azo is two-2-methylbutyronitrile azo (azo) compounds such as (2,2 '-azobis-2-methyl butyronitrile); The per-compound of dibenzoyl peroxide (benzoylperoxide) etc.
Alkali soluble resin of the present invention (A) is with gel permeation chromatography (GPC; Stripping solvent tetrahydrofuran) weight average molecular weight of the polystyrene conversion of being measured is generally 3,000 to 50,000, and is good with 4,000 to 40,000, is good with 4,500 to 35,000 especially.When using the alkali soluble resin of the weight average molecular weight with qualification like this, can obtain the good photosensitive resin composition of development property, the pattern edge that is formed is distinct by this.
(B) contain the compound of ethene unsaturated group
With 100 weight portion alkali soluble resins (A) is benchmark, and the use amount that the present invention contains the compound (B) of ethene unsaturated group is preferably the 5-220 weight portion, is more preferred from the 50-160 weight portion.
The above-mentioned compound (B) that contains the ethene unsaturated group is the ethene unsaturated compound with at least one ethene unsaturated group.
The object lesson that wherein has the compound of an ethene unsaturated group has acrylamide, (methyl) acryloyl morpholine, (methyl) acrylic acid-7-amino-3,7-dimethyl monooctyl ester, isobutoxy methyl (methyl) acrylamide, (methyl) acrylic acid isobornyl 2-ethoxyethyl acetate, (methyl) isobornyl acrylate, (methyl) acrylic acid-2-ethyl caproite, ethyl diglycol (methyl) acrylate, uncle's octyl group (methyl) acrylamide, two acetone (methyl) acrylamide, (methyl) acrylic acid dimethylamino ester, (methyl) dodecylacrylate, (methyl) acrylic acid two cyclopentene 2-ethoxyethyl acetates, (methyl) acrylic acid two cyclopentene esters, N, N-dimethyl (methyl) acrylamide, (methyl) acrylic acid tetrachloro phenyl ester, (methyl) acrylic acid-2-tetrachloro phenoxy ethyl, (methyl) tetrahydrofurfuryl acrylate, (methyl) tetrabromophenyl acrylate, (methyl) acrylic acid-2-tetrabromo phenoxy ethyl, (methyl) acrylic acid-2-Trichlorophenoxy ethyl ester, (methyl) acrylic acid tribromophenyl, (methyl) acrylic acid-2-tribromophenoxy ethyl ester, (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) acrylic acid-2-hydroxypropyl acrylate, caprolactam, N-vinyl skin junket alkane ketone, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid pentachlorophenyl ester, (methyl) acrylic acid pentabromo-phenyl ester, poly-single (methyl) acrylic acid glycol ester, poly-single (methyl) acrylic acid propylene glycol ester, (methyl) acrylic acid norbornene ester.
The concrete example of ethene unsaturated compound with 2 or 2 above ethene unsaturated groups is as follows: ethylene glycol bisthioglycolate (methyl) acrylate, two (methyl) acrylic acid, two cyclopentene esters, triethylene glycol diacrylate, tetraethylene glycol two (methyl) acrylate, three (2-hydroxyethyl) isocyanates two (methyl) acrylate, three (2-hydroxyethyl) isocyanates three (methyl) acrylate, three (2-hydroxyethyl) isocyanates three (methyl) acrylate of caprolactone upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester, three (methyl) acrylic acid trihydroxy methyl propyl ester of oxirane (hereinafter to be referred as EO) upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester of epoxypropane (hereinafter to be referred as PO) upgrading, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, polyester two (methyl) acrylate, polyglycol two (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate of caprolactone upgrading, dipentaerythritol five (methyl) acrylate of caprolactone upgrading, four (methyl) acrylic acid, two trihydroxy methyl propyl ester, bisphenol-A two (methyl) acrylate of EO upgrading, bisphenol-A two (methyl) acrylate of PO upgrading, hydrogenated bisphenol A two (methyl) acrylate of EO upgrading, hydrogenated bisphenol A two (methyl) acrylate of PO upgrading, the glycerin tripropionate of PO upgrading, Bisphenol F two (methyl) acrylate of EO upgrading, phenolic aldehyde polyglycidyl ether (methyl) acrylate or the like.
In the aforementioned ethene unsaturated compound, the preferably is dipentaerythritol acrylate, the tetrapropylene acid two trihydroxy methyl propyl ester of three acrylic acid trihydroxy methyl propyl ester, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, dipentaerythritol five acrylate, dipentaerythritol tetraacrylate, the caprolactone upgrading of three acrylic acid trihydroxy methyl propyl ester, the PO upgrading of three acrylic acid trihydroxy methyl propyl ester, EO upgrading, the glycerin tripropionate of PO upgrading.
(C) light initiator
The compound (B) that contains the ethene unsaturated group with 100 weight portions is a benchmark, and the use amount of light initiator of the present invention (C) is preferably the 20-120 weight portion, is more preferred from the 30-100 weight portion.
Above-mentioned smooth initiator (C) can be selected from: acetophenone based compound (acetophenone) or diimidazole based compound (biimidazole).
Wherein the acetophenone based compound as: to dimethylamine acetophenone (p-dimethylamino-acetophenone), α, α '-dimethoxy azoxy acetophenone (α, α '-dimethoxyazoxyacetophenone), 2,2 '-dimethyl-2-phenyl acetophenone (2,2 '-dimethyl-2-phenylacetophenone), acetanisole (p-methoxyacetophenone), 2-methyl-[4-(methyl mercapto) phenol] 2-methyl-[4-(methylthio) phenol] }, 2-morpholino-1-acetone (2-morpholino-1-propanone), 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone [2-benzyl-2-N, N-dimethylamino-1-(4-morpholinophenyl)-1-butanone].
And diimidazole based compound (biimidazole) is as 2,2 '-two (neighbour-chlorphenyl)-4,4 ', 5, and 5 '-tetraphenyl diimidazole [2,2 '-bis (o-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-two (ortho-fluorophenyl base)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (o-fluorophenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole], 2,2 '-two (neighbour-aminomethyl phenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (o-methyl phenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole], 2,2 '-two (o-methoxyphenyl)-4,4 ', 5, and 5 '-tetraphenyl diimidazole [2,2 '-bis (o-methoxyphenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole], 2,2 '-two (p-methoxyphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (p-methoxyphenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole], 2,2 '-two (2,2 ', 4,4 '-tetramethoxy phenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (2,2 ', 4,4 '-tetramethoxyphenyl)-4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole], 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole] etc.
Wherein with 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole and the light initiator effect of using are preferable.
In the present invention's the photosensitive resin composition for colour filter, can further add benzophenone (benzophenone) based compound is the light initiator, as thioxanthones (thioxanthone), 2,4-diethyl thioxanthone (2,4-diethylthioxanthanone), thioxanthones-4-sulfone (thioxanthone-4-sulfone), benzophenone (benzophenone), 4,4 '-two (dimethylamine) benzophenone [4,4 '-bis (dimethylamino) benzophenone], 4,4 '-two (diethylamine) benzophenone [4,4 '-bis (diethylamino) benzophenone] etc.
Other still has α-diketone (class of α-diketone), keto-alcohol (acyloin) class of diphenylhydroxyethanone (benzoin) etc. of benzil (benzil), acetyl group (acetyl) etc.; Keto-alcohol ether (acyloin ether) class of diphenylhydroxyethanone methyl ether (benzoin methylether), diphenylhydroxyethanone ether (benzoin ethylether), diphenylhydroxyethanone isopropyl ether (benzoin isopropylether) etc.; 2,4,6-trimethyl benzoyl diphenyl phosphine oxide (2,4,6-trimethyl-benzoyl diphenylphosphineoxide), two-(2,6-dimethoxy benzoyl)-2,4, and 4-trimethylphenyl phosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethylbenzylphosphineoxide] etc. acyl phosphine oxide (acylphosphineoxide) class; Anthraquinone (anthraquinone), 1, and the 4-naphthoquinones (1, the 4-naphthoquinone) quinone of grade (quinone) class; The halogenide of chloroacetophenone (phenacylchloride), trisbromomethyl benzene sulfone (tribromomethyl phenylsulfone), three (trichloromethyl)-s-triazines [tris (trichloromethyl)-s-triazine] etc.; The superoxide of two-tert-butyl peroxide (di-tertbutylperoxide) etc.
Wherein with benzophenone (benzophenone) based compound the best, especially with 4,4 '-two (diethylamine) benzophenone best results.
(D) organic solvent
Photosensitive resin composition for colour filter of the present invention system with aforementioned alkali soluble resin (A), contain the compound (B) of ethene unsaturated group, and the pigment (E) of light initiator (C) and aftermentioned is neccessary composition, can add the additive composition of aftermentioned in case of necessity.
Usually, be that pigment (E) each composition in addition is dissolved in the suitable solvent (D), be modulated into aqueous constituent.In the selection of aforementioned solvents (D), need are selected solubilized alkali soluble resin (A), are contained the compound (B) of ethene unsaturated group, and light initiator (C), and do not react to each other with these compositions, and have suitable volatility person.
With 100 weight portion alkali soluble resins (A) is benchmark, and the use amount of the solvent of photosensitive resin composition for colour filter of the present invention (D) is preferably the 300-2500 weight portion, is more preferred from the 500-2000 weight portion.
Above-mentioned solvent (D) can be selected from the solvent that is used in aforementioned bases soluble resin (A) polymerization process, does not give unnecessary details at this.Above-mentioned solvent can use separately, or uses mixing more than 2 kinds or 2 kinds.
In the aforementioned solvents (D), also preferable with 1-Methoxy-2-propyl acetate, 3-ethoxyl ethyl propionate.
(E) pigment
The use amount of pigment of the present invention (E) is a benchmark with the alkali soluble resin (A) of 100 weight portions, is preferably 20 ~ 500 weight portions, and the best is 50 ~ 400 weight portions.
Pigment of the present invention (E) is to use known so far various inorganic pigments or organic pigment.There is the metallic compound of metal oxide, the wrong salt of metal or the like in inorganic pigment system, particularly can lift the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, inferior lead, antimony etc., and the composite oxides of aforementioned metal is example.
Organic pigment can be exemplified below:
C.I. pigment yellow 1,3, and 11,12,13,14,15,16,17,20,24,31,53,55,60,61,65,71,73,74,81,83,93,95,97,98,99,100,101,104,106,108,109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,155,156,166,167,168,175
C.I. pigment orange 1,5, and 13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71,73.
C.I. paratonere 1,2, and 3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,19,21,22,23,30,31,32,37,38,40,41,42,48: 1,48: 2,48: 3,48: 4,49: 1,49: 2,50: 1,52: 1,53: 1,57,57: 1,57: 2,58: 2,58: 4,60: 1,63: 1,63: 2,64: 1,81: 1,83,88,90: 1,97,101,102,104,105,106,108,112,113,114,122,123,144,146,149,150,151,155,166,168,170,171,172,174,175,176,177,178,179,180,185,187,188,190,193,194,202,206,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265.
C.I. pigment violet 1,19,23,29,32,36,38,39.
C.I. pigment blue 1,2,15,15: 3,15: 4,15: 6,16,22,60,66.
C.I. pigment Green 7,36,37.
C.I. pigment brown 23,25, and 28.
C.I. pigment black 1,7.
Aforementioned pigment can separately or mix use more than 2 kinds.
Colorant in the present invention (E) according to desired person, also can be followed the use spreading agent.The interface activating agent that these spreading agents can be lifted kation system, negative ion system, nonionic system, both sexes, polysiloxane series, fluorine system etc. is an example.
Wherein the interface activating agent for example has: the polyethylene oxide alkyl ethers class of polyethylene oxide lauryl ether, polyethylene oxide stearoyl ether, polyethylene oxide oil ether etc.; The polyethylene oxide alkyl benzene ethers of polyethylene oxide octyl group phenylate, polyethylene oxide nonyl phenylate etc.; The polyethylene glycol di class of polyethylene glycol dilaurate, polyglycol distearate etc.; The sorbitan fatty acid ester class; The polyesters of fatty acid upgrading; The polyurethane class of 3 grades of amine upgradings; Below be trade name: KP (SHIN-ETSU HANTOTAI's chemical industry system), SF-8427 (Toray Dow Corning Silicon system), Puli's furlong (Polyflow, common prosperity society oil chemistry industry system), Ai Fuduopu [F-Top, De Kemupuluo is big make now in the storehouse (Tochem Products Co., Ltd.)], Mei Kafuke (Megafac, the black chemical industry system of big Japan's seal), Fu Luoduo (Fluorade, Sumitomo 3M system), asafoetide card many (Asahi Guard), Sa Fulong (Surflon, Asahi Glass system) or the like.These interface activating agents can separately or mix plural number and plant above the use.
Be the raising coating in the photosensitive resin composition of the present invention, and can follow and use the interface activating agent.With respect to the alkali soluble resin (A) of 100 weight portions, the use amount of interface activating agent of the present invention generally is between 0～6 weight portion, being good between 0～3 weight portion, above-mentioned interface activating agent for example with the interface activating agent that is used in the aforementioned pigment.
In addition, in the present invention's the photosensitive resin composition, can concoct various additives in case of necessity, for example in addition macromolecular compound of filling agent, alkali soluble resin (A), adherence promoter, antioxidant, ultraviolet light absorber, anti-agglutinant etc.With respect to the alkali soluble resin (A) of 100 weight portions, the use amount of additive of the present invention generally is 0 ~ 10 weight portion, and is preferable with 0 ~ 6 weight portion, and is the best with 0 ~ 3 weight portion.
The concrete example of these additives has: the filling agent of glass, aluminium; Alkali soluble resin (A) macromolecular compound in addition of polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, poly-perfluoroalkyl acrylate alkane ester etc.; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxyethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-epoxy prapanol propyl trimethoxy silicane, 3-epoxy prapanol propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, 3-metacryloxy propyl trimethoxy silicane, adherence promoter such as 3-mercapto propyl trimethoxy silicane; 2,2-thiobis (4-methyl-6-tert butyl phenol), 2, the antioxidant of 6-two-tert-butyl phenol etc.; 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorphenyl ultraviolet light absorbers such as nitrogen, alkoxy benzophenone that change; Reach anti-agglutinants such as sodium polyacrylate.
Photosensitive resin composition for colour filter of the present invention is that mentioned component (A)-(E) is uniformly mixed into solution state in stirrer, can add other adjuvants such as incoming interface activating agent, adherence auxiliary agent in case of necessity.
Colored filter of the present invention is with in the photosensitive compoistion, the molecular weight of this alkali soluble resin (A) accounts for below the 0.6 weight % of the solid shape branch (except the solvent) of photosensitive resin composition at the content of the oligomer below 1000, be preferably below the 0.5 weight %, be more preferred from below the 0.4 weight %.
The molecular weight of the present invention's alkali soluble resin (A) means in the definition of the content of the oligomer below 1000, molecular weight is lower than 1000, and is measured whole content of volume bodies such as bodies or four amount bodies by the two amount bodies or three that the monomer that constitutes alkali soluble resin (A) is derived.
If accounting for photosensitive resin composition at the content of the oligomer 1000 below, the molecular weight of this alkali soluble resin (A) consolidates 0.6 weight % of shape branch when above, after baked then development, back, ITO (transparent electrode layer) resistance value of the thermotolerance variation of picture element and LCD was higher.
The molecular weight of above-mentioned alkali soluble resin (A) in the content of the oligomer below 1000 can the polymerization process by alkali soluble resin (A), the enter material way of the selection of the kind of initiator and consumption, chain-transferring agent and monomer, monomer and initiator, temperature of reaction and reaction time and alkali soluble resin (A) controlled in modes such as poor vehicle treated.
The present invention's photosensitive resin composition is by coating methods such as revolution coating, curtain coating coating or print roll coatings constituent to be coated on the substrate.After the coating, removal of solvents is formed the photosensitive resin composition layer in pre-roasting (prebake) mode.
Substrate of the present invention, for example be useful on the alkali-free glass, soda-lime glass, hard glass (Pai Lesi glass), quartz glass of liquid crystal indicator etc. and in these persons that adheres to the nesa coating on glass, or be used for photo-electric conversion device substrate (as silicon substrate) of solid-state image sensor etc. or the like.These substrates generally are to form the black demoulding of isolating each picture element.
Pre-roasting condition becomes the kind of branchs according to each, and cooperation ratio and different carried out under 70～90 ℃ of temperature 1 minute-15 minutes usually.After pre-roasting, this photosensitive resin composition layer exposes between between specified light shield (mask), impregnated in developer solution and developed in 30 seconds-5 minutes under 23 ± 2 ℃ of temperature, and the part of not wanting is removed and formed pattern.The light of exposure use be good with the ultraviolet ray of g line, h line, i line etc., and UV-device can be (surpassing) high mercury vapor lamp and metal halid lamp.
Moreover, developer solution system uses as NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sal tartari, saleratus, sodium silicate, sodium methyl silicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrroles, croak pyridine, 1,8-diazabicylo-(5,4,0)-alkali compounds such as 7-hendecene, the concentration of developer solution is preferably 0.001～10wt%, the alkaline aqueous solution that the best is constituted by 0.01～1wt%.
When using the developer solution that these alkaline aqueous solutions constitute, generally lie in after the video picture clean to wash again.Secondly with pressurized air or compressed nitrogen that pattern is air-dry.
Make last heat treated with heating arrangements such as hot plate or baking ovens more afterwards.To decide heating-up temperature be 150～250 ℃, be 5 minutes～60 minutes heat time heating time when using hot plate, be 30 minutes～90 minutes the heat time heating time when using baking oven for heating.
(mainly comprising red, green, blue three looks) of all kinds repeats above-mentioned steps, just can make the picture element of colored filter.Secondly, to the vacuum of 250 ℃ of degree, forming the ITO vapor-deposited film with 220 ℃ on the picture element, in case of necessity, the ITO film is being implemented after etching and the wiring, coating of liquid crystalline alignment film polyimide again, and then burn till it, promptly can be used as the colored filter that LCD is used.
Embodiment and comparative example
State and other technology contents, characteristics and effect before the present invention,, can know and understand in the explanation of following cooperation embodiment and comparative example.
The synthesis example of alkali soluble resin (A)
Synthesis example a
On four cervical vertebra bottles of 1000 milliliters of volumes, nitrogen inlet, stirrer, well heater, condenser pipe and thermometer are set, and import nitrogen and add the feed composition thing according to consumption shown in the table one, above-mentioned feed composition thing comprises: compound (2) 10 weight portions, methacrylic acid monomer (hereinafter to be referred as MAA) 15 weight portions, methacrylic acid benzene methyl monomer (hereinafter to be referred as BzMA) 75 weight portions, and solvent 3-ethoxyl ethyl propionate (hereinafter to be referred as EEP) 200 weight portions.Wherein, the enter material way of monomer mixture is for once all adding.
When within the four cervical vertebra bottles during tolerant being stirred, the temperature of oil bath is promoted to 100 ℃, then according to shown in the table one with polymerization with initiator 2,2 '-azo is two-and 2-methylbutyronitrile (hereinafter to be referred as AMBN) 4 weight portions are dissolved among the organic solvent EEP, and are added in the four cervical vertebra bottles at interval at one hour with the amount of five equal portions.
The temperature of reaction of polymerization process is kept 100 ℃, polymerization time 6 hours.After polymerization was finished, in this polymer solution, the toluene (poor solvent) that adds 200 weight portions is agitator treating in addition, and polymkeric substance is separated out, and again through centrifugal filtration, can get alkali soluble resin (a).
Synthesis example b
With the method for operating of synthesis example a, difference system changes polymerization with the kind of monomer and mix consumption, and after polymerization finishes, in the washing process, consumption adjustment system 400 weight portions of toluene, its prescription and reaction conditions are stated from table one.Synthesis example c
With the method for operating of synthesis example a, difference system changes polymerization with the kind of monomer and mix consumption, and after polymerization finishes, washing, the step of centrifugal filtration repeats twice, and its prescription and reaction conditions are stated from table one.
Synthesis example d
With the method for operating of synthesis example a, difference system changes polymerization with the kind of monomer and mix consumption, and after polymerization finishes, washing, the step triplicate of centrifugal filtration, its prescription and reaction conditions are stated from table one.
Synthesis example e
On four cervical vertebra bottles of 1000 milliliters of volumes, nitrogen inlet, stirrer, well heater, condenser pipe and thermometer are set, and import nitrogen.Its polymerization methods is earlier solvent EEP 200 weight portions to be added in the four cervical vertebra bottles, is stirred, and after the temperature of oil bath is promoted to 85 ℃, adds the described monomer mixture of table one again.
The enter material way of this monomer mixture is to add continuously, addition manner is with compound (6) 3 weight portions, MAA 6 weight portions, BzMA 45 weight portions, the monomer mixture of MA 12 weight portions one of after the temperature of oil bath is promoted to 85 ℃ hour in, add continuously, in addition with compound (6) 2 weight portions, MAA 4 weight portions, BzMA 20 weight portions, the monomer mixture of MA 8 weight portions is in the temperature of oil bath is promoted to after 85 ℃ five hours, add continuously, and after the temperature of oil bath is promoted to 85 ℃, according to shown in the table one polymerization being dissolved among the organic solvent EEP with initiator AMBN 4 weight portions, and be added in the four cervical vertebra bottles at interval at one hour with the amount of five equal portions.
The temperature of reaction of polymerization process is kept 85 ℃, polymerization time 6 hours.After polymerization was finished, in this polymer solution, the toluene (poor solvent) that adds 50 weight portions is agitator treating in addition, and polymkeric substance is separated out, and again through centrifugal filtration, can get alkali soluble resin (e).
Synthesis example f～g
With the method for operating of synthesis example a, difference system changes polymerization with the kind of monomer and mix consumption, and after polymerization finishes, and polymkeric substance is without washing, the step of centrifugal filtration, and its prescription and reaction conditions are stated from table one.
Synthesis example h
With the method for operating of synthesis example a, difference system changes polymerization with the kind of monomer and mix consumption, and after polymerization finishes, in the washing process, consumption adjustment system 50 weight portions of toluene, its prescription and reaction conditions are stated from table one.
Synthesis example i
With the method for operating of synthesis example a, difference is after polymerization is finished, and polymkeric substance is without washing, the step of centrifugal filtration, and its prescription and reaction conditions are stated from table one.
Synthesis example j
With the method for operating of synthesis example d, difference is after polymerization is finished, and polymkeric substance is without washing, the step of centrifugal filtration, and its prescription and reaction conditions are stated from table one.
The embodiment of photosensitive resin composition and comparative example
Embodiment 1
Use alkali soluble resin (a) 100 weight portions (solid) of aforementioned synthesis example gained, with the dipentaerythritol acrylate shown in the table two (hereinafter to be referred as B-1) 120 weight portions, 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone (hereinafter to be referred as C-1) 22 weight portions, 4,4 '-two (diethylamine) benzophenone (hereinafter to be referred as C-2), 22 weight portions, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole (hereinafter to be referred as C-3), 22 weight portions, the potpourri of pigment CI254 (hereinafter to be referred as E-1) 130 weight portions, after adding solvent 3-ethoxyl ethyl propionate (hereinafter to be referred as D-1) 1000 weight portions, with swing-out stirrer, dissolved mixed, can modulate and photosensitive resin composition for colour filter, each evaluation of measuring mode of the following note of this photosensitive resin composition is estimated, and the gained result as shown in Table 2.
Concrete evaluation method is as follows:
(1), oligomer content
After photosensitive resin composition was dissolved in acetone, mat has the gas chromatographic detector (GC) of flame ionization detector (FID), and (Hewlett Packard company made; Model 5890A) analyzes and measure.Unit is weight %.
(2), thermotolerance
Obtained photosensitive resin composition in the rotary coating mode, is coated on 10 centimeters * 10 centimeters glass substrates, can obtains filming of about 8 μ m, 85 ℃ of pre-down baking 5 minutes.Then this is filmed with ultraviolet light (exposure machine Canon PLA-501F) 200mJ/cm
2Irradiation, the developer solution that impregnated in 23 ℃ afterwards developed in 2 minutes, cleaned with pure water, baked 40 minutes after 200 ℃ again, can form photo-sensitive resin on glass substrate.
With the photo-sensitive resin on the obtained glass substrate, its light transmission rate of light measurement with 400 ~ 700nm wavelength changes, place in 250 ℃ then after 60 minutes, its transmitance of light measurement with 400 ~ 700nm wavelength changes again, and according to its variation ratio with following benchmark evaluation.
Zero: transmitance changes below 5%
△: transmitance changes 5 ~ 10%
*: transmitance changes more than 10%
(3), alkali resistance
With the photo-sensitive resin on the obtained glass substrate, its light transmission rate of light measurement with 400 ~ 700nm wavelength changes, place in 2%NaOH then after 10 minutes, its transmitance of light measurement with 400 ~ 700nm wavelength changes again, and according to its variation ratio with following benchmark evaluation.
Zero: transmitance changes below 5%
△: transmitance changes 5 ~ 10%
*: transmitance changes more than 10%
(4), ITO (transparent electrode layer) resistance value
After aforementioned obtained photo-sensitive resin forms, ITO film (transparent electrode layer) on sputter on the resin bed.The back is appointed and is got 3 points on this ITO film.With mitsubishi chemical industry system, model MCP-T600 instrument measures its resistance value respectively again, gets its mean value.The Ω of unit.
(5), residue
Aforementioned obtained photosensitive resin composition in the rotary coating mode, is coated on 10 centimeters * 10 centimeters glass substrates, can obtains filming of about 8 μ m, 85 ℃ of pre-down baking 5 minutes.Then this is filmed between between specified mask pattern with ultraviolet light (exposure machine Canon PLA-501F) 300mJ/cm
2Irradiation, the developer solution that impregnated in 23 ℃ afterwards developed unexposed partly removing on substrate in 2 minutes, clean with pure water, after 200 ℃, baked 40 minutes again, can on glass substrate, form the photoresist pattern of being wanted, with electron microscope observation, determine whether the surface has residue to exist.
Zero: no residue
△: a little residue
*: residue is a lot
Embodiment 2～7 and comparative example 1～5
With the method for operating of embodiment 1, difference system changes the kind and the consumption of alkali soluble resin (A), solvent (D) and pigment (E), and its prescription and evaluation result are stated from table two.
Evaluation result by comparative example 1～3 is learnt, when the copolymerization of alkali soluble resin (A) with monomer if do not contain any tool aromatic series functional group and the monomer below the dipole moment 1.5D, then photosensitive resin composition for colour filter is via after coating, exposure, developing, part and light shield layer (black matrix) level of residue upward unexposed on substrate are more, develop, the back roasting after, the thermotolerance of picture element, alkali resistance is relatively poor and the ITO of LCD (transparent electrode layer) resistance value is higher.And learn by comparative example 4,5, when the molecular weight of alkali soluble resin (A) accounts for 0.6 weight % of the solid shape branch of photosensitive resin composition when above at the content of the oligomer below 1000, after baked then development, back, ITO (transparent electrode layer) resistance value of the thermotolerance variation of picture element and LCD was higher.Learn by the evaluation result of various embodiments of the present invention again, when the copolymerization of alkali soluble resin (A) contains a kind of tool aromatic series functional group and the monomer of dipole moment (dipole moment) below the 1.5D at least with monomer, and the molecular weight of this alkali soluble resin (A) accounts for 0.6 weight % of the solid shape branch of photosensitive resin composition when following at the content of the oligomer below 1000, then photosensitive resin composition for colour filter is via coating, exposure, after the development, part and light shield layer (black matrix) level of residue upward unexposed on substrate are less, develop, after the back is roasting, the thermotolerance of picture element, alkali resistance is preferable and ITO (transparent electrode layer) resistance value LCD is lower.
The above person of thought, only for the present invention's preferred embodiment, when the scope that can not limit the invention process with this, promptly the simple equivalent of being done according to the present patent application claim and description of the invention content generally changes and modifies, and all should still belong in the scope that patent of the present invention contains.
Table one: each proportion of composing of alkali soluble resin in various embodiments of the present invention and the comparative example (A).
Table two: each embodiment of resin combination of the present invention and the proportion of composing and the evaluation result of comparative example.
Each proportion of composing of table one, alkali soluble resin (A)
| Synthesis example | Constituent (weight portion) | Temperature of reaction | Poor solvent washing (weight portion) and washing times thereof | ||||||||||
| The copolymerization monomer | Initiator | Solvent | Poor solvent | Washing times | |||||||||
| Compound (2) | Compound (6) | ??SM | ??THP | ????MAA | ????BzMA | ????MA | Enter material way | ??AMBN | ??EEP | ?(℃) | Toluene | (inferior) | |
| ????a | ?10 | ????15 | ????75 | Once add | ??4 | ??200 | ?100 | ??200 | ??1 | ||||
| ????b | ?5 | ??5 | ????15 | ????75 | Once add | ??4 | ??200 | ?100 | ??400 | ??1 | |||
| ????c | ?5 | ????20 | ????65 | ????10 | Once add | ??4 | ??200 | ?100 | ??200 | ??2 | |||
| ????d | ?15 | ????15 | ????70 | Once add | ??4 | ??200 | ?100 | ??200 | ??3 | ||||
| ????e | ?5 | ????10 | ????65 | ????20 | Add continuously | ??4 | ??200 | ?85 | ??50 | ??1 | |||
| ????f | ????15 | ????85 | Once add | ??4 | ??200 | ?100 | ??0 | ??0 | |||||
| ????g | ????15 | ????65 | ????20 | Once add | ??4 | ??200 | ?100 | ??0 | ??0 | ||||
| ????h | ??5 | ????15 | ????80 | Once add | ??4 | ??200 | ?100 | ??50 | ??1 | ||||
| ????i | ?10 | ????15 | ????75 | Once add | ??4 | ??200 | ?100 | ??0 | ??0 | ||||
| ????j | ?15 | ????15 | ????70 | Once add | ??4 | ??200 | ?100 | ??0 | ??0 | ||||
English name
Be called for short Chinese and claim dipole moment (D)
Compound (2) coumarone benzo furan 0.57
Compound (6) vinylcarbazole vinyl carbazole 0.81
SM styrene monomer styrene monomer 0.02
THP oxinane tetrahydropyrane 0.95
MAA methacrylic acid monomer methacrylic acid 1.77
BzMA methacrylic acid benzene methyl monomer benzyl methacrylate 1.84
MA methacrylate monomer methyl acrylate 1.72
AMBN 2, and 2 '-azo is two-2-methylbutyronitrile 2,2 '-azobis-2-methyl butyronitrile-
EEP 3-ethoxyl ethyl propionate ethyl 3-ethoxypropionate-
Table two. each embodiment of resin combination of the present invention and the proportion of composing and the evaluation result of comparative example
| Composition | Embodiment | Comparative example | |||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | 3 | 4 | 5 | ||
| Alkali soluble resin (A) (weight portion) | a | 100 | 100 | ||||||||||
| b | 100 | 100 | |||||||||||
| c | 100 | ||||||||||||
| d | 100 | ||||||||||||
| e | 100 | ||||||||||||
| f | 100 | ||||||||||||
| g | 100 | ||||||||||||
| h | 100 | ||||||||||||
| i | 100 | ||||||||||||
| j | 100 | ||||||||||||
| The compound (B) (weight portion) that contains the ethene unsaturated group | B-1 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 |
| Light initiator (C) (weight portion) | C-1 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 |
| C-2 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | |
| C-3 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | |
| Solvent (D) (weight portion) | D-1 | 1000 | 1000 | 1000 | 1000 | 830 | 1000 | 830 | 1000 | 1000 | 830 | 1000 | 1000 |
| D-2 | 170 | 170 | 170 | ||||||||||
| Pigment (E) (weight portion) | E-1 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | ||
| E-2 | 130 | ||||||||||||
| E-3 | 100 | ||||||||||||
| The oligomer content (weight %) of the molecular weight of alkali soluble resin (A) below 1000 | 0.09 | 0.08 | 0.07 | 0.05 | 0.10 | 0.11 | 0.10 | 0.01 | 0.08 | 0.25 | 0.80 | 0.95 | |
| Evaluation result | Thermotolerance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | △ | △ | △ | △ |
| Alkali resistance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | × | △ | ○ | ○ | |
| Residue | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ | × | △ | ○ | ○ | |
| The resistance value of ITO (Ω) | 20 | 19 | 20 | 21 | 21 | 19 | 19 | 45 | 48 | 38 | 38 | 40 | |
B-1 dipentaerythritol acrylate dipentaerythritol hexaacrylate
C-1 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone 2-benzyl-2-N, N-dimethylamino-1-(4-morpholinophenyl)-1-butanone
C-2 4,4 '-two (diethylamine) benzophenone 4,4 '-bis (diethylamino) benzophenone
C-3 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole 2,2 '-bis (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole
D-1 3-ethoxyl ethyl propionate Ethyl 3-ethoxypropionate
D-2 1-Methoxy-2-propyl acetate propylene glycol methyl ether acetate
E-1 pigment CI254
E-2 pigment G36
E-3 pigment B15: 6
Claims (2)
1. photosensitive resin composition for colour filter comprises:
(A) alkali soluble resin;
(B) contain the compound of ethene unsaturated group;
(C) light initiator;
(D) organic solvent; And
(E) pigment;
It is characterized in that this alkali soluble resin (A) comprises the monomer and other copolymerizable monomer that contain at least below a kind of tool aromatic series functional group and dipole moment (dipole moment) 1.5D and is polymerized; And the molecular weight of this alkali soluble resin (A) accounts for below the 0.6 weight % of the solid shape branch of photosensitive resin composition at the content of the oligomer below 1000.
2. photosensitive resin composition for colour filter according to claim 1, it is characterized in that, in the said alkali soluble resin (A), total based on tool aromatic series functional group and the monomer below the dipole moment 1.5D and other copolymerizable monomer is measured 100 weight portions, and the following monomer of this tool aromatic series functional group and dipole moment (dipole moment) 1.5D accounts for 1～35 weight portion.
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| CN 03160135 CN1220114C (en) | 2003-09-27 | 2003-09-27 | Light-sensitive resin composition for colour filter film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100380142C (en) * | 2005-02-24 | 2008-04-09 | 奇美实业股份有限公司 | Photosensitive resin composition for colour absorter |
| CN100409073C (en) * | 2004-12-30 | 2008-08-06 | 财团法人工业技术研究院 | Alkali soluble resin, and composition containing the resin and capable of sensing optical activity |
| CN100445778C (en) * | 2004-12-07 | 2008-12-24 | 东进世美肯株式会社 | Photosensitive resin composition for color filter and method for mfg. LCD color filter by same |
| CN101154043B (en) * | 2006-09-26 | 2011-04-20 | 新应材股份有限公司 | High-resolution negative-type photoresist |
| CN103964698A (en) * | 2013-02-04 | 2014-08-06 | 台湾永光化学工业股份有限公司 | Use of positive photoresist composition |
| WO2015024316A1 (en) * | 2013-08-20 | 2015-02-26 | 京东方科技集团股份有限公司 | Polyether compound, preparation method and photoresist composition thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100445778C (en) * | 2004-12-07 | 2008-12-24 | 东进世美肯株式会社 | Photosensitive resin composition for color filter and method for mfg. LCD color filter by same |
| CN100409073C (en) * | 2004-12-30 | 2008-08-06 | 财团法人工业技术研究院 | Alkali soluble resin, and composition containing the resin and capable of sensing optical activity |
| CN100380142C (en) * | 2005-02-24 | 2008-04-09 | 奇美实业股份有限公司 | Photosensitive resin composition for colour absorter |
| CN101154043B (en) * | 2006-09-26 | 2011-04-20 | 新应材股份有限公司 | High-resolution negative-type photoresist |
| CN103964698A (en) * | 2013-02-04 | 2014-08-06 | 台湾永光化学工业股份有限公司 | Use of positive photoresist composition |
| WO2015024316A1 (en) * | 2013-08-20 | 2015-02-26 | 京东方科技集团股份有限公司 | Polyether compound, preparation method and photoresist composition thereof |
| US9541833B2 (en) | 2013-08-20 | 2017-01-10 | Boe Technology Group Co., Ltd. | Polyether compound, method for preparing same and photoresist composition |
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| CN1220114C (en) | 2005-09-21 |
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