CN100340878C - Sensitive resin composition of color light filter - Google Patents
Sensitive resin composition of color light filter Download PDFInfo
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- CN100340878C CN100340878C CNB2005100559350A CN200510055935A CN100340878C CN 100340878 C CN100340878 C CN 100340878C CN B2005100559350 A CNB2005100559350 A CN B2005100559350A CN 200510055935 A CN200510055935 A CN 200510055935A CN 100340878 C CN100340878 C CN 100340878C
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Abstract
The present invention provides a light sensitive resin composition for color filters. Amount of residue on an unexposed part and a shading layer on a basal plate is little after the color filter is coated, exposed and developed, and heat resistance and alkali resistance of picture elements is good and resistance value of an ITO transparent electrode layer of a liquid crystal display is small after the color filter is developed and roasted. The composition contains alkali soluble resin (A), a compound (B) containing ethylene unsaturated groups, light initiator (C), organic solvent (D), pigment (E) and a compound (F) whose one molecule contains at least two epoxy groups, wherein hydroxyl value of the alkali soluble resin (A) is between 0.1 to 20 KOH mg/g, and thermal loss of weight temperature of 5 wt% of the alkali soluble resin measured by a thermo-gravimetric analyzer is more than 300 DEG C. use amount of the compound (F) whose one molecule contains at least two epoxy groups is 0.1 to 30 parts by weight measured by 100 parts by weight of the alkali soluble resin (A).
Description
Technical field
The 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 coating, 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 tin indium oxide of LCD (Indium Tin Oxide, hereinafter to be referred as ITO) the 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), generally be earlier to coat photosensitive resin composition on the substrate and carry out drying (pre-roasting), see through light shield and implement ultraviolet exposure, sclerosis, again by alkaline-based developer develop forms pattern after, at last this is heat-treated (bake the back).Particularly, as cured films such as red, blue, the green picture element (pixel) in the colored filter, resin light shield layer (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 process, 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 polymeric composition comprising body institute's copolymerization and multipolymer be used as photoresist with the relevant report of cementing agent, 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 ℃ of thermal treatment in this type patent, and 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, its method is with the resin of dyeing possibility (as natural gelatin, casein etc.) patterning in advance in the past, and then with dyeing red, blue, green picture element.But,, generally all have the not 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, adopt 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 the work cleaned with thin developer solution or water under high pressure liquid, so, easily make manufacturing process's number of colored filter complicated.
Summary of the invention
The object of the present invention is to provide a kind of photosensitive resin composition for colour filter of LCD.Particularly provide a kind of via after coating, 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 transparent electrode layer impedance value of LCD is little, and the photosensitive resin composition for colour filter that can alkaline-based developer develops.
This constituent comprises: the compound (F) that contains 2 epoxy radicals in alkali soluble resin (A), the compound (B) that contains the ethene unsaturated group, light initiator (C), organic solvent (D), pigment (E) and 1 molecule at least; Wherein, the hydroxyl value of this alkali soluble resin (A) is between 0.1～20KOHmg/g, and is more than 300 ℃ with the hot loss of weight temperature that hot loss of weight analyser (TGA) is measured its 5 weight %; And based on alkali soluble resin (A) 100 weight portions, the use amount that contains the compound (F) of 2 epoxy radicals in 1 molecule at least is 0.1～30 weight portion.
The photosensitive resin composition for colour filter that beneficial effect of the present invention is to be provided is after coating, exposure, developing, level of residue on unexposed part and light shield layer on the substrate is few, and after bake development, back, thermotolerance, the alkali resistance of picture element are good, the ito transparent electrode layer impedance value of LCD is little, and can develop with alkaline-based developer.
Embodiment
Below one by one each composition of the present invention is described in detail:
Alkali soluble resin (A)
Alkali soluble resin of the present invention (A) be by the ethene insatiable hunger of hydroxyl close monomer (a-1) (being designated hereinafter simply as the unsaturated monomer that contains hydroxyl), ethene insatiable hunger with one or more carboxyl closes monomer (a-2) (being designated hereinafter simply as the unsaturated monomer that contains carboxyl) and forms with other copolymerizable ethylene unsaturated monomer (a-3) (being designated hereinafter simply as other unsaturated monomer) copolymerization.
The above-mentioned unsaturated monomer (a-1) that contains hydroxyl is for example: 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy 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, N-neighbour-hydroxy phenyl maleimide, between N--the hydroxy phenyl maleimide, N-is right-the hydroxy phenyl maleimide, N-hydroxyethyl acrylamide, the N-hydroxyethyl methacrylamide, dipropylene glycol acrylate (dipropylene glycol acrylate), dipropylene glycol methacrylate (dipropylene glycol methacrylate), butylene glycol aerylate, the butylene glycol methacrylate, polyethylene glycol methacrylate-styrene polymer (polyethylene glycol methacrylate), polypropylene glycol acrylate (polypropylene glycol acrylate), polypropylene glycol methacrylate (polypropylene glycol methacrylate), polyethylene glycol-propylene glycol methacrylate (polyethylene glycol-polypropylene glycol methacrylate), polyglycol-1,4-butylene glycol methacrylate (polyethylene glycol-1,4-butanediol methacrylate), 2-acryloxy ethanol-2-hydroxyl ethanol phthalic acid ester (2-acryloxy ethyl-2-hydroxy ethyl phthalate), caprolactone upgrading acrylate (caprolactone modified acrylate), caprolactone upgrading methacrylate (caprolactone modified methacrylate), acrylic acid-2-hydroxyl-3-phenoxy group propyl ester (2-hydroxy-3-phenoxy-propyl acrylate, the ARONIX M-5700 of East Asia Synesis Company system) etc.Wherein cited person is preferable with 2-acryloxy ethanol-2-hydroxyl ethanol phthalic acid ester, acrylic acid-2-hydroxyl-3-phenoxy group propyl ester, acrylic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxy propyl ester, 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate.These unsaturated monomers that contain hydroxyl can use separately, perhaps mix two or more and usefulness.
The above-mentioned unsaturated monomer (a-2) that contains carboxyl for example is: 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 (a-3) for example is: the aromatic ethenyl compound of styrene, α-Jia Jibenyixi, vinyltoluene, vinyl chloride, methoxy styrene etc.; The unsaturated carboxylate type that contains the aromatic series functional group of acrylic acid benzene methyl, methacrylic acid benzene methyl, phenyl acrylate, phenyl methacrylate etc.; Between N-phenylmaleimide, N-neighbour-aminomethyl phenyl maleimide, N--aminomethyl phenyl maleimide, N-be right-aminomethyl phenyl maleimide, N-neighbour-methoxyphenyl maleimide, N-between-methoxyphenyl maleimide, N-be right-maleimide such as methoxyphenyl maleimide, N-cyclohexyl maleimide; 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, the acrylic acid tributyl, the methacrylic acid tributyl, allyl acrylate, allyl methacrylate, acrylic acid triethylene glycol methoxyethoxy ester (methoxy triethylene glycol acrylate), methacrylic acid triethylene glycol methoxyethoxy ester (methoxy triethylene glycol methacrylate), lauryl methacrylate (lauryl methacrylate), methacrylic acid myristyl ester (tertadecylmethacrylate), methacrylic acid cetyl ester (cetyl methacrylate), methacrylic acid stearyl (octadecylmethacrylate), methacrylic acid eicosyl ester (eicosyl methacrylate), the unsaturated carboxylate type of methacrylic acid docosyl ester (docosyl methacrylate) etc.; 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-unsaturated carboxylic acid ammonia alkane ester classes such as 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 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 amides of acrylamide, Methacrylamide, α-chloropropene acid amides etc.; The aliphatics conjugated diene of 1,3-butadiene, different propylene, chloropropene etc.
Wherein cited person is preferable with styrene, acrylic acid benzene methyl, methacrylic acid benzene methyl, N-phenylmaleimide, methyl acrylate, methyl methacrylate.These other unsaturated monomers can separately or mix plural number and plant use.
Alkali soluble resin of the present invention (A), its copolymerization adds up to 100 weight portions based on its copolymerization with monomer (a-1), (a-2), (a-3) three, as shown below with the use amount of monomer.
The use amount that contains the unsaturated monomer (a-1) of hydroxyl is preferably 1～35 weight portion, is more preferred from 2～32 weight portions, and the best is 3～30 weight portions.The use amount that contains the unsaturated monomer (a-2) of carboxyl is preferably 1～30 weight portion, is more preferred from 2～25 weight portions, and the best is 3～20 weight portions; The use amount of other unsaturated monomer (a-3) is preferably 35～98 weight portions, is more preferred from 43～96 weight portions, and the best is 50～94 weight portions.
The hydroxyl value of alkali soluble resin of the present invention (A) is preferable between 0.1～20KOHmg/g, is more preferred between 0.3～15KOHmg/g, and the best is between 0.5～10KOHmg/g.
The hydroxyl value system of alkali soluble resin of the present invention (A) gets [JIS JIS-K0070 puts down on May 1st, 4 for JISC's review (JSA's distribution) and corrects] according to the neutralization titration mensuration of JIS K0070.Hydroxyl value is defined as that 1 gram test portion can combine with hydroxyl via acetylation in the potassium hydroxide that forms acetic acid and required milligram number.
The hydroxyl value of alkali soluble resin of the present invention (A) can be by in the polymerization process by alkali soluble resin (A), contains the kind of unsaturated monomer (a-1) of hydroxyl and use amount etc. and is controlled.
Alkali soluble resin of the present invention (A) is with hot loss of weight analysis-e/or determining, and the hot loss of weight temperature of its 5 weight % is preferably more than 300 ℃, is more preferred from more than 305 ℃, and the best is more than 310 ℃.This hot loss of weight temperature can be by in the polymerization process by alkali soluble resin (A), and the enter material way of the kind of monomer and initiator and use amount, monomer and initiator, temperature of reaction and alkali soluble resin (A) are controlled with poor vehicle treated etc.
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 one dipropyl two ferment methyl ethers that contract, the dipropylene glycol ether, the dipropylene glycol positive propyl ether, the dipropylene glycol n-butyl ether, tripropylene glycol methyl ether (tripropylene glycol monomethyl ether), (gathering) alkylene glycol mono alkane ethers of tripropylene glycol ether (tripropylene glycol mono ethyl ether) etc.; (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.
Employed initiator when alkali soluble resin (A) is made, 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.Wherein, with 2,2 '-azo is two-and the 2-methylbutyronitrile is preferable.
The present invention's alkali soluble resin (A) is with gel permeation chromatography (GPC; Stripping solvent tetrahydrofuran) measure, the weight average molecular weight of conversion polystyrene is preferably 3,000 to 50,000, is more preferred from 4,000 to 40,000, and the best is 4,500 to 35,000.Weight average molecular weight can obtain the photosensitive resin composition of preferable development when aforementioned range, distinct by this formed pattern edge.
The compound (B) that contains the ethene unsaturated group
Based on alkali soluble resin (A) 100 weight portions, the use amount that the present invention contains the compound (B) of ethene unsaturated group is preferably 5～220 weight portions, is more preferred from 50～160 weight portions, and the best is 70～140 weight portions.
The above-mentioned compound (B) that contains the ethene unsaturated group is the ethene unsaturated compound with at least one ethene unsaturated group.
The concrete example 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, trioctylphosphine (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.
Light initiator (C)
Based on the compound that contains the ethene unsaturated group (B) 100 weight portions, the use amount of light initiator of the present invention (C) is preferably 20～120 weight portions, is more preferred from 30～100 weight portions, and the best is 40～80 weight portions.
The concrete example of above-mentioned smooth initiator (C) is: 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 isophthalic acid-(4-methyl thio-phenyl)-2-morpholino-1-acetone (2-methyl-1-(4-methylthio phenyl)-2-morpholino-propane-1-on), 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-methylphenyl)-4,4 ', 5,5 '-tetraphenyl biimidazole], 2,2 '-two (o-methoxyphenyl)-4,4 ', 5, and 5 '-tetraphenyl diimidazole [2,2 '-bis (o-methoxyphenyl)-4,4 ', 5,5 '-tetraphenyl biimidazole], 2,2 '-two (p-methoxyphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (p-methoxyphenyl)-4,4 ', 5,5 '-tetraphenyl biimidazole], 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 '-tetraphenyl biimidazole], 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl biimidazole] etc.
Wherein with 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone, 2,2 '-two (2-chlorphenyl)-4,4 ', 5, the light initiator effect of 5 '-tetraphenyl diimidazole and usefulness is preferable.
In the photosensitive resin composition for colour filter of the present invention, 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 isopropyl ether) 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-trimethylbenzyl phosphineoxide] 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 (phenacyl chloride), trisbromomethyl benzene sulfone (tribromomethyl phenylsulfone), three (trichloromethyl)-s-triazines [tris (trichloromethyl)-s-triazine] etc.; The superoxide of two-Di tributyl superoxide (di-tertbutylperoxide) etc.
Wherein with benzophenone (benzophenone) based compound the best, especially with 4,4 '-two (diethylamine) benzophenone best results.
Organic solvent (D)
Photosensitive resin composition for colour filter of the present invention is with aforementioned alkali soluble resin (A), the compound (B) that contains the ethene unsaturated group, light initiator (C), and organic solvent (D) and pigment described later (E) is necessary composition, can add additive composition described later in case of necessity.
Usually, pigment (E) each composition in addition is dissolved in the suitable organic solvent (D), is modulated into aqueous constituent.In the selection of aforementioned organic solvent (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.
Based on alkali soluble resin (A) 100 weight portions, the use amount of the organic solvent of photosensitive resin composition for colour filter of the present invention (D) is preferably 300～2500 weight portions, is more preferred from 400～2200 weight portions, and the best is 500～2000 weight portions.
Above-mentioned organic solvent (D) can be selected from employed solvent 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 organic solvent (D), also preferable with 1-Methoxy-2-propyl acetate, 3-ethoxyl ethyl propionate.
Pigment (E)
Based on alkali soluble resin (A) 100 weight portions, the use amount of pigment of the present invention (E) is preferably 20～500 weight portions, is more preferred from 50～400 weight portions, and the best is 80～300 weight portions.
Pigment of the present invention (E) can use known so far various inorganic pigments or organic pigment.Inorganic pigment can be given an example as the metallic compound of: metal oxide, the wrong salt of metal or the like, particularly, as: the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, inferior lead, antimony etc., and the composite oxides of aforementioned metal are 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.
Pigment in the present invention (E) according to desired person, also can be followed the use spreading agent.The interfacial 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 interfacial 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 interfacial agents can separately or mix plural number and plant above the use.
At least the compound (F) that contains 2 epoxy radicals in 1 molecule
Based on alkali soluble resin (A) 100 weight portions, the use amount that contains the compound (F) of 2 epoxy radicals in 1 molecule at least is preferably 0.1～30 weight portion, is more preferred from 1～25 weight portion, and the best is 2～20 weight portions.
At least the concrete example of compound (F) that contains 2 epoxy radicals in 1 molecule of the present invention is as bisphenol A type epoxy resin (bisphenol A type epoxy resin, for example: oiling Shell Epoxy corporate system, trade name Epikote828, Epikote 1001, Epikote 1002, Epikote 1004 etc.), the epoxy resin that the pure type hydroxyl (alcoholic hydroxyl) of bisphenol A type epoxy resin gets with epichlorokydrin (epichlorohydrin) reaction (for example: Japanese chemical drug corporate system, trade name NER-1302, epoxide equivalent 323,76 ℃ of softening points), bisphenol f type epoxy resin (bisphenol F type epoxy resin, for example: oiling Shell Epoxy corporate system, trade name Epikote 807, Epikote 4001, Epikote 4002, Epikote 4004 etc.), the pure type hydroxyl of bisphenol f type epoxy resin and epichlorohydrin reaction and epoxy resin (for example: Japanese chemical drug corporate system, trade name NER-7406, epoxide equivalent 350,66 ℃ of softening points), bisphenol-s epoxy resin (bisphenol S type epoxy resin), diphenyl glycidol ether (biphenyl glycidyl ether, for example: oiling Shell Epoxy corporate system, trade name Epikote YX4000), (benzene) phenol aldehyde type epoxy resin (phenol Novolac type epoxy resin, for example: Japanese chemical drug corporate system, trade name EPPN-201, oiling Shell Epoxy corporate system, trade name Epikote 152, Epikote 154, Epikote157S65, Epikote 157S70, Dow Chemical's system, trade name DEN-438), first (benzene) phenol aldehyde type epoxy resin (cresol Novolac type epoxy resin, for example: Japanese chemical drug corporate system, trade name EOCN-102S, EOCN-1020, EOCN-104S), three-glycidyl chlorinated isocyanurates (triglycidyl isocyanurate, for example: daily output chemical company system, trade name TEPIC), triphenol methane type epoxy resin (trisphenol methane type epoxyresin, for example: Japanese chemical drug corporate system, trade name EPPN-501, EPPN-502, EPPN-503), fluorenes epoxy resin (fluorene epoxy resin, for example: chemical company of Nippon Steel system, trade name ESF-300), alicyclic epoxy resin (for example: Daicel chemical industrial company system, trade name Gelloxide 2021P, Celloxide EHPE) and POLYBUTADIENE EPOXY RESIN (epoxidized polybutadiene, for example: Daicel chemical industrial company system, trade name Epolead PB3600) etc.
At least contain in 1 molecule of the present invention in the compound (F) of 2 epoxy radicals, better with (benzene) phenol aldehyde type epoxy resin and POLYBUTADIENE EPOXY RESIN.At least the compound that contains 2 epoxy radicals in these 1 molecules can use separately, also can mix use more than 2 kinds or 2 kinds.
In the photosensitive resin composition for colour filter of the present invention, when the hydroxyl value of (1) alkali soluble resin (A) between 0.1～20KOHmg/g, (2) alkali soluble resin (A) the hot loss of weight temperature of measuring its 5 weight % with hot loss of weight analyser (TGA) be more than 300 ℃ and (3) based on alkali soluble resin (A) 100 weight portions, at least the use amount that contains the compound (F) of 2 epoxy radicals in 1 molecule is that conditions such as 0.1～30 weight portion are when satisfying, then photosensitive resin composition is via coating, exposure, after the development, part and light shield layer (black matrix) level of residue upward unexposed on substrate are few, and develop, after the back is roasting, the thermotolerance of picture element, alkali resistance is good, and the ito transparent electrode layer impedance value of LCD reduces.
Be the raising coating in the photosensitive resin composition of the present invention, and can follow the use interfacial agent.Based on alkali soluble resin (A) 100 weight portions, the use amount of interfacial agent of the present invention is preferable between 0～6 weight portion, better for 0～5 weight portion, best between 0～4 weight portion, above-mentioned interfacial agent for example with employed interfacial agent in the aforementioned pigment.
In addition, in the photosensitive resin composition of the present invention, 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.Based on alkali soluble resin (A) 100 weight portions, the use amount of additive of the present invention is preferable between 0～10 weight portion, and is more between 0～6 weight portion, best between 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-tributyl phenol), 2, the antioxidant of 6-two-Di tributyl phenol etc.; 2-(3-the tributyl-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 above-mentioned composition (A)～(F) is uniformly mixed into solution state in stirrer, can add other adjuvants such as interfacial agent, adherence auxiliary agent in case of necessity.
Photosensitive resin composition of the present invention is by by coating methods such as revolution coating, curtain coating coating or print roll coatings constituent being coated on the substrate.After the coating, removal of solvents is formed photo-sensitive resin 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 according to the kind of each composition, cooperates ratio and different, carries 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 to develop in 30 seconds～5 minutes under 23 ± 2 ℃ of temperature, and that does not want partly removes and form 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, piperidines, 1,8-diazabicylo-(5,4,0)-alkali compounds such as 7-hendecene, the concentration of developer solution is preferably 0.001～10 weight %, be more preferred from 0.005～5 weight %, the best is the alkaline aqueous solution that 0.01～1 weight % is constituted.
When using the developer solution that these alkaline aqueous solutions constitute, generally be clean to wash again after video picture.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
Aforementioned and other technology contents, characteristics and effect of the present invention in the explanation of following cooperation embodiment and comparative example, can be known and understand.
1, the synthesis example of alkali soluble resin (A)
Synthesis example A-1
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 3-ethoxyl ethyl propionate (hereinafter to be referred as 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 acrylic acid-2-hydroxyl-3-phenoxy group propyl ester (hereinafter to be referred as M-5700) 5 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, the monomer mixture of methacrylate monomer (hereinafter to be referred as MA) 5 weight portions is in the temperature of oil bath is promoted to after 90 ℃ 5 hours, add continuously, and after the temperature of oil bath is promoted to 90 ℃, 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 the solution of AMBN and EEP is divided into five equal portions, the amount of equal portions is added in the four cervical vertebra bottles at interval with each hour one.
The temperature of reaction of polymerization process is kept 90 ℃, 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-1.
Synthesis example A-2～A-5
With the method for operating of synthesis example A-1, difference is use amount and the washing times that changes the polymerization kind of monomer, mixing consumption, temperature of reaction, reaches toluene (poor solvent) in the poor solvent washing process, and its prescription and reaction conditions are stated from table one.
Synthesis example A-6～A-7
With the method for operating of synthesis example A-1, difference is to change kind, mixing consumption, the temperature of reaction of polymerization with monomer, and its prescription and reaction conditions are stated from table one.
Synthesis example A-8
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: methacrylic acid-2-hydroxy methacrylate (hereinafter to be referred as HEMA) 15 weight portions, MAA 10 weight portions, BzMA 70 weight portions, MA 5 weight portions, and solvent EEP 200 weight portions.Wherein, the enter material way of monomer mixture is for once all adding.
When the content of four cervical vertebra bottles is stirred, the temperature of oil bath is promoted to 95 ℃, then according to shown in the table one polymerization being dissolved among the organic solvent EEP with initiator AMBN 4 weight portions, and the solution of AMBN and EEP is divided into five equal portions, the amount of equal portions is added in the four cervical vertebra bottles at interval with each hour one.
The temperature of reaction of polymerization process is kept 95 ℃, polymerization time 6 hours.After polymerization is finished, polymerizate is taken out in four cervical vertebra bottles,, can get alkali soluble resin A-8 the solvent devolatilization.
Synthesis example A-9～A-11
With the method for operating of synthesis example A-8, difference is the kind that changes polymerization usefulness monomer, the consumption and the temperature of reaction of mixing consumption, polymerization usefulness initiator AMBN, and its prescription and reaction conditions are stated from table one.
2, the embodiment of photosensitive resin composition and comparative example
Embodiment 1
Use the alkali soluble resin A-1100 weight portion (solid) of aforementioned synthesis example gained, with dipentaerythritol acrylate 100 weight portions shown in the table two, 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone 40 weight portions, 4,4 '-two (diethylamine) benzophenone 5 weight portions, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole, 5 weight portions, pigment CI254 160 weight portions and (benzene) phenol aldehyde type epoxy resin (oiling SHELL Epoxy corporate system, trade name Epikote 157S70) potpourri of 3 weight portions, after adding solvent 1-Methoxy-2-propyl acetate (hereinafter to be referred as PGMEA) 170 weight portions and EEP 830 weight portions, with swing-out stirrer, dissolved mixing, 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.
Embodiment 2～5 and comparative example 1～8 its prescription and evaluation result also are stated from table two.
Evaluation method
One, hydroxyl value
According among the JIS K0070 and titration measuring.
Two, the hot loss of weight temperature of 5 weight % of alkali soluble resin (A)
In the presence of nitrogen, place hot loss of weight analyser (to be called for short TGA 10 milligrams of prepared alkali soluble resins (A), TA corporate system model Thermal Analyst 2100), be warming up to 100 ℃ and lasting 10 minutes earlier and remove moisture content, heat up with 10 ℃/minute speed again, when the weight of test portion reduces by 5 weight %, measure temperature at that time, be the hot loss of weight temperature of 5 weight %.
Three, thermotolerance
Prepared 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 CanonPLA-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 prepared glass substrate, its light transmission rate of light measurement with 400～700nm wavelength, in 250 ℃, place then after 60 minutes, with its light transmission rate of light measurement of 400～700nm wavelength, change ratio with following benchmark evaluation again according to its light transmission rate.
Zero: transmitance changes below 5%
△: transmitance changes 5～10%
*: transmitance changes more than 10%
Four, alkali resistance
With the photo-sensitive resin on the prepared glass substrate, its light transmission rate of light measurement with 400～700nm wavelength, in 2%NaOH, place then after 10 minutes, change ratio with following benchmark evaluation again with its light transmission rate of light measurement of 400～700nm wavelength, and according to its light transmission rate.
Zero: transmitance changes below 5%
△: transmitance changes 5～10%
*: transmitance changes more than 10%
Five, ito transparent electrode layer impedance value
After aforementioned prepared photo-sensitive resin formed, with 250 ℃ vacuum splashing and plating condition, sputter ITO film formed transparent electrode layer on 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.
Six, residue
Prepared 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 mask pattern (mask) is adjacent to this roasting in advance filming, with ultraviolet light (exposure machine Canon PLA-501F) 300mJ/cm
2Irradiation, the developer solution 2 minutes that impregnated in 23 ℃ afterwards develops, on the substrate unexposed partly remove after, 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 2～5 and comparative example 1～8
With the method for operating of embodiment 1, difference is to change kind and the consumption that contains the compound (F) of 2 epoxy radicals in alkali soluble resin (A), pigment (E) and 1 molecule at least, and its prescription and evaluation result are stated from table two.
But the above person, it only is preferred embodiment of the present invention, when not limiting scope of the invention process with this, promptly the simple equivalent of being done according to claims of the present invention 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.
The subordinate list explanation:
Table one: the proportion of composing and the evaluation result of alkali soluble resin of the present invention (A) synthesis example.
Table two: the proportion of composing of the embodiment of the invention and comparative example and evaluation result thereof.
The proportion of composing and the evaluation result of the synthesis example of table one, alkali soluble resin (A)
| Resin | Constituent (weight portion) | Temperature of reaction | Poor solvent washing | Hydroxyl value | Hot loss of weight temperature | |||||||||
| The copolymerization monomer | Initiator | Solvent | Poor solvent | Washing times | ||||||||||
| (a-1) | (a-2) | (a-3) | Enter material way | Toluene | ||||||||||
| M-5700 | HEMA | MAA | BzMA | SM | MA | AMBN | EEP | ℃ | (weight portion) | (inferior) | mg/g | ℃ | ||
| A-1 | 5 | 15 | 75 | 5 | Add continuously | 4 | 200 | 90 | 200 | 1 | 1.4 | 321 | ||
| A-2 | 5 | 15 | 75 | 5 | Add continuously | 4 | 200 | 95 | 400 | 1 | 1.5 | 323 | ||
| A-3 | 10 | 2 | 10 | 70 | 8 | Add continuously | 4 | 200 | 95 | 400 | 3 | 4 | 325 | |
| A-4 | 20 | 10 | 65 | 5 | Add continuously | 4 | 200 | 95 | 200 | 2 | 6.1 | 321 | ||
| A-5 | 25 | 2 | 5 | 65 | 3 | Add continuously | 4 | 200 | 90 | 400 | 1 | 8.6 | 314 | |
| A-6 | 15 | 80 | 5 | Add continuously | 4 | 200 | 90 | 200 | 1 | 0 | 330 | |||
| A-7 | 40 | 20 | 40 | Add continuously | 4 | 200 | 95 | 200 | 1 | 21 | 325 | |||
| A-8 | 15 | 10 | 70 | 5 | Once add | 4 | 200 | 95 | 0 | 0 | 8 | 285 | ||
| A-9 | 30 | 10 | 55 | 5 | Once add | 9 | 200 | 95 | 0 | 0 | 15.7 | 272 | ||
| A-10 | 15 | 15 | 65 | 5 | Once add | 4 | 200 | 120 | 0 | 0 | 7.9 | 275 | ||
| A-11 | 15 | 65 | 20 | Once add | 4 | 200 | 95 | 0 | 0 | 0 | 288 | |||
Be called for short the Chinese English name
M-5700 acrylic acid-2-hydroxyl-3-phenoxy group propyl ester 2-hydroxy-3-phenoxy-propyl acrylate
HEMA methacrylic acid-2-hydroxy methacrylate 2-hydroxyethyl methacrylate
MAA methacrylic acid monomer methacrylic acid
BzMA methacrylic acid benzene methyl monomer benzyl methacrylate
SM styrene monomer styrene monomer
MA methacrylate monomer methyl acrylate
AMBN 2, and 2 '-azo is two-2-methylbutyronitrile 2,2 '-azobis-2-methyl butyronitrile
EEP 3-ethoxyl ethyl propionate ethyl 3-ethoxypropionate
The proportion of composing of table two, embodiment and comparative example and evaluation result thereof
| Composition | The embodiment numbering | The comparative example numbering | ||||||||||||
| 1 | 2 | 3 | 4 | 5 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | ||
| Alkali soluble resin (A) (weight portion) | A-1 | 100 | 100 | |||||||||||
| A-2 | 100 | 100 | ||||||||||||
| A-3 | 100 | |||||||||||||
| A-4 | 100 | |||||||||||||
| A-5 | 100 | |||||||||||||
| A-6 | 100 | |||||||||||||
| A-7 | 100 | |||||||||||||
| A-8 | 100 | |||||||||||||
| A-9 | 100 | |||||||||||||
| A-10 | 100 | |||||||||||||
| A-11 | 100 | |||||||||||||
| The compound (B) (weight portion) that contains the ethene unsaturated group | B-1 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Light initiator (C) (weight portion) | C-1 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| C-2 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| C-3 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| Organic solvent (D) (weight portion) | D-1 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 |
| D-2 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | |
| Pigment (E) (weight portion) | E-1 | 160 | 160 | 160 | 160 | 160 | 160 | 160 | 160 | 160 | 160 | 160 | ||
| E-2 | 160 | |||||||||||||
| E-3 | 160 | |||||||||||||
| At least the compound (F) (weight portion) that contains 2 epoxy radicals in 1 molecule | F-1 | 3 | 10 | 15 | 35 | 3 | 10 | 10 | ||||||
| F-2 | 10 | 20 | 3 | 10 | ||||||||||
| Assessment item | The resistance value of ITO | 18 | 17 | 16 | 16 | 15 | 45 | 15 | 37 | 18 | 41 | 42 | 45 | 38 |
| Alkali resistance | ○ | ○ | ○ | ○ | ○ | × | ○ | × | △ | △ | △ | × | × | |
| Residue | ○ | ○ | ○ | ○ | ○ | ○ | × | ○ | × | ○ | △ | △ | ○ | |
| Thermotolerance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | × | × | × | |
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 1-Methoxy-2-propyl acetate propylene glycol methyl ether acetate
D-2 3-ethoxyl ethyl propionate Ethyl 3-ethoxypropionate
E-1 pigment CI254
E-2 pigment G36
E-3 pigment B15:6
F-1 novalac epoxy (oiling SHELL EPOXY corporate system, trade name Epikote 157S70)
F-2 epoxidized polybutadiene (Daicel corporate system, trade name Epolead PB3600)
Claims (5)
1. a photosensitive resin composition for colour filter is characterized in that, this constituent comprises:
Alkali soluble resin (A) 100 weight portions;
Compound (B) 5～220 weight portions that contain the ethene unsaturated group;
Light initiator (C) 20～120 weight portions;
Organic solvent (D) 300～2500 weight portions;
Pigment (E) 20～500 weight portions;
And 1 compound (F) 0.1～30 weight portion that contains 2 epoxy radicals in the molecule at least;
At least contain the use amount of the compound (F) of 2 epoxy radicals in the above-mentioned compound (B) that contains the ethene unsaturated group, light initiator (C), organic solvent (D), pigment (E), 1 molecule, be based on alkali soluble resin (A) 100 weight portions;
The hydroxyl value of above-mentioned alkali soluble resin (A) is between 0.1～20KOHmg/g, and is more than 300 ℃ with the hot loss of weight temperature of its 5 weight of hot loss of weight analysis-e/or determining %.
2. a kind of photosensitive resin composition for colour filter according to claim 1 is characterized in that, the hydroxyl value of alkali soluble resin (A) is between 0.3～15KOHmg/g.
3. a kind of photosensitive resin composition for colour filter according to claim 1 is characterized in that, the hydroxyl value of alkali soluble resin (A) is between 0.5～10KOHmg/g.
4. a kind of photosensitive resin composition for colour filter according to claim 1 is characterized in that, based on alkali soluble resin (A) 100 weight portions, the use amount that contains the compound (F) of 2 epoxy radicals in 1 molecule at least is 1～25 weight portion.
5. a kind of photosensitive resin composition for colour filter according to claim 1 is characterized in that, based on alkali soluble resin (A) 100 weight portions, the use amount that contains the compound (F) of 2 epoxy radicals in 1 molecule at least is 2～20 weight portions.
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| CN 200410059898 CN1584638A (en) | 2004-06-15 | 2004-06-15 | Light sensitive resin composition for color filter |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2894155B2 (en) * | 1993-06-28 | 1999-05-24 | 凸版印刷株式会社 | Photosensitive coloring composition and color filter using the same |
| US6432614B1 (en) * | 1998-07-31 | 2002-08-13 | Dai Nippon Printing Co., Ltd. | Photosensitive resin composition and color filter |
| US6531076B2 (en) * | 2000-02-04 | 2003-03-11 | Ppg Industries Ohio, Inc. | Photochromic organic resin composition |
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2005
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2894155B2 (en) * | 1993-06-28 | 1999-05-24 | 凸版印刷株式会社 | Photosensitive coloring composition and color filter using the same |
| US6432614B1 (en) * | 1998-07-31 | 2002-08-13 | Dai Nippon Printing Co., Ltd. | Photosensitive resin composition and color filter |
| US6531076B2 (en) * | 2000-02-04 | 2003-03-11 | Ppg Industries Ohio, Inc. | Photochromic organic resin composition |
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