CN1301993A - Photosensitive resin composition - Google Patents
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- CN1301993A CN1301993A CN 99127535 CN99127535A CN1301993A CN 1301993 A CN1301993 A CN 1301993A CN 99127535 CN99127535 CN 99127535 CN 99127535 A CN99127535 A CN 99127535A CN 1301993 A CN1301993 A CN 1301993A
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Abstract
The photosensitive resin composite consists of carboxyl group containing organic adhesive, unsaturated compound containing ethenyl group, light primer, organic solvent and pigment. The organic adhesive has a molecular weight distribution of: molecules with molecular weight smaller than 10,000 in 15-40 wt%, those with molecular weight of 10,000-45,000 in 55-80 wt% and those with molecular weight larger than 45,000 in 5-30 wt%. The light primer is at least one selected from acetophenone and biimidazone. The photosensitive resin composite can form hardened film with high strength, and has excellent long term stability, compactness, heat resistance and solvent resistance.
Description
But the present invention relates to a kind of mat rayed and the photosensitive resin composition of video picture is carried out in polymerization again with alkaline solution.In detail, promptly relevant a kind ofly have excellent long term storage stability and existing picture property, and properties such as close outstanding property, thermotolerance and solvent resistance all have the good photosensitive resin composition of cured film intensity of improvement.
Generally speaking, at present make the method for colored filter, consider based on cost of manufacture and quality, commonly used have four kinds of decoration method, print process, electricity work method and pigment dispersing methods, the making of colored filter is on glass substrate, with the organic pigment of Red, be produced within each picture element.Because the colored filter of pigment dispersing method made has high precision and preferable photostability and thermotolerance, become the manufacturing main flow of colored filter at present.
In the solids content of the photosensitive resin composition described in the present invention, account for 10～60% pigment, employed UV light source produces effects such as absorption, scattering when understanding exposure, so photosensitive resin composition is to the transmitance of UV light, the eurymeric photoresist of using far beyond semiconductor is low, so the pigment-dispersing type photoresist must adopt the photoreaction system of high sensitivity.The most representative photoreaction system then is the photosensitive resin composition of acrylic acid series radical polymerization mould assembly.The photosensitive resin composition of acrylic acid series radical polymerization mould assembly is the minus photoresist, has advantages such as high sensitivity, stability of material are good, design diversity, low cost, is the material that is widely used most at present.Its composition comprises multiple functional radical monomer, pigment, photonasty initiator, organic cohesive agent, solvent and adjuvant etc.
Employed in the past photosensitive resin composition is not because its molecular weight can't be done well distributed control, and selects suitable light initiator, so can't take into account the stability of its long-term seasoning, existing picture, thermotolerance and the solvent resistance of filming.
Fundamental purpose of the present invention is at the above-mentioned shortcoming of prior art and research improvement with keen determination, and then provide a kind of organic cohesive resin that contains to have the photosensitive resin composition that the particular molecule amount distributes, and cooperate specific light initiator, making has good close outstanding property, now picture property, thermotolerance and solvent resistance to glass substrate; And can take into account the stability of its long term storage.
For realizing above-mentioned purpose, a kind of photosensitive resin composition of the present invention, its composition comprise carboxylic organic cohesive agent (A), contain the compound (B) of ethene unsaturated group, light initiator (C), organic solvent (D), pigment (E); Wherein carboxylic organic cohesive agent (A) with the molecular weight distribution that gel permeation chromatography records is: molecular weight accounts for 15～40 weight % of whole organic cohesive agent less than 10,000; Molecular weight is 10,000～45,000 to account for 55～80 weight % of whole organic cohesive agent; Molecular weight is greater than 45,000 5～30 weight % that account for whole organic binder bonds; And it is at least a acetophenone based compound (acetophenone) and at least a diimidazole based compound (biimidazole) that is selected from of being selected from that light rises as agent (C).
The good photosensitive resin composition of above-mentioned cured film intensity has excellent long term storage stability and reaches picture property now, and properties such as close outstanding property, thermotolerance and solvent resistance all have improvement.
Below for of the present invention each form and to do a detailed explanation.
(1) carboxylic organic cohesive agent (A):
Generally speaking, photosensitive resin composition all can add organic cohesive agent.It can give its long term storage stability, close outstanding property, coating, existing advantages such as picture property, thermotolerance and solvent resistance.
Generally for photosensitive resin composition can be dissolved in the alkaline imaging liquid, the normal prescription that uses is carboxylic acrylic acid series or metha crylic resin.
Organic cohesive agent used in the present invention is carboxylic multipolymer, refers to contain the ethylene unsaturated monomer of one or more carboxyls and the multipolymer of copolymerizable ethylene unsaturated monomer especially.
Above-mentioned carboxylic unsaturated monomer can be exemplified below: the unsaturated monocarboxylic acid class of acrylic acid, methacrylic acid, butenoic acid, α-Lv Bingxisuan, ethylacrylic acid and cinnamic acid etc.; Unsaturated dicarboxylic acid (acid anhydride) class of maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid etc.; Unsaturated polyvalent carboxylic acid (acid anhydride) class that trivalent is above or the like.These carboxylic ethylene unsaturated monomers can be used alone or in mixture of two or more.Again, aforementioned other copolymerizable ethylene unsaturated monomers can be lifted the aromatic ethenyl compound of styrene, α-Jia Jibenyixi, vinyltoluene, vinyl chloride, methoxy styrene etc.; Methyl acrylate, methyl methacrylate, ethyl acrylate, Jia Jibingxisuanyizhi, propyl acrylate, propyl methacrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, acrylic acid benzene methyl and methacrylic acid benzene methyl, lauryl methacrylate, methacrylic acid myristyl ester, the methacrylic acid cetyl ester, methacrylic acid stearoyl ester, the methacrylic acid stearyl, methacrylic acid docosyl ester, the unsaturated carboxylate type of methacrylic acid eicosyl ester etc.; Carboxylic acid ammonia alkane ester class is closed in the insatiable hunger of acrylic acid ammonia ethyl ester, aminoethyl methacrylate, acrylic acid ammonia propyl ester, methacrylic acid ammonia propyl ester etc.; The acrylic acid epoxy propyl diester, the unsaturated carboxylic acid glycidyl ester class of methacrylic acid glycidyl ester etc.; The vinyl carboxylates class of vinyl acetate, propionate, vinyl butyrate, benzoic acid vinyl acetate etc.; The unsaturated ether of methoxy ethylene, ethyl vinyl ether, allyl glycidyl ethers, methylallyl glycidyl ethers etc.; The vinyl cyanide based compound of vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, the inferior ethene of cyaniding etc.; The unsaturated amides or the unsaturated acid imide of acrylamide, Methacrylamide, α-chloropropene acid amides, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, maleic amide etc.; The aliphatics conjugated diene of 1,3-butadiene, different propylene, chloropropene etc.; Polystyrene, polymethyl acrylate, polymethylmethacrylate, butyl polyacrylate, poly-n-butyl methacrylate, poly-oxosilane etc. have the huge monomer class of single acryloyl group or monomethyl acryloyl group etc. at the polymer molecule chain end.These other unsaturated monomers can be used alone or in mixture of two or more.Aforesaid carboxylic multipolymer be for 1. acrylic acid and/or methacrylic acid and the multipolymer that 2. is selected from least a other unsaturated monomers in the cohort that is constituted by methyl methacrylate, acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, acrylic acid benzene methyl, methacrylic acid benzene methyl, styrene, the huge monomer of polystyrene and the huge monomer of polymethylmethacrylate be good.The concrete example of preferable carboxylic multipolymer can have been lifted: acrylic acid/acrylic acid benzene methyl multipolymer, acrylic acid/acrylic acid benzene methyl/styrol copolymer, acrylic acid/methyl acrylate/styrol copolymer, acrylic acid/huge the monomer copolymer of acrylic acid benzene methyl/tygon, acrylic acid/huge the monomer copolymer of acrylic acid benzene methyl/polymethylmethacrylate, the huge monomer copolymer of acrylic acid/methyl acrylate/tygon, the huge monomer copolymer of acrylic acid/methyl acrylate/polymethylmethacrylate, acrylic acid/methacrylic acid benzene methyl multipolymer, acrylic acid/methacrylic acid benzene methyl/styrol copolymer, acrylic acid/methyl methacrylate/styrol copolymer, acrylic acid/huge the monomer copolymer of methacrylic acid benzene methyl/tygon, acrylic acid/huge the monomer copolymer of methacrylic acid benzene methyl/polymethylmethacrylate, the huge monomer copolymer of acrylic acid/methyl methacrylate/tygon, the huge monomer copolymer of acrylic acid/methyl methacrylate/polymethylmethacrylate, acrylic acid/methacrylic acid 2-hydroxyethyl ester/huge the monomer copolymer of methacrylic acid benzene methyl/tygon, acrylic acid/methacrylic acid 2-hydroxyethyl ester/huge the monomer copolymer of metering system benzene methyl/polymethylmethacrylate, methacrylic acid/acrylic acid benzene methyl/styrol copolymer, methacrylic acid/methyl acrylate/styrol copolymer, methacrylic acid/huge the monomer copolymer of acrylic acid benzene methyl/tygon, methacrylic acid/huge the monomer copolymer of acrylic acid benzene methyl/polymethylmethacrylate, the huge monomer copolymer of methacrylic acid/methyl acrylate/tygon, the huge monomer copolymer of methacrylic acid/methyl acrylate/polymethylmethacrylate, methacrylic acid/methacrylic acid benzene methyl multipolymer, methacrylic acid/methacrylic acid benzene methyl/styrol copolymer, methacrylic acid/methyl methacrylate/styrol copolymer, methacrylic acid/huge the monomer copolymer of methacrylic acid benzene methyl/tygon, methacrylic acid/huge the monomer copolymer of methacrylic acid benzene methyl/polymethylmethacrylate, the huge monomer copolymer of methacrylic acid/methyl methacrylate/tygon, the huge monomer copolymer of methacrylic acid/methyl methacrylate/polymethylmethacrylate, methacrylic acid/methacrylic acid 2-hydroxyethyl ester/huge the monomer copolymer of methacrylic acid benzene methyl/tygon, methacrylic acid/methacrylic acid 2-hydroxyethyl ester/huge monomer copolymer of methacrylic acid benzene methyl/polymethylmethacrylate or the like.In these carboxylic multipolymers, special good is methacrylic acid/methacrylic acid benzene methyl multipolymer, methacrylic acid/methacrylic acid benzene methyl/styrol copolymer, methacrylic acid/methyl methacrylate/styrol copolymer, methacrylic acid/huge the monomer copolymer of methacrylic acid benzene methyl/tygon, methacrylic acid/huge the monomer copolymer of methacrylic acid benzene methyl/polymethylmethacrylate, the huge monomer copolymer of methacrylic acid/methyl methacrylate/tygon, the huge monomer copolymer of methacrylic acid/methyl methacrylate/polymethylmethacrylate, methacrylic acid/methacrylic acid 2-hydroxyethyl ester/huge the monomer copolymer of methacrylic acid benzene methyl/tygon, methacrylic acid/methacrylic acid 2-hydroxyethyl ester/huge the monomer copolymer of methacrylic acid benzene methyl/polymethylmethacrylate.
Moreover if the carboxylate of organic cohesive agent C10 used in the present invention～C22 alkyl, the close outstanding property that it is filmed is better, and phenomenon is good.
Carboxylic organic cohesive agent of the present invention (A) with the molecular weight distribution that gel permeation chromatography records is:
Molecular weight is less than 10,000 account for 15～40 weight % of whole organic cohesive agent, and it is the best during with 20～30 weight %, if molecular weight is less than 10,000 distributions that account for whole organic cohesive agent are less than 15 weight %, the bin stability variation of resin combination; If it is greater than 40 weight %, the heat-resisting and solvent resistance variation of resin combination.
Molecular weight is 10,000～45,000 to account for 55～80 weight % of whole organic cohesive agent, and it is the best during with 60～70 weight %; If molecular weight be 10,000～45,000 distributions that account for whole organic cohesive agent less than 55 weight %, its heat-resisting and solvent resistance variation, if it is greater than 80 weight %, the bin stability variation of resin combination.
Molecular weight accounts for 5～30 weight % of whole organic cohesive agent greater than 45,000, and it is the best during with 10～20 weight %.If molecular weight greater than 45,000 compositions that account for whole organic cohesive agent less than 5 weight %, its heat-resisting and solvent resistance variation; If it is greater than 30 weight %, the bin stability variation of resin combination.
(2) contain compound, the light initiator (B, C) of ethene unsaturated group
Photosensitive resin composition is to utilize free radical chain reactions, to obtain the characteristic of high sensitivity.The major defect of radical polymerization mould assembly photoresist causes sensitivity to descend for being subjected to the influence that oxygen stops polyreaction easily.All improved this phenomenon by on the photoresistance film, being coated with one deck oxygen blocking film more in the past.At present, via selecting suitable multiple functional radical monomer, light initiator, and find out the ratio of itself and organic cohesive agent, multiple functional radical monomer, light initiator, also can obtain good sensitivity, residual film ratio height and phenomenon are good.
The compound (B) of ethene unsaturated group that contains used in the present invention is for having the ethene unsaturated compound of an ethene unsaturated group, for example have: acrylamide, (methyl) acryloyl morpholine, 7-amino-3,7-dimethyl octyl group (methyl) acrylate, isobutoxy methyl (methyl) acrylamide, isobornyl hydroxyethyl (methyl) acrylate, isobornyl (methyl) acrylate, 2-ethylhexyl (methyl) acrylate, ethyl diethylene glycol (methyl) acrylate, uncle's octyl group (methyl) acrylamide, two acetone (methyl) acrylamide, dimethyl aminoethyl (methyl) acrylate, dodecyl (methyl) acrylate, two cyclopentene hydroxyethyl (methyl) acrylate, two cyclopentene (methyl) acrylate, N, N-dimethyl (methyl) acrylamide, tetrachloro phenyl (methyl) acrylate, 2-tetrachloro phenoxy group ethyl (methyl) acrylate, tetrahydrofurfuryl (methyl) acrylate, tetrabromo phenyl (methyl) acrylate, 2-tetrabromo phenoxy group ethyl (methyl) acrylate, 2-Trichlorophenoxy ethyl (methyl) acrylate, tribromo phenyl (methyl) acrylate, 2-tribromophenoxy ethyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, caprolactam, the N-vinyl pyrrolidone, phenoxy group ethyl (methyl) acrylate, five chlorophenyl (methyl) acrylate, penta-bromophenyl (methyl) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, bornyl (methyl) acrylate, methyl triethylene glycol (methyl) acrylate.
Ethene unsaturated compound with two above ethene unsaturated groups, can be exemplified below: ethylene glycol bisthioglycolate (methyl) acrylate, two cyclopentene two (methyl) acrylate, triethylene glycol diacrylate, TEG two (methyl) acrylate, tristane two base 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, trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris (methyl) acrylate of oxirane (being designated hereinafter simply as EO) upgrading, trimethylolpropane tris (methyl) acrylate of epoxypropane (hereinafter to be referred as PO) upgrading, tripropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, two ends (methyl) the acrylic acid condiment of bisphenol A diglycidyl ether, 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, two trimethylolpropane four (methyl) acrylate, bisphenol-A two (methyl) acrylate of EO upgrading, bisphenol-A two (methyl) acrylate of PO upgrading, bisphenol-A two (methyl) acrylate of EO upgrading hydrogenation, bisphenol-A two (methyl) acrylate of PO upgrading hydrogenation, Bisphenol F two (methyl) acrylate of EO upgrading, (methyl) acrylate of phenol polyglycidyl ether or the like.
In the aforementioned ethene unsaturated compound, special good person is trimethylolpropane tris (methyl) acrylate, the trimethylolpropane tris of EO upgrading (methyl) acrylate, the trimethylolpropane tris of PO upgrading (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (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, two trimethylolpropane four (methyl) acrylate.
Organic cohesive agent (A) with the hydroxyl of 100 weight portions is a benchmark, and the use amount that contains the compound (B) of ethene unsaturated group used in the present invention is 20～300 weight portions.
Smooth initiator used in the present invention (C) is at least a acetophenone based compound (acetophenone) and at least a diimidazole based compound (biimidazole) that is selected from of being selected from, wherein acetophenone based compound (acetophenone) as: to dimethylamine acetophenone (p-dimethylaminoacetophenone), α, α '-dimethoxy azoxy acetophenone (α, α '-dimethoxyazoxyacetophenone), 2,2 '-dimethyl-2-phenyl acetophenone (2,2 '-dimethyl-2-phenylacetophenone), acetanisole (p-methoxy-acetophenone), 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), as: 2,2 '-(o-chlorphenol (4,4 ', 5,5 '-biphenol imidazoles [2,2 '-(o-chlorophenyl)-4,4 ', 5,5 '-diphenylimidazole], 2,2 '-(ortho-fluorophenyl phenol)-4,4 ', 5,5 '-diphenyl-imidazole [2,2 '-(o-fluorophenyl)-4,4 ', 5,5 '-diphenylimidazole], 2,2 '-(o-methoxyphenol)-4,4 ', 5,5 '-biphenol imidazoles (2,2-(o-methoxyphenyl)-4,4, ' 5,5 '-diphenylimidazole), 2,2 '-(p methoxy phenol)-4,4 ', 5,5 '-biphenol imidazoles [2,2 '-(p-methoxyphenyl)-4,4 ', 5,5 '-diphenylimidazole], 2,2 '-[2,2 ', 4,4 '-metoxyphenol]-4,4'5,5 '-biphenol imidazoles [2,2 '-(2,2 ', 4,4 '-methoxyphenyl)-4,4'5,5 '-diphenylimidazole], 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole [2,2 '-bis (2-chlorophenyl)-4,4, ', 5,5 '-tetraphenyl-1,2 '-biimidazole] etc.Wherein with 2-phenyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone [2-benzyl-2-N, N-dimethylamino-1-(4-morpholinophenyl)-1-butanone] and 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole [2,2 '-bis (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-biimidazole] and the light initiator effect of usefulness preferable.It is the light initiator that photosensitive resin composition of the present invention can further add benzophenone (benzophenone) based compound, 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) benzophone], 4,4 '-two (diethylamine) benzophenone [4,4 '-bis (diethylamino) benzophenone] etc.; Other still has benzil (benzil); (the class of α-diketone) such as the α-diketone of acetyl group (acetyl) etc.; keto-alcohol (acyloin) class of diphenylhydroxyethanone (benzoin) etc.; diphenylhydroxyethanone methyl ether (benzoin methylether); diphenylhydroxyethanone ether (benzoinethylether); keto-alcohol ether (acyloinether) class of diphenylhydroxyethanone isopropyl ether (benzoin isopropyl ether) etc.; 2; 4; 6-trimethyl benzoyl diphenyl phosphine oxide (2; 4; 6-trimethyl-benzoyldiphenylphosphineoxide); two-(2; 6-dimethoxy benzoyl)-2; 4; [bis-(2 for 4-trimethylphenyl phosphine oxide; 6-dimethoxy-benzoyl)-2; 4; 4-trimethylbenzyl phosphineoxide] etc. acyl phosphine oxide (acylphosphineoxide) class; anthraquinone (anthraquinone); 1; 4-naphthoquinones (1; 4-naphthoquinone) the quinone of Denging (quinone) class; chloroacetophenone (phenacyl chloride); trisbromomethyl benzene sulfone (tribromomethyl phenylsulfone), the halogen compound of three (trichloromethyl)-s-triazines [tris (trichloromethyl)-s-triazine] etc., the superoxide of two-tert-butyl peroxide (di-tert-butylperoxide) etc.Be good wherein with benzophenone (benzophenone) based compound, especially with 4,4 '-two (diethylamine) benzophenone [4,4 '-bis (diethylamino) benzophenone] best results.Use the selected light initiator of the present invention, can obtain the good photosensitive resin composition of phenomenon, the use amount of aforementioned lights initiator is that benchmark is 1～50 weight % with the compound (B) that contains the ethene unsaturated group.
(3) organic solvent (D)
Photosensitive resin composition all contains organic solvent usually, and its fundamental purpose is for adjusting its flowability and viscosity.If it is incorrect that organic solvent is selected, can cause the not good and coating variation of bin stability of photosensitive resin composition.
Solvent used in the present invention for can dissolve fully with other organic principle and also its volatility must the height under normal pressure, need only it being evaporated a little heat from dispersion liquid.Therefore its boiling point is lower than 180 ℃ the most normal use of solvent under the normal pressure, and these solvents comprise that aromatic series (Aromatic) is, as benzene, toluene and dimethylbenzene; Alcohol (Alcohol) is, as methyl alcohol and ethanol; Ethers, dialkyl ether such as ethylene glycol propyl ether; The ester class is as diethylene glycol dimethyl ether (diethyleneglycol dimethyl ether), tetrahydrofuran, glycol monomethyl ether (ethyleneglycol monomethyl ether), ethylene glycol monoethyl ether (ethyleneglycol monoethyl ether), methyl glycol acetate (methyl cellosolveacetate), ethoxyethyl acetate(EA) (ethyl cellosolve acetate), methyl carbitol (diethyleneglycol monomethyl ether), diethylene glycol one ether (diethyleneglycolmonoethyl ether), diethylene glycol monobutyl ether (diethyleneglycol monobutyl ether), propylene glycol monomethyl ether acetic acid esters (propyleneglycol monomethyl ether acetate), ethoxy propyl acetate (propyleneglycol monoethyl ether acetate), propylene glycol one propyl ether acetic acid esters (propyleneglycol monopropyl ether acetate); Ketone (Ketone) is, as MEK, acetone.Be preferable wherein with the ester class.Again with propylene glycol methyl ether acetate (propyleneglycolmethyl ether acetate), propylene-glycol ethyl ether acetic acid esters (propyleneglycol ethyl etheracetate), or both and usefulness, it is to bin stability and coating the best of photosensitive resin composition.The use amount of organic solvent of the present invention (D) is 60～90 weight % that account for whole photosensitive resin compositions.
(4) pigment (E)
Pigment of the present invention (E) is to use known so far various inorganic pigments or organic pigment.Inorganic pigment is the metallic compound that metal oxide, the wrong salt of metal or the like are arranged, and 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 11,24, and 31,53,83,99,108,109,110,138,139,150,151,154,167
C.I. pigment orange 36,38,43,51
C.I. paratonere 105,122, and 149,150,155,171,175,176,177,209,254
C.I. pigment violet 19,23, and 32,39
C.I. pigment blue 1,2,15,15:3,15:6,16,22,60,66
C.I. pigment Green 7,36,37
C.I. pigment brown 23,25, and 28
C.I. pigment black 1,7.
Aforementioned pigment can be used alone or in mixture of two or more.(A) with 100 weight portions is benchmark, and use amount (E) is 20～500 weight portions.In the present invention, pigment also can be followed the use spreading agent according to desired person.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.Aforesaid 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 many, Sa Fulong (Asahi Glass system) or the like for trade name: KP (SHIN-ETSU HANTOTAI's chemical industry system), Puli's furlong (common prosperity society oil chemistry industry system), Ai Fuduopu (De Kemupuluo is big, and make now in the storehouse), Mei Kafuke (the black chemical industry system of big Japan's seal), Fu Luoduo (Sumitomo 3M system), asafoetide card.These interfacial agents can be used alone or in mixture of two or more.With respect to the pigment (E) of 100 weight portions, aforesaid interfacial agent generally is to use and is lower than 30 weight portions, and is good to use 5～20 weight portions.
In the constituent of the present invention, can concoct various additives in case of necessity, for example the macromolecular compound beyond filling agent, the adhesion resin of the present invention, close outstanding promoter, antioxidant, ultraviolet light absorber, anti-agglutinant etc.
The concrete example of these additives can be lifted: the filling agent of glass, aluminium etc.; Organic cohesive agent (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, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy 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, the adherence work promoter of 3-sulfhydryl propyl trimethoxy silicane etc.; 2,2-thiobis (4-methyl-6-tert butyl phenol), 2, the antioxidant of 6-two-tert-butyl phenol etc.; The ultraviolet light absorber of 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzene and benzophenone etc.; And the anti-agglutinant of sodium polyacrylate etc.
Constituent of the present invention is mentioned component (A)～(E), and then can use various mixers, dispersion machine to mix in case of necessity to disperse and modulate other adjuvants and solvent.Mixer, dispersion machine can use known so far person.For example have: the sandstone muller of homogenizer, kneading machine, bowl mill, 2 or 3 shaft type mullers, coating vibrator, sandstone muller, plastic film muller etc.
Preferable modulation method is, at first pigment and organic cohesive agent added after solvent evenly mixes, mixes while use 1 or 2 stirrers to heat in case of necessity, makes pigment and organic cohesive agent fused fully, is the method for the body that stains of acquisition homogeneous.Secondly, in the body that stains of gained, add solvent, can add spreading agent or various adjuvant in case of necessity, use with bowl mill or beaded glass various puddle mixers (as the plastic film muller) and disperse as dispersion medium.At this moment, if the particle diameter of beaded glass is littler, then obtain to heal little dispersion.At this moment, make dispersion liquid be controlled at certain temperature, and obtain the good dispersion results of repeatability.
In the dispersion of this gained, can thick particle be extractd by centrifuging or decant in case of necessity.With the pigment particles size of the dispersion liquid of this gained being good below 1 μ.And then be good with 0.2 μ～0.3 μ again.Will with this gained stain dispersion with contain ethene unsaturated group compound and the light initiator mixes, can get photosensitive resin composition of the present invention.
Constituent of the present invention is to form radioactivity-sensitive constituent layer by the coating process coating of rotary coating, curtain coating coating, print roll coating etc. on substrate, between between specified mask pattern, expose, by impregnated in developer solution 30 seconds～5 minutes and after the video picture, form pattern again through staining in 23 ± 2 ℃.The radioactive ray that use this moment, the ultraviolet ray of g line, h line, i line etc. is good to use particularly.
Substrate, for example be useful on the soda-lime glass, hard glass (Pai Lesi glass), quartz glass of liquid crystal indicator etc. and in these attached outstanding nesa coating persons 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.
Moreover, developer solution is to use as NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sal tartari, saleratus, sodium silicate, sodium methyl silicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethyl-ammonium hydroxylate, tetraethyl ammonium hydroxylate, choline, pyrroles, piperidines, 1,8-diaza-[5,4,0]-alkali compounds of 7-hendecene etc., with 0.001～10 weight %, be preferably the alkaline aqueous solution that 0.01～1 weight % is constituted through dissolving.And, when using the developer solution that these alkaline aqueous solutions constitute, generally be clean to wash again after video picture.
The explanation of the further mat the following example of the present invention.
[Production Example of organic cohesive agent (A)]
The 1000ml four cervical flexure round-bottomed flasks that one nitrogen inlet, stirrer, well heater, condenser pipe and a thermometer are set are imported the polymerizable monomer mixture of each constituent as shown in Table 1 under nitrogen atmosphere.When the content of four neck round-bottomed flasks is stirred, the temperature of oil bath is promoted to 100 ℃, then will be as 2 of the listed amount of table one, the two butyronitrile (2 of 2 '-azo methyl, 2 '-azobis-2-methyl-butyronitrile) (be called for short AMBN), be dissolved in the solution of the propylene glycol monomethyl ether acetic acid esters (propyleneglycol monomethyl ether acetate) (being called for short PGMEA) of 100g, is added in the four neck round-bottomed flasks under at interval at one hour with the amount of five five equilibriums.After finishing polymerization, polymerizate is taken out in four neck round-bottomed flasks.Thus, can get resin solution a～f.For all monomer mixtures, transforming degree is 99.5% or higher.
With the sample of above resin solution thoroughly remove solvent with the solids content of resin solution is 30%, the molecular weight distribution that the resin solution that is generated records with gel permeation chromatography.Gained the results are shown in table one.
[embodiment 1～5 and comparative example 1～8]
Use the resin solution of aforementioned synthetic embodiment gained, according to the various photosensitive resin compositions of the formulation shown in the table two.
Prepared various constituent mixes with swing-out stirrer.Then, on glass substrate, obtain about 2 μ m and film, 85 ℃ of pre-down baking 5 minutes in the rotary coating mode.And then with ultraviolet light (exposure machine Canon PLA-501F) 20mJ/cm
2Irradiation impregnated in developer solution 2 minutes in 23 ℃, cleaned with pure water then, again with 200 ℃ of bakings 60 minutes, and obtained plated film on the glass substrate.
Evaluation method
Whether the stability of long term storage: placing two weeks back observation pigment has sedimentation.
Zero: no sedimentation
△: no sedimentation, viscosity uprises
*: sedimentation is arranged
Phenomenon: observe the integrality that forms in the glass substrate epigraph.
Zero: the image lines are smooth
*: the out-of-flatness of image lines has burr
Close outstanding property: be pursuant in JIS.5400 (1900) the 8.5 close outstanding property tests, the basal disc order method of 8.5.2 is measured, and is slit at 100 basal disc orders with pocket knife, is stained with adhesive tape and tears after sticking, and calculate and be torn basal disc purpose number, according to following benchmark evaluation:
Below zero: 5
△: 6～49
*: more than 50
Thermotolerance: the plated film on the prepared glass substrate, its transmitance 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 in 5%
*: transmitance changes more than 5%
Solvent resistance: the plated film on the prepared glass substrate, its transmitance of light measurement with 400～700nm wavelength changes, then under the room temperature (23 ± 2 ℃) with NMP dipping 30 minutes after, again in 120 ℃ of bakings 30 minutes, change with its transmitance of the light measurement of 400～700nm wavelength, and according to its variation ratio with following benchmark evaluation:
Zero: transmitance changes in 5%
*: transmitance changes more than 5%
The table three that the results are shown in according to above evaluation method.
Table one: each proportion of composing of making organic binder bond (A)
AMBN:2, the two butyronitrile (2 of 2 '-azo methyl, 2 '-azobis-2-methylbutyronitrile) PGMEA: propylene glycol monomethyl ether acetic acid esters (propyleneglycol nonomethyl ether acetate) ADVN:2,2 '-azo two-2,4-methyl pentane nitrile (2,2 '-azobis-2,4-dimethylvaleronitrile)
| Resin | Constituent (weight ratio %) | Molecular weight distribution | |||||||
| ???PGMEA | The methacrylic acid benzene methyl | Acrylic acid | Methacrylic acid stearoyl ester | ??AMBN | ??ADVN | ??＜10000 | ?10000～45000 | ????＞45000 | |
| ????a | ????70 | ????24.2 | ????5.2 | ????0.6 | ????23 | ????65 | ????12 | ||
| ????b | ????70 | ????24.1 | ????5.1 | ????0.8 | ????16 | ????70 | ????14 | ||
| ????c | ????70 | ????24.3 | ????5.3 | ????0.4 | ????31 | ????58 | ????11 | ||
| ????d | ????70 | ????23.7 | ????4.7 | ????1.6 | ????5 | ????62 | ????33 | ||
| ????e | ????70 | ????24.4 | ????5.4 | ????0.2 | ????42 | ????53 | ????5 | ||
| ????f | ????70 | ????24.2 | ????5.2 | ????0.6 | ????6 | ????55 | ????44 | ||
| ????g | ????70 | ????20.7 | ????3.7 | ????5 | ????0.6 | ????22 | ????66 | ????12 | |
Table two:
(1) total data is represented weight portion.(2) organic cohesive agent (A) is the resin solution (therefore, the resin solution of 8.4g contains the solids content of 2.52g weight portion) with solids content of 30%.(3) DPHA is the abbreviation of dipentaerythritol six (methyl) acrylate.
| Composition | The experimental example numbering | The comparative example numbering | ||||||||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ||
| Organic cohesive agent (A) | ????a | ????8.4 | ????8.4 | ??8.4 | ????8.4 | ????8.4 | ????8.4 | ????8.4 | ||||||
| ????b | ????8.4 | |||||||||||||
| ????c | ????8.4 | |||||||||||||
| ????d | ????8.4 | |||||||||||||
| ????e | ??8.4 | |||||||||||||
| ????f | ????8.4 | |||||||||||||
| ????g | ???8.4 | |||||||||||||
| The compound (B) that contains the ethene unsaturated group | ????DPHA | ??2.4 | ??2.4 | ??2.4 | ???2.4 | ??2.4 | ????2.4 | ??2.4 | ????2.4 | ??2.4 | ????2.4 | ????2.4 | ????2.4 | ????2.4 |
| Light initiator (C) | 2-benzyl-2-nitrogen nitrogen-dimethylamine 1-(4-morpholinyl phenyl)-1-butanone | ??0.14 | ??0.14 | ??0.14 | ???0.14 | ??0.14 | ????0.14 | ??0.14 | ????0.14 | ????0.16 | ????0.20 | |||
| Benzophenone | ????0.14 | ????0.14 | ||||||||||||
| 4,4 '-two (diethylamine) benzophenone | ??0.04 | ??0.04 | ??0.04 | ??0.04 | ????0.04 | ??0.04 | ????0.04 | ????0.04 | ????0.04 | |||||
| 2,2 ,-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-imidazoles | ??0.02 | ??0.02 | ??0.02 | ??0.02 | ??0.16 | ????0.02 | ??0.02 | ????0.02 | ??0.20 | ????0.02 | ||||
| Organic solvent (D) | ????PGMEA | ?29.54 | ?29.54 | ?29.54 | ?29.54 | ?29.54 | ???29.54 | ?29.54 | ???29.54 | ?29.54 | ???29.54 | ???29.54 | ???29.54 | ???29.54 |
| Pigment (E) | ????C1177 | ??4.00 | ??4.00 | ??4.00 | ??4.00 | ??4.00 | ????4.00 | ??4.00 | ????4.00 | ??4.00 | ????4.00 | ????4.00 | ????4.00 | ????4.00 |
Table three:
| Experiment numbers | Bin stability | Close outstanding property | Now as property | Thermotolerance | Solvent resistance | |
| Embodiment | ??1 | ????○ | ????○ | ????○ | ??????○ | ????○ |
| ??2 | ????△ | ????○ | ????○ | ??????○ | ????○ | |
| ??3 | ????○ | ????△ | ????○ | ??????○ | ????○ | |
| ??4 | ????○ | ????○ | ????○ | ??????○ | ????○ | |
| ??5 | ????○ | ????○ | ????○ | ??????○ | ????○ | |
| Comparative example | ??1 | ????× | ????○ | ????○ | ??????○ | ????○ |
| ??2 | ????○ | ????○ | ????○ | ??????× | ????× | |
| ??3 | ????× | ????× | ????○ | ??????○ | ????○ | |
| ??4 | ????○ | ????△ | ????× | ??????○ | ????○ | |
| ??5 | ????○ | ????△ | ????× | ??????○ | ????○ | |
| ??6 | ????○ | ????△ | ????× | ??????○ | ????○ | |
| ??7 | ????○ | ????△ | ????× | ??????○ | ????○ | |
| ??8 | ????○ | ????△ | ????× | ??????○ | ????○ | |
Claims (8)
1, photosensitive resin composition is characterized in that: its composition comprises carboxylic organic cohesive agent (A), contains the compound (B) of ethene unsaturated group, light initiator (C), organic solvent (D), pigment (E); Wherein carboxylic organic cohesive agent (A) with the molecular weight distribution that gel permeation chromatography records is: molecular weight accounts for 15～40 weight % of whole organic cohesive agent less than 10,000; Molecular weight is 10,000～45,000 to account for 55～80 weight % of whole organic cohesive agent, and molecular weight accounts for 5～30 weight % of whole organic cohesive agent greater than 45,000; And light initiator (C) is at least a acetophenone based compound and at least a diimidazole based compound that is selected from of being selected from.
2, photosensitive resin composition according to claim 1 is characterized in that: carboxylic organic cohesive agent (A) is the copolymer that contains more than one ethylene unsaturated monomer of carboxyl and copolymerizable ethylene unsaturated monomer.
3, photosensitive resin composition according to claim 1, it is characterized in that: light initiator (C) is to use 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone and 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1, the light initiator of 2 '-diimidazole and usefulness.
4, photosensitive resin composition according to claim 1 is characterized in that: light initiator (C) can be the light initiator with the benzophenone based compound also still.
5, photosensitive resin composition according to claim 4 is characterized in that: benzophenone series series of compounds 4,4 '-two (diethylamine) benzophenone.
6, photosensitive resin composition according to claim 1 is characterized in that: organic solvent (D) is the organic solvent for the ester class.
7, photosensitive resin composition according to claim 1 is characterized in that: organic solvent (D) is that to be selected from least a esters such as diethylene glycol dimethyl ether, tetrahydrofuran, glycol monomethyl ether, ethylene glycol monoethyl ether, methyl glycol acetate, ethoxyethyl acetate(EA), methyl carbitol, diethylene glycol one ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol propyl ether acetic acid esters be organic solvent.
8, photosensitive resin composition according to claim 1 is characterized in that: organic solvent (D) is to be selected from propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, or both and usefulness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99127535 CN1126005C (en) | 1999-12-30 | 1999-12-30 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99127535 CN1126005C (en) | 1999-12-30 | 1999-12-30 | Photosensitive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1301993A true CN1301993A (en) | 2001-07-04 |
| CN1126005C CN1126005C (en) | 2003-10-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99127535 Expired - Lifetime CN1126005C (en) | 1999-12-30 | 1999-12-30 | Photosensitive resin composition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100350281C (en) * | 2002-12-19 | 2007-11-21 | Jsr株式会社 | Radioactive-ray sensitive composition for colour optical filter, colouring-layer for mation method and use |
| CN101124517B (en) * | 2004-11-25 | 2011-04-13 | 东京应化工业株式会社 | Photosensitive resin composition and photosensitive dry film using same |
| CN113419403A (en) * | 2021-06-25 | 2021-09-21 | 江西惠美兴科技有限公司 | Aqueous photosensitive resin and photoresist dry film thereof |
| CN116285542A (en) * | 2023-03-16 | 2023-06-23 | 咸宁南玻节能玻璃有限公司 | Tearable masking film coating, preparation method thereof and method for preparing coated pattern glass by using tearable masking film coating |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434948C (en) * | 2004-11-16 | 2008-11-19 | 奇美实业股份有限公司 | Photosensitive resin composition for colour filter |
-
1999
- 1999-12-30 CN CN 99127535 patent/CN1126005C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100350281C (en) * | 2002-12-19 | 2007-11-21 | Jsr株式会社 | Radioactive-ray sensitive composition for colour optical filter, colouring-layer for mation method and use |
| CN101124517B (en) * | 2004-11-25 | 2011-04-13 | 东京应化工业株式会社 | Photosensitive resin composition and photosensitive dry film using same |
| CN113419403A (en) * | 2021-06-25 | 2021-09-21 | 江西惠美兴科技有限公司 | Aqueous photosensitive resin and photoresist dry film thereof |
| CN116285542A (en) * | 2023-03-16 | 2023-06-23 | 咸宁南玻节能玻璃有限公司 | Tearable masking film coating, preparation method thereof and method for preparing coated pattern glass by using tearable masking film coating |
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| Publication number | Publication date |
|---|---|
| CN1126005C (en) | 2003-10-29 |
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