CN1144096C - Photosensitive resin composition - Google Patents
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- CN1144096C CN1144096C CNB001028561A CN00102856A CN1144096C CN 1144096 C CN1144096 C CN 1144096C CN B001028561 A CNB001028561 A CN B001028561A CN 00102856 A CN00102856 A CN 00102856A CN 1144096 C CN1144096 C CN 1144096C
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Abstract
The present invention relates to a photosensitive resin composition which comprises: organic cementing agents (A) containing carboxyl, a compound (B) containing ethene unsaturation bases, optical initiators (C), organic solvents (D) and pigment (E), wherein the organic cementing agents (A) containing carboxyl are prepared from 5 to 50 wt% of ethene unsaturation monomers containing one or more than one carboxyl, and 95 to 50 wt% of ethene unsaturation monomers which can be copolymerized. The pigment (E) is red pigment of a diketopyrrolopyrrole system. The proportion of the compound (B) containing ethene unsaturation bases to the organic cementing agents (A) containing carboxyl is 100/100 to 160/100.
Description
The present invention be relevant a kind of can the polymerization of mat rayed, the photosensitive resin composition that develops with alkaline solution again, more detailed it, promptly relevant a kind of have excellent development and adherence, the photosensitive resin composition that light transmission is good and the development aberration is very little, cured film intensity is good.Belong to photosensitive material.
Generally speaking, consider based on cost of manufacture and quality, make the method for colored filter at present, commonly used have decoration method, print process, electricity four kinds of method and pigment dispersing methods, the making of colored filter is on glass plate, 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, therefore, has become the manufacturing main flow of colored filter at present.
In the solids content of photosensitive resin composition of the present invention, account for effects such as UV light source generation absorption that the pigment of 10-60% can the time be used exposure, scattering, so the eurymeric photoresist that the present invention's photosensitive resin composition is used far beyond semiconductor the transmitance of UV light is low, for these reasons, 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; Aforesaid propylene acid is that the photosensitive resin composition of radical polymerization mould assembly is the minus photoresist, and advantage such as high sensitivity, material safety are good, design diversity, low cost that it has is the material that is widely used most at present.Its composition then comprises: multiple functional radical monomer, pigment, photonasty initiator, organic property adhesive, solvent and adjuvant etc.
Employed in the past pigment-dispersing type photoresist, because red pigment light transmission deficiency, the ratio between constituent is not done good control, and does not select suitable light initiator, so can't take into account development, adherence and development aberration, its light transmission is also not good.
For overcoming above-mentioned deficiency, fundamental purpose of the present invention is: a kind of photosensitive resin composition is provided, it is via the red pigment of selecting for use specific diketopyrrolo-pyrrole (diketopyrrolopyrrole) to be, and cooperate organic property cohesiveness resin that contains carboxyl and the operating weight that contains ethene unsaturated group thing than regulation and control, with the purpose of attainable cost invention.Further, a kind of photosensitive resin composition of the present invention will have more significant effect for adherence, development, development aberration and the light transmission etc. of glass substrate if cooperate specific light initiator.
A kind of photosensitive resin composition of the present invention, its composition comprises: contain organic property adhesive (A) of carboxyl, the compound (B) that contains the ethene unsaturated group, light initiator (C), organic solvent (D), pigment (E); Wherein, the organic property adhesive (A) that contains carboxyl is made up of ethylene unsaturated monomer 5～50 weight % that contain one or more carboxyls, and pigment (E) is the red pigment of diketopyrrolo-pyrrole system; And the compound (B) that contains the ethene unsaturated group is 100/100～160/100 with the usage ratio that contains organic property adhesive (A) of carboxyl.
Wherein, the ratio that contains the compound (B) of ethene unsaturated group/contain organic property adhesive (A) of carboxyl is 110/100～150/100.
Wherein, light initiator (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, light initiator (C) is and with 2-benzyl-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-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1, and 2 '-diimidazole [2,2 '-bis (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-biimidazole].
Wherein, light initiator (C) still can and be used benzophenone (benzophenone) based compound.
Wherein, benzophenone (benzophenone) based compound is 4,4 '-two (diethylamine) benzophenone [4,4 '-bis (diethylamino) benzophenone].
Advantage of the present invention is: cost of manufacture is low, good manufacturability, the specific light initiator of cooperation, can have good effect to adherence, development, development aberration and the light transmission etc. of glass substrate.
Below form to do a detailed explanation for each of the present invention:
(A) contain organic property adhesive of carboxyl:
Generally speaking, photosensitive resin composition all can add organic property adhesive, and it can give advantages such as photosensitive resin composition long term storage stability, adherence, coating, development, thermotolerance and solvent resistance; Generally in order to make photosensitive resin composition can be dissolved in alkaline-based developer, normal acrylic acid series or the metha crylic resin of prescription that uses for containing carboxyl.
The organic property adhesive (A) that contains carboxyl used herein is a kind of multipolymer that contains carboxyl, especially refer to comprise the unsaturated and monomer 5-50% weight of the ethene that contains one or more carboxyls, and the multipolymer of copolymerizable ethylene unsaturated monomer 95-50% weight.
Unsaturated and the monomer of the above-mentioned ethene that contains carboxyl can be exemplified below: the unsaturated unified carboxylic acids 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 and polyvalent carboxylic acid's (acid anhydride) class that 3 valencys are above or the like.These contain the unsaturated and monomer of the ethene of carboxyl and can be used alone or in mixture of two or more; And above-mentioned other can be for the ethene of polymerization unsaturated and monomer just for example: the aromatic ethenyl compound of styrene, α-Jia Jibenyixi, vinyltoluene, vinyl chloride, methoxy styrene etc.; The unsaturated carboxylate type of methyl acrylate, methyl methacrylate, ethyl acrylate, Jia Jibingxisuanyizhi, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-sample ethyl ester, acrylic acid benzene methyl and methacrylic acid benzene methyl, methacrylic acid cetyl ester, methacrylic acid stearyl, methacrylic acid docosyl ester, methacrylic acid eicosyl ester etc.; The unsaturated carboxylic acid ammonia alkane ester class of acrylic acid ammonia ethyl ester, aminoethyl methacrylate, acrylic acid ammonia propyl ester, methacrylic acid ammonia propyl ester etc.; The unsaturated carboxylic acid glycidyl ester class of acrylic acid epoxy propyl diester, methacrylic acid glycidyl ester etc.; The vinyl carboxylates class of vinyl acetate ester group first, 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 vinegar amine or the unsaturated vinegar imines class of acrylamide, metering system vinegar amine, α-chloropropene vinegar amine, N-hydroxyethyl acrylamide, N-hydroxyethyl metering system vinegar amine, Malaysia vinegar amine etc.; The aliphatics conjugated diene of 1,3-butadiene, different propylene, chloropropene etc.; Polymer molecule chain ends such as polystyrene, polymethyl acrylate, polymethylmethacrylate, butyl polyacrylate, poly-n-butyl methacrylate, polysiloxane have the huge monomer class of single propylene anilide or monomethyl propylene anilide etc.
These other unsaturated monomers can separately or mix two or more use; And the present invention's preferable carboxylic multipolymer is: the 1. acrylic acid of 5-50 weight % and/or methacrylic acid, and the 2. multipolymer that is selected from least a other unsaturated monomer in the cohort that is made of 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 of 95-50 weight %.
The preferable concrete example that contains the multipolymer of carboxyl 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/big the monomer copolymer of acrylic acid benzene methyl/tygon, acrylic acid/huge the monomer copolymer of acrylic acid benzene methyl/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 acid/huge monomer copolymer of methacrylic acid benzene methyl/polymethylmethacrylate, methacrylic acid/acrylic acid benzene methyl/styrol copolymer, methacrylic acid/methyl acrylate/styrol copolymer, the huge monomer copolymer methacrylic acid of the methacrylic acid/acrylic acid benzene methyl/tygon/huge 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/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 acid/huge 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 the above-mentioned multipolymer that contains carboxyl, characteristic is methacrylic acid/methylmethacrylate copolymer, methacrylic acid/methacrylic acid benzene methyl/styrol copolymer, methacrylic acid/methyl methacrylate/styrol copolymer, the huge monomer copolymer of methacrylic acid/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 methyl methacrylate/polymethylmethacrylate, methacrylic acid/methacrylic acid 2-hydroxyethyl acid/huge monomer copolymer of methacrylic acid benzene methyl/tygon, methacrylic acid/methacrylic acid 2-hydroxyethyl acid/huge monomer copolymer of methacrylic acid benzene methyl/polymethylmethacrylate.
Moreover the organic binder (A) that contains carboxyl used herein is as if the carboxylic ester units that contains the C10-C22 alkyl, and the adherence that it is filmed is better, and development is good.
(B, C) contains compound, the light initiator of ethene unsaturated group
Photosensitive resin composition system utilizes free radical chain reactions, to obtain the characteristic of high sensitivity; Only the major defect of radical polymerization mould assembly photoresist is for being subjected to the influence that oxygen stops polyreaction easily, cause sensitivity to descend, in order to improve this phenomenon, tied up in the past and be coated with one deck oxygen blocking film on the photoresistance film again, then be functional group monomer, light initiator more than selecting suitably at present, and find out the ratio of itself and organic property adhesive, multiple functional radical monomer, light initiator, obtain having good sensitivity, the photosensitive resin composition that residual film ratio height and development are good.
The compound (B) that contains the ethene unsaturated group used in the present invention can be the ethene unsaturated compound of the ethene unsaturated group that has more than or 2 or 2, wherein, example with ethene unsaturated compound of an ethene unsaturated group has: acrylamide, (methyl) propylene vinegar morpholine, 7-amino-3,7-Methyl Octyl (methyl) acrylate, isobutoxy methyl (methyl) acrylic amine, isobornyl hydroxyethyl (methyl) acrylate, ethyl diethylene glycol (methyl) acrylate, trioctylphosphine (methyl) acrylic amine, 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, the stupid base of tribromo (methyl) acrylate, 2-tribromophenoxy ethyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, vinegar amine in vinyl is own, the N-vinyl pyrrolidone, phenoxy group ethyl (methyl) acrylate, the stupid base of pentachloro-(methyl) acrylate, the stupid base of pentabromo-(methyl) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, bornyl (methyl) acrylate, methyl triethylene glycol (methyl) acrylate.
Ethene unsaturated compound with 2 or 2 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 glycol two methylene base two (methyl) acrylate, three (2-hydroxyethyl) isocyanates two (methyl) acrylate, three (2-hydroxyethyl) isocyanates three (methyl) acrylate, three (2-hydroxyethyl) isocyanates two (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 2 at " 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, 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, double 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, phenol polyglycidyl ether (methyl) acrylate or the like.
In the above-mentioned 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), dipentaerythritol six (methyl) acrylate of caprolactone upgrading, dipentaerythritol five (methyl) acrylate of caprolactone upgrading, double trimethylolpropane four (methyl) acrylate.
The organic property adhesive (A) that contains carboxyl with 100 weight portions is a benchmark, and the use amount that contains the compound (B) of ethene unsaturated group used herein is the 100-160 weight portion, is preferable with the 110-150 weight portion especially; When the use amount of the compound that contains the ethene unsaturated group (B) during less than 100 weight portions, the adherence of filming of resin combination can be out of shape, and if the use amount of above-claimed cpd is greater than 160 weight portions, and then the development of resin combination is not good.
Light initiator (C) used herein is to be selected from 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) is as to a dimethylamine acetophenone (pdimethylaminoacetophenone), α, α '-dimethoxy azoxy acetophenone (α, α '-dimethoxyazoxyacetophenone) 2,2 '-dimethyl-2-phenyl acetophenone (2,2 '-dimethy1-2-phenylacetophenone), right-methoxyacetophenone (2-methoxyacetophenone), the 2-methyl-(4-(methyl mercapto) phenol) 2-methyl-[4-(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 '-two (neighbour-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl imidazoles [2,2 '-bis (o-chlorophenyl)-4,4 ', 5,5 '-tertphenyl-imidazole], 2,2 '-two (ortho-fluorophenyl bases)-4,4 ', 5,5 '-tetraphenyl imidazoles [2,2 '-bis (o-fluorophenyl)-4,4 ' 5,5 '-tertphenylimidazole], 2,2 '-two (neighbour-methoxyphenyl)-4,4 ', 5,5 '-tetraphenyl imidazoles [2,2 '-bis (o-methoxyphenyl)-4,4 ' 5,5 '-terthphenylimidazole] 2,2 '-two (right-methoxyphenyl)-4,4 ' 5,5 '-tetraphenyl imidazoles [2,2 '-bis (p-methoxyphenyl)-4,4 ' 5,5 '-terthphenylimidazole], 2,2 '-two (2,2 ', 4,4 '-tetramethoxy phenyl)-4,4 ' 5, [2,2 '-bis (2,2 ' for 5 '-tetraphenyl imidazoles, 4,4 '-tertmethoxyphenyl)-4,4 ' 5,5 '-tertphenyl-imidazole], 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-dimethylamio-1-(4-morpholimophenyl)-1-butanone] and 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1, and 2 '-diimidazole [2,2 '-bis (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-biimidazole].
It is the light initiator that the present invention's photosensitive resin composition can further add benzophenone (benzophenone) based compound, above-mentioned benzophenone based compound for example is: thioxanthones (Thioxanthone), 2,4-diethyl thioxanthone (2,4-diethyl thioxanthanone), 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 light initiators that still can further add for example are: benzene idol vinegar (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 (benzoin ethylether), keto-alcohol ether (acyloin ether) class of diphenylhydroxyethanone isopropyl ether (benzoin isopropylether) etc., 2,4,6-trimethylbenzene vinegar diphenyl phosphine oxide (2,4,6-trimethyl-benzoyl diphenylphosphineoxide), two-(2,6-dimethoxy benzene vinegar)-2,4, [bis-(2 for 4-trimethylphenyl phosphine oxide, 6-dimethoxy-benzoyl)-2,4,4-trimethylbenzyl phosphineoxide] etc. vinegar phosphine oxide (acylphosphineoxide) class, anthraquinone (anthraquinone), 1-4-benzoquinones (1,4-naphthoquinone) the quinone of grade (quinone) class, benzene vinegar methyl chloride (phenacyl chloride), trisbromomethyl benzene sulfone (tribromomethyl phenylsulfone), the halogen compound of three (trichloromethyl)-s-triazines [tris (trichloromethyl)-s-triazine] etc., the superoxide of two-Di tributyl superoxide (di-tert-butylperoxide) etc.Wherein, be good with benzophenone (benzophenone) based compound, especially with 4,4 '-two (diethylamine) benzophenone [4,4 '-bis (diethylamino) benzophenone] best results.Use the selected light initiator (C) of the present invention, the little photosensitive resin composition of aberration that can obtain developing, the use amount of aforementioned lights initiator (C) is 1～50 weight % of benchmark with the compound (B) that contains the ethene unsaturated group.
(D) organic solvent
Photosensitive resin composition all contains organic solvent usually, and its fundamental purpose is for adjusting its flowability and viscosity, and is incorrect when organic solvent selection, can cause the not good and coating variation of storage stability of photosensitive resin composition.
Solvent used herein is for dissolving fully with other organic principle, and its volatility must be high under normal pressure, need only it be evaporated a little heat from dispersion liquid.Therefore, 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 dimethylether), tetrahydrofuran, glycol monoethyl ether (ethyleneglycol monomethylether), ethylene glycol monoethyl ether (ethyleneglycol monoethyl ether), glycol monoethyl ether acetate fat (ethyl cellosolve acetate), ethylene glycol monoethyl ether acetate (ethyl cellosolveacetate), diethylene glycol monomethyl ether (diethyleneglycol monomethyl ether), diethylene glycol monoethyl ether (diethyleneglycol monoethyl ether), diethylene glycol monobutyl ether (diethyleneglycol monobutyl ether), propylene glycol monomethyl ether acetate fat (propyleneglycol monomethyl ether acetate), interior 2-ethoxyethanol acetic acid esters (propyleneglycol monoethyl ether acetate), propylene glycol monopropyl ether acetic acid esters (propyleneglycol monopropyl ether acetate); Ketone (Ketone) is, as MEK, acetone, is preferable with the ester class wherein; Again with propylene glycol methyl ether acetate (propyleneglycol methyl ether acetate), propylene-glycol ethyl ether acetic acid esters (propyleneglycol ethyl ether acetate), or both and usefulness, for storage stability and coating the best of photosensitive resin composition, the use amount of the present invention's organic solvent (D) is 60～90 weight % that account for whole photosensitive resin compositions.
(E) pigment:
The red pigment that pigment used herein (E) for diketopyrrolo-pyrrole (diketopyrrolopyrrole) is, its concrete example has: C.I. paratonere 254 and C.I. paratonere 255 etc.Aforementioned pigment can separately or mix use more than 2 kinds, and the organic cohesive agent (A) that contains carboxyl with 100 weight portions is a benchmark, and the use amount of pigment (E) is 20～500 weight portions, can make the good photosensitive resin composition of light transmission; In the present invention, pigment also can be followed the use spreading agent according to desired person; Above-mentioned spreading agent can be lifted: the interfacial agent of kation system, negative ion system, nonionic system, both sexes, polysiloxane system, fluorine system etc. is an example; Wherein, interfacial agent for example has: the polyethylene oxide alkyl ethers class of polyethylene oxide lauryl ether, the stearic vinegar ether of polyethylene oxide, 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; The following trade name of peddling: KP341 (SHIN-ETSU HANTOTAI's chemical industry system) for the market, Puli's furlong No.75, No.90, No.95 (common prosperity society oil chemistry industry system), Solsperse 3000,5000,9000,12000,13240,13940,17000,20000,24000,26000,28000 (Jie Likang fine chemicals companies), Mei Kafuke F171, F172, F173 (the black chemical industry system of big Japan's seal), the many FC430 of Fei Luo, FC431 (Sumitomo 3M system), the many AG710 of asafoetide card, Sa furlong S382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-1068 (Asahi Glass system) or the like; These interfacial agents can separately or mix more than 2 kinds and to use, and with respect to the pigment (E) of 100 weight portions, aforementioned interfacial agent generally is to use to be lower than 100 weight portions, and are good to use 5～50 weight portions.
In the present invention's the constituent, can further add various additives in case of necessity, for example: organic cohesive agent (A) of filling agent, hydroxyl of the present invention high molecular polymer, adherence promoter, antioxidant, ultraviolet in addition opened absorbing agent, anti-agglutinant etc.
The concrete example of these additives can have been 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.; Vinyl trimethoxy silicon alkane, vinyl triethoxyl silicon alkane, vinyl three (2-methoxyethoxy) silicon alkane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxy oxygen base silicon alkane, N-(2-amino-ethyl)-3-aminopropyl trimethoxy silicon alkane, 3-aminopropyl triethoxy silicon alkane, 3-glycidoxy propyl trimethoxy silicon alkane, 3-glycidoxy propyl group methyl dimethoxy oxygen base silicon alkane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silicon alkane, 3-chloropropyl methyl dimethoxy oxygen base silicon alkane, 3-r-chloropropyl trimethoxyl silicon alkane, 3-metacryloxy propyl trimethoxy silicon alkane, the adherence promoter of 3-sulfhydryl propyl trimethoxy silicon alkane etc.; 2,2-thiobis (4-methyl-6-tributyl phenol), 2, the antioxidant of 6-two-Di tributyl phenol etc.; The ultraviolet light absorber of 2-(3-the tributyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzene and benzophenone etc.; And the anti-agglutinant of sodium polyacrylate etc.
The present invention's constituent is fastened and is stated composition (A)～(E), can use various mixers, dispersion machine mixing dispersion in case of necessity, and modulate other adjuvants and solvent.Mixer, dispersion machine can use known so far person.For example have: the sandstone grinding machine of homogenizer, kneading machine, bowl mill, 2 or 3 shaft type mullers, coating vibrator, sandstone muller, Da Yilong muller etc.
The preferable modulation genealogy of law adds solvent with pigment (E) and organic cohesive agent (A) and evenly mixes, use in case of necessity 1 or 2 stirrers-heating-limit, limit mix, make pigment (E) and organic cohesive agent (A) fused fully, can obtain the tingle body of homogeneous.Secondly, in the tingle body of gained, add solvent, can add spreading agent or various adjuvant in case of necessity, re-use with bowl mill or beaded glass various puddle mixers (as the Da Yilong muller) and disperse as dispersion medium.At this moment, if the particle diameter of beaded glass is littler, can obtain the little dispersion that heals.Make dispersion liquid be controlled at certain temperature simultaneously, also can obtain the good dispersion results of repeatability.
In this point prose style free from parallelism, can thick particle be extractd by centrifuging or decant in case of necessity.Pigment particles footpath with the diffusing liquid of this point is big or small to be good below 1 μ, and above-mentioned particle diameter is preferable with 0.02 μ～0.3 μ again.Will with the painted dispersion of this gained with contain ethene unsaturated group compound and the light initiator mixes, get final product the present invention's photosensitive resin composition.The present invention's constituent lies on the substrate to form by the coating process coating of rotary coating, curtain coating coating, print roll coating etc. and helps to change radioactivity constituent layer, between between specified mask pattern, expose, and impregnated in 23 ± 2 ℃ the developer solution 30 seconds～5 minutes and carry out video picture, again through painted and form pattern.The radioactive ray of use this moment are good with the ultraviolet ray of using g line, h line, i line etc.
Substrate, for example be useful on the low soda-lime 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 the silicon substrate) of solid-state image sensor etc. or the like.These substrates generally are to form the black matrix" of isolating each picture element.
Moreover, developer solution system use as: NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sal tartari, saleratus, SODIUM SILICATE, methyl SODIUM SILICATE, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethyl-ammonium hydroxy compound, tetraethyl ammonium hydroxy compound, choline, pyrroles, piperidines, 1,8-diaza-[5,4,0]-alkali compounds of 7-hendecene etc., its use amount is 0.001～10 weight %, is preferably the alkaline aqueous solution through dissolving that 0.01～1 weight % is constituted.And when using the developer solution that these alkaline aqueous solutions constitute, generally lie in after the development clean to wash again.
The further mat the following example of the present invention illustrates it.
[embodiment 1]
Flask at the bottom of the 1000ml four neck gardens of one nitrogen inlet, stirrer, well heater, condenser pipe and a thermometer imports propylene glycol methyl ether acetate 25.7 weight portions, methacrylic acid benzene formicester 24.2 weight portions, acrylic acid 5.2 weight portions under nitrogen atmosphere polymerizable monomer mixture will be set.When within the flask at the bottom of the four neck gardens during tolerant being stirred, the temperature of oil bath is promoted to 100 ℃, then with 2, two butyronitrile 0.6 weight portions of 2 '-azo methyl are dissolved in the solution of 30g propylene glycol methyl ether acetate, with the amount of branch such as five at the bottom of one hour is added on four neck gardens under the interval in the flask.After finishing polymerization, from taking out in the flask at the bottom of the four neck gardens, transforming degree is more than 99.5% with polymerizate, and the solids content of above resin solution is 35%.Organic cohesive agent (A) 13.29 weight portions that contain carboxyl and compound (B) 5.58 weight portions, the 2-benzyl-2-N that contain the ethene unsaturated group with above preparation, N dimethylamine-1-(4-morpholino phenyl)-1-butanone 1.00 weight portions, 4,4 '-two (diethylamine) benzophenone 1.00 weight portions, ethyl (three-ethoxy) acrylate 43.13 weight portions, and the CI254 of 6.00 weight portions, and be mixed and made into photosensitive resin composition with stirrer.Then, on glass substrate, obtain filming of about 2 μ m in the rotary coating mode, and 85 ℃ after down pre-roasting 5 minutes again with ultraviolet light (exposure machine CanonPLA-501F) 200mJ/cm
2Irradiation, impregnated in 23 ℃ developer solution 2 minutes afterwards, clean with pure water again, and under 200 ℃, toasted 60 minutes, can obtain the plated film on the glass substrate, obtained plated film is estimated its development, adherence, development aberration (△ Eab*) and light transmission according to following mode, and evaluation result as shown in Table 1.
[embodiment 2～5 and comparative example 1～7]
According to the method for making of embodiment 1, the composition thing makes the photosensitive resin composition of embodiment 2～5 and comparative example 1～7 by respectively this weight portion shown in the table one.Plated film preparation on the glass substrate and evaluation method are all as embodiment 1, and evaluation result as shown in Table 1.
[embodiment 6]
According to the method for making of embodiment 1, the composition thing removes 2-benzyl-2-N, and N dimethylamine-1-(4-morpholino phenyl)-1-butanone 1.00 weight portions change into outside benzophenone 1.00 weight portions, and other composition and weight portion are with embodiment 1; And the plated film on the glass substrate is also according to embodiment 1 preparation, and the development of obtained plated film, adherence and light transmission are good, and development aberration (△ Eab*) is 2.88.
[evaluation method]
(1) development: observe in the integrality of glass substrate epigraph formation.
Zero: the image lines are smooth
*: the out-of-flatness of image lines has burr
(2) adherence: be pursuant to the 8.5.2 assay method in JIS.5400 (1900) the 8.5 adherences tests, be slit into 100 basal disc orders, be stained with adhesive tape again and tear after glutinous, calculate the number that is torn the basal disc order with pocket knife, according to following benchmark evaluation:
Below zero: 5
△: 6～49
*: more than 50
(3) development aberration (△ Eab*): on glass substrate, photosensitive resin composition is obtained filming of 2 μ m in the rotary coating mode, 85 ℃ of pre-down baking 5 minutes, again with ultraviolet light (exposure machine Canon PLA-501F) 200MJ/cm
2After colourity was measured with colorimeter in the irradiation back, will film impregnated in 23 ℃ of developer solutions 2 minutes, again to measure colourity after the pure water cleaning, drying again.The difference of front and back chromatic value can be tried to achieve development aberration (△ Eab*).
(4) light transmission: on glass substrate, photosensitive resin composition is obtained filming of about 2 μ m in the rotary coating mode, 85 ℃ down pre-roasting 5 minutes, measure colourity with colorimeter, chromatic value is about 0.574 ± 0.02 o'clock of X value fixedly, gained Y value:
Zero: the Y value is greater than 25.0, and light transmission is good
△: the Y value is between 23.5 and 25.0, and light transmission still can
*: the Y value is less than 23.5, and light transmission is poor
's 100/100～160/100 scope according to photosensitive resin composition of the present invention in compound that contains the ethene unsaturated groupization (B) and organic binder (A) ratio that contains carboxyl, and select the red pigment of two carbonyl pyrrolo-pyrrolo systems for use, the combination of light initiator can be further arranged in pairs or groups specific, development property, adherence, light transmission is good and the development aberration is very little photosensitive resin composition can be obtained.
Table one:
(1) the composition tabulated data is except [contain the compound (B) of ethene unsaturated group/contain organic property adhesive (A) of carboxyl], being organic property adhesive (A) that weight portion (2) contains carboxyl is the resin solution with 35% solids content, and therefore the organic binder that contains carboxyl (A) of 13.29 weight portions contains the whole content of solid of 4.65 weight portions.(3) DPHA is that the abbreviation of dipentaerythritol six (methyl) acrylate: DPTA is that abbreviation (4) EEP of dipentaerythritol four (methyl) acrylate is that the C1177 of abbreviation (5) pigment (E) of ethyl (three-ethoxy) acrylate is the red pigment that anthraquinone (anthraquinone) is
| Composition | Embodiment compiles | The comparative example numbering | |||||||||||
| 1 | 2 | 3 | 4 | 5 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | ||
| The organic property adhesive (A) that contains carboxyl | 13.29 | 12.99 | 10.63 | 10.88 | 13.29 | 13.29 | 14.29 | 14.29 | 16.43 | 9.05 | 9.60 | 10.08 | |
| The compound (B) that contains the ethene unsaturated group | DPHA | 5.58 | 5.00 | 5.58 | 6.09 | 11.30 | 4.00 | 4.00 | 4.60 | 5.70 | 6.05 | 6.35 | |
| DPTA | 5.58 | ||||||||||||
| Light initiator (C) | 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.50 | 1.00 | 0.50 | ||
| Benzophenone | 1.00 | 1.00 | |||||||||||
| 4,4 '-two (diethylamine) benzophenone | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.14 | |
| 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |||||
| Organic solvent (D) | EEP | 43.13 | 43.01 | 44.79 | 45.04 | 43.13 | 37.41 | 42.71 | 42.21 | 39.97 | 46.25 | 45.85 | 44.43 |
| Pigment (E) | C1254 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | |
| C1177 | 6.00 | ||||||||||||
| Contain the compound (B) of ethene unsaturated group/the contain ratio of organic property adhesive (A) of carboxyl | 120/100 | 110/100 | 150/100 | 160/100 | 120/100 | 120/100 | 80/100 | 80/100 | 80/100 | 180/100 | 180/100 | 180/100 | |
| Assessment item | Development | ○ | ○ | ○ | △ | ○ | ○ | ○ | ○ | ○ | × | × | × |
| Adherence | ○ | ○ | ○ | ○ | ○ | ○ | × | × | × | ○ | ○ | ○ | |
| Development aberration (△ Eab *) | 0.82 | 1.23 | 0.66 | 0.62 | 0.73 | 0.77 | 2.59 | 2.44 | 3.12 | 0.43 | 0.55 | 2.94 | |
| Light transmission | ○ | ○ | ○ | ○ | ○ | × | ○ | ○ | ○ | ○ | ○ | ○ | |
Claims (8)
1, a kind of photosensitive resin composition is characterized in that: this constituent comprises: contain organic property adhesive (A) of carboxyl, the compound (B) that contains the ethene unsaturated group, light initiator (C), organic solvent (D), pigment (E); Wherein, the organic property adhesive (A) that contains carboxyl is by ethylene unsaturated monomer 5～50 weight % that contain one or more carboxyls, and copolymerizable ethylene unsaturated monomer 95～50 weight % form, and pigment (E) is the red pigment of diketopyrrolo-pyrrole system; And the compound (B) that contains the ethene unsaturated group is 100/100～160/100 with the ratio that contains organic property adhesive (A) of carboxyl; Wherein, as follows with magnitude relation between the each component: the organic property adhesive (A) that contains carboxyl with 100 weight portions is a benchmark, and the described use amount that contains the compound (B) of ethene unsaturated group is the 100-160 weight portion; The use amount of its light initiator (C) is 1～50 weight % of benchmark with the compound (B) that contains the ethene unsaturated group; The use amount of its organic solvent (D) is 60～90 weight % that account for whole photosensitive resin compositions; The organic cohesive agent (A) that contains carboxyl with 100 weight portions is a benchmark, and the use amount of pigment (E) is 20～500 weight portions, can make the good photosensitive resin composition of light transmission.
2, the photosensitive resin composition according to claim 1, it is characterized in that: the wherein said use amount that contains the compound (B) of ethene unsaturated group is preferable with the 110-150 weight portion especially.
3, the photosensitive resin composition according to claim 1, it is characterized in that: wherein, pigment (E) is C.I. paratonere 254.
4, the photosensitive resin composition according to claim 1 is characterized in that: wherein, the ratio that contains the compound (B) of ethene unsaturated group/contain organic property adhesive (A) of carboxyl is 110/100～150/100.
5, the photosensitive resin composition according to claim 1, it is characterized in that: wherein, 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.
6, the photonasty power fat composition according to claim 4 is characterized in that: wherein, light initiator (C) is and with 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone and 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole.
7, the photosensitive resin composition according to claim 4 is characterized in that: wherein, light initiator (C) still can and be used the benzophenone based compound.
8, the photosensitive resin composition according to claim 5 is characterized in that: wherein, and benzophenone series series of compounds 4,4 '-two (diethylamine) benzophenone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001028561A CN1144096C (en) | 2000-03-03 | 2000-03-03 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001028561A CN1144096C (en) | 2000-03-03 | 2000-03-03 | Photosensitive resin composition |
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| Publication Number | Publication Date |
|---|---|
| CN1311458A CN1311458A (en) | 2001-09-05 |
| CN1144096C true CN1144096C (en) | 2004-03-31 |
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| CNB001028561A Expired - Lifetime CN1144096C (en) | 2000-03-03 | 2000-03-03 | Photosensitive resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5291893B2 (en) * | 2007-05-08 | 2013-09-18 | 太陽ホールディングス株式会社 | Photocurable resin composition and cured product thereof |
| JP5449688B2 (en) * | 2008-03-26 | 2014-03-19 | 太陽ホールディングス株式会社 | Photo-curable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using them |
| CN101598898A (en) * | 2008-06-06 | 2009-12-09 | Jsr株式会社 | Red pixel forms coloured composition, color filter and the color liquid crystal display device of usefulness |
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| CN1311458A (en) | 2001-09-05 |
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