JPH08202036A - Photosensitive resin composition - Google Patents
Photosensitive resin compositionInfo
- Publication number
- JPH08202036A JPH08202036A JP739295A JP739295A JPH08202036A JP H08202036 A JPH08202036 A JP H08202036A JP 739295 A JP739295 A JP 739295A JP 739295 A JP739295 A JP 739295A JP H08202036 A JPH08202036 A JP H08202036A
- Authority
- JP
- Japan
- Prior art keywords
- water
- soluble
- photopolymerization initiator
- vinyl acetate
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 10
- 239000002612 dispersion medium Substances 0.000 claims abstract description 8
- 238000007127 saponification reaction Methods 0.000 claims description 16
- YVXDRFYHWWPSOA-BQYQJAHWSA-N 1-methyl-4-[(e)-2-phenylethenyl]pyridin-1-ium Chemical group C1=C[N+](C)=CC=C1\C=C\C1=CC=CC=C1 YVXDRFYHWWPSOA-BQYQJAHWSA-N 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 5
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 238000003860 storage Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- -1 halogen ion Chemical class 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229920002601 oligoester Polymers 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- XNVDIDQQGRBQQA-UHFFFAOYSA-N (4-benzoyl-2-prop-2-enoyloxyphenyl)methyl-dimethylazanium;bromide Chemical compound [Br-].C1=C(OC(=O)C=C)C(C[NH+](C)C)=CC=C1C(=O)C1=CC=CC=C1 XNVDIDQQGRBQQA-UHFFFAOYSA-N 0.000 description 1
- YEACGXMAEGBJSM-UHFFFAOYSA-N 1,3,5-triphenyl-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(C=2C=CC=CC=2)C(=O)N(C=2C=CC=CC=2)C(=O)N1C1=CC=CC=C1 YEACGXMAEGBJSM-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- GXZPMXGRNUXGHN-UHFFFAOYSA-N 1-ethenoxy-2-methoxyethane Chemical compound COCCOC=C GXZPMXGRNUXGHN-UHFFFAOYSA-N 0.000 description 1
- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
- BGJQNPIOBWKQAW-UHFFFAOYSA-N 1-tert-butylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)(C)C BGJQNPIOBWKQAW-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- SNGZGCFWZHOVOS-UHFFFAOYSA-N 2-(2-methyloctoxymethyl)oxirane Chemical compound CCCCCCC(C)COCC1CO1 SNGZGCFWZHOVOS-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NLGIEISQJFZTIS-UHFFFAOYSA-N 4-n-(4-chlorophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(Cl)C=C1 NLGIEISQJFZTIS-UHFFFAOYSA-N 0.000 description 1
- XHVFCOOFJKCIAP-UHFFFAOYSA-N 4-n-(4-nitrophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C([N+]([O-])=O)C=C1 XHVFCOOFJKCIAP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HSZUHSXXAOWGQY-UHFFFAOYSA-N [2-methyl-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)COC(=O)C=C HSZUHSXXAOWGQY-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- ZJHJWUVWYXNFLY-UHFFFAOYSA-N n-methoxy-n-phenylaniline Chemical compound C=1C=CC=CC=1N(OC)C1=CC=CC=C1 ZJHJWUVWYXNFLY-UHFFFAOYSA-N 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 238000011907 photodimerization Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、感光性樹脂組成物に関
する。さらに詳しく述べるならば、本発明は、容易に調
合することができ、かつ、水現像性、耐水性、耐溶剤
性、保存性および解像性にすぐれ、スクリーン印刷版な
どの作製に有用な感光性樹脂組成物に関する。FIELD OF THE INVENTION The present invention relates to a photosensitive resin composition. More specifically, the present invention can be easily prepared, and is excellent in water developability, water resistance, solvent resistance, storability and resolution, and is useful for the production of screen printing plates and the like. Resin composition.
【０００２】[0002]
【従来の技術】特開昭６０−１０２４５には、水溶性光
架橋剤を含有するケン化度７０〜９９モル％の部分ケン
化酢酸ビニル重合体の水溶液およびそれ自体で光架橋性
を有する光架橋性基を含有するケン化度７０〜９９モル
％の部分ケン化酢酸ビニル重合体の水溶液から選ばれる
分散媒中に、疎水性重合体粒子からなる分散質および光
重合開始剤を含有する水不溶性または水難溶性で光活性
な１つまたは２つ以上のエチレン性不飽和基を有する化
合物からなる分散質を分散した感光性樹脂組成物が提案
されている。2. Description of the Related Art JP-A-60-10245 discloses an aqueous solution of a partially saponified vinyl acetate polymer containing a water-soluble photocrosslinking agent and having a saponification degree of 70 to 99 mol%, and a photocrosslinkable photopolymerizable polymer itself. Water containing a dispersoid composed of hydrophobic polymer particles and a photopolymerization initiator in a dispersion medium selected from an aqueous solution of a partially saponified vinyl acetate polymer containing a crosslinkable group and having a saponification degree of 70 to 99 mol%. A photosensitive resin composition in which a dispersoid comprising an insoluble or poorly water-soluble compound having one or more photoactive ethylenically unsaturated groups is dispersed has been proposed.
【０００３】この組成物においては、特開昭６０−１０
２４５に記載されているように、光重合開始剤はエチレ
ン性不飽和基を有する化合物中に含有されていなけれ
ば、この化合物を光照射によって重合させることができ
ないと考えられていた。そのため、エチレン性不飽和基
を有する化合物と光重合開始剤とは相溶化することが必
要であり、相溶化しないエチレン性不飽和基を有する化
合物と光重合開始剤との組み合わせによる感光性樹脂組
成物の製造は不可能であった。In this composition, JP-A-60-10 is used.
As described in No. 245, it was thought that if the photopolymerization initiator was not contained in the compound having an ethylenically unsaturated group, the compound could not be polymerized by irradiation with light. Therefore, it is necessary to compatibilize the compound having an ethylenically unsaturated group and the photopolymerization initiator, and a photosensitive resin composition obtained by combining a compound having an ethylenically unsaturated group that does not compatibilize and a photopolymerization initiator. It was impossible to manufacture a product.
【０００４】また、光重合開始剤を予めエチレン性不飽
和基を有する化合物に溶解しなければならないため、保
存安定性の低い光重合開始剤を使用した場合、製造した
感光性樹脂組成物の保存安定性も低くなり、使用時に品
質上の問題が生じる等の欠点があった。Further, since the photopolymerization initiator must be previously dissolved in a compound having an ethylenically unsaturated group, when a photopolymerization initiator having low storage stability is used, the prepared photosensitive resin composition is preserved. The stability is also low, and there are drawbacks such as quality problems during use.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記従来技
術の問題点を解消し、容易に調合することができ、使用
に際して保存安定性の問題が生じず、かつ、耐水性、耐
溶剤性、解像性および水現像性にすぐれた感光性樹脂組
成物を提供しようとするものである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, can be easily prepared, does not cause a problem of storage stability during use, and has water resistance and solvent resistance. Another object of the present invention is to provide a photosensitive resin composition having excellent resolution and water developability.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記課題を解
決するため、水溶性光架橋剤とケン化度７０〜９９モル
％の部分ケン化酢酸ビニル重合体との混合物の水溶液お
よび光架橋性基を有するケン化度７０〜９９モル％の部
分ケン化酢酸ビニル重合体の水溶液から選ばれる少なく
とも１種の水溶液からなる分散媒中に、この分散媒中に
分散された疎水性重合体粒子および水不溶性または水難
溶性で光活性なエチレン系不飽和基を有する化合物とと
もに、油溶性光重合開始剤および水溶性光重合開始剤か
ら選ばれる少なくとも１種の光重合開始剤を含み、前記
エチレン系不飽和基を有する化合物と前記光重合開始剤
とが独立して存在することを特徴とする感光性樹脂組成
物を提供する。In order to solve the above-mentioned problems, the present invention provides an aqueous solution and photocrosslinking of a mixture of a water-soluble photocrosslinking agent and a partially saponified vinyl acetate polymer having a saponification degree of 70 to 99 mol%. Hydrophobic polymer particles dispersed in a dispersion medium composed of an aqueous solution of at least one kind selected from aqueous solutions of partially saponified vinyl acetate polymers having a saponification degree of 70 to 99 mol% and having a functional group. And a water-insoluble or sparingly water-soluble compound having a photoactive ethylenic unsaturated group, and at least one photopolymerization initiator selected from an oil-soluble photopolymerization initiator and a water-soluble photopolymerization initiator, Provided is a photosensitive resin composition, wherein a compound having an unsaturated group and the photopolymerization initiator are independently present.
【０００７】本発明のこの組成物においては、光重合開
始剤とエチレン性不飽和基を有する化合物とは、分散媒
中に、それぞれ独立して含有されており、前述した特開
昭６０−１０２４５に記載されている感光性樹脂組成物
における如く光重合開始剤とエチレン性不飽和基を有す
る化合物とが相溶化されている必要はない。従来、エチ
レン性不飽和基を有する化合物は、光重合開始剤を相溶
化していないと光照射しても光重合しないか、あるいは
光重合しても光重合の度合が完全にならないと考えられ
ていた。ところが、本発明の感光性樹脂組成物によれ
ば、エチレン性不飽和基を有する化合物と光重合開始剤
とが相溶化せずに、分散媒中にそれぞれ別々に含まれい
ても、これを乾燥して得られる感光層中において、前記
エチレン性不飽和基を有する化合物は完全に光重合され
るということが、予期せず見出されたのである。光重合
開始剤を相溶化していないエチレン性不飽和基を有する
化合物が光照射によって完全に光重合される理由につい
ては、十分に明らかではないけれども、エチレン性不飽
和基を有する化合物が感光性樹脂組成物中に微粒子の分
散滴として存在し、この微粒子に隣接して光重合開始剤
が存在すれば、微粒子の周囲から光重合が開始され、そ
の中心部に向って重合が移行し、かつ、微粒子であるが
ために極めて短時間に粒子全体の重合が完結することに
よるものと考えられる。なお、重合を短時間内に完結さ
せるためには、エチレン系不飽和基を有する化合物の分
散滴の粒径は１０μ以下であるのが好ましい。In this composition of the present invention, the photopolymerization initiator and the compound having an ethylenically unsaturated group are contained in the dispersion medium independently of each other. It is not necessary that the photopolymerization initiator and the compound having an ethylenically unsaturated group are compatibilized as in the photosensitive resin composition described in 1. Conventionally, a compound having an ethylenically unsaturated group is not considered to be photopolymerized by irradiation with light unless the photopolymerization initiator is compatibilized, or the degree of photopolymerization is not complete even if photopolymerized. Was there. However, according to the photosensitive resin composition of the present invention, the compound having an ethylenically unsaturated group and the photopolymerization initiator are not compatibilized, and even if they are separately contained in the dispersion medium, they are dried. It was unexpectedly found that the compound having an ethylenically unsaturated group is completely photopolymerized in the photosensitive layer thus obtained. The reason why the compound having an ethylenically unsaturated group that does not compatibilize the photopolymerization initiator is completely photopolymerized by irradiation with light is not sufficiently clear, but the compound having an ethylenically unsaturated group is not Exists as dispersed droplets of fine particles in the resin composition, and if a photopolymerization initiator is present adjacent to the fine particles, photopolymerization is started from the periphery of the fine particles, and the polymerization moves toward the center thereof, and However, it is considered that the polymerization of the entire particles is completed in an extremely short time because they are fine particles. In order to complete the polymerization within a short period of time, it is preferable that the particle size of the dispersed droplets of the compound having an ethylenically unsaturated group is 10 μm or less.
【０００８】本発明の感光性樹脂組成物においては、従
来は相溶化が不可能であったかまたは製造工程上きわめ
て困難であった高粘度なエチレン性不飽和基を有する化
合物と光重合開始剤との組み合わせにおいても相溶化が
不要となり、また水溶性の光重合開始剤を用いることも
できるので、特別の制約を受けることなく、エチレン性
不飽和基を有する化合物と光重合開始剤とを広範囲に選
択して組み合わせることが可能となる。In the photosensitive resin composition of the present invention, a compound having a highly viscous ethylenically unsaturated group and a photopolymerization initiator, which have hitherto been incompatible or extremely difficult in the production process, Compatibilization is not necessary even in combination, and since a water-soluble photopolymerization initiator can be used, a compound having an ethylenically unsaturated group and a photopolymerization initiator can be selected in a wide range without any special restrictions. It becomes possible to combine them.
【０００９】また、特にスチルバゾリウム基を側鎖に有
する部分ケン化酢酸ビニル重合体を本発明の感光性樹脂
組成物の成分とした場合、光重合開始剤がエチレン性不
飽和基を有する化合物中に内包されておらず、エチレン
系不飽和基を有するスチルバゾリウム基にも隣接して存
在するため、スチルバゾリウム基同志の光二量化反応に
関与できなかったスチルバゾリウム基中のエチレン系不
飽和基は光重合開始剤によって光重合を開始し、エチレ
ン系不飽和基を有する化合物と共重合するためか、得ら
れる硬化組成物は、架橋密度が向上し、光重合開始剤を
相溶化しているエチレン性不飽和基を有する化合物およ
びスチルバゾリウム基を側鎖に有する部分ケン化酢酸ビ
ニル重合体からなる感光性樹脂組成物と比較して、耐水
性および耐溶剤性にすぐれたものとなる等の利点が得ら
れる。In particular, when a partially saponified vinyl acetate polymer having a stilbazolium group in its side chain is used as a component of the photosensitive resin composition of the present invention, the photopolymerization initiator is added to the compound having an ethylenically unsaturated group. The ethylenically unsaturated group in the stilbazolium group that could not participate in the photodimerization reaction of the stilbazolium group because it is not included and is adjacent to the stilbazolium group having an ethylenically unsaturated group is a photopolymerization initiator. Probably because the photopolymerization is initiated by the copolymerization with the compound having an ethylenically unsaturated group, the resulting cured composition has an improved crosslink density and an ethylenically unsaturated group that compatibilizes the photopolymerization initiator. Resistance and solvent resistance as compared with a photosensitive resin composition comprising a compound having a silane and a partially saponified vinyl acetate polymer having a stilbazolium group in its side chain The advantage of such a thing that was good is obtained.
【００１０】また、本発明の感光性樹脂組成物において
は、特開昭５９−１０７３４３や特開昭６０−１０２４
５に記載された感光性樹脂組成物では使用することが困
難であった保存安定性の低い光重合開始剤であっても、
予めエチレン性不飽和基を有する化合物中に相溶化させ
る必要がないため、使用前の短時間内に光重合開始剤を
添加混合して組成物を調合することが可能となるので、
所望の特性を損なう前に安心して使用することができる
という利点も得られる。Further, in the photosensitive resin composition of the present invention, JP-A-59-107343 and JP-A-60-1024 are used.
Even with a photopolymerization initiator having low storage stability, which was difficult to use with the photosensitive resin composition described in 5,
Since it is not necessary to compatibilize the compound having an ethylenically unsaturated group in advance, the composition can be prepared by adding and mixing a photopolymerization initiator within a short time before use.
The advantage is that it can be used with confidence before the desired properties are impaired.
【００１１】本発明に用いるケン化度７０〜９９モル％
の部分ケン化酢酸ビニル重合体は、重合度３００〜３５
００の範囲にあるのが好ましい。ここで、酢酸ビニル重
合体は、酢酸ビニルのホモ重合体および共重合体のいず
れであってもよく、部分ケン化酢酸ビニル重合体とブチ
ルアルデヒドスルホン酸、ベンズアルデヒドスルホン酸
等とのアセタール化物であってもよい。Degree of saponification used in the present invention 70 to 99 mol%
The partially saponified vinyl acetate polymer has a degree of polymerization of 300 to 35.
It is preferably in the range of 00. Here, the vinyl acetate polymer may be either a homopolymer or a copolymer of vinyl acetate, and is an acetalized product of a partially saponified vinyl acetate polymer and butyraldehyde sulfonic acid or benzaldehyde sulfonic acid. May be.
【００１２】側鎖にスチルバゾリウム基を有するケン化
度７０〜９９モル％の部分ケン化酢酸ビニル重合体とし
ては下記式（１）A partially saponified vinyl acetate polymer having a stilbazolium group in its side chain and a saponification degree of 70 to 99 mol% is represented by the following formula (1).
【００１３】[0013]
【化１】 Embedded image
【００１４】（上式中、Ｒ1 は水素原子、アルキル基ま
たはアラルキル基を示し、Ｒ2 は水素原子または炭素数
１〜６の低級アルキル基を示し、Ｘ- はハロゲンイオ
ン、リン酸イオン、ｐ−トルエンスルホン酸イオンまた
はこれら陰イオンの混合物を示し、ｍは０または１であ
り、ｎは１〜６の整数である）で示される単位を有する
部分ケン化酢酸ビニル重合体があり、このようなスチル
バゾリウム基を側鎖に有する部分ケン化酢酸ビニル重合
体は特開昭５５−２３１６３、特開昭５５−６２９０５
等に開示されて公知である。(In the above formula, R 1 represents a hydrogen atom, an alkyl group or an aralkyl group, R 2 represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, X − represents a halogen ion, a phosphate ion, p-toluenesulfonate ion or a mixture of these anions, m is 0 or 1, and n is an integer from 1 to 6), and a partially saponified vinyl acetate polymer having a unit represented by Such partially saponified vinyl acetate polymers having a stilbazolium group in the side chain are disclosed in JP-A-55-23163 and JP-A-55-62905.
Etc. and is publicly known.
【００１５】本発明で使用する側鎖にスチルバゾリウム
基を有する部分ケン化酢酸ビニル誘導体において、スチ
ルバゾリウム基の導入率は、酢酸ビニルケン化物単位あ
たり０．３〜２０モル％であるのが好ましく、０．５〜
４モル％であるのが特に好ましい。本発明の感光性樹脂
組成物は、上記した側鎖にスチルバゾリウム基を有する
部分ケン化酢酸ビニル誘導体を含めて部分ケン化酢酸ビ
ニル重合体の固形分１００重量部に対して、固形分とし
て、好ましくは５〜４０００重量部、より好ましくは１
０〜２０００重量部の疎水性重合体粒子を含有している
のがよい。疎水性重合体粒子は、感光性樹脂組成物の光
架橋後の硬化物に耐水性および高解像性を与えるために
加えるものであり、その含有量が部分ケン化酢酸ビニル
重合体１００重量部に対して５重量部未満では十分な耐
水性および解像性が得られないことがあり、また４００
０重量部を超えると未硬化部分の水現像が困難となるお
それがある。In the partially saponified vinyl acetate derivative having a stilbazolium group in the side chain used in the present invention, the introduction ratio of the stilbazolium group is preferably 0.3 to 20 mol% per vinyl acetate saponification unit, and 5-
It is particularly preferably 4 mol%. The photosensitive resin composition of the present invention preferably contains, as a solid content, 100 parts by weight of the solid content of the partially saponified vinyl acetate polymer including the partially saponified vinyl acetate derivative having a stilbazolium group in the above side chain. Is 5 to 4000 parts by weight, more preferably 1
It preferably contains 0 to 2000 parts by weight of hydrophobic polymer particles. The hydrophobic polymer particles are added in order to impart water resistance and high resolution to the cured product of the photosensitive resin composition after photocrosslinking, and the content thereof is 100 parts by weight of the partially saponified vinyl acetate polymer. On the other hand, if it is less than 5 parts by weight, sufficient water resistance and resolution may not be obtained.
If it exceeds 0 parts by weight, water development of the uncured portion may become difficult.
【００１６】このような疎水性重合体粒子を構成する疎
水性重合体としては、例えば、ポリ酢酸ビニル、酢酸ビ
ニル／エチレン共重合体、酢酸ビニル／アクリル酸エス
テル共重合体（アクリル酸エステルとしては、例えば、
アクリル酸メチル、アクリル酸２−エチルヘキシル等が
ある）、スチレン／ブタジエン共重合体、メタクリル酸
メチル／ブタジエン共重合体、アクリロニトリル／ブタ
ジエン共重合体、クロロプレン重合体、イソプレン重合
体、ポリアクリル酸、ポリメタクリル酸、ポリ塩化ビニ
ル、ポリ塩化ビニリデン、ポリスチレン、シリコーン樹
脂、ポリエチレン、ポリウレタン、フツ素樹脂等が挙げ
られる。Examples of the hydrophobic polymer which constitutes such hydrophobic polymer particles include polyvinyl acetate, vinyl acetate / ethylene copolymer, vinyl acetate / acrylic acid ester copolymer (as acrylic acid ester, , For example,
Methyl acrylate, 2-ethylhexyl acrylate, etc.), styrene / butadiene copolymer, methyl methacrylate / butadiene copolymer, acrylonitrile / butadiene copolymer, chloroprene polymer, isoprene polymer, polyacrylic acid, poly Methacrylic acid, polyvinyl chloride, polyvinylidene chloride, polystyrene, silicone resin, polyethylene, polyurethane, fluorine resin and the like can be mentioned.
【００１７】本発明の感光性樹脂組成物に有用なエチレ
ン系不飽和基を有する化合物としては、アクリロイル
基、メタクリロイル基、アリル基、ビニルエーテル基、
アクリルアミド基、メタクリルアミド基等の光活性なエ
チレン系不飽和基を１個以上有し、水に不溶もしくは難
溶性であり、前述した部分ケン化酢酸ビニル重合体の水
溶液中に分散可能な化合物がある。特に、エチレン系不
飽和基を２個以上有する化合物は、耐溶剤性の良好な硬
化物を与えるので好ましい。このエチレン系不飽和基を
有する化合物には、通常ビニル単量体と呼ばれる化合物
に加えて、分子量が１００００以下であるようなプレポ
リマーないしオリゴマーも含まれる。The compounds having an ethylenically unsaturated group useful in the photosensitive resin composition of the present invention include acryloyl group, methacryloyl group, allyl group, vinyl ether group,
A compound having at least one photoactive ethylenically unsaturated group such as an acrylamide group or a methacrylamide group, which is insoluble or sparingly soluble in water and which can be dispersed in an aqueous solution of the partially saponified vinyl acetate polymer described above is obtained. is there. In particular, a compound having two or more ethylenically unsaturated groups is preferable because it gives a cured product having good solvent resistance. The compound having an ethylenically unsaturated group includes a compound usually called a vinyl monomer and a prepolymer or oligomer having a molecular weight of 10,000 or less.
【００１８】このような化合物の例としては、ペンタエ
リスリトールトリ（メタ）アクリレート、ペンタエリス
リトールテトラ（メタ）アクリレート、トルメチロール
プロパントリ（メタ）アクリレート、トルメチロールエ
タントリ（メタ）アクリレート、ジブロムネオペンチル
グリコールジ（メタ）アクリレート、２，８−ジブロモ
プロピル（メタ）アクリレート、トリアリルイソシアヌ
レート、メトキシエチルビニルエーテル、ターシャリー
ブチルビニルエーテル、ラウリル（メタ）アクリレー
ト、メトキシエチレングリコール（メタ）アクリレー
ト、２−エチルヘキシル（メタ）アクリレート、イソデ
シル（メタ）アクリレート、ステアリル（メタ）アクリ
レート、ベンジル（メタ）アクリレート、ヘキシルジグ
リコール（メタ）アクリレート、エチレングリコールジ
（メタ）アクリレート、ジヘキサエチレングリコールジ
（メタ）アクリレート、エチレングリコールジグリシジ
ルエーテル（メタ）アクリレート、２−エチルヘキシル
グリシジルエーテル（メタ）アクリレート、フエニルグ
リシジルエーテル（メタ）アクリレート、２−メチルオ
クチルグリシジルエーテル（メタ）アクリレート、トル
メチロールプロパンポリグリシジルエーテルポリ（メ
タ）アクリレート、テレフタル酸ジグリシジルエーテル
（メタ）アクリレート、トリレンジイソシアネートと２
−ヒドロキシプロピル（メタ）アクリレートとの反応生
成物、フエニルイソシアヌレートと２−ヒドロキシエチ
ル（メタ）アクリレートとの反応生成物、マレイン酸グ
リコールエステル等のエチレン性不飽和基をもつ分子量
１００００以下の不飽和ポリエステルが挙げられる。上
記において、「（メタ）アクリレート」は、アクリレー
トまたはメタクリレートのいずれかを意味する。Examples of such compounds include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dibromoneopentyl. Glycol di (meth) acrylate, 2,8-dibromopropyl (meth) acrylate, triallyl isocyanurate, methoxyethyl vinyl ether, tertiary butyl vinyl ether, lauryl (meth) acrylate, methoxyethylene glycol (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, hexyl diglycol (meth) acrylate Rate, ethylene glycol di (meth) acrylate, dihexaethylene glycol di (meth) acrylate, ethylene glycol diglycidyl ether (meth) acrylate, 2-ethylhexyl glycidyl ether (meth) acrylate, phenyl glycidyl ether (meth) acrylate, 2 -Methyl octyl glycidyl ether (meth) acrylate, trimethylolpropane polyglycidyl ether poly (meth) acrylate, terephthalic acid diglycidyl ether (meth) acrylate, tolylene diisocyanate and 2
-A reaction product of hydroxypropyl (meth) acrylate, a reaction product of phenyl isocyanurate and 2-hydroxyethyl (meth) acrylate, and an ethylenically unsaturated group-containing monomer having a molecular weight of 10,000 or less such as maleic acid glycol ester. Saturated polyester is mentioned. In the above, "(meth) acrylate" means either acrylate or methacrylate.
【００１９】これらの化合物は、単独であるいは２種以
上の併用で用いられてよく、固形分として、部分ケン化
酢酸ビニル重合体と疎水性重合体粒子との合計１００重
量部に対して、好ましくは５〜１０００重量部、より好
ましくは２０〜５００重量部の範囲の量で使用されるの
がよい。この量が少なすぎると硬化物の耐水性が充分で
なくなり、また多すぎると組成物を塗布乾燥した皮膜に
上記化合物の分離析出が生じるおそれがある。These compounds may be used singly or in combination of two or more kinds, and are preferable as a solid content relative to 100 parts by weight in total of the partially saponified vinyl acetate polymer and the hydrophobic polymer particles. Is preferably used in an amount in the range of 5 to 1000 parts by weight, more preferably 20 to 500 parts by weight. If this amount is too small, the water resistance of the cured product will be insufficient, and if it is too large, the compounds described above may be separated and deposited in the film formed by coating and drying the composition.
【００２０】本発明の感光性樹脂組成物は、上記各成分
に加えて、光重合開始剤を含有している。この光重合開
始剤は、前述した部分ケン化酢酸ビニル重合体の水溶液
からなる分散媒中に、水溶性光重合開始剤の場合には溶
解されており、あるいは油溶性光重合開始剤の場合には
予めエタノール等の有機溶媒に溶解させてから分散され
るのがよく、感光性樹脂組成物が露光された際にエチレ
ン性不飽和基を有する化合物および側鎖にスチルバゾリ
ウム基を有する部分ケン化酢酸ビニル重合体のスチルバ
ゾリウム基の一部を硬化させる。The photosensitive resin composition of the present invention contains a photopolymerization initiator in addition to the above components. This photopolymerization initiator is dissolved in the case of a water-soluble photopolymerization initiator in a dispersion medium composed of an aqueous solution of the partially saponified vinyl acetate polymer described above, or in the case of an oil-soluble photopolymerization initiator. Is preferably dissolved in an organic solvent such as ethanol in advance and then dispersed, and when the photosensitive resin composition is exposed to light, a compound having an ethylenically unsaturated group and a partially saponified acetic acid having a stilbazolium group in its side chain. It cures some of the stilbazolium groups of the vinyl polymer.
【００２１】水溶性の光重合開始剤としては、例えば、
（４−ベンゾイルベンジル）塩化トルメチルアンモニウ
ム、２−（３−ジメチルアミノ−２−ヒドロキシプロポ
キシ）−３，４−ジメチル−９Ｈ−チオキサントン−９
−オンメソクロリド、（２−アクリロイルオキシ）（４
−ベンゾイルベンジル）ジメチル臭化アンモニウム等を
用いることができる。また、油溶性の光重合開始剤とし
て、例えば、ベンゾイルアルキルエーテル、ミヒラーズ
ケトン、ジターシャリーブチルパーオキサイド、トリブ
ロムアセトフェノン、ターシャリーブチルアントラキノ
ン等のアントラキノン誘導体、クロロチオキサントン等
のチオキサントン誘導体等を用いることができる。これ
らの光重合開始剤は、エチレン性不飽和基を有する化合
物１００重量部に対して０．１〜１５重量部、特に０．
３〜１０重量部の範囲の量で使用するのが好ましい。As the water-soluble photopolymerization initiator, for example,
(4-benzoylbenzyl) tolumethylammonium chloride, 2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone-9
-One mesochloride, (2-acryloyloxy) (4
-Benzoylbenzyl) dimethyl ammonium bromide or the like can be used. As the oil-soluble photopolymerization initiator, for example, benzoylalkyl ether, Michler's ketone, ditertiary butyl peroxide, tribromacetophenone, anthraquinone derivative such as tertiary butyl anthraquinone, and thioxanthone derivative such as chlorothioxanthone can be used. . These photopolymerization initiators are used in an amount of 0.1 to 15 parts by weight, particularly 0.1% by weight, based on 100 parts by weight of the compound having an ethylenically unsaturated group.
It is preferably used in an amount in the range of 3 to 10 parts by weight.
【００２２】本発明の感光性樹脂組成物において、ケン
化度７０〜９９モル％の部分ケン化酢酸ビニル重合体と
してそれ自体で所要の光架橋性を有する光架橋性基を有
していないものを使用するときは、上記各成分に加え
て、光架橋剤を使用しなければならない。この光架橋剤
は、本発明の感光性樹脂組成物に含まれる部分ケン化酢
酸ビニル重合体の水溶液中に含有されており、感光性樹
脂組成物が露光された際に部分ケン化酢酸ビニル重合体
を光架橋して硬化させる。従って、この光架橋剤として
は、水溶性の部分ケン化酢酸ビニル重合体と相溶化され
るように水溶性のものを用いることが重要である。In the photosensitive resin composition of the present invention, a partially saponified vinyl acetate polymer having a saponification degree of 70 to 99 mol% does not have a photocrosslinkable group having the required photocrosslinkability by itself. When using, a photocrosslinking agent must be used in addition to the above components. This photocrosslinking agent is contained in the aqueous solution of the partially saponified vinyl acetate polymer contained in the photosensitive resin composition of the present invention, and when the photosensitive resin composition is exposed to light, the partially saponified vinyl acetate polymer is added. The cross-linking is photo-crosslinked and cured. Therefore, it is important to use a water-soluble photocrosslinking agent so as to be compatibilized with the water-soluble partially saponified vinyl acetate polymer.
【００２３】このような光架橋剤としては、例えば、重
クロム酸アンモニウム、重クロム酸カリウム、重クロム
酸ナトリウム等の重クロム酸塩類、ｐ−ジアゾジフェニ
ルアミンもしくは３−メトキシ−４−ジアゾジフェニル
アミンと４，４′−ビスメトキシメチルジフェニルエー
テルとの縮合物の硫酸塩、リン酸塩および塩化亜鉛複塩
陰イオンコンプレックスのジアゾ樹脂、ｐ−ジアゾジフ
ェニルアミンとパラホルムアルデヒドとの縮合物の硫酸
塩、リン酸塩および塩化亜鉛複塩陰イオンコンプレック
スのジアゾ樹脂を用いることができる。この種のジアゾ
樹脂としては、パラアミノジフェニルアミンの他に、４
−アミノ−４′−メチルジフェニルアミン、４−アミノ
−４′−エチルジフェニルアミン、４−アミノ−４′−
メトキシジフェニルアミン、４−アミノ−４′−クロロ
ジフエニルアミン、４−アミノ−４′−ニトロジフェニ
ルアミン等のジフェニルアミン類のジアゾ化物を、パラ
ホルムアルデヒド、アセトアルデヒド、プロピオンアル
デヒド、ｎ−ブチルアルデヒド等のアルデヒド類を用い
て縮合させた水溶性のジアゾ樹脂をもちいることができ
る。Examples of such photocrosslinking agents include dichromates such as ammonium dichromate, potassium dichromate, sodium dichromate, p-diazodiphenylamine or 3-methoxy-4-diazodiphenylamine. , 4'-Bismethoxymethyldiphenyl ether condensate sulfate, phosphate and zinc chloride double salt anion complex diazo resin, p-diazodiphenylamine condensate sulfate, phosphate and A diazo resin having a zinc chloride double salt anion complex can be used. As this kind of diazo resin, in addition to paraaminodiphenylamine, 4
-Amino-4'-methyldiphenylamine, 4-amino-4'-ethyldiphenylamine, 4-amino-4'-
Diazo compounds of diphenylamines such as methoxydiphenylamine, 4-amino-4'-chlorodiphenylamine, 4-amino-4'-nitrodiphenylamine and aldehydes such as paraformaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, etc. It is possible to use a water-soluble diazo resin which has been condensed.
【００２４】これら光架橋剤は、単独でまたは２種以上
の併用で用いることができ、部分ケン化酢酸ビニル重合
体１００重量部に対して、２〜２０重量部の範囲の量で
用いるのが好ましい。光架橋剤が２重量部未満では耐水
性に優れた硬化樹脂が得られず、２０重量部を超えて使
用すると組成物の保存安定性が低下する。また、これら
光架橋剤は、部分ケン化酢酸ビニル重合体自体が側鎖に
光架橋性基を有するときにも、より強固な光硬化部を与
えるために追加的に加えることができる。These photo-crosslinking agents may be used alone or in combination of two or more, and are used in an amount of 2 to 20 parts by weight based on 100 parts by weight of the partially saponified vinyl acetate polymer. preferable. If the photocrosslinking agent is less than 2 parts by weight, a cured resin having excellent water resistance cannot be obtained, and if it is used in excess of 20 parts by weight, the storage stability of the composition is lowered. Further, these photocrosslinking agents can be additionally added in order to provide a stronger photocured portion even when the partially saponified vinyl acetate polymer itself has a photocrosslinkable group in its side chain.
【００２５】上記の各成分から本発明の組成物を得るに
は、通常、次のような方法がとられる。すなわち、部分
ケン化酢酸ビニル重合体を所定量の水に溶解して水溶液
とする。エチレン系不飽和基を有する化合物を上記のケ
ン化重合体水溶液に添加し、ニーダーやスクリュー式攪
拌機等で攪拌して乳化させる。この乳化液と別途に、乳
化重合等により得られた疎水性重合体粒子および水溶性
光重合開始剤または有機溶剤に溶解した油溶性光重合開
始剤とを混合し、さらに必要に応じて着色剤、消泡剤等
の任意成分を添加し、攪拌、混合する。最後に、少量の
水に溶解した光架橋剤を添加して混合することにより、
本発明の組成物が得られる。In order to obtain the composition of the present invention from the above components, the following methods are usually used. That is, the partially saponified vinyl acetate polymer is dissolved in a predetermined amount of water to obtain an aqueous solution. A compound having an ethylenically unsaturated group is added to the above saponified polymer aqueous solution, and the mixture is stirred with a kneader or a screw stirrer to emulsify it. Separately from this emulsion, hydrophobic polymer particles obtained by emulsion polymerization and a water-soluble photopolymerization initiator or an oil-soluble photopolymerization initiator dissolved in an organic solvent are mixed, and if necessary, a colorant. , An antifoaming agent, etc. are added, and the mixture is stirred and mixed. Finally, by adding and mixing the photocrosslinking agent dissolved in a small amount of water,
A composition of the invention is obtained.
【００２６】なお、光架橋剤を予めケン化重合体水溶液
の調製段階で添加し、溶解させておくこともできるが、
光架橋剤を含む組成物は保存性が低下するので、組成物
の使用直前に光架橋剤を添加するのが好ましい。また、
光重合開始剤も、上記したように、予め感光性樹脂組成
物の調製段階で添加しておくこともできるが、光重合開
始剤のなかには保存安定性が低いものもあるため、組成
物の使用直前に光重合開始剤を添加することもできる。The photo-crosslinking agent may be added and dissolved in advance at the stage of preparing the saponified polymer aqueous solution.
Since the composition containing the photocrosslinking agent has low storage stability, it is preferable to add the photocrosslinking agent immediately before using the composition. Also,
As described above, the photopolymerization initiator can also be added in advance at the preparation stage of the photosensitive resin composition, but since some photopolymerization initiators have low storage stability, use of the composition A photopolymerization initiator may be added immediately before.
【００２７】[0027]
【実施例】以下、実施例により本発明をさらに説明す
る。 実施例１ 重合度１７００、ケン化度８８モル％の部分ケン化酢酸
ビニル重合体１４０ｇを水８６０ｇに溶解し、部分ケン
化酢酸ビニル重合体の水溶液を得た。部分ケン化酢酸ビ
ニル重合体（保護コロイドＰＶＡ）を保護コロイドとす
るポリ酢酸ビニルの水性エマルジョン（固形分：４０
％、固形分中の保護コロイドＰＶＡ量：１０％、保護コ
ロイドＰＶＡ：重合度１７００、ケン化度８８モル％）
２５０ｇに上記部分ケン化酢酸ビニル重合体水溶液１５
０ｇおよびエチレン系不飽和基を有する化合物としてオ
リゴエステルアクリレート「アロニックスＭ−６２０
０」（東亜合成化学（株）商標）４０ｇとトルメチロー
ルエタントリアクリレート２０ｇの混合物を攪拌しなが
ら加えて乳化させた（エチレン性不飽和基を有する化合
物分散滴の粒径１．５μ）。次いで、光重合開始剤とし
て２−（３−ジメチルアミノ−２−ヒドロキシプロポキ
シ）−３，４−ジメチル−９Ｈ−チオキサントン−９−
オンメソクロライドの１０％水溶液１８ｇおよび光架橋
剤として３−メトキシ−４−ジアゾジフエニルアミンと
４，４′−ビスメトキシメチルジフェニルエーテルとの
縮合物の硫酸塩の２０％水溶液１５ｇを前記乳化液に混
合して、感光性樹脂組成物からなる感光液を作製した。EXAMPLES The present invention will be further described below with reference to examples. Example 1 140 g of a partially saponified vinyl acetate polymer having a degree of polymerization of 1700 and a saponification degree of 88 mol% was dissolved in 860 g of water to obtain an aqueous solution of the partially saponified vinyl acetate polymer. Aqueous emulsion of polyvinyl acetate with a partially saponified vinyl acetate polymer (protective colloid PVA) as a protective colloid (solid content: 40
%, Amount of protective colloid PVA in solid content: 10%, protective colloid PVA: degree of polymerization 1700, degree of saponification 88 mol%)
250 g of the above partially saponified vinyl acetate polymer aqueous solution 15
As a compound having 0 g and an ethylenically unsaturated group, an oligoester acrylate “Aronix M-620” is used.
0 "(trademark of Toagosei Kagaku Co., Ltd.) and 20 g of trimethylolethane triacrylate were added with stirring to emulsify (particle size of compound dispersion droplet having ethylenically unsaturated group: 1.5 µ). Then, 2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone-9-as a photopolymerization initiator
18 g of a 10% aqueous solution of onmesochloride and 15 g of a 20% aqueous solution of a sulfate of a condensate of 3-methoxy-4-diazodiphenylamine and 4,4'-bismethoxymethyldiphenyl ether as a photocrosslinking agent were added to the emulsion. By mixing, a photosensitive liquid composed of the photosensitive resin composition was prepared.
【００２８】この感光液を２５０メッシュの黄色テトロ
ン紗上に塗工して、膜厚１５μの感光層を作製した。こ
のスクリーン感光版の感光層に８０μの細線を有するプ
リント配線用のポジフィルムを真空密着し、４kWの超高
圧水銀灯で１ｍの距離から２分間露光し、露光後水現像
して、プリント基板用の版を作製した。得られた版の解
像性は、ポジフィルムの８０μの細線を再現性良く解像
するものであった。また、この版を使用して５０００枚
の印刷を行ったところ、終始印刷再現性に変化はなく、
良好な結果が得られた。This photosensitive solution was coated on 250-mesh yellow tetron gauze to form a photosensitive layer having a film thickness of 15 μm. A positive film for printed wiring having a fine line of 80 μ is vacuum-contacted to the photosensitive layer of this screen photosensitive plate, exposed for 2 minutes from a distance of 1 m with a super-high pressure mercury lamp of 4 kW, and after exposure, water-developed to produce a printed circuit board. A plate was made. The resolution of the obtained plate was such that 80 .mu. Fine lines of the positive film could be resolved with good reproducibility. Also, when printing 5000 sheets using this plate, there was no change in printing reproducibility from beginning to end,
Good results have been obtained.
【００２９】比較例１ エチレン系不飽和基を有する化合物の分散滴の粒径が１
５μであったこと以外は実施例１と同一の条件下に感光
液を作製した。この感光液を用い、実施例１と同じ操作
により、塗工、露光および水現像を行ったところ、感光
層が水で膨潤してしまい、良好な画像を得ることができ
なかった。また、この版を用いて印刷を行ったところ、
数枚の印刷回数で画像膜が破壊されてしまった。Comparative Example 1 The particle size of dispersed droplets of a compound having an ethylenically unsaturated group was 1
A photosensitive solution was prepared under the same conditions as in Example 1 except that the thickness was 5 μm. When coating, exposure and water development were performed using this photosensitive solution by the same operations as in Example 1, the photosensitive layer was swollen with water and a good image could not be obtained. Also, when I printed using this plate,
The image film was destroyed after printing several times.
【００３０】これは、エチレン系不飽和基を有する化合
物分散滴の粒径が１５μと大きかったために、分散滴粒
子の中心部まで光重合が完了できなかったことによるも
のと考えられる。 実施例２ 光重合開始剤としてベンゾイルアルキルエーテルの２０
％エタノール溶液２０ｇを用いたことを除き、実施例１
に述べた操作を繰り返した。It is considered that this is because the particle diameter of the compound-dispersed droplet having an ethylenically unsaturated group was as large as 15 μm, so that the photopolymerization could not be completed up to the central portion of the dispersed-droplet particle. Example 2 20 of benzoyl alkyl ether as a photopolymerization initiator
Example 1 except that 20 g of a 10% ethanol solution was used.
The above-mentioned operation was repeated.
【００３１】実施例１と同様に良好な結果が得られた。 比較例２ エチレン系不飽和基を有する化合物の分散滴の粒径が１
５μであったこと以外は実施例２と同一の条件下に感光
液を作製した。この感光液を用い、実施例１と同じ操作
により、塗工、露光および水現像を行ったところ、比較
例１と同様の好ましくない結果が得られた。Good results were obtained in the same manner as in Example 1. Comparative Example 2 The particle size of dispersed droplets of a compound having an ethylenically unsaturated group is 1
A photosensitive solution was prepared under the same conditions as in Example 2 except that the thickness was 5 μm. Using this photosensitive solution, coating, exposure and water development were carried out by the same operations as in Example 1, and the same unfavorable results as in Comparative Example 1 were obtained.
【００３２】実施例３ 重合度１７００、ケン化度８８モル％の部分ケン化ポリ
酢酸ビニルにＮ−メチル−γ−（ｐ−ホルミルスチリ
ル）ピリジニウムメトキシ硫酸塩１．３モル％を付加縮
合させて得られたたスチルバゾリウム付加ポリマーの１
４％水溶液１５０ｇに、部分ケン化酢酸ビニル重合体
（保護コロイドＰＶＡ）を保護コロイドとするトルメチ
ロールプロパントリアクリレート重合体の水性エマルジ
ョン（固形分：４０％、固形分中の保護コロイドＰＶ
Ａ：５％、保護コロイドＰＶＡ：重合度１４００、ケン
化度８８モル％）２５０ｇおよびエチレン系不飽和基を
有する化合物としてオリゴエステルアクリレート「アロ
ニックスＭ−６２５０」（東亜合成化学（株）商標）２
０ｇとトルメチロールプロパントリアクリレート４０ｇ
の混合物を攪拌しながら加えて乳化させた（エチレン性
不飽和基を有する化合物分散滴の粒径０．５μ）。次い
で、光重合開始剤として（４−ベンゾイルベンジル）塩
化トルメチルアンモニウムの２０％水溶液１８ｇを前記
乳化液に混合して、感光性樹脂組成物からなる感光液を
作製した。Example 3 A partially saponified polyvinyl acetate having a degree of polymerization of 1700 and a degree of saponification of 88 mol% was subjected to addition condensation with 1.3 mol% of N-methyl-γ- (p-formylstyryl) pyridinium methoxysulfate. 1 of the obtained stilbazolium addition polymers
Aqueous emulsion of trimethylolpropane triacrylate polymer with partially saponified vinyl acetate polymer (protective colloid PVA) as protective colloid in 150 g of 4% aqueous solution (solid content: 40%, protective colloid PV in solid content
A: 5%, protective colloid PVA: polymerization degree 1400, saponification degree 88 mol%) 250 g and an oligoester acrylate “Aronix M-6250” (trademark of Toagosei Co., Ltd.) as a compound having an ethylenically unsaturated group 2
0g and 40g of trimethylolpropane triacrylate
The resulting mixture was added with stirring to emulsify (particle size of compound-dispersed droplets having an ethylenically unsaturated group: 0.5 μ). Next, 18 g of a 20% aqueous solution of (4-benzoylbenzyl) tolumethylammonium chloride as a photopolymerization initiator was mixed with the emulsion to prepare a photosensitive solution composed of a photosensitive resin composition.
【００３３】この感光液を用い、実施例１と同じ操作に
より、プリント基板用の版を作製した。得られた版の解
像性は、ポジフィルムの８０μの細線を再現性良く解像
するものであった。また、この版上の画像膜をｎ−メチ
ルピロリドンを浸み込ませた木綿布で往復１００回擦る
ことにより磨耗試験を行ったが、画像膜に損傷は認めら
れなかった。Using this photosensitive solution, a plate for a printed circuit board was prepared in the same manner as in Example 1. The resolution of the obtained plate was such that 80 .mu. Fine lines of the positive film could be resolved with good reproducibility. Further, an abrasion test was conducted by rubbing the image film on this plate with a cotton cloth impregnated with n-methylpyrrolidone 100 times back and forth, but no damage was observed in the image film.
【００３４】比較例３ オリゴエステルアクリレート「アロニックスＭ−６２５
０」２０ｇとトルメチロールプロパントリアクリレート
４０ｇの混合物に代えてベンゾイルアルキルエーテル４
ｇを相溶化させたオリゴエステルアクリレート「アロニ
ックスＭ−６２５０」２０ｇとトルメチロールプロパン
トリアクリレート４０ｇの混合物を用いたことを除き、
実施例３の操作を繰り返した（エチレン系不飽和基を有
する化合物分散滴の粒径０．５μ）。Comparative Example 3 Oligoester acrylate "Aronix M-625
0 "benzoyl alkyl ether 4 instead of a mixture of 20 g and trimethylolpropane triacrylate 40 g
except that a mixture of 20 g of an oligoester acrylate “Aronix M-6250” and 40 g of trimethylolpropane triacrylate in which g was compatibilized was used.
The procedure of Example 3 was repeated (particle size of the compound-dispersed droplet having an ethylenically unsaturated group: 0.5 μ).
【００３５】得られた版の解像性は、ポジフィルムの８
０μの細線を再現性良く解像するものであった。しか
し、版上の画像膜の磨耗試験では、画像膜が磨耗し、破
壊された。The resolution of the obtained plate was 8 for a positive film.
The fine line of 0 μ was resolved with good reproducibility. However, in the abrasion test of the image film on the plate, the image film was worn and destroyed.
【００３６】[0036]
【発明の効果】以上のとおり、本発明の感光性樹脂組成
物によれば、容易に調合することができ、使用に際して
保存安定性の問題が生じず、かつ、耐水性、耐溶剤性、
解像性および水現像性にすぐれた感光膜を得ることがで
きるという利点がある。As described above, according to the photosensitive resin composition of the present invention, the composition can be easily prepared, the problem of storage stability does not occur upon use, and the water resistance, solvent resistance, and
There is an advantage that a photosensitive film excellent in resolution and water developability can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松林 悟 栃木県宇都宮市平出工業団地27−２ 王子 化工株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoru Matsubayashi 27-2 Hiraide Industrial Park, Utsunomiya City, Tochigi Prefecture Oji Kako Co., Ltd.
Claims (4)
ル％の部分ケン化酢酸ビニル重合体との混合物の水溶液
および光架橋性基を有するケン化度７０〜９９モル％の
部分ケン化酢酸ビニル重合体の水溶液から選ばれる少な
くとも１種の水溶液からなる分散媒中に、この分散媒中
に分散された疎水性重合体粒子および水不溶性または水
難溶性で光活性なエチレン系不飽和基を有する化合物と
ともに、油溶性光重合開始剤および水溶性光重合開始剤
から選ばれる少なくとも１種の光重合開始剤とを含み、
前記エチレン系不飽和基を有する化合物と前記光重合開
始剤とが独立して存在することを特徴とする感光性樹脂
組成物。1. An aqueous solution of a mixture of a water-soluble photocrosslinking agent and a partially saponified vinyl acetate polymer having a saponification degree of 70 to 99 mol%, and a partial saponification having a photocrosslinkable group and having a saponification degree of 70 to 99 mol%. In a dispersion medium composed of at least one aqueous solution selected from an aqueous solution of a vinyl acetate polymer, hydrophobic polymer particles dispersed in the dispersion medium and a water-insoluble or sparingly water-soluble photoactive ethylenically unsaturated group Together with a compound having, at least one photopolymerization initiator selected from oil-soluble photopolymerization initiator and water-soluble photopolymerization initiator,
A photosensitive resin composition, wherein the compound having an ethylenically unsaturated group and the photopolymerization initiator are independently present.
が粒径１０μ以下の分散滴として存在する請求項１記載
の感光性樹脂組成物。2. The photosensitive resin composition according to claim 1, wherein the compound having an ethylenically unsaturated group is present as dispersed droplets having a particle size of 10 μm or less.
９９モル％の部分ケン化酢酸ビニル重合体の光架橋性基
がこの部分ケン化酢酸ビニル重合体の側鎖として存在す
るスチルバゾリウム基である請求項１または２記載の感
光性樹脂組成物。3. The degree of saponification having the photocrosslinkable group is from 70 to 70.
The photosensitive resin composition according to claim 1 or 2, wherein the photocrosslinkable group of 99 mol% of the partially saponified vinyl acetate polymer is a stilbazolium group present as a side chain of the partially saponified vinyl acetate polymer.
びジアゾ樹脂から選ばれる請求項１〜３のいずれかに記
載の感光性樹脂組成物。4. The photosensitive resin composition according to claim 1, wherein the water-soluble photocrosslinking agent is selected from a dichromate and a diazo resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP739295A JPH08202036A (en) | 1995-01-20 | 1995-01-20 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP739295A JPH08202036A (en) | 1995-01-20 | 1995-01-20 | Photosensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08202036A true JPH08202036A (en) | 1996-08-09 |
Family
ID=11664655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP739295A Pending JPH08202036A (en) | 1995-01-20 | 1995-01-20 | Photosensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08202036A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012215862A (en) * | 2011-03-26 | 2012-11-08 | Suntype Co Ltd | Photosensitive resin composition, photosensitive film and screen plate for screen printing |
| WO2014049882A1 (en) * | 2012-09-25 | 2014-04-03 | 株式会社サンタイプ | Photosensitive resin composition for screen printing, photosensitive film, and screen plate |
-
1995
- 1995-01-20 JP JP739295A patent/JPH08202036A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012215862A (en) * | 2011-03-26 | 2012-11-08 | Suntype Co Ltd | Photosensitive resin composition, photosensitive film and screen plate for screen printing |
| WO2014049882A1 (en) * | 2012-09-25 | 2014-04-03 | 株式会社サンタイプ | Photosensitive resin composition for screen printing, photosensitive film, and screen plate |
| US9588424B2 (en) | 2012-09-25 | 2017-03-07 | Suntype Co., Ltd. | Photosensitive resin composition for screen printing, photosensitive film, and screen plate |
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