JPS63280244A - Photosensitive resin composition - Google Patents
Photosensitive resin compositionInfo
- Publication number
- JPS63280244A JPS63280244A JP11567687A JP11567687A JPS63280244A JP S63280244 A JPS63280244 A JP S63280244A JP 11567687 A JP11567687 A JP 11567687A JP 11567687 A JP11567687 A JP 11567687A JP S63280244 A JPS63280244 A JP S63280244A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- photosensitive resin
- resin composition
- acid
- equiv
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims description 36
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- 229920003986 novolac Polymers 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 11
- 239000001294 propane Substances 0.000 claims abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- 238000007259 addition reaction Methods 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 27
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 22
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000013007 heat curing Methods 0.000 claims description 5
- 239000004843 novolac epoxy resin Substances 0.000 claims 1
- 229910000679 solder Inorganic materials 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000012948 isocyanate Substances 0.000 abstract description 10
- 150000002513 isocyanates Chemical class 0.000 abstract description 10
- 239000003063 flame retardant Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000011161 development Methods 0.000 description 9
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 8
- -1 Isocyanatoethyl Chemical group 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 7
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FEIQOMCWGDNMHM-KBXRYBNXSA-N (2e,4e)-5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)\C=C\C=C\C1=CC=CC=C1 FEIQOMCWGDNMHM-KBXRYBNXSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- CDUQMGQIHYISOP-RMKNXTFCSA-N (e)-2-cyano-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C\C1=CC=CC=C1 CDUQMGQIHYISOP-RMKNXTFCSA-N 0.000 description 1
- XHXSXTIIDBZEKB-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octamethylanthracene-9,10-dione Chemical compound CC1=C(C)C(C)=C2C(=O)C3=C(C)C(C)=C(C)C(C)=C3C(=O)C2=C1C XHXSXTIIDBZEKB-UHFFFAOYSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- HEXHLHNCJVXPNU-UHFFFAOYSA-N 2-(trimethoxysilylmethyl)butane-1,4-diamine Chemical compound CO[Si](OC)(OC)CC(CN)CCN HEXHLHNCJVXPNU-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- YJQMXVDKXSQCDI-UHFFFAOYSA-N 2-ethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3SC2=C1 YJQMXVDKXSQCDI-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- ZCJLOOJRNPHKAV-UHFFFAOYSA-N 3-(furan-2-yl)prop-2-enoic acid Chemical compound OC(=O)C=CC1=CC=CO1 ZCJLOOJRNPHKAV-UHFFFAOYSA-N 0.000 description 1
- JMLIYQBCNLVLNQ-UHFFFAOYSA-N 3-methylbutyl 2,3-dimethylbenzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC(C)=C1C JMLIYQBCNLVLNQ-UHFFFAOYSA-N 0.000 description 1
- ARXVXVOLXMVYIT-UHFFFAOYSA-N 3-methylbutyl 2-(dimethylamino)benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1N(C)C ARXVXVOLXMVYIT-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- LHMRXAIRPKSGDE-UHFFFAOYSA-N benzo[a]anthracene-7,12-dione Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)C1=CC=CC=C1C2=O LHMRXAIRPKSGDE-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- BGTFCAQCKWKTRL-YDEUACAXSA-N chembl1095986 Chemical compound C1[C@@H](N)[C@@H](O)[C@H](C)O[C@H]1O[C@@H]([C@H]1C(N[C@H](C2=CC(O)=CC(O[C@@H]3[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O)=C2C=2C(O)=CC=C(C=2)[C@@H](NC(=O)[C@@H]2NC(=O)[C@@H]3C=4C=C(C(=C(O)C=4)C)OC=4C(O)=CC=C(C=4)[C@@H](N)C(=O)N[C@@H](C(=O)N3)[C@H](O)C=3C=CC(O4)=CC=3)C(=O)N1)C(O)=O)=O)C(C=C1)=CC=C1OC1=C(O[C@@H]3[C@H]([C@H](O)[C@@H](O)[C@H](CO[C@@H]5[C@H]([C@@H](O)[C@H](O)[C@@H](C)O5)O)O3)O[C@@H]3[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O[C@@H]3[C@H]([C@H](O)[C@@H](CO)O3)O)C4=CC2=C1 BGTFCAQCKWKTRL-YDEUACAXSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ORBFAMHUKZLWSD-UHFFFAOYSA-N ethyl 2-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(C)C ORBFAMHUKZLWSD-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、印刷配線板製造、金属精密加工等に使用され
る保護膜形成用の感光性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photosensitive resin composition for forming a protective film used in printed wiring board manufacturing, metal precision processing, and the like.
(従来の技術)
従来、印刷配線板業界において、ソルダマスク、化学メ
ッキ用レジスト等に使用可能な、優れた特性を有する感
光性樹脂組成物が知られている。(Prior Art) Photosensitive resin compositions having excellent properties that can be used as solder masks, resists for chemical plating, etc. are known in the printed wiring board industry.
ソルダマスクの主な目的は、ハンダ付は時のハンダ付は
領域を限定し、ハンダブリッジ等を防ぐこと、裸の銅導
体の腐蝕を防止すること、及び長期にわたって導体間の
電気絶縁性を保持することである。The main purpose of a solder mask is to limit the area during soldering and prevent solder bridging, etc., to prevent corrosion of bare copper conductors, and to maintain electrical insulation between conductors over a long period of time. That's true.
ところで、通常ソルダマスクとしては、エポキシ樹脂、
アミノプラスト樹脂等の熱硬化性樹脂を主成分とするも
の(印刷マスク)が用いられる。By the way, solder masks are usually made of epoxy resin,
A mask whose main component is a thermosetting resin such as aminoplast resin (printed mask) is used.
しかし、近年、印刷配線板の配線密度が高まり、また導
体間の電気絶縁性の要求も厳しくなり、それらに用いる
ソルダマスクも厚膜で、寸法精度の優れたものが要求さ
れるようになり、スクリーン印刷方式のものでは対処で
きなくなっている。However, in recent years, the wiring density of printed wiring boards has increased, and the requirements for electrical insulation between conductors have also become stricter, and the solder masks used for them are also required to be thick and have excellent dimensional accuracy. Printing methods are no longer able to cope with this problem.
そこで、写真法(像状露光に続く現像により画像を形成
)で厚膜(通常導体上25μmが望まれている)で、か
つ寸法精度の優れた高信頼性のソルダマスクを形成する
感光性樹脂組成物の出現が望まれている。Therefore, a photosensitive resin composition that forms a thick film (usually 25 μm on a conductor is desired) and a highly reliable solder mask with excellent dimensional accuracy using a photographic method (image formation by imagewise exposure followed by development). The appearance of things is desired.
従来、ソルダマスク形成用感光性樹脂組成物としては、
(1)アクリル系ポリマ及び光重合性モノマを主成分と
する感光性樹脂組成物(特開昭53−5′6018号公
報、特開昭54−1018号公報等)、(2)光反応性
が付与されたエポキシ樹脂及びエポキシ樹脂硬化剤を主
成分とする感光性樹脂組成物(特開昭52−37996
号公報、特開昭58−62636号公報等)、
(3)イソシアナートエチルメタクリレート変性感光性
樹脂組成物(特開昭61−132947号公報)等が知
られている。Conventionally, as photosensitive resin compositions for forming solder masks, (1) photosensitive resin compositions containing an acrylic polymer and a photopolymerizable monomer as main components (JP-A-53-5'6018, JP-A-54 -1018, etc.), (2) A photosensitive resin composition containing as main components an epoxy resin imparted with photoreactivity and an epoxy resin curing agent (Japanese Patent Laid-Open No. 52-37996)
(3) Isocyanatoethyl methacrylate-modified photosensitive resin composition (Japanese Patent Application Laid-open No. 61-132947), etc. are known.
しかしながら、前記(1)の感光性樹脂組成物は、通常
のエツチング及びメッキ用フィルム状感光材料(例えば
デュポン社製、商品名リストン、日立化成工業■製、商
品名フオテック等)に使用されている難燃性の1.1.
1−トリクロルエタンで現像可能であり、高解像度のソ
ルダマスクを形成することはできるが、このような感光
性樹脂組成物はフィルム性付与のため、アクリル系ポリ
マを多量に使用するので、硬化被膜の耐熱性が充分でな
いという欠点がある。However, the photosensitive resin composition of (1) above is used in ordinary film photosensitive materials for etching and plating (for example, manufactured by DuPont, trade name Riston, manufactured by Hitachi Chemical Co., Ltd., trade name Photec, etc.). Flame retardant 1.1.
Although it can be developed with 1-trichloroethane and can form a high-resolution solder mask, such photosensitive resin compositions use a large amount of acrylic polymer to impart film properties, so the hardening of the cured film is difficult. It has the disadvantage of not having sufficient heat resistance.
また、前記(2)の感光性樹脂組成物は、エポキシ樹脂
をベースとしており、硬化被膜の耐熱性には優れている
が、1.’l、1−トリクロルエタン等の難燃性有機溶
剤に不溶性であるため、現像液としてシクロヘキサノン
等の可燃性有機溶剤を使用する必要があり、安全上好ま
しくないという欠点がある。Further, the photosensitive resin composition (2) above is based on an epoxy resin and has excellent heat resistance of the cured film, but 1. Since it is insoluble in flame-retardant organic solvents such as 1,1-trichloroethane, it is necessary to use a flammable organic solvent such as cyclohexanone as a developer, which is disadvantageous in terms of safety.
更に、前記(3)の感光性樹脂組成物は、1゜1.1−
トリクロルエタン等の現像液で現像でき、かつ解像度、
耐熱性にも優れ、特開昭58−62636号公報で示さ
れているタルクを主体とした充填剤を混合すると、印刷
配線板と硬化被膜との粘着力を向上させ、高信頼性のソ
ルダマスクを形成するが、現像のダメージによって被膜
表面に光沢がないという欠点がある。このため、電子部
品等の最終製品に使用されるまでに外的要因ですりきず
を生じ、ソルダマスクとしての価値を損うという問題点
がある。 ・
(発明の目的)
本発明は、上記問題点に鑑み、1.1.1−トリクロル
エタン等の、難燃性現像液により現像でき、かつ解像度
、耐熱性及び表面光沢性に優れた、信頼度の高いソルダ
マスクを形成することのできる感光性樹脂組成物を提供
することを目的とする。Furthermore, the photosensitive resin composition of (3) above has a 1°1.1-
Can be developed with a developer such as trichloroethane, and has high resolution and
It also has excellent heat resistance, and when mixed with a filler mainly consisting of talc as disclosed in JP-A No. 58-62636, it improves the adhesion between the printed wiring board and the cured film, making it possible to create a highly reliable solder mask. However, the drawback is that the surface of the film lacks gloss due to damage during development. For this reason, there is a problem that scratches occur due to external factors before being used in final products such as electronic components, which impairs its value as a solder mask. (Objective of the Invention) In view of the above-mentioned problems, the present invention has been developed to provide a reliable and reliable product that can be developed with a flame-retardant developer such as 1.1.1-trichloroethane and has excellent resolution, heat resistance, and surface gloss. An object of the present invention is to provide a photosensitive resin composition that can form a high-quality solder mask.
(問題点を解決するための手段)
本発明は、オルソクレゾールノボラック型エポキシ樹脂
、フェノールノボラック型エポキシ樹脂及びハロゲン化
フェノールノボラック型エポキシ樹脂からなる群より選
ばれる1種または2種以上のノボラック型エポキシ樹脂
と不飽和カルボン酸とを、酸当量/エポキシ当量比が0
.1〜0.98の範囲で付加反応させて得られる不飽和
化合物の2級水酸基に、イソシアナートエチルメタクリ
レートをイソシアナート当量/水酸基当量比が0゜1〜
1.2の範囲で反応させて得られる光重合性不飽和化合
物100重量部、
(b)2−メチル−[4−(メチルチオ)フェニルコー
2−モルフォリノ−1−プロパン2〜15重量部、
(c)微粒状充填剤20〜100重量部および(d)加
熱硬化剤1〜10重量部
を含有してなる感光性樹脂組成物に関する。(Means for Solving the Problems) The present invention provides one or more novolac-type epoxy resins selected from the group consisting of orthocresol novolac-type epoxy resins, phenol novolac-type epoxy resins, and halogenated phenol novolak-type epoxy resins. The resin and the unsaturated carboxylic acid have an acid equivalent/epoxy equivalent ratio of 0.
.. Isocyanate ethyl methacrylate is added to the secondary hydroxyl group of an unsaturated compound obtained by addition reaction in the range of 1 to 0.98, and the isocyanate equivalent/hydroxyl group equivalent ratio is 0°1 to 0.98.
(b) 2-15 parts by weight of 2-methyl-[4-(methylthio)phenyl-2-morpholino-1-propane, ( c) A photosensitive resin composition comprising 20 to 100 parts by weight of a particulate filler and (d) 1 to 10 parts by weight of a heat curing agent.
本発明になる感光性樹脂組成物は、必須成分(a)とし
て、オルソクレゾールノボラック型エポキシ樹脂、フェ
ノールノボラック型エポキシ樹脂及びハロゲン化フェノ
ールノボラック型エポキシ樹脂からなる群より選ばれる
1種または2種以上のノボラック型エポキシ樹脂と不飽
和カルボン酸とを、酸当量/エポキシ当量比を、0.1
〜0゜98の範囲として付加反応させて得られる不飽和
化合物の2級水酸基に、イソシアナートエチルメタクリ
レートをイソシアナート当量/水酸基当量比を0.1〜
1.2の範囲として反応させて得られる光重合性不飽和
化合物を含有する。The photosensitive resin composition of the present invention has one or more types selected from the group consisting of orthocresol novolac type epoxy resin, phenol novolac type epoxy resin, and halogenated phenol novolac type epoxy resin as essential component (a). of novolak type epoxy resin and unsaturated carboxylic acid, the acid equivalent/epoxy equivalent ratio is 0.1
The isocyanate ethyl methacrylate is added to the secondary hydroxyl group of the unsaturated compound obtained by addition reaction in the range of 0.98 to 0.98 to an isocyanate equivalent/hydroxyl group equivalent ratio of 0.1 to 0.98.
Contains a photopolymerizable unsaturated compound obtained by reaction as a range of 1.2.
本発明に用いられるノボラック型エポキシ樹脂は、例え
ばオルソクレゾール、フェノール、ハロゲン化フェノー
ル等とアルデヒドを、酸触媒の存在下に反応させて得ら
れるノボラック型樹脂のフェノール性水酸基に、アルカ
リの存在下に、エピクロルヒドリンを反応させて得られ
るもので、商業的にも入手可能である。The novolak-type epoxy resin used in the present invention is obtained by reacting, for example, orthocresol, phenol, halogenated phenol, etc. with an aldehyde in the presence of an acid catalyst. It is obtained by reacting epichlorohydrin and is commercially available.
オルソクレゾールノボラック型エポキシ樹脂としては、
例えばヂバ・ガイギー社製、アラルダイトEcN129
9 (軟化点99℃、エポキシ当量230>、ECN1
280 (軟化点80℃、エポキシ当量230>、EC
N1273 (軟化点73℃、エポキシ当@230)
、日本生薬■製、EOCN104(軟化点90〜100
℃、エポキシ当量225〜245)、ECN123 (
軟化点80〜90℃、エポキシ当量215〜235>、
ECN127
量215〜235>、EOCNlol (軟化点65〜
69℃、エポキシ当量205〜225)等が挙げられる
。Orthocresol novolac type epoxy resins include:
For example, Araldite EcN129 manufactured by Ziba Geigy.
9 (softening point 99°C, epoxy equivalent 230>, ECN1
280 (softening point 80°C, epoxy equivalent 230>, EC
N1273 (softening point 73℃, epoxy weight @230)
, made by Nippon Herbal Medicine ■, EOCN104 (softening point 90-100
°C, epoxy equivalent 225-245), ECN123 (
Softening point 80-90°C, epoxy equivalent 215-235>,
ECN127 amount 215~235>, EOCNlol (softening point 65~
69°C, epoxy equivalent: 205 to 225).
フェノールノボラック型エポキシ樹脂としては、例えば
シェル社製、エピコート154(エポキシ当量176〜
181)、ダウケミカル社製、DEN431 (エポキ
シ当量172〜179)、DEN438 (エポキシ当
量175〜1B2>、東部化成■製、YDPN−638
(エポキシ当@170〜190)、YDPN−601(
エポキシ当量180〜220>、YDPN−602(エ
ポキシ当量180〜220)等が挙げられる。As the phenol novolak type epoxy resin, for example, Epikote 154 (epoxy equivalent: 176 to
181), manufactured by Dow Chemical Company, DEN431 (epoxy equivalent: 172-179), DEN438 (epoxy equivalent: 175-1B2>, manufactured by Tobu Kasei ■, YDPN-638)
(Epoxy @ 170-190), YDPN-601 (
Epoxy equivalent: 180-220>, YDPN-602 (epoxy equivalent: 180-220), and the like.
ハロゲン化フェノールノボラック型エポキシ樹脂として
は、例えば日本生薬■’74. BREN (エポキシ
当量270〜300.臭素含有量35〜37%、軟化点
80〜90℃)等の臭素化フェノールノボラック型エポ
キシ樹脂等が挙げられる。Examples of the halogenated phenol novolac type epoxy resin include Nippon Herbal Pharmaceutical ■'74. Examples include brominated phenol novolak type epoxy resins such as BREN (epoxy equivalent: 270-300, bromine content: 35-37%, softening point: 80-90°C).
また不飽和カルボン酸としては、アクリル酸、メタクリ
ル酸、β−フリルアクリル酸、β−スチリルアクリル酸
、α−シアノケイ皮酸、ケイ皮酸等が用いられる。Further, as the unsaturated carboxylic acid, acrylic acid, methacrylic acid, β-furylacrylic acid, β-styrylacrylic acid, α-cyanocinnamic acid, cinnamic acid, etc. are used.
本発明においてこれらのノボラック型エポキシ樹脂と不
飽和カルボン酸との付加反応は、常法により式(1)に
示すように、酸当量/エポキシ当量比を0.1〜0.9
8の範囲として行なわれる。In the present invention, the addition reaction between these novolak-type epoxy resins and unsaturated carboxylic acids is carried out by a conventional method at an acid equivalent/epoxy equivalent ratio of 0.1 to 0.9 as shown in formula (1).
This is done as a range of 8.
酸当量/エポキシ当量比が0.1未満ではイメージ露光
後の現像処理により、光硬化被膜が膨潤し易い。酸当量
/エポキシ当量比が0.98を越える場合には、密着性
、耐熱性等が低下する。When the acid equivalent/epoxy equivalent ratio is less than 0.1, the photocured film is likely to swell during development treatment after image exposure. If the acid equivalent/epoxy equivalent ratio exceeds 0.98, adhesiveness, heat resistance, etc. will decrease.
例えば、上記ノボラック型エポキシ樹脂をメチルエチル
ケトン、メチルセロソルブアセテート、エチルセロソル
ブアセテート、シクロヘキサノン等の不活性有機溶剤に
溶解し、触媒としてトリエチルアミン、トリーn−ブチ
ルアミン、ジエチルシクロヘキシルアミン等の3級アミ
ン、塩化ベンジルトリメチルアンモニウム、塩化ベンジ
ルトリエチルアンモニウム等の4級アンモニウム塩等を
、また重合禁止剤としてハイドロキノン、p−メトキシ
フェノール等を用い、70〜110℃で前記不飽和カル
ボン酸と、上記の当量比の範囲で攪拌反応させることに
より、不飽和化合物が得られる。For example, the above novolac type epoxy resin is dissolved in an inert organic solvent such as methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanone, etc., and a tertiary amine such as triethylamine, tri-n-butylamine, diethylcyclohexylamine, benzyltrimethyl chloride, etc. is used as a catalyst. Using a quaternary ammonium salt such as ammonium, benzyltriethylammonium chloride, etc., and hydroquinone, p-methoxyphenol, etc. as a polymerization inhibitor, the unsaturated carboxylic acid is stirred at 70 to 110°C in the equivalent ratio range mentioned above. By reacting, an unsaturated compound is obtained.
上記のように、ノボラック型エポキシ樹脂を不飽和カル
ボン酸と付加反応させて得られる不飽和化合物の2級水
酸基に対するイソシアナートエチルメタクリレートの反
応は常法により式(2)に示すように、イソシアナート
当量/水酸基当量比を0.1〜1.2の範囲として行な
われる。As mentioned above, the reaction of isocyanate ethyl methacrylate with the secondary hydroxyl group of the unsaturated compound obtained by addition reaction of novolak type epoxy resin with unsaturated carboxylic acid is carried out by a conventional method as shown in formula (2). This is carried out with the equivalent/hydroxyl group equivalent ratio in the range of 0.1 to 1.2.
イソシアナート当量/水酸基当量比が、0.1未満の場
合には、1,1.1−トリクロルエタン等の難燃性有機
溶剤による現像が困難となり、また光硬化性も低下する
。イソシアナート当量/水酸基当量比が1,2を越える
場合には、反応時にゲル化し易くなり、また耐熱性等の
特性も低下する。反応後、メタノール、エタノール、2
−ヒドロキシエチルメタクリレート等の1級アルコール
を用いて、残存するイソシアナートエチルメタクリレー
トをウレタン化し、失活させることが安全上及び保存安
定性向上の上で望ましい。イソシアナートエチルメタク
リレートとしては、例えばダウケミカル社製のものが用
いられる。When the isocyanate equivalent/hydroxyl equivalent ratio is less than 0.1, development with a flame-retardant organic solvent such as 1,1,1-trichloroethane becomes difficult, and photocurability also decreases. When the isocyanate equivalent/hydroxyl group equivalent ratio exceeds 1.2, gelation tends to occur during the reaction, and properties such as heat resistance also deteriorate. After reaction, methanol, ethanol, 2
- It is desirable for safety and to improve storage stability to urethanize and deactivate the remaining isocyanatoethyl methacrylate using a primary alcohol such as hydroxyethyl methacrylate. As the isocyanate ethyl methacrylate, for example, one manufactured by Dow Chemical Company is used.
例えば、前記のノボラック型エポキシ樹脂と不飽和カル
ボン酸との付加反応を行ない、次いでこの生成物にジブ
チルチンジラウレート、ジブチルデンジ2エチルヘキソ
エート等のウレタン化触媒を添加し上記の当量比の範囲
で、イソシアナートエチルメタクリレートを50〜11
0℃で贋拌反応させることにより、光重合性不飽和化合
物が得られる。このような反応条件下では、ウレタン結
合とエポキシ基との反応、不飽和結合の熱重合等の副反
応を防止することができ、その結果ゲル状物を生成させ
ることなく、光重合性不飽和化合物を得ることができる
。For example, an addition reaction is carried out between the above-mentioned novolac type epoxy resin and an unsaturated carboxylic acid, and then a urethanization catalyst such as dibutyltin dilaurate or dibutyldendi-2-ethylhexoate is added to the product to maintain the equivalent ratio within the above range. So, isocyanate ethyl methacrylate is 50 to 11
A photopolymerizable unsaturated compound is obtained by carrying out a stirring reaction at 0°C. Under such reaction conditions, side reactions such as the reaction between urethane bonds and epoxy groups and thermal polymerization of unsaturated bonds can be prevented, and as a result, photopolymerizable unsaturated compound can be obtained.
本発明において、特に好ましい光重合性不飽和化合物と
しては、オルソクレゾールノボラック型エポキシ樹脂/
アクリル酸/イソシアナートエチルメタクリレート系反
応物(酸当量/エポキシ当量比0.1〜0.98、イソ
シアナート当量/水酸基当量比0.1〜1.2)
オルソクレゾールノボラック型エポキシ樹脂/メタクリ
ル酸/イソシアナートエチルメタクリレート系反応物(
酸当量/エポキシ当量比0.1〜0.98、イソシアナ
ート当@/水酸基当量比0゜1〜1.2)等が挙げられ
る。In the present invention, particularly preferred photopolymerizable unsaturated compounds include orthocresol novolac type epoxy resin/
Acrylic acid/isocyanatoethyl methacrylate-based reactant (acid equivalent/epoxy equivalent ratio 0.1-0.98, isocyanate equivalent/hydroxyl group equivalent ratio 0.1-1.2) Orthocresol novolac type epoxy resin/methacrylic acid/ Isocyanatoethyl methacrylate-based reactant (
Acid equivalent/epoxy equivalent ratio of 0.1 to 0.98, isocyanate equivalent/hydroxyl equivalent ratio of 0.1 to 1.2), and the like.
次に本発明になる感光性樹脂組成物は必須成分(b)と
して、次式(3)で表わされる2−メチル−[4−(メ
チルチオ)フェニル]−2−モルフォリノ−1−プロパ
ン
を光重合開始剤として含有する。Next, the photosensitive resin composition of the present invention has 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane represented by the following formula (3) as an essential component (b), which is photopolymerized. Contains as an initiator.
2−メチル−[4−(メチルチオ)フェニル]−2−モ
ルフォリノ−1−プロパンとしては、例えばチバ・ガイ
ギー社製IRGACURE907が挙げられる。Examples of 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane include IRGACURE 907 manufactured by Ciba Geigy.
本発明に用いられる必須成分(b)は、単独で使用して
もよいが、置換または非置換の多核キノン類、例えば、
2−エチルアントラキノン、2−t−ブチルアントラキ
ノン、オクタメチルアントラキノン、1,2−ベンズア
ントラキノン、2゜3−ジフェニルアントラキノン等、
ジアセチルベンジル等のケトアルドニル化合物、ベンゾ
イン。The essential component (b) used in the present invention may be used alone, but may include substituted or unsubstituted polynuclear quinones, such as
2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2゜3-diphenylanthraquinone, etc.
Ketoaldonyl compounds such as diacetylbenzyl, benzoin.
ピロン等のα−ケトアルドニルアルコール類及びエーテ
ル類、α−炭化水素置換芳香族アシロイン類、例えばα
−フェニル−ベンゾイン、α、α−ジェトキシアセトフ
ェノン等、ベンゾフェノン、4.4′−ビスジアルキル
アミノベンゾフェノン等の芳香族ケトン類、2メチルチ
オキサントン、2.4−ジエチルチオキサントン、2−
り田しチオキサントン、2−イソプロピルチオキサント
ン、2−エチルチオキサントン等のチオキサントン類の
増感剤の1種または2種以上と併用してもよい。α-ketoaldonyl alcohols and ethers such as pyrone, α-hydrocarbon-substituted aromatic acyloins, e.g.
-Phenyl-benzoin, α,α-jethoxyacetophenone, etc., benzophenone, aromatic ketones such as 4,4'-bisdialkylaminobenzophenone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2-
It may be used in combination with one or more thioxanthone sensitizers such as thioxanthone, 2-isopropylthioxanthone, and 2-ethylthioxanthone.
また、それ自体で光開始性はないが、前記物質と組合せ
て用いることにより、全体として光開始性能のより良好
な増感剤系となるような添加剤、例えば、ベンゾフェノ
ンに対するトリエタノールアミン等の3級アミン、チオ
キサントン類に対するジメチルアミノ安息香酸イソアミ
ル、N−メチルジエタールアミン、ごスエチルアミノベ
ンゾフエノン等を用いることもできる。In addition, additives which do not have photoinitiating properties by themselves but which, when used in combination with the above substances, result in a sensitizer system with better photoinitiating performance as a whole, such as triethanolamine for benzophenone, etc. Tertiary amines, isoamyl dimethylaminobenzoate for thioxanthone, N-methyldietalamine, suethylaminobenzophenone, etc. can also be used.
次に本発明の感光性樹脂組成物は、必須成分(c)とし
て微粒状充填剤を含有する。Next, the photosensitive resin composition of the present invention contains a fine particulate filler as an essential component (c).
微粒状充填剤としては、例えばタルク、シリカ、酸化チ
タン、クレイ、炭酸カルシウム、含水珪酸、水酸化アル
ミニウム、アルミナ、硫酸バリウム、三酸化アンチモン
、炭酸マグネシウム、マイカ粉、珪酸アルミニウム、珪
酸マグネシウム等が用いられる。As the particulate filler, for example, talc, silica, titanium oxide, clay, calcium carbonate, hydrated silicic acid, aluminum hydroxide, alumina, barium sulfate, antimony trioxide, magnesium carbonate, mica powder, aluminum silicate, magnesium silicate, etc. are used. It will be done.
微粒状充填剤の粒径は、解像度、硬化被膜の密着性等の
低下防止の点から、好ましくは0.01〜10μm1よ
り好ましくは0.01〜1.5μmである。微粒状充填
剤は感光性樹脂組成物中に均一に分散されていることが
好ましい。The particle size of the particulate filler is preferably 0.01 to 10 μm, more preferably 0.01 to 1.5 μm, from the viewpoint of preventing deterioration of resolution, adhesion of the cured film, and the like. It is preferable that the particulate filler is uniformly dispersed in the photosensitive resin composition.
また、充填剤と前記光重合性不飽和化合物との間の接着
力を増すために、充填剤の表面を水@基、アミン基、エ
ポキシ基、ビニル基等の官能基を有するシランカップリ
ング剤で処理することもできる。シランカップリング剤
としては、例えばγ−アミノプロピルトリエトキシシラ
ン、β−アミノエチル−γ−アミノプロピルトリメトキ
シシラン、γ−グリシドオキシプロピルトリメトキシシ
ラン、γ−メタアクリロキシプロピルトリメトキシシラ
ン等が挙げられる。In addition, in order to increase the adhesive strength between the filler and the photopolymerizable unsaturated compound, the surface of the filler is coated with a silane coupling agent having a functional group such as a water group, an amine group, an epoxy group, or a vinyl group. It can also be processed with Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Can be mentioned.
また本発明の感光性樹脂組成物は必須成分(d)として
加熱硬化剤を含有する。Further, the photosensitive resin composition of the present invention contains a heat curing agent as an essential component (d).
加熱硬化剤の例として、例えばジシアンジアミド、三フ
ッ化ホウ素モノエチルアミンコンブツクス、2−メチル
イミダゾール、2−ヘプタデシルイミダゾール、1−ベ
ンジル−2−メチルイミダゾール、1−シアノエチル−
2−フェニルイミダゾール、1−シアノエチル−2−メ
チルイミダゾールトリメリテート、1−シアノエチル−
2−ウンデシルイミダゾールトリメリテート、2.4−
ジアミノ−6−[2′−メチル−イミダゾール−(1)
”]−]エチルー1.3.5−トリアジン2.4−ジア
ミノ−6−[2”−エチル−4′メチルイミダゾリル−
(1)1−エチル−1,3゜5−トリアジン、2,4−
ジアミノ−6−[2”−ウンデシルーイミダゾリルー(
1)”]−]エチルー1.3.5−トリアジンの潜在性
硬化剤が好ましい。Examples of heat curing agents include dicyandiamide, boron trifluoride monoethylamine combination, 2-methylimidazole, 2-heptadecyl imidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-
2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-
2-Undecyl imidazole trimellitate, 2.4-
Diamino-6-[2'-methyl-imidazole-(1)
”]-]ethyl-1.3.5-triazine2.4-diamino-6-[2”-ethyl-4'methylimidazolyl-
(1) 1-ethyl-1,3゜5-triazine, 2,4-
Diamino-6-[2”-undecyl imidazolyl (
1)'']-]ethyl-1.3.5-triazine latent curing agent is preferred.
本発明になる感光性樹脂組成物においては、光重合性不
飽和化合物(a)100重量部に対して、2−メチル−
[4−(メチルチオ)フェニル]−2−モルフtリノー
1−プロパン(b)を2〜15重量部、微粒状充填剤(
c)を20〜100重量部および加熱硬化剤(d)を1
〜10重量部の範囲で用いられる。In the photosensitive resin composition of the present invention, 2-methyl-
2 to 15 parts by weight of [4-(methylthio)phenyl]-2-morph t-lino-1-propane (b), a fine particulate filler (
20 to 100 parts by weight of c) and 1 part of heat curing agent (d)
It is used in a range of 10 parts by weight.
本発明において、成分(a>(c)および(d)は2種
以上を併用してもよい。成分(b)が2重量部未満では
光硬化性に劣り、15重量部を越えると表面の硬化が速
すぎて内部が硬化しにくくなる。成分(c)が20重量
部未満では硬化収縮の際の残留歪が大でクラック、はが
れを生じやすく、100重量部を越えると現像後その粒
子が表面に露出しやすくなり、耐水性、光沢が劣る。成
分(cI)はエポキシ基の反応性、耐溶剤性、および現
像残りの点から1〜10重量部゛の範囲とされる。In the present invention, two or more of the components (a>(c) and (d)) may be used in combination. If the component (b) is less than 2 parts by weight, the photocurability will be poor, and if it exceeds 15 parts by weight, the surface Curing is too fast, making it difficult to harden the inside. If component (c) is less than 20 parts by weight, the residual strain during curing shrinkage is large and cracks and peeling are likely to occur. If it exceeds 100 parts by weight, the particles will be difficult to harden after development. The amount of component (cI) is set in the range of 1 to 10 parts by weight in view of the reactivity of the epoxy group, solvent resistance, and development residue.
また、本発明になる感光性樹脂組成物は他の光重合性化
合物を含有してもよい。Moreover, the photosensitive resin composition of the present invention may contain other photopolymerizable compounds.
他の光重合性化合物としては、例えばトリメチロールプ
ロパントリアクリレート、ペンタエリスリトールトリア
クリレート、トリメチルへキサメチレンジイソシアナー
ト/2−ヒドロキシエチルアクリレート(1/2モル比
)反応物、イソシアナートエチルメタクリレート/水(
2/1モル比)反応物等が挙げられる。また、特開昭5
3−56018号公報に示される光重合性化合物を用い
ることもできる。しかし、これらの他の光重合性化合物
の含有量は耐熱性の保持上から、光重合性不飽和化合物
(a)に対して10重量%以下とすることが好ましい。Other photopolymerizable compounds include, for example, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylhexamethylene diisocyanate/2-hydroxyethyl acrylate (1/2 molar ratio) reaction product, isocyanate ethyl methacrylate/water (
2/1 molar ratio) reactants, etc. Also, JP-A-5
Photopolymerizable compounds shown in JP 3-56018 can also be used. However, from the viewpoint of maintaining heat resistance, the content of these other photopolymerizable compounds is preferably 10% by weight or less based on the photopolymerizable unsaturated compound (a).
更に本発明の感光性樹脂組成物は他の副次的成分を含有
していてもよい。副次的成分としては、高分子結合剤、
熱重合防止剤、染料、顔料、塗工性向上剤、消泡剤、難
燃剤、密着性向上剤等が挙げられる。Furthermore, the photosensitive resin composition of the present invention may contain other subsidiary components. Secondary components include polymer binders,
Examples include thermal polymerization inhibitors, dyes, pigments, coatability improvers, antifoaming agents, flame retardants, and adhesion improvers.
本発明の感光性樹脂組成物はディップコート法、70−
コート法、スクリーン印刷法等の常法により加工保護す
べき基板上に直接塗工し、厚さ10〜150μmの感光
層を容易に形成することができる。塗工にあたり必要な
らば組成物を溶剤に溶解させて行なうこともできる。溶
剤としては、例えばメチルエチルケトン、メチルセロソ
ルブアセテート、エチルセロソルブアセテート、シクロ
ヘキサノン、メチルセロソルブ、塩化メチレン、1゜1
.1−トリクロルエタン等を挙げることができる。The photosensitive resin composition of the present invention can be prepared by dip coating, 70-
A photosensitive layer having a thickness of 10 to 150 μm can be easily formed by directly coating the substrate to be processed and protected by a conventional method such as a coating method or a screen printing method. When coating, if necessary, the composition can be dissolved in a solvent. Examples of the solvent include methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanone, methyl cellosolve, methylene chloride, 1.1
.. Examples include 1-trichloroethane.
またこの溶液を例えばポリエチレンテレフタレートフィ
ルム、ポリイミドフィルム等のフィルム上に、ナイフコ
ート法、ロールコート法等により塗布し、乾燥して得ら
れる感光性エレメントを熱ロールを用いて基板上に加熱
加圧積層して感光層を形成することもできる。この際基
板が導体配線ラインの形成された印刷配線板等の10μ
m以上の凹凸を有する場合には、空気の巻き込みを防ぐ
ため、200mm1−1g以下の真空下で積層すること
が好ましい。このための装置としては、例えば特公昭5
5−13341号公報に記載される積層装置が用いられ
る。なお活性光に不透明な支持体フィルムを用いる場合
には、露光時に支持体フィルムを剥離する必要がある。In addition, this solution is applied onto a film such as a polyethylene terephthalate film or a polyimide film by a knife coating method or a roll coating method, and the photosensitive element obtained by drying is laminated by heating and pressure on a substrate using a hot roll. It is also possible to form a photosensitive layer. At this time, the board is a printed wiring board etc. with conductor wiring lines formed on it.
In the case of having irregularities of m or more, it is preferable to laminate under a vacuum of 200 mm 1-1 g or less in order to prevent air from being entrained. As a device for this purpose, for example,
A laminating apparatus described in Japanese Patent No. 5-13341 is used. In addition, when using a support film that is opaque to actinic light, it is necessary to peel off the support film at the time of exposure.
こうして形成された感光層の露光及び現像は、常法によ
り行なわれる。すなわち、光源として超高圧水銀灯、高
圧水銀灯等を用い、感光性樹脂組成物の層上に直接また
はポリエチレンテレフタレートフィルム等の透明フィル
ムを介し、ネガマスクを通して像的に露光する。露光後
、透明フィルムが残っている場合には、これを剥離した
後現像する。Exposure and development of the photosensitive layer thus formed are carried out by conventional methods. That is, using an ultra-high-pressure mercury lamp, high-pressure mercury lamp, or the like as a light source, the layer of the photosensitive resin composition is imagewise exposed directly or through a negative mask through a transparent film such as a polyethylene terephthalate film. If a transparent film remains after exposure, it is peeled off and developed.
現像液としては、例えば1,1.’l−トリクロルエタ
ン等のハロゲン化炭化水素が用いられる。Examples of the developer include 1, 1. A halogenated hydrocarbon such as 'l-trichloroethane is used.
また1、1.1−トリクロルエタンを主成分とする洗浄
剤、例えばスリーワンEX(東亜合成化学■製)を使用
することもできる。It is also possible to use a cleaning agent containing 1,1,1-trichloroethane as a main component, such as Three-One EX (manufactured by Toagosei Chemical Co., Ltd.).
上記の方法で得られた像的な保護被膜は、通常のエツチ
ング、メッキ等のための耐蝕膜としての特性を持ってい
るが、現像後に活性光の露光及び80〜200℃の加熱
処理を行なうことにより、すりきず性、密着性、耐熱性
、耐溶剤性等の特性を向上でき、ソルダマスク等の感光
性樹脂組成物としての特性を満足する永久的な保護膜が
得られる。The image-like protective film obtained by the above method has properties as a corrosion-resistant film for ordinary etching, plating, etc., but after development, exposure to active light and heat treatment at 80 to 200°C are performed. By doing so, properties such as scratch resistance, adhesion, heat resistance, and solvent resistance can be improved, and a permanent protective film that satisfies the properties of a photosensitive resin composition such as a solder mask can be obtained.
(実施例)
次に本発明に係る感光性樹脂組成物について、その実施
例を説明する。実施例中の「部」は重量部を意味する。(Example) Next, examples of the photosensitive resin composition according to the present invention will be described. "Parts" in the examples mean parts by weight.
実施例]
(a)光重合性不飽和化合物の合成
A、オルソクレゾールノボラック型エポキシ樹脂、EO
CN−102(エポキシ当世230)1095部
エチルセロソルブアセデート 800部B、アクリ
ル酸 69部塩化ベンジルトリ
メチルアンモニウム塩7部
p−メトキシフェノール 3部エチルセロ
ソルブアセテート 100部C,イソシアナートエ
チルメタクリレート163部
ジブチルチンジラウレート 0.5部エチルセロ
ソルブアセテート 100部り、メタノール
10部温度計、攪拌装置、冷却管及び
滴下器の付いた加熱及び冷却可能な51の反応器に、前
記Aを加え、攪拌しながら60℃に昇温し、均一に溶解
させた。反応温度を60℃に保ちながら、これに約1時
間かけてBを滴下した。Bの滴下後、2時間かけて80
℃に昇温し、so’cで約15時間攪拌を続は反応系の
酸価を1以下にした。Examples] (a) Synthesis A of photopolymerizable unsaturated compound, orthocresol novolac type epoxy resin, EO
CN-102 (Epoxy Tosei 230) 1095 parts Ethyl cellosolve acetate 800 parts B, acrylic acid 69 parts Benzyltrimethylammonium chloride 7 parts p-methoxyphenol 3 parts Ethyl cellosolve acetate 100 parts C, isocyanate Ethyl methacrylate 163 parts Dibutyltin Dilaurate 0.5 parts Ethyl cellosolve acetate 100 parts, methanol
The above A was added to a 10-part reactor equipped with a thermometer, a stirrer, a cooling tube, and a dropper and capable of heating and cooling, and the temperature was raised to 60° C. while stirring to uniformly dissolve the mixture. B was added dropwise thereto over about 1 hour while maintaining the reaction temperature at 60°C. 80 over 2 hours after dropping B.
The temperature was raised to .degree. C. and stirred for about 15 hours under SO'C, and the acid value of the reaction system was brought to 1 or less.
次いで温度を60℃に下げ、反応温度を60℃に保ちな
がら、約3時間かけて均一にCを滴下した。Cの滴下後
、約5時間かけて徐々に反応温度を80℃まで昇温した
後、温度を60℃に下げ、Dを加え、約1時間攪拌を続
けた。こうして不揮発分57重量%のオルソクレゾール
ノボラック型エポキシ樹脂/アクリル酸/イソシアナー
トエチルメタクリレート(酸当量/エポキシ当量比=0
゜2、イソシアナート当量/水酸基当量比=1.1)系
光重合性不飽和化合物の溶液(1)を得た。Next, the temperature was lowered to 60°C, and C was uniformly added dropwise over about 3 hours while maintaining the reaction temperature at 60°C. After dropping C, the reaction temperature was gradually raised to 80° C. over about 5 hours, then lowered to 60° C., D was added, and stirring was continued for about 1 hour. In this way, orthocresol novolac type epoxy resin with nonvolatile content of 57% by weight/acrylic acid/isocyanatoethyl methacrylate (acid equivalent/epoxy equivalent ratio = 0)
2, isocyanate equivalent/hydroxyl group equivalent ratio=1.1) solution (1) of a photopolymerizable unsaturated compound was obtained.
(b)感光性樹脂組成物の調整
(a)で得られた光重合性不飽和化合物の溶液(1)1
75部(不揮発分100部)に2−メチル−[4−(メ
チルチオ)フェニル]−2−モルフtリノ−1−プロパ
ン(チバ・ガイギー社製IRGACLJRE 907
.以下同じ)10部、ミクロエースp−4(日本タルク
製、超微粒子タルク、平均粒径1.5μm>7部、クリ
スタライト5V(龍森製、超微粒子シリカ、平均粒径5
μm)36部、フタロシアニングリーン0.1部、2−
メチルイミダゾール3部及び七ダブロー(三菱モンサン
ド製、ポリメタクリレート系レベリング材)0.1部を
配合し、3本ロールで混合分散させて、感光性樹脂組成
物の溶液を調整した。(b) Preparation of photosensitive resin composition Solution of photopolymerizable unsaturated compound obtained in (a) (1) 1
75 parts (non-volatile content: 100 parts) of 2-methyl-[4-(methylthio)phenyl]-2-morph t-lino-1-propane (IRGACLJRE 907 manufactured by Ciba Geigy)
.. Same hereafter) 10 parts, Micro Ace p-4 (manufactured by Nippon Talc, ultrafine particle talc, average particle size 1.5 μm>7 parts, Crystallite 5V (manufactured by Ryumori, ultrafine particle silica, average particle size 5)
μm) 36 parts, phthalocyanine green 0.1 part, 2-
3 parts of methylimidazole and 0.1 part of Seven Dovelow (manufactured by Mitsubishi Monsando, polymethacrylate leveling material) were blended and mixed and dispersed using three rolls to prepare a solution of the photosensitive resin composition.
(c)硬化被膜の形成
(b)で得られた感光性樹脂組成物の溶液を、銅張り積
層板(日立化成工業社製 MCL−E−61)上に塗布
し、室温で20分、80℃で20分間乾燥し、厚さ40
μmの感光層を形成した。(c) Formation of a cured film The solution of the photosensitive resin composition obtained in (b) was coated on a copper-clad laminate (MCL-E-61 manufactured by Hitachi Chemical Co., Ltd.), and the solution was applied for 20 minutes at room temperature. Dry for 20 minutes at ℃ to a thickness of 40℃.
A photosensitive layer of μm was formed.
次いでネガマスクを通してオーク製作所■製、フェニッ
クス3000型露光機を用い、400mJ/CIrtで
露光した。露光後80℃で5分間加熱し、常温で30分
放置した後、1,1.1−トリクロルエタンを用いて2
0℃で60秒間スプレー現像した。次いで東芝電材v/
J製、東芝紫外線照射装置(定格電圧200V、定格消
費型カフ、2KW、適合ランプH5600L/2、ラン
プ本数1本)を使用し、1J/cmで照射した後、15
0℃で30分間加熱処理してネガマスクに相応する寸法
精度の優れたソルダマスクを得た。このソルダマスクは
表面光沢を有し、耐冷熱衝撃性に優れ、ロジン系フラッ
クスA−226(タムラ化研観製)を用いて、260℃
で10秒間、ハンダ付は処理し、更にトリクレンで25
℃で10分間清浄化処理した後、MIL−5TD−20
2E107D条件B(−65℃30分間1.常温5分以
内、125℃3O分間〉、50サイクルの冷熱衝撃試験
でクラックの発生及び被膜の剥がれは認められず、長期
間の信頼性が非常に優れていることがわかった。The film was then exposed to light through a negative mask at 400 mJ/CIrt using a Phoenix 3000 type exposure machine manufactured by Oak Manufacturing Co., Ltd. After exposure, it was heated at 80°C for 5 minutes, left at room temperature for 30 minutes, and then treated with 1,1,1-trichloroethane.
Spray development was performed at 0° C. for 60 seconds. Next, Toshiba Electric Materials v/
After irradiating at 1 J/cm using a Toshiba ultraviolet irradiation device manufactured by J (rated voltage 200 V, rated consumption type cuff, 2 KW, compatible lamp H5600L/2, number of lamps 1),
A solder mask with excellent dimensional accuracy corresponding to a negative mask was obtained by heat treatment at 0° C. for 30 minutes. This solder mask has a glossy surface and excellent resistance to cold and thermal shock.
Solder the solder for 10 seconds with
After cleaning for 10 minutes at ℃, MIL-5TD-20
2E107D Condition B (-65℃ 30 minutes 1. Room temperature within 5 minutes, 125℃ 30 minutes) No cracking or peeling of the coating was observed in 50 cycles of thermal shock test, and the long-term reliability is very good. I found out that
実施例2
(a>光重合性不飽和化合物の合成
A、オルソクレゾールノボラック型エポキシ樹脂、日本
生薬viJ製 商品名 EOCN−104(エポキシ当
量230> 920部ハロゲン化フェノール
ノボラック型エポキシ樹脂2日本化薬■製 商品名 B
REN (エポキシ当量285> 2
85部メチルセロソルブアセテート 600部B、
アクリル酸 288部塩化ベンジ
ルトリエチルアンモニウム塩7部
p−メトキシフェノール 3部メチルセロ
ソルブアセテート 100部C,イソシアナートエ
チルメタクリレート620部
ジブチルチンジラウレート 0.5部メチルセロ
ソルブアセテート 100部り、メタノール
10部上記A−Dを用い、その他は
実施例1(a)と同様にして、不揮発分54重量%のオ
ルンクレゾールノボラック型エポキシ樹脂/アクリル酸
/イソシアナートエチルメタクリレート(酸当量/エポ
キシ当量比=0.8、イソシアナート当量/水酸基当量
比=1)系光重合性不飽和化合物の溶液(2)を得た。Example 2 (a>Synthesis A of photopolymerizable unsaturated compounds, orthocresol novolak type epoxy resin, manufactured by Nippon Kayaku viJ, product name EOCN-104 (epoxy equivalent: 230> 920 parts, halogenated phenol novolak type epoxy resin 2 Nippon Kayaku) ■Made product name B
REN (epoxy equivalent 285>2
85 parts methyl cellosolve acetate 600 parts B,
Acrylic acid 288 parts Benzyltriethylammonium chloride 7 parts p-methoxyphenol 3 parts Methyl cellosolve acetate 100 parts C, isocyanate Ethyl methacrylate 620 parts Dibutyltin dilaurate 0.5 parts Methyl cellosolve acetate 100 parts
Using 10 parts of the above A-D, the other procedures were the same as in Example 1(a), and a non-volatile content of 54% by weight of oruncresol novolac type epoxy resin/acrylic acid/isocyanatoethyl methacrylate (acid equivalent/epoxy equivalent ratio = 0.8, isocyanate equivalent/hydroxyl group equivalent ratio=1) A solution (2) of a photopolymerizable unsaturated compound was obtained.
(b)感光性樹脂組成物の調整
上記(a)で得られた光重合性不飽和化合物の溶液(2
>185部(不揮発分100部)に、三酸化アンチモン
(平均粒径0.15μm>3部、2−メチル−[4−(
メチルチオ)フェニル]−2−モルフォリノ−1−プロ
パン5部、2−メチルチオキサントン1部、ホスマーM
(油脂製品社製、リン酸エステル)とベンゾトリアゾー
ルとの等モル塩0.1部、ビクトリアごュアブル−0゜
02部、2−メチルイミダゾール2部を、3本ロールで
混合分散させて、感光性樹脂組成物の溶液を調整した。(b) Preparation of photosensitive resin composition The solution of the photopolymerizable unsaturated compound obtained in (a) above (2
> 185 parts (non-volatile content: 100 parts), antimony trioxide (average particle size 0.15 μm > 3 parts, 2-methyl-[4-(
5 parts of methylthio)phenyl-2-morpholino-1-propane, 1 part of 2-methylthioxanthone, Hosmer M
(manufactured by Yushi Products Co., Ltd., phosphoric acid ester) and 0.1 part of an equimolar salt of benzotriazole, 0.02 parts of Victoria Guarable Blue, and 2 parts of 2-methylimidazole were mixed and dispersed using three rolls, and exposed to light. A solution of a synthetic resin composition was prepared.
以下、実施例1(c)と同様にして、表面光沢を有し耐
熱性に優れた硬化被膜を得た。Thereafter, a cured film having surface gloss and excellent heat resistance was obtained in the same manner as in Example 1(c).
実施例3
(a)光重合性不飽和化合物の合成
A、オルソクレゾールノボラック型エポキシ樹脂、京都
化成@製 YDPN−638(エポキシ当量180)
857部エチルセロソルブアセ
テート 600部B、ケイ皮酸
176部アクリル酸 8
6部塩化ベンジルトリメチルアンモニウム塩7部
p−メトキシフェノール 3部エチルセロ
ソルブアセテート 100部C,イソシアナートエ
チルメタクリレート369部
ジブチルチンジラウレート 0.1部エチルセロ
ソルブアセテート 100部り、メタノール
10部上記A−Dを用い1.その他
は実施例1(a)と同様にして、不揮発分65重量%の
オルソクレゾールノボラック型エポキシ樹脂/ケイ皮酸
/アクリル酸/イソシアナートエチルメタクリレート(
酸当量/エポキシ当量比=0.5、イソシアナート当量
/水酸基当量比=1)系光重合性不飽和化合物の溶液(
3)を得た。Example 3 (a) Synthesis of photopolymerizable unsaturated compound A, orthocresol novolac type epoxy resin, YDPN-638 manufactured by Kyoto Kasei@ (epoxy equivalent: 180)
857 parts ethyl cellosolve acetate 600 parts B, cinnamic acid
176 parts acrylic acid 8
6 parts Benzyltrimethylammonium chloride salt 7 parts p-methoxyphenol 3 parts Ethyl cellosolve acetate 100 parts C, isocyanate Ethyl methacrylate 369 parts Dibutyltin dilaurate 0.1 part Ethyl cellosolve acetate 100 parts Methanol
1. Using 10 parts A-D above. Otherwise, the same procedure as in Example 1(a) was carried out.
Acid equivalent/epoxy equivalent ratio = 0.5, isocyanate equivalent/hydroxyl equivalent ratio = 1) A solution of a photopolymerizable unsaturated compound (
3) was obtained.
(b)感光性樹脂組成物の調整
(a)で得られた光重合性不飽和化合物の溶液(3)1
54部(不揮発分100部)に、クリスタライト210
1−41 (龍森製、γ−グリシドキシプロピルトリメ
トキシシラン処理超微粒子シリカ、平均粒径1μm)5
0部、2−メチル−[4−(メチルチオ)フェニル]−
2−モルフォリノ−1−プロパン10部、ジメチルアミ
ノ安息香酸エチル1部、フタロシアニングリーン0.1
部、ジシアンジアミド2部、2−メチルイミダゾール1
部及びメチルセロソルブ5部を3本ロール ゛で混合
分散させて、感光性樹脂組成物の溶液を調整した。(b) Preparation of photosensitive resin composition Solution of photopolymerizable unsaturated compound obtained in (a) (3) 1
54 parts (non-volatile content: 100 parts), Crystallite 210
1-41 (Tatsumori, γ-glycidoxypropyltrimethoxysilane-treated ultrafine silica, average particle size 1 μm) 5
0 parts, 2-methyl-[4-(methylthio)phenyl]-
10 parts of 2-morpholino-1-propane, 1 part of ethyl dimethylaminobenzoate, 0.1 part of phthalocyanine green
parts, 2 parts of dicyandiamide, 1 part of 2-methylimidazole
A solution of the photosensitive resin composition was prepared by mixing and dispersing 1 part and 5 parts of methyl cellosolve using a three-roll roll.
以下、実施例1(c)と同様にして、表面光沢を有し耐
熱性に優れた硬化被膜を得た。Thereafter, a cured film having surface gloss and excellent heat resistance was obtained in the same manner as in Example 1(c).
比較例1
実施例1(a)で得た光重合性不飽和化合物の溶液(1
)175部に、ベンゾフェノン10部、ミクロエースp
−47部、クリスタライト5■36部、フタロシアニン
グリーン0.1部、2−メチルイミダゾール3部、モダ
フロー0.1部を配合し、3本ロールで混合分散させて
、実施例1(c)と同様にして得られた硬化被膜は、耐
熱性に優れていたが、表面光沢を有していなかった。Comparative Example 1 The solution of the photopolymerizable unsaturated compound obtained in Example 1(a) (1
) 175 parts, 10 parts of benzophenone, Micro Ace p
-47 parts of Crystallite 5, 36 parts of Crystallite 5, 0.1 part of Phthalocyanine Green, 3 parts of 2-methylimidazole, and 0.1 part of Modaflow were blended and mixed and dispersed using three rolls. The cured film obtained in the same manner had excellent heat resistance, but did not have surface gloss.
比較例2
実施例2(a)で得た光重合性不飽和化合物の溶液(2
)175部に、三酸化アンチモン3部、2−メチルチオ
キサントン5部、ジメチル安息香酸イソアミル1部、ホ
スマーMとベンゾトリゾールとの等モル塩0.1部、ビ
クトリアピュアブルー0.02部、2−メチルイミダゾ
ール2部を配合し、3本ロールで混合分散させて、実施
例1(c)と同様にして得られた硬化被膜は、比較例1
と同様に耐熱性に優れていたが、表面光沢を有していな
かった。Comparative Example 2 The solution of the photopolymerizable unsaturated compound obtained in Example 2(a) (2
) 175 parts, 3 parts of antimony trioxide, 5 parts of 2-methylthioxanthone, 1 part of isoamyl dimethylbenzoate, 0.1 part of an equimolar salt of Phosmer M and benzotrizole, 0.02 part of Victoria Pure Blue, 2 - A cured film obtained in the same manner as in Example 1(c) by blending 2 parts of methylimidazole and mixing and dispersing it with three rolls was obtained in Comparative Example 1.
It had excellent heat resistance as well, but did not have surface gloss.
比較例3
実施例3(a)で得た光重合性不飽和化合物の溶液(3
)154部に、クリスタライト2101−41.50部
、ジメチルベンジルケタール(ヂバ・ガイギー製、商品
名IRGACURE651)7部、フタロシアニングリ
ーン0.1部、ジシアンジアミド2部、2−メチルイミ
ダゾール1部及びメチルセロソルブ5部を配合し、3本
ロールで混合分散させて、実施例1(c)と同様にして
1qられた硬化被膜は、耐熱性に優れていたが、表面光
沢を有していなかった。Comparative Example 3 The solution of the photopolymerizable unsaturated compound obtained in Example 3(a) (3
), 154 parts of Crystallite 2101-41.50 parts, 7 parts of dimethylbenzyl ketal (manufactured by Ziba Geigy, trade name IRGACURE 651), 0.1 part of phthalocyanine green, 2 parts of dicyandiamide, 1 part of 2-methylimidazole, and methyl A cured film obtained by blending 5 parts of Cellosolve and mixing and dispersing it with a three-roll roll to produce 1q in the same manner as in Example 1(c) had excellent heat resistance, but did not have surface gloss.
(発明の効果)
本発明になる感光性樹脂組成物を用いて得られる保護被
膜は、上記実施例1及び比較例1からも明らかなように
耐熱性、耐冷熱衝撃性に優れているので、エツチング、
メッキ等のための耐蝕膜、ソルダマスク等の永久的な保
護膜と1ノで使用することができる。(Effects of the Invention) The protective film obtained using the photosensitive resin composition of the present invention has excellent heat resistance and cold shock resistance, as is clear from the above Example 1 and Comparative Example 1. etching,
It can be used in combination with a corrosion-resistant film for plating, etc., and a permanent protective film such as a solder mask.
また、本発明の感光性樹脂組成物を用いることにより、
1.1.1−トリクロルエタン等の難燃性現像液により
現像でき、解像度、耐熱性及び表面光沢性に優れたソル
ダマスクを形成することができ、しかも写真法により厚
膜のソルダマスク等を形成することも可能である。Furthermore, by using the photosensitive resin composition of the present invention,
1.1.1-Can be developed with a flame-retardant developer such as trichloroethane, can form a solder mask with excellent resolution, heat resistance, and surface gloss, and can form a thick film solder mask etc. by photographic method It is also possible.
更に本発明の感光性樹脂組成物を用いて形成される被膜
は、優れた化学的、物理的特性を有し、このため多層印
刷配線板の層間絶縁層、感光性接着剤、塗料、プラスチ
ックレリーフ、印刷版材料、金属精密加工材料等にも用
いることができる。Furthermore, the film formed using the photosensitive resin composition of the present invention has excellent chemical and physical properties, and therefore can be used as an interlayer insulating layer of multilayer printed wiring boards, photosensitive adhesives, paints, and plastic reliefs. It can also be used for printing plate materials, metal precision processing materials, etc.
またこの被膜は、トリクレン、メチルエチルケトン、イ
ソプロピルアルコール、トルエン等の有機溶剤に充分耐
え、酸性水溶液またはアルカリ水溶液にも耐える等の効
果を有する。Furthermore, this coating has the effect of sufficiently resisting organic solvents such as tricrene, methyl ethyl ketone, isopropyl alcohol, and toluene, and also resisting acidic or alkaline aqueous solutions.
Claims (1)
脂、フェノールノボラック型エポキシ樹脂及びハロゲン
化フェノールノボラック型エポキシ樹脂からなる群より
選ばれる1種または2種以上のノボラック型エポキシ樹
脂と不飽和カルボン酸とを、酸当量/エポキシ当量比を
0.1〜0.98の範囲として付加反応させて得られる
不飽和化合物の2級水酸基に、イソシアナートエチルメ
タクリレートをイソシアナート当量/水酸基当量比を0
.1〜1.2の範囲として反応させて得られる光重合性
不飽和化合物100重量部、 (b)2−メチル−[4−(メチルチオ)フェニル]−
2−モルフォリノ−1−プロパン2〜15重量部、 (c)微粒状充填剤20〜100重量部および(d)加
熱硬化剤1〜10重量部 を含有してなる感光性樹脂組成物。(1) (a) One or more novolak epoxy resins selected from the group consisting of orthocresol novolac epoxy resins, phenol novolak epoxy resins, and halogenated phenol novolak epoxy resins and an unsaturated carboxylic acid. , isocyanate ethyl methacrylate is added to the secondary hydroxyl group of an unsaturated compound obtained by addition reaction with an acid equivalent/epoxy equivalent ratio in the range of 0.1 to 0.98.
.. (b) 2-methyl-[4-(methylthio)phenyl]-
A photosensitive resin composition comprising 2 to 15 parts by weight of 2-morpholino-1-propane, (c) 20 to 100 parts by weight of a particulate filler, and (d) 1 to 10 parts by weight of a heat curing agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62115676A JPH0814697B2 (en) | 1987-05-12 | 1987-05-12 | Photosensitive resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62115676A JPH0814697B2 (en) | 1987-05-12 | 1987-05-12 | Photosensitive resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63280244A true JPS63280244A (en) | 1988-11-17 |
JPH0814697B2 JPH0814697B2 (en) | 1996-02-14 |
Family
ID=14668527
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62115676A Expired - Lifetime JPH0814697B2 (en) | 1987-05-12 | 1987-05-12 | Photosensitive resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0814697B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0329951A (en) * | 1989-06-09 | 1991-02-07 | Morton Thiokol Inc | Optical image forming composite |
JP2007136870A (en) * | 2005-11-18 | 2007-06-07 | Eastman Kodak Co | Imaging element and imaging method |
CN111116833A (en) * | 2019-12-30 | 2020-05-08 | 先临三维科技股份有限公司 | Resin composition for 3D printing, anti-oxygen polymerization-resistant resin, 3D printing product and preparation method |
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JPS61132947A (en) * | 1984-11-30 | 1986-06-20 | Hitachi Chem Co Ltd | Photosensitive resin composition |
JPS61199691A (en) * | 1985-02-28 | 1986-09-04 | 日立化成工業株式会社 | Manufacture of printed wiring board |
JPS61264341A (en) * | 1985-05-20 | 1986-11-22 | Hitachi Chem Co Ltd | Photosensitive resin composition |
JPS61264340A (en) * | 1985-05-20 | 1986-11-22 | Hitachi Chem Co Ltd | Photosensitive resin composition |
JPS6210642A (en) * | 1985-07-09 | 1987-01-19 | Sony Corp | Photosensitive resin composition |
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1987
- 1987-05-12 JP JP62115676A patent/JPH0814697B2/en not_active Expired - Lifetime
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61132947A (en) * | 1984-11-30 | 1986-06-20 | Hitachi Chem Co Ltd | Photosensitive resin composition |
JPS61199691A (en) * | 1985-02-28 | 1986-09-04 | 日立化成工業株式会社 | Manufacture of printed wiring board |
JPS61264341A (en) * | 1985-05-20 | 1986-11-22 | Hitachi Chem Co Ltd | Photosensitive resin composition |
JPS61264340A (en) * | 1985-05-20 | 1986-11-22 | Hitachi Chem Co Ltd | Photosensitive resin composition |
JPS6210642A (en) * | 1985-07-09 | 1987-01-19 | Sony Corp | Photosensitive resin composition |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0329951A (en) * | 1989-06-09 | 1991-02-07 | Morton Thiokol Inc | Optical image forming composite |
JP2007136870A (en) * | 2005-11-18 | 2007-06-07 | Eastman Kodak Co | Imaging element and imaging method |
CN111116833A (en) * | 2019-12-30 | 2020-05-08 | 先临三维科技股份有限公司 | Resin composition for 3D printing, anti-oxygen polymerization-resistant resin, 3D printing product and preparation method |
Also Published As
Publication number | Publication date |
---|---|
JPH0814697B2 (en) | 1996-02-14 |
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