JPH1124254A - Photosensitive resin composition - Google Patents
Photosensitive resin compositionInfo
- Publication number
- JPH1124254A JPH1124254A JP17582297A JP17582297A JPH1124254A JP H1124254 A JPH1124254 A JP H1124254A JP 17582297 A JP17582297 A JP 17582297A JP 17582297 A JP17582297 A JP 17582297A JP H1124254 A JPH1124254 A JP H1124254A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- resin composition
- photosensitive resin
- component
- 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 abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 11
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 9
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 19
- 229910000679 solder Inorganic materials 0.000 abstract description 19
- 230000035945 sensitivity Effects 0.000 abstract description 13
- 239000000243 solution Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000007795 chemical reaction product Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 28
- 229920003986 novolac Polymers 0.000 description 14
- -1 bisphenol A type Chemical compound 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 8
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229930003836 cresol Natural products 0.000 description 7
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 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 6
- 238000011417 postcuring Methods 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 3
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical group OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 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 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 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 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-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
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 1
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-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
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- UMLWXYJZDNNBTD-UHFFFAOYSA-N 2-(dimethylamino)-1-phenylethanone Chemical compound CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 1
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-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
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-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
- 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 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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 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
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- WDHYRUBXLGOLKR-UHFFFAOYSA-N phosphoric acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OP(O)(O)=O WDHYRUBXLGOLKR-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、紫外線露光及び希
アルカリ水溶液による現像で画像形成可能であって、高
感度であり、しかも耐熱性、電気絶縁性及び耐薬品性が
良好なパターンを与えることができ、プリント配線板製
造用ソルダーレジストとして好適な感光性樹脂組成物に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a pattern which can form an image by exposure to ultraviolet light and development with a dilute alkaline aqueous solution, has high sensitivity, and has good heat resistance, electrical insulation and chemical resistance. The present invention relates to a photosensitive resin composition suitable as a solder resist for producing a printed wiring board.
【０００２】[0002]
【従来の技術】近年、印刷配線板では、導体回路の永久
保護被膜形成用としてソルダーレジストが広く用いられ
ている。このソルダーレジストは、回路導体のはんだ付
けする部分を除いた全面に被膜形成するために用いられ
るもので、印刷配線板に電子部品をはんだ付けする際
に、はんだが不必要な部分に付着するのを防止するとと
もに、回路導体が空気に直接さらされて酸化や湿度によ
り腐食されるのを防止する保護膜としても機能するもの
である。2. Description of the Related Art In recent years, in printed wiring boards, solder resists have been widely used for forming permanent protective films on conductor circuits. This solder resist is used to form a film on the entire surface of the circuit conductor except for the part to be soldered. When soldering electronic components to the printed wiring board, the solder resist does not adhere to unnecessary parts. And also functions as a protective film for preventing the circuit conductors from being directly exposed to air and corroded by oxidation and humidity.
【０００３】従来、ソルダーレジストは、基板上にスク
リーン印刷法でパターンを形成し、紫外線又は熱により
硬化させるものが主流とされてきたが、最近、印刷配線
基板については、配線密度の向上が要求されるようにな
り、それに伴ってソルダーレジストについても高解像性
及び高精度化が要求されるようになってきている。その
結果、民生用基板、産業用基板を問わず、従来のスクリ
ーン印刷法に代わり、位置精度や導体エッジ部の被覆性
が良好な液状ホトソルダーレジスト法が注目されるよう
になり、これまで例えばビスフェノール型エポキシアク
リレート樹脂、増感剤、エポキシ化合物、エポキシ硬化
剤などから成るソルダーレジスト組成物を用いた液状ホ
トソルダーレジスト法が提案されている（特開昭５０−
１４４４３１号公報、特公昭５１−４０４５１号公
報）。Conventionally, solder resists have been mainly used in which a pattern is formed on a substrate by a screen printing method and cured by ultraviolet rays or heat. Recently, however, it has been required to improve the wiring density of a printed wiring board. Accordingly, high resolution and high precision are also required for solder resists. As a result, regardless of consumer substrates or industrial substrates, liquid photo solder resist methods with good positional accuracy and good coverage of conductor edges have come to the spotlight instead of conventional screen printing methods. A liquid photo solder resist method using a solder resist composition comprising a bisphenol type epoxy acrylate resin, a sensitizer, an epoxy compound, an epoxy curing agent and the like has been proposed (Japanese Patent Laid-Open Publication No. Sho.
144443, JP-B-51-40451).
【０００４】これらのソルダーレジスト組成物は、印刷
配線板上に液状の該組成物を全面塗布し、有機溶媒を揮
発させたのち露光し、次いで未露光部分を有機溶剤を用
いて除去することにより現像していた。しかしながら、
この有機溶剤による未露光部分の除去には、有機溶剤を
多量に使用するため、環境汚染や火災の危険性の問題が
避けられず、特に環境汚染については人体に対する影響
が最近大きくクローズアップされ、その対策に苦慮して
いるのが現状である。[0004] These solder resist compositions are obtained by applying a liquid composition on the entire surface of a printed wiring board, volatilizing an organic solvent, exposing the exposed liquid, and then removing an unexposed portion using the organic solvent. Was developing. However,
In order to remove unexposed parts with this organic solvent, the use of a large amount of organic solvent inevitably raises the problem of environmental pollution and fire hazard. At present, it is difficult to take measures.
【０００５】この解決策として、希アルカリ水溶液で現
像可能なアルカリ現像型ホトソルダーレジスト、例え
ば、エポキシ樹脂に不飽和モノカルボン酸を反応させ、
さらに多塩基酸無水物を付加させた反応生成物をベース
ポリマーとするもの（特開昭５６−４０３２９号公報、
特開昭５７−４５７８５号公報）、ノボラック型エポキ
シ樹脂とモノカルボン酸との反応物に、飽和又は不飽和
多塩基酸無水物を反応させて得られる活性エネルギー線
硬化性樹脂を用いたもの（特公平１−５４３９０号公
報）などが提案されている。As a solution to this problem, an unsaturated monocarboxylic acid is allowed to react with an alkali developing type photo solder resist that can be developed with a dilute aqueous alkali solution, for example, an epoxy resin.
Further, a reaction product to which a polybasic acid anhydride is added is used as a base polymer (JP-A-56-40329,
JP-A-57-45785) using an active energy ray-curable resin obtained by reacting a saturated or unsaturated polybasic anhydride with a reaction product of a novolak type epoxy resin and a monocarboxylic acid ( Japanese Patent Publication No. 1-54390) has been proposed.
【０００６】これらの液状ソルダーレジストは、エポキ
シアクリレートにカルボキシル基を導入することによっ
て、光感応性及び希アルカリ水溶液による現像性を付与
させたものであるが、最近のより高感度化に対する要求
に応ずるには、まだ十分なものとはいえない。[0006] These liquid solder resists are provided with photosensitivity and developability with a dilute alkaline aqueous solution by introducing a carboxyl group into epoxy acrylate, but meet recent demands for higher sensitivity. Is still not enough.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、紫外線露光及び希アルカリ水溶液による
現像で画像形成可能であって、高感度であり、しかも耐
熱性、電気絶縁性及び耐薬品性が優れたパターンを与え
ることができる、プリント配線板製造用ソルダーレジス
トとして好適な感光性樹脂組成物を提供することを目的
としてなされたものである。SUMMARY OF THE INVENTION Under such circumstances, the present invention is capable of forming an image by ultraviolet exposure and development with a dilute aqueous alkaline solution, has high sensitivity, and has heat resistance and electrical insulation. Another object of the present invention is to provide a photosensitive resin composition which can provide a pattern having excellent chemical resistance and is suitable as a solder resist for manufacturing a printed wiring board.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、液状ソル
ダーレジストとして適した感光性樹脂組成物を開発すべ
く鋭意研究を重ねた結果、特定の感光性プレポリマー
に、光重合開始剤、反応性希釈剤及び熱硬化性化合物を
組み合わせた組成物により、その目的を達成しうること
を見出し、この知見に基づいて本発明を完成するに至っ
た。Means for Solving the Problems The present inventors have intensively studied to develop a photosensitive resin composition suitable as a liquid solder resist, and as a result, a photopolymerization initiator, It has been found that the object can be achieved by a composition in which a reactive diluent and a thermosetting compound are combined, and the present invention has been completed based on this finding.
【０００９】すなわち、本発明は、（Ａ）多官能性エポ
キシ樹脂のエポキシ基の少なくとも一部にアクリル酸又
はメタクリル酸を反応させ、さらに多塩基酸無水物を反
応させることにより生成したカルボキシル基にグリシジ
ルアクリレート又はグリシジルメタクリレートを反応さ
せて得られる感光性プレポリマー、（Ｂ）光重合開始
剤、（Ｃ）反応性希釈剤及び（Ｄ）熱硬化性化合物を含
有することを特徴とする希アルカリ水溶液で現像可能な
感光性樹脂組成物を提供するものである。That is, the present invention relates to (A) a method for reacting at least a part of epoxy groups of a polyfunctional epoxy resin with acrylic acid or methacrylic acid, and further reacting a polybasic acid anhydride with a carboxyl group formed by the reaction. A diluted alkaline aqueous solution containing a photosensitive prepolymer obtained by reacting glycidyl acrylate or glycidyl methacrylate, (B) a photopolymerization initiator, (C) a reactive diluent, and (D) a thermosetting compound. The present invention provides a photosensitive resin composition which can be developed by using
【００１０】[0010]
【発明の実施の形態】本発明組成物における（Ａ）成分
の感光性プレポリマーの出発原料として用いられる多官
能性エポキシ樹脂としては、分子中にエポキシ基を２個
以上有するものであってエポキシ当量が、通常１，００
０以下、好ましくは１００〜５００の範囲のものが用い
られる。このようなものとしては、例えばビスフェノー
ルＡ型、ビスフェノールＦ型、フェノールノボラック
型、クレゾールノボラック型などのエポキシ樹脂及びこ
れらに臭素原子や塩素原子などのハロゲン原子を導入し
たものなどが挙げられる。これらの中で、耐熱性などを
考慮するとノボラック型エポキシ樹脂が好適である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyfunctional epoxy resin used as a starting material for the photosensitive prepolymer of the component (A) in the composition of the present invention is a polyfunctional epoxy resin having two or more epoxy groups in the molecule. The equivalent is usually 1,00
A value of 0 or less, preferably in the range of 100 to 500 is used. Examples of such a resin include epoxy resins such as bisphenol A type, bisphenol F type, phenol novolak type, and cresol novolac type, and epoxy resins having a halogen atom such as a bromine atom or a chlorine atom introduced therein. Among these, a novolak type epoxy resin is preferable in consideration of heat resistance and the like.
【００１１】（Ａ）成分の感光性プレポリマーを調製す
るには、前記の多官能性エポキシ樹脂のエポキシ基の少
なくとも一部に、アクリル酸又はメタクリル酸を反応さ
せて、分子中にラジカル反応性の二重結合を導入する。
この際、アクリル酸又はメタクリル酸は、多官能性エポ
キシ樹脂のエポキシ基に対し、実質上化学量論的量反応
させるのが好ましい。この反応により、エポキシ基に由
来する水酸基が生成する。次いで、このようにして生成
した水酸基に多塩基酸無水物を反応させる。この際用い
られる多塩基酸無水物としては、例えば無水フタル酸、
テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル
酸、メチルテトラヒドロ無水フタル酸、エンドメチレン
テトラヒドロ無水フタル酸、メチルエンドメチレンテト
ラヒドロ無水フタル酸、無水マレイン酸、テトラメチレ
ン無水マレイン酸、無水トリメリット酸、無水クロレン
ド酸、無水ピロメリット酸、シクロペンタンテトラカル
ボン酸二無水物などが挙げられる。これらの中で、得ら
れる組成物の性能などの点から、ヘキサヒドロ無水フタ
ル酸が好適である。In order to prepare the photosensitive prepolymer of the component (A), acrylic acid or methacrylic acid is reacted with at least a part of the epoxy groups of the above-mentioned polyfunctional epoxy resin to form a radical reactive polymer in the molecule. Is introduced.
At this time, it is preferable that acrylic acid or methacrylic acid react with the epoxy group of the polyfunctional epoxy resin in a substantially stoichiometric amount. By this reaction, a hydroxyl group derived from the epoxy group is generated. Next, a polybasic acid anhydride is reacted with the hydroxyl group thus generated. As the polybasic acid anhydride used at this time, for example, phthalic anhydride,
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, maleic anhydride, tetramethylene maleic anhydride, trimellitic anhydride, chlorendic anhydride, Pyromellitic anhydride, cyclopentanetetracarboxylic dianhydride and the like can be mentioned. Among these, hexahydrophthalic anhydride is preferred from the viewpoint of the performance of the resulting composition and the like.
【００１２】これらの多塩基酸無水物は、生成した水酸
基１モルに対し、通常０．４〜１．０モルの割合で反応
させるが、高感度のものが得られる点から、０．６〜
１．０モルの割合で反応させるのが好ましい。さらに、
上記多塩基酸無水物の反応により生成したカルボキシル
基にグリシジルアクリレート又はグリシジルメタクリレ
ートを反応させることにより、（Ａ）成分として用いる
反応生成物が得られる。この際、グリシジルアクリレー
ト又はグリシジルメタクリレートは、生成したカルボキ
シル基１モルに対し、通常０．３〜０．８モルの割合で
反応させるが、得られる組成物の現像性及び電気特性な
どを考慮すると０．４〜０．７モルの割合で反応させる
のが有利である。These polybasic acid anhydrides are usually reacted at a ratio of 0.4 to 1.0 mol with respect to 1 mol of the generated hydroxyl groups.
The reaction is preferably performed at a ratio of 1.0 mol. further,
By reacting glycidyl acrylate or glycidyl methacrylate with the carboxyl group generated by the reaction of the polybasic acid anhydride, a reaction product used as the component (A) is obtained. At this time, glycidyl acrylate or glycidyl methacrylate is usually reacted at a ratio of 0.3 to 0.8 mol with respect to 1 mol of the generated carboxyl group. The reaction is advantageously carried out in a proportion of from 0.4 to 0.7 mol.
【００１３】本発明組成物における、（Ｂ）成分の光重
合開始剤としては特に制限はなく、従来光重合開始剤と
して慣用されているものの中から任意のものを選択して
用いることができる。この光重合開始剤の例としては、
ベンゾイン、ベンゾインメチルエーテル、ベンゾインエ
チルエーテル、ベンゾインイソプロピルエーテル、ベン
ゾイン‐ｎ‐ブチルエーテル、ベンゾインイソブチルエ
ーテル、アセトフェノン、ジメチルアミノアセトフェノ
ン、２，２‐ジメトキシ‐２‐フェニルアセトフェノ
ン、２，２‐ジエトキシ‐２‐フェニルアセトフェノ
ン、２‐ヒドロキシ‐２‐メチル‐１‐フェニルプロパ
ン‐１‐オン、１‐ヒドロキシシクロヘキシルフェニル
ケトン、２‐メチル‐１‐［４‐（メチルチオ）フェニ
ル］‐２‐モルホリノ‐プロパン‐１‐オン、４‐（２
‐ヒドロキシエトキシ）フェニル‐２‐（ヒドロキシ‐
２‐プロピル）ケトン、ベンゾフェノン、ｐ‐フェニル
ベンゾフェノン、４，４′‐ジエチルアミノベンゾフェ
ノン、ジクロロベンゾフェノン、２‐メチルアントラキ
ノン、２‐エチルアントラキノン、２‐ｔｅｒｔ‐ブチ
ルアントラキノン、２‐アミノアントラキノン、２‐メ
チルチオキサントン、２‐エチルチオキサントン、２‐
クロロチオキサントン、２，４‐ジメチルチオキサント
ン、２，４‐ジエチルチオキサントン、ベンジルジメチ
ルケタール、アセトフェノンジメチルケタール、ｐ‐ジ
メチルアミン安息香酸エステルなどが挙げられる。これ
らは単独で用いてもよいし、２種以上を組み合わせて用
いてもよい。その配合量は（Ａ）成分の反応生成物１０
０重量部に対して、通常０．５〜５０重量部の範囲で選
ばれる。この配合量が０．５重量部未満では、（Ａ）成
分の反応生成物の光硬化反応が進行しにくいし、５０重
量部を超えるとその量の割には効果の向上がみられず、
むしろ経済的に不利となり、また硬化塗膜の機械物性が
低下するおそれがある。光硬化性、経済性、硬化塗膜の
機械物性などの面から、この光重合開始剤のより好まし
い配合量は２〜３０重量部の範囲である。The photopolymerization initiator of the component (B) in the composition of the present invention is not particularly limited, and any one can be selected from those conventionally used as photopolymerization initiators. Examples of this photopolymerization initiator include:
Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenyl Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one , 4- (2
-Hydroxyethoxy) phenyl-2- (hydroxy-
2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone 2,2-ethylthioxanthone, 2-
Chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate and the like. These may be used alone or in combination of two or more. The compounding amount is 10%.
It is usually selected in the range of 0.5 to 50 parts by weight based on 0 parts by weight. When the amount is less than 0.5 part by weight, the photocuring reaction of the reaction product of the component (A) hardly proceeds, and when the amount exceeds 50 parts by weight, the effect is not improved for the amount.
Rather, it is economically disadvantageous, and the mechanical properties of the cured coating film may be reduced. From the viewpoints of photocurability, economy, mechanical properties of the cured coating film, and the like, the more preferable amount of the photopolymerization initiator is in the range of 2 to 30 parts by weight.
【００１４】本発明組成物における（Ｃ）成分の反応性
希釈剤は、前記（Ａ）成分の反応生成物の光硬化をさら
に十分にして、耐酸性、耐熱性、耐アルカリ性などを有
する塗膜を得るために使用するもので、１分子中に二重
結合を少なくとも２個有する化合物が好ましく用いられ
る。このような反応性希釈剤としては、例えば１，４‐
ブタンジオールジ（メタ）アクリレート、１，６‐ヘキ
サンジオールジ（メタ）アクリレート、ネオペンチルグ
リコールジ（メタ）アクリレート、ポリエチレングリコ
ールジ（メタ）アクリレート、ネオペンチルグリコール
アジペートジ（メタ）アクリレート、ヒドロキシピバリ
ン酸ネオペンチルグリコールジ（メタ）アクリレート、
ジシクロペンタニルジ（メタ）アクリレート、カプロラ
クトン変性ジシクロペンテニルジ（メタ）アクリレー
ト、エチレンオキシド変性リン酸ジ（メタ）アクリレー
ト、アリル化シクロヘキシルジ（メタ）アクリレート、
イソシアヌレートジ（メタ）アクリレート、トリメチロ
ールプロパントリ（メタ）アクリレート、ジペンタエリ
スリトールトリ（メタ）アクリレート、プロピオン酸変
性ジ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トリ（メタ）アクリレート、プロ
ピレンオキシド変性トリメチロールプロパントリ（メ
タ）アクリレート、トリス（アクリロキシエチル）イソ
シアヌレート、プロピオン酸変性ジペンタエリスリトー
ルペンタ（メタ）アクリレート、ジペンタエリスリトー
ルヘキサ（メタ）アクリレート、カプロラクトン変性ジ
ペンタエリスリトールヘキサ（メタ）アクリレートなど
が挙げられる。The reactive diluent of the component (C) in the composition of the present invention further enhances photocuring of the reaction product of the component (A), and provides a coating film having acid resistance, heat resistance, alkali resistance and the like. A compound having at least two double bonds in one molecule is preferably used. Such reactive diluents include, for example, 1,4-
Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid Neopentyl glycol di (meth) acrylate,
Dicyclopentanyldi (meth) acrylate, caprolactone-modified dicyclopentenyldi (meth) acrylate, ethylene oxide-modified di (meth) acrylate phosphate, allylated cyclohexyldi (meth) acrylate,
Isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate,
Pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Examples include caprolactone-modified dipentaerythritol hexa (meth) acrylate.
【００１５】これらの反応性希釈剤は単独で用いてもよ
いし、２種以上を組み合わせて用いてもよく、その配合
量は、前記（Ａ）成分の反応生成物１００重量部に対し
て、通常２〜４０重量部の範囲で選ばれる。この配合量
が２重量部未満では光硬化が不十分であって、硬化塗膜
の耐酸性や耐熱性の向上効果が十分に発揮されないし、
４０重量部を超えるとタックが激しく、露光の際アート
ワークフィルムの基板への付着が生じやすくなり、所望
の硬化塗膜が得られにくくなる。光硬化性、硬化塗膜の
物性、アートワークフィルムの基板への付着防止性など
の面から、この反応性希釈剤のより好ましい配合量は４
〜２０重量部の範囲である。These reactive diluents may be used alone or in combination of two or more. The amount of the reactive diluent is based on 100 parts by weight of the reaction product of the component (A). Usually, it is selected in the range of 2 to 40 parts by weight. If the amount is less than 2 parts by weight, the photocuring is insufficient, and the effect of improving the acid resistance and heat resistance of the cured coating film is not sufficiently exhibited,
If the amount is more than 40 parts by weight, the tack becomes severe, and the artwork film is likely to adhere to the substrate during exposure, and it becomes difficult to obtain a desired cured coating film. From the viewpoints of photocurability, physical properties of the cured coating film, and prevention of adhesion of the artwork film to the substrate, the more preferable amount of the reactive diluent is 4
It is in the range of ２０20 parts by weight.
【００１６】本発明組成物においては、ポストキュアー
後において、十分に強靭な塗膜を得るために、（Ｄ）成
分として熱硬化性化合物を含有させることが必要であ
る。この熱硬化性化合物としては、例えばビスフェノー
ルＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹
脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボ
ラック型エポキシ樹脂、クレゾールノボラック型エポキ
シ樹脂、脂環式エポキシ樹脂、さらには（プロピレン、
ポリプロピレン）グリコールジグリシジルエーテル、ポ
リテトラメチレングリコールジグリシジルエーテル、グ
リセロールポリグリシジルエーテル、トリメチロールプ
ロパンポリグリシジルエーテル、レゾルシンジグリシジ
ルエーテル、１，６‐ヘキサンジオールジグリシジルエ
ーテル、（エチレン、プロピレン）グリコールジグリシ
ジルエーテル、ソルビトールポリグリシジルエーテル、
ソルビタンポリグリシジルエーテル、ペンタエリスリト
ールポリグリシジルエーテル、トリス（２，３‐エポキ
シプロピル）イソシアヌレート、トリグリシジルトリス
（２‐ヒドロキシエチル）イソシアヌレートなどの１分
子中に２個以上のエポキシ基を有するエポキシ化合物が
好ましい。In the composition of the present invention, it is necessary to contain a thermosetting compound as the component (D) in order to obtain a sufficiently tough coating film after post-curing. Examples of the thermosetting compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, and (propylene,
Polypropylene) glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, (ethylene, propylene) glycol diglycidyl Ether, sorbitol polyglycidyl ether,
Epoxy compounds having two or more epoxy groups in one molecule, such as sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate Is preferred.
【００１７】これらの熱硬化性化合物は単独で用いても
よいし、２種以上を組み合わせて用いてもよく、またメ
ラミン化合物、イミダゾール化合物、フェノール化合物
などの公知のエポキシ硬化促進剤などを併用することも
できるこのような熱硬化性化合物を配合することによ
り、ポストキュアー後において、耐熱性、耐酸性、耐溶
剤性、密着性、硬度などを向上させた塗膜が得られる。These thermosetting compounds may be used alone or in combination of two or more, and a known epoxy curing accelerator such as a melamine compound, an imidazole compound or a phenol compound may be used in combination. By adding such a thermosetting compound, a coating film having improved heat resistance, acid resistance, solvent resistance, adhesion, hardness and the like after post-curing can be obtained.
【００１８】この熱硬化性化合物は、前記（Ａ）成分の
反応生成物１００重量部に対して、通常２〜４０重量部
の割合で配合される。この配合量が２重量部未満ではポ
ストキュアー後において、所望の物性を有する塗膜が得
られないし、４０重量部を超えると（Ａ）成分の光硬化
性が低下するおそれがある。ポストキュアー後の塗膜物
性及び（Ａ）成分の光硬化性などの面から、この熱硬化
性化合物のより好ましい配合量は４〜２０重量部の範囲
である。The thermosetting compound is usually blended at a ratio of 2 to 40 parts by weight based on 100 parts by weight of the reaction product of the component (A). When the amount is less than 2 parts by weight, a coating film having desired physical properties cannot be obtained after post-curing. When the amount exceeds 40 parts by weight, the photocurability of the component (A) may be reduced. The amount of the thermosetting compound is more preferably in the range of 4 to 20 parts by weight in view of the properties of the coating film after post-curing and the photocurability of the component (A).
【００１９】本発明の感光性樹脂組成物には、必要に応
じ、種々の添加成分、例えばシリカ、アルミナ、タル
ク、炭酸カルシウム、硫酸バリウムなどの無機顔料、フ
タロシアニン系、アゾ系などの有機顔料、消泡剤、レベ
リング剤などの塗料用添加剤などを含有させることがで
きる。The photosensitive resin composition of the present invention may contain, if necessary, various additional components such as inorganic pigments such as silica, alumina, talc, calcium carbonate and barium sulfate, and organic pigments such as phthalocyanine and azo. A coating additive such as an antifoaming agent or a leveling agent can be contained.
【００２０】このようにして得られた本発明の感光性樹
脂組成物は、例えば基板上に所望の厚さで塗布し、６０
〜８０℃程度の温度で１５〜６０分間程度加熱して溶媒
を揮散させたのち、これに所望のパターンのネガフィル
ムを密着させ、その上から紫外線を照射し、次いで希ア
ルカリ水溶液で非露光部を除去することにより、塗膜が
現像される。この際使用する希アルカリ水溶液として
は、０．５〜５重量％濃度の炭酸ナトリウム水溶液が一
般的であるが、他のアルカリも使用することができる。
次いで、熱風循環式などの乾燥機により、１４０〜１６
０℃程度の温度で１０〜６０分間程度ポストキュアーす
ることにより、所望のレジスト被膜を形成させることが
できる。The thus-obtained photosensitive resin composition of the present invention is applied, for example, on a substrate to a desired thickness.
After heating at a temperature of about 80 ° C. for about 15 to 60 minutes to volatilize the solvent, a negative film of a desired pattern is adhered to the film, irradiated with ultraviolet light from above, and then exposed with a dilute alkaline aqueous solution to a non-exposed part. Is removed, whereby the coating film is developed. As the dilute aqueous alkali solution used at this time, a 0.5 to 5% by weight aqueous sodium carbonate solution is generally used, but other alkalis can also be used.
Next, 140 to 16 by a dryer such as a hot air circulation type.
By performing post-curing at a temperature of about 0 ° C. for about 10 to 60 minutes, a desired resist film can be formed.
【００２１】[0021]
【発明の効果】本発明の感光性樹脂組成物は、紫外線露
光及び希アルカリ水溶液による現像で画像形成可能であ
って、高感度であり、しかも、耐熱性、電気絶縁性及び
耐薬品性が優れたパターンを与えることができ、プリン
ト配線板用のソルダーレジストとして好適に用いられ
る。また、これ以外にエッチングレジストやめっきレジ
ストを初めとし塗料、感光性接着剤、プラスチックレリ
ーフ材料、印刷版用材料などの幅広い用途に使用するこ
とができる。The photosensitive resin composition of the present invention can form an image by exposure to ultraviolet light and development with a dilute alkaline aqueous solution, has high sensitivity, and has excellent heat resistance, electrical insulation and chemical resistance. It can be used as a solder resist for printed wiring boards. In addition, it can be used for a wide range of applications such as etching resists, plating resists, paints, photosensitive adhesives, plastic relief materials, and printing plate materials.
【００２２】[0022]
【実施例】次に、本発明を実施例によりさらに詳細に説
明するが、本発明は、これらの例によってなんら限定さ
れるものではない。なお、感光性樹脂組成物の感度及び
塗膜性能（はんだ耐熱性、耐薬品性、耐溶剤性、電気特
性）は、以下に示す方法に従って評価した。ただし、塗
膜性能は、予め面処理済みの基板に、スクリーン印刷法
により、感光性樹脂組成物を３５μｍの厚さ（乾燥前）
に塗布し、８０℃で２０分間予備乾燥後、６００ｍＪ／
ｃｍ2の露光量で紫外線を照射し、次いで１重量％炭酸
ナトリウム水溶液で６０秒間現像処理したのち、１５０
℃で３０分間ポストキュアーすることにより、硬化塗膜
を作製し、このものについて評価を行った。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the sensitivity and coating film performance (solder heat resistance, chemical resistance, solvent resistance, and electrical properties) of the photosensitive resin composition were evaluated according to the following methods. However, the coating film performance was measured by applying the photosensitive resin composition to a 35 μm thick substrate (before drying) by screen printing on a surface-treated substrate in advance.
And pre-dried at 80 ° C for 20 minutes.
After irradiating with ultraviolet light at an exposure amount of 2 cm 2 and then developing with a 1% by weight aqueous sodium carbonate solution for 60 seconds,
A cured coating film was prepared by post-curing at 30 ° C. for 30 minutes, and this was evaluated.
【００２３】（１）感度 予備乾燥後の塗工基板に感度測定用ステップタブレット
（コダック１４段）を設置し、ステップタブレットを通
し、メインピークが３６５ｎｍの波長の紫外線の照射光
量をオーク製作所製の積算光量計を用い３００ｍＪ／ｃ
ｍ2照射したものをテストピースとし、１重量％の炭酸
ナトリウム水溶液を用い、２．０ｋｇ／ｃｍ2のスプレ
ー圧で６０秒間現像を行った後の露光部分の除去されな
い部分を数字にて表わした。(1) Sensitivity A step tablet for sensitivity measurement (Kodak, 14 steps) is set on the pre-dried coated substrate, and the amount of ultraviolet light having a main peak of 365 nm is passed through the step tablet. 300mJ / c using integrated light meter
The test piece irradiated with m 2 was used as a test piece, and a portion where the exposed portion was not removed after developing for 60 seconds with a spray pressure of 2.0 kg / cm 2 using a 1% by weight aqueous solution of sodium carbonate was represented by a numeral. .
【００２４】（２）はんだ耐熱性 硬化塗膜を、ＪＩＳ Ｃ ６４８１の試験方法に従っ
て、２６０℃のはんだ槽に３０秒間浸せき後、セロハン
テープによるピーリング試験を１サイクルとした計１〜
３サイクルを行った後の塗膜状態を評価した。 ◎：３サイクル後も塗膜に変化がないもの ○：３サイクル後にほんのわずか変化しているもの △：２サイクル後に変化しているもの ×：１サイクル後に剥離を生じるもの(2) Solder Heat Resistance According to the test method of JIS C 6481, the cured coating film was immersed in a solder bath at 260 ° C. for 30 seconds, and then a peeling test using a cellophane tape was performed in one cycle.
After three cycles, the state of the coating film was evaluated. ◎: No change in coating film after 3 cycles ○: Slight change after 3 cycles Δ: Change after 2 cycles ×: Detachment after 1 cycle
【００２５】（３）耐薬品性 硬化塗膜を１０重量％の塩酸に３０分間浸せきした後の
塗膜状態を評価した。 ◎：全く変化が認められないもの ○：ほんのわずか変化しているもの △：顕著に変化しているもの ×：塗膜が膨潤して剥離したもの(3) Chemical Resistance The state of the cured coating film was evaluated after immersing it in 10% by weight of hydrochloric acid for 30 minutes. ◎: No change observed ○: Very slight change △: Notable change ×: Coating swelled and peeled
【００２６】（４）耐溶剤性 硬化塗膜を塩化メチレンに３０分間浸せきした後の塗膜
状態を評価した。 ◎：全く変化が認められないもの ○：ほんのわずか変化しているもの △：顕著に変化しているもの ×：塗膜が膨潤して剥離したもの(4) Solvent Resistance The state of the coated film after immersing the cured coating film in methylene chloride for 30 minutes was evaluated. ◎: No change observed ○: Very slight change △: Notable change ×: Coating swelled and peeled
【００２７】（５）電気特性（絶縁抵抗及び変色） 塗膜にＩＰＣ−ＳＭ−８４０Ｂ Ｂ−２５テストクーポ
ンのくし型電極を置き、６０℃、９０％ＲＨの恒温恒湿
槽中で、１００Ｖの直流電圧を印加し、５００時間後の
絶縁抵抗及び変色を評価した。 ◎：全く変色していないもの ○：薄く変色しているもの △：顕著に変色しているもの ×：黒く焦げ付いているもの(5) Electrical Characteristics (Insulation Resistance and Discoloration) A comb-shaped electrode of an IPC-SM-840B B-25 test coupon was placed on the coating film, and was placed in a constant temperature and humidity chamber at 60 ° C. and 90% RH. A DC voltage was applied, and the insulation resistance and discoloration after 500 hours were evaluated. ◎: Not discolored at all ：: Thinly discolored △: Notably discolored ×: Black scorched
【００２８】製造例１ カルビトールアセテート２５０重量部に、クレゾールノ
ボラック型エポキシ樹脂［住友化学工業（株）製，ＥＳ
ＣＮ−２２０，エポキシ当量２２０）２２０重量部及び
アクリル酸７２重量部を溶解し、還流下に反応させて、
クレゾールノボラック型エポキシアクリレートを得た。
次いで、このエポキシアクリレートにヘキサヒドロ無水
フタル酸１３６．８重量部を加え、酸価が理論値になる
まで還流下で反応させたのち、グリシジルメタクリレー
ト５６．８重量部を加え、さらに反応させて、固形分６
６重量％の感光性プレポリマーを得た。Production Example 1 Cresol novolak type epoxy resin [manufactured by Sumitomo Chemical Co., Ltd., ES, 250 parts by weight of carbitol acetate]
220 parts by weight of CN-220, epoxy equivalent 220) and 72 parts by weight of acrylic acid are dissolved and reacted under reflux,
A cresol novolak type epoxy acrylate was obtained.
Next, 136.8 parts by weight of hexahydrophthalic anhydride was added to the epoxy acrylate, and the mixture was reacted under reflux until the acid value reached the theoretical value. After that, 56.8 parts by weight of glycidyl methacrylate was added, and further reacted to obtain a solid. Min 6
6% by weight of photosensitive prepolymer was obtained.
【００２９】製造例２ カルビトールアセテート２５０重量部に、クレゾールノ
ボラック型エポキシ樹脂［住友化学工業（株）製，ＥＳ
ＣＮ−２２０，エポキシ当量２２０）２２０重量部及び
アクリル酸７２重量部を溶解し、還流下に反応させて、
クレゾールノボラック型エポキシアクリレートを得た。
次いで、このエポキシアクリレートにヘキサヒドロ無水
フタル酸１２１．６重量部を加え、酸価が理論値になる
まで還流下で反応させたのち、グリシジルメタクリレー
ト３５．５重量部を加え、さらに反応させて、固形分６
４重量％の感光性プレポリマーを得た。Production Example 2 Cresol novolak type epoxy resin [manufactured by Sumitomo Chemical Co., Ltd., ES, 250 parts by weight of carbitol acetate]
220 parts by weight of CN-220, epoxy equivalent 220) and 72 parts by weight of acrylic acid are dissolved and reacted under reflux,
A cresol novolak type epoxy acrylate was obtained.
Next, 121.6 parts by weight of hexahydrophthalic anhydride is added to the epoxy acrylate, and the mixture is reacted under reflux until the acid value reaches a theoretical value. Then, 35.5 parts by weight of glycidyl methacrylate is added, and the mixture is further reacted. Min 6
4% by weight of photosensitive prepolymer was obtained.
【００３０】製造例３ カルビトールアセテート２５０重量部に、クレゾールノ
ボラック型エポキシ樹脂［住友化学工業（株）製，ＥＳ
ＣＮ−２２０，エポキシ当量２２０）２２０重量部及び
アクリル酸７２重量部を溶解し、還流下に反応させて、
クレゾールノボラック型エポキシアクリレートを得た。
次いで、このエポキシアクリレートにヘキサヒドロ無水
フタル酸１５．２重量部を加え、酸価が理論値になるま
で還流下で反応させ、固形分５５．０重量％の感光性プ
レポリマーを得た。Production Example 3 Cresol novolak type epoxy resin [manufactured by Sumitomo Chemical Co., Ltd., ES, 250 parts by weight of carbitol acetate]
220 parts by weight of CN-220, epoxy equivalent 220) and 72 parts by weight of acrylic acid are dissolved and reacted under reflux,
A cresol novolak type epoxy acrylate was obtained.
Next, 15.2 parts by weight of hexahydrophthalic anhydride was added to the epoxy acrylate, and the mixture was reacted under reflux until the acid value reached the theoretical value to obtain a photosensitive prepolymer having a solid content of 55.0% by weight.
【００３１】製造例４ カルビトールアセテート２５０重量部に、クレゾールノ
ボラック型エポキシ樹脂［住友化学工業（株）製，ＥＳ
ＣＮ−２２０，エポキシ当量２２０）２２０重量部及び
アクリル酸７２重量部を溶解し、還流下に反応させて、
クレゾールノボラック型エポキシアクリレートを得た。
次いで、このエポキシアクリレートにヘキサヒドロ無水
フタル酸１３６．８重量部を加え、酸価が理論値になる
まで還流下で反応させ、固形分６３．１重量％の感光性
プレポリマーを得た。Production Example 4 Cresol novolac type epoxy resin [ES, manufactured by Sumitomo Chemical Co., Ltd., 250 parts by weight of carbitol acetate]
220 parts by weight of CN-220, epoxy equivalent 220) and 72 parts by weight of acrylic acid are dissolved and reacted under reflux,
A cresol novolak type epoxy acrylate was obtained.
Next, 136.8 parts by weight of hexahydrophthalic anhydride was added to the epoxy acrylate, and the mixture was reacted under reflux until the acid value reached the theoretical value to obtain a photosensitive prepolymer having a solid content of 63.1% by weight.
【００３２】実施例１ 製造例１で得られた感光性プレポリマー１００重量部に
対し、２‐メチル‐１‐［４‐（メチルチオ）フェニ
ル］‐２‐モルフォリノ‐プロパノン‐１を８．０重量
部、トリメチロールプロパントリアクリレートを８．０
重量部、トリグリシジルトリス（２‐ヒドロキシエチ
ル）イソシアヌレートを８．０重量部、フタロシアニン
グリーンを０．５重量部及びタルクを８．０重量部の割
合で配合し、３本ロールで混合分散させて、感光性樹脂
組成物の溶液を調製した。この感光性樹脂組成物の感度
及び塗膜性能を表１に示す。Example 1 8.0 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 was added to 100 parts by weight of the photosensitive prepolymer obtained in Production Example 1. Parts, 8.0 parts of trimethylolpropane triacrylate
Parts by weight, 8.0 parts by weight of triglycidyl tris (2-hydroxyethyl) isocyanurate, 0.5 parts by weight of phthalocyanine green, and 8.0 parts by weight of talc are mixed and dispersed with three rolls. Thus, a solution of the photosensitive resin composition was prepared. Table 1 shows the sensitivity and coating film performance of this photosensitive resin composition.
【００３３】実施例２ 製造例１で得られた感光性プレポリマー１００重量部に
対し、２‐メチル‐１‐［４‐（メチルチオ）フェニ
ル］‐２‐モルフォリノ‐プロパノン‐１を８．０重量
部、ジエチルチオキサントンを０．８重量部、トリメチ
ロールプロパントリアクリレートを８．０重量部、トリ
グリシジルトリス（２‐ヒドロキシエチル）イソシアヌ
レートを８．０重量部、フタロシアニングリーンを０．
５重量部及びタルクを８．０重量部の割合で配合し、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
調製した。この感光性樹脂組成物の感度及び塗膜性能を
表１に示す。Example 2 8.0 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 was added to 100 parts by weight of the photosensitive prepolymer obtained in Production Example 1. 0.8 parts by weight of diethylthioxanthone, 8.0 parts by weight of trimethylolpropane triacrylate, 8.0 parts by weight of triglycidyltris (2-hydroxyethyl) isocyanurate, and 0.1 part by weight of phthalocyanine green.
5 parts by weight and talc at a ratio of 8.0 parts by weight,
By mixing and dispersing with this roll, a solution of the photosensitive resin composition was prepared. Table 1 shows the sensitivity and coating film performance of this photosensitive resin composition.
【００３４】実施例３ 製造例２で得られた感光性プレポリマー１００重量部に
対し、２‐メチル‐１‐［４‐（メチルチオ）フェニ
ル］‐２‐モルフォリノ‐プロパノン‐１を８．０重量
部、ジエチルチオキサントンを０．８重量部、ジペンタ
エリスリトールヘキサアクリレートを８．０重量部、ト
リグリシジルトリス（２‐ヒドロキシエチル）イソシア
ヌレートを８．０重量部、フタロシアニングリーンを
０．５重量部及びタルクを８．０重量部の割合で配合
し、３本ロールで混合分散させて、感光性樹脂組成物の
溶液を調製した。この感光性樹脂組成物の感度及び塗膜
性能を表１に示す。EXAMPLE 3 8.0 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 was added to 100 parts by weight of the photosensitive prepolymer obtained in Production Example 2. 0.8 parts by weight of diethylthioxanthone, 8.0 parts by weight of dipentaerythritol hexaacrylate, 8.0 parts by weight of triglycidyltris (2-hydroxyethyl) isocyanurate, 0.5 part by weight of phthalocyanine green and Talc was blended at a ratio of 8.0 parts by weight, and mixed and dispersed with a three-roll mill to prepare a solution of the photosensitive resin composition. Table 1 shows the sensitivity and coating film performance of this photosensitive resin composition.
【００３５】比較例１ 製造例３で得られた感光性プレポリマー１００重量部に
対し、２‐メチル‐１‐［４‐（メチルチオ）フェニ
ル］‐２‐モルフォリノ‐プロパノン‐１を８．０重量
部、トリメチロールプロパントリアクリレートを８．０
重量部、トリグリシジルトリス（２‐ヒドロキシエチ
ル）イソシアヌレートを８．０重量部、フタロシアニン
グリーンを０．５重量部及びタルクを８．０重量部の割
合で配合し、３本ロールで混合分散させて、感光性樹脂
組成物の溶液を調製した。この感光性樹脂組成物の感度
及び塗膜性能を表１に示す。Comparative Example 1 8.0 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 was added to 100 parts by weight of the photosensitive prepolymer obtained in Production Example 3. Parts, 8.0 parts of trimethylolpropane triacrylate
Parts by weight, 8.0 parts by weight of triglycidyl tris (2-hydroxyethyl) isocyanurate, 0.5 parts by weight of phthalocyanine green, and 8.0 parts by weight of talc are mixed and dispersed with three rolls. Thus, a solution of the photosensitive resin composition was prepared. Table 1 shows the sensitivity and coating film performance of this photosensitive resin composition.
【００３６】比較例２ 製造例４で得られた感光性プレポリマー１００重量部に
対し、２‐メチル‐１‐［４‐（メチルチオ）フェニ
ル］‐２‐モルフォリノ‐プロパノン‐１を８．０重量
部、ジエチルチオキサントンを０．８重量部、トリメチ
ロールプロパントリアクリレートを８．０重量部、フタ
ロシアニングリーンを０．５重量部及びタルクを８．０
重量部の割合で配合し、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製した。この感光性樹脂組
成物の感度及び塗膜性能を表１に示す。Comparative Example 2 8.0 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 was added to 100 parts by weight of the photosensitive prepolymer obtained in Production Example 4. Parts, 0.8 parts by weight of diethylthioxanthone, 8.0 parts by weight of trimethylolpropane triacrylate, 0.5 parts by weight of phthalocyanine green, and 8.0 parts of talc.
Parts by weight, mixed and dispersed with three rolls,
A solution of the photosensitive resin composition was prepared. Table 1 shows the sensitivity and coating film performance of this photosensitive resin composition.
【００３７】[0037]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｇ０３Ｆ 7/028 Ｇ０３Ｆ 7/028 7/032 ５０１ 7/032 ５０１ Ｈ０５Ｋ 3/28 Ｈ０５Ｋ 3/28 Ｄ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI G03F 7/028 G03F 7/028 7/032 501 7/032 501 H05K 3/28 H05K 3/28 D
Claims (6)
基の少なくとも一部にアクリル酸又はメタクリル酸を反
応させ、さらに多塩基酸無水物を反応させることにより
生成したカルボキシル基にグリシジルアクリレート又は
グリシジルメタクリレートを反応させて得られる感光性
プレポリマー、（Ｂ）光重合開始剤、（Ｃ）反応性希釈
剤及び（Ｄ）熱硬化性化合物を含有することを特徴とす
る希アルカリ水溶液で現像可能な感光性樹脂組成物。1. A glycidyl acrylate or glycidyl is formed on a carboxyl group formed by reacting acrylic acid or methacrylic acid with at least a part of epoxy groups of a polyfunctional epoxy resin and further reacting with polybasic acid anhydride. A photosensitive prepolymer obtained by reacting methacrylate, (B) a photopolymerization initiator, (C) a reactive diluent, and (D) a thermosetting compound, which can be developed with a dilute alkaline aqueous solution. Photosensitive resin composition.
樹脂のエポキシ基に対し、アクリル酸又はメタクリル酸
を実質上化学量論的量反応させ、さらに多塩基酸無水物
を、生成した水酸基１モルに対し、０．４〜１．０モル
の割合で反応させる請求項１記載の感光性樹脂組成物。2. In the component (A), acrylic acid or methacrylic acid is reacted with the epoxy group of the polyfunctional epoxy resin in a substantially stoichiometric amount, and further, a polybasic acid anhydride is formed. The photosensitive resin composition according to claim 1, wherein the reaction is carried out at a ratio of 0.4 to 1.0 mol per mol.
レート又はグリシジルメタクリレートを、カルボキシル
基１モルに対し、０．３〜０．８モルの割合で反応させ
る請求項１又は２記載の感光性樹脂組成物。3. The photosensitive resin composition according to claim 1, wherein, in the component (A), glycidyl acrylate or glycidyl methacrylate is reacted at a ratio of 0.3 to 0.8 mol based on 1 mol of the carboxyl group. .
０重量部当り、０．５〜５０重量部である請求項１、２
又は３記載の感光性樹脂組成物。4. The composition according to claim 1, wherein the content of the component (B) is 10%.
The amount is 0.5 to 50 parts by weight per 0 parts by weight.
Or the photosensitive resin composition according to 3.
に二重結合２個以上を有する化合物であり、かつその含
有量が、（Ａ）成分１００重量部当り、２〜４０重量部
である請求項１ないし４のいずれかに記載の感光性樹脂
組成物。5. The reactive diluent of the component (C) is a compound having two or more double bonds in one molecule, and its content is 2 to 40 per 100 parts by weight of the component (A). The photosensitive resin composition according to any one of claims 1 to 4, which is in parts by weight.
にエポキシ基２個以上を有するエポキシ化合物であり、
かつその含有量が、（Ａ）成分１００重量部当り、２〜
４０重量部である請求項１ないし５のいずれかに記載の
感光性樹脂組成物。6. The thermosetting compound as the component (D) is an epoxy compound having two or more epoxy groups in one molecule,
And the content thereof is 2 to 100 parts by weight of the component (A).
The photosensitive resin composition according to any one of claims 1 to 5, wherein the amount is 40 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17582297A JP3672414B2 (en) | 1997-07-01 | 1997-07-01 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17582297A JP3672414B2 (en) | 1997-07-01 | 1997-07-01 | Photosensitive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1124254A true JPH1124254A (en) | 1999-01-29 |
| JP3672414B2 JP3672414B2 (en) | 2005-07-20 |
Family
ID=16002838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17582297A Expired - Lifetime JP3672414B2 (en) | 1997-07-01 | 1997-07-01 | Photosensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3672414B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247649A (en) * | 1999-12-28 | 2001-09-11 | Dainippon Ink & Chem Inc | Photosensitive resin, method for producing the same, and solder resist ink composition |
| JP2002174900A (en) * | 2000-12-08 | 2002-06-21 | Goo Chemical Co Ltd | Ultraviolet-curable resin composition, photo-soldering resist ink, preliminarily dried coating film, substrate, printed wiring board and dry film |
| EP1296188A3 (en) * | 2001-09-21 | 2003-04-23 | Tamura Kaken Corporation | Photosensitive resin composition and printed wiring board |
| JP2004131526A (en) * | 2002-10-08 | 2004-04-30 | Great Eastern Resins Industrial Co Ltd | Photosensitive thermosetting resin, method for producing the same, and solder-resistant ink composition containing the resin |
| EP1455227A3 (en) * | 2002-09-30 | 2004-10-27 | Tamura Kaken Corporation | Photosensitive resin composition and printed wiring board |
| EP1413926A3 (en) * | 2002-09-30 | 2004-10-27 | Tamura Kaken Corporation | Photosensitive resin composition and printing wiring board |
| EP1296189A3 (en) * | 2001-09-21 | 2004-10-27 | Tamura Kaken Corporation | Photosensitive resin composition and printed wiring board |
| WO2006129697A1 (en) * | 2005-05-31 | 2006-12-07 | Taiyo Ink Manufacturing Co., Ltd. | Photocuring/thermosetting resin composition, curing/setting product thereof and printed wiring board obtained using the same |
| JP2007003590A (en) * | 2005-06-21 | 2007-01-11 | Dainippon Ink & Chem Inc | Resist ink composition |
| WO2007004334A1 (en) * | 2005-06-30 | 2007-01-11 | Dainippon Ink And Chemicals, Inc. | Photosensitive resin composition |
| US7278709B2 (en) | 2004-05-14 | 2007-10-09 | Samsung Electronics Co., Ltd. | Photo-curable resin composition, method of patterning the same, and ink jet head and method of fabricating the same |
| KR101506752B1 (en) * | 2010-07-05 | 2015-03-27 | 주식회사 엘지화학 | Alkali soluble binder resin having enhanced resolubility and photoresist resin composition comprising the same |
-
1997
- 1997-07-01 JP JP17582297A patent/JP3672414B2/en not_active Expired - Lifetime
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247649A (en) * | 1999-12-28 | 2001-09-11 | Dainippon Ink & Chem Inc | Photosensitive resin, method for producing the same, and solder resist ink composition |
| JP2002174900A (en) * | 2000-12-08 | 2002-06-21 | Goo Chemical Co Ltd | Ultraviolet-curable resin composition, photo-soldering resist ink, preliminarily dried coating film, substrate, printed wiring board and dry film |
| EP1296189A3 (en) * | 2001-09-21 | 2004-10-27 | Tamura Kaken Corporation | Photosensitive resin composition and printed wiring board |
| EP1296188A3 (en) * | 2001-09-21 | 2003-04-23 | Tamura Kaken Corporation | Photosensitive resin composition and printed wiring board |
| SG118156A1 (en) * | 2001-09-21 | 2006-01-27 | Tamura Kaken Corp | Photosensitive resin composition and printed wiring board |
| EP1494073A3 (en) * | 2001-09-21 | 2005-04-06 | Tamura Kaken Corporation | Photosensitive resin composition and printed wiring board |
| EP1455227A3 (en) * | 2002-09-30 | 2004-10-27 | Tamura Kaken Corporation | Photosensitive resin composition and printed wiring board |
| EP1413926A3 (en) * | 2002-09-30 | 2004-10-27 | Tamura Kaken Corporation | Photosensitive resin composition and printing wiring board |
| JP2004131526A (en) * | 2002-10-08 | 2004-04-30 | Great Eastern Resins Industrial Co Ltd | Photosensitive thermosetting resin, method for producing the same, and solder-resistant ink composition containing the resin |
| US7278709B2 (en) | 2004-05-14 | 2007-10-09 | Samsung Electronics Co., Ltd. | Photo-curable resin composition, method of patterning the same, and ink jet head and method of fabricating the same |
| WO2006129697A1 (en) * | 2005-05-31 | 2006-12-07 | Taiyo Ink Manufacturing Co., Ltd. | Photocuring/thermosetting resin composition, curing/setting product thereof and printed wiring board obtained using the same |
| JP4999685B2 (en) * | 2005-05-31 | 2012-08-15 | 太陽ホールディングス株式会社 | Photocurable / thermosetting resin composition, cured product thereof, and printed wiring board obtained using the same |
| JP2007003590A (en) * | 2005-06-21 | 2007-01-11 | Dainippon Ink & Chem Inc | Resist ink composition |
| WO2007004334A1 (en) * | 2005-06-30 | 2007-01-11 | Dainippon Ink And Chemicals, Inc. | Photosensitive resin composition |
| US8114574B2 (en) | 2005-06-30 | 2012-02-14 | Dic Corporation | Photosensitive resin composition |
| KR101506752B1 (en) * | 2010-07-05 | 2015-03-27 | 주식회사 엘지화학 | Alkali soluble binder resin having enhanced resolubility and photoresist resin composition comprising the same |
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| Publication number | Publication date |
|---|---|
| JP3672414B2 (en) | 2005-07-20 |
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