JP4538484B2 - Photocurable thermosetting resin composition and printed wiring board using the same - Google Patents
Photocurable thermosetting resin composition and printed wiring board using the same Download PDFInfo
- Publication number
- JP4538484B2 JP4538484B2 JP2007275227A JP2007275227A JP4538484B2 JP 4538484 B2 JP4538484 B2 JP 4538484B2 JP 2007275227 A JP2007275227 A JP 2007275227A JP 2007275227 A JP2007275227 A JP 2007275227A JP 4538484 B2 JP4538484 B2 JP 4538484B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- thermosetting resin
- photocurable thermosetting
- carboxyl group
- white
- 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.)
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- 239000011342 resin composition Substances 0.000 title claims description 40
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 38
- 229920005989 resin Polymers 0.000 claims description 45
- 239000011347 resin Substances 0.000 claims description 45
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 44
- 239000003999 initiator Substances 0.000 claims description 43
- -1 oxime ester Chemical group 0.000 claims description 42
- 229910000679 solder Inorganic materials 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- 239000003085 diluting agent Substances 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 125000000466 oxiranyl group Chemical group 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920006243 acrylic copolymer Polymers 0.000 claims description 4
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 24
- 229920000647 polyepoxide Polymers 0.000 description 24
- 239000003822 epoxy resin Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 16
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 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 11
- 239000000126 substance Substances 0.000 description 10
- 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 9
- 238000002845 discoloration Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-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
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 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
- 239000002253 acid Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 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 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- 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 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
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- QGZHYFIQDSBZCB-UHFFFAOYSA-N (2-ethylphenyl)-(2,4,6-trimethylbenzoyl)phosphinic acid Chemical compound CCC1=CC=CC=C1P(O)(=O)C(=O)C1=C(C)C=C(C)C=C1C QGZHYFIQDSBZCB-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- SQNWFKZOFAOCHM-IHWYPQMZSA-N (Z)-3-amino-2-methylacrylic acid Chemical compound N/C=C(/C)C(O)=O SQNWFKZOFAOCHM-IHWYPQMZSA-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
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-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
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 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 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- SHJIJMBTDZCOFE-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-methoxyethanol Chemical compound COC(O)COCCOCCOCCO SHJIJMBTDZCOFE-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-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
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Materials For Photolithography (AREA)
- Epoxy Resins (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Description
本発明は、プリント配線板の永久マスクとしての使用に適し、露光後、アルカリ水溶液で現像することにより画像形成し、その後加熱硬化することにより、高反射率のソルダーレジスト膜を形成することができる光硬化性熱硬化性樹脂組成物、および回路形成されたプリント配線板表面に、該組成物を用いてソルダーレジストパターンを形成して得られるプリント配線板に関する。 The present invention is suitable for use as a permanent mask of a printed wiring board, and after exposure, an image can be formed by developing with an aqueous alkali solution, and then heat-cured to form a highly reflective solder resist film. The present invention relates to a photocurable thermosetting resin composition and a printed wiring board obtained by forming a solder resist pattern on the surface of a printed wiring board on which a circuit is formed, using the composition.
プリント配線板は、一般的に積層板に張り合わせた銅箔の不用な部分をエッチングにより除去して回路配線を形成したものであり、電子部品がはんだ付けにより所定の場所に配置されている。このようなプリント配線板の作製には、ソルダーレジスト膜が使用されている。すなわち、ソルダーレジスト膜は、電子部品をはんだ付けする際の回路の保護膜として使用される。ソルダーレジスト膜は、はんだ付けの際に、はんだが不必要な部分に付着するのを防止すると共に、回路導体が空気に直接曝されて、酸素や湿分と反応することを防止する。さらに、回路基板の永久保護膜としても機能する。そのため、密着性、電気絶縁性、はんだ耐熱性、耐溶剤性、耐薬品性などの諸特性が要求される。 A printed wiring board is generally formed by removing unnecessary portions of a copper foil bonded to a laminated board by etching to form circuit wiring, and electronic components are arranged at predetermined locations by soldering. For producing such a printed wiring board, a solder resist film is used. That is, the solder resist film is used as a protective film for a circuit when soldering an electronic component. The solder resist film prevents solder from adhering to unnecessary portions during soldering, and prevents the circuit conductor from being directly exposed to air and reacting with oxygen and moisture. Furthermore, it functions as a permanent protective film for the circuit board. Therefore, various properties such as adhesion, electrical insulation, solder heat resistance, solvent resistance, and chemical resistance are required.
また、プリント配線板は、高密度化実現のため微細化（ファイン化）、多層化およびワンボード化の一途をたどっており、実装方式も、表面実装技術（ＳＭＴ）へと推移している。そのため、ソルダーレジスト膜も、ファイン化、高解像性、高精度、高信頼性の要求が高まっている。 In addition, printed wiring boards have been increasingly miniaturized (finer), multilayered, and one-boarded to achieve higher density, and the mounting method has also shifted to surface mounting technology (SMT). Therefore, the demand for finer, high resolution, high accuracy, and high reliability of the solder resist film is also increasing.
このようなソルダーレジストのパターンを形成する技術として、微細なパターンを正確に形成できるフォトレジスト法が、特に環境面の配慮等から、アルカリ現像型のフォトレジスト法が主流となっている。 As a technique for forming such a solder resist pattern, an alkali developing type photoresist method is mainly used as a photoresist method capable of accurately forming a fine pattern, particularly in consideration of the environment.
例えば、特許文献１および特許文献２には、ノボラック型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アルカリ水溶液で現像可能な液状レジストインキ組成物が開示されている。 For example, in Patent Document 1 and Patent Document 2, development is possible with an aqueous alkali solution using a reaction product obtained by reacting a novolak epoxy resin with an unsaturated monocarboxylic acid and further adding a polybasic acid anhydride as a base polymer. A liquid resist ink composition is disclosed.
一方で、近年、携帯端末、パソコン、テレビ等の液晶ディスプレイのバックライト、また照明器具の光源など、低電力で発光する発光ダイオード（ＬＥＤ）を、ソルダーレジスト膜が被覆形成されたプリント配線板に直接実装する用途が増えてきている。 On the other hand, in recent years, light-emitting diodes (LEDs) that emit light at low power, such as backlights for liquid crystal displays in portable terminals, personal computers, televisions, etc., and light sources for lighting fixtures, have been applied to printed wiring boards coated with solder resist films. Applications for direct mounting are increasing.
そこで、ＬＥＤの光を効率よく利用するために、高反射率のソルダーレジスト膜を有するプリント配線板が求められている。
高反射率のソルダーレジスト膜は、白色の光硬化性熱硬化性樹脂組成物を用いて形成できると考えられる。しかしながら、白色の光硬化性熱硬化性樹脂組成物は、それ自身が高い反射率を有するので、光を照射した際に、その硬化に必要な光を十分に吸収することができず、パターン潜像を正確に形成することが困難となり、解像性に劣る。 It is considered that the solder resist film having a high reflectance can be formed using a white photocurable thermosetting resin composition. However, since the white photocurable thermosetting resin composition itself has a high reflectance, it cannot sufficiently absorb the light necessary for curing when irradiated with light, and the pattern latent It becomes difficult to form an image accurately, and the resolution is poor.
従って本発明の目的は、高反射率のソルダーレジスト膜を形成できる光硬化性熱硬化性樹脂組成物であって、光を照射した際にパターン潜像を正確に形成することができる白色の光硬化性熱硬化性樹脂組成物、およびこの白色の光硬化性熱硬化性樹脂組成物を用いて形成される高反射率のソルダーレジスト膜を有するプリント配線板を提供することにある。 Therefore, an object of the present invention is a photocurable thermosetting resin composition capable of forming a solder resist film having a high reflectance, and is a white light capable of accurately forming a pattern latent image when irradiated with light. An object of the present invention is to provide a curable thermosetting resin composition and a printed wiring board having a high-reflectance solder resist film formed using the white photocurable thermosetting resin composition.
本発明者等は鋭意研究した結果、光重合開始剤として少なくとも１種のオキシムエステル系光重合開始剤を含むことにより、反射率が高い白色の樹脂組成物であっても、光を照射した際に正確にパターン潜像を形成することができ、良好な解像性を有することを見出した。また、芳香環を有さないカルボキシル基含有樹脂と白色顔料としてルチル型酸化チタンを使用することにより、樹脂の芳香環および酸化チタンの光活性に起因する、光による樹脂の劣化（黄変）を抑えることができ、高反射率を長期間に渡って達成することができる。 As a result of diligent research, the present inventors have found that at least one oxime ester-based photopolymerization initiator is included as a photopolymerization initiator, and thus even when a white resin composition having a high reflectance is irradiated with light. It was found that a pattern latent image can be formed accurately and has good resolution. In addition, by using a carboxyl group-containing resin that does not have an aromatic ring and rutile titanium oxide as a white pigment, resin degradation (yellowing) due to light caused by the aromatic activity of the resin and the photoactivity of the titanium oxide. And high reflectivity can be achieved over a long period of time.
すなわち、本発明の第１の側面によれば、（Ａ）芳香環を有さないカルボキシル基含有樹脂、（Ｂ）少なくとも１種のオキシムエステル系光重合開始剤含む光重合開始剤、（Ｃ）エポキシ化合物、（Ｄ）ルチル型酸化チタン、および（Ｅ）希釈剤を含むことを特徴とする白色の光硬化性熱硬化性樹脂組成物が提供される。 That is, according to the first aspect of the present invention, (A) a carboxyl group-containing resin having no aromatic ring, (B) a photopolymerization initiator containing at least one oxime ester photopolymerization initiator, (C) A white photocurable thermosetting resin composition comprising an epoxy compound, (D) rutile-type titanium oxide, and (E) a diluent is provided.
また、本発明の他の側面によれば、回路形成されたプリント配線板表面に、第１の側面による白色の光硬化性熱硬化性樹脂組成物を用いてソルダーレジスト膜を形成して得られるプリント配線板が提供される。 According to another aspect of the present invention, it is obtained by forming a solder resist film on the surface of a printed wiring board on which a circuit has been formed, using the white photocurable thermosetting resin composition according to the first aspect. A printed wiring board is provided.
本発明によれば、ソルダーレジストとして使用することにより、高反射率のソルダーレジスト膜を形成できる光硬化性熱硬化性樹脂組成物であって、光を照射した際にパターン潜像を正確に形成することができ、良好な解像性を有する白色の光硬化性熱硬化性樹脂組成物、およびこの光硬化性熱硬化性樹脂組成物を用いて形成された高反射率を有するソルダーレジスト膜を有するプリント配線板を提供することができる。 According to the present invention, it is a photocurable thermosetting resin composition that can be used as a solder resist to form a high reflectance solder resist film, and accurately forms a pattern latent image when irradiated with light. A white photocurable thermosetting resin composition having good resolution, and a solder resist film having a high reflectance formed using the photocurable thermosetting resin composition The printed wiring board which has can be provided.
以下、本発明をさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail.
本発明の白色の光硬化性熱硬化性樹脂組成物は、（Ａ）芳香環を有さないカルボキシル基含有樹脂、（Ｂ）少なくとも１種のオキシムエステル系光重合開始剤含む光重合開始剤、（Ｃ）エポキシ化合物、（Ｄ）ルチル型酸化チタン、および（Ｅ）希釈剤を含む。 The white photocurable thermosetting resin composition of the present invention comprises (A) a carboxyl group-containing resin having no aromatic ring, (B) a photopolymerization initiator containing at least one oxime ester photopolymerization initiator, (C) an epoxy compound, (D) a rutile type titanium oxide, and (E) a diluent.
芳香環を有さないカルボキシル基含有樹脂（Ａ）としては、芳香環を持たないカルボキシル基を有する樹脂であれば、それ自体に感光性の不飽和二重結合を１個以上有する感光性のカルボキシル基含有樹脂、および感光性の不飽和二重結合を有さないカルボキシル基含有樹脂のいずれも使用可能であり、特定のものに限定されるものではない。このような芳香環を有さないカルボキシル基含有樹脂（Ａ）が、脂肪族重合性モノマーから生成されるカルボキシル基含有樹脂が好ましい。また、特に以下に列挙する樹脂の中で芳香環を有さないもの（オリゴマーまたはポリマーのいずれでもよい）を好適に使用することができる。すなわち、
（１）不飽和カルボン酸と不飽和二重結合を有する化合物の共重合によって得られるカルボキシル基含有樹脂、
（２）カルボキシル基含有（メタ）アクリル系共重合樹脂に、１分子中にオキシラン環とエチレン性不飽和基を有する化合物との反応により得られる感光性のカルボキシル基含有樹脂、
（３）１分子中にそれぞれ１個のエポキシ基と不飽和二重結合を有する化合物と、不飽和二重結合を有する化合物の共重合体に、不飽和モノカルボン酸を反応させ、生成した第２級の水酸基に飽和または不飽和多塩基酸無水物を反応させて得られる感光性のカルボキシル基含有樹脂、
（４）水酸基含有ポリマーに、飽和または不飽和多塩基酸無水物を反応させた後、生成したカルボン酸に、１分子中にそれぞれ１個のエポキシ基と不飽和二重結合を有する化合物を反応させて得られる感光性の水酸基およびカルボキシル基含有樹脂
である。
As the carboxyl group-containing resin (A) not having an aromatic ring, a photosensitive carboxyl having at least one photosensitive unsaturated double bond in itself is a resin having a carboxyl group not having an aromatic ring. Either a group-containing resin or a carboxyl group-containing resin having no photosensitive unsaturated double bond can be used, and is not limited to a specific one. The carboxyl group-containing resin (A) having no aromatic ring is preferably a carboxyl group-containing resin produced from an aliphatic polymerizable monomer. In particular, among the resins listed below, those having no aromatic ring (any of oligomers or polymers) can be preferably used. That is,
(1) a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having an unsaturated double bond,
(2) a photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin with a compound having an oxirane ring and an ethylenically unsaturated group in one molecule;
(3) A compound formed by reacting an unsaturated monocarboxylic acid with a copolymer of a compound having one epoxy group and an unsaturated double bond in each molecule and a compound having an unsaturated double bond. A photosensitive carboxyl group-containing resin obtained by reacting a secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride,
(4) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, the resulting carboxylic acid is reacted with a compound having one epoxy group and an unsaturated double bond in each molecule. A photosensitive hydroxyl group- and carboxyl group-containing resin.
これらの中でも、上記（２）の感光性のカルボキシル基含有樹脂である、（ａ）カルボキシル基含有（メタ）アクリル系共重合樹脂と、（ｂ）１分子中にオキシラン環とエチレン性不飽和基を有する化合物との反応により得られるカルボキシル基を有する共重合系樹脂が好ましい。 Among these, (a) the carboxyl group-containing (meth) acrylic copolymer resin (2), which is the photosensitive carboxyl group-containing resin of (2), and (b) an oxirane ring and an ethylenically unsaturated group in one molecule. A copolymer resin having a carboxyl group obtained by a reaction with a compound having an aromatic group is preferred.
（ａ）のカルボキシル基含有（メタ）アクリル系共重合樹脂は、（メタ）アクリル酸エステルと、１分子中に１個の不飽和基と少なくとも１個のカルボキシル基を有する化合物とを共重合させて得られる。共重合樹脂（ａ）を構成する（メタ）アクリル酸エステルとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート等の（メタ）アクリル酸アルキルエステル類、２−ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、カプロラクトン変性２−ヒドロキシエチル（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル類、メトキシジエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、イソオクチルオキシジエチレングリコール（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート等のグリコール変性（メタ）アクリレート類などが挙げられる。これらは単独で用いても、２種以上を混合して用いてもよい。なお、本明細書中において、（メタ）アクリレートとは、アクリレートおよびメタアクリレートを総称する用語であり、他の類似の表現についても同様である。 The carboxyl group-containing (meth) acrylic copolymer resin (a) is obtained by copolymerizing a (meth) acrylic acid ester and a compound having one unsaturated group and at least one carboxyl group in one molecule. Obtained. Examples of the (meth) acrylic acid ester constituting the copolymer resin (a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl ( Hydroxyl groups such as (meth) acrylic acid alkyl esters such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate Containing (meth) acrylic acid esters, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, methoxy Triethylene glycol (meth) acrylate, glycol-modified (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate. These may be used alone or in combination of two or more. In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.
また、１分子中に１個の不飽和基と少なくとも１個のカルボキシル基を有する化合物としては、アクリル酸、メタクリル酸、不飽和基とカルボン酸の間が鎖延長された変性不飽和モノカルボン酸、例えばβ−カルボキシエチル（メタ）アクリレート、２−アクリロイルオキシエチルコハク酸、２−アクリロイルオキシエチルヘキサヒドロフタル酸、ラクトン変性等によりエステル結合を有する不飽和モノカルボン酸、エーテル結合を有する変性不飽和モノカルボン酸、さらにはマレイン酸等のカルボキシル基を分子中に２個以上含むものなどが挙げられる。これらは単独で用いても、２種以上を混合して用いてもよい。 In addition, examples of the compound having one unsaturated group and at least one carboxyl group in one molecule include acrylic acid, methacrylic acid, and a modified unsaturated monocarboxylic acid in which a chain is extended between the unsaturated group and the carboxylic acid. For example, β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acid having an ester bond due to lactone modification, etc., modified unsaturated having an ether bond Examples thereof include monocarboxylic acids, and those containing two or more carboxyl groups in the molecule, such as maleic acid. These may be used alone or in combination of two or more.
（ｂ）１分子中にオキシラン環とエチレン性不飽和基を有する化合物としては、１分子中にエチレン性不飽和基とオキシラン環を有する化合物であればよく、例えば、グリシジル（メタ）アクリレート、α−メチルグリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、３，４−エポキシシクロヘキシルエチル（メタ）アクリレート、３，４−エポキシシクロヘキシルブチル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチルアミノアクリレート等を挙げることができる。中でも、３，４−エポキシシクロヘキシルメチル（メタ）アクリレートが好ましい。これら（ｂ）１分子中にオキシラン環とエチレン性不飽和基を有する化合物は、単独で用いても２種以上を混合して用いてもよい。 (B) The compound having an oxirane ring and an ethylenically unsaturated group in one molecule may be a compound having an ethylenically unsaturated group and an oxirane ring in one molecule. For example, glycidyl (meth) acrylate, α -Methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexyl Examples include methylamino acrylate. Among these, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferable. These (b) compounds having an oxirane ring and an ethylenically unsaturated group in one molecule may be used alone or in admixture of two or more.
芳香環を有さないカルボキシル基含有樹脂（Ａ）は、その酸価が５０〜２００ｍｇＫＯＨ／ｇの範囲にあることが必要である。酸価が５０ｍｇＫＯＨ／ｇ未満の場合には、弱アルカリ水溶液での未露光部分の除去が難しい。２００ｍｇＫＯＨ／ｇを超えると、硬化被膜の耐水性、電気特性が劣るなどの問題がある。また、カルボキシル基含有樹脂（Ａ）の重量平均分子量は、５，０００〜１００，０００の範囲にあることが好ましい。重量平均分子量が５０００未満であると指触乾燥性が著しく劣る傾向がある。また、重量平均分子量が１００，０００を超えると現像性、貯蔵安定性が著しく悪化する問題を生じるために好ましくない。 The carboxyl group-containing resin (A) not having an aromatic ring needs to have an acid value in the range of 50 to 200 mgKOH / g. When the acid value is less than 50 mgKOH / g, it is difficult to remove the unexposed portion with a weak alkaline aqueous solution. When it exceeds 200 mgKOH / g, there are problems such as poor water resistance and electrical properties of the cured coating. Moreover, it is preferable that the weight average molecular weight of carboxyl group-containing resin (A) exists in the range of 5,000-100,000. When the weight average molecular weight is less than 5000, the dryness to touch tends to be extremely poor. On the other hand, if the weight average molecular weight exceeds 100,000, it is not preferable because developability and storage stability are remarkably deteriorated.
本発明に用いられる少なくとも１種のオキシムエステル系光重合開始剤含む光重合開始剤（Ｂ）中のオキシムエステル系光重合開始剤は、下記式（Ｉ）で表される基を有する化合物であればよく、中でも、チオキサントン構造を有する化合物が好ましい。このようなチオキサントン構造を有する化合物としては、下記式（ＩＩ）の化合物を挙げることができる。
（式中、Ｒ１は、水素原子、炭素数１〜７のアルキル基、またはアリール基を表し、Ｒ２は、炭素数１〜７のアルキル基、またはアリール基を表す）。
本発明の樹脂組成物に含まれる光重合開始剤の中にオキシムエステル系光重合開始剤を含むことによって、白色の光硬化性熱硬化性樹脂組成物であっても、光を照射した際にパターン潜像を正確に形成することができる。本発明の光重合開始剤としては、オキシムエステル系光重合開始剤を単独で用いてもよいし、少なくとも１種のオキシムエステル系光重合開始剤を含んでいれば、他の光重合開始剤を併用して用いてもよい。本発明においてオキシムエステル系光重合開始剤と共に用いられる他の光重合開始剤としては、例えば、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等のベンゾインとベンゾインアルキルエーテル類；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、２，２−ジエトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン等のアセトフェノン類；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ン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルフォリニル）フェニル］−１−ブタノン等のアミノアルキルフェノン類；２−メチルアントラキノン、２−エチルアントラキノン、２−ターシャリーブチルアントラキノン、１−クロロアントラキノン等のアントラキノン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；ベンゾフェノン等のベンゾフェノン類；キサントン類；（２，６−ジメトキシベンゾイル）−２，４，４−ペンチルホスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、エチル−２，４，６−トリメチルベンゾイルフェニルホスフィネイト等のホスフィンオキサイド類；各種パーオキサイド類；チタノセン系開始剤などが挙げられる。これらのオキシムエステル系光重合開始剤と併用される他の光重合開始剤は、１種類でもよいし、２種以上を組み合わせて用いてもよい。 By including an oxime ester photopolymerization initiator in the photopolymerization initiator contained in the resin composition of the present invention, even when it is a white photocurable thermosetting resin composition, when it is irradiated with light A pattern latent image can be formed accurately. As the photopolymerization initiator of the present invention, an oxime ester photopolymerization initiator may be used alone, or as long as it contains at least one oxime ester photopolymerization initiator, other photopolymerization initiators may be used. You may use together. Examples of other photopolymerization initiators used together with the oxime ester photopolymerization initiator in the present invention include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2, Acetophenones such as 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2- [ (4-Methylphenyl) me Amino] alkylphenones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone, and the like. Ketones such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6- Phosphine oxides such as trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate; Id like; titanocene initiators, and the like. One type of other photopolymerization initiators used in combination with these oxime ester photopolymerization initiators may be used, or two or more types may be used in combination.
本発明の少なくとも１種のオキシムエステル系光重合開始剤含む光重合開始剤（Ｂ）は、Ｎ，Ｎ−ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ−ジメチルアミノ安息香酸イソアミルエステル、ペンチル−４−ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類のような光増感剤等と併用しても良い。 The photopolymerization initiator (B) containing at least one oxime ester photopolymerization initiator of the present invention includes N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4- You may use together with photosensitizers, such as tertiary amines, such as a dimethylamino benzoate, a triethylamine, and a triethanolamine.
少なくとも１種のオキシムエステル系光重合開始剤含む光重合開始剤（Ｂ）の配合量は、芳香環を有さないカルボキシル基含有樹脂（Ａ）１００質量部に対して好ましくは１〜３０質量部、より好ましくは２〜２５質量部である。少なくとも１種のオキシムエステル系光重合開始剤含む光重合開始剤（Ｂ）の配合量が１質量部未満の場合、光硬化性が低下し、露光・現像後のパターン形成が困難になるので好ましくない。一方、３０質量部を超えた場合、厚膜硬化性が低下し、またコスト高の原因となるので好ましくない。 The blending amount of the photopolymerization initiator (B) including at least one oxime ester photopolymerization initiator is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A) having no aromatic ring. More preferably, it is 2 to 25 parts by mass. When the blending amount of the photopolymerization initiator (B) containing at least one oxime ester photopolymerization initiator is less than 1 part by mass, the photocurability is lowered, and pattern formation after exposure / development becomes difficult. Absent. On the other hand, when the amount exceeds 30 parts by mass, the thick film curability is lowered and the cost is increased.
次に、エポキシ化合物（Ｃ）としては、各種エポキシ樹脂を用いることができ、例えばビスフェノールＳ型エポキシ樹脂、ジグリシジルフタレート樹脂、トリグリシジルイソシアヌレート（例えば日産化学（株）製のＴＥＰＩＣ−Ｈ（Ｓ−トリアジン環骨格面に対し３個のエポキシ基が同一方向に結合した構造をもつβ体）や、ＴＥＰＩＣ（β体と、Ｓ−トリアジン環骨格面に対し１個のエポキシ基が他の２個のエポキシ基と異なる方向に結合した構造をもつα体との混合物）等）などの複素環式エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂、テトラグリシジルキシレノイルエタン樹脂などの希釈剤に難溶性のエポキシ樹脂や、ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型または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、ビスフェノールＡのノボラック型エポキシ樹脂、キレート型エポキシ樹脂、グリオキザール型エポキシ樹脂、アミノ基含有エポキシ樹脂、ゴム変性エポキシ樹脂、ジシクロペンタジエンフェノリック型エポキシ樹脂、シリコーン変性エポキシ樹脂、ε−カプロラクトン変性エポキシ樹脂などの希釈剤に可溶性のエポキシ樹脂などが挙げられる。これらのエポキシ樹脂は、単独でまたは２種以上を組み合わせて用いることができる。 Next, as the epoxy compound (C), various epoxy resins can be used. For example, bisphenol S type epoxy resin, diglycidyl phthalate resin, triglycidyl isocyanurate (for example, TEPIC-H (S manufactured by Nissan Chemical Co., Ltd.) -Β isomer having a structure in which three epoxy groups are bonded in the same direction to the triazine ring skeleton surface, and TEPIC (β isomer and one other epoxy group for the S-triazine ring skeleton surface) Diluting agents such as heterocyclic epoxy resins, bixylenol type epoxy resins, biphenol type epoxy resins, tetraglycidyl xylenoyl ethane resins, etc.) Insoluble epoxy resin, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol Knoll F type resin, brominated bisphenol A type epoxy resin, phenol novolac type or cresol novolak type epoxy resin, alicyclic epoxy resin, bisphenol A novolak type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing Examples include epoxy resins that are soluble in diluents such as epoxy resins, rubber-modified epoxy resins, dicyclopentadiene phenolic epoxy resins, silicone-modified epoxy resins, and ε-caprolactone-modified epoxy resins. These epoxy resins can be used alone or in combination of two or more.
エポキシ化合物（Ｃ）の配合量は、芳香環を有さないカルボキシ基含有樹脂（Ａ）１００質量部に対して好ましくは５〜７０質量部、より好ましくは５〜６０質量部である。エポキシ化合物（Ｃ）の配合量が７０質量部を超えると、現像液での未露光部分の溶解性が低下し、現像残りが発生しやすくなり、実用上使用することが難しい。一方、５質量部未満であると、カルボキシル基含有樹脂（Ａ）のカルボキシル基が未反応の状態で残存するため、硬化塗膜の電気特性、はんだ耐熱性、耐薬品性が充分に得られ難くなる傾向がある。 The compounding amount of the epoxy compound (C) is preferably 5 to 70 parts by mass, more preferably 5 to 60 parts by mass with respect to 100 parts by mass of the carboxy group-containing resin (A) having no aromatic ring. When the compounding quantity of an epoxy compound (C) exceeds 70 mass parts, the solubility of the unexposed part in a developing solution will fall, it will become easy to generate | occur | produce the image development residue, and it is difficult to use it practically. On the other hand, if the amount is less than 5 parts by mass, the carboxyl group of the carboxyl group-containing resin (A) remains in an unreacted state, and thus it is difficult to sufficiently obtain the electrical properties, solder heat resistance, and chemical resistance of the cured coating film. Tend to be.
芳香環を有さないカルボキシル基含有樹脂（Ａ）のカルボキシル基と、エポキシ化合物（Ｃ）のエポキシ基とは、開環重合により反応するが、希釈剤（Ｅ）や組成物中の他の物質に易溶性エポキシ樹脂を用いた場合、乾燥時の熱により架橋が進みやすい。そのため、架橋反応を抑制して乾燥時間を長くとりたい場合には、難溶性のエポキシ樹脂単独で、または易溶性のエポキシ樹脂と共に用いることが望ましい。 The carboxyl group of the carboxyl group-containing resin (A) not having an aromatic ring and the epoxy group of the epoxy compound (C) react by ring-opening polymerization, but the diluent (E) and other substances in the composition When an easily soluble epoxy resin is used, crosslinking is likely to proceed due to heat during drying. Therefore, when it is desired to suppress the crosslinking reaction and increase the drying time, it is desirable to use the hardly soluble epoxy resin alone or together with the easily soluble epoxy resin.
本発明では、白色顔料として、ルチル型酸化チタン（Ｄ）を用いることも特徴の１つとしている。アナターゼ型酸化チタンは、ルチル型と比較して白色度が高いためによく使用される。しかしながら、アナターゼ型酸化チタンは、光触媒活性を有するために、光硬化性熱硬化性樹脂組成物中の樹脂の変色を引き起こすことがある。これに対し、ルチル型酸化チタンは、白色度はアナターゼ型と比較して若干劣るものの、光活性を殆ど有さないために、安定したソルダーレジスト膜を得ることができる。ルチル型酸化チタン（Ｄ）としては、公知のルチル型のものを使用することができる。具体的には、富士チタン工業（株）製ＴＲ−６００、ＴＲ−７００、ＴＲ−７５０、ＴＲ−８４０、石原産業（株）製Ｒ−５５０、Ｒ−５８０、Ｒ−６３０、Ｒ−８２０、ＣＲ−５０、ＣＲ−６０、ＣＲ−９０、チタン工業（株）製ＫＲ−２７０、ＫＲ−３１０、ＫＲ−３８０等を使用することができる。 In the present invention, one feature is that rutile titanium oxide (D) is used as the white pigment. Anatase-type titanium oxide is often used because of its high whiteness compared to the rutile type. However, since anatase type titanium oxide has photocatalytic activity, it may cause discoloration of the resin in the photocurable thermosetting resin composition. In contrast, rutile titanium oxide has a slightly lower whiteness than the anatase type, but has almost no photoactivity, so that a stable solder resist film can be obtained. As a rutile type titanium oxide (D), a well-known rutile type thing can be used. Specifically, TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titanium Industry Co., Ltd., R-550, R-580, R-630, R-820 manufactured by Ishihara Sangyo Co., Ltd., CR-50, CR-60, CR-90, KR-270, KR-310, KR-380, etc. manufactured by Titanium Industry Co., Ltd. can be used.
ルチル型酸化チタン（Ｄ）の配合量は、芳香環を有さないカルボキシ基含有樹脂（Ａ）１００質量部に対して、好ましくは５０〜３００質量部、より好ましくは６０〜２６０質量部である。配合量が３００質量部を超えると、光硬化性が低下し、硬化深度が低くなり好ましくない。一方、５０質量部未満であると、隠ぺい力が小さく、高反射率のソルダーレジスト膜を得ることができない。 The compounding amount of the rutile type titanium oxide (D) is preferably 50 to 300 parts by mass, more preferably 60 to 260 parts by mass with respect to 100 parts by mass of the carboxy group-containing resin (A) having no aromatic ring. . If the blending amount exceeds 300 parts by mass, the photocurability is lowered and the curing depth is lowered, which is not preferable. On the other hand, if it is less than 50 parts by mass, the hiding power is small, and a solder resist film having a high reflectance cannot be obtained.
また、本発明では、シリカ粒子（Ｆ）を併用すると、より深い硬化深度を有する光硬化性熱硬化性樹脂組成物を得ることができる。これは、シリカの屈折率が、芳香環を有さないカルボキシル基含有樹脂（Ａ）と比較的近いためと考えられる。 Moreover, in this invention, when a silica particle (F) is used together, the photocurable thermosetting resin composition which has a deeper hardening depth can be obtained. This is considered because the refractive index of silica is relatively close to the carboxyl group-containing resin (A) having no aromatic ring.
このようなシリカ粒子（Ｆ）としては、公知のものを使用することができる。例えば、球状シリカ（アドマテックス社製アドマファインＳＯ−Ｅ１、ＳＯ−Ｅ２、ＳＯ−Ｅ５等）、微粉状酸化ケイ素、無定形シリカ、結晶性シリカ、溶融シリカ等を挙げることができる。これらシリカ粒子は、単独でまたは２種以上を組み合わせて用いることができる。シリカ粒子（Ｆ）の配合量は、芳香環を有さないカルボキシ基含有樹脂（Ａ）１００質量部に対して、好ましくは５０〜２００質量部である。 Known silica particles (F) can be used. For example, spherical silica (Admafine SO-E1, SO-E2, SO-E5, etc. manufactured by Admatechs), finely divided silicon oxide, amorphous silica, crystalline silica, fused silica and the like can be mentioned. These silica particles can be used alone or in combination of two or more. The compounding amount of the silica particles (F) is preferably 50 to 200 parts by mass with respect to 100 parts by mass of the carboxy group-containing resin (A) having no aromatic ring.
本発明で使用される希釈剤（Ｅ）としては、光重合性モノマー及び／又は有機溶剤が挙げられる。光重合性モノマーとしては、２−ヒドロキシエチルアクリレート、２−ヒドロキシブチルアクリレートなどのヒドロキシアルキルアクリレート類；エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコールのモノ又はジアクリレート類；Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−メチロールアクリルアミドなどのアクリルアミド類；Ｎ，Ｎ−ジメチルアミノエチルアクリレートなどのアミノアルキルアクリレート類；ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリス−ヒドロキシエチルイソシアヌレートなどの多価アルコール又はこれらのエチレンオキサイドもしくはプロピレンオキサイド付加物の多価アクリレート類；フェノキシアクリレート、ビスフェノールＡジアクリレート及び、これらのフェノール類のエチレンオキサイドあるいはプロピレンオキサイド付加物などのアクリレート類；グルセリンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテルなどのグリシジルエーテルのアクリレート類；メラミンアクリレート；及び／又は上記アクリレート類に対応するメタクリレート類等を挙げることができる。 As a diluent (E) used by this invention, a photopolymerizable monomer and / or an organic solvent are mentioned. As photopolymerizable monomers, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; N, Acrylamides such as N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, etc. Polyhydric alcohols or polyhydric acrylates of these ethylene oxide or propylene oxide adducts Acrylates such as phenoxy acrylate, bisphenol A diacrylate and ethylene oxide or propylene oxide adducts of these phenols; acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether; melamine acrylate; And / or methacrylates corresponding to the above acrylates.
一方、有機溶剤としては、メチルエチルケトン、シクロヘキサノンなどのケトン類；トルエン、キシレン、テトラメチルベンゼンなどの芳香族炭化水素類；メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロプレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテルなどのグリコールエーテル類；酢酸エチル、酢酸ブチル、セロソルブアセテート、ジエチレングリコールモノエチルエーテルアセテート及び上記グリコールエーテル類のエステル化物などのエステル類；エタノール、プロパノール、エチレングリコール、プロピレングリコールなどのアルコール類；オクタン、デカンなどの脂肪族炭化水素類；石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサなどの石油系溶剤等を挙げることができる。 On the other hand, as organic solvents, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esterified products of the above glycol ethers Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; Mention may be made of petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, a petroleum solvent or the like, such as solvent naphtha; Tan, aliphatic hydrocarbons such as decane.
上記のような希釈剤（Ｅ）は、単独で又は２種以上の混合物として用いることができる。芳香環を有さないカルボキシル基含有樹脂（Ａ）１００質量部に対して、２０〜３００質量部の希釈剤（Ｅ）を用いることが好ましい。前記希釈剤の使用目的は、光重合性モノマーは、塗布しやすい状態にするだけでなく、活性エネルギー線硬化性樹脂を希釈し、光重合性を増強するものであり、一方、有機溶剤は、乾燥させることにより造膜せしめたるためである。従って、用いる希釈剤に応じて、フォトマスクを塗膜に接触させる接触方式あるいは非接触方式のいずれかの露光方式が用いられる。 The diluent (E) as described above can be used alone or as a mixture of two or more. It is preferable to use 20 to 300 parts by mass of the diluent (E) with respect to 100 parts by mass of the carboxyl group-containing resin (A) having no aromatic ring. The purpose of use of the diluent is to not only make the photopolymerizable monomer easy to apply, but also dilute the active energy ray-curable resin to enhance photopolymerization, while the organic solvent is This is because the film is formed by drying. Therefore, either a contact method or a non-contact exposure method in which the photomask is brought into contact with the coating film is used depending on the diluent used.
さらに、本発明の白色の光硬化性熱硬化性樹脂組成物においては、酸化防止剤およびヒンダードアミン系光安定剤を含有させることにより、より熱劣化や光劣化を減少させることができる。酸化防止剤としては、特に限定されるものではないが、好ましくはヒンダードフェノール系化合物である。ヒンダードフェノール系化合物としては、例えばノクラック２００、ノクラックＭ−１７、ノクラックＳＰ、ノクラックＳＰ−Ｎ、ノクラックＮＳ−５、ノクラックＮＳ−６、ノクラックＮＳ−３０、ノクラック３００、ノクラックＮＳ−７、ノクラックＤＡＨ（以上いずれも大内新興化学工業（株）製）；ＭＡＲＫ ＡＯ−３０、ＭＡＲＫ ＡＯ−４０、ＭＡＲＫ ＡＯ−５０、ＭＡＲＫ ＡＯ−６０、ＭＡＲＫ ＡＯ６１６、ＭＡＲＫ ＡＯ−６３５、ＭＡＲＫ ＡＯ−６５８、ＭＡＲＫ ＡＯ−１５、ＭＡＲＫ ＡＯ−１８、ＭＡＲＫ ３２８、ＭＡＲＫ ＡＯ−３７（以上いずれもアデカアーガス化学（株）製）；イルガノックス２４５、イルガノックス２５９、イルガノックス５６５、イルガノックス１０１０、イルガノックス１０３５、イルガノックス１０７６、イルガノックス１０８１、イルガノックス１０９８、イルガノックス１２２２、イルガノックス１３３０、イルガノックス１４２５ＷＬ（以上いずれもチバ・スペシャリティ・ケミカル社製）などが挙げられる。 Furthermore, in the white photocurable thermosetting resin composition of the present invention, thermal degradation and photodegradation can be further reduced by containing an antioxidant and a hindered amine light stabilizer. The antioxidant is not particularly limited, but is preferably a hindered phenol compound. Examples of hindered phenol compounds include Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH. (All are manufactured by Ouchi Shinsei Chemical Co., Ltd.); MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO616, MARK AO-635, MARK AO-658, MARK AO -15, MARK AO-18, MARK 328, MARK AO-37 (all manufactured by Adeka Argus Chemical Co., Ltd.); Irganox 245, Irganox 259, Irganox 565, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1081, Irganox 1098, Irganox 1222, Irganox 1330, Irganox 1425WL (all of which are manufactured by Ciba Specialty Chemicals).
また、ヒンダードアミン系光安定剤としては、例えば、チヌビン６２２ＬＤ、チヌビン１４４；ＣＨＩＭＡＳＳＯＲＢ ９４４ＬＤ、ＣＨＩＭＡＳＳＯＲＢ １１９ＦＬ（以上いずれもチバ・スペシャリティ・ケミカル社製）；ＭＡＲＫ ＬＡ−５７、ＬＡ−６２、ＬＡ−６７、ＬＡ−６３、ＬＡ−６８（以上いずれもアデカア−ガス化学（株）製）；サノールＬＳ−７７０、ＬＳ−７６５、ＬＳ−２９２、ＬＳ−２６２６、ＬＳ−１１１４、ＬＳ−７４４（以上いずれも三共ライフテック（株）製）などが挙げられる。 Moreover, as a hindered amine light stabilizer, for example, Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all of these are manufactured by Ciba Specialty Chemicals); MARK LA-57, LA-62, LA-67, LA -63, LA-68 (all manufactured by Adeka Gas Chemical Co., Ltd.); Sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (all above Sankyo Life) Tech Co., Ltd.).
上記酸化防止剤および光安定剤は、芳香環を有さないカルボキシル基含有樹脂（Ａ）１００質量部に対して０．１〜１０質量部添加することが好ましい。 The antioxidant and light stabilizer are preferably added in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A) having no aromatic ring.
さらに、必要に応じて、硬化促進剤、熱重合禁止剤、増粘剤、消泡剤、レベリング剤、カップリング剤、難燃助剤等が使用できる。 Furthermore, a curing accelerator, a thermal polymerization inhibitor, a thickener, an antifoaming agent, a leveling agent, a coupling agent, a flame retardant aid and the like can be used as necessary.
本発明の白色の光硬化性熱硬化性樹脂組成物は、液状、ペースト状の形態で提供することができる。 The white photocurable thermosetting resin composition of the present invention can be provided in a liquid or paste form.
本発明の白色の光硬化性熱硬化性樹脂組成物を、必要に応じて希釈して塗布方法に適した粘度に調整する。これを、回路形成されたプリント配線板に、スクリーン印刷法、カーテンコート法、スプレーコート法、ロールコート法等の方法により塗布し、例えば７０〜９０℃の温度で組成物中に含まれる有機溶剤を揮発乾燥させることにより、タックフリーの塗膜を形成できる。その後、フォトマスクを通して選択的に活性エネルギー線により露光し、未露光部をアルカリ水溶液により現像してレジストパターンを形成することにより、本発明のプリント配線板を得ることができる。ここで用いられるアルカリ水溶液としては、０．５〜５重量％の炭酸ナトリウム水溶液が一般的であるが、他のアルカリ水溶液を使用することも可能である。他のアルカリ水溶液としては、例えば、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類等のアルカリ水溶液を挙げることができる。また、露光するための照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ又はメタルハライドランプなどを用いることができる。その他、レーザー光線なども活性光線として利用できる。 The white photocurable thermosetting resin composition of the present invention is diluted as necessary to adjust the viscosity to be suitable for the coating method. This is applied to a printed wiring board on which a circuit is formed by a method such as a screen printing method, a curtain coating method, a spray coating method, or a roll coating method, and an organic solvent contained in the composition at a temperature of 70 to 90 ° C., for example. A tack-free coating film can be formed by evaporating and drying. Then, the printed wiring board of this invention can be obtained by exposing with an active energy ray selectively through a photomask, and developing an unexposed part with aqueous alkali solution, and forming a resist pattern. As the alkaline aqueous solution used here, a 0.5 to 5% by weight aqueous sodium carbonate solution is generally used, but other alkaline aqueous solutions may be used. Examples of other alkaline aqueous solutions include alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like. As an irradiation light source for exposure, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. In addition, a laser beam can also be used as an actinic beam.
このようにして得られたソルダーレジスト膜の耐熱性を向上させるために、１００〜２００℃の熱、紫外線または遠赤外線により、ソルダーレジスト膜を二次硬化させることが望ましい。 In order to improve the heat resistance of the solder resist film thus obtained, it is desirable to secondarily cure the solder resist film with heat of 100 to 200 ° C., ultraviolet rays or far infrared rays.
本発明の光硬化性熱硬化性樹脂組成物を用いて形成されたソルダーレジスト膜は、高反射率を有し、また、耐熱性、耐溶剤性並びに電気特性等のソルダーレジストに要求される性質を有する。本発明により形成されたソルダーレジストは、加速劣化試験後も高い反射率を保つ。 The solder resist film formed using the photocurable thermosetting resin composition of the present invention has a high reflectance, and properties required for the solder resist such as heat resistance, solvent resistance and electrical properties. Have The solder resist formed by the present invention maintains a high reflectance even after an accelerated deterioration test.
以下、本発明を実施例により説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
芳香環を有さないカルボキシル基含有樹脂の合成
攪拌機、温度計、還流冷却器、滴下ロートおよび窒素導入管を備えた２リットルセパラブルフラスコに、溶媒としてジエチレングリコールジメチルエーテル９００ｇ、および重合開始剤としてｔ−ブチルパーオキシ２−エチルヘキサノエート（日本油脂（株）製パーブチルＯ）２１．４ｇを加えて９０℃に加熱した。加熱後、ここに、メタクリル酸３０９．９ｇ、メタクリル酸メチル１１６．４ｇ、およびラクトン変性２−ヒドロキシエチルメタクリレート（ダイセル化学工業（株）製プラクセルＦＭ１）１０９．８ｇを、重合開始剤であるビス（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート（日本油脂（株）製パーロイルＴＣＰ）２１．４ｇと共に３時間かけて滴下して加え、さらに６時間熟成することにより、カルボキシル基含有共重合樹脂を得た。なお、反応は、窒素雰囲気下で行った。
Synthesis of carboxyl group-containing resin having no aromatic ring A 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube was charged with 900 g of diethylene glycol dimethyl ether as a solvent and t-as a polymerization initiator. 21.4 g of butyl peroxy 2-ethylhexanoate (Nippon Yushi Co., Ltd. perbutyl O) was added and heated to 90 ° C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Daicel Chemical Industries, Ltd., Plaxel FM1) were added to the bis ( 4-t-butylcyclohexyl) peroxydicarbonate (Perroyl TCP manufactured by Nippon Oil & Fats Co., Ltd.) was added dropwise over 3 hours, and further aged for 6 hours to obtain a carboxyl group-containing copolymer resin. It was. The reaction was performed under a nitrogen atmosphere.
次に、得られたカルボキシル基含有共重合樹脂に、３，４−エポキシシクロヘキシルメチルアクリレート（ダイセル化学（株）製サイクロマーＡ２００）３６３．９ｇ、開環触媒としてジメチルベンジルアミン３．６ｇ、重合抑制剤としてハイドロキノンモノメチルエーテル１．８０ｇを加え、１００℃に加熱し、攪拌することによりエポキシの開環付加反応を行った。１６時間後、固形分の酸価が１０８．９ｍｇＫＯＨ／ｇ、重量平均分子量が２５，０００の、芳香環を有さないカルボキシル基含有樹脂を５３．８重量％（不揮発分）含む溶液を得た。以下、この反応溶液をＡ−１ワニスと呼ぶ。 Next, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (Daicel Chemical Co., Ltd. Cyclomer A200), 3.6 g of dimethylbenzylamine as a ring-opening catalyst, polymerization inhibition were added to the obtained carboxyl group-containing copolymer resin. As an agent, 1.80 g of hydroquinone monomethyl ether was added, heated to 100 ° C., and stirred to carry out an epoxy ring-opening addition reaction. After 16 hours, a solution containing 53.8% by weight (nonvolatile content) of a carboxyl group-containing resin having no aromatic ring and having an acid value of solids of 108.9 mgKOH / g and a weight average molecular weight of 25,000 was obtained. . Hereinafter, this reaction solution is referred to as A-1 varnish.
実施例１〜６、比較例１〜６
表１および２に従って各成分を配合、攪拌して３本ロールにて分散させてそれぞれ光硬化性熱硬化性樹脂組成物とした。表中の数字は、質量部を示す。
Each component was blended according to Tables 1 and 2, stirred, and dispersed with a three-roll roll to obtain a photocurable thermosetting resin composition. The numbers in the table indicate parts by mass.
Ｒ８２０：石原産業社製ルチル型酸化チタン
８２８：ジャパンエポキシレジン製 ビスフェノールＡ型エポキシ樹脂
ＳＯ−Ｅ５：アドマテック製球状シリカ
開始剤１：２−（アセチルオキシイミノメチル）チオキサンテン−９−オン
（オキシムエステル系光重合開始剤）
開始剤２：チバスペシャルティケミカルズ製 ＯＸＥ０２
（オキシムエステル系光重合開始剤）
開始剤３：チバスペシャルティケミカルズ製 ＩＲＧＡＣＵＲＥ ９０７
開始剤４：チバスペシャルティケミカルズ製 ＩＲＧＡＣＵＲＥ ３６９
開始剤５：チバスペシャルティケミカルズ製 ＤＡＲＯＣＵＲ ＴＰＯ
モノマー：ジペンタエリスリトルヘキサアクリレート
ＫＳ−６６：信越シリコーン製シリコーンオイル
溶剤：カルビトールアセテート。
R820: Rutile type titanium oxide 828 manufactured by Ishihara Sangyo Co., Ltd. bisphenol A type epoxy resin SO-E5 manufactured by Japan Epoxy Resin Co., Ltd. Spherical silica initiator manufactured by Admatech 1: 2- (acetyloxyiminomethyl) thioxanthen-9-one
(Oxime ester photoinitiator)
Initiator 2: OXE02 manufactured by Ciba Specialty Chemicals
(Oxime ester photoinitiator)
Initiator 3: IRGACURE 907 manufactured by Ciba Specialty Chemicals
Initiator 4: IRGACURE 369 manufactured by Ciba Specialty Chemicals
Initiator 5: DAROCUR TPO manufactured by Ciba Specialty Chemicals
Monomer: Dipentaeryth little hexaacrylate KS-66: Shin-Etsu silicone silicone oil Solvent: carbitol acetate
各光硬化性熱硬化性樹脂組成物を用いて形成されるソルダーレジスト膜の諸性質を調べるために、以下のようにして試験し、評価を行った。 In order to examine various properties of the solder resist film formed using each photocurable thermosetting resin composition, the test was conducted as follows and evaluated.
（１）解像性
各光硬化性熱硬化性樹脂組成物を、１００ｍｍ×１５０ｍｍの大きさで１．６ｍｍの厚さのＦＲ−４銅張り積層板にスクリーン印刷法にて、膜厚４０μｍとなるように１００メッシュポリエステルバイアス製の版を使用してベタで印刷し、８０℃で１０分間熱風循環式乾燥炉にて乾燥させた。さらにそれぞれの上記乾燥塗膜に、同様の方法で光硬化性熱硬化性樹脂組成物を重ねて印刷して、８０℃で２０分間熱風循環式乾燥炉にて乾燥させた。プリント配線板用露光機オーク製作所製ＨＭＷ−６８０ＧＷを用いて、８０μｍおよび１００μｍのラインを描画させるマスクパターンを使用し、５００ｍＪ／ｃｍ２の積算光量で紫外線露光した。その後、３０℃で１％の炭酸ナトリウム水溶液を現像液として、プリント配線板用現像機にて６０秒間現像し、続いて１５０℃で６０分間、熱風循環式乾燥炉で熱硬化を行い、試験片を作製した。この試験片に残存しているライン幅を確認し、解像性の評価とした。結果を表３および４に示す。この中で、８０μｍのラインが残存しているものを二重丸、１００μｍのラインが残存しているものを丸印、１００μｍのラインが残存していないものをバツ印とした。
表３から明らかなように、少なくとも１種のオキシムエステル系光重合開始剤を含む本発明の光硬化性熱硬化性樹脂組成物を用いた実施例１〜６においては、良好な解像性が得られることがわかる。一方、表４のオキシムエステル系光重合開始剤を含まない比較例１〜３は、実施例に含まれる光重合開始剤量と同量の開始剤を含むが、現像後にラインが残存せず、良好な解像性を有さないことがわかる。そこで、比較例４〜６において、解像性を上げることを目的として倍量の光重合開始剤を用いているが、この場合にも現像後にラインは残存しなかった。 As apparent from Table 3, in Examples 1 to 6 using the photocurable thermosetting resin composition of the present invention containing at least one oxime ester photopolymerization initiator, good resolution was obtained. It turns out that it is obtained. On the other hand, Comparative Examples 1 to 3 that do not contain the oxime ester photopolymerization initiator in Table 4 contain the same amount of initiator as the amount of photopolymerization initiator contained in the examples, but no line remains after development, It can be seen that there is no good resolution. Therefore, in Comparative Examples 4 to 6, a double amount of the photopolymerization initiator was used for the purpose of improving the resolution, but in this case as well, no line remained after development.
（２）耐光性
実施例１〜６の光硬化性熱硬化性樹脂組成物を、１００ｍｍ×１５０ｍｍの大きさで１．６ｍｍの厚さのＦＲ−４銅張り積層板にスクリーン印刷法にて、膜厚４０μｍとなるように１００メッシュポリエステルバイアス製の版を使用してベタパターンで印刷し、８０℃で３０分間に渡って熱風循環式乾燥炉にて乾燥させた。プリント配線板用露光機オーク製作所製ＨＭＷ−６８０ＧＷを用いて、３０ｍｍ角のネガパターンを残すように、５００ｍＪ／ｃｍ２の積算光量で紫外線露光した。その後、３０℃で１％の炭酸ナトリウム水溶液を現像液として、プリント配線板用現像機にて６０秒間現像し、続いて１５０℃で６０分間、熱風循環式乾燥炉で熱硬化を行い、特性試験用の試験片を作製した。
(2) Light resistance The photocurable thermosetting resin compositions of Examples 1 to 6 were screen printed on an FR-4 copper-clad laminate having a size of 100 mm × 150 mm and a thickness of 1.6 mm, A 100-mesh polyester bias plate was printed with a solid pattern so as to have a film thickness of 40 μm, and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. Using an exposure machine for printed wiring board Oak Manufacturing Co., Ltd., HMW-680GW, UV exposure was performed with an integrated light amount of 500 mJ / cm 2 so as to leave a 30 mm square negative pattern. After that, a 1% sodium carbonate aqueous solution is used as a developer at 30 ° C., and development is performed for 60 seconds with a developing machine for printed wiring boards. Test specimens were prepared.
得られた試験片をミノルタ製色彩色差計ＣＲ−４００で測定した。その後ＵＶコンベア炉（出力１５０Ｗ／ｃｍ メタルハライドランプ コールドミラー）で５０Ｊ／ｃｍ２、１００Ｊ／ｃｍ２、１５０Ｊ／ｃｍ２の光を照射して加速劣化させた。結果を表５および６に示す。
表５において、ＹはＸＹＺ表色系の反射率を示し、Ｌ＊は、Ｌ＊ａ＊ｂ＊表色系の明度を表わす。ａ＊は赤方向、−ａ＊は緑方向、ｂ＊は黄方向、−ｂ＊は青方向を示し、ゼロに近いほど彩度がないことを示す。ΔＥ＊ａｂは、色の変化を示す。この値が小さいほど色の変化が小さいことを示す。目視評価項目については、二重丸は変色が感じられない、丸印は殆ど変色がない、三角印はやや変色がある、バツ印は明らかな変色があることを示す。 In Table 5, Y represents the reflectance of the XYZ color system, and L * represents the brightness of the L * a * b * color system. a * indicates the red direction, -a * indicates the green direction, b * indicates the yellow direction, and -b * indicates the blue direction. The closer to zero, the lower the saturation. ΔE * ab indicates a change in color. A smaller value indicates a smaller color change. As for the visual evaluation items, the double circle shows no discoloration, the circle shows almost no discoloration, the triangle shows some discoloration, and the cross indicates clear discoloration.
表５から明らかな通り、本発明の組成物を用いた実施例１〜６においては、加速劣化後も、反射率は大きく低下せず、明度の変化も小さく、および色の変化であるΔＥ＊ａｂの値が小さいことがわかる。また、目視評価でも変色は全くないか、殆どない。 As is apparent from Table 5, in Examples 1 to 6 using the composition of the present invention, even after accelerated deterioration, the reflectance does not decrease greatly, the change in brightness is small, and ΔE * which is a change in color It can be seen that the value of ab is small. In addition, there is no or almost no discoloration by visual evaluation.
表６から、実施例の倍量の光重合開始剤を用いている比較例４〜６は、加速劣化後、反射率Ｙおよび明度Ｌ＊は共に低い値となり、および色の変化であるΔＥ＊ａｂの値も大きい。また、目視評価においても、変色が認められる。このことから、倍量の光重合開始剤を用いても解像性は改善されない上に、さらに耐光性にも劣ることがわかった。 From Table 6, in Comparative Examples 4 to 6 using the photopolymerization initiator twice as much as the example, after accelerated deterioration, both the reflectance Y and the lightness L * are low values, and ΔE * which is a color change The value of ab is also large. Moreover, discoloration is recognized also in visual evaluation. From this, it was found that even when a double amount of the photopolymerization initiator was used, the resolution was not improved and the light resistance was also inferior.
（３）耐熱性
（２）と同様に作製した各試験片に、ロジン系フラックスを塗布して２６０℃のはんだ槽で１０秒間フローさせた。その後、プロピレングリコールモノメチルエーテルアセテートで洗浄し、乾燥させた後に、セロハン粘着テープによるピールテストを行い、塗膜の剥がれについて評価した。結果を表７および８に示す。ここで、丸印は、塗膜の剥がれがなかったこと、バツ印は、塗膜の剥がれがあったことを示す。
(3) Heat resistance Each test piece produced in the same manner as in (2) was coated with rosin-based flux and allowed to flow in a solder bath at 260 ° C. for 10 seconds. Then, after washing with propylene glycol monomethyl ether acetate and drying, a peel test with a cellophane adhesive tape was performed to evaluate the peeling of the coating film. The results are shown in Tables 7 and 8. Here, the circle mark indicates that the coating film has not been peeled off, and the cross mark indicates that the coating film has been peeled off.
（４）耐溶剤性
（２）と同様に作製した各試験片を、プロピレングリコールモノメチルエーテルアセテートに３０分間浸漬し、乾燥させた後に、セロハン粘着テープによるピールテストを行い、塗膜の剥がれと変色について評価した。結果を表７および８に併せて示す。ここで、丸印は、塗膜の剥がれや変色がなかったこと、バツ印は、塗膜の剥がれや変色があったことを示す。
(4) Solvent resistance Each test piece prepared in the same manner as in (2) was dipped in propylene glycol monomethyl ether acetate for 30 minutes and dried, and then a peel test with a cellophane adhesive tape was performed to peel off and discolor the coating film. Was evaluated. The results are shown in Tables 7 and 8 together. Here, the circle mark indicates that there was no peeling or discoloration of the coating film, and the cross mark indicates that there was peeling or discoloration of the coating film.
（５）鉛筆硬度試験
（２）と同様に作製した各試験片に、芯の先が平らになるように研がれたＢから９Ｈの鉛筆を、約４５°の角度で押し付けて、塗膜の剥がれが生じない鉛筆の硬さを記録した。結果を、表７および８に併せて示す。
(5) Pencil hardness test A B to 9H pencil sharpened so that the tip of the core is flattened against each test piece prepared in the same manner as in (2) at an angle of about 45 ° to form a coating film The hardness of the pencil where no peeling occurred was recorded. The results are shown in Tables 7 and 8 together.
（６）絶縁抵抗試験
ＦＲ−４銅張り積層板の代わりにＩＰＣ Ｂ−２５テストパターンのクシ型電極Ｂクーポンを用いること以外は（２）と同様の条件で試験片を作製した。この試験片に、ＤＣ５００Ｖのバイアスを印加し、絶縁抵抗値を測定した。結果を、表７および８に併せて示す。
表７から明らかなように、本発明の光硬化性熱硬化性樹脂組成物を用いた実施例１〜６において、ソルダーレジスト膜に要求される良好な耐熱性、耐溶剤性、密着性および電気絶縁性を有することがわかった。 As is clear from Table 7, in Examples 1 to 6 using the photocurable thermosetting resin composition of the present invention, good heat resistance, solvent resistance, adhesion and electricity required for the solder resist film. It was found to have insulating properties.
上記の結果から、光重合開始剤にオキシムエステル系光重合開始剤を含むことによって、良好な耐光性、耐熱性、耐溶剤性、密着性および電気絶縁性の性質を保ったまま、高い解像性が得られるということがわかった。 From the above results, by including an oxime ester photopolymerization initiator in the photopolymerization initiator, high resolution while maintaining good light resistance, heat resistance, solvent resistance, adhesion and electrical insulation properties. It was found that sex can be obtained.
以上詳述した通り、本発明によれば、高反射率のソルダーレジスト膜を形成することができる白色の光硬化性熱硬化性樹脂組成物を得ることができる。本発明の白色の光硬化性熱硬化性樹脂組成物は、光を照射した際にパターン潜像を正確に形成することができ、良好な解像性を有する。 As described in detail above, according to the present invention, a white photocurable thermosetting resin composition capable of forming a solder resist film having a high reflectance can be obtained. The white photocurable thermosetting resin composition of the present invention can form a pattern latent image accurately when irradiated with light, and has good resolution.
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| JP5485599B2 (en) * | 2008-08-26 | 2014-05-07 | 株式会社タムラ製作所 | Photosensitive resin composition, solder resist composition for printed wiring board, and printed wiring board |
| TW201016777A (en) * | 2008-10-17 | 2010-05-01 | Taiyo Ink Mfg Co Ltd | Curable resin composition and reflective sheet |
| TWI408150B (en) * | 2008-10-17 | 2013-09-11 | Taiyo Ink Mfg Co Ltd | A solder resist composition and a printed circuit board using the same |
| JP2010235799A (en) * | 2009-03-31 | 2010-10-21 | Taiyo Ink Mfg Ltd | Curable resin composition and printed wiring board and reflector using the same |
| JP5479821B2 (en) * | 2009-08-28 | 2014-04-23 | 太陽ホールディングス株式会社 | Solder resist layer and printed wiring board |
| JP4855507B2 (en) * | 2009-09-18 | 2012-01-18 | 株式会社タムラ製作所 | Method for manufacturing printed wiring board having reflector function |
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| JP5147820B2 (en) * | 2009-12-24 | 2013-02-20 | 株式会社タムラ製作所 | White solder resist composition for spray painting |
| JP5676889B2 (en) * | 2010-02-12 | 2015-02-25 | 互応化学工業株式会社 | Photosensitive resin composition, solder resist composition and printed wiring board |
| JP4975834B2 (en) * | 2010-02-17 | 2012-07-11 | 太陽ホールディングス株式会社 | Solder resist composition and printed wiring board |
| JP2011170050A (en) * | 2010-02-17 | 2011-09-01 | Taiyo Holdings Co Ltd | Solder resist composition and printed circuit board |
| JP2011216687A (en) * | 2010-03-31 | 2011-10-27 | Taiyo Holdings Co Ltd | White coating layer, method of forming the same, and printed circuit board |
| CN102844711A (en) * | 2010-03-31 | 2012-12-26 | 太阳控股株式会社 | Solder resist composition and printed-circuit board |
| JP5542915B2 (en) * | 2010-03-31 | 2014-07-09 | 太陽ホールディングス株式会社 | Thermosetting resin composition and printed wiring board |
| JP5645446B2 (en) * | 2010-03-31 | 2014-12-24 | 太陽ホールディングス株式会社 | Photocurable resin composition |
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| JP5838200B2 (en) * | 2011-04-13 | 2016-01-06 | 太陽インキ製造株式会社 | Curable resin composition, cured product thereof and printed wiring board using the same |
| JP5663506B2 (en) * | 2012-02-06 | 2015-02-04 | 太陽ホールディングス株式会社 | Solder resist composition |
| JP5244991B1 (en) * | 2012-03-30 | 2013-07-24 | 太陽インキ製造株式会社 | Photocurable thermosetting resin composition, cured product, printed wiring board, and light source module |
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