JP6078595B2 - Curable resin composition and printed wiring board and reflector using the same - Google Patents
Curable resin composition and printed wiring board and reflector using the same Download PDFInfo
- Publication number
- JP6078595B2 JP6078595B2 JP2015147989A JP2015147989A JP6078595B2 JP 6078595 B2 JP6078595 B2 JP 6078595B2 JP 2015147989 A JP2015147989 A JP 2015147989A JP 2015147989 A JP2015147989 A JP 2015147989A JP 6078595 B2 JP6078595 B2 JP 6078595B2
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- JP
- Japan
- Prior art keywords
- resin composition
- curable resin
- mass
- parts
- carboxyl group
- 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 27
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 229910052623 talc Inorganic materials 0.000 claims description 12
- 239000000454 talc Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 229920006243 acrylic copolymer Polymers 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000005476 soldering Methods 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 24
- 229910000679 solder Inorganic materials 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- -1 hydroxypropyl Chemical group 0.000 description 20
- 239000003822 epoxy resin Substances 0.000 description 19
- 229920000647 polyepoxide Polymers 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- 230000006866 deterioration Effects 0.000 description 12
- 238000002310 reflectometry Methods 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 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 6
- 238000002845 discoloration Methods 0.000 description 6
- 239000000243 solution Substances 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
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 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 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 125000000466 oxiranyl group Chemical group 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000001035 drying 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
- 239000003208 petroleum 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
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000001252 acrylic acid derivatives 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-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
- 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
- 229930185605 Bisphenol Natural products 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
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 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
- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding 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
- 239000003085 diluting agent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 150000007519 polyprotic acids 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
- 238000007650 screen-printing Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JLLAWIKMLAQZCZ-UHFFFAOYSA-N (2,6-dichlorophenyl)-diphenylphosphorylmethanone Chemical compound ClC1=CC=CC(Cl)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 JLLAWIKMLAQZCZ-UHFFFAOYSA-N 0.000 description 1
- SUEDCWGEKSLKOM-UHFFFAOYSA-N (2,6-dimethoxyphenyl)-diphenylphosphorylmethanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 SUEDCWGEKSLKOM-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-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
- YTLYLLTVENPWFT-UPHRSURJSA-N (Z)-3-aminoacrylic acid Chemical compound N\C=C/C(O)=O YTLYLLTVENPWFT-UPHRSURJSA-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
- 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
- BVEIKFLZWBDLJG-UHFFFAOYSA-N 1-butylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCC BVEIKFLZWBDLJG-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
- 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
- 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
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-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
- 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
- LELKUNFWANHDPG-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane;prop-2-enoic acid Chemical class OC(=O)C=C.C1OC1COCC1CO1 LELKUNFWANHDPG-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
- MCNPOZMLKGDJGP-QPJJXVBHSA-N 2-[(e)-2-(4-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1\C=C\C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 MCNPOZMLKGDJGP-QPJJXVBHSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- VGPAWZMSGVLDHR-UHFFFAOYSA-N 2-[2-(4-methoxyphenyl)ethenyl]-4-(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C=CC1=NC=NC(C(Cl)(Cl)Cl)=N1 VGPAWZMSGVLDHR-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
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- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Description
本発明は硬化性樹脂組成物およびそれを用いたプリント配線板と反射板に関し、特にプリント配線板の永久マスクとしての使用に適した硬化性樹脂組成物、およびこの組成物を用いて形成したソルダーレジストを有するプリント配線板と反射パターンを有する反射板に関する。 The present invention relates to a curable resin composition, and a printed wiring board and a reflecting plate using the same, and more particularly, a curable resin composition suitable for use as a permanent mask of a printed wiring board, and a solder formed using the composition The present invention relates to a printed wiring board having a resist and a reflecting plate having a reflecting pattern.
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要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には、電子部品をはんだ付けする際の回路の保護膜として、基材に塗布して硬化させて形成するソルダーレジストが使用されている。
このソルダーレジストは、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、酸素や湿分による劣化を防止する。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。
In general, a printed wiring board is formed by removing unnecessary portions of a copper foil bonded to a laminated board by etching to form a circuit wiring, and electronic components are arranged at predetermined positions by soldering. In such a printed wiring board, a solder resist formed by applying and curing to a base material is used as a protective film for a circuit when soldering an electronic component.
This solder resist prevents the solder from adhering to unnecessary portions during soldering, and the circuit conductor is directly exposed to air to prevent deterioration due to 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 is increasing for the solder resist.
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リソグラフィー法が用いられており、特に環境面の配慮等から、アルカリ現像型のフォトリソグラフィー法が主流となっている（特許文献１、２参照）。 As a technique for forming such a solder resist pattern, a photolithography method capable of accurately forming a fine pattern is used, and an alkali development type photolithography method has become the mainstream, especially in consideration of environmental aspects. (See Patent Documents 1 and 2).
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 of portable terminals, personal computers, televisions, etc., and light sources for lighting fixtures, are directly applied to printed wiring boards coated with solder resist. The use of mounting is increasing.
これに対し従来、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が種々提案されている。例えば、特定の酸化チタンを用いることにより、劣化特性を向上させたソルダーレジストが提案されている（特許文献３参照）。
しかしながら、特許文献３に記載の樹脂組成物は、劣化特性の改善を目的としたものであり、光の拡散性に優れたものではない。このような白色の平面な塗膜から拡散反射特性を得るのは難しい。
On the other hand, conventionally, various solder resists with high reflectivity have been proposed in order to efficiently use the light of the LED. For example, a solder resist having improved deterioration characteristics by using specific titanium oxide has been proposed (see Patent Document 3).
However, the resin composition described in Patent Document 3 is intended to improve deterioration characteristics and is not excellent in light diffusibility. It is difficult to obtain diffuse reflection characteristics from such a white flat coating film.
すなわち、最近では、高反射率である特性を維持しながら、光源からの光の反射は鏡のように一方向への全反射ではなく、あらゆる方向に散りばめる拡散反射が求められている。これは、ＬＥＤのような指向性を持った光を照明等に使用する際に、部屋の一点を照らすのではなく、広い範囲を明るくしたいためである。
このように、反射特性を改善した塗膜パターンが開発されれば、ディスプレイ用途などの反射板用途としても期待される。
That is, recently, while maintaining the characteristics of high reflectivity, the reflection of light from the light source is not a total reflection in one direction like a mirror, but a diffuse reflection that is scattered in all directions. This is because when a light having directivity such as an LED is used for illumination or the like, it is not intended to illuminate a single point in the room but to brighten a wide range.
Thus, if a coating film pattern with improved reflection characteristics is developed, it can be expected as a reflector application such as a display.
本発明の目的は、高反射率で光による劣化を抑えつつ、硬化物の光の拡散性にも優れる硬化性樹脂組成物と、それを用いて形成したソルダーレジストを有するプリント配線板と反射板を提供することにある。 An object of the present invention is to provide a curable resin composition having high reflectivity and suppressing deterioration due to light, and having excellent light diffusibility of a cured product, and a printed wiring board and a reflector having a solder resist formed using the same Is to provide.
発明者らは、上記目的の実現に向け鋭意研究した結果、シリカで表面処理された酸化チタンを使用することにより、光に対する劣化を抑えられることを見出した。さらに、シリカで表面処理された酸化チタンと、硫酸バリウムおよびタルクから選ばれるいずれか少なくとも1種とを併用することによって、高反射率で光を拡散させる特性が得られることも見出し、本発明を想到するに至った。 As a result of diligent research aimed at realizing the above object, the inventors have found that the use of titanium oxide surface-treated with silica can suppress degradation to light. Furthermore, it has also been found that by using titanium oxide surface-treated with silica in combination with at least one selected from barium sulfate and talc, a property of diffusing light with high reflectivity can be obtained. I came up with an idea.
すなわち、本発明の硬化性樹脂組成物は、１分子内にエチレン性不飽和基とカルボキシル基を含む樹脂と、光重合開始剤と、光重合性モノマーと、シリカで表面処理された酸化チタンと、有機溶剤とを含むことを特徴とする。
より好ましい態様としては、さらに硫酸バリウムおよびタルクのいずれか少なくとも１種を含むことを特徴とする。
That is, the curable resin composition of the present invention comprises a resin containing an ethylenically unsaturated group and a carboxyl group in one molecule, a photopolymerization initiator, a photopolymerizable monomer, and titanium oxide surface-treated with silica. And an organic solvent.
A more preferred embodiment is characterized by further containing at least one of barium sulfate and talc.
本発明によれば、高反射率で光による劣化を抑えつつ、硬化物の光の拡散性にも優れる硬化性樹脂組成物と、それを用いて形成したソルダーレジストを有するプリント配線板と反射板を提供することができる。 According to the present invention, a curable resin composition having a high reflectance and suppressing deterioration due to light, and having excellent light diffusibility of a cured product, and a printed wiring board and a reflector having a solder resist formed using the curable resin composition Can be provided.
以下、本発明の硬化性樹脂組成物の各構成成分について具体的に説明する。
１分子内にエチレン性不飽和基とカルボキシル基を含む樹脂としては、１分子内に光硬化性のためのエチレン性不飽和基と弱アルカリ水溶液による現像を可能にするカルボキシル基を有する樹脂であれば使用可能であり、特定のものに限定されるものではない。このような１分子内にエチレン性不飽和基とカルボキシル基を含む樹脂は、以下に列挙する樹脂（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）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、
（２）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、
（３）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。
Hereinafter, each structural component of the curable resin composition of this invention is demonstrated concretely.
The resin containing an ethylenically unsaturated group and a carboxyl group in one molecule may be a resin having an ethylenically unsaturated group for photocuring in one molecule and a carboxyl group that enables development with a weak alkaline aqueous solution. It can be used and is not limited to a specific one. As such a resin containing an ethylenically unsaturated group and a carboxyl group in one molecule, the following resins (any of oligomers or polymers) can be preferably used. That is,
(1) 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;
(2) 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,
(3) 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、前記（１）に記載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) a carboxyl group-containing (meth) acrylic copolymer resin, which is the photosensitive carboxyl group-containing resin described in (1), and (b) an oxirane ring and an ethylenic group in one molecule. A copolymer resin having a carboxyl group obtained by reaction with a compound having a saturated group is preferred.
この場合、特に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（ｂ）として、脂肪族重合性モノマーから生成される化合物を用いれば、樹脂の芳香環から起因する光による劣化も抑えられるので好ましい。 In this case, if a compound produced from an aliphatic polymerizable monomer is used as the compound (b) having an oxirane ring and an ethylenically unsaturated group in one molecule, deterioration due to light originating from the aromatic ring of the resin is also suppressed. This is preferable.
（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）の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、特に脂肪族モノマーから生成される化合物を用いることが好ましく、具体例としては、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、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート等を挙げることができる。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。 As the compound having an oxirane ring and an ethylenically unsaturated group in one molecule of (b), it is particularly preferable to use a compound produced from an aliphatic monomer. Specific examples include 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-epoxycyclohexylmethyl Examples thereof include amino acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate. 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.
１分子内にエチレン性不飽和基とカルボキシル基を含む樹脂は、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 resin containing an ethylenically unsaturated group and a carboxyl group in one molecule 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光重合開始剤としては、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、１ ，１−ジクロロアセトフェノン、２−ヒドロキシ−１−｛４−（２−ヒドロキシ−２−メチル−プロピオニル）−２−メチル−プロパン−１−オ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−モルホリノフェニル）−ブタン−１−オン、Ｎ，Ｎ−ジメチルアミノアセトフェノン、２−（ジメチルアミノ）−２−｛（４−メチルフェニル）メチル｝−１−｛４−（４-モルフォルニル）フェニル｝−１−ブタノン等のアミノアセトフェノン類； ２−メチルアントラキノン、２−エチルアントラキノン、２−ｔ−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；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、２−クロロチオキサントン、２，４−ジイソプロピルチオキサントン等のチオキサントン類； 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、４，４ ’−ビスジエチルアミノベンゾフェノン等のベンゾフェノン類又はキサントン類；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や、２−トリクロロメチル−５−スチリル−１，３，４−オキサジアゾール、２−トリクロロメチル−５−（ｐ−シアノスチリル）−１，３，４−オキサジアゾール等のハロメチルオキサジアゾール系化合物；２，４−ビス（ トリクロロメチル）−６−（ｐ−メトキシ−フェニルビニル）−１，３，５−トリアジン、２，４−ビス（トリクロロメチル）−６−ｐ−メトキシスチリル−ｓ−トリアジン、２，４−ビス（トリクロロメチル）−６−（１−ｐ−ジメチルアミノフェニル−１，３−ブタジエニル）−ｓ−トリアジン等のハロメチル−ｓ−トリアジン系化合物、１，２−オクタンジオン，１−[−４−（フェニルチオ）−，２−（Ｏ−ベンゾイルオキシム）]、エタノン，１−[９−エチル−６−（２−メチルベンゾイル）９Ｈ−カルバゾ−ル−３−イル]−１−（０−アセチルオキシム）等が挙げられるが、ビスアシルフォスフィンオキサイド系光重合開始剤とモノアシルフォスフィンオキサイド系光重合開始剤を併用することが望ましい。ビスアシルフォスフィンオキサイド系光重合開始剤としては、ビス−（２，６−ジクロロベンゾイル）フェニルフォスフィンオキサイド、ビス−（２，６−ジクロロベンゾイル）−２，５−ジメチルフェニルフォスフィンオキサイド、ビス−（２，６−ジクロロベンゾイル）−４−プロピルフェニルフォスフィンオキサイド、ビス−（２，６−ジクロロベンゾイル）−１−ナフチルフォスフィンオキサイド、ビス−（２，６−ジメトキシベンゾイル）フェニルフォスフィンオキサイド、ビス−（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルフォスフィンオキサイド、ビス−（２，６−ジメトキシベンゾイル）−２，５−ジメチルフェニルフォスフィンオキサイド、ビス−（２，４，６−トリメチルベンゾイル）フェニルフォスフィンオキサイド、（２，５，６−トリメチルベンゾイル）−２，４，４−トリメチルペンチルフォスフィンオキサイド等が挙げられる。中でもビス−（２，４，６−トリメチルベンゾイル）フェニルフォスフィンオキサイド（チバ・ジャパン社製、商品名；イルガキュア８１９）が入手しやすく実用的である。 Examples of the photopolymerization initiator used in the present invention include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2 Acetophenones such as -diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-1- {4- (2-hydroxy-2-methyl-propionyl) -2-methyl-propan-1-one; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, N , N-dimethylaminoacetophenone, 2- (di Aminoacetophenones such as tilamino) -2-{(4-methylphenyl) methyl} -1- {4- (4-morpholinyl) phenyl} -1-butanone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t Anthraquinones such as butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal and benzyldimethyl ketal Ketones such as benzophenone, 4,4′-bisdiethylaminobenzophenone, or xanthones; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-trichloromethyl Halomethyloxadiazole compounds such as -5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole; 4-bis (trichloromethyl) -6- (p-methoxy-phenylvinyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2, Halomethyl-s-triazine compounds such as 4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 1,2-octanedione, 1-[- 4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) 9H-carbazol-3-yl] -1- ( 0-acetyloxime) and the like, but it is desirable to use a bisacylphosphine oxide photopolymerization initiator and a monoacylphosphine oxide photopolymerization initiator in combination. Examples of the bisacylphosphine oxide photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis -(2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide Bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 4,6-trimethylbenzoyl) pheni Phosphine oxide, and (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide and the like. Among them, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by Ciba Japan, trade name; Irgacure 819) is easily available and practical.
モノアシルフォスフィンオキサイド系光重合開始剤としては、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、２，６−ジメトキシベンゾイルジフェニルフォスフィンオキサイド、２，６−ジクロロベンゾイルジフェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイルフェニルフォスフィン酸メチルエステル、２−メチルベンゾイルジフェニルフォスフィンオキサイド、ピバロイルフェニルフォスフィン酸イソプロピルエステル等が挙げられる。中でも２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド（チバ・ジャパン社製、商品名；ダロキュアＴＰＯ）が入手しやすく実用的である。 Examples of the monoacylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2, Examples include 4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, and pivaloylphenylphosphinic acid isopropyl ester. Among them, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by Ciba Japan, trade name: Darocur TPO) is easily available and practical.
上記ビスアシルフォスフィンオキサイド系光重合開始剤と前記モノアシルフォスフィンオキサイド系光重合開始剤を併用することにより、酸化チタンを配合した高反射率の塗膜でも必要な光を吸収でき、高精細なパターン形成ができるようになるが、その配合比率を変えることにより微調整が可能となる。パターンの断面形状で基材面側の深部の硬化性が不足してアンダーカットが出やすいときには、上記ビスアシルフォスフィンオキサイド系光重合開始剤の比率を大きくし、表面硬化性が不足して現像後に表面状態が悪いときには前記モノアシルフォスフィンオキサイド系光重合開始剤の比率を大きくする。光重合開始剤の配合量は、１分子内にエチレン性不飽和基とカルボキシル基を含む樹脂（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。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、光重合開始剤由来の塗膜の色つきが大きくなり、またコスト高の原因となるので好ましくない。 By using the above bisacylphosphine oxide photopolymerization initiator and the monoacylphosphine oxide photopolymerization initiator in combination, the coating film with high reflectivity blended with titanium oxide can absorb the necessary light and achieve high definition. However, fine adjustment is possible by changing the blending ratio. When the cross-sectional shape of the pattern has insufficient curability at the deep part on the substrate surface side and undercut is likely to occur, the ratio of the above bisacylphosphine oxide photopolymerization initiator is increased to develop with insufficient surface curability. When the surface condition is poor later, the ratio of the monoacylphosphine oxide photopolymerization initiator is increased. The blending amount of the photopolymerization initiator is preferably 1 to 30 parts by mass, more preferably 2 to 25 parts by mass with respect to 100 parts by mass of the resin (A) containing an ethylenically unsaturated group and a carboxyl group in one molecule. is there. When the blending amount is less than 1 part by mass, the photocurability is lowered, and pattern formation after exposure / development becomes difficult. On the other hand, when the amount exceeds 30 parts by mass, the color of the coating film derived from the photopolymerization initiator is increased and the cost is increased.
本発明に用い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。 Examples of the photopolymerizable monomer used in the present invention include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono- or di-glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. Acrylates; acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris- Of polyhydric alcohols such as hydroxyethyl isocyanurate or their ethylene oxide or propylene oxide adducts Acrylates such as phenoxy acrylate, bisphenol A diacrylate and ethylene oxide or propylene oxide adducts of these phenols; glycidyl ether acrylates such as glycerin diglycidyl ether and trimethylolpropane triglycidyl ether; Melamine acrylate; and / or methacrylates corresponding to the above acrylates.
これらの光重合性モノマーの配合量は、１分子内にエチレン性不飽和基とカルボキシル基を含む樹脂１００質量部に対して、好ましくは１０〜１００質量部、より好ましくは２０〜８０質量部である。配合量が１００質量部を超えると、硬化塗膜がソルダーレジストとしての物性が低下して好ましくない。一方、１０質量部未満であると充分な光硬化性がなく、高精細なパターンが得られない。 The blending amount of these photopolymerizable monomers is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the resin containing an ethylenically unsaturated group and a carboxyl group in one molecule. is there. When the blending amount exceeds 100 parts by mass, the cured coating film is not preferable because the physical properties as a solder resist are lowered. On the other hand, if it is less than 10 parts by mass, sufficient photocurability is not obtained and a high-definition pattern cannot be obtained.
シリカで表面処理された酸化チタンは、アナターゼ型もルチル型も用いることができるが、ルチル型が好ましい。アナターゼ型酸化チタンは、ルチル型と比較して紫外線領域の短波長側での反射率が高いため、反射率としては望ましいが、光触媒活性を有するために、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、白色度の点ではアナターゼ型と比較して紫外線領域の短波長側での反射率が劣るものの、光活性を殆ど有さないために、樹脂の劣化を抑えることができ、安定した硬化物を得ることができる。また、ルチル型酸化チタンの中でも塩素法で製造したものが、樹脂の劣化をさらに抑えるので特に好ましい。 The titanium oxide surface-treated with silica can be anatase type or rutile type, but the rutile type is preferred. Anatase-type titanium oxide has higher reflectivity on the short wavelength side in the ultraviolet region than rutile type, so it is desirable as a reflectivity, but it has photocatalytic activity and therefore causes discoloration of the resin in the composition. There is. On the other hand, rutile titanium oxide has poor reflectivity on the short wavelength side of the ultraviolet region in terms of whiteness compared to anatase type, but suppresses deterioration of the resin because it has almost no photoactivity. And a stable cured product can be obtained. Further, among the rutile type titanium oxides, those produced by the chlorine method are particularly preferable because the deterioration of the resin is further suppressed.
シリカで表面処理された酸化チタンとしては、タイペークＲ−８２０、タイペークＲ−８３０、タイペークＲ−５５０、タイペークＲ−７８０、タイペークＲ−７８０−２、タイペークＲ−８５０、タイペークＲ−８５５、タイペークＣＲ−８０、タイペークＣＲ−９０、タイペークＣＲ−９０、タイペークＣＲ−９０−２、タイペークＣＲ−９３、タイペークＣＲ−９５、タイペークＣＲ−９５３、タイペークＣＲ−６３、タイペークＣＲ−８５（石原産業株式会社製）、タイピュアＲ−１００、タイピュアＲ−１０１、タイピュアＲ−１０２、タイピュアＲ−１０３、タイピュアＲ−１０４、タイピュアＲ−１０５、タイピュアＲ−１０８、タイピュアＲ−９００、タイピュアＲ−９０２、タイピュアＲ−９６０、タイピュアＲ−７０６、タイピュアＲ−９３１（デュポン株式会社製）、ＴＩＴＯＮ Ｒ−２５、ＴＩＴＯＮ Ｒ−２１、ＴＩＴＯＮ Ｒ−３２、ＴＩＴＯＮ Ｒ−７Ｅ、ＴＩＴＯＮ Ｒ−５Ｎ、ＴＩＴＯＮ Ｒ−６１Ｎ、ＴＩＴＯＮ Ｒ−６２Ｎ、ＴＩＴＯＮ Ｒ−４２、ＴＩＴＯＮ Ｒ−４５Ｍ、ＴＩＴＯＮ Ｒ−４４、ＴＩＴＯＮ Ｒ−４９Ｓ、ＴＩＴＯＮ ＧＴＲ−１００、ＴＩＴＯＮ ＧＴＲ−３００、ＴＩＴＯＮ Ｄ−９１８、ＴＩＴＯＮ ＴＣＲ−２９、ＴＩＴＯＮ ＴＣＲ−５２、ＴＩＴＯＮ ＦＴＲ−７００（堺化学工業株式会社製）等を使用することができる。 Examples of the titanium oxide surface-treated with silica include Taipei R-820, Taipei R-830, Taipei R-550, Taipei R-780, Taipei R-780-2, Taipei R-850, Taipei R-855, and Taipei CR. -80, Type CR-90, Type CR-90, Type CR-90-2, Type CR-93, Type CR-95, Type CR-953, Type CR-63, Type CR-85 (manufactured by Ishihara Sangyo Co., Ltd.) ), Pure Pure R-100, Tai Pure R-101, Tai Pure R-102, Tai Pure R-103, Tai Pure R-104, Tai Pure R-105, Tai Pure R-108, Tai Pure R-900, Tai Pure R-902, Tai Pure R- 960, Taipure R-706 Taipure R-931 (manufactured by DuPont), TITON R-25, TITON R-21, TITON R-32, TITON R-7E, TITON R-5N, TITON R-61N, TITON R-62N, TITON R-42 , TITON R-45M, TITON R-44, TITON R-49S, TITON GTR-100, TITON GTR-300, TITON D-918, TITON TCR-29, TITON TCR-52, TITON FTR-700 Etc.) can be used.
このようなシリカで表面処理された酸化チタンの配合量は、組成物中の有機溶剤を除いた不揮発分の質量の好ましくは３０〜８０質量部、より好ましくは３０〜７０質量部である。配合量が８０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、３０質量部未満であると、隠ぺい力が小さく、高反射率の塗膜を得ることができない。 The amount of titanium oxide surface-treated with such silica is preferably 30 to 80 parts by mass, more preferably 30 to 70 parts by mass of the non-volatile content excluding the organic solvent in the composition. If the blending amount exceeds 80 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 30 parts by mass, the hiding power is small and a highly reflective coating film cannot be obtained.
本発明で使用される硫酸バリウムおよびタルクから選ばれるいずれか少なくとも１種は、シリカで表面処理された酸化チタンとの併用で光の拡散性に寄与するものである。
このような硫酸バリウムとしては、沈降性硫酸バリウム ♯１００、沈降性硫酸バリウム ♯３００、沈降性硫酸バリウム ＳＳ−５０、ＢＡＲＩＡＣＥ Ｂ−３０、ＢＡＲＩＡＣＥ Ｂ−３１、ＢＡＲＩＡＣＥ Ｂ−３２、ＢＡＲＩＡＣＥ Ｂ−３３、ＢＡＲＩＡＣＥ Ｂ−３４、ＢＡＲＩＦＩＮＥ ＢＦ−１、ＢＡＲＩＦＩＮＥ ＢＦ−１０、ＢＡＲＩＦＩＮＥ ＢＦ−２０、ＢＡＲＩＦＩＮＥ ＢＦ−４０（堺化学工業株式会社製）、Ｗ−１、Ｗ−６、Ｗ−１０、Ｃ−３００（竹原化学工業株式会社製）などが挙げられる。
タルクとしては、ＬＭＳ−１００、ＬＭＳ−２００、ＬＭＳ−３００、ＬＭＳ−３５００、ＬＭＳ−４００、ＬＭＰ−１００、ＰＫＰ−５３、ＰＫＰ−８０、ＰＫＰ−８１（富士タルク工業株式会社製）、Ｄ−６００、Ｄ−８００、Ｄ−１０００、Ｐ−２、Ｐ−３、Ｐ−４、Ｐ−６、Ｐ−８、ＳＧ−９５（日本タルク株式会社製）等が上げられる。これらは単独あるいは複数組み合わして使用できる。
At least one selected from barium sulfate and talc used in the present invention contributes to light diffusibility in combination with titanium oxide surface-treated with silica.
Examples of such barium sulfate include precipitated barium sulfate # 100, precipitated barium sulfate # 300, precipitated barium sulfate SS-50, BARIACE B-30, BARIACE B-31, BARIACE B-32, BARIACE B-33, BARIACE B-34, BARIFINE BF-1, BARIFINE BF-10, BARIFINE BF-20, BARIFINE BF-40 (manufactured by Sakai Chemical Industry Co., Ltd.), W-1, W-6, W-10, C-300 (Takehara Chemical Industry Co., Ltd.).
As talc, LMS-100, LMS-200, LMS-300, LMS-3500, LMS-400, LMP-100, PKP-53, PKP-80, PKP-81 (manufactured by Fuji Talc Industrial Co., Ltd.), D- 600, D-800, D-1000, P-2, P-3, P-4, P-6, P-8, SG-95 (manufactured by Nippon Talc Co., Ltd.) and the like. These can be used alone or in combination.
本発明で使用される有機溶剤は、硬化性樹脂組成物を塗布しやすい状態にし、塗布後乾燥させて造膜させるために用いられる。このような有機溶剤としては、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。 The organic solvent used in the present invention is used to make the curable resin composition easy to apply and to form a film by drying after application. Examples of such organic solvents include 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 Glycol ethers such as ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esterified products of the above glycol ethers Esters; 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; octane, aliphatic hydrocarbons such as decane.
前記有機溶剤は、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。１分子内にエチレン性不飽和基とカルボキシル基を含む樹脂１００質量部に対して、２０〜３００質量部が好ましい。 The said organic solvent can be used individually or in mixture of 2 or more types. 20-300 mass parts is preferable with respect to 100 mass parts of resin which contains an ethylenically unsaturated group and a carboxyl group in 1 molecule.
本発明の硬化性樹脂組成物は、プリント配線板のソルダーレジスト用途のように耐熱性が必要な場合には、エポキシ化合物を配合して熱硬化を併用することで耐熱性を得ることができる。
このようなエポキシ化合物としては、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、ビフェニル型エポキシ樹脂、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。
When heat resistance is required for the curable resin composition of the present invention as in a solder resist application of a printed wiring board, heat resistance can be obtained by blending an epoxy compound and using thermosetting together.
Examples of such an epoxy compound include bisphenol S-type epoxy resin, diglycidyl phthalate resin, triglycidyl isocyanurate (for example, TEPIC-H (manufactured by Nissan Chemical Co., Ltd. having three epoxy groups with respect to the S-triazine ring skeleton surface). Β-form having a structure bonded in the same direction) or TEPIC (β-form and α having a structure in which one epoxy group is bonded to the other two epoxy groups in the S-triazine ring skeleton surface in a different direction. Etc.) and other epoxy resins that are sparingly soluble in diluents such as bixylenol-type epoxy resins, biphenyl-type epoxy resins, tetraglycidylxylenoylethane resins, and bisphenol A-type epoxy resins , Hydrogenated bisphenol A type epoxy resin, bisphenol F type resin, brominated bisphenol A type epoxy Si resin, phenol novolac type or cresol novolac type epoxy resin, alicyclic epoxy resin, bisphenol A novolac type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclo Examples thereof include an epoxy resin that is soluble in a diluent such as a pentadiene phenolic epoxy resin, a silicone-modified epoxy resin, and an ε-caprolactone-modified epoxy resin. These epoxy resins can be used alone or in combination of two or more.
このようなエポキシ化合物の配合量は、１分子内にエチレン性不飽和基とカルボキシル基を含む樹脂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、１分子内にエチレン性不飽和基とカルボキシル基を含む樹脂のカルボキシル基が未反応の状態で残存するため、ソルダーレジストとして使用する場合は硬化塗膜の耐熱性が充分に得られ難くなる傾向がある。 The compounding amount of such an epoxy compound 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 resin containing an ethylenically unsaturated group and a carboxyl group in one molecule. When the compounding quantity of an epoxy compound 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, when the amount is less than 5 parts by mass, the carboxyl group of the resin containing an ethylenically unsaturated group and a carboxyl group remains in an unreacted state in one molecule. It tends to be difficult to obtain sufficient properties.
本発明では、塗膜にかかる熱が原因の劣化による変色を少なくする目的で、酸化防止剤を配合することができる。前記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・ジャパン社製）などが挙げられる。 In the present invention, an antioxidant can be blended for the purpose of reducing discoloration due to deterioration caused by heat applied to the coating film. 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 these are manufactured by Ciba Japan).
前記酸化防止剤の配合量は、１分子内にエチレン性不飽和基とカルボキシル基を含む樹脂（Ａ）１００質量部に対して好ましくは２５質量部以下、より好ましくは０．４〜１５質量部である。０．４質量部以下では塗膜にかかる熱が原因の劣化による変色防止効果が少なく、２５質量部以上では現像性の低下をおこし、パターニングに不具合が出る。 The blending amount of the antioxidant is preferably 25 parts by mass or less, more preferably 0.4 to 15 parts by mass with respect to 100 parts by mass of the resin (A) containing an ethylenically unsaturated group and a carboxyl group in one molecule. It is. Below 0.4 part by mass, the effect of preventing discoloration due to deterioration caused by heat applied to the coating film is small, and at 25 parts by mass or more, developability is lowered, resulting in a problem in patterning.
さらに、本発明の硬化性樹脂組成物においては、ヒンダードアミン系光安定剤を含有させることにより、光劣化を減少させることができる。
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。
Furthermore, in the curable resin composition of this invention, photodegradation can be reduced by containing a hindered amine light stabilizer.
Examples of the hindered amine light stabilizer include Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by Ciba Specialty Chemicals); MARK LA-57, LA-62, LA-67, LA-63. LA-68 (all are manufactured by Adeka Gas Chemical Co., Ltd.); Sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (all are Sankyo Lifetech ( Etc.).
上記光安定剤は、１分子内にエチレン性不飽和基とカルボキシル基を含む樹脂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 light stabilizer is preferably added in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin containing an ethylenically unsaturated group and a carboxyl group in one molecule.
本発明の硬化性樹脂組成物においては、分散剤を含有させることにより酸化チタンの分散性、沈降性を改善することができる。例えば、ＡＮＴＩ−ＴＥＲＲＡ−Ｕ、ＡＮＴＩ−ＴＥＲＲＡ−Ｕ１００、ＡＮＴＩ−ＴＥＲＲＡ−２０４、ＡＮＴＩ−ＴＥＲＲＡ−２０５、ＤＩＳＰＥＲＢＹＫ−１０１、ＤＩＳＰＥＲＢＹＫ−１０２、ＤＩＳＰＥＲＢＹＫ−１０３、ＤＩＳＰＥＲＢＹＫ−１０６、ＤＩＳＰＥＲＢＹＫ−１０８、ＤＩＳＰＥＲＢＹＫ−１０９、ＤＩＳＰＥＲＢＹＫ−１１０、ＤＩＳＰＥＲＢＹＫ−１１１、ＤＩＳＰＥＲＢＹＫ−１１２、ＤＩＳＰＥＲＢＹＫ−１１６、ＤＩＳＰＥＲＢＹＫ−１３０、ＤＩＳＰＥＲＢＹＫ−１４０、ＤＩＳＰＥＲＢＹＫ−１４２、ＤＩＳＰＥＲＢＹＫ−１４５、ＤＩＳＰＥＲＢＹＫ−１６１、ＤＩＳＰＥＲＢＹＫ−１６２、ＤＩＳＰＥＲＢＹＫ−１６３、ＤＩＳＰＥＲＢＹＫ−１６４、ＤＩＳＰＥＲＢＹＫ−１６６、ＤＩＳＰＥＲＢＹＫ−１６７、ＤＩＳＰＥＲＢＹＫ−１６８、ＤＩＳＰＥＲＢＹＫ−１７０、ＤＩＳＰＥＲＢＹＫ−１７１、ＤＩＳＰＥＲＢＹＫ−１７４、ＤＩＳＰＥＲＢＹＫ−１８０、ＤＩＳＰＥＲＢＹＫ−１８２、ＤＩＳＰＥＲＢＹＫ−１８３、ＤＩＳＰＥＲＢＹＫ−１８５、ＤＩＳＰＥＲＢＹＫ−１８４、ＤＩＳＰＥＲＢＹＫ−２０００、ＤＩＳＰＥＲＢＹＫ−２００１、ＤＩＳＰＥＲＢＹＫ−２００９、ＤＩＳＰＥＲＢＹＫ−２０２０、ＤＩＳＰＥＲＢＹＫ−２０２５、ＤＩＳＰＥＲＢＹＫ−２０５０、ＤＩＳＰＥＲＢＹＫ−２０７０、ＤＩＳＰＥＲＢＹＫ−２０９６、ＤＩＳＰＥＲＢＹＫ−２１５０、ＢＹＫ−Ｐ１０４、ＢＹＫ−Ｐ１０４Ｓ、ＢＹＫ−Ｐ１０５、ＢＹＫ−９０７６、ＢＹＫ−９０７７、ＢＹＫ−２２０Ｓ（ビックケミー・ジャパン株式会社製）、ディスパロン２１５０、ディスパロン１２１０、ディスパロンＫＳ−８６０、ディスパロンＫＳ−８７３Ｎ、ディスパロン７００４、ディスパロン１８３０、ディスパロン１８６０、ディスパロン１８５０、ディスパロンＤＡ−４００Ｎ、ディスパロンＰＷ−３６、ディスパロンＤＡ−７０３−５０（楠本化成株式会社製）、フローレンＧ−４５０、フローレンＧ−６００、フローレンＧ−８２０、フローレンＧ−７００、フローレンＤＯＰＡ−４４、フローレンＤＯＰＡ−１７（共栄社化学株式会社製）が挙げられる。
分散剤の含有量は、酸化チタン１００質量部に対して、０．１〜１０質量部、好ましくは０．５〜５質量部が好ましい。
In the curable resin composition of this invention, the dispersibility and sedimentation property of a titanium oxide can be improved by containing a dispersing agent. For example, ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, 63 DISPERBYSPER 166, DISP RBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBYK-ER, 2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9076, BYK-776 Big Chemie Manufactured by Japan), Disparon 2150, Disparon 1210, Disparon KS-860, Disparon KS-873N, Disparon 7004, Disparon 1830, Disparon 1860, Disparon 1850, Disparon DA-400N, Disparon PW-36, Disparon DA-703-50 (Manufactured by Enomoto Kasei Co., Ltd.), florene G-450, florene G-600, florene G-820, florene G-700, florene DOPA-44, florene DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.).
Content of a dispersing agent is 0.1-10 mass parts with respect to 100 mass parts of titanium oxides, Preferably 0.5-5 mass parts is preferable.
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.
以下に硬化性樹脂組成物の使用の一例として、ソルダーレジストに使用する場合のプリント配線板の製造について説明する。
まず、本発明の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。
次に、粘度調整した組成物を、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する。
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し、１００℃〜２００℃で熱硬化することにより、ソルダーレジストパターンを形成してなる本発明のプリント配線板を製造することができる。
As an example of the use of the curable resin composition, the production of a printed wiring board when used for a solder resist will be described below.
First, the curable resin composition of the present invention is diluted as necessary to adjust the viscosity to be suitable for the coating method.
Next, the composition whose viscosity has been adjusted is applied to a printed wiring board on which a circuit has been formed by a method such as a screen printing method, a curtain coating method, a spray coating method, a roll coating method, and the composition at a temperature of 70 to 90 ° C., for example. A tack-free coating film is formed by evaporating and drying the organic solvent contained in the product.
Then, selectively exposed with active energy rays through a photomask, the unexposed portion is developed with an aqueous alkaline solution to form a resist pattern, and thermally cured at 100 ° C. to 200 ° C. to form a solder resist pattern. The printed wiring board of this invention which becomes can be manufactured.
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。
現像液であるアルカリ水溶液としては、０．５〜５質量％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。
このような本発明に係るプリント配線板は、反射率の高い酸化チタンを含有する本発明の硬化性樹脂組成物を用いて作製され、高反射率で拡散性に優れたパターンを有するものである。
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.
As the alkaline aqueous solution that is a developer, a 0.5 to 5% by mass aqueous sodium carbonate solution is generally used, but other alkaline aqueous solutions can also 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.
Such a printed wiring board according to the present invention is produced using the curable resin composition of the present invention containing titanium oxide having a high reflectivity, and has a pattern with high reflectivity and excellent diffusibility. .
以下、実施例及び比較例を示して、本発明を具体的に説明するが、本発明はこれに限定されるものではないことはもとよりである。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, it cannot be overemphasized that this invention is not limited to this.
樹脂溶液１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、商品名；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、商品名；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、商品名；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 resin solution 1:
In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introducing tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (Nippon Yushi) as a polymerization initiator 21.4 g of trade name; Perbutyl O) manufactured by Co., Ltd. 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 (manufactured by Daicel Chemical Industries, Ltd., trade name: Plaxel FM1) were used as a polymerization initiator. By adding 21.4 g of bis (4-t-butylcyclohexyl) peroxydicarbonate (trade name: Parroyl TCP, manufactured by NOF Corporation) over 3 hours, and further aging for 6 hours A carboxyl group-containing copolymer resin was obtained. The reaction was performed in 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、商品名；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質量％（不揮発分）含む溶液を得た。以下、この反応溶液を樹脂溶液１と呼ぶ。 Next, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name: Cyclomer A200) was added to the carboxyl group-containing copolymer resin, and dimethylbenzylamine 3. 6 g and 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor were 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 mass (nonvolatile content) of a carboxyl group-containing resin having no aromatic ring and having an acid value of solid content of 108.9 mgKOH / g and a weight average molecular weight of 25,000 was obtained. . Hereinafter, this reaction solution is referred to as “resin solution 1”.
実施例１〜８、参考例１〜３及び比較例１〜５の配合：
表１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、それぞれ硬化性樹脂組成物を作製した。表中の数字は、質量部を示す。
Formulation of Examples 1 to 8, Reference Examples 1 to 3 and Comparative Examples 1 to 5:
Each component was blended according to Table 1, stirred, and dispersed with a three roll to prepare curable resin compositions. The numbers in the table indicate parts by mass.
光重合開始剤１：イルガキュア８１９（チバ・ジャパン社製）
光重合開始剤２：ダロキュアＴＰＯ（チバ・ジャパン社製）
光重合性モノマー：ジペンタエリスリトールヘキサアクリレート
酸化チタン１（アルミナ＋シリカで表面処理）：タイペークＣＲ−９０（石原産業社製）
酸化チタン２（アルミナ＋シリカ＋有機物で表面処理）：タイペークＣＲ−９０−２（石原産業社製）
酸化チタン３（アルミナで表面処理）：タイペークＣＲ−５０（石原産業社製）
硫酸バリウム：沈降性硫酸バリウム ♯１００（堺化学工業製）
タルク：ＬＭＳ−２００（富士タルク工業製）
シリカ：ＦＢ−３ＳＤＣ（電気化学工業製）
有機溶剤：カルビトールアセテート
エポキシ化合物（ビフェニル型）：ＹＸ−４０００（ジャパンエポキシレジン製）
硬化剤：ジシアンジアミド
消泡剤（シリコーンオイル）：ＫＳ−６６（信越シリコーン製）
Photopolymerization initiator 1: Irgacure 819 (manufactured by Ciba Japan)
Photopolymerization initiator 2: Darocur TPO (manufactured by Ciba Japan)
Photopolymerizable monomer: Dipentaerythritol hexaacrylate titanium oxide 1 (surface treatment with alumina + silica): Taipei CR-90 (Ishihara Sangyo Co., Ltd.)
Titanium oxide 2 (alumina + silica + organic surface treatment): Taipei CR-90-2 (Ishihara Sangyo Co., Ltd.)
Titanium oxide 3 (surface treatment with alumina): Taipei CR-50 (Ishihara Sangyo Co., Ltd.)
Barium sulfate: precipitated barium sulfate # 100 (manufactured by Sakai Chemical Industry)
Talc: LMS-200 (Fuji talc industry)
Silica: FB-3SDC (manufactured by Denki Kagaku Kogyo)
Organic solvent: carbitol acetate epoxy compound (biphenyl type): YX-4000 (manufactured by Japan Epoxy Resin)
Curing agent: Dicyandiamide antifoaming agent (silicone oil): KS-66 (manufactured by Shin-Etsu Silicone)
実施例１〜８、参考例１〜３及び比較例１〜５で得られた各硬化性樹脂組成物について、以下のようなソルダーレジストの諸性質を試験し、評価した。 About each curable resin composition obtained in Examples 1-8, Reference Examples 1-3, and Comparative Examples 1-5, the following various properties of the solder resist were tested and evaluated.
（１）耐光性試験
実施例１〜８、参考例１〜３及び比較例１〜５の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（基板全面）でパターンを印刷し、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ＨＭＷ−６８０ＧＷ（オーク製作所製）を用いて、３０ｍｍ角のネガパターンを残すように、７００ｍＪ／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。
得られた試験片を、分光測色計ＣＭ−２６００ｄ（コニカミノルタ製）でＳＣＩ方式で、ＸＹＺ表色法のＹ値を測定して初期値として、光による劣化試験を行なった。コンベア型ＵＶ照射機ＱＲＭ−２０８２−Ｅ−０１（オーク製作所製）を用いて、メタルハライドランプ、コールドミラー、８０Ｗ／ｃｍ２×３灯、コンベアスピード６．５ｍ／分（積算光量１０００ｍＪ／ｃｍ２）の条件で１００回、３００回繰り返してＵＶを照射した。その後、試験片を同様の方法でＸＹＺ表色法のＹ値を測定した。その結果を表２に示す。
(1) Lightfastness test The curable resin compositions of Examples 1 to 8, Reference Examples 1 to 3 and Comparative Examples 1 to 5 were FR-4 copper-clad with a size of 100 mm × 150 mm and a thickness of 1.6 mm. Print a pattern with a solid (over the entire surface of the substrate) using a 100-mesh polyester (made by bias) plate so that the film thickness becomes 40 μm by screen printing, and circulate hot air at 80 ° C. for 30 minutes. It dried in the type drying oven. Using a printed wiring board exposure machine HMW-680GW (manufactured by Oak Seisakusho), UV exposure was performed with an integrated light amount of 700 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.
The obtained test piece was subjected to a light deterioration test using the spectrophotometer CM-2600d (manufactured by Konica Minolta) by the SCI method and measuring the Y value of the XYZ colorimetric method as an initial value. Conditions of metal halide lamp, cold mirror, 80W / cm2 × 3 lamp, conveyor speed 6.5m / min (integrated light quantity 1000mJ / cm2) using conveyor type UV irradiator QRM-2082-E-01 (manufactured by Oak Seisakusho) UV irradiation was repeated 100 times and 300 times. Thereafter, the Y value of the XYZ colorimetric method was measured for the test piece in the same manner. The results are shown in Table 2.
表２に示す結果から明らかなように、本発明の硬化性樹脂組成物によれば、シリカで表面処理した酸化チタンを選択することによって、耐光性を向上させることができることがわかる。 As is clear from the results shown in Table 2, it can be seen that according to the curable resin composition of the present invention, light resistance can be improved by selecting titanium oxide surface-treated with silica.
（２）拡散性
前記（１）と同様に作製した試験片を、分光測色計ＣＭ−２６００ｄ（コニカミノルタ製）でＳＣＩ方式とＳＣＥ方式で、それぞれＸＹＺ表色法のＹ値を測定した。ＳＣＩ方式は分光測色計の光源から照明された光が測定物にあたり、その角度と逆方向の同じ角度にはね返った光である正反射光と測定物にあたり拡散した光を含めて測定する。一方、ＳＣＩ方式は拡散光のみを測定する。そして、Ｙ値は測定した反射率の大きさを示し、大きいほど反射率が高いことを示す。また、ＳＣＩ方式とＳＣＥ方式のＹ値の差が小さいほど、拡散性が優れていることを示す。ＳＣＩ方式のＹ値、ＳＣＥ方式のＹ値、ＳＣＩ方式とＳＣＥ方式のＹ値の差を、それぞれ表２に示す。
(2) Diffusivity Y values of the XYZ colorimetric methods were measured for the test pieces prepared in the same manner as in (1) above, using the spectrophotometer CM-2600d (manufactured by Konica Minolta) in the SCI method and the SCE method. In the SCI method, the light illuminated from the light source of the spectrocolorimeter hits the object to be measured, and includes the specularly reflected light that is reflected at the same angle opposite to the angle and the light diffused by the object to be measured. On the other hand, the SCI method measures only diffused light. And Y value shows the magnitude | size of the measured reflectance, and it shows that a reflectance is so high that it is large. Further, the smaller the difference between the Y values of the SCI method and the SCE method, the better the diffusibility. Table 2 shows the Y value of the SCI method, the Y value of the SCE method, and the difference between the Y values of the SCI method and the SCE method.
表２に示す結果から明らかなように、実施例１〜８はシリカで処理された酸化チタンと硫酸バリウムまたはタルクを併用したもので、いずれもＳＣＩ方式とＳＣＥ方式のＹ値の差がかなり小さく、拡散性の向上が見られることがわかる。 As is clear from the results shown in Table 2, Examples 1 to 8 are a combination of titanium oxide treated with silica and barium sulfate or talc, both of which have a very small difference in Y value between the SCI method and the SCE method. It can be seen that an improvement in diffusivity is observed.
（２）はんだ耐熱性
前記（１）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。その結果を表３に示す。
(2) Solder heat resistance A rosin-based flux was applied to each test piece prepared in the same manner as in (1) above 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 Table 3.
（３）耐溶剤性
前記（１）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。その結果を表３に示す。
(3) Solvent resistance Each test piece prepared in the same manner as in (1) above was immersed in propylene glycol monomethyl ether acetate for 30 minutes and dried, and then a peel test with a cellophane adhesive tape was performed to remove the coating film. The discoloration was evaluated. The results are shown in Table 3.
（４）鉛筆硬度試験
前記（１）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。その結果を表３に示す。
(4) Pencil hardness test 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 (1) above at an angle of about 45 °, and then applied. The hardness of the pencil at which no film peeling occurred was recorded. The results are shown in Table 3.
（５）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、前記（１）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。その結果を表３に示す。
(5) Insulation resistance test A test piece was prepared under the same conditions as in (1) above, except that a comb-type electrode B coupon having an IPC B-25 test pattern was used instead of the FR-4 copper-clad laminate. A DC 500 V bias was applied to the test piece, and the insulation resistance value was measured. The results are shown in Table 3.
前記（３）はんだ耐熱性、前記（４）耐溶剤性、前記（５）鉛筆硬度試験の評価基準は以下の通りである。
○・・・塗膜の剥がれや変色なし
×・・・塗膜の剥がれや変色あり
The evaluation criteria of the (3) solder heat resistance, the (4) solvent resistance, and the (5) pencil hardness test are as follows.
○ ・ ・ ・ No peeling or discoloration of coating film × ・ ・ ・ There is peeling or discoloration of coating film
表３に示す結果から明らかなように、本発明の硬化性樹脂組成物は、ソルダーレジスト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分かった。 As is apparent from the results shown in Table 3, it was found that the curable resin composition of the present invention has good heat resistance, solvent resistance, adhesion and electrical insulation required for the solder resist.
以上詳述した通り、本発明の硬化性樹脂組成物は、シリカで表面処理した酸化チタンを使用することにより、高反射率で光による劣化を最小限にしたソルダーレジストと反射板を提供できることが分かった。また、シリカで表面処理した酸化チタンと硫酸バリウムやタルクを併用することにより、光を拡散させる特性も備えたソルダーレジストと反射板を提供できることが分かった。 As described above in detail, the curable resin composition of the present invention can provide a solder resist and a reflector that have high reflectivity and minimize deterioration due to light by using titanium oxide surface-treated with silica. I understood. Further, it was found that by using titanium oxide surface-treated with silica together with barium sulfate and talc, it is possible to provide a solder resist and a reflector having a property of diffusing light.
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