JPH0580521A - Photosetting resist composition and production of printed circuit board by using this composition and printed circuit board - Google Patents
Photosetting resist composition and production of printed circuit board by using this composition and printed circuit boardInfo
- Publication number
- JPH0580521A JPH0580521A JP24106991A JP24106991A JPH0580521A JP H0580521 A JPH0580521 A JP H0580521A JP 24106991 A JP24106991 A JP 24106991A JP 24106991 A JP24106991 A JP 24106991A JP H0580521 A JPH0580521 A JP H0580521A
- Authority
- JP
- Japan
- Prior art keywords
- printed circuit
- resist
- circuit board
- copper
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000007747 plating Methods 0.000 claims abstract description 103
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910052802 copper Inorganic materials 0.000 claims abstract description 79
- 239000010949 copper Substances 0.000 claims abstract description 79
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000004641 Diallyl-phthalate Substances 0.000 claims abstract description 10
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 51
- 239000000126 substance Substances 0.000 claims description 45
- 239000000758 substrate Substances 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 15
- 239000004020 conductor Substances 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 11
- 239000011889 copper foil Substances 0.000 claims description 9
- 239000002518 antifoaming agent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- -1 methacrylate compound Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000002318 adhesion promoter Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 239000003822 epoxy resin Substances 0.000 abstract description 9
- 229920000647 polyepoxide Polymers 0.000 abstract description 9
- 238000009413 insulation Methods 0.000 abstract description 8
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 8
- 230000006378 damage Effects 0.000 abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 2
- 229910000679 solder Inorganic materials 0.000 description 46
- 238000000034 method Methods 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000654 additive Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 6
- 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
- 238000010828 elution Methods 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 244000028419 Styrax benzoin Species 0.000 description 4
- 235000000126 Styrax benzoin Nutrition 0.000 description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229960002130 benzoin Drugs 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 235000019382 gum benzoic Nutrition 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 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 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- ZXLYUNPVVODNRE-UHFFFAOYSA-N 6-ethenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=C)=N1 ZXLYUNPVVODNRE-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
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002601 oligoester Polymers 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- DVVXXHVHGGWWPE-UHFFFAOYSA-N 2-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=CC=C1C(O)=O DVVXXHVHGGWWPE-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- HIPQTCQUXOFTFI-UHFFFAOYSA-N 2-methoxy-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(OC)C(=O)C1=CC=CC=C1 HIPQTCQUXOFTFI-UHFFFAOYSA-N 0.000 description 1
- ROHTVIURAJBDES-UHFFFAOYSA-N 2-n,2-n-bis(prop-2-enyl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N(CC=C)CC=C)=N1 ROHTVIURAJBDES-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 229940116411 terpineol Drugs 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
(57)【要約】
【目的】信頼性の高い、超高密度プリント回路板の製造
法を提供する。
【構成】超高密度プリント回路板製造に用いるレジスト
は、固形のジアリルフタレートプレポリマを主材とする
ため密着露光性及び絶縁性が良好であり、光重合促進剤
のモノマに多官能アクリレートもしくはメタクリレート
化合物を用いるため、ＵＶ光に対して高感度である。ま
た、所定の化合物で銅との密着性を確保するため、従来
のような熱硬化成分、例えば、エポキシ樹脂を含まずに
耐めっき反応性が付与でき、現像時の樹脂の溶け出し及
び抜け出し等のダメージを極力抑えることができる。
(57) [Summary] [Objective] To provide a highly reliable manufacturing method of an ultra high density printed circuit board. [Structure] The resist used for the production of ultra-high density printed circuit boards is mainly composed of solid diallyl phthalate prepolymer, so that it has good adhesion exposure and insulation properties, and the photopolymerization accelerator monomer is a polyfunctional acrylate or methacrylate. Since it uses a compound, it is highly sensitive to UV light. Further, in order to secure the adhesion to copper with a predetermined compound, it is possible to impart resistance to plating without using a conventional thermosetting component, for example, an epoxy resin, and to dissolve and escape the resin during development. You can minimize the damage of.
Description
【０００１】[0001]
【産業上の利用分野】本発明は光硬化性レジスト組成物
と、これを用いたプリント回路板に関する。FIELD OF THE INVENTION The present invention relates to a photocurable resist composition and a printed circuit board using the same.
【０００２】[0002]
【従来の技術】従来のプリント回路板製造時に用いるＵ
Ｖ露光、現像型レジストには、その一例として、特公昭
５１−４０４５１号、特開昭６０−２０８３７７号、特
開昭６２−４３９０号、特開昭６２−１５３８５１号公
報などを挙げることができる。これらレジストは、図２
に示すプリント回路板の製造方法で主に用いられるもの
であった。図２はサブトラクト法として知られるプリン
ト回路板の製造方法であり、四層板を例に示してある。
この工程では、内層を形成し、上下面に銅箔をラミネー
トした銅張り積層板を出発材料として、所定位置に孔を
あけ、孔内に触媒を付与した後、スルーホールを含む全
面に電気銅めっきを施し、エッチングで所定の回路パタ
ーンを形成し、最後にソルダレジストを塗布するもので
ある。このソルダレジストには、これまでスクリーン印
刷でパターンを形成するエポキシ樹脂系の熱硬化型のも
のが用いられてきたが、プリント回路板の配線密度の増
大にともなって、塗布精度の良いＵＶ露光、現像型のソ
ルダレジストが開発されたものである。U used in the manufacture of conventional printed circuit boards.
Examples of V-exposure and development type resists include JP-B-51-40451, JP-A-60-208377, JP-A-62-4390 and JP-A-62-153851. .. These resists are shown in FIG.
It was mainly used in the method for manufacturing a printed circuit board shown in. FIG. 2 shows a method of manufacturing a printed circuit board known as the subtract method, and shows a four-layer board as an example.
In this process, starting from a copper-clad laminate with inner layers formed and copper foil laminated on the top and bottom surfaces, holes are drilled at predetermined positions, a catalyst is applied to the holes, and then electrolytic copper is applied to the entire surface including through holes. The plating is applied, a predetermined circuit pattern is formed by etching, and finally a solder resist is applied. For this solder resist, a thermosetting epoxy resin type that forms a pattern by screen printing has been used so far, but with the increase in the wiring density of the printed circuit board, UV exposure with good coating accuracy, A development type solder resist was developed.
【０００３】一方、図１に示すパートリアディティブ法
のプリント回路板の製造方法では、図２に示すサブトラ
クト法のプリント回路板に用いるソルダレジストとは全
く異なる特性を付与した耐めっき反応性のソルダレジス
トを用いることが不可欠である。On the other hand, in the method of manufacturing a printed circuit board of the part-additive method shown in FIG. 1, a solder having a plating-reactive property imparting characteristics completely different from those of the solder resist used in the printed circuit board of the subtract method shown in FIG. It is essential to use a resist.
【０００４】パートリアディティブ法では、サブトラク
ト法と異なり、銅張り積層板の所定の位置に孔をあけ、
触媒を付与した後、先に導体回路を形成する。次いで、
所定部に耐めっき反応性をもつソルダレジストを形成し
た後、最後に、化学銅めっきを用いてスルーホール、ラ
ンド、コネクタ等の必要な個所のみにめっきを施すもの
である。Unlike the subtractive method, in the part-additive method, holes are made at predetermined positions in the copper-clad laminate,
After applying the catalyst, the conductor circuit is first formed. Then
After a solder resist having a plating resistance is formed on a predetermined part, finally, chemical copper plating is used to plate only necessary portions such as through holes, lands, and connectors.
【０００５】この製造方法は、サブトラクト法に比較し
て、安価、高精度の利点がある。すなわち、サブトラク
ト法のように全面にめっきを施さず、必要な個所のみに
部分的にのみめっきをすることや、導体回路形成におけ
るエッチングも銅張り積層板の薄い銅箔のみのエッチン
グでよいことなどから、工程が簡略で損失が少なく、高
精度の配線が可能である。This manufacturing method has advantages of low cost and high accuracy as compared with the subtract method. That is, unlike the subtractive method, the entire surface is not plated, only the required parts are partially plated, and the etching in the conductor circuit formation may be performed only on the thin copper foil of the copper-clad laminate. Therefore, the process is simple, the loss is small, and highly accurate wiring is possible.
【０００６】しかし、このような利点を活かすには、パ
ートリアディティブ法で用いるソルダレジストに特殊な
機能が要求される。すなわち、高温、強アルカリの過酷
な化学銅めっき液に長時間浸漬され、かつ、ソルダレジ
ストの下の銅の配線パターンに化学銅めっきの析出電位
−０．６〜−０．９Ｖ（飽和カロメル電極参照）が長時
間作用する。かかる過酷な工程を経た後にも、ソルダレ
ジストとして必要な耐熱性や、永久レジストとしてプリ
ント回路板を保護するために必要な絶縁性等の特性を何
等、劣化してはならない極めて高度な機能である。However, in order to take advantage of such advantages, a special function is required for the solder resist used in the part additive method. That is, it is immersed in a harsh chemical copper plating solution of high temperature and strong alkali for a long time, and the deposition potential of the chemical copper plating on the copper wiring pattern under the solder resist is -0.6 to -0.9 V (saturated calomel electrode). (See) acts for a long time. Even after undergoing such a harsh process, it is an extremely advanced function that must not deteriorate the characteristics such as heat resistance required as a solder resist and insulation required for protecting a printed circuit board as a permanent resist. ..
【０００７】この目的に適した耐めっき反応性のソルダ
レジストとして、スクリーン印刷でパターンを形成する
エポキシ樹脂系の熱硬化型のものが知られており、その
例が特開昭５８−１４７４１６号公報に開示されてい
る。以上の公知例から耐めっき反応性をもち、ＵＶ露
光、現像でパターンを形成できレジストを用いれば極め
て精度が良く、超高密度プリント回路板の製造が可能と
なる。ところが、従来技術によれば銅とレジストとの密
着性を向上させるのにエポキシ樹脂及びその熱硬化剤を
含む必要がある。このエポキシ樹脂及びその熱硬化剤
は、ＵＶ光で重合しないため、感度が低下し易く、現像
工程でエポキシ樹脂及びその熱硬化剤が溶け出しレジス
ト表面のダメージを受け易い欠点をもつ。As a plating resist resistant solder resist suitable for this purpose, an epoxy resin type thermosetting type resist which forms a pattern by screen printing is known, and an example thereof is Japanese Patent Application Laid-Open No. 58-147416. Is disclosed in. From the above-mentioned known examples, it is possible to form an ultrahigh-density printed circuit board with extremely high accuracy by using a resist that has resistance to plating reaction and can form a pattern by UV exposure and development. However, according to the prior art, it is necessary to include an epoxy resin and its thermosetting agent in order to improve the adhesion between the copper and the resist. Since this epoxy resin and its thermosetting agent do not polymerize with UV light, the sensitivity is likely to decrease, and the epoxy resin and its thermosetting agent are liable to melt during the developing process and damage the resist surface.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、上記した従
来技術の欠点のない耐めっき反応性をもつＵＶ露光、現
像型のソルダレジストを実現し、パートリアディティブ
法の高密度プリント回路板の製造を容易ならしめること
を目的としている。実用的なレジストとして備えるべき
特性は、多岐にわたり、その中の一つでも欠けると実用
性が著しく損なわれる。従って、本発明の課題は、単に
従来技術の組み合わせのみでは実現できない、多くの特
性を同時に満足させたレジスト組成を提供することであ
る。このために解決すべき課題を列挙すると次のように
なる。SUMMARY OF THE INVENTION The present invention realizes a UV exposure and development type solder resist having plating resistance, which does not have the above-mentioned drawbacks of the prior art, and can be used for a high density printed circuit board of a part additive method. The purpose is to facilitate manufacturing. There are various characteristics that should be provided as a practical resist, and if even one of them is lacking, the practicality is significantly impaired. Therefore, an object of the present invention is to provide a resist composition satisfying many properties at the same time, which cannot be realized only by combining conventional techniques. The problems to be solved for this are listed below.
【０００９】ａ）本発明のレジストは、ＵＶ光で反応し
ない樹脂を含まないことが必須である。レジスト成分中
にＵＶ光で反応しない樹脂を含んでいると、現像工程で
エポキシ樹脂及びその熱硬化剤が溶け出しレジスト表面
のダメージを受けやすくなり、諸特性の低下及び不安定
性を招く恐れがある。そのため、露光量を多くするか現
像時間を短くしなければならない。露光量を多くすると
解像度が低下し、また現像時間を短くするとレジスト残
りが発生し、後のめっき工程で未着或いは、接着不良が
発生する。従って、本発明のレジストはＵＶ光で反応し
ない樹脂を含まずに、以下の課題を同時に満足させねば
ならない。A) It is essential that the resist of the present invention does not contain a resin that does not react with UV light. If the resist component contains a resin that does not react with UV light, the epoxy resin and its thermosetting agent will melt during the developing process, and the resist surface will be easily damaged, which may lead to deterioration of various characteristics and instability. .. Therefore, it is necessary to increase the exposure amount or shorten the development time. When the exposure amount is increased, the resolution is lowered, and when the development time is shortened, a resist residue is generated, which causes non-adhesion or defective adhesion in the subsequent plating process. Therefore, the resist of the present invention must satisfy the following problems at the same time without containing a resin that does not react with UV light.
【００１０】ｂ）本発明のレジストは、ＵＶ光の露光で
硬化することが必須である。すなわち、プリント回路板
の製造に適した３００〜４００ｎｍのＵＶ光（紫外線）
の照射により、架橋反応を生じ、照射部分のみが硬化す
る必要がある。また、照射量として実用的な０．０５〜
１Ｊ／ｃｍ2の範囲で硬化することが望ましい。B) The resist of the present invention must be cured by exposure to UV light. That is, 300 to 400 nm UV light (ultraviolet light) suitable for manufacturing printed circuit boards.
It is necessary to cause a crosslinking reaction and cure only the irradiated portion. In addition, a practical dose of 0.05-
It is desirable to cure in the range of 1 J / cm 2 .
【００１１】ｃ）本発明のレジストは、ＵＶ照射により
硬化した部分と未硬化部分の、現像液に対する溶解度差
が適切で、現像後の解像度が良好であることが必須であ
る。いいかえれば、適当な溶剤による、優れた現像性を
備えていなければならない。C) It is essential that the resist of the present invention has an appropriate difference in solubility in a developing solution between a portion cured by UV irradiation and an uncured portion, and has good resolution after development. In other words, it must have excellent developability with a suitable solvent.
【００１２】ｄ）本発明のレジストは、プリント回路板
の両面に塗布して、両面同時に露光できることが必須で
ある。すなわち、片面から露光したＵＶ光がレジストお
よび基材中を透過し、他面のレジストを硬化させる、い
わゆる、裏写りがあってはならない。かかる課題を解決
しないと、基材の両面に用いるネガマスクパターンの違
いが反対面にも現れるため、実用性を著しく損なう。D) It is essential that the resist of the present invention can be applied on both sides of a printed circuit board and exposed on both sides simultaneously. That is, there must be no so-called show-through that UV light exposed from one side transmits through the resist and the base material and cures the resist on the other side. If this problem is not solved, the difference in the negative mask patterns used on both sides of the base material will appear on the opposite side as well, impairing practicality.
【００１３】ｅ）本発明のレジストは、ＵＶ露光の際、
ネガマスクをレジストに密着して露光できることが必須
である。かかる課題を解決しないと、レジスト自体の粘
着性や、露光時の昇温によるレジストの軟化が原因とな
り、レジストとネガマスクが接着する。すると、露光毎
にネガマスクを洗浄する必要が生じ、実用性が著しく損
なわれてしまう。E) The resist of the present invention, when exposed to UV,
It is essential that the negative mask can be brought into close contact with the resist to be exposed. If this problem is not solved, the resist and the negative mask adhere to each other due to the tackiness of the resist itself and the softening of the resist due to the temperature rise during exposure. Then, it is necessary to wash the negative mask after each exposure, which significantly impairs practicality.
【００１４】ｆ）本発明のレジストは、塗布性が良好で
あることが必須である。すなわち、プリント回路板の片
面にスクリーン印刷やロールコータ等でレジストを塗布
する際、厚さが均一で、かつ、ボイドが残らないよう
に、適切なインクとしての粘度特性を備えている必要が
ある。F) It is essential that the resist of the present invention has good coatability. That is, when a resist is applied to one surface of a printed circuit board by screen printing or a roll coater, it is necessary to have a uniform thickness and viscosity characteristics as an ink so that voids do not remain. ..
【００１５】ｇ）本発明のレジストは、片面にレジスト
を塗布した後、予備乾燥させ、他面にもレジストを塗布
できなくてはならない。予備乾燥が不足すると、片面に
粘稠なレジストを塗布したままで、他面にレジストを印
刷することができなくなる。予備乾燥が過剰になると、
レジストの反応が進み、両面のレジストの特性に差が生
じる。このような問題がないように、適切に予備乾燥で
きることが必須である。G) With respect to the resist of the present invention, it must be possible to coat the resist on one side and then to predry it so that the resist can be coated on the other side. If the preliminary drying is insufficient, it becomes impossible to print the resist on the other surface with the viscous resist applied on one surface. When pre-drying becomes excessive,
The reaction of the resist progresses, resulting in a difference in the characteristics of the resist on both sides. It is essential to be able to properly pre-dry so as to avoid such problems.
【００１６】ｈ）本発明のレジストは、製品であるプリ
ント回路板上に形成されており、ソルダレジストとし
て、繰返しはんだ付けに耐える良好な耐熱性をもつこと
が必須である。すなわち、およそ２６０℃、１０秒のは
んだ浸漬を約十回繰り返しても、あるいはこれに相当す
る熱風、赤外線、溶剤蒸気等によるはんだ付けによって
も、プリント回路板上のレジストにふくれ、剥離等の異
常が生じないことが必須である。かかる特性は、過酷な
化学銅めっきの工程を経た後のレジストに要求されるも
のであることが、強調されるべきである。H) The resist of the present invention is formed on a printed circuit board as a product, and it is essential that the resist has good heat resistance to withstand repeated soldering as a solder resist. That is, even if solder dipping at about 260 ° C. for 10 seconds is repeated about ten times, or by soldering with hot air, infrared rays, solvent vapor, etc. corresponding to this, abnormalities such as swelling and peeling of the resist on the printed circuit board are caused. Is required to occur. It should be emphasized that such properties are required of the resist after undergoing the harsh chemical copper plating process.
【００１７】ｉ）本発明のレジストは、製品であるプリ
ント回路板上に形成されており、高い絶縁性を保持でき
ることが必須である。すなわち、配線間の絶縁劣化を生
じない優れた絶縁性、特に、吸湿時の絶縁性を保持でき
ることが必要である。かかる特性は、過酷な化学銅めっ
きの工程を経た後のレジストに要求されるものであるこ
とが、強調されるべきである。I) The resist of the present invention is formed on a printed circuit board which is a product, and it is essential that it can maintain high insulation. That is, it is necessary to maintain excellent insulation properties that do not cause insulation deterioration between wirings, particularly insulation properties when absorbing moisture. It should be emphasized that such properties are required of the resist after undergoing the harsh chemical copper plating process.
【００１８】ｊ）本発明のレジストは、製品であるプリ
ント回路板上に形成されており、耐薬品性に優れること
が必須である。すなわち、プリント回路板に部品を搭載
する実装工程で用いられるはんだ付けフラックス、洗浄
溶剤等により、レジストが溶解、変質しない必要があ
る。かかる特性は、過酷な化学銅めっきの工程を経た後
のレジストに要求されるものであることが、強調される
べきである。J) The resist of the present invention is formed on a printed circuit board which is a product, and it is essential that it has excellent chemical resistance. That is, it is necessary that the resist is not dissolved or deteriorated by the soldering flux, the cleaning solvent, etc. used in the mounting process of mounting the component on the printed circuit board. It should be emphasized that such properties are required of the resist after undergoing the harsh chemical copper plating process.
【００１９】ｋ）本発明のレジストは、製品であるプリ
ント回路板上に形成した後、良好な耐アルカリ性をもつ
ことが必須である。すなわち、過酷な化学銅めっきの工
程を経るので、高温、強アルカリの化学銅めっき液によ
って、レジストが溶解、変質しない必要がある。K) It is essential that the resist of the present invention has good alkali resistance after being formed on a printed circuit board as a product. That is, since the process of harsh chemical copper plating is performed, it is necessary that the resist is not dissolved or deteriorated by the chemical copper plating solution of high temperature and strong alkali.
【００２０】ｌ）本発明のレジストは、製品であるプリ
ント回路板上に形成した後、良好な耐めっき反応性をも
つことが必須である。かかる特性は、具体的には次のよ
うなものである。パートリアディティブ法でプリント回
路板を製造する際、化学銅めっきの工程で、導体回路上
のレジストが剥離しないことが必須である。レジストを
形成したプリント回路板は、高温、強アルカリの過酷な
化学銅めっき液に長時間浸漬され、かつ、ソルダレジス
トの下の銅の配線パターンに化学銅めっきの析出電位−
０．６〜−０．９Ｖが長時間作用する。かかる過酷な工
程を経た後でも、銅とレジストの界面で、密着力の低下
や剥離が生じてはならない。L) It is essential that the resist of the present invention has good resistance to plating reaction after being formed on a printed circuit board as a product. Specifically, such characteristics are as follows. When manufacturing a printed circuit board by the part additive method, it is essential that the resist on the conductor circuit is not peeled off in the step of chemical copper plating. The printed circuit board on which the resist is formed is immersed in a severe chemical copper plating solution of high temperature and strong alkali for a long time, and the deposition potential of the chemical copper plating on the copper wiring pattern under the solder resist-
0.6 to -0.9V works for a long time. Even after such a harsh process, the adhesion and the peeling should not be reduced at the interface between the copper and the resist.
【００２１】密着力の低下や剥離が生じる機構は定かで
はないが、経験的に、化学銅めっきの析出電位が剥離反
応の駆動力となることや、銅とレジストの界面に酸化銅
が存在すると剥離が著しく急速に進行することなどが判
っている。これらのことから、化学銅めっき析出電位に
よって、回路銅箔とレジスト界面の酸化物が電気化学的
に還元される結果、密着力の原因となる銅とレジスト間
の結合が破壊され、剥離が生じると推定している。従っ
て、耐めっき反応性（耐剥離性）は一種の耐カソード剥
離性でもある。Although the mechanism of the decrease in adhesion and peeling is not clear, empirically, the deposition potential of the chemical copper plating serves as the driving force for the peeling reaction, and the presence of copper oxide at the interface between copper and the resist. It is known that peeling progresses remarkably rapidly. From these facts, the chemical copper plating deposition potential electrochemically reduces the oxide at the interface between the circuit copper foil and the resist, resulting in the destruction of the bond between the copper and the resist, which causes adhesion, resulting in peeling. Is estimated. Therefore, the plating reaction resistance (peeling resistance) is also a kind of cathode peeling resistance.
【００２２】この耐めっき反応性と、一般的に云われる
耐めっき性とは、厳密に区別すべきである。一般に耐め
っき性と称する内容は、耐アルカリ性を示している場合
が多く、これは、耐めっき反応性（耐剥離性）とは全く
異なるものである。This plating resistance and the generally called resistance to plating should be strictly distinguished. In general, the content called “plating resistance” often indicates alkali resistance, which is completely different from plating reaction resistance (peeling resistance).
【００２３】耐めっき反応性（耐剥離性）の課題は、パ
ートリアディティブ法でプリント回路板を製造する際、
最も留意すべき点の一つで、この問題が解決されない
と、回路銅箔上のレジストが剥離してしまい、全く実用
性が失われる。The problem of plating reaction resistance (peeling resistance) is that when manufacturing a printed circuit board by the part additive method,
One of the most important points to note is that if this problem is not solved, the resist on the circuit copper foil will be stripped off, and the utility will be lost altogether.
【００２４】ｍ）本発明のレジストは、プリント回路板
上に形成した後、化学銅めっきの工程で、レジストから
めっき液中に有害な成分が溶出または抽出されないこと
が必須である。レジストからの、溶出または抽出された
成分が、銅めっきの析出反応に悪影響をおよぼす結果、
めっき反応が停止、ないし、遅滞したり、析出した銅の
物性を著しく劣化し、はんだ付け時のスルーホール信頼
性が損なわれる。つまり、レジストからめっき液中に有
害な成分が溶出または抽出されると、スルーホール部の
めっき皮膜の物性が低下し、スルーホールのコーナ部に
クラックとして現れる。また、この銅皮膜物性の低下
は、めっき液中に投入されるレジスト負荷面積が大きい
ほどその影響は顕著に現れる。有害な成分が銅めっきの
析出反応に悪影響をおよぼす機構は、めっき反応が還元
剤の銅表面における触媒反応を含んでいるため、著しく
複雑であり、経験的にレジストの組成を選択して、耐め
っき溶出性を確保する必要がある。M) After the resist of the present invention is formed on a printed circuit board, it is essential that harmful components are not eluted or extracted from the resist into the plating solution in the step of chemical copper plating. As a result of the components eluted or extracted from the resist adversely affecting the deposition reaction of copper plating,
The plating reaction is stopped or delayed, the physical properties of the deposited copper are significantly deteriorated, and the reliability of through holes during soldering is impaired. That is, when a harmful component is eluted or extracted from the resist into the plating solution, the physical properties of the plated film in the through hole portion deteriorate and appear as cracks at the corner portion of the through hole. Further, the effect of the deterioration of the physical properties of the copper film becomes more remarkable as the resist load area charged in the plating solution is larger. The mechanism by which harmful components have an adverse effect on the deposition reaction of copper plating is extremely complicated because the plating reaction involves the catalytic reaction on the copper surface of the reducing agent. It is necessary to secure plating elution.
【００２５】さらに、耐めっき溶出性と耐アルカリ性と
は厳密に区別すべきである。すなわち、耐アルカリ性が
不足すると、レジスト自体がアルカリに溶解してしまう
のに対し、耐めっき溶出性が不足すると、レジスト中の
特定成分のみがめっき液に溶出する。Furthermore, it is necessary to strictly distinguish between plating elution resistance and alkali resistance. That is, when the alkali resistance is insufficient, the resist itself is dissolved in alkali, whereas when the plating elution resistance is insufficient, only specific components in the resist are eluted into the plating solution.
【００２６】本発明の目的は、上記したａ）からｍ）ま
での課題を全て満足する光硬化性レジスト組成物を提供
することにある。An object of the present invention is to provide a photocurable resist composition which satisfies all the above problems a) to m).
【００２７】本発明の他の目的は、上記したａ）から
ｍ）までの課題を全て満足する光硬化性レジスト組成物
を用いたプリント回路板の製造方法を提供することであ
る。Another object of the present invention is to provide a method for producing a printed circuit board using a photocurable resist composition which satisfies all the above problems a) to m).
【００２８】本発明の他の目的は、上記したａ）から
ｍ）までの課題を全て満足する光硬化性レジスト組成物
を用いたプリント回路板を提供することである。Another object of the present invention is to provide a printed circuit board using a photocurable resist composition satisfying all the above problems a) to m).
【００２９】[0029]
【課題を解決するための手段】上記目的を達成するため
に、本発明は耐めっき性をもつ感光性ソルダレジスト組
成物として、室温で固形状の多官能不飽和化合物と、重
合促進剤であるモノマと、銅との密着向上剤と、光重合
開始剤と、消泡剤と、顔料と、有機溶剤とを含んでなる
ことを途特徴とする光硬化性レジスト組成物を用いる。In order to achieve the above object, the present invention provides a photosensitive solder resist composition having plating resistance, which is a polyfunctional unsaturated compound solid at room temperature and a polymerization accelerator. A photocurable resist composition comprising a monomer, an adhesion improver for copper, a photopolymerization initiator, an antifoaming agent, a pigment, and an organic solvent is used.
【００３０】本発明で用いる室温で固形状の多官能不飽
和化合物とは、例えば、ジアリルフタレート樹脂のよう
に、分子内に多数の不飽和基をもつ化合物で、この固形
樹脂に適切なものを用いることで、前記した多くの課題
を同時に満足するレジストを得ることができる。The polyfunctional unsaturated compound which is solid at room temperature used in the present invention is a compound having a large number of unsaturated groups in the molecule, such as diallyl phthalate resin, which is suitable for this solid resin. By using it, it is possible to obtain a resist that simultaneously satisfies many of the problems described above.
【００３１】具体的に、ジアリルフタレート樹脂とは、
オルト、イソまたはテレフタル酸のジアリルエステルの
プレポリマを含んでなるものである。市販品は、ダイソ
ーＫ．Ｋ．より入手することも可能である。本発明で用
いるのに好ましいプレポリマは、分子量として約３００
０〜３００００であり、３０００以下ではネガマスクと
の密着露光性が劣り、また、３００００以上では現像性
に支障が生じる。また、プレポリマを用いる場合にも、
プレポリマの合成にともなって残留もしくは生成するジ
アリルフタレートモノマもしくは三次元網状構造のγ-
ポリマの少量が含まれることを妨げるものではない。Specifically, the diallyl phthalate resin is
It comprises a prepolymer of a diallyl ester of ortho, iso or terephthalic acid. The commercially available product is Daiso K.K. K. It is also available. A preferred prepolymer for use in the present invention has a molecular weight of about 300.
It is 0 to 30,000, and if it is 3,000 or less, the contact exposure property with a negative mask is poor, and if it is 30,000 or more, developability is impaired. Also, when using prepolymer,
Diallyl phthalate monomer or three-dimensional network γ-residue or formed during the synthesis of prepolymer
It does not prevent inclusion of small amounts of polymer.
【００３２】さらに、本発明の耐めっき性を有する感光
性ソルダレジスト組成物は、少なくとも二個以上の二重
結合を分子内に有する重合促進剤であるモノマを含んで
なるものである。かかる化合物は、例えば、不飽和カル
ボン酸と二価以上のポリヒドロキシ化合物とのエステル
化反応によって得られる。不飽和カルボン酸としては、
アクリル酸、メタクリル酸、イタコン酸、クロトン酸、
マレイン酸等であり、一方、二価以上ののポリヒドロキ
シ化合物は、エチレングリコール、ジエチレングリコー
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やその誘導体を挙げることがで
きる。Further, the photosensitive solder resist composition having plating resistance of the present invention comprises a monomer which is a polymerization accelerator having at least two double bonds in the molecule. Such a compound can be obtained, for example, by an esterification reaction of an unsaturated carboxylic acid and a dihydroxy or higher polyhydroxy compound. As the unsaturated carboxylic acid,
Acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
Maleic acid and the like, on the other hand, polyhydroxy compounds having a valence of 2 or more include ethylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol,
Examples include dipentaerythritol and its derivatives.
【００３３】かかる、不飽和カルボン酸とポリヒドロキ
シ化合物とのエステル化反応によって得られた化合物
は、ジエチレングリコールジアクリレート、ポリエチレ
ングリコールジアクリレート、ネオペンチルグリコール
ジアクリレート、1.5ペンタンジオールジアクリレー
ト、1.6ヘキサンジオールジアクリレート、トリメチロ
ールプロパントリアクリレート、ペンタエリスリトール
トリアクリレート、ジエチレングリコールジメタクリレ
ート、1.3ブタンジオールジメタクリレート等に代表さ
れるジアクリレート、ジメタクリレート、トリアクリレ
ート化合物やジペンタエリスリトールのトリ、テトラ、
ペンタ、ヘキサアクリレートもしくはメタクリレート、
ソルビトールのトリ、テトラ、ペンタ、ヘキサアクリレ
ートもしくはメタクリレートなどに代表される多官能ア
クリレート、メタクリレート化合物や、オリゴエステル
アクリレート、オリゴエステルメタクリレート等を挙げ
ることができる。The compound obtained by the esterification reaction of the unsaturated carboxylic acid and the polyhydroxy compound is diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1.5 pentanediol diacrylate, 1.6 hexanediol diacrylate. Acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, diethylene glycol dimethacrylate, diacrylate represented by 1.3 butanediol dimethacrylate, dimethacrylate, triacrylate compound and dipentaerythritol tri, tetra,
Penta, hexaacrylate or methacrylate,
Examples thereof include polyfunctional acrylates and methacrylate compounds represented by sorbitol tri-, tetra-, penta-, hexa-acrylates and methacrylates, and oligoester acrylates and oligoester methacrylates.
【００３４】また、二価以上のエポキシ樹脂と不飽和カ
ルボン酸付加反応によって生成される化合物を用いるこ
ともできる。この化合物の例は、ビスフェノールＡ型や
ノボラック型のエポキシ樹脂とアクリル酸もしくはメタ
クリル酸との付加反応により生成された化合物を挙げる
ことができる。It is also possible to use a compound produced by an addition reaction of an unsaturated carboxylic acid with a divalent or higher epoxy resin. Examples of this compound include compounds produced by an addition reaction of a bisphenol A type or novolak type epoxy resin and acrylic acid or methacrylic acid.
【００３５】多官能不飽和化合物の分子内に含む官能基
の数は多い程、好ましく、少なくとも二以上、好ましく
は三以上、さらに好ましくは六以上である。The larger the number of functional groups contained in the molecule of the polyfunctional unsaturated compound, the more preferable, and at least two or more, preferably three or more, and more preferably six or more.
【００３６】以上の例は、単官能不飽和化合物の添加を
制限するものではないし、必要により多官能不飽和化合
物との混合物も使用できる。The above examples do not limit the addition of the monofunctional unsaturated compound, and a mixture with a polyfunctional unsaturated compound can be used if necessary.
【００３７】さらに、本発明の耐めっき性を有する感光
性ソルダレジスト組成物は、銅との密着向上剤を含んで
なるものである。銅との密着向上剤としては、分子中に
二重結合とアミノ基がそれぞれ少なくとも一個以上含ま
れる化合物が好適である。これらの化合物には、たとえ
ば、アクリルアミド、メタクリルアミド、アリルアミ
ン、2,4-ジアミノ-6-ビニル-s-トリアジン、2,4-ジアミ
ノ-6-アクリル-s-トリアジン、2,4-ジアミノ-6-メタク
リル-s-トリアジン、2,4-ジアミノ-6-アリル-s-トリア
ジン、ジアリルメラミンなどの代表的なものがある。ま
た、2,4-ジアミノ-6-ビニル-s-トリアジンとエポキシと
の反応性の高いアルキルイミダゾールとの付加反応で得
られる2,4-ジアミノ-6{2'-メチルイミダゾール-(1')}エ
チル-s-トリアジン、2,4-ジアミノ-6{2'-エチル-4'-メ
チルイミダゾール-(1')}エチル-s-トリアジン、2,4-ジ
アミノ-6{2'-ウンデシルイミダゾール-(1')}エチル-s-
トリアジン、2,4-ジアミノ-6{2'-フェニルイミダゾール
-(1')}エチル-s-トリアジンと、二重結合を分子中に含
むモノエポキシ化合物、たとえば、アリルグリシジルエ
ーテル、メタクリル酸グリシジル、アクリル酸グリシジ
ル、テトラヒドロフルフリルアクリレート等とを有機溶
剤中で反応して得た反応物が挙げられる。特にレジスト
の銅との密着性向上及び樹脂との反応性という点から2,
4-ジアミノ-6{2'-ウンデシルイミダゾール-(1')}エチル
-s-トリアジンとアクリル酸グリシジルの熱反応で得ら
れる生成物が好ましい。Further, the photosensitive solder resist composition having plating resistance of the present invention contains an adhesion improver for copper. As the adhesion improver with copper, a compound having at least one double bond and at least one amino group in the molecule is preferable. These compounds include, for example, acrylamide, methacrylamide, allylamine, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-acryl-s-triazine, 2,4-diamino-6. -Methacrylic-s-triazine, 2,4-diamino-6-allyl-s-triazine, diallyl melamine and the like are typical ones. In addition, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6 {2'-methylimidazole- (1 ') obtained by addition reaction of highly reactive alkylimidazole with epoxy } Ethyl-s-triazine, 2,4-diamino-6 {2'-ethyl-4'-methylimidazole- (1 ')} ethyl-s-triazine, 2,4-diamino-6 {2'-undecyl Imidazole- (1 ')} ethyl-s-
Triazine, 2,4-diamino-6 {2'-phenylimidazole
-(1 ')} ethyl-s-triazine and a monoepoxy compound containing a double bond in the molecule, for example, allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate and the like in an organic solvent. The reaction product obtained by the reaction may be mentioned. Especially from the viewpoint of improving the adhesiveness with the copper of the resist and the reactivity with the resin,
4-diamino-6 {2'-undecylimidazole- (1 ')} ethyl
The product obtained by the thermal reaction of -s-triazine and glycidyl acrylate is preferred.
【００３８】この銅との密着向上剤は光重合性の不飽和
結合をもつため、ソルダレジスト組成物の光硬化時に光
硬化樹脂の骨格中に組み込まれ、現像や化学銅めっき液
に対するによる溶け出し及び脱落が無くなる。このた
め、ソルダレジスト組成物の成分溶出に起因するめっき
銅皮膜の物性低下を効果的に抑制することができる。ま
た、加熱時に分子中に含有するアミノ基と銅とが反応し
密着性を向上させる。これは、耐めっき反応性を充分確
保するものである。Since this adhesion improver with copper has a photopolymerizable unsaturated bond, it is incorporated into the skeleton of the photocurable resin during photocuring of the solder resist composition, and is dissolved by development and chemical copper plating solution. And there is no dropout. Therefore, it is possible to effectively suppress the deterioration of the physical properties of the plated copper film due to the elution of the components of the solder resist composition. Further, upon heating, the amino group contained in the molecule reacts with copper to improve the adhesion. This ensures a sufficient resistance to plating reaction.
【００３９】以上の例は、他のアミノ基含有化合物と二
重結合を含むモノエポキシとの反応生成物の添加を制限
するものではないし、必要により上述の化合物との混合
物も使用できる。The above examples do not limit the addition of the reaction product of another amino group-containing compound and the monoepoxy containing the double bond, and if necessary, a mixture with the above compound can be used.
【００４０】さらに、本発明の耐めっき性をもつ感光性
ソルダレジスト組成物は、光重合開始剤を含んでなるも
のである。光重合開始剤例として、アセトフェノン、ベ
ンゾフェノン、ミヒラーケトン、ベンジル、ベンゾイ
ン、ベンゾインアルキルエーテル、ベンゾインアルキル
ケタール、チオキサントン、チオキサントン、アントラ
キノン、アントラキノンやその誘導体もしくは類似物、
1-ヒドロキシシクロヘキシルフェニルケトンやその誘導
体もしくは類似物、2-メチル-1-[4-(メチルチオ)フェニ
ル]-2-モルフォリノ-プロペン-1に代表されるα-アミノ
ケトン化合物等が挙げられる。必要により、光重合開始
剤の混合物を使用できる。また必要により、光重合開始
剤の作用を増感するアミン化合物等を使用することも可
能である。Furthermore, the photosensitive solder resist composition having plating resistance of the present invention contains a photopolymerization initiator. Examples of the photopolymerization initiator, acetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin alkyl ether, benzoin alkyl ketal, thioxanthone, thioxanthone, anthraquinone, anthraquinone or a derivative or analog thereof,
Examples thereof include 1-hydroxycyclohexyl phenyl ketone, derivatives or analogs thereof, and α-aminoketone compounds represented by 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propene-1. If necessary, a mixture of photopolymerization initiators can be used. If necessary, it is also possible to use an amine compound or the like that sensitizes the action of the photopolymerization initiator.
【００４１】さらに、本発明の耐めっき性を有する感光
性ソルダレジスト組成物は、消泡剤を含んでなるもので
ある。このような消泡剤は、シリコーンオイルに代表さ
れるシロキサン結合を含む有機珪素化合物が主に用いら
れる。Furthermore, the photosensitive solder resist composition having plating resistance of the present invention comprises an antifoaming agent. As such a defoaming agent, an organosilicon compound containing a siloxane bond, represented by silicone oil, is mainly used.
【００４２】さらに、本発明の耐めっき性をもつ感光性
ソルダレジスト組成物は、顔料を含んでなるものであ
る。かかる顔料は、耐熱性の優れたフタロシアニン骨格
をもつ顔料である、フタロシアニン、フタロシアニング
リーン、フタロシアニンブルーなどが主に用いられる。Further, the photosensitive solder resist composition having plating resistance of the present invention contains a pigment. As such a pigment, phthalocyanine, phthalocyanine green, phthalocyanine blue, and the like, which are pigments having a phthalocyanine skeleton excellent in heat resistance, are mainly used.
【００４３】さらに、本発明の耐めっき性を有する感光
性ソルダレジスト組成物は、有機溶剤を含んでなるもの
である。かかる有機溶剤としては、メチル、エチル、ブ
チルセルソルブやそのアセテートなどや、メチル、エチ
ル、ブチルカルビトールなどや、テルピネオールなどの
高沸点溶剤などが主に用いられる。Further, the photosensitive solder resist composition having resistance to plating of the present invention contains an organic solvent. As such an organic solvent, methyl, ethyl, butyl cellosolve or its acetate, methyl, ethyl, butyl carbitol, or a high boiling solvent such as terpineol is mainly used.
【００４４】さらに、本発明の耐めっき性をもつ感光性
ソルダレジスト組成物は、必要に応じて他の添加剤を加
えて、さらに性能を向上させることもできる。このよう
な添加剤は、レジストの粘度を調整するための揺変剤
や、レジストの耐熱性を調整するための充填剤や、レジ
ストの解像度を調整するための紫外線吸収剤や、レジス
トの保存安定性を調整するための重合禁止剤などを挙げ
ることができる。Further, the photosensitive solder resist composition having resistance to plating of the present invention can further improve its performance by adding other additives as required. Such additives include thixotropic agents for adjusting the viscosity of the resist, fillers for adjusting the heat resistance of the resist, ultraviolet absorbers for adjusting the resolution of the resist, and storage stability of the resist. Examples thereof include a polymerization inhibitor for adjusting the properties.
【００４５】かかる揺変剤の一例は、石英超微粉末であ
り、かかる充填剤の一例は、石英の微粉末等であり、か
かる紫外線吸収剤の一例は、4-t-ブチル-4'-メトキシ-
ジベンゾイルメタン、2-エチルヘキシル-p-メトキシシ
ンナメート、2-(2'-ヒドロキシ-3',5'-ジ-tert-ブチル
フェニル)ベンゾトリアゾール、2-(2'-ヒドロキシ-3'-t
ert-ブチル-5'-メチルフェニル)-5-クロロベンゾトリア
ゾール、2-(2'-ヒドロキシ-3',5'-ジ-tert-ブチルフェ
ニル)-5-クロロベンゾトリアゾール、2-{2'-ヒドロキシ
-3-(3'',4'',5'',6''-テトラヒドロフタルイミドメチ
ル)-5'-メチルフェニル}ベンゾトリアゾール等である。
かかる重合禁止剤の一例は、ハイドロキノンもしくはそ
の誘導体などである。An example of such a thixotropic agent is ultrafine quartz powder, an example of such a filler is fine quartz powder, and an example of such an ultraviolet absorber is 4-t-butyl-4′-. Methoxy-
Dibenzoylmethane, 2-ethylhexyl-p-methoxycinnamate, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t
ert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- {2' -Hydroxy
-3- (3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl} benzotriazole and the like.
An example of such a polymerization inhibitor is hydroquinone or its derivative.
【００４６】本発明の組成物を構成するのに好ましい配
合割合は、室温で固形状の多官能不飽和化合物を１００
重量部に対して、光重合促進剤の多官能アクリレートを
５ないし８０重量部、好ましくは１０ないし６０重量
部、さらに好ましくは２０ないし５０重量部であり、銅
との密着向上剤の化合物は、特許請求の範囲第５項の化
合物である化１及び化２を用いる場合は、１ないし１０
重量部であり、化３と化４の反応物を用いる場合は、５
ないし４０重量部である。また、光重合開始剤を２ない
し２０重量部であり、消泡剤を０．５ないし１０重量部
であり、顔料を０．２ないし１０重量部であり、有機溶
剤を５０ないし１００重量部である。The preferred blending ratio for forming the composition of the present invention is 100% of the polyfunctional unsaturated compound which is solid at room temperature.
5 to 80 parts by weight, preferably 10 to 60 parts by weight, more preferably 20 to 50 parts by weight, of a polyfunctional acrylate as a photopolymerization accelerator, and the compound of the adhesion improver with copper is When the compounds 1 and 2 which are the compounds of claim 5 are used, 1 to 10 are used.
5 parts by weight when the reaction products of Chemical formulas 3 and 4 are used.
To 40 parts by weight. Further, the photopolymerization initiator is 2 to 20 parts by weight, the defoaming agent is 0.5 to 10 parts by weight, the pigment is 0.2 to 10 parts by weight, and the organic solvent is 50 to 100 parts by weight. is there.
【００４７】かかる配合割合の上、下限は、前述した本
発明の課題（ａ）から（ｍ）までが、すべて同時に満足
できるように、注意深く選択された結果から選ばれたも
のである。The upper and lower limits of the blending ratio are selected from the results carefully selected so that the above-mentioned problems (a) to (m) of the present invention can be simultaneously satisfied.
【００４８】次に、本発明の第二の目的である、上記の
耐めっき性をもつ感光性ソルダレジスト組成物を用い
て、パートリアディティブ法でプリント回路板を製造す
る手段を、図１に従って述べる。Next, a second object of the present invention is to provide a means for producing a printed circuit board by the part additive method using the above-mentioned photosensitive solder resist composition having plating resistance, according to FIG. State.
【００４９】業者には一般に周知の方法で銅張り積層板
（ａ）に孔をあけた後、化学銅めっき用触媒をスルホー
ル内を含む基板の全面に付与する。（ｂ） 次いで、当該業者に周知の方法で所定部をエッチングし
て、基板の両面に導体回路を形成する。（ｃ） 次いで、本発明の耐めっき性をもつ感光性ソルダレジス
ト組成物を導体回路を含む基板の片面に塗布し、レジス
トが塗布された基板を乾燥し、レジストを固化する。か
かる方法を繰返し裏面で行なうか、あるいは、耐めっき
性をもつ感光性ソルダレジスト組成物を基板の両面に同
時に塗布してから乾燥することで、基板の両面に固化し
たレジスト層を形成する。乾燥温度は６０ないし１００
℃で、乾燥時間は０．２ないし２時間が好ましい。After making holes in the copper-clad laminate (a) by a method generally known to those skilled in the art, a chemical copper plating catalyst is applied to the entire surface of the substrate including the inside of the through holes. (B) Next, a predetermined portion is etched by a method known to those skilled in the art to form conductor circuits on both surfaces of the substrate. (C) Next, the photosensitive solder resist composition having plating resistance of the present invention is applied to one surface of a substrate including a conductor circuit, and the substrate coated with the resist is dried to solidify the resist. This method is repeated on the back surface, or a photosensitive solder resist composition having plating resistance is simultaneously applied to both surfaces of the substrate and then dried to form a solidified resist layer on both surfaces of the substrate. Drying temperature is 60 to 100
At 0 ° C., the drying time is preferably 0.2 to 2 hours.
【００５０】次いで、基板両面の固化したレジスト層上
にネガマスクを密着させ、両面から同時に０．１ないし
１Ｊ／ｃｍ2のＵＶ光を照射して露光する。次いで、レ
ジスト面からネガマスクを剥離し、未露光部を現像によ
り溶解、除去する。このような現像に適する溶剤とし
て、１，１，１−トリクロロエタンの如き不燃性の塩素
系溶剤が用いられ、現像時間として０．５ないし３分が
選択される。Next, a negative mask is brought into close contact with the solidified resist layers on both sides of the substrate, and UV rays of 0.1 to 1 J / cm 2 are simultaneously irradiated from both sides for exposure. Then, the negative mask is peeled from the resist surface, and the unexposed portion is dissolved and removed by development. As a solvent suitable for such development, a nonflammable chlorine-based solvent such as 1,1,1-trichloroethane is used, and the development time is selected to be 0.5 to 3 minutes.
【００５１】次いで、基板を加熱して形成したレジスト
と銅との密着性を向上させる。加熱条件は１２０ないし
１８０℃、０．２ないし２時間が選択される。また、好
ましくは、加熱を、真空あるいは、不活性ガス雰囲気中
で行う。Next, the adhesion between the resist formed by heating the substrate and the copper is improved. The heating conditions are selected from 120 to 180 ° C. and 0.2 to 2 hours. Further, preferably, the heating is performed in vacuum or in an inert gas atmosphere.
【００５２】以上の工程を経て、基板上にレジスト層が
形成される。（ｄ） 次いで、基板は化学銅めつき液に浸漬され、スルホール
孔内、ランド上をはじめとする主要部分のみに厚い化学
銅めつきが施され、パートリアディティブ法によるプリ
ント回路板が製造される。（ｅ）銅めつきの厚さは、通
常、１０ないし４０μｍが選択される。かかる化学銅め
つき中に、回路銅箔上のレジストに剥離を生じないこと
は、本発明の特筆すべき重要な利点である。Through the above steps, a resist layer is formed on the substrate. (D) Next, the substrate is immersed in a chemical copper plating solution, and thick chemical copper plating is applied only to the main parts such as inside the through holes and on the lands, and a printed circuit board is manufactured by the part additive method. It (E) The thickness of copper plating is usually selected to be 10 to 40 μm. It is a significant advantage of the present invention that the resist on the circuit copper foil does not peel during such chemical copper plating.
【００５３】以上のようなパートリアディティブ法によ
るプリント回路板の製造において、本発明のレジストは
前述した本発明の課題（ａ）から（ｍ）を、すべて同時
に満足できる。このためパートリアディティブ法による
高密度プリント回路板の製造が可能となったのである。In the production of the printed circuit board by the above-mentioned part additive method, the resist of the present invention can simultaneously satisfy all the above-mentioned problems (a) to (m) of the present invention. Therefore, it has become possible to manufacture high-density printed circuit boards by the part-additive method.
【００５４】[0054]
【実施例】以下、本発明の耐めっき性を有する感光性ソ
ルダレジスト組成物と、これを用いたプリント回路板の
製造について、具体的に説明する。以下の各実施例およ
び比較例に用いた、感光性ソルダレジスト組成物は、共
通して次のような方法で製造した。EXAMPLES The photosensitive solder resist composition having plating resistance of the present invention and the production of a printed circuit board using the same will be specifically described below. The photosensitive solder resist compositions used in the following Examples and Comparative Examples were commonly manufactured by the following method.
【００５５】本発明で用いる室温で固形状の多官能不飽
和化合物としてのジアリルフタレート樹脂を秤量し、セ
パラブルフラスコに入れ、これに、秤量した有機溶剤を
加え、混合した後、８０ないし１００℃で３０分ないし
２時間の間、撹拌しながら溶解する。溶解物を室温まで
冷却した後、残りのレジストの素材を加え、充分に撹拌
して混合する。次いで、三本ロールミルを用いて２ない
し４回の混練を施し、スクリーン印刷用のレジストイン
クを調整する。 一方、プリント回路板の製造は、共通
して次のような方法に従った。The diallyl phthalate resin as a polyfunctional unsaturated compound which is solid at room temperature used in the present invention is weighed and placed in a separable flask, to which the weighed organic solvent is added and mixed, and then at 80 to 100 ° C. Dissolve with stirring for 30 minutes to 2 hours. After the melt is cooled to room temperature, the remaining resist materials are added and mixed thoroughly with stirring. Then, kneading is performed 2 to 4 times using a three-roll mill to prepare a resist ink for screen printing. On the other hand, the manufacture of the printed circuit board commonly follows the following method.
【００５６】１．６ｍｍ厚で３５μｍの銅箔をもつガラ
スエポキシ両面銅張り積層板（ａ）の所定の位置にドリ
ルで孔をあけた後、化学銅めっき用触媒をスルホール内
を含む基板の全面に付与した。（ｂ） 次いで、エッチング用のドライフィルムレジストを用い
て、テンティング法により、所定部をエッチングして、
基板の両面に導体回路を形成した。（ｃ） 次いで、前記の方法で調整した感光性ソルダレジストイ
ンクを導体回路を含む基板の片面にスクリーン印刷法で
塗布し、レジストが塗布された基板を乾燥し、レジスト
を固化した。かかる方法を繰返し裏面で行ない、基板の
両面に固化したレジスト層を形成した。乾燥温度は８０
℃で、乾燥時間は一時間である。After drilling a hole in a predetermined position of a glass epoxy double-sided copper-clad laminate (a) having a thickness of 1.6 mm and a copper foil of 35 μm, the entire surface of the substrate including the chemical copper plating catalyst in through holes Granted to. (B) Next, a dry film resist for etching is used to etch a predetermined portion by a tenting method,
Conductor circuits were formed on both sides of the substrate. (C) Next, the photosensitive solder resist ink prepared by the above method was applied to one side of the substrate including the conductor circuit by a screen printing method, and the substrate coated with the resist was dried to solidify the resist. This method was repeated on the back side to form solidified resist layers on both sides of the substrate. Drying temperature is 80
At ° C, the drying time is 1 hour.
【００５７】次いで、基板両面の固化したレジスト層上
にネガマスクを密着させ、両面から同時に０．５Ｊ／ｃ
ｍ2のＵＶ光を照射して露光した。次いで、レジスト面
からネガマスクを剥離し、未露光部を現像により溶解、
除去した。現像溶剤として１，１，１−トリクロロエタ
ンを用い、現像時間として一分を選択した。Next, a negative mask is brought into close contact with the solidified resist layers on both sides of the substrate, and 0.5 J / c is simultaneously applied from both sides.
Exposure was performed by irradiating m 2 of UV light. Next, the negative mask is peeled off from the resist surface, and the unexposed portion is dissolved by development
Removed. 1,1,1-Trichloroethane was used as the developing solvent, and 1 minute was selected as the developing time.
【００５８】さらに、基板を加熱してレジストと銅を密
着させた。加熱条件は真空中１４０℃、一時間行った。Further, the substrate was heated to bring the resist into close contact with copper. The heating conditions were 140 ° C. in vacuum for 1 hour.
【００５９】以上の工程を経て、基板上にレジスト層を
形成した。（ｄ） 次いで、基板を化学銅めつき液に浸漬し、スルホール孔
内、ランド上をはじめとする主要部分のみに厚い化学銅
めつきを施した。（ｄ）化学銅めつき液には、次の組成
のものを用いた。めつき条件は浴温７０℃、浴ｐＨが１
２．５、めっき時間は１５時間であり、この間、めっき
液組成、めつき条件が常に一定となるように、めっき液
成分の自動補給を行なった。析出電位は、約−０．７Ｖ
（飽和カロメル電極参照）であり、めっき厚は約３０μ
ｍとなった。Through the above steps, a resist layer was formed on the substrate. (D) Next, the substrate was dipped in a chemical copper plating solution, and thick chemical copper plating was applied only to the main portions such as the through holes and the land. (D) The chemical copper plating solution used had the following composition. The plating conditions are a bath temperature of 70 ° C and a bath pH of 1.
2.5, the plating time was 15 hours, and during this period, the components of the plating solution were automatically replenished so that the composition of the plating solution and the plating conditions were always constant. Deposition potential is about -0.7V
(See saturated calomel electrode), plating thickness is about 30μ
It became m.
【００６０】化学銅めつき液の組成 ＣｕＳＯ4・５Ｈ2Ｏ…………………１２ｇ ＥＤＴＡ・２Ｎａ……………………４２ｇ ３７％ホルマリン……………………３ｍｌ ＮａＯＨ……………ｐＨ１２．５とする量 エトキシ界面活性剤……………１００ｍｇ 2,2'-ジピリジル………………… ５０ｍｇ 脱イオン水……………全量を１ｌとする量 本発明の耐めっき性をもつ感光性ソルダレジスト組成物
と、これを用いたプリント回路板の特性については、共
通して、以下の項目と評価方法に従って判定した。 Composition of chemical copper plating solution CuSO 4 .5H 2 O …………………… 12g EDTA • 2Na …………………… 42g 37% formalin …………………… 3ml NaOH… ………… Amount to make pH 12.5 ethoxy surfactant ……………… 100 mg 2,2′-dipyridyl ……………… 50 mg deionized water ………… Amount to make 1 liter total amount of the present invention The properties of the photosensitive solder resist composition having plating resistance and the printed circuit board using the same were commonly determined according to the following items and evaluation methods.
【００６１】１）塗布性：スクリーン印刷後の塗膜中に
残存するボイド、気泡等がなく、平滑な面をもつものを
良とした。1) Applicability: A film having a smooth surface with no voids or bubbles remaining in the coating film after screen printing was regarded as good.
【００６２】２）密着露光性：レジスト面にネガマスク
を密着してＵＶ光で露光した後、ネガマスクを剥離する
際、ネガマスクにレジストが付着しないものを良とし
た。2) Contact exposure property: After the negative mask was brought into close contact with the resist surface and exposed with UV light, when the negative mask was peeled off, one in which the resist did not adhere to the negative mask was regarded as good.
【００６３】３）現像性：１，１，１，−トリクロロエ
タンのスプレー現像を常温で一分間施した際、未露光部
が完全に溶解し、かつ、露光部のレジストに膨潤等がな
いものを良とした。3) Developability: When 1,1,1, -trichloroethane was spray-developed at room temperature for 1 minute, the unexposed area was completely dissolved and the resist in the exposed area was not swollen. It was good.
【００６４】４）耐裏写り性：１．６ｍｍ厚のガラスエ
ポキシ積層板の両面に、約４０μｍの厚さにレジストを
塗布して、乾燥した後、片面から０．５Ｊ／ｃｍ2のＵ
Ｖ光を照射して露光する。現像後の観察で、裏面のレジ
ストが硬化せずに、完全に溶解できるものを良とした。4) Show-through resistance: A resist having a thickness of about 40 μm was applied to both surfaces of a glass epoxy laminate having a thickness of 1.6 mm, dried, and then U of 0.5 J / cm 2 was applied from one surface.
Exposure is performed by irradiating V light. In the observation after the development, the one that could be completely dissolved without hardening the resist on the back surface was regarded as good.
【００６５】５）耐アルカリ性：化学銅めっき後の目視
観察で、レジストの表面が、溶解、変色、粗化されてい
ないものを良とした。5) Alkali resistance: When the surface of the resist was not dissolved, discolored or roughened by visual observation after chemical copper plating, it was regarded as good.
【００６６】６）耐めっき反応性：化学銅めっき後の観
察で、銅めっき析出部と接続している導体回路上に塗布
されているレジストに、剥離や変色のないものを良とし
た。6) Resistance to plating reaction: In the observation after the chemical copper plating, the resist applied on the conductor circuit connected to the copper plating deposit was free from peeling or discoloration.
【００６７】７）耐熱性：化学銅めっき後のプリント回
路板にはんだ用のフラックスを塗布し、２６０℃のはん
だ槽に１０秒間浸漬して、室温まで空冷する。この操作
を十回繰り返した後の観察で、レジストにふくれ、剥離
等の異常がないものを良とした。7) Heat resistance: A flux for soldering is applied to a printed circuit board after chemical copper plating, immersed in a solder bath at 260 ° C. for 10 seconds, and air-cooled to room temperature. Observations after repeating this operation ten times were evaluated as good when there was no abnormality such as swelling or peeling of the resist.
【００６８】８）絶縁性：ガラスエポキシ銅張り積層板
に形成したＪＩＳ−Ｃ−２５１９に準じた櫛形パターン
上にレジストを塗布し、化学銅めっき後の吸湿時の絶縁
抵抗が１０9Ω以上となるものを良とした。8) Insulating property: A resist was applied on a comb pattern conforming to JIS-C-2519 formed on a glass epoxy copper-clad laminate, and the insulation resistance after moisture absorption after chemical copper plating was 10 9 Ω or more. What was good was good.
【００６９】９）スルーホール信頼性：レジスト負荷面
積１ｄｍ2／ｌプリント回路板を化学銅めっき後、２６
０℃のはんだ槽に１０秒間浸漬してはんだ付けを行い、
室温まで空冷する。この操作を五回繰り返した後の観察
で、スルーホール部めっき膜にクラック等の異常がない
ものを良とした。9) Through-hole reliability: resist load area 1 dm 2 / l printed circuit board was plated with chemical copper 26
Immerse in a solder bath at 0 ° C for 10 seconds to solder,
Air cool to room temperature. In the observation after repeating this operation five times, the plating film having no abnormality such as cracks in the through-hole plating film was regarded as good.
【００７０】〈実施例１〉本発明の耐めっき反応性を有
する感光性ソルダレジスト組成物を表１に従って調整
し、１）ないし９）の特性を判定した。その結果を表２
に示す。Example 1 The photosensitive solder resist composition having plating resistance of the present invention was prepared according to Table 1 and the properties 1) to 9) were evaluated. The results are shown in Table 2.
Shown in.
【００７１】[0071]
【表１】 [Table 1]
【００７２】[0072]
【表２】 [Table 2]
【００７３】本発明の室温で固形状の多官能不飽和化合
物としてジアリルフタレート樹脂（ダイソーダップＡ：
ダイソーＫ．Ｋ．製、平均分子量１００００）を用い、
光重合促進剤の多官能不飽和化合物としてペンタエリス
リトールテトラアクリレートを使用した。光重合開始剤
には、ベンゾフェノンと4,4'-ビス(N,N'-ジエチルアミ
ノ)ベンゾフェノンの混合物を用いた。銅との密着向上
剤として表２に示すような化合物を添加した。消泡剤と
してシリコーンオイルＳＨ−２０３（トーレシリコーン
Ｋ．Ｋ．製）を用い、顔料にはフタロシアニングリーン
を使用した。有機溶剤にはエチルセルソルブアセテート
とブチルセルソルブアセテートの混合物を用いた。The room-temperature solid polyfunctional unsaturated compound of the present invention is a diallyl phthalate resin (Dysoup A:
Daiso K. K. Manufactured, average molecular weight 10000),
Pentaerythritol tetraacrylate was used as the polyfunctional unsaturated compound of the photopolymerization accelerator. As the photopolymerization initiator, a mixture of benzophenone and 4,4′-bis (N, N′-diethylamino) benzophenone was used. A compound as shown in Table 2 was added as an adhesion improver with copper. Silicone oil SH-203 (manufactured by Toray Silicone KK) was used as the defoaming agent, and phthalocyanine green was used as the pigment. As the organic solvent, a mixture of ethyl cellosolve acetate and butyl cellosolve acetate was used.
【００７４】かかるレジストを用いて、プリント回路板
を製造した結果、全ての特性を満足するには、本発明の
銅との密着向上剤を用いればよいことが判った。また、
その添加量は、室温で固形状の多官能不飽和化合物の１
００重量部に対して、１ないし１０重量部が適切である
ことも判った。一重量部未満では、レジストと導体回路
との密着力が不足し、耐めっき反応性が充分でなく、１
０重量部を超えると、過剰の密着向上剤が化学銅めっき
液にわずかに溶け出し、析出した銅の物性が低下し、ス
ルーホール信頼性が低下することが判った。As a result of producing a printed circuit board using such a resist, it was found that the adhesion improving agent for copper of the present invention should be used to satisfy all the characteristics. Also,
The addition amount is 1 of the polyfunctional unsaturated compound which is solid at room temperature.
It has also been found that 1 to 10 parts by weight is suitable for 00 parts by weight. If the amount is less than 1 part by weight, the adhesion between the resist and the conductor circuit will be insufficient, and the plating reaction resistance will be insufficient.
It has been found that if the amount exceeds 0 parts by weight, the excess adhesion improver slightly dissolves in the chemical copper plating solution, the physical properties of the deposited copper deteriorate, and the through hole reliability decreases.
【００７５】〈実施例２〉本発明の耐めっき反応性を有
する感光性ソルダレジスト組成物を表３に従って調整
し、前記１）乃至９）の特性を判定した。Example 2 The photosensitive solder resist composition of the present invention having plating resistance was prepared according to Table 3 and the properties 1) to 9) were evaluated.
【００７６】[0076]
【表３】 [Table 3]
【００７７】本例では、表４に示すような二重結合を含
むモノエポキシ化合物とアミノ基を含む化合物とを有機
溶剤中で１２０℃で一時間反応させて得た反応物の銅と
の密着向上効果を求めた。その結果を第５に示す。In this example, a monoepoxy compound having a double bond as shown in Table 4 and a compound having an amino group were reacted in an organic solvent at 120 ° C. for 1 hour to obtain a close contact with copper. I demanded an improvement effect. The result is shown in the fifth.
【００７８】[0078]
【表４】 [Table 4]
【００７９】[0079]
【表５】 [Table 5]
【００８０】かかるレジストを用いて、プリント回路板
を製造した結果、全ての特性を満足するには、本発明の
銅との密着向上剤を用いればよいことが判った。また、
その添加量は、室温で固形状の多官能不飽和化合物の１
００重量部に対して、５ないし４０重量部が適切である
ことも判った。５重量部未満では、レジストと導体回路
との密着力が不足し、耐めっき反応性が充分でなく、４
０重量部を超えると、過剰の密着向上剤が化学銅めっき
液にわずかに溶け出し、析出した銅の物性が低下し、ス
ルーホール信頼性が低下することが判った。As a result of producing a printed circuit board using such a resist, it was found that the adhesion improving agent for copper of the present invention should be used to satisfy all the characteristics. Also,
The addition amount is 1 of the polyfunctional unsaturated compound which is solid at room temperature.
It has also been found that 5 to 40 parts by weight are suitable with respect to 00 parts by weight. If the amount is less than 5 parts by weight, the adhesion between the resist and the conductor circuit will be insufficient, and the plating reaction resistance will be insufficient.
It has been found that if the amount exceeds 0 parts by weight, the excess adhesion improver slightly dissolves in the chemical copper plating solution, the physical properties of the deposited copper deteriorate, and the through hole reliability decreases.
【００８１】〈実施例３〉本発明の耐めっき反応性を有
する感光性ソルダレジスト組成物を表６に従って調整
し、前記１）乃至９）の特性を判定した。その結果を表
７に示す。Example 3 The photosensitive solder resist composition having the plating resistance of the present invention was prepared according to Table 6 and the properties 1) to 9) were evaluated. The results are shown in Table 7.
【００８２】[0082]
【表６】 [Table 6]
【００８３】[0083]
【表７】 [Table 7]
【００８４】本例では、室温で固形状の多官能不飽和化
合物と、光重合促進剤の効果を求めた。In this example, the effects of the polyfunctional unsaturated compound solid at room temperature and the photopolymerization accelerator were determined.
【００８５】表７に示すように、室温で固形状の多官能
不飽和化合物として、ダイソーダップＡ（分子量１００
００）とダップＬ（分子量３５００）とイソダップ（分
子量８０００）を比較したところ、顕著な差異はなく、
いずれも耐めっき反応性の感光性ソルダレジストに使用
できることが判った。As shown in Table 7, as a polyfunctional unsaturated compound solid at room temperature, Daiso Dup A (molecular weight 100
00) and Dapp L (molecular weight 3500) and Isodap (molecular weight 8000) were compared, there was no remarkable difference,
It was found that any of them can be used as a photosensitive solder resist having resistance to plating.
【００８６】一方、光重合促進剤として２、３、４、６
官能脂肪族不飽和化合物とビスフェノールＡ系芳香族二
官能アクリレートを用いた場合を比較した。表７に示す
ように、光重合促進剤の添加量が５ないし８０重量部、
好ましくは１０ないし６０重量部、さらに好ましくは２
０ないし５０重量部で全ての特性を満足するレジストが
得られることが判った。添加量が不足の場合には、露光
時の架橋が不足して、現像の際、レジストが膨潤してし
まい、添加量が過剰の場合には、密着露光性に難が生じ
ることも判った。On the other hand, 2, 3, 4, 6 as a photopolymerization accelerator
The case where the functional aliphatic unsaturated compound and the bisphenol A aromatic bifunctional acrylate were used was compared. As shown in Table 7, the addition amount of the photopolymerization accelerator is 5 to 80 parts by weight,
Preferably 10 to 60 parts by weight, more preferably 2
It was found that a resist satisfying all the properties can be obtained with 0 to 50 parts by weight. It was also found that when the added amount is insufficient, the crosslinking during exposure is insufficient and the resist swells during development, and when the added amount is excessive, the contact exposure property becomes difficult.
【００８７】さらに、不飽和化合物の官能基数は多い方
が、添加量の適正範囲が広いことも判った。かかる観点
から、官能基数は２以上、好ましくは３以上が望まし
く、さらに６官能脂肪族アクリレートが最も優れている
ことも判った。Further, it was also found that the larger the number of functional groups of the unsaturated compound, the wider the appropriate range of the added amount. From this viewpoint, it is desirable that the number of functional groups is 2 or more, preferably 3 or more, and the 6-functional aliphatic acrylate is the most excellent.
【００８８】〈実施例４〉本発明の耐めっき反応性をも
つ感光性ソルダレジスト組成物を表８に従って調整し、
前記１）ないし９）の特性を判定した。その結果を表９
に示す。Example 4 A photosensitive solder resist composition having plating resistance according to the present invention was prepared according to Table 8,
The characteristics of 1) to 9) above were evaluated. The results are shown in Table 9
Shown in.
【００８９】[0089]
【表８】 [Table 8]
【００９０】[0090]
【表９】 [Table 9]
【００９１】本例では、感光性ソルダレジストの特性に
与える光重合開始剤とＵＶ吸収剤と顔料の影響について
求めた。In this example, the effects of the photopolymerization initiator, UV absorber and pigment on the characteristics of the photosensitive solder resist were determined.
【００９２】表９の結果から、顔料のフタロシアニング
リーンを全く含まないレジストでは、レジスト中のＵＶ
光の透過性が大きすぎるため、耐裏写り性が不充分であ
ることが判った。裏写り性を良好とするには、ＵＶ吸収
作用を有するフタロシアニングリーンの如き顔料を、約
０．２重量部以上、レジストに添加すれば良いことも判
った。From the results shown in Table 9, it can be seen that the resist containing no phthalocyanine green pigment does not contain UV in the resist.
It was found that the show-through resistance was insufficient because the light transmittance was too large. It was also found that a pigment such as phthalocyanine green having a UV absorbing function may be added to the resist in an amount of about 0.2 parts by weight or more to improve the show-through property.
【００９３】また、光重合開始剤はベンゾフェノンや4,
4'-ビス(N,N'-ジエチルアミノ)ベンゾフェノン、2-メチ
ル-1-{4-(メチルチオ)フェニル}-2-モルフォリノ-1-プ
ロパン-1、ベンゾインアルキルエーテル、チオキサンソ
ン誘導体とジメチルアミノ安息香酸エステルなどの、各
種のラジカル発生型の光重合開始剤が適していることが
判った。光重合開始剤の最適配合量は、およそ、２ない
し１２重量部であることも判った。ＵＶ吸収作用を有す
る光重合開始剤が不足すると、レジストのＵＶ透過性が
高まり、裏写り性に難が生じるとともに、ＵＶ露光時の
架橋不足から、レジストの耐アルカリ性も劣化する。The photopolymerization initiator is benzophenone or 4,
4'-bis (N, N'-diethylamino) benzophenone, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholino-1-propane-1, benzoin alkyl ether, thioxanthone derivative and dimethylaminobenzoic acid It has been found that various radical-generating photopolymerization initiators such as esters are suitable. It was also found that the optimum compounding amount of the photopolymerization initiator is approximately 2 to 12 parts by weight. When the photopolymerization initiator having a UV absorbing action is insufficient, the UV transparency of the resist is increased, and the show-through property is difficult, and the alkali resistance of the resist is deteriorated due to insufficient crosslinking during UV exposure.
【００９４】さらに、顔料や光重合開始剤のＵＶ吸収作
用は、ＵＶ吸収剤の添加によっても、ある程度は補償で
きることも判った。すなわち、4-t-メトキシベンゾイル
メタンのようなＵＶ吸収剤をレジストに添加することに
より、顔料を全く含まない場合でも、耐裏写り性を改善
できることも判った。Further, it was also found that the UV absorption action of the pigment and the photopolymerization initiator can be compensated to some extent even by adding the UV absorber. That is, it was also found that by adding a UV absorber such as 4-t-methoxybenzoylmethane to the resist, it is possible to improve the show-through resistance even when the pigment is not contained at all.
【００９５】〈実施例５〉本発明の耐めっき反応性をも
つ感光性ソルダレジスト組成物を表１０に従って調整
し、前記１）乃至９）の特性を判定した。その結果を表
１１に示す。Example 5 The photosensitive solder resist composition having a plating resistance of the present invention was prepared according to Table 10, and the characteristics 1) to 9) were evaluated. The results are shown in Table 11.
【００９６】[0096]
【表１０】 [Table 10]
【００９７】[0097]
【表１１】 [Table 11]
【００９８】本例では、消泡剤と有機溶剤の配合量と特
性の関係を調べた。In this example, the relationship between the compounding amount of the defoaming agent and the organic solvent and the characteristics was examined.
【００９９】表１１に示すように、シリコーンオイルＳ
Ｈ−２０３のような消泡剤は、０．５ないし１０重量部
が好ましく、不足すると印刷時の泡抜けが悪く、塗布性
が不良となり、過剰では密着露光性に難が生じることも
判った。As shown in Table 11, silicone oil S
It was also found that the defoaming agent such as H-203 is preferably 0.5 to 10 parts by weight, and when it is insufficient, the defoaming during printing is poor and the coatability becomes poor, and when it is excessive, the contact exposure property becomes difficult. ..
【０１００】また、セルソルブアセテートやカルビトー
ルのような有機溶剤の配合量は、５０ないし１００重量
部が適切であることも判った。有機溶剤の配合量も、不
足すると塗布性が不良となり、過剰ではレジストインク
の粘度が低くなりすぎて、印刷し難くなることも判っ
た。It has also been found that an appropriate amount of organic solvent such as cellosolve acetate or carbitol is 50 to 100 parts by weight. It was also found that if the amount of the organic solvent blended is insufficient, the coatability becomes poor, and if it is excessive, the viscosity of the resist ink becomes too low, making it difficult to print.
【０１０１】〈実施例６〉本発明の耐めっき反応性を有
する感光性ソルダレジスト組成物を用いてパートリアデ
ィティブ法プリント回路板を製造し、配線密度の限界を
求めた。すなわち、回路のライン幅が０．４、０．２、
０．１５、０．１、０．０５ｍｍ及びスルホール径が
１．０、０．７、０．５、０．３、０．２ｍｍの異なる
配線密度のプリント回路板を、実施例２の組成（ロ）と
同じレジストを用いて製造した。この結果、パートリア
ディティブ法では、配線密度の違いにも拘らず、ほぼ、
同等の歩留りでプリント回路板が製造できることが判っ
た。Example 6 A part-additive method printed circuit board was manufactured using the photosensitive solder resist composition having plating resistance of the present invention, and the limit of wiring density was determined. That is, the line width of the circuit is 0.4, 0.2,
A printed circuit board having different wiring densities of 0.15, 0.1, 0.05 mm and through-hole diameters of 1.0, 0.7, 0.5, 0.3, 0.2 mm was prepared according to the composition of Example 2 ( It was manufactured using the same resist as in (b). As a result, in the part-additive method, despite the difference in wiring density,
It has been found that printed circuit boards can be manufactured with an equivalent yield.
【０１０２】一方、サブトラクト法で、配線密度の異な
るプリント回路板を製造したところ、回路のライン幅が
０．２ｍｍ以下で、回路のエッチングに伴う歩留りが、
また、スルホール径が０．５ｍｍ以下で、スルホール孔
内の電気銅めっきの均一性に伴う歩留りが、それぞれ低
下した。On the other hand, when printed circuit boards having different wiring densities were manufactured by the subtract method, the line width of the circuit was 0.2 mm or less, and the yield due to the etching of the circuit was
Further, when the through hole diameter was 0.5 mm or less, the yield due to the uniformity of electrolytic copper plating in the through hole was reduced.
【０１０３】この結果から、本発明は回路のライン幅が
０．２ｍｍ以下、スルホール径が０．５ｍｍ以下の高密
度プリント回路板の製造に、特に有利であることが判っ
た。From these results, it was found that the present invention is particularly advantageous for manufacturing a high density printed circuit board having a circuit line width of 0.2 mm or less and a through hole diameter of 0.5 mm or less.
【０１０４】〈比較例〉本発明の耐めっき反応性の感光
性ソルダレジスト組成物と比較するため、表１２に従っ
て調整し、銅との密着向上剤として表１３に示すような
分子中に二重結合のみ、或いは、アミノ基のみを含む化
合物を用い前記１）ないし９）の特性を判定した。<Comparative Example> In order to compare with the plating-reactive photosensitive solder resist composition of the present invention, the composition was adjusted according to Table 12, and a double bond was added in the molecule as shown in Table 13 as an adhesion promoter with copper. The properties of 1) to 9) above were evaluated using a compound containing only a bond or only an amino group.
【０１０５】[0105]
【表１２】 [Table 12]
【０１０６】[0106]
【表１３】 [Table 13]
【０１０７】結果は表１３に示すようで、二重結合のみ
を含む化合物では、レジストと導体回路との密着力が不
足し、耐めっき反応性が充分でなく、アミノ基のみを含
む化合物では、密着向上剤が化学銅めっき液にわずかに
溶け出し、析出した銅の物性が低下し、スルーホール信
頼性が低下することが判った。The results are shown in Table 13. In the compound containing only a double bond, the adhesion between the resist and the conductor circuit was insufficient, the plating reaction resistance was not sufficient, and in the compound containing only an amino group, It was found that the adhesion improver slightly dissolved in the chemical copper plating solution, the physical properties of the deposited copper deteriorated, and the through hole reliability deteriorated.
【０１０８】[0108]
【発明の効果】本発明の耐めっき反応性を有する感光性
ソルダレジスト組成物は塗布性、密着露光性、現像性、
耐裏写り性、耐アルカリ性、耐めっき反応性、耐めっき
溶出性、耐熱性、絶縁性、スルーホール信頼性に優れ、
これらの特性を同時に満たすことができ、パートリアデ
ィティブ法プリント回路板製造への適用を可能としたこ
とにより、実用に耐える高密度プリント回路板を簡略化
した方法で得ることができる。EFFECTS OF THE INVENTION The photosensitive solder resist composition having resistance to plating of the present invention has excellent coating property, adhesion exposure property, developability,
It has excellent show-through resistance, alkali resistance, plating reactivity, plating elution resistance, heat resistance, insulation, and through-hole reliability.
Since these characteristics can be satisfied at the same time and the application to the manufacturing method of a printed circuit board as a part-additive method is possible, a high-density printed circuit board that can be used practically can be obtained by a simplified method.
【図１】本発明に係るパートリアディティブ法プリント
回路板の製造順序を示す断面図、FIG. 1 is a cross-sectional view showing a manufacturing sequence of a partially additive printed circuit board according to the present invention,
【図２】サブトラクト法プリント回路板の製造順序を示
す断面図。FIG. 2 is a cross-sectional view showing a manufacturing method of a subtracted printed circuit board.
１…銅箔、 １'…回路パターン、 ２…スルーホール、 ２'…小径バイヤホール、 ３…感光性ソルダレジスト、 ３'…熱硬化性ソルダレジスト、 ４…化学銅めっき膜、 ４'…電気銅めっき膜。 DESCRIPTION OF SYMBOLS 1 ... Copper foil, 1 '... Circuit pattern, 2 ... Through hole, 2' ... Small diameter via hole, 3 ... Photosensitive solder resist, 3 '... Thermosetting solder resist, 4 ... Chemical copper plating film, 4' ... Electricity Copper plating film.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０３Ｆ 7/028 9019−2Ｈ Ｈ０５Ｋ 3/06 Ｈ 6921−4Ｅ 3/18 Ｄ 6736−4Ｅ (72)発明者 菊池 廣 神奈川県横浜市戸塚区吉田町292番地株式 会社日立製作所生産技術研究所内 (72)発明者 矢野 玲子 神奈川県横浜市戸塚区吉田町292番地株式 会社日立製作所生産技術研究所内 (72)発明者 岡 齊 神奈川県横浜市戸塚区吉田町292番地株式 会社日立製作所生産技術研究所内 (72)発明者 谷口 幸弘 神奈川県横浜市戸塚区戸塚町216番地株式 会社日立製作所戸塚工場内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI Technical display location G03F 7/028 9019-2H H05K 3/06 H 6921-4E 3/18 D 6736-4E (72) Inventor Hiro Kikuchi, 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa, Ltd., Institute of Industrial Science, Hitachi, Ltd. (72) Inventor Reiko Yano, 292, Yoshida-cho, Totsuka-ku, Yokohama, Kanagawa, Ltd., Institute of Industrial Science, Hitachi (72) Inventor Osamu Osamu 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa, Ltd.Hitachi, Ltd., Institute of Industrial Science (72) Inventor, Yukihiro Taniguchi 216 Totsuka-cho, Totsuka-ku, Yokohama, Kanagawa Hitachi, Ltd., Totsuka Plant
Claims (13)
重合促進剤のモノマと、銅との密着向上剤と光重合開始
剤とを含んでなることを特徴とする光硬化性レジスト組
成物。1. A photocurable resist comprising a polyfunctional unsaturated compound which is solid at room temperature, a monomer of a photopolymerization accelerator, an adhesion promoter for copper, and a photopolymerization initiator. Composition.
不飽和化合物がジアリルフタレートのプレポリマであ
り、光重合促進剤のモノマが多官能アクリレートもしく
はメタクリレート化合物である光硬化性レジスト組成
物。2. The photocurable resist composition according to claim 1, wherein the polyfunctional unsaturated compound which is solid at room temperature is a prepolymer of diallyl phthalate, and the monomer of the photopolymerization accelerator is a polyfunctional acrylate or methacrylate compound.
プレポリマの分子量が３０００乃至３００００であり、
多官能アクリレートもしくはメタクリレート化合物の官
能基数が二個以上である光硬化性レジスト組成物。3. The prepolymer of diallyl phthalate according to claim 2, wherein the molecular weight is from 3,000 to 30,000,
A photocurable resist composition having a polyfunctional acrylate or methacrylate compound having two or more functional groups.
分子中少なくとも一個以上のアミノ基と二重結合をそれ
ぞれ含む化合物である光硬化性レジスト組成物。4. The photocurable resist composition according to claim 1, wherein the adhesion promoter with copper is a compound containing at least one amino group and a double bond in one molecule.
記一般式 【化１】 【化２】 で示される化合物であること、あるいは、下記一般式 【化３】 【化４】 で示される化合物の反応物である光硬化性レジスト組成
物。5. The adhesion improver for copper according to claim 1, which is represented by the following general formula: [Chemical 2] Or a compound represented by the following general formula: [Chemical 4] A photocurable resist composition which is a reaction product of the compound represented by
がジアリルフタレートのプレポリマ１００重量部に対
し、化１化２は１ないし２０重量部、化３と化４の反応
物は５ないし４０重量部である光硬化性レジスト組成
物。6. The compound according to claim 5, wherein the compound and the reaction product are 1 to 20 parts by weight of Chemical Formula 1 and 2 to 5 parts by weight of the reaction product of Chemical Formula 3 and Chemical Formula 4 with respect to 100 parts by weight of a prepolymer of diallyl phthalate. Part photocurable resist composition.
重量部に対し、光重合促進剤の多官能アクリレートもし
くはメタクリレート化合物の配合量が５ないし８０重量
部、銅との密着向上剤の配合量が１ないし２０重量部、
光重合開始剤の配合量が２ないし１２重量部である光硬
化性レジスト組成物。7. A prepolymer 100 of diallyl phthalate.
5 to 80 parts by weight of a polyfunctional acrylate or methacrylate compound as a photopolymerization accelerator, 1 to 20 parts by weight of an adhesion improver with copper, and
A photocurable resist composition containing 2 to 12 parts by weight of a photopolymerization initiator.
物が、消泡剤を０．５ないし１０重量部、溶剤を５０な
いし１００重量部、顔料を０．２ないし１０重量部含ん
でなる光硬化性レジスト組成物。8. The photocurable resist composition according to claim 7, comprising 0.5 to 10 parts by weight of an antifoaming agent, 50 to 100 parts by weight of a solvent, and 0.2 to 10 parts by weight of a pigment. Photocurable resist composition.
８において、両面銅張積層板の所定位置に孔をあける工
程、スルホール内を化学銅めっき用触媒で活性化する工
程、所定部をエッチングして基板の両面に導体回路を形
成する工程、前記レジストを塗布し、乾燥し、露光し、
現像し、加熱し、基板の両面にレジスト層を形成する工
程、少なくともスルホール内を含む所定部に厚く化学銅
めっきを施す工程からなるプリント回路板の製造方法。9. The step of forming a hole in a predetermined position of a double-sided copper clad laminate according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the through hole is activated by a chemical copper plating catalyst. Step, a step of etching a predetermined portion to form conductor circuits on both surfaces of the substrate, applying the resist, drying and exposing,
A method of manufacturing a printed circuit board, which comprises the steps of developing and heating to form a resist layer on both surfaces of a substrate, and a step of performing thick chemical copper plating on a predetermined portion including at least the inside of a through hole.
は８において、両面銅張積層板の所定位置に孔をあける
工程、スルホール内を化学銅めっき用触媒で活性化する
工程、所定部をエッチングして基板の両面に導体回路を
形成する工程、前記レジストを塗布し、乾燥し、露光
し、現像し、真空或いは不活性ガス雰囲気中で加熱し、
基板の両面にレジスト層を形成する工程、少なくとも、
スルホール内を含む所定部に厚く化学銅めっきを施す工
程からなるプリント回路板の製造方法。10. The step of forming a hole in a predetermined position of a double-sided copper clad laminate according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the inside of the through hole is activated by a chemical copper plating catalyst. Step, a step of etching a predetermined portion to form conductor circuits on both sides of the substrate, coating the resist, drying, exposing, developing, heating in a vacuum or an inert gas atmosphere,
A step of forming a resist layer on both sides of the substrate, at least,
A method of manufacturing a printed circuit board, comprising a step of thickly plating a predetermined portion including a through hole with a chemical copper plating.
は８において、前記光硬化性レジスト組成物を用いるプ
リント回路板。11. A printed circuit board according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the photocurable resist composition is used.
板が、銅箔回路上に光硬化性レジストを形成した後、化
学銅めっきによりスルホール接続なされたものであるプ
リント回路板。12. The printed circuit board according to claim 11, wherein the printed circuit board is through-hole connected by chemical copper plating after forming a photocurable resist on a copper foil circuit.
て、前記プリント回路板が、銅箔回路幅として０．２ｍ
ｍ以下、スルホール径として０．５ｍｍ以下であるプリ
ント回路板。13. The printed circuit board according to claim 9, 10, 11 or 12, wherein a copper foil circuit width is 0.2 m.
A printed circuit board having a diameter of m or less and a through hole diameter of 0.5 mm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24106991A JPH0580521A (en) | 1991-09-20 | 1991-09-20 | Photosetting resist composition and production of printed circuit board by using this composition and printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24106991A JPH0580521A (en) | 1991-09-20 | 1991-09-20 | Photosetting resist composition and production of printed circuit board by using this composition and printed circuit board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0580521A true JPH0580521A (en) | 1993-04-02 |
Family
ID=17068837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24106991A Pending JPH0580521A (en) | 1991-09-20 | 1991-09-20 | Photosetting resist composition and production of printed circuit board by using this composition and printed circuit board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0580521A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5529602A (en) * | 1994-02-23 | 1996-06-25 | Hitachi Powdered Metals Co., Ltd. | Sintered iron alloy resistant to abrasion at high temperature and method of manufacturing the same |
| KR20150136530A (en) * | 2013-03-29 | 2015-12-07 | 다이요 홀딩스 가부시키가이샤 | Thermoplastic resin film base for optical firing, conductive circuit board using same, and method for manufacturing said conductive circuit board |
-
1991
- 1991-09-20 JP JP24106991A patent/JPH0580521A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5529602A (en) * | 1994-02-23 | 1996-06-25 | Hitachi Powdered Metals Co., Ltd. | Sintered iron alloy resistant to abrasion at high temperature and method of manufacturing the same |
| KR20150136530A (en) * | 2013-03-29 | 2015-12-07 | 다이요 홀딩스 가부시키가이샤 | Thermoplastic resin film base for optical firing, conductive circuit board using same, and method for manufacturing said conductive circuit board |
| JPWO2014156844A1 (en) * | 2013-03-29 | 2017-02-16 | 太陽ホールディングス株式会社 | Thermoplastic resin film substrate for photobaking, conductive circuit board using the same, and method for producing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0428870B1 (en) | Photosensitive resin composition for forming conductor patterns and multilayer circuit boards using same | |
| FR2580828A1 (en) | PHOTOCURABLE LIQUID PHOTORESIST INK COMPOSITION | |
| JPH05339356A (en) | Photopolymerizable unsaturated compound, and photosensitive resin composition of alkali development type | |
| JP3750101B2 (en) | Photosensitive resin composition and printed wiring board | |
| US5268255A (en) | Photo-setting resist composition, a process for producing a printed circuit board by using the composition, and a printed circuit board obtained by using the composition | |
| JP2792298B2 (en) | Photo solder resist composition | |
| JP3672414B2 (en) | Photosensitive resin composition | |
| JP2778323B2 (en) | Printed wiring board and method of manufacturing the same | |
| US5091283A (en) | Photocurable diallyl phthalate resin composition and printed circuit board using the same | |
| US6555592B2 (en) | Photothermosetting composition comprising acrylated epoxy resin | |
| JPH0580521A (en) | Photosetting resist composition and production of printed circuit board by using this composition and printed circuit board | |
| JP3849641B2 (en) | Manufacturing method of photosensitive film for circuit formation and printed wiring board | |
| CN1255489C (en) | Liquid state photo sensitive insulating ink used for cascade circuit board | |
| EP0490118A1 (en) | Photoimagable solder mask and photosensitive composition | |
| JP2693135B2 (en) | Multilayer printed circuit board and manufacturing method thereof | |
| JP2677916B2 (en) | Photosensitive resin composition and photosensitive element using the same | |
| JPH03281622A (en) | Photocurable diallyl phthalate resin composition and printed circuit board using the same | |
| JP4261635B2 (en) | UV curable through-hole filler | |
| JPH05194686A (en) | Photocurable resist composition, method for producing printed circuit board using the same, and printed circuit board | |
| JP3797332B2 (en) | Photosensitive element, method for producing resist pattern using the same, method for producing printed wiring board, and method for producing lead frame | |
| JP2596089B2 (en) | Photosensitive resin composition and photosensitive resin composition laminate | |
| JP3098638B2 (en) | Resist film for electroless plating | |
| JP2003295429A (en) | Photosensitive resin composition | |
| JPH04195051A (en) | Photocurable resist composition and printed board using the same | |
| JPH04195052A (en) | Photocurable resist composition and printed circuit board using the same |