JPH03281622A - Photocurable diallyl phthalate resin composition and printed circuit board prepared by using the same - Google Patents
Photocurable diallyl phthalate resin composition and printed circuit board prepared by using the sameInfo
- Publication number
- JPH03281622A JPH03281622A JP8071190A JP8071190A JPH03281622A JP H03281622 A JPH03281622 A JP H03281622A JP 8071190 A JP8071190 A JP 8071190A JP 8071190 A JP8071190 A JP 8071190A JP H03281622 A JPH03281622 A JP H03281622A
- Authority
- JP
- Japan
- Prior art keywords
- diallyl phthalate
- photocurable
- resin composition
- parts
- 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
- 239000004641 Diallyl-phthalate Substances 0.000 title claims abstract description 49
- 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 title claims abstract description 49
- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 238000007747 plating Methods 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 229910000679 solder Inorganic materials 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000011161 development Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 238000010292 electrical insulation Methods 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- 238000001723 curing Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 14
- 239000004020 conductor Substances 0.000 claims description 13
- -1 ester acrylate Chemical class 0.000 claims description 11
- 230000009257 reactivity Effects 0.000 claims description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 9
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 238000013007 heat curing Methods 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 150000002440 hydroxy compounds Chemical class 0.000 claims 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000006096 absorbing agent Substances 0.000 abstract 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 42
- 230000018109 developmental process Effects 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 239000000654 additive Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 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
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 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
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-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
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-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 1
- HSOOIVBINKDISP-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(CCC)OC(=O)C(C)=C HSOOIVBINKDISP-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 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
- 239000005977 Ethylene Substances 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
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 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
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- GAZZTULIUXRAAI-UHFFFAOYSA-N [2,3-bis(diethylamino)phenyl]-phenylmethanone Chemical compound CCN(CC)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N(CC)CC GAZZTULIUXRAAI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 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
- 150000001412 amines Chemical class 0.000 description 1
- 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 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005540 biological transmission 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
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 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
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 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
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 239000000178 monomer Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、プリント回路板の製造にかがわる光硬化性ジ
アリルフタレート樹脂組成物とこれを紫外線（ＵＶ）露
光現像型の耐めっき反応性ソルダレジストとして用いた
プリント回路板の製造方法に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a photocurable diallyl phthalate resin composition used in the production of printed circuit boards, and a method for applying the same to ultraviolet (UV) exposure and development type plating reactivity. The present invention relates to a method of manufacturing a printed circuit board using a solder resist.
従来のプリント回路板用ＵＶ露光現像型ソルダレジスト
は例えば、特公昭５］、−４０４５１号、特公昭５２−
３０９６９号、特開昭６０−２０８３７７号、特開昭６
２−４３９０号、特開昭６２−２５３６１３号などの記
載を挙げることができる。かかるレジストは、第２図に
示すプリント板の製造方法で主に用いられるものであっ
た。第２図はサブトラクト法の製造工程を４層板を例に
示しである。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、触媒を付与した後、スルーホールを
含む全面に電気網めっきを施し、エツチングで所定の回
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。かかるソルダレジストには古くからスクリ
ーン印刷でパターン形成をするエポキシ樹脂系の熱硬化
型のものが用いられて来たが、プリント回路板の配線密
度の増大に伴って、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。Conventional UV exposure and development type solder resists for printed circuit boards include, for example, Japanese Patent Publication No. 5], -40451, and Japanese Patent Publication No. 52-
No. 30969, JP-A-60-208377, JP-A-Sho 6
2-4390, JP-A No. 62-253613, and the like. Such a resist was mainly used in the method of manufacturing a printed board shown in FIG. FIG. 2 shows the subtract method manufacturing process using a four-layer board as an example. In this process, starting material is a copper-clad laminate with an inner layer formed and copper foil laminated on the top and bottom surfaces, holes are drilled at predetermined positions, a catalyst is applied, and then electrical mesh plating is applied to the entire surface including the through holes. A predetermined circuit pattern is formed by etching, and finally a solder resist is applied. Epoxy resin-based thermosetting solder resists, which are pattern-formed by screen printing, have long been used as such solder resists, but as the wiring density of printed circuit boards increases, UV exposure and development with good coating accuracy has been used. A type of solder resist was developed.
一方、第１図に示すパートリアディティブ法のプリント
板製造法では、第２図に示すサブトラクト法で用いるソ
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 part-reactive printed board manufacturing method shown in FIG. 1, it is essential to use a plating-resistant solder resist that has completely different characteristics from the solder resist used in the subtract method shown in FIG.
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穴をあけ、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、ランド部等必要な箇所のみ
にめっきを施すものである。In the part-reactive method, unlike the subtract method, holes are made at predetermined positions in a copper-clad laminate, a catalyst is applied, and a conductor circuit is first formed. Next, a plating-resistant reactive solder resist is formed in predetermined areas, and finally, chemical copper plating is used to plate only necessary areas such as through-holes and land areas.
かかる製造方法は、サブトラクト法に比較して安価、高
精度の利点がある。サブトラクト法のように全面にめっ
きを施さず、必要な箇所のみに部分的にめっきすること
や、導体回路形成におけるエツチングも銅張り積層板の
薄い銅箔のみのエツ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。パー
トリアディティブ法では、耐めっきソルダレジストの下
の配線パターンに化学銅めっきの析呂電位が−０，６〜
−０，９Ｖかかり、かつ高温、強アルカリのめっき液に
長時間浸漬されるという過酷な工程を経た後にも、永久
レジストとして使用するため、ソルダレジストとしての
機能を持つことが必要である。かかる目的に適した耐め
っきソルダレジストとして、スクリーン印刷でパターン
を形成する工ボキシ樹脂系熱硬化型のものが知られてい
た。かかる耐めっき性を有するソルダレジストは特開昭
５８−１４７４１６に開示されている。また、従来の耐
めっき性を有するＵＶ露光・現像型レジスト例えば特開
昭６２−２６５３２１では、耐裏写り性が全く考慮され
ていないため、ネガマスクを密着させパターンを焼き付
けるＵＶ照射時において、両面同時露光が出来ず、片面
ずつ露光作業を行うため作業性が劣っていた。また、耐
熱性においても、プロセスマージンや半田付は条件等の
要求特性の高まりと相いまって、まだ十分でないことが
わかった。This manufacturing method has the advantage of being cheaper and more accurate than the subtract method. The process is simplified because it does not plate the entire surface as in the subtract method, but only partially plating where it is needed, and etching only the thin copper foil of the copper-clad laminate when forming the conductor circuit. It is simple, has low loss, and enables high-precision wiring. In the part-reactive method, the potential of chemical copper plating on the wiring pattern under the plating-resistant solder resist is -0.6 to -0.6.
Since it can be used as a permanent resist even after going through the harsh process of being immersed in a high-temperature, strong alkaline plating solution at -0.9V for a long time, it needs to have the function of a solder resist. As a plating-resistant solder resist suitable for such a purpose, a thermosetting type based on a boxy resin in which a pattern is formed by screen printing has been known. A solder resist having such plating resistance is disclosed in JP-A-58-147416. In addition, conventional UV exposure/development type resists with plating resistance, such as JP-A-62-265321, do not take bleed-through resistance into consideration at all, so when UV irradiation is carried out to print a pattern with a negative mask in close contact, both sides are exposed simultaneously. Exposure was not possible, and workability was poor because the exposure work was done one side at a time. In addition, it was found that heat resistance was still insufficient due to the increasing requirements for process margins and soldering conditions.
上記従来技術は、パートリアディティブ法に用いるため
には、例えば特公昭５２−３０９６９号記載のＵＶ露光
現像型レジストでは耐めっき反応性が全くなく、一方、
特開昭５８−１４７４１６号記載のソルダレジストでは
耐めっき性はあるものの、ＵＶ露光現像型でないために
、高精度にパターンの形成が出来ない、耐裏写り性が全
く考慮されておらず作業性に劣る等の問題があった。In the above conventional technology, for example, the UV exposure and development type resist described in Japanese Patent Publication No. 52-30969 has no plating reactivity at all in order to be used in the part-reactive method.
The solder resist described in JP-A-58-147416 has plating resistance, but because it is not a UV exposure and development type, it is not possible to form patterns with high precision, and there is no consideration given to show-through resistance, making it difficult to work. There were problems such as inferiority.
本発明は、パートリアディティブ法に用いることができ
るＵＶ露光現像型の耐めっき反応性ソルダレジストに用
いる光硬化性ジアリルフタレート樹脂組成物を提供する
ことを第１の目的としている。すなわち、実用的なレジ
ストとして備えるべき特性は多岐にわたっており、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合せでは得られ
ない多くの特性を同時に満足するレジストを提供するこ
とにある。かかる課題を列挙すると次のようになる。The first object of the present invention is to provide a photocurable diallyl phthalate resin composition for use in a UV exposure and development type plating-resistant reactive solder resist that can be used in a part-additive method. That is, there are a wide variety of properties that a practical resist should have, and if even one of them is lacking, its practicality will be significantly impaired. Therefore, an object of the present invention is simply to provide a resist that simultaneously satisfies many properties that cannot be obtained by combining conventional techniques. A list of such issues is as follows.
ａ）本発明のレジストはＵＶ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の紫外線（ＵＶ）光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０．０２〜ＩＯＪ／ｄの範囲で硬化す
る必要がある。a) It is essential that the resist of the present invention be cured with UV light. That is, 300~ suitable for manufacturing printed circuit boards.
Irradiation with 400 nm ultraviolet (UV) light causes a crosslinking reaction, and only the irradiated portions need to be cured. Further, it is necessary to cure the resin within a practical range of 0.02 to IOJ/d as the irradiation amount.
ｂ）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、現像性
いわゆる現像後の解像度が良好であることか必須である
。b) 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 developability, so-called resolution after development.
Ｃ）本発明のレジストは、プリント基板の両面に塗布し
て、正常に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。C) It is essential that the resist of the present invention can be applied to both sides of a printed circuit board and exposed normally on both sides at the same time. That is, there must be no so-called show-through, in which UV light exposed from one side passes through the resist and the base material and hardens the resist on the other side.
かかる課題を解決しない場合には、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われるため、
実用性を著しく損なう。If this problem is not solved, the difference in the negative mask patterns used on both sides of the base material will also appear on the opposite side.
It seriously impairs practicality.
ｄ）本発明のレジストは、解像度を高めるため０■露先
の際、問題なく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レジス
トでは、レジスト自身の粘性や、露光時の昇温のためレ
ジストが軟化するなどの原因で、レジストがネガマスク
に貼り付く。d) In order to improve the resolution of the resist of the present invention, it is essential that the negative mask can be exposed in close contact with the resist without any problem during the 0-inch exposure. With resists that do not solve this problem, the resist sticks to the negative mask due to its own viscosity or softening due to the rise in temperature during exposure.
かかる場合には露光毎にネガマスクを洗浄せねばならず
、実用性が著しく損なわれる。したがって、ネガマスク
をレジストに密着して露光しても、マスクにレジストが
貼り付かないことが必須となる。In such a case, the negative mask must be cleaned after each exposure, which significantly impairs practicality. Therefore, even if the negative mask is brought into close contact with the resist and exposed, it is essential that the resist does not stick to the mask.
ｅ）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、プリント回路板全面にスクリーン
印刷法やロールコータ等でレジストを塗布する際、厚さ
が均一になりかつボイドが残らない適切なインクとして
の特性を有するのみならず、作業中にもその特性が変化
しないことが必要である。e) It is essential that the resist of the present invention has good coating properties. In other words, when applying a resist to the entire surface of a printed circuit board using a screen printing method or a roll coater, it not only has the characteristics of an appropriate ink that provides a uniform thickness and does not leave voids, but also has the characteristics of an appropriate ink that can be used during the work. It is necessary that the values do not change.
ｆ）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、繰り返しはんだ付けに耐える良好な
耐熱性を有することが必須である。f) The resist of the present invention is formed on a printed circuit board as a product, and it is essential that it has good heat resistance to withstand repeated soldering.
すなわち、およそ２８０℃、１０秒のはんだ浸漬を約１
０回繰り返しても、或はこれに相当する熱風、赤外線、
ヘーパ等によるはんだ付けによってもプリント回路板上
のレジストにフクレ、剥離等の異常が生じないことが必
要である。That is, about 10 seconds of solder immersion at about 280°C
Even if repeated 0 times, or equivalent hot air, infrared rays,
It is necessary that abnormalities such as blistering and peeling do not occur in the resist on the printed circuit board even when soldering with a soldering agent or the like.
ｇ）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１Ｉ４Ａ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することが
必要である。g) The resist of the present invention is formed on a printed circuit board as a product, and it is essential that it can maintain high 1I4A edge properties. That is, it is necessary to maintain excellent insulation properties that do not cause insulation deterioration between wirings, especially insulation properties when moisture is absorbed.
ｈ）本発明のレジストは、製品であるプリント回踏板上
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、プリント回路板実装時のフランクス、洗浄
、はんだ付は等に用いられる溶剤により、レジストが溶
解、変質しない必要がある。h) The resist of the present invention is formed on a printed circuit board as 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 solvents used in franking, cleaning, soldering, etc. during printed circuit board mounting.
ｉ）本発明のレジストは、プリント回路板上に形成した
後、良好な耐アルカリ性および耐めっき反応性いわゆる
耐カソード剥離性を有することが必須である。具体的に
は、化学網めっき液の高温、高アルカリかつ−０，６〜
−０，９ｖの析出電位がかかる過酷な条件に長時間浸漬
しても、レジスト表面が溶解、変質せず、さらに基材お
よび導体回路上で剥離してはならない。より具体的には
、化学銅めっきを施す際、回路銅箔とレジスト間の剥離
や密着力の劣化が生じないことが必須である。i) After the resist of the present invention is formed on a printed circuit board, it is essential that it has good alkali resistance and plating reaction resistance, so-called cathode peeling resistance. Specifically, the chemical mesh plating solution is high temperature, highly alkaline and -0.6~
Even when immersed for a long time in severe conditions with a deposition potential of -0.9V, the resist surface must not dissolve or change in quality, and furthermore, it must not peel off on the base material or conductor circuit. More specifically, when applying chemical copper plating, it is essential that no peeling or deterioration of adhesion between the circuit copper foil and the resist occurs.
ｓｍに至る機構はさだかではないが、次のようなことで
はないかと思われる。種々検討した結果、剥離が化学網
めっき反応が生じている個所と接続している導体回路の
上に塗布したレジストにのみ見られること、更に、レジ
スト塗布前の導体回路銅箔が酸化していると極めて短時
間にレジスト剥離が起きる。また、導体回路がレジスト
で完全にカバーされている個所、いわゆるめっきの析出
電位（−０，６〜−〇、９Ｖ）がかからないと剥離しな
い。Although the mechanism leading to sm is not entirely clear, it seems to be as follows. As a result of various studies, we found that peeling was observed only in the resist applied on the conductor circuit connected to the areas where the chemical net plating reaction was occurring, and that the conductor circuit copper foil was oxidized before the resist was applied. The resist peels off in an extremely short time. Further, it will not peel off unless a so-called plating deposition potential (-0.6 to -0.9 V) is applied to a portion where the conductor circuit is completely covered with resist.
これらの事象から、めっき中に水分がレジスト膜を通し
て回路銅箔との界面に到達し、析出電位により、回路銅
箔表面の酸化銅が還元されるため。As a result of these events, moisture passes through the resist film during plating and reaches the interface with the circuit copper foil, and the copper oxide on the surface of the circuit copper foil is reduced by the deposition potential.
レジストとの結合が切れＭ離が起きる。これは。The bond with the resist is broken and separation occurs. this is.
従来から言われているレジストの耐めっき性とは異なり
、耐めっき反応性（耐カソード剥離性）として区別して
いる。プリント回路板製造時に、回路銅箔上に酸化銅の
形成を防ぐ事が重要であることを見いだし、我々はレジ
スト組成を限定する事で対処した。Unlike the conventional plating resistance of resist, it is distinguished as plating reactivity resistance (cathode peeling resistance). We discovered that it is important to prevent the formation of copper oxide on circuit copper foils during printed circuit board manufacturing, and we addressed this by limiting the resist composition.
かかる課題は、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、最も留意すべき点であり、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するため、
実用性が全くなくなるのである。This problem is the most important point to keep in mind when manufacturing printed circuit boards using the part additive method. If this problem is not resolved, the resist on the circuit copper foil will peel off.
It becomes completely impractical.
ｊ）本発明のレジストは、プリント回路板上に形成した
後、化学網めっきを施す際、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、いわゆる耐
めっき溶出性が必須である。j) The resist of the present invention must have so-called plating elution resistance, that is, no harmful components will be eluted or extracted from the resist into the plating solution when chemical net plating is applied after being formed on a printed circuit board.
かかる問題が未解決であると、レジストからの溶出また
は抽出された成分がめっきの析出反応に悪影響を及ぼす
結果、めっき反応が停止、ないし遅滞したり、析出した
銅の物性が著しく劣化する。If such problems are unresolved, components eluted or extracted from the resist will have an adverse effect on the plating precipitation reaction, resulting in the plating reaction being stopped or delayed, and the physical properties of the deposited copper significantly deteriorating.
かかる問題がないことが必須の課題である。本発明の第
２の目的は、上記ａ）からｊ）の課題を全て満足する所
定の光硬化性ジアリルフタレート樹脂組成物からなるＵ
Ｖ露露光現像型力っきレジスト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方法を提供するこ
とである。さらに本発明の第３の目的は、かかる方法で
製造されたプリント回路板を提供することにある。It is essential to avoid such problems. A second object of the present invention is to provide U, which is made of a predetermined photocurable diallyl phthalate resin composition that satisfies all of the above problems a) to j).
It is an object of the present invention to provide a method for manufacturing a printed circuit board by a part-reactive method using a V-exposure and development type force-plated resist. Furthermore, a third object of the present invention is to provide a printed circuit board manufactured by such a method.
さらに１本発明の第４の目的は、本発明のプリント回路
板を用いた電子機器を提供することである。Furthermore, a fourth object of the present invention is to provide an electronic device using the printed circuit board of the present invention.
上記目的を達成するために１本発明は耐めっき反応性ソ
ルダレジスト組成物、いわゆる光硬化性ジアリルフタレ
ート樹脂組成物として以下のものを用いる。ジアリルフ
タレートのプレポリマーと、多官能不飽和化合物と、光
重合開始剤と、エポキシ樹脂と、所定のエポキシ硬化剤
と、紫外線吸収剤と、消泡剤と、充填剤と、上記ジアリ
ルフタレートのプレポリマーとエポキシ樹脂を溶解する
ための有機溶剤とを含んでなるものである。In order to achieve the above object, the present invention uses the following as a plating-resistant solder resist composition, a so-called photocurable diallyl phthalate resin composition. A prepolymer of diallyl phthalate, a polyfunctional unsaturated compound, a photopolymerization initiator, an epoxy resin, a predetermined epoxy curing agent, an ultraviolet absorber, an antifoaming agent, a filler, and the prepolymer of diallyl phthalate. It contains a polymer and an organic solvent for dissolving the epoxy resin.
本発明のジアリルフタレートのプレポリマーはβ−ポリ
マーとも称され、例えば、吉見直喜著「ジアリルフタレ
ート樹脂」日刊工業新聞社列（昭４４）に、その詳しい
製法、性質が記載されている。本発明に必須のプレポリ
マーの分子量は３ 、０００〜３０，０００が好ましい
。３，０００以下では、ネガマスクとの密着露光性が劣
り、また、３０．０００以上では、現像性が悪い。The diallyl phthalate prepolymer of the present invention is also referred to as a β-polymer, and its detailed manufacturing method and properties are described, for example, in Naoki Yoshimi, "Diallyl Phthalate Resin," Nikkan Kogyo Shimbun Sha Series (1972). The molecular weight of the prepolymer essential to the present invention is preferably 3,000 to 30,000. If it is less than 3,000, the adhesion exposure property with a negative mask will be poor, and if it is more than 30,000, the developability will be poor.
またプレポリマーを含むとの記載はポリマーの合成にと
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
マーあるいは三次元網状構造のγ−ポリマーが少量台ま
れることを妨げるものではない。Further, the statement that a prepolymer is included does not preclude the inclusion of a small amount of diallyl phthalate monomer or three-dimensional network-structured γ-polymer that remains or is produced during polymer synthesis.
さらに本発明の組成物中の多官能不飽和化合物は、少な
くとも２個以上のエチレン結合を分子内に有する化合物
である。例えば、不飽和カルボン酸と２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。Further, the polyfunctional unsaturated compound in the composition of the present invention is a compound having at least two or more ethylene bonds in the molecule. For example, it can be obtained by an esterification reaction between an unsaturated carboxylic acid and a divalent or higher polyhydroxy compound.
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２
価以上のポリヒドロキシ化合物としては、エチレングリ
コール、ジエチレングリコール、プロピレングリコール
、トリエチレングリコール、ヒドロキノン、ピロガロー
ル等である。Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, etc.
Examples of the polyhydroxy compound having a higher molecular weight include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, hydroquinone, and pyrogallol.
これらを原料にしてエステル化反応によって得られる化
合物としては、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、１，５−ベン
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、ペンタニル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、トリメチロールプ
ロパントリメタクリレート、１，３−ブタンジオールジ
メタクリレートなどに代表されるジアクリレート、ジメ
タ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価ア
クリレート、ないし多価メタクリレート化合物やオリゴ
マエステルアクリレート、オリゴマエステルメタクリレ
ートなど、またエポキシ樹脂とアクリル酸ないしメタク
リル酸との反応により合成するエポキシアクリレートな
いしエポキシメタクリレート等が挙げられる。以上の例
は、多官能不飽和化合物を単独で使用しているが、２種
以上を混合しても使用できる。また単官能不飽和化合物
の併用も可能である。Compounds obtained by esterification reaction using these raw materials include diethylene glycol diacrylate,
Polyethylene glycol diacrylate, 1,5-bentanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentanylthritol triacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 1,3- Diacrylate and dimethacrylate compounds represented by butanediol dimethacrylate, polyvalent acrylates represented by tri, tetra, pentaacrylate or methacrylate of dipentaerythritol, tri, tetra, penta, hexaacrylate or methacrylate of sorbitol, etc. , polyvalent methacrylate compounds, oligomer ester acrylates, oligomer ester methacrylates, and epoxy acrylates and epoxy methacrylates synthesized by reacting epoxy resins with acrylic acid or methacrylic acid. In the above examples, a single polyfunctional unsaturated compound is used, but a mixture of two or more types can also be used. It is also possible to use monofunctional unsaturated compounds in combination.
さらに本発明の組成物中、光重合開始剤としては、例え
ば、アセトフェノンとその誘導体、ベンゾフェノンとそ
の誘導体、ミヒラーケント、ベンジルとその誘導体、ベ
ンゾインとその誘導体、チオキサントンとその誘導体、
アントラキノンとその誘導体、１−ヒドロキシシクロへ
キシルフェニルケトン、２−メチル−１−［４−（メチ
ルチオ）フェニルコー２−モルフォリノ−１−プロパン
−１に代表されるα−アミノケトン化合物などを含んで
なるものである。これらは単独ないし必要に応じて混合
して用いる。また光重合開始剤の作用を増感するアミン
化合物を併用することも可能である。Further, in the composition of the present invention, examples of photopolymerization initiators include acetophenone and its derivatives, benzophenone and its derivatives, Michler-Kent, benzyl and its derivatives, benzoin and its derivatives, thioxanthone and its derivatives,
Contains anthraquinone and its derivatives, α-aminoketone compounds represented by 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl-2-morpholino-1-propane-1, etc. It is something. These may be used alone or in combination as necessary. It is also possible to use an amine compound that sensitizes the action of the photopolymerization initiator.
さらに本発明の組成物はエポキシ樹脂を含んでなるもの
である。かかるエポキシ樹脂としては、平均して１分子
当り２個以上のエポキシ基を有するもので、ビスフェノ
ールＡ、ビスフェノールＦ、ハロゲン化ビスフェノール
Ａ、等のビスフェノール類とエピクロルヒドリンを塩基
性触媒の存在下で反応じて得られるビスフェノール型の
ポリグリシジルエーテル、ノボラック型ないしクレゾー
ル型フェノール樹脂とエピクロルヒドリンとを反応じて
得られるエポキシノボラックおよびエポキシクレゾール
等が特に好ましい。Furthermore, the composition of the present invention contains an epoxy resin. Such epoxy resins have two or more epoxy groups per molecule on average, and are made by reacting bisphenols such as bisphenol A, bisphenol F, and halogenated bisphenol A with epichlorohydrin in the presence of a basic catalyst. Particularly preferred are bisphenol-type polyglycidyl ethers obtained by the above method, epoxy novolacs and epoxy cresols obtained by reacting novolac-type or cresol-type phenol resins with epichlorohydrin, and the like.
さらに本発明の組成物は所定のエポキシ樹脂用硬化剤を
含んでなるものである。かかる所定のエポキシ樹脂用硬
化剤とはジシアンジアミドと下記の一般式で示されるエ
ポキシ樹脂に対して潜在硬化性を有するジアミノトリア
ジン変性イミダゾール化合物である。Furthermore, the composition of the present invention contains a predetermined curing agent for epoxy resin. The predetermined curing agent for epoxy resins is dicyandiamide and a diaminotriazine-modified imidazole compound that has latent curing properties for epoxy resins represented by the following general formula.
２Ｎ
（Ｒはイミダゾール化合物である。）
例えば、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−４２−メチルイミダゾール
−
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−トリアジンもし
くは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・インシアヌール
酸付加物などがある。2N (R is an imidazole compound.) For example, 2,4-diamino-6(2'-methylimidazole-(1''))ethyl-s-triazine, 2,4-diamino-6(2'-ethyl- 42-Methylimidazole-triazine, 2,4-diamino-6(2'-undecylimidazole-(1'))ethyl-S-triazine or 2,4-diamino-6(2'methylimidazole-
(1')) Ethyl-S-triazine incyanuric acid adduct and the like.
さらに本発明の組成物は紫外線吸収剤と消泡剤と充填剤
と溶剤を含んでなるものである。かかる紫外線吸収剤と
しては３００ｎｍ以上の光波長領域において光吸収を生
じるが、樹脂組成物の光硬化反応とは関係しない化合物
を用いることが出来る。その例として、紫外線の照射に
より吸光係数をか減少する４−ｔ−ブチル−４′−メト
キシ−ジベンゾイルメタン、２−エチルへキシル−Ｐ−
メトキシシンナメイト、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′ｔｅｒｔ−
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’−ｔ
ａｒｔ−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
。紫外線吸収剤は、両面同時露光時における反対面から
のＵＶ光によるレジストの硬化、いわゆる裏写りの防止
、ならびにハレーションを防ぎ解像度を高める。Furthermore, the composition of the present invention comprises an ultraviolet absorber, an antifoaming agent, a filler, and a solvent. As such an ultraviolet absorber, a compound that absorbs light in a light wavelength region of 300 nm or more but is not related to the photocuring reaction of the resin composition can be used. Examples include 4-t-butyl-4'-methoxy-dibenzoylmethane, 2-ethylhexyl-P-
Methoxycinnamate, 2-(2'-hydroxy-3'
5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'tert-
Butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3'5'-t
art-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3-(3", 4"
, 5”, 6”-tetrahydrophthalimidomethyl)
-5''-methylphenyl)benzotriazole, etc. The ultraviolet absorber prevents hardening of the resist by UV light from the opposite side during simultaneous double-sided exposure, prevents so-called show-through, and prevents halation and increases resolution.
一方、かかる消泡剤としては、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。さらに、かかる充填材は、１０μｍ以下の微粒
子石英粉末が望ましい。−船釣に光硬化性樹脂は、光硬
化した皮膜の機械的性質、耐熱性が低い。本発明の目的
を達するには、充填材を多量に加えて上記性質を大幅に
改善する必要かある。しかし光硬化性樹脂であるので、
充填材によって紫外線の透過が阻害し、光硬化が阻害す
ることがあってはならない。充填材としての石英粉末は
紫外線を透過し、あるいは、その表面で散乱するので光
硬化反応は阻害されることはない。On the other hand, as such an antifoaming agent, an organic silicon compound containing a siloxane bond, typified by silicone oil, is mainly used. Furthermore, such a filler is preferably a fine quartz powder with a particle size of 10 μm or less. - Photocurable resins used for boat fishing have low mechanical properties and heat resistance of the photocured film. To achieve the objectives of the present invention, it is necessary to add a large amount of filler to significantly improve the above properties. However, since it is a photocurable resin,
The filler must not impede the transmission of ultraviolet light and inhibit photocuring. The quartz powder used as a filler transmits ultraviolet light or scatters it on its surface, so the photocuring reaction is not inhibited.
この充填材の使用により、上記性質の大幅な改善ととも
に、耐めっき溶出性、耐めっき反応性をも改善される。By using this filler, not only the above-mentioned properties are significantly improved, but also the plating elution resistance and plating reactivity resistance are improved.
さらに本発明の組成物はジアリルフタレートのプレポリ
マーやエポキシ樹脂を溶解するための有機溶剤を含んで
なるものである。かかる有機溶剤としてメチルセルソル
ブ、エチルセルソルブ、ブチルセルソルブ、メチルセル
ソルブアセテート、エチルセルソルブアセテート、ブチ
ルセルソルブアセテート、メチルカルピトール、エチル
カルピトール、ブチルカルピトール、テルピネオールな
どの高沸点溶剤が好ましい。Furthermore, the composition of the present invention contains an organic solvent for dissolving the diallyl phthalate prepolymer and epoxy resin. Such organic solvents include high boiling point solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl calpitol, ethyl calpitol, butyl calpitol, and terpineol. preferable.
本発明の光硬化性ジアリルフタレート樹脂組成物は、必
要に応じて他の添加剤、例えば石英超微粉末等の揺変剤
を加えることが出来る。The photocurable diallyl phthalate resin composition of the present invention may contain other additives, for example, a thixotropic agent such as ultrafine quartz powder, if necessary.
本発明の組成物を構成する好ましい配合割合は、ジアリ
ルフタレートプレポリマー１００重量部に対して、多官
能不飽和化合物４乃至３０重量部と。A preferred blending ratio of the composition of the present invention is 4 to 30 parts by weight of the polyfunctional unsaturated compound per 100 parts by weight of diallylphthalate prepolymer.
光重合開始剤０．５乃至１２重量部とエポキシ樹脂３乃
至３５重量部と、消泡剤０．５乃至１０重量部と、上記
ジアリルフタレートのプレポリマーを溶解するための溶
剤５５乃至１００重量部、所定のエポキシ硬化剤して、
ジシアンジアミドとジアミノトリアジン変性イミダゾー
ル化合物との配合比が１６７１乃至５／１でこれら混合
物の添加量がエポキシ樹脂１００重量部に対して２乃至
２０重量部であり、さらに紫外線吸収剤を、０．１乃至
１０重量部、好ましくはジアリルフタレート樹脂組成物
の塗膜を通過する紫外線光量をｏ、ｏｘ、ｙｃｉ以下と
する量。0.5 to 12 parts by weight of a photopolymerization initiator, 3 to 35 parts by weight of an epoxy resin, 0.5 to 10 parts by weight of an antifoaming agent, and 55 to 100 parts by weight of a solvent for dissolving the diallyl phthalate prepolymer. , with a given epoxy hardener,
The blending ratio of dicyandiamide and diaminotriazine-modified imidazole compound is 1671 to 5/1, the amount of these mixtures added is 2 to 20 parts by weight per 100 parts by weight of the epoxy resin, and the ultraviolet absorber is further added in the range of 0.1 to 5/1. 10 parts by weight, preferably an amount that reduces the amount of ultraviolet light passing through the coating film of the diallyl phthalate resin composition to below o, ox, yci.
また充填材の添加量はジアリルフタレートプレポリマー
１００重量部に対して２０乃至１００重量部である。The amount of filler added is 20 to 100 parts by weight per 100 parts by weight of diallyl phthalate prepolymer.
さらに詳しく述へると本発明においては、ジシアンジア
ミドとジアミノトリアジン変性イミダゾール化合物との
配合比を厳密に規定することが必須であり、第３図に示
す斜線の範囲内であることか必要である。More specifically, in the present invention, it is essential to strictly define the blending ratio of dicyandiamide and diaminotriazine-modified imidazole compound, and it is necessary that it be within the shaded range shown in FIG.
かかる組成の上、下限は、前述した本発明の課題（ａ）
から（ｊ）までが全て同時に満足できるよう注意深く選
択された物である。The upper and lower limits of this composition are the above-mentioned problem (a) of the present invention.
These items have been carefully selected so that all of the items from (j) to (j) can be satisfied at the same time.
次に本発明の第２の目的である上記の光硬化性ジアリル
フタレート樹脂組成物を耐めっき反応性ソルダレジスト
として用いて、パートリアディティブ法でプリント回路
板を製造する手段について述べる。Next, the second object of the present invention, which is a means for producing a printed circuit board by a part-reactive method using the above-mentioned photocurable diallyl phthalate resin composition as a plating-resistant reactive solder resist, will be described.
第１図に従って、当該業者に周知の方法で銅張り積層板
に孔あけ、化学銅めっき触媒核を付与し［第１図、２）
］ 、当該業者に周知の方法で所定部をエツチングして
、基板の両面に導体回路を形成する［第１図、３）コ。According to Fig. 1, holes are made in the copper-clad laminate by a method well known to those skilled in the art, and chemical copper plating catalyst nuclei are provided [Fig. 1, 2].
] Then, conductor circuits are formed on both sides of the substrate by etching the predetermined portions by a method well known to those skilled in the art [Fig. 1, 3).
次で、本発明の光硬化性ジアリルフタレート樹脂組成物
を導体回路を含む基板全面に塗布する。Next, the photocurable diallyl phthalate resin composition of the present invention is applied to the entire surface of the substrate including the conductor circuit.
次いで、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。かかる方法を繰り返し裏面で行なうか、あ
るいは、光硬化性ジアリルフタレート樹脂組成物を基板
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。乾燥条件は、６０
−１００℃で、乾燥時間は、０．２〜２時間が好ましい
。Next, the substrate coated with the resist is dried to solidify the resist. Solidified resist layers are formed on both sides of the substrate by repeating this method on the back side, or by simultaneously applying the photocurable diallyl phthalate resin composition on both sides of the substrate and then drying. The drying conditions are 60
At -100°C, the drying time is preferably 0.2 to 2 hours.
次いで、両面のレジスト上にネガマスクを密着して、両
面から同時にＵＶ光を照射して露光する。Next, a negative mask is closely attached to the resist on both sides, and UV light is irradiated and exposed from both sides at the same time.
かかる照射量は片面当り０．１〜１．Ｊ／ｄが好ましい
。さらに、かかる照射量範囲においても、片面に入射し
たＵＶ光が他面のレジストを全く、硬化しないことも、
強調されるべきことである。The amount of irradiation is 0.1 to 1. J/d is preferred. Furthermore, even within this irradiation dose range, UV light incident on one side does not harden the resist on the other side at all.
This should be emphasized.
次で、レジスト面からネガマスクを剥離し、未露光部を
現像する。かかる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、現像時間も０．５〜５分が選択される。Next, the negative mask is peeled off from the resist surface, and the unexposed areas are developed. As a solvent suitable for such development, 1.1.1-
A nonflammable chlorinated solvent such as trichloroethane is used, and a developing time of 0.5 to 5 minutes is selected.
次で、基板を加熱して、パターンを形成したレジスト部
を硬化する。硬化条件は、１４０〜１８０’Ｃ。Next, the substrate is heated to harden the resist portion on which the pattern is formed. Curing conditions are 140-180'C.
０．２〜２時間が選択される。0.2-2 hours is selected.
次で、基板上のレジストに、再度ＵＶ光を照射し、レジ
ストの硬化を完了する。かがるポスト露光に適した露光
量は１〜ＩＯＪ／Ｃｉである。Next, the resist on the substrate is irradiated with UV light again to complete curing of the resist. The exposure amount suitable for the post-darkening exposure is 1 to IOJ/Ci.
以上の工程を経て、基板上にレジスト層が形成される［
第１図、４）コ９
次で、基板け化学銅めっき中に浸漬され、スルーホール
孔内、ランド上をはじめとする生栗部分のみに厚い化学
網めっきが施され、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九る［第１図、５）コ。ががる銅め
っき中に、回路銅箔上のレジストに全く剥離が生じない
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 [
Figure 1, 4) 9 Next, the board is immersed in chemical copper plating, and thick chemical net plating is applied only to the raw chestnut parts such as inside the through-hole and on the land, and then the part additive method is applied. The printed circuit board is manufactured (Fig. 1, 5). A particularly important advantage of the present invention is that there is no peeling of the resist on the circuit copper foil during galling copper plating.
以上のようなパートリアディティブプリント基板製造に
おいて、本発明のレジストは前述の課題を全て同時に満
足できる。このために、パートリアディティブ法による
高密度プリント板の製造が可能となったのである。In the above-described part additive printed circuit board manufacturing, the resist of the present invention can simultaneously satisfy all of the above-mentioned problems. For this reason, it has become possible to manufacture high-density printed boards using the parti-additive method.
実施例１〜３９
以下、本発明の光硬化性ジアリルフタレート樹脂組成物
並びにこれを耐めっき反応性ソルダレジストとして用い
たプリント回路板の製造方法を具体的に説明する。第１
図に従って、３５μｍの銅箔を張ったガラスエポキシ両
面網張り積層板に当該業者に周知の方法で孔をあけ、め
っき核となる触媒を付与し［第１図、２］、当該業者に
周知の方法で銅箔の所定部をエツチングして、基板の両
面に導体回路を形成する。Examples 1 to 39 Hereinafter, the photocurable diallyl phthalate resin composition of the present invention and a method for manufacturing a printed circuit board using the same as a plating-resistant reactive solder resist will be specifically described. 1st
According to the diagram, holes are made in a glass epoxy double-sided mesh laminate covered with 35 μm copper foil using a method well known to those skilled in the art, and a catalyst that will serve as a plating core is applied [Fig. 1, 2]. A conductor circuit is formed on both sides of the board by etching a predetermined portion of the copper foil.
次いで、本発明の光硬化性ジアリルフタレート樹脂組成
物（表１〜４、実施例１〜３９）を導体回路を含む基板
全面に塗布する。実施例１の光硬化性ジアリルフタレー
ト樹脂組成物は下記の方法で製造した。例えば表１の実
施例１の組成物は（イ）ジアリルフタレートのプレポリ
マー（ダイソーダツブＡ：ダイソーに、に、製、平均分
子量７０００） １００ ｇ、（ロ）１−リメチロール
プロパントリメタクリレート２０ｇ、（ハ）二ピコート
８２８（ビスフェノールＡ型エポキシ樹脂：油化シェル
エポキシに、Ｋ。Next, the photocurable diallyl phthalate resin composition of the present invention (Tables 1 to 4, Examples 1 to 39) is applied to the entire surface of the substrate including the conductor circuit. The photocurable diallyl phthalate resin composition of Example 1 was produced by the following method. For example, the composition of Example 1 in Table 1 contains (a) 100 g of diallyl phthalate prepolymer (Daisodatsubu A: manufactured by Daiso Nihon Co., Ltd., average molecular weight 7,000), (b) 20 g of 1-rimethylolpropane trimethacrylate, ( C) Nipicote 828 (bisphenol A type epoxy resin: oil-based shell epoxy, K).
製）１５ｇ、（ニ）２−メチル−１−［４−（メチル）
フェニル−２−モルフォリノ−１−プロパン−１６ｇ、
（ホ）４．４’ ビス−（ジエチルアミノ）ベンゾフェ
ノン２ｇ、（へ）ジシアンジアミド１．５ｇ、（ト）２
，４−ジアミノ−６［２１−メチルイミダゾール−（１
’）］］エチルー８−トリアジン０．２ｇ（チ）紫外線
吸収剤：４−ｔ−ブチル−４′−メトキシ−ベンゾイル
メタン３ｇ、２−エチルへキシル−Ｐ−メトキシシンナ
メイト３ｇ、（す）消泡剤：シリコーンオイル５Ｈ−２
０３（東しシリコーンに、に、製）５ｇ、（ヌ）溶剤：
エチルセルソルブアセテート３５ｇ、ブチルセルソルブ
アセテート３３ｇ、（ル）揺変剤（石英微粉末アエロジ
ルＡ３８０：日本アエロジルに、に、製）３ｇ、（オ）
充填材（グリスタライト５Ｘ：龍森に、に、製９粒子径
： １ μｍ） ５０ｇを秤量する。) 15g, (d)2-methyl-1-[4-(methyl)
16 g of phenyl-2-morpholino-1-propane,
(E) 2 g of 4.4' bis-(diethylamino)benzophenone, (H) 1.5 g of dicyandiamide, (G) 2
,4-diamino-6[21-methylimidazole-(1
')]] Ethyl-8-triazine 0.2 g (h) Ultraviolet absorber: 4-t-butyl-4'-methoxy-benzoylmethane 3 g, 2-ethylhexyl-P-methoxycinnamate 3 g, (h) quencher Foaming agent: silicone oil 5H-2
03 (manufactured by Toshi Silicone) 5g, (nu) solvent:
Ethyl cellosolve acetate 35g, butyl cellosolve acetate 33g, (l) Thixotropic agent (fine quartz powder Aerosil A380: manufactured by Nippon Aerosil) 3g, (e)
Weigh 50 g of filler (Glistalite 5X: manufactured by Tatsumori Nihon Co., Ltd. 9 particle size: 1 μm).
上記成分の内（イ）〜（ホ）及び（ヌ）をセパラブルフ
ラスコに入れ、混合し８０〜１００℃で、３０分間〜２
時間加熱溶解する。これら混合物を常温に戻した後、（
へ）〜（す）、（ル）、（オ）を加えて充分に撹拌した
後、三本ロールミルを用いて混線する。更にスクリーン
印刷、ロールコータ塗布等に適するように（ヌ）の有機
溶剤を加えて粘度調整を行なう。Put the above ingredients (a) to (e) and (nu) into a separable flask, mix and heat at 80 to 100°C for 30 minutes to 2 minutes.
Dissolve by heating for an hour. After returning these mixtures to room temperature, (
After adding the ingredients (F) to (S), (L), and (E) and stirring thoroughly, mix the mixture using a three-roll mill. Furthermore, the viscosity is adjusted by adding an organic solvent (N) to make it suitable for screen printing, roll coater application, etc.
次いで、レジストが塗布された基板を８０℃で３０分間
の乾燥を施して、レジストを固化する。裏面でも、かか
る方法を繰り返しレジスト同化層を形成する。次いで表
裏両面のレジスト上にネガマスクを密着させ１両面から
同時にＵＶ光を１．Ｊ／ａｊ照射して露光する。Next, the substrate coated with the resist is dried at 80° C. for 30 minutes to solidify the resist. The same method is repeated on the back side to form a resist assimilation layer. Next, a negative mask is closely attached to the resist on both the front and back sides, and UV light is applied to both sides at the same time. Expose by irradiating with J/aj.
次いで、レジスト面からネガマスクを剥離し、現像液と
して１．１．１− トリクロロエタンを用いたスプレー
現像により常温で１分間で、未露光部を除去する。Next, the negative mask is peeled off from the resist surface, and the unexposed areas are removed by spray development using 1.1.1-trichloroethane as a developer at room temperature for 1 minute.
次いで、基板を１５０℃で、４０分間加熱してパターン
形成したレジスト部を硬化する。更に基板上のレジスト
にポスト露光としてＵＶ光を５Ｊ／ａｄ照射してレジス
トの硬化を完了する［第１図、４）］。次に下記の組成
の化学銅めっき液（シラプレー社製）中に１５分間浸漬
して、約０．４μｍの４付け化学銅めっきを施す。Next, the substrate is heated at 150° C. for 40 minutes to harden the patterned resist portion. Further, the resist on the substrate is irradiated with 5 J/ad of UV light as post-exposure to complete curing of the resist [FIG. 1, 4)]. Next, it is immersed in a chemical copper plating solution (manufactured by Silapray Co., Ltd.) having the composition shown below for 15 minutes to perform 4-layer chemical copper plating of about 0.4 μm.
カッパーミックス ３２８Ａ・・１２５ｍＱカッパーカ
ッパーミックスＬ・・１２５ｍＲカッパーカッパーミッ
クスＣ・・ ２５ｍｕ蒸留水 ・・・全量をＩＱと
する量その後、下記の組成の化学網めっき液中に１５時
間浸漬してスルーホールの孔内、ランド部、端子部上を
はじめとする必要な部分に、約３０μｍの厚付は化学銅
めっきを施しプリント回路板が製造される［第１図、５
）コ。Copper mix 328A... 125mQ Copper Copper mix L... 125mR Copper Copper mix C... 25mu distilled water ...Total amount as IQ After that, soak it in a chemical mesh plating solution with the following composition for 15 hours to prepare through holes. A printed circuit board is manufactured by applying chemical copper plating to a thickness of about 30 μm on necessary parts such as inside the holes, lands, and terminals [Fig. 1, 5
)Ko.
ＣｕＳＯ４・５Ｈ２ｏ ・・・１２ｇＥＤＴＡ・２Ｎ
ａ ・・・４２ｇ
Ｎａ０Ｈ（めっき液のＰＨを１２，３に調整する量）ア
ミン系界面活性剤 ・・０．１ｇ
αα′−ジピリジル ・・０．０５ ｇ３７％ホルマ
リン °５ｍ１２
ＫｚＳ −−０，００１ｇ
蒸留水 全量をＩＱとする量
めっき条件：液温度７０℃
ｐＨ１２，５
時間 １５時間
析出電位 −０，６〜−〇、９Ｖ
めっき槽内のめっき液成分は、自動管理装置、及び副生
成物を除去する液再生装置を取り付は常に一定に保った
。CuSO4・5H2o...12gEDTA・2N
a...42g Na0H (amount to adjust the pH of the plating solution to 12.3) Amine surfactant...0.1g αα'-dipyridyl...0.05 g37% formalin °5m12 KzS --0,001g
Distilled water The total amount is IQ Plating conditions: Liquid temperature 70℃ pH 12.5 hours 15 hours Deposition potential -0.6 to -〇, 9V The plating solution components in the plating tank are controlled by automatic management equipment and by-products. The attachment of the removing liquid regenerator was kept constant.
上記のプリント回路板製造プロセスでは、４付は化学銅
めっき工程をレジスト膜形成後に行なっているが、レジ
スト膜形成前に行なっても一向に差し支えない、ＵＶ光
がガラスエポキシ基材を透過してスルーホール内に到達
するのを遮蔽する効果もある。In the above printed circuit board manufacturing process, the chemical copper plating step in item 4 is performed after the resist film is formed, but it can also be performed before the resist film is formed. It also has the effect of blocking it from reaching the hall.
上記の光硬化性ジアリルフタレート樹脂組成物をはじめ
として、実施例１〜３９では樹脂組成物の各成分の配合
量がプリント回路板の製造工程並びに製品に与える影響
について検討し、その結果を表１．２に示す。特に本発
明で重要な特性の１つである耐めっき反応性を左右する
エポキシ硬化剤の配合量について、第３図に示す。検討
した項目および評価方法は下記の通りである。In Examples 1 to 39, including the above-mentioned photocurable diallyl phthalate resin composition, the influence of the blending amount of each component of the resin composition on the manufacturing process and product of printed circuit boards was investigated, and the results are shown in Table 1. Shown in .2. In particular, FIG. 3 shows the amount of the epoxy curing agent that affects the plating reactivity, which is one of the important characteristics in the present invention. The items examined and evaluation methods are as follows.
（１）塗布性：塗膜中に残存ボイドが無く、平滑な面を
有するものを良とした。（２）密着露光性：ネガマスク
を密着させ、ＵＶ光で露光後にネガマスクへのレジスト
付着が無いものを良とした。(1) Coatability: A coating film with no residual voids and a smooth surface was rated as good. (2) Adhesion exposure property: A negative mask was placed in close contact with the negative mask, and after exposure to UV light, no resist was adhered to the negative mask, which was evaluated as good.
（３）現像性：現像液として１．１．１− トリクロロ
エタンを用いたスプレー現像を常温で１分間施し、未露
光部が完全に溶解するもので、かつ露光部のレジストが
膨潤しないものを良とした。（４）耐裏写り性：厚み１
．６■のガラスエポキシ積層板の両面にレジストを、約
４０μｍの厚さで塗布し乾燥する。ネガマスクをレジス
ト上に密着させ片面からＵＶ光をＩＪ／ｃｉ照射後に現
像する。裏面のレジストが硬化せずレジスト残りのない
ものを良とした。（５）耐めっき溶出性：化学銅めっき
の膜物性（抗張力、伸び）を低下させないものを良とし
た。具体的には化学銅めっき液１Ω当り４００ｄのレジ
スト膜を入れた。（６）耐めっき反応性（耐カソード剥
離性）：化学網めっきが行なわれているスルーホールや
ランド部ないし端子部等に接続している導体回路上に塗
布されているレジストに化学網めっき後、剥離や変色が
無いものを良とした。（７）電気絶縁性：銅張リガラス
エポキシ積層板にＪＩＳ−Ｃ−２５１９に準じた櫛形パ
ターンをつくり、その上にレジスト膜を形成し、前述の
化学銅、めっき工程を経た後、吸湿時の絶縁抵抗が１ｏ
ｇΩ以上のものを良とした。(3) Developability: Perform spray development using 1.1.1-trichloroethane as a developer for 1 minute at room temperature, and the unexposed areas should be completely dissolved and the resist in the exposed areas should not swell. And so. (4) Anti-bleed-through: Thickness 1
．． A resist is applied to both sides of the glass epoxy laminate plate No. 6 to a thickness of about 40 μm and dried. A negative mask is brought into close contact with the resist, and UV light is irradiated from one side with IJ/ci, followed by development. If the resist on the back side was not hardened and there was no resist residue, it was considered good. (5) Plating elution resistance: Those that did not reduce the film properties (tensile strength, elongation) of chemical copper plating were rated as good. Specifically, a resist film of 400 d was applied per 1Ω of chemical copper plating solution. (6) Resistance to plating reactions (resistance to cathode peeling): After chemical mesh plating is applied to the resist coated on conductor circuits connected to through-holes, lands, terminals, etc. where chemical mesh plating is performed. , Those with no peeling or discoloration were considered good. (7) Electrical insulation: A comb-shaped pattern according to JIS-C-2519 is made on a copper-clad glass epoxy laminate, a resist film is formed on it, and after passing through the chemical copper and plating process described above, when moisture is absorbed insulation resistance is 1o
Those with a value of gΩ or more were considered good.
（８）耐熱性ニブリント回路板にフラックスを塗布し、
２８０℃の半田槽に１０秒間漬は常温に戻す。(8) Apply flux to the heat-resistant niblint circuit board,
Dip in a 280°C solder bath for 10 seconds and return to room temperature.
これを１０回繰り返した後レジストにフクレ、剥離等の
異常が無いものを良とした。After repeating this process 10 times, the resist had no abnormality such as blistering or peeling, and was judged as good.
本発明を構成する好ましい配合割合は、ジアリルフタレ
ートプレポリマー１００重量部に対して、多官能不飽和
化合物４乃至３０重量部、光重合開始剤０．５乃至１２
重量部、エポキシ樹脂３乃至３５重量部、消泡剤０．５
乃至１０重量部、有機溶剤５５乃至１００重量部、エポ
キシ硬化剤としてジシアンジアミドとドアミノトリアジ
ン変性イミダゾール化合物との配合比が１６／１乃至５
／１でこれら混合物の添加量がエポキシ樹脂１００重量
部に対して２乃至２０重量部、紫外線吸収剤０．１乃至
１０重量部の組成範囲において、プリント回路板の製造
に必要な全ての特性を同時に満足することができた。The preferred blending ratio constituting the present invention is 4 to 30 parts by weight of the polyfunctional unsaturated compound and 0.5 to 12 parts by weight of the photopolymerization initiator to 100 parts by weight of the diallyl phthalate prepolymer.
Parts by weight, 3 to 35 parts by weight of epoxy resin, 0.5 parts by weight of antifoaming agent
10 to 10 parts by weight, 55 to 100 parts by weight of an organic solvent, and a blending ratio of dicyandiamide and doaminotriazine-modified imidazole compound as an epoxy curing agent of 16/1 to 5.
/1, the amount of these mixtures added is 2 to 20 parts by weight per 100 parts by weight of the epoxy resin and 0.1 to 10 parts by weight of the ultraviolet absorber, all the properties necessary for manufacturing printed circuit boards can be achieved. I was satisfied at the same time.
実施例４０
本発明にかかわるプリント回路板製造工程の最適化を図
るため、各工程条件の諸特性に及ぼす影響について、実
施例１に示した光硬化性ジアリルラタレート樹脂組成物
をソルダレジストとして用いて検討した。尚、検討項目
以外の工程条件は実施例１と同じとした。Example 40 In order to optimize the printed circuit board manufacturing process related to the present invention, the photocurable diallyl ratate resin composition shown in Example 1 was used as a solder resist to examine the effects of each process condition on various characteristics. I considered it. Note that the process conditions other than the items to be examined were the same as in Example 1.
本発明のレジストは、液状であり塗布後ネガマスクと密
着可能な状態にするために、乾燥する必要がある。最適
乾燥条件は６０〜１００℃で０．２〜２時間であった。The resist of the present invention is in a liquid state and needs to be dried after application in order to be able to adhere to a negative mask. The optimum drying conditions were 60-100°C for 0.2-2 hours.
５０℃、２時間の乾燥では溶剤が残存し、密着露光が出
来ない。一方、１１０℃で、２時間乾燥するとエポキシ
樹脂の熱硬化が進み、現像によるパターン形成が８来な
い。次に、熱硬化工程は耐めっき性に影響を及ぼすエポ
キシ樹脂の硬化に係わるため、最も重要である。最適硬
化条件は１４０〜１８０℃で、０．２〜２時間であった
。１３０℃で、２時間ではエポキシ樹脂の硬化が不完全
となり耐めっき溶比性が悪く、また１９０℃の硬化では
、回路銅箔が酸化されるため耐めっき反応性が悪く、実
用に供し得なかった。次に後露光について検討した。耐
熱性を高めるのに有効であり、最適条件は１〜Ｊ、０Ｊ
ｌｃｄであった。If dried at 50°C for 2 hours, the solvent will remain and contact exposure will not be possible. On the other hand, if the epoxy resin is dried at 110° C. for 2 hours, the epoxy resin will be thermally hardened, and pattern formation by development will not be possible. Next, the heat curing step is the most important because it involves curing of the epoxy resin, which affects plating resistance. The optimum curing conditions were 140-180°C for 0.2-2 hours. Curing at 130°C for 2 hours will result in incomplete curing of the epoxy resin, resulting in poor plating resistance, and curing at 190°C will oxidize the circuit copper foil, resulting in poor plating reactivity, making it unsuitable for practical use. Ta. Next, we considered post-exposure. Effective for increasing heat resistance, optimal conditions are 1-J, 0J
It was lcd.
ソルダレジストとして上記実施例１〜３９の光硬化性ジ
アリルフタレート組成物の組成範囲ならびに工程条件を
用いて製造したプリント回路板をＪＩＳ−Ｃ−５０１２
の冷熱サイクル試験を繰り返し１００回行なったが回路
網箔上のレジストのフクレや剥離ならびにスルーホール
部のクランクやフクレ等の異常は生じなかった。JIS-C-5012 printed circuit boards manufactured using the composition range and process conditions of the photocurable diallyl phthalate compositions of Examples 1 to 39 as solder resists were used as solder resists.
The thermal cycle test was repeated 100 times, but no abnormalities such as blistering or peeling of the resist on the circuit network foil or cranking or blistering of the through-holes occurred.
比較例１〜２６
ソルダレジストとして上記実施例１〜３９の光硬化性ジ
アリルフタレート組成物の組成範囲外で、実施例１の工
程条件を用いてプリント回路板を製造した（表５〜７、
比較例１〜２６）。塗布性、密着露光性、耐裏写り性、
現像性、耐めっき溶出性、耐めっき反応性（耐カソード
剥離性）、電気絶縁性、耐熱性を同時に満足することが
出来ないため、実用に供しうるプリント回路板が得られ
なかった。Comparative Examples 1 to 26 Printed circuit boards were manufactured using the process conditions of Example 1 but outside the composition range of the photocurable diallyl phthalate compositions of Examples 1 to 39 as solder resists (Tables 5 to 7,
Comparative Examples 1 to 26). Coatability, close exposure, anti-bleed-through,
Since it was not possible to simultaneously satisfy developability, plating elution resistance, plating reactivity resistance (cathode peeling resistance), electrical insulation properties, and heat resistance, a printed circuit board that could be used for practical purposes could not be obtained.
本発明に係る光硬化性ジアリルフタレート樹脂組成物は
、パートリアディティブ法によるプリント回路板に適用
できるだけでなく、サブトラクト法や、フルアデイティ
ブ法によるプリント回路板へも適用が可能である。The photocurable diallyl phthalate resin composition according to the present invention can be applied not only to printed circuit boards produced by a part-additive method, but also to printed circuit boards produced by a subtract method or a fully additive method.
（以下余白）
第
７
表
〔発明の効果〕
以上説明したように、本発明の光硬化性ジアリルフタレ
ート樹脂組成物は塗布性、密着露光性、現像性、耐めっ
き溶出性、耐めっき反応性（耐カソード剥離性）、電気
特性、耐熱性に優れ、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板製造への適
用を可能にしたことにより、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出来る。(The following is a blank space) Table 7 [Effects of the Invention] As explained above, the photocurable diallyl phthalate resin composition of the present invention has coating properties, adhesion exposure properties, developability, plating elution resistance, plating reactivity ( It has excellent cathode peeling resistance), electrical properties, and heat resistance, and by satisfying these properties at the same time and making it possible to apply the part-reactive method to printed board manufacturing, we are able to create high-density printed circuit boards that can withstand practical use. It can be obtained using a simplified method.
第１図は、本発明に係るパートリアディティブ法プリン
ト板の製造順序を示す断面図。
第２図は、サブトラクト法によるプリント板の製造順序
を示す断面図。
第３図は、実施例１の光硬化性ジアリルフタレート樹脂
組成物を用い、ジシアンジアミドとジアミノトリアジン
変性イミダゾール化合物が、プリント板製造に必要な特
性を同時に満足する、最適第
１
凶
第
圀FIG. 1 is a cross-sectional view showing the manufacturing sequence of a part-reactive printed board according to the present invention. FIG. 2 is a cross-sectional view showing the manufacturing order of a printed board by the subtract method. FIG. 3 shows an optimal first embodiment in which the photocurable diallyl phthalate resin composition of Example 1 is used, and the dicyandiamide and diaminotriazine-modified imidazole compounds simultaneously satisfy the characteristics necessary for manufacturing printed boards.
Claims (1)
和化合物と、光重合開始剤と、エポキシ樹脂と、所定の
エポキシ硬化剤と、紫外線吸収剤と、消泡剤と、充填材
と、上記ジアリルフタレートのプレポリマーならびにエ
ポキシ樹脂を溶解するための溶剤を必須成分とする塗布
性、密着露光性、現像性、耐裏写り性、耐めっき溶出性
、耐めっき反応性いわゆる耐カソード剥離性、電気絶縁
性、耐熱性が優れたソルダレジストに適した、紫外線露
光・溶剤現像でパターン形成が可能な光硬化性ジアリル
フタレート樹脂組成物。 ２、上記ジアリルフタレートのプレポリマーの分子量が
３，０００乃至３０，０００であり、また、上記多官能
不飽和化合物が、ヒドロキシ化合物のアクリレートある
いはメタクリレート、オリゴマエステルアクリレートあ
るいはメタクリレート、エポキシアクリレートあるいは
メタクリレート、の中から選ばれた少なくとも１種であ
ることを特徴とする請求項１記載の光硬化性ジアリルフ
タレート樹脂組成物。 ３、上記エポキシ硬化剤が、ジシアンジアミドとジアミ
ノトリアジン変性イミダゾール化合物との混合物である
ことを特徴とする請求項１記載の光硬化性ジアリルフタ
レート樹脂組成物。 ４、上記光硬化性ジアリルフタレート樹脂組成物の配合
割合は、ジアリルフタレートプレポリマー１００重量部
に対して、多官能不飽和化合物４乃至３０重量部と、光
重合開始剤０．５乃至１２重量部と、エポキシ樹脂３乃
至３５重量部と、消泡剤０．５乃至１０重量部と、充填
材２０〜１００重量部と、上記ジアリルフタレートのプ
レポリマーならびにエポキシ樹脂を溶解するための溶剤
５５乃至１００重量部、所定のエポキシ硬化剤として、
ジシアンジアミドとジアミノトリアジン変性イミダゾー
ル化合物との配合比が重量部で１６／１乃至５／１でこ
れら混合物の添加量がエポキシ樹脂１００重量部に対し
て２乃至２０重量部であり、さらに紫外線吸収剤は、０
．１乃至１０重量部であることを特徴とする請求項１記
載の光硬化性ジアリルフタレート樹脂組成物。 ５、請求項１記載の光硬化性ジアリルフタレート樹脂組
成物を用いたプリント回路板。 ６、請求項１記載の光硬化性ジアリルフタレート樹脂組
成物を耐めっき反応性フォトソルダレジストとして用い
た下記の工程を具備するプリント回路板製造方法。銅張
り積層板に、ａ、孔をあけ、孔内壁に化学銅めっき触媒
核を付着させ、ｂ、エッチング法により絶縁基板上に導
体回路を形成し、ｃ、必要に応じ導体回路とスルーホー
ル部等に薄付け化学銅めっきを行ない、ｄ、基板全面に
請求項１記載の光硬化性ジアリルフタレート樹脂組成物
を塗布し、ｅ、光硬化性ジアリルフタレート樹脂組成物
を乾燥後、化学銅めっきが必要な孔内壁（スルーホール
）部やその周辺のランド部、コネクタ部、ならびに、Ｉ
Ｃ接続部など以外に紫外線を照射し、ｆ、溶剤現像を行
い未硬化のジアリルフタレート樹脂組成物を除去しパタ
ーンを形成し、ｇ、加熱硬化させ、ｈ、必要に応じ再度
紫外線照射をし、ｉ、化学銅めっきを施す。[Claims] 1. Prepolymer of diallyl phthalate, polyfunctional unsaturated compound, photopolymerization initiator, epoxy resin, predetermined epoxy curing agent, ultraviolet absorber, antifoaming agent, filling coating properties, adhesion exposure properties, developability, show-through resistance, plating elution resistance, plating reactivity resistance, so-called cathode resistance. A photocurable diallyl phthalate resin composition that can be patterned by UV exposure and solvent development, and is suitable for solder resists with excellent removability, electrical insulation, and heat resistance. 2. The molecular weight of the diallyl phthalate prepolymer is 3,000 to 30,000, and the polyfunctional unsaturated compound is acrylate or methacrylate of a hydroxy compound, oligomer ester acrylate or methacrylate, epoxy acrylate or methacrylate. The photocurable diallyl phthalate resin composition according to claim 1, characterized in that the photocurable diallyl phthalate resin composition is at least one selected from among these. 3. The photocurable diallyl phthalate resin composition according to claim 1, wherein the epoxy curing agent is a mixture of dicyandiamide and a diaminotriazine-modified imidazole compound. 4. The blending ratio of the photocurable diallyl phthalate resin composition is 4 to 30 parts by weight of the polyfunctional unsaturated compound and 0.5 to 12 parts by weight of the photopolymerization initiator to 100 parts by weight of the diallyl phthalate prepolymer. 3 to 35 parts by weight of an epoxy resin, 0.5 to 10 parts by weight of an antifoaming agent, 20 to 100 parts by weight of a filler, and 55 to 100 parts of a solvent for dissolving the diallyl phthalate prepolymer and epoxy resin. Parts by weight, as a given epoxy curing agent,
The blending ratio of dicyandiamide and diaminotriazine-modified imidazole compound is 16/1 to 5/1 in parts by weight, and the amount of the mixture added is 2 to 20 parts by weight per 100 parts by weight of the epoxy resin, and the ultraviolet absorber is ,0
．． The photocurable diallyl phthalate resin composition according to claim 1, characterized in that the amount is 1 to 10 parts by weight. 5. A printed circuit board using the photocurable diallyl phthalate resin composition according to claim 1. 6. A printed circuit board manufacturing method comprising the following steps, using the photocurable diallyl phthalate resin composition according to claim 1 as a plating-resistant photo solder resist. A. Drill a hole in the copper-clad laminate and attach a chemical copper plating catalyst nucleus to the inner wall of the hole. b. Form a conductor circuit on the insulating substrate by etching. c. Form the conductor circuit and through-hole portion as necessary. d. Applying the photocurable diallyl phthalate resin composition according to claim 1 to the entire surface of the substrate, and e. After drying the photocurable diallyl phthalate resin composition, chemical copper plating is applied. Necessary hole inner wall (through hole) part, land part around it, connector part, and I
C. Irradiate ultraviolet rays to areas other than the connecting parts, f. Perform solvent development to remove uncured diallyl phthalate resin composition and form a pattern, g. Heat cure, h. Irradiate ultraviolet rays again if necessary, i. Apply chemical copper plating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8071190A JPH03281622A (en) | 1990-03-30 | 1990-03-30 | Photocurable diallyl phthalate resin composition and printed circuit board prepared by using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8071190A JPH03281622A (en) | 1990-03-30 | 1990-03-30 | Photocurable diallyl phthalate resin composition and printed circuit board prepared by using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03281622A true JPH03281622A (en) | 1991-12-12 |
Family
ID=13725922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8071190A Pending JPH03281622A (en) | 1990-03-30 | 1990-03-30 | Photocurable diallyl phthalate resin composition and printed circuit board prepared by using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03281622A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013200577A (en) * | 2011-12-05 | 2013-10-03 | Hitachi Chemical Co Ltd | Formation method of cured resin film pattern, photosensitive resin composition, photosensitive element, manufacturing method of touch panel and cured resin film |
| JP2015146038A (en) * | 2011-12-05 | 2015-08-13 | 日立化成株式会社 | Formation method of cured resin film pattern, photosensitive resin composition, photosensitive element, manufacturing method of touch panel and cured resin film |
| 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 |
| US9348223B2 (en) | 2011-12-05 | 2016-05-24 | Hitachi Chemical Company, Ltd. | Method for forming resin cured film pattern, photosensitive resin composition, photosensitive element, method for producing touch panel, and resin cured film |
| US9488912B2 (en) | 2011-12-05 | 2016-11-08 | Hitachi Chemical Company, Ltd. | Method of forming protective film for touch panel electrode, photosensitive resin composition and photosensitive element, and method of manufacturing touch panel |
-
1990
- 1990-03-30 JP JP8071190A patent/JPH03281622A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013200577A (en) * | 2011-12-05 | 2013-10-03 | Hitachi Chemical Co Ltd | Formation method of cured resin film pattern, photosensitive resin composition, photosensitive element, manufacturing method of touch panel and cured resin film |
| JP2015146038A (en) * | 2011-12-05 | 2015-08-13 | 日立化成株式会社 | Formation method of cured resin film pattern, photosensitive resin composition, photosensitive element, manufacturing method of touch panel and cured resin film |
| US9348223B2 (en) | 2011-12-05 | 2016-05-24 | Hitachi Chemical Company, Ltd. | Method for forming resin cured film pattern, photosensitive resin composition, photosensitive element, method for producing touch panel, and resin cured film |
| US9488912B2 (en) | 2011-12-05 | 2016-11-08 | Hitachi Chemical Company, Ltd. | Method of forming protective film for touch panel electrode, photosensitive resin composition and photosensitive element, and method of manufacturing touch panel |
| US9964849B2 (en) | 2011-12-05 | 2018-05-08 | Hitachi Chemical Company, Ltd. | Method for forming resin cured film pattern, photosensitive resin composition, photosensitive element, method for producing touch panel, and resin cured film |
| US10042254B2 (en) | 2011-12-05 | 2018-08-07 | Hitachi Chemical Company, Ltd. | Method of forming protective film for touch panel electrode photosensitive resin composition and photosensitive element, and method of manufacturing touch panel |
| US10386719B2 (en) | 2011-12-05 | 2019-08-20 | Hitachi Chemical Company, Ltd. | Method for forming resin cured film pattern, photosensitive resin composition, photosensitive element, method for producing touch panel, and resin cured film |
| US10663861B2 (en) | 2011-12-05 | 2020-05-26 | Hitachi Chemical Company, Ltd. | Method for forming resin cured film pattern, photosensitive resin composition, photosensitive element, method for producing touch panel, and resin cured film |
| 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 |
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