JPH0457866A - Hole-filling ink for manufacturing copper through-hole printed wiring board - Google Patents
Hole-filling ink for manufacturing copper through-hole printed wiring boardInfo
- Publication number
- JPH0457866A JPH0457866A JP2168070A JP16807090A JPH0457866A JP H0457866 A JPH0457866 A JP H0457866A JP 2168070 A JP2168070 A JP 2168070A JP 16807090 A JP16807090 A JP 16807090A JP H0457866 A JPH0457866 A JP H0457866A
- Authority
- JP
- Japan
- Prior art keywords
- hole
- resin
- alkaline aqueous
- copper
- filling ink
- 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
- 238000011049 filling Methods 0.000 title claims abstract description 110
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 71
- 239000010949 copper Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 239000004088 foaming agent Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000805 composite resin Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000004604 Blowing Agent Substances 0.000 claims description 15
- 230000008859 change Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- -1 dimethyldinitroterephthalamide Chemical compound 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004156 Azodicarbonamide Substances 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 3
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- ULUZGMIUTMRARO-UHFFFAOYSA-N (carbamoylamino)urea Chemical compound NC(=O)NNC(N)=O ULUZGMIUTMRARO-UHFFFAOYSA-N 0.000 claims description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical group C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- UETLMBWMVIQIGU-UHFFFAOYSA-N calcium azide Chemical compound [Ca+2].[N-]=[N+]=[N-].[N-]=[N+]=[N-] UETLMBWMVIQIGU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 150000007857 hydrazones Chemical class 0.000 claims description 2
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- CQSQUYVFNGIECQ-UHFFFAOYSA-N 1-n,4-n-dimethyl-1-n,4-n-dinitrosobenzene-1,4-dicarboxamide Chemical compound O=NN(C)C(=O)C1=CC=C(C(=O)N(C)N=O)C=C1 CQSQUYVFNGIECQ-UHFFFAOYSA-N 0.000 claims 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 51
- 238000004090 dissolution Methods 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000470 constituent Substances 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 101
- 238000000034 method Methods 0.000 description 32
- 238000007747 plating Methods 0.000 description 32
- 238000001035 drying Methods 0.000 description 19
- 230000008569 process Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005498 polishing Methods 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- FEUATHOQKVGPEK-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarbaldehyde Chemical compound OC1=CC=C(C=O)C=C1C=O FEUATHOQKVGPEK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-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
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 101150100678 Pon1 gene Proteins 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- KOWWOODYPWDWOJ-LVBPXUMQSA-N elatine Chemical compound C([C@]12CN(C3[C@@]45OCO[C@]44[C@H]6[C@@H](OC)[C@@H]([C@H](C4)OC)C[C@H]6[C@@]3([C@@H]1[C@@H]5OC)[C@@H](OC)CC2)CC)OC(=O)C1=CC=CC=C1N1C(=O)CC(C)C1=O KOWWOODYPWDWOJ-LVBPXUMQSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 229940015043 glyoxal Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は銅スルーホールプリント配線基板の製造工程に
おいて、エツチングレジスト層を形成する際に使用する
弱アルカリ性水溶液による現像に対する耐性を有するこ
とにより、小径スルーホール、ランドレススルーホール
付き高密度銅スルーホールプリント配線基板を高精度、
低コスト、高信頼性で両面の配線を接続することを可能
とならしめ、かつ強アルカリ水溶液にて溶解除去可能な
銅スルーホールプリント配線基板製造用の孔埋めインキ
に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention has resistance to development with a weak alkaline aqueous solution used when forming an etching resist layer in the manufacturing process of copper through-hole printed wiring boards. High-precision, high-density copper through-hole printed wiring board with small diameter through-holes and landless through-holes.
The present invention relates to a hole-filling ink for manufacturing copper through-hole printed wiring boards, which makes it possible to connect wiring on both sides at low cost and with high reliability, and which can be dissolved and removed with a strong alkaline aqueous solution.
(従来の技術)
銅スルーホールプリント配線基板は通常以下の方法によ
り製造される(第1図参照)。(Prior Art) A copper through-hole printed wiring board is usually manufactured by the following method (see FIG. 1).
すなわち、エポキシ樹脂、ポリイミド樹脂、ポリエステ
ル樹脂等からなる絶縁板や、絶縁板の両面に銅箔を被着
した銅張り積層板に、スルーホールとなる貫通孔をあけ
洗浄した後、無電解銅めっき、あるいは無電解銅めっき
と電解銅めっきとの併用によって上記スルーホール用孔
の内壁及び基板表面に回路となる銅めっき層を形成する
。In other words, through-holes are drilled and cleaned in an insulating board made of epoxy resin, polyimide resin, polyester resin, etc., or a copper-clad laminate with copper foil coated on both sides of the insulating board, and then electroless copper plating is applied. Alternatively, a copper plating layer forming a circuit is formed on the inner wall of the through hole and the surface of the substrate by using electroless copper plating and electrolytic copper plating in combination.
次にスルーホール内にエツチング液からスルーホール内
壁を保護するために孔埋めインキを充填し、加熱乾燥あ
るいは紫外線硬化させ、基板表面の銅めっき層に付着し
ている孔埋めインキを表面機械研磨等により除去する。Next, hole-filling ink is filled into the through-hole to protect the inner wall of the through-hole from the etching solution, and the hole-filling ink is heated and dried or cured with ultraviolet light, and the hole-filling ink adhering to the copper plating layer on the surface of the board is removed by surface mechanical polishing. Remove by.
その後スルーホール上も含めて銅めっき層の表面に配線
パターンに対応したエツチングレジスト層を形成させる
。次にこのエツチングレジスト層をマスクとして、銅め
っき層を含む銅箔をエツチングして所望の配線パターン
を形成した後、苛性ソーダ水溶液を用いてエツチングレ
ジスト層と孔埋めインキを除去することにより目的の銅
スルーホールプリント配線基板を得る。上記製造工程に
おいてエツチングレジスト層としては、加熱乾燥型ある
いは紫外線硬化型スクリーン印刷用エツチングレジスト
インキ及びドライフィルムが一般に使用されている。Thereafter, an etching resist layer corresponding to the wiring pattern is formed on the surface of the copper plating layer including on the through holes. Next, using this etching resist layer as a mask, the copper foil containing the copper plating layer is etched to form the desired wiring pattern, and then the etching resist layer and hole-filling ink are removed using a caustic soda aqueous solution to form the desired copper foil. Obtain a through-hole printed wiring board. In the above manufacturing process, heat-dried or ultraviolet-curable screen printing etching resist inks and dry films are generally used as the etching resist layer.
(発明が解決しようとする課題)
第2図A、Bは孔埋めインキとして従来一般に使用され
ている熱乾燥型の孔埋めインキ及び無溶剤型で紫外線硬
化型孔埋めインキを用いた場合について、エツチング処
理を行う前のスルーホール付近の状態を示している。(Problems to be Solved by the Invention) FIGS. 2A and 2B show cases in which a heat-drying type hole-filling ink and a solvent-free ultraviolet curing type hole-filling ink, which are conventionally commonly used as hole-filling inks, are used. It shows the state around the through hole before etching.
絶縁基板1の表裏両面及びスルーホール用孔10の内壁
面には銅めっき層2が設けられており、スルーホール用
孔10の内部には孔埋めインキ4が充填されている。こ
の銅めっき層2の上に所望の回路パターンに対応してエ
ツチングレジスト層3によるエツチングパターンを形成
している。A copper plating layer 2 is provided on both the front and back surfaces of the insulating substrate 1 and on the inner wall surface of the through-hole hole 10, and the inside of the through-hole hole 10 is filled with hole-filling ink 4. On this copper plating layer 2, an etching pattern is formed by an etching resist layer 3 corresponding to a desired circuit pattern.
従来の銅スルーホールプリント配線基板製造用の孔埋め
インキは、ロジン又はロジン変性樹脂等のアルカリ可溶
性樹脂を主成分としているため、pH7以上のアルカリ
水溶液に容易に溶解し得る。Conventional hole-filling inks for manufacturing copper through-hole printed wiring boards mainly contain alkali-soluble resins such as rosin or rosin-modified resins, and therefore can be easily dissolved in alkaline aqueous solutions with a pH of 7 or higher.
このためファインライン化、ランドレススルーホール等
小径スルーホール化が進む最近の高密度銅スルーホール
プリント配線基板製造において、従来の技術では解決し
得ないいくつかの問題が発生している。For this reason, in the recent manufacturing of high-density copper through-hole printed wiring boards in which fine-line and small-diameter through-holes such as landless through-holes are being made, several problems have arisen that cannot be solved by conventional techniques.
1)スクリーン印刷用エツチングレジストインキによる
配線パターン形成では、200t11n以下のファイン
パターンを精度良く再現し量産することが難しい。1) When wiring patterns are formed using etching resist ink for screen printing, it is difficult to accurately reproduce and mass-produce fine patterns of 200t11n or less.
2)ドライフィルムによるエツチングレジスト層の形成
では、パターン用マスクフィルム(以下マスクフィルム
と言う)を位置合わせする際にランドレススルーホール
、小径スルーホール等では特に高度な位置合わせ技術を
要し、位置がずれたり露光回数によりマスクフィルムが
伸びたりした場合、マスクフィルム位置がずれてドライ
フィルムの露光後、無機の弱アルカリ性水溶液等の現像
液がスルーホール内へ侵入し孔埋めインキが溶解してし
まう。このためエツチング処理を行ったときにこの部分
の銅めっき層までエツチングされてしまい、スルーホー
ル欠けによる断線等の問題が発生する(第2図C,D参
照)。2) When forming an etching resist layer using a dry film, when aligning the pattern mask film (hereinafter referred to as mask film), particularly advanced alignment techniques are required for landless through holes, small diameter through holes, etc. If the mask film is misaligned or stretched due to the number of exposures, the mask film position will shift and after the dry film is exposed, a developer such as an inorganic weakly alkaline aqueous solution will enter the through holes and dissolve the hole-filling ink. For this reason, when etching is performed, the copper plating layer in this area is etched away, causing problems such as disconnection due to missing through holes (see FIGS. 2C and 2D).
また、従来の熱乾燥型孔埋めインキを用いてスルーホー
ルの孔埋めを行った場合には、孔埋めインキ4を充填し
た直後は表面が平坦であっても(第3図C−1)、加熱
乾燥させると孔埋めインキ4中の溶剤が揮発して体積が
20〜50%収縮するため、充填された孔埋めインキ4
が凹状となる(第3図C−1)。この後銅箔2′及び銅
めっき層2上に配線パターンに対応したパターンのエツ
チングレジスト層3を形成する際、孔埋めインキ4の表
面が凹状となっているため、ドライフィルムのラミネー
ト後に孔埋めインキとドライフィルムの間に空気層9を
残存し、その後の露光、現像、エツチング処理工程時に
破裂、剥離して信頼性に欠ける問題がある(第3図C−
1,C−2参照)。Furthermore, when through-holes are filled using conventional heat-drying hole-filling ink, even if the surface is flat immediately after filling with hole-filling ink 4 (Fig. 3 C-1), When heated and dried, the solvent in the hole-filling ink 4 evaporates and the volume shrinks by 20 to 50%, so the filled hole-filling ink 4
becomes concave (Fig. 3 C-1). After this, when forming an etching resist layer 3 with a pattern corresponding to the wiring pattern on the copper foil 2' and the copper plating layer 2, since the surface of the hole-filling ink 4 is concave, the hole-filling ink 4 must be filled after laminating the dry film. There is a problem in that an air layer 9 remains between the ink and the dry film, causing rupture and peeling during the subsequent exposure, development, and etching processes, resulting in a lack of reliability (Fig. 3C-
1, C-2).
また、エツチングレジストインキをスクリーン印刷した
場合、銅スルーホールのエツジ上のレジストインキの膜
厚が薄くなったり(第3図り参照)、あるいはカバーし
きれずに銅めっき層が露出する(第3図C−1)。この
場合、引き続くエツチング処理により、銅めっき層2及
び銅スルーホールエツジ部2′がエツチングされ断線等
の問題が発生する。In addition, when screen printing etching resist ink, the film thickness of the resist ink on the edge of the copper through-hole becomes thin (see Figure 3), or the copper plating layer is exposed due to insufficient coverage (Figure 3C). -1). In this case, the copper plating layer 2 and the copper through hole edge portion 2' are etched by the subsequent etching process, causing problems such as disconnection.
そこでこれらの凹状となる熱乾燥型孔埋めインキ4の体
積収縮分を補う目的のために、孔埋めインキ中に熱で体
積が増加する発泡剤あるいは膨張剤をそのままあるいは
マイクロカプセル化して混入させる方法が知られている
(例えば、特開昭54−139065号、特開昭61−
212092号及び特開昭63−226992号)。し
かしながら、いずれの場合にも加熱乾燥工程での孔埋め
インキの体積変化率が数10倍から数100倍と非常に
大きく、加熱による体積変化率のコントロールが困難で
ある。このため銅スルーホール内に孔埋めインキを充填
し、加熱乾燥したあとの孔埋めインキは、プリント基板
の厚み以上に膨張したり(第3図C−1)、孔埋めイン
キが膨張しすぎて破裂したり(第3図C−1)という状
態となり、その後の銅めっき層2上の孔埋めインキ4′
を機械研磨する際に研磨機にかかる負担が大きく、研磨
によって孔埋めインキが除去しきれず銅めっき層に残存
する等の問題がある。Therefore, in order to compensate for the volumetric shrinkage of the heat-drying hole-filling ink 4 that forms these concave shapes, there is a method in which a foaming agent or expansion agent whose volume increases with heat is mixed into the hole-filling ink as it is or in the form of microcapsules. are known (for example, JP-A-54-139065, JP-A-61-
No. 212092 and JP-A-63-226992). However, in either case, the volume change rate of the hole-filling ink during the heating and drying process is extremely large, ranging from several tens of times to several hundreds of times, and it is difficult to control the volume change rate due to heating. For this reason, after filling the copper through holes with hole-filling ink and heating and drying, the hole-filling ink may expand beyond the thickness of the printed circuit board (Figure 3 C-1), or the hole-filling ink may expand too much. The hole-filling ink 4' on the copper plating layer 2 ruptures (Fig. 3 C-1).
When mechanically polishing, a large load is placed on the polishing machine, and there are problems such as the hole-filling ink is not completely removed by polishing and remains on the copper plating layer.
また、研磨機を数回通過させて、膨張しすぎた孔埋めイ
ンキを平坦化させる際、過度の研磨によりスルーホール
エツジ部2′の孔埋めインキじが欠けたり(第3図H参
照)、銅めっき層2及びスルーホールエツジ部2′の銅
の厚みが減少し、その後のエツチング処理により断線や
パターン幅の減少が生じるなど、信頼性の低下を招くと
いう問題がある。In addition, when passing through the polisher several times to flatten the excessively expanded hole-filling ink, the hole-filling ink at the through-hole edge portion 2' may be chipped due to excessive polishing (see Figure 3 H). There is a problem that the thickness of the copper in the copper plating layer 2 and the through-hole edge portion 2' is reduced, and the subsequent etching process causes wire breakage and a reduction in pattern width, resulting in a decrease in reliability.
そこで本発明の課題は、上記した高密度銅スルーホール
プリント配線基板製造用の孔埋めインキとして、加熱乾
燥後の孔埋めインキの充填率が好ましくは90〜100
%とスルーホール用孔部を高度に平坦化させ、かつ無機
の弱アルカリ現像液中への溶出を防止することにより、
ランドレススルーホール、小径スルーホール等のスルー
ホールの信頼性を高めることのできる銅スルーホールプ
リント配線基板製造用の孔埋めインキを提供することに
ある。Therefore, an object of the present invention is to provide a hole-filling ink for producing the above-mentioned high-density copper through-hole printed wiring board, which preferably has a filling rate of 90 to 100 after heating and drying.
% and through-holes are highly flattened, and by preventing elution into the inorganic weakly alkaline developer,
An object of the present invention is to provide a hole-filling ink for manufacturing a copper through-hole printed wiring board that can improve the reliability of through-holes such as landless through-holes and small-diameter through-holes.
(課題を解決するための手段)
本発明者等は、銅スルーホールプリント配線基板製造に
おいてスルーホールに充填する孔埋めインキとして、従
来の孔埋めインキ中のアルカリ可溶性樹脂に代えて、弱
アルカリ性現像液耐性があって強アルカリ性水溶液にて
除去可能な樹脂を用い、さらに低体積変化率を有する粉
末状発泡剤の樹脂複合体を含ませることにより上記課題
を解決しうろことを見出し本発明に到達した。(Means for Solving the Problems) The present inventors used weak alkaline development to replace an alkali-soluble resin in conventional hole-filling ink as a hole-filling ink to fill through-holes in the production of copper through-hole printed wiring boards. By using a resin that is liquid resistant and removable with a strong alkaline aqueous solution, and further including a powdered foaming agent resin composite having a low volume change rate, the above problems were solved and scales were discovered, resulting in the present invention. did.
すなわち本発明は、弱アルカリ性水溶液に耐性を有し、
強アルカリ性水溶液にて溶解除去可能な樹脂、溶剤、粉
末状発泡剤の樹脂複合体、及び必要に応じて不活性固体
粉末を含む銅スルーホールプリント配線基板製造用の孔
埋めインキに関するものであり、この孔埋めインキは再
溶解可能な乾燥塗膜を形成する。That is, the present invention has resistance to weakly alkaline aqueous solutions,
The present invention relates to a hole-filling ink for producing copper through-hole printed wiring boards, which includes a resin composite of a resin, a solvent, and a powdered blowing agent that can be dissolved and removed in a strongly alkaline aqueous solution, and optionally an inert solid powder. This pore-filling ink forms a dry coating that is resolvable.
本発明の孔埋めインキでは、弱アルカリ性水溶液耐性を
有し強アルカリ性水溶液にて溶解除去可能な樹脂を用い
、この樹脂は後述のエツチング液に対しエツチング液耐
性を有する必要がある。ここでいう弱アルカリ性水溶液
とはpHが7を越え12以下、好ましくは11〜12の
水溶液であり、強アルカリ性水溶液とはpHが12を越
え14以下、好ましくは13〜14の水溶液である。こ
の弱アルカリ性水溶液耐性を′有し強アルカリ性水溶液
にて溶解除去可能な樹脂として、好ましくはフェノール
、クレゾール、レゾルシン、キシレノール、p−tブチ
ルフェノール、エチルフェノール、ブチルフェノール、
フェニルフェノール、クロルフェノール、ブロムフェノ
ール、カテコール、ヒドロキノンなどのフェノール類の
単独又は二種以上の混合物とホルムアルデヒド、パラホ
ルムアルデヒド、アセトアルデヒド、ブチルアルデヒド
、トリオキサン、アクロレイン、ベンズアルデヒド、サ
リチルアルデヒド、グリオキザール、グルタルアルデヒ
ド、アセトアルデヒド、セバシンアルデヒド、テレフタ
ルアルデヒド、イソフタルアルデヒド、5−ホルミルサ
リチルアルデヒドなどのアルデヒド類の単独又は二種以
上の混合物との付加縮合体、及び前記フェノール類の単
独又は二種以上の混合物と1.2−ジクロルエタン、1
.3−ジクロルプロパン、l、4−ジクロルブタンなど
のジハロアルカン類もしくはブタジェン、1.4−ペン
タジェンなどのジエン類の単独又は二種以上の混合物と
の付加体、バラヒドロキシスレン樹脂等が挙げられ、特
に好ましくは前記フェノール類の単独又は二種以上の混
合物とホルムアルデヒド、パラホルムアルデヒド、アセ
トアルデヒド、ブチルアルデヒド、トリオキサン、アク
ロレイン、ベンズアルデヒド、サリチルアルデヒドなど
の単独又は二種以上の混合物との付加縮合体又はパラヒ
ドロキシスチレン樹脂を使用しうる。The hole-filling ink of the present invention uses a resin that has resistance to a weakly alkaline aqueous solution and can be dissolved and removed in a strongly alkaline aqueous solution, and this resin must have resistance to an etching solution described below. The weak alkaline aqueous solution referred to herein is an aqueous solution with a pH of more than 7 and 12 or less, preferably 11-12, and the strong alkaline aqueous solution is an aqueous solution with a pH of more than 12 and 14 or less, preferably 13-14. As the resin which has resistance to weakly alkaline aqueous solution and can be dissolved and removed in strongly alkaline aqueous solution, it is preferable to use phenol, cresol, resorcinol, xylenol, pt-butylphenol, ethylphenol, butylphenol,
Phenylphenol, chlorophenol, bromophenol, catechol, a mixture of two or more of phenols such as hydroquinone, formaldehyde, paraformaldehyde, acetaldehyde, butyraldehyde, trioxane, acrolein, benzaldehyde, salicylaldehyde, glyoxal, glutaraldehyde, acetaldehyde , addition condensates with aldehydes such as sebacinaldehyde, terephthalaldehyde, isophthalaldehyde, and 5-formylsalicylaldehyde alone or with a mixture of two or more, and with the above phenols alone or with a mixture of two or more. dichloroethane, 1
.. Examples include adducts of dihaloalkanes such as 3-dichloropropane, 1,4-dichlorobutane, or dienes such as butadiene and 1,4-pentadiene, alone or in a mixture of two or more, and rose hydroxythrene resins. Particularly preferred are addition condensates or para-hydroxy of the above-mentioned phenols alone or in mixtures of two or more thereof and formaldehyde, paraformaldehyde, acetaldehyde, butyraldehyde, trioxane, acrolein, benzaldehyde, salicylaldehyde, etc. alone or in mixtures of two or more thereof. Styrene resin can be used.
インキ化するために使用する溶剤としては、これを揮発
させるための加熱乾燥工程における温度が銅スルーホー
ルプリント配線基板の耐熱限界を超えず、なおかつ孔埋
めインキを充填する際にインキ表面がすぐに乾燥しない
よう、沸点が140℃〜220℃の有機溶剤を使用する
ことが望ましい。The solvent used to make the ink must be such that the temperature during the heating and drying process to volatilize it does not exceed the heat resistance limit of the copper through-hole printed circuit board, and that the ink surface quickly forms when filling the hole-filling ink. It is desirable to use an organic solvent with a boiling point of 140°C to 220°C to prevent drying.
例えばセロソルブアセテート、ブチルセロソルブアセテ
ート、プロピレングリコールモノメチルエーテルアセテ
ート等のエステル類、ブチルセロソルブ、メチルカルピ
トール、エチルカルピトール等のエーテル類、石油エー
テル、石油ナフサ、ソルベントナフサ等の石油系溶剤な
どが挙げられる。Examples include esters such as cellosolve acetate, butyl cellosolve acetate, and propylene glycol monomethyl ether acetate, ethers such as butyl cellosolve, methyl carpitol, and ethyl carpitol, and petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha.
本発明の孔埋めインキに用いる粉末状発泡剤の樹脂複合
体とは、粉末状発泡剤を樹脂の中に均一に分散させたも
のである。ここで用いられる粉末状発泡剤は例えば、ジ
ニトロソペンタメチレンテトラミン、アゾジカルボンア
ミド、4.4’−オキンベンゼンスルホニルヒドラジド
、パラトルエンスルホニルヒドラジド、パラトルエンス
ルホニルアセトンヒドラゾン、ヒドラゾジカルボンアミ
ド、N N’−ジメチル−N N’−ジニトロソテレフ
タルアミド、ジメチルジニトロテレフタルアミド、アゾ
ビスイソブチロニトリル、ジアゾアミノベンゼン、アゾ
ジカルボン酸バリウム、3.3−ジスルホンヒドラジド
ジフェニルスルホン、重炭酸ソーダ、炭酸アンモニウム
、重炭酸アンモニウム、カルシウムアジドあるいはこれ
らの混合物などを挙げうる。The resin composite of the powdered foaming agent used in the pore-filling ink of the present invention is one in which the powdered foaming agent is uniformly dispersed in a resin. Powdered blowing agents used here include, for example, dinitrosopentamethylenetetramine, azodicarbonamide, 4,4'-oxinebenzenesulfonyl hydrazide, para-toluenesulfonyl hydrazide, para-toluenesulfonylacetone hydrazone, hydrazodicarbonamide, N N '-Dimethyl-N N'-dinitrosoterephthalamide, dimethyldinitroterephthalamide, azobisisobutyronitrile, diazoaminobenzene, barium azodicarboxylate, 3,3-disulfonehydrazide diphenylsulfone, sodium bicarbonate, ammonium carbonate, bicarbonate Examples include ammonium, calcium azide, and mixtures thereof.
発泡剤の平均粒径は、好ましくは0.1〜10μs、よ
り好ましくは0.5〜5pである。また発泡剤を分散さ
せる樹脂は熱可塑性樹脂でも熱硬化性樹脂でもよいが、
網目状の熱硬化性樹脂が効果的である。The average particle size of the blowing agent is preferably 0.1 to 10 μs, more preferably 0.5 to 5 p. In addition, the resin for dispersing the foaming agent may be a thermoplastic resin or a thermosetting resin, but
A mesh thermosetting resin is effective.
例えば、エポキシ樹脂、フェノール樹脂、ポリアミド樹
脂、ポリエステル樹脂、ポリウレタン樹脂などを例示し
うる。Examples include epoxy resin, phenol resin, polyamide resin, polyester resin, and polyurethane resin.
樹脂複合体中の発泡剤の含量としては1〜95重量%、
特に5〜60重量%であることが好ましい。The content of the blowing agent in the resin composite is 1 to 95% by weight,
In particular, it is preferably 5 to 60% by weight.
発泡剤を分散させる方法は特に限定されるものでなく、
公知のどのような方法でもよい。例えば、樹脂が軟化す
る温度で発泡剤を練り込んだり、プレポリマー中に発泡
剤を分散し硬化させたりすることにより上記樹脂複合体
が得られる。また樹脂複合体は微粒子状であることが好
ましく、その粒径は好ましくは100μs以下、特に好
ましくは5〜801Jである。微粒子化は、得られた樹
脂複合体を公知の方法により粉砕したり、硬化する前に
複合体を水中で分散して微小化するなどにより達成され
る。得られた複合体は加熱することによって、発泡剤の
分解温度に応じて膨張するが、加熱による体積変化率が
10倍以下、特に1.5〜2倍であるものが好ましい。The method of dispersing the blowing agent is not particularly limited;
Any known method may be used. For example, the resin composite can be obtained by kneading a foaming agent at a temperature at which the resin softens, or by dispersing the foaming agent into a prepolymer and curing it. Further, the resin composite is preferably in the form of fine particles, and the particle size thereof is preferably 100 μs or less, particularly preferably 5 to 801 J. Atomization is achieved by pulverizing the obtained resin composite by a known method, or by dispersing the composite in water to make it fine before curing. When the obtained composite is heated, it expands according to the decomposition temperature of the blowing agent, and it is preferable that the rate of volume change upon heating is 10 times or less, particularly 1.5 to 2 times.
なお、この体積変化率とは、樹脂複合体の加熱後の体積
を加熱前の体積で割った値を意味し、加熱温度は孔埋め
インキの加熱乾燥工程における温度範囲である。Note that the volume change rate means a value obtained by dividing the volume of the resin composite after heating by the volume before heating, and the heating temperature is the temperature range in the heating drying process of the hole-filling ink.
必要に応じて含まれる不活性固体粉末とは、孔埋めイン
キ流動特性及び粘度を調整するとともに、孔埋めインキ
を識別容易な色調に着色するために用いられている慣用
のものであり、例えば、タルク、シリカ、アルミナ、酸
化チタン、硫酸バリウム等の無機化合物、ポリエチレン
、ナイロン、ポリエステル等の有機重合体の微粒子等で
ある。また耐酸性、耐候性、耐熱性等の特性を有する染
料及び有機顔料の着色剤も適宜使用される。The inert solid powder included as necessary is a commonly used powder that is used to adjust the flow characteristics and viscosity of the hole-filling ink and to color the hole-filling ink in an easily distinguishable color tone, such as: These include fine particles of inorganic compounds such as talc, silica, alumina, titanium oxide, and barium sulfate, and organic polymers such as polyethylene, nylon, and polyester. Coloring agents such as dyes and organic pigments having characteristics such as acid resistance, weather resistance, and heat resistance are also used as appropriate.
以上の4成分を含む本発明の孔埋めインキの配合比は、
弱アルカリ性水溶液耐性を有し強アルカリ性水溶液にて
溶解除去可能な樹脂が好ましくは5〜90重量%、より
好ましくは10〜60重量%、溶剤が好ましくは5〜5
0重量%、より好ましくは10〜40重量%、粉末状発
泡剤の樹脂複合体が好ましくは01〜20重量%、より
好ましくは1〜10重量%、不活性固体粉末が好ましく
は0〜80重量%、より好ましくは20〜70重量%の
範囲である。The blending ratio of the pore-filling ink of the present invention containing the above four components is as follows:
The resin is preferably 5 to 90% by weight, more preferably 10 to 60% by weight, more preferably 10 to 60% by weight, and the solvent is preferably 5 to 5% by weight.
0% by weight, more preferably 10-40% by weight, powdered blowing agent resin composite preferably 01-20% by weight, more preferably 1-10% by weight, inert solid powder preferably 0-80% by weight. %, more preferably in the range of 20 to 70% by weight.
本発明の銅スルーホールプリント配線基板製造用の孔埋
めインキは、例えば、弱アルカリ性水溶液耐性を有し強
アルカリ性水溶液にて溶解除去可能な樹脂に、適当量の
溶剤及び必要に応じて慣用の不活性固体粉末等を加えて
粘稠な液体、又はペーストを得、ついで粉末状発泡剤の
樹脂複合体を加えて混合することにより調製しうる。The hole-filling ink for manufacturing copper through-hole printed wiring boards of the present invention is prepared by adding, for example, a resin that has resistance to weakly alkaline aqueous solutions and can be removed by dissolving in strongly alkaline aqueous solutions, an appropriate amount of solvent, and, if necessary, a conventional additive. It can be prepared by adding an active solid powder or the like to obtain a viscous liquid or paste, and then adding and mixing a powdered blowing agent resin complex.
このようにして得られる本発明の孔埋めインキは再溶解
可能な乾燥塗膜を形成しうるものであり、また銅スルー
ホールプリント配線基板のスルーホール内に充填した後
、加熱乾燥するだけで容易に体積の調節機能を果たす。The hole-filling ink of the present invention obtained in this way can form a dry coating film that can be redissolved, and can be easily applied by simply heating and drying after filling the through-holes of a copper through-hole printed wiring board. plays a volume regulating function.
この孔埋めインキにおいては低体積変化率の粉末状発泡
剤の樹脂複合体を使用しているため、加熱乾燥後の体積
変化率を容易に調整でき、銅スルーホール内全体積の9
0〜1(10%まで孔埋めインキを充填することができ
、従って孔埋め部を高度に平坦化させることが可能であ
る。This hole-filling ink uses a resin composite of powdered foaming agent with a low volume change rate, so the volume change rate after heating and drying can be easily adjusted.
The hole-filling ink can be filled up to 0 to 1 (10%), and therefore the hole-filling portion can be highly flattened.
以下本発明の孔埋めインキの使用法の具体例を図面に従
って説明する。第1図は、孔埋めインキを用いる銅スル
ーホールプリント配線基板の製造法を示す工程流れ図で
あり、この工程流れ図に従って順次説明する。また第4
図に、工程途中におけるスルーホール付近の断面図を示
すが、図面中従来例と同様の構造部分には同じ符号を付
した。A specific example of how to use the hole-filling ink of the present invention will be described below with reference to the drawings. FIG. 1 is a process flowchart showing a method of manufacturing a copper through-hole printed wiring board using hole-filling ink, and the process will be sequentially explained according to this process flowchart. Also the fourth
The figure shows a cross-sectional view of the vicinity of the through-hole in the middle of the process, and the same reference numerals are given to structural parts similar to those of the conventional example in the drawing.
エポキシ樹脂、ポリイミド樹脂、ポリエステル樹脂等か
らなる絶縁板1や、絶縁板1の両面に銅箔2′を被着し
た銅張り積層板、アルミニウム、鉄等の金属をエポキシ
樹脂等で絶縁処理した金属系絶縁板、あるいはセラミッ
ク基板等通常のプリント配線基板に用いられている材料
からなる絶縁板1に、スルーホールとなる貫通孔10を
あけた後、無電解銅めっき、あるいは無電解銅めっきと
電解銅めっきとの併用によって、上記スルーホール用孔
10の内壁及び基板表面に回路となる銅めっき層2を形
成する。次に、エツチング液からスルーホール内壁を保
護するために、スルーホール10内に孔埋めインキ4を
充填し、80℃〜125℃程度の温度で30分〜4時間
加熱乾燥させる。この際本発明による孔埋めインキを用
いて充填、乾燥した後のスルーホール内の孔埋めインキ
4は、プリント配線基板の厚みを超えることなく、スル
ーホール内体積の90〜100%の充填率となる(第4
図A、 B参照)。それゆえ次の銅めっき層2表面の孔
埋めインキ4′を除去する機械研磨において、低研磨圧
で容易に除去可能である。このため銅めっき層2及びス
ルーホールエツジ部2′を過度に研磨することはなく、
スルーホールのエツジ部2′の孔埋めインキじの欠けも
発生せず、銅めっき層表面の研磨後でも、スルーホール
内孔埋めインキ充填率は90〜100%を保持すること
が可能である(第4図C参照)。Insulating board 1 made of epoxy resin, polyimide resin, polyester resin, etc., copper-clad laminate with copper foil 2' coated on both sides of insulating board 1, metal such as aluminum or iron insulated with epoxy resin, etc. After drilling through-holes 10 in an insulating board 1 made of a material used for ordinary printed wiring boards, such as a system insulating board or a ceramic board, electroless copper plating or electroless copper plating and electrolytic copper plating are applied. In combination with copper plating, a copper plating layer 2 that becomes a circuit is formed on the inner wall of the through-hole hole 10 and on the surface of the substrate. Next, in order to protect the inner walls of the through holes from the etching solution, the through holes 10 are filled with hole-filling ink 4 and dried by heating at a temperature of about 80 DEG C. to 125 DEG C. for 30 minutes to 4 hours. At this time, the hole-filling ink 4 in the through-hole after filling and drying using the hole-filling ink according to the present invention has a filling rate of 90 to 100% of the internal volume of the through-hole without exceeding the thickness of the printed wiring board. Become (4th
(See Figures A and B). Therefore, in the next mechanical polishing for removing the hole-filling ink 4' on the surface of the copper plating layer 2, it can be easily removed with low polishing pressure. Therefore, the copper plating layer 2 and the through hole edge portion 2' are not polished excessively.
There is no chipping of the filling ink at the edge part 2' of the through hole, and even after polishing the surface of the copper plating layer, the filling rate of the filling ink in the through hole can be maintained at 90 to 100% ( (See Figure 4C).
次にエツチングレジスト層を形成する方法としては以下
の方法がある。Next, as a method for forming an etching resist layer, there are the following methods.
1)スクリーン印刷法
2)ドライフィルム法
3)電着法
4)液状レジスト法
1)スクリーン印刷法においては、本発明の孔埋めイン
キを用いるとスルーホール内の孔埋めインキの平坦性が
優れているため、エツチングレジストインキを孔部及び
その周辺部に所望の配線パターンで精度よく均一に印刷
することが可能である。1) Screen printing method 2) Dry film method 3) Electrodeposition method 4) Liquid resist method 1) In the screen printing method, when the hole-filling ink of the present invention is used, the flatness of the hole-filling ink in the through hole is excellent. Therefore, it is possible to uniformly and accurately print the etching resist ink in the hole and its surrounding area in a desired wiring pattern.
2)ドライフィルム法では、スルーホール内に孔埋めイ
ンキを充填、乾燥し、銅めっき層表面の孔埋めインキを
機械研磨後、ドライフィルムをラミネートし、マスクフ
ィルム位置合わせ後真空下紫外線露光、その後弱アルカ
リ性水溶液にて現像しエツチングレジスト層を形成する
。この場合、スルーホール内孔埋めインキが本発明の孔
埋めインキのように弱アルカリ性現像液耐性があり、な
おかつ高度に平坦化し得るものであれば、従来のように
マスクフィルムのずれが生じても、現像液により孔埋め
インキが溶出することはなく、またマスクフィルム合わ
せ後真空時にマスクフィルムの位置ずれも生じず、高精
度で高密度な配線パターンのエツチングレジスト層を形
成することが可能である。2) In the dry film method, the through holes are filled with hole-filling ink, dried, the hole-filling ink on the surface of the copper plating layer is mechanically polished, the dry film is laminated, the mask film is aligned, and then exposed to ultraviolet rays under vacuum. Develop with a weakly alkaline aqueous solution to form an etching resist layer. In this case, if the through-hole filling ink is resistant to a weakly alkaline developer like the hole-filling ink of the present invention and can be highly flattened, it can be used even if the mask film shifts as in the past. The hole-filling ink will not be eluted by the developer, and the mask film will not be misaligned when vacuumed after the mask film is assembled, making it possible to form an etching resist layer with a high-precision, high-density wiring pattern. .
3)電着法では、スルーホール内へ孔埋めインキを充填
後乾燥し、銅めっき層表面の孔埋めインキを機械研磨後
、電着液槽内へ孔埋めインキを充填した銅スルーホール
プリント基板を浸漬し、写真現像性を有する電着レジス
トを銅めっき層に電着させ、電着レジスト中の水分及び
溶剤を揮発させて電着レジストを乾燥し、ドライフィル
ム法同様マスクフィルムを直接接触させ紫外線露光後、
弱アルカリ性水溶液にて現像しエツチングレジスト層を
形成する。この場合、ネガ型電着レジストを使用する。3) In the electrodeposition method, the through-holes are filled with hole-filling ink, dried, the hole-filling ink on the surface of the copper plating layer is mechanically polished, and the electrodeposition liquid bath is filled with the hole-filling ink to create a copper through-hole printed circuit board. A photo-developable electrodeposited resist is electrodeposited on the copper plating layer, the water and solvent in the electrodeposited resist are evaporated, the electrodeposited resist is dried, and a mask film is brought into direct contact as in the dry film method. After UV exposure,
Develop with a weakly alkaline aqueous solution to form an etching resist layer. In this case, a negative electrodeposited resist is used.
この際、本発明の孔埋めインキを用いた場合には、ドラ
イフィルム法同様マスクフィルムのずれは極度に少なく
、またたとえマスクフィルムがずれても現像液に孔埋め
インキが溶出することなく、高精度で高密度な配線パタ
ーンのエツチングレジスト層を形成することが可能であ
る。At this time, when the hole-filling ink of the present invention is used, the shift of the mask film is extremely small as in the dry film method, and even if the mask film shifts, the hole-filling ink does not dissolve into the developer, resulting in high It is possible to form an etching resist layer with an accurate and high-density wiring pattern.
4)液状レジスト法では、ドライフィルムの替わりに写
真現像性を有する液状レジストを、スプレー法、ロール
コータ−法等によりコーティング、乾燥後マスクフィル
ムの位置合わせを行い、紫外線露光後弱アルカリ性水溶
液にて現像し、エツチングレジスト層を形成させる。こ
の場合も、本発明の孔埋めインキを用いると上記2)及
び3)と同様、高精度、高密度配線パターンのエツチン
グレジスト層を形成することが可能である。4) In the liquid resist method, instead of a dry film, a photo-developable liquid resist is coated by a spray method, a roll coater method, etc. After drying, the mask film is aligned, and after exposure to ultraviolet rays, it is coated with a weak alkaline aqueous solution. Develop to form an etching resist layer. In this case as well, if the hole-filling ink of the present invention is used, it is possible to form an etching resist layer with a high-precision, high-density wiring pattern, as in 2) and 3) above.
次いでエツチング工程に付する。エツチング液としては
、塩化第二鉄液、塩化第二銅液等の酸性エツチング液が
使用されるが、pH8〜9のアルカリ性エツチング液を
使用することも可能である。Next, it is subjected to an etching process. As the etching solution, an acidic etching solution such as a ferric chloride solution or a cupric chloride solution is used, but it is also possible to use an alkaline etching solution with a pH of 8 to 9.
この場合上記pHに耐性のあるエツチングレジスト層を
形成させる必要がある。In this case, it is necessary to form an etching resist layer that is resistant to the above pH.
最後に苛性ソーダ、苛性カリ、メタケイ酸ソーダ等の無
機の強アルカリ性物質の水溶液(本明細書中、単に強ア
ルカリ性水溶液ともいう) (pFl=12を越え1
4以下)により、エツチングレジスト層及び本発明の孔
埋めインキを溶解除去し、目的とする銅スルーホールプ
リント配線基板を得る。Finally, an aqueous solution of an inorganic strong alkaline substance such as caustic soda, caustic potash, or sodium metasilicate (herein also simply referred to as a strong alkaline aqueous solution)
4), the etching resist layer and the hole-filling ink of the present invention are dissolved and removed to obtain the intended copper through-hole printed wiring board.
(作 用)
このように、低体積変化率をもつ粉末状発泡剤の樹脂複
合体を含有し、弱アルカリ性水溶液耐性を有し強アルカ
リ性水溶液にて溶解除去可能な樹脂を用いた孔埋めイン
キを使用することにより、従来のものより高精度、低コ
ストかつ高信頼性で高密度銅スルーホールプリント配線
基板を製造することが可能となった。(Function) In this way, a pore-filling ink containing a powdered blowing agent resin composite with a low volume change rate, a resin that is resistant to weakly alkaline aqueous solutions and can be dissolved and removed in strongly alkaline aqueous solutions is used. By using this method, it has become possible to manufacture high-density copper through-hole printed wiring boards with higher precision, lower cost, and higher reliability than conventional ones.
孔埋めインキが、弱アルカリ性現像液に耐性があって、
強アルカリ性水溶液によって除去可能であり加熱乾燥後
に高度に平坦化されていれば、ドライフィルム及び電着
レジストの露光時にマスクフィルムがずれてスルーホー
ル上にエツチングレジスト層がなくても、エツチング処
理によってスルーホールが断線することはな(、またエ
ツチング処理後レジスト層を除去する際にインキを同時
に除去することが可能である。The hole-filling ink is resistant to weak alkaline developers,
If it can be removed with a strong alkaline aqueous solution and is highly flattened after heating and drying, even if the mask film shifts during exposure of the dry film and electrodeposited resist and there is no etching resist layer on the through hole, the etching process will remove the through hole. The holes will not be disconnected (and the ink can be removed at the same time as the resist layer is removed after etching).
(実施例)
以下、製造例、実施例、比較例により本発明をさらに詳
細に説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Production Examples, Examples, and Comparative Examples.
製造例1(粉末状発泡剤の樹脂複合体の製造)l!反応
釜にポリオキシエチレンノニルフェノールエーテル15
gを溶解した水5[lfl gを仕込んだ。Production Example 1 (Production of resin composite of powdered blowing agent) l! Polyoxyethylene nonylphenol ether 15 in the reaction pot
5 [lfl g] of water in which 5 g of water was dissolved was charged.
次に、ポリメチレンポリフェニルイソシアネート70g
1ポリテトラメチレングリコール30g1アゾジカルボ
ンアミド(平均粒径11J)I[1g、塩化メチレン
l 00 mlの均一な混合物を仕込み、撹拌回転数6
00 rpmで10分撹拌した。その後、撹拌回転数を
20Orpmにして、温度40℃で2時間、更に、70
℃で3時間樹脂を硬化させると同時に塩化メチレンを留
出させた。得られた微粒子の水分散体を遠心が過し、更
に乾燥させて粉末状発泡剤の樹脂複合体の粒子を得た。Next, 70g of polymethylene polyphenylisocyanate
1 polytetramethylene glycol 30 g 1 azodicarbonamide (average particle size 11 J) I [1 g, methylene chloride
Pour 100 ml of homogeneous mixture and stir at 6 rotations.
Stirred at 00 rpm for 10 minutes. After that, the stirring rotation speed was set to 20 Orpm, the temperature was 40°C for 2 hours, and the stirring speed was increased to 70°C.
While the resin was cured for 3 hours at 0.degree. C., methylene chloride was distilled off. The obtained aqueous dispersion of fine particles was centrifuged and further dried to obtain particles of a resin composite of a powdered foaming agent.
その平均粒径は25μsであつた。また、この樹脂複合
体を 120℃に加熱した際の体積変化率は151.6
%であった。The average particle size was 25 μs. In addition, the volume change rate when this resin composite was heated to 120°C was 151.6.
%Met.
製造例2(粉末状発泡剤の樹脂複合体の製造)ミレック
スX L−2252(三井東圧社製)90gと4.4′
−オキシビスベンゼンスルホニルヒドラジド(平均粒径
1μs) IGOgを混合し、それをロール混線機に
かけ、90℃で、111gのトリメチロールプロパン・
トルエンジイソシアネート付加体を添加しながら混練し
、均一な混合体とした。ここでプレポリマーは反応して
溶剤不溶となった。次いで得られた発泡剤の樹脂複合体
を室温まで冷却し、粉砕機及びミルで微粒子化した。平
均粒径36IJAの発泡剤の樹脂複合体が得られた。ま
た、この樹脂複合体を120℃に加熱した際の体積変化
率は163.0%であった。Production Example 2 (Production of resin composite of powdered blowing agent) Mirex X L-2252 (manufactured by Mitsui Toatsu) 90g and 4.4'
- Oxybisbenzenesulfonyl hydrazide (average particle size 1 μs).
The mixture was kneaded while adding the toluene diisocyanate adduct to form a homogeneous mixture. Here, the prepolymer reacted and became insoluble in the solvent. The resulting foaming agent resin composite was then cooled to room temperature and pulverized using a pulverizer and a mill. A foaming agent resin composite having an average particle size of 36 IJA was obtained. Further, the volume change rate when this resin composite was heated to 120°C was 163.0%.
実施例1〜4、比較例1〜5
弱アルカリ性水溶液耐性を有し強アルカリ性水溶液にて
溶解除去可能な樹脂、溶剤、不活性固体粉末を下記表1
の割合で配合し、三本ロールミルでペースト状にインキ
化した。次に出来上ったペーストに、製造例1.2で調
製した粉末状発泡剤の樹脂複合体を配合し、ペースト中
に均一に分散させて孔埋めインキを得た。このような配
合の粉末状発泡剤の樹脂複合体を含有する孔埋めインキ
を、銅スルーホール基板の孔に充填し、温度120℃、
90分、強制排気付き箱型オーブン中にて乾燥し、 た
。Examples 1 to 4, Comparative Examples 1 to 5 Resins, solvents, and inert solid powders that have resistance to weakly alkaline aqueous solutions and can be dissolved and removed in strongly alkaline aqueous solutions are shown in Table 1 below.
The mixture was mixed into a paste-like ink using a three-roll mill. Next, the powdered blowing agent resin composite prepared in Production Example 1.2 was blended into the resulting paste and uniformly dispersed in the paste to obtain a hole-filling ink. Hole-filling ink containing a resin composite of powdered foaming agent with such a composition was filled into the holes of a copper through-hole board, and heated at a temperature of 120°C.
Dry for 90 minutes in a box oven with forced exhaust air.
また、下記表2の割合で配合し、上記と同様にして比較
例1〜5の孔埋めインキを調製した。In addition, hole-filling inks of Comparative Examples 1 to 5 were prepared in the same manner as above by blending in the proportions shown in Table 2 below.
調製した各々の孔埋めインキについて、充填率、研磨性
、エツチングレジスト層形成性、現像液耐性、エツチン
グ耐性、溶解除去性、溶解除去残渣の有無について評価
し、その結果を下記表3にまとめた。Each of the prepared pore-filling inks was evaluated for filling rate, abrasiveness, etching resist layer forming property, developer resistance, etching resistance, dissolution removability, and presence or absence of dissolution and removal residue, and the results are summarized in Table 3 below. .
なお、各々の試験項目の評価方法及び条件は以下の通り
である。The evaluation method and conditions for each test item are as follows.
1)充填率及び状態
加熱乾燥後の銅スルーホール内孔埋めインキの状態を、
顕微鏡で観察しその断面写真より充填率を測定した。1) Filling rate and condition The condition of the ink filling the copper through hole after heating and drying.
It was observed with a microscope and the filling rate was measured from the cross-sectional photograph.
2)研磨性
孔埋めインキを充填、加熱乾燥した銅スルーホール基板
を、オシレーション機構付き4軸両面研磨機(■方弁表
記製)にて銅スルーホール基板表面を研磨し、スルーホ
ール内孔埋めインキの欠けの有無、銅めっき層上の残渣
について測定した。2) The surface of the copper through-hole board is filled with abrasive hole-filling ink, heated and dried, and the surface of the copper through-hole board is polished using a 4-axis double-sided polishing machine with an oscillation mechanism (manufactured by Hoben notation). The presence or absence of chips in the filling ink and the residue on the copper plating layer were measured.
3)エツチングレジスト層形成性
エツチングレジスト層としてドライフィルムリストン3
1H(Du Pon1 Japan Lid、製)、電
着レシストゾンネEDUV (関西ペイント■製)を用
いた。3) Formation of etching resist layer Dry film Liston 3 as etching resist layer
1H (manufactured by Du Pon1 Japan Lid) and Electrodeposition Resist Sonne EDUV (manufactured by Kansai Paint ■) were used.
4)現像液耐性
炭酸ソーダ1重量%の水溶液を用いて、温度25℃、ス
プレー圧2kg1&、60秒の条件下にてエツチングレ
ジスト層を現像し、耐性を評価した。この際、孔埋めイ
ンキ上のエツチングレジスト層が現像されるようにマス
クフィルムを調整し、孔埋めインキを現像液中で露出さ
せその耐性も同時に評価した。4) Developer Resistance The etching resist layer was developed using an aqueous solution containing 1% by weight of sodium carbonate at a temperature of 25° C. and a spray pressure of 2 kg 1 for 60 seconds, and its resistance was evaluated. At this time, the mask film was adjusted so that the etching resist layer on the hole-filling ink was developed, and the hole-filling ink was exposed in a developer to evaluate its resistance at the same time.
5)エツチング耐性
塩化第二銅液を用いて温度40℃、スプレー圧2kg/
、J、3分の条件下、銅箔及び銅めっき層をエツチング
し、その耐性を評価した。5) Using an etching-resistant cupric chloride solution at a temperature of 40°C and a spray pressure of 2 kg/
The copper foil and copper plating layer were etched under conditions of , J, 3 minutes, and their resistance was evaluated.
6)溶解除去性
苛性ソーダ5重量%の水溶液を用いて温度40℃、スプ
レー圧2kg/ail、60秒の条件下、エツチングレ
ジスト層及び孔埋めインキを溶解除去し、その溶解性を
評価した。6) Dissolution and removal The etching resist layer and hole-filling ink were dissolved and removed using a 5% by weight aqueous solution of caustic soda at a temperature of 40° C. and a spray pressure of 2 kg/ail for 60 seconds, and their solubility was evaluated.
7)溶解除去残渣の有無
銅スルーホール内に孔埋めインキが残った場合、電子部
品を搭載後半田付けの際に半田が付がないという問題が
発生する。そこで、噴流式半田層にて半田付けを行い、
スルーホール内の半田の付き具合を観察し、溶解除去残
渣の有無を評価した。7) Presence of dissolution and removal residue If hole-filling ink remains in the copper through-hole, there will be a problem that the solder will not adhere when electronic components are mounted and soldered. Therefore, we soldered using a jet solder layer.
The adhesion of solder inside the through-hole was observed, and the presence or absence of dissolution and removal residue was evaluated.
上記表3の結果からも明らかなように本発明の孔埋めイ
ンキは、従来の孔埋めインキと比較して良好な特性を有
する。As is clear from the results in Table 3 above, the hole-filling ink of the present invention has better characteristics than conventional hole-filling inks.
(発明の効果)
銅スルーホールプリント配線基板のスルーホール部に、
本発明の孔埋めインキを使用することによって、簡便に
スルーホール部の高度な平坦化を達成しうると共に、エ
ツチングレジスト層形成の際、露光時のマスクフィルム
のずれも少なく、たとえマスクフィルムがずれてスルー
ホール部が露出しても、エツチング液に侵されることな
く銅めっき層を保護し、ランドレススルーホール、小径
スルーホール等のスルーホールの信頼性を高め、高密度
銅スルーホールプリント配線基板の生産性及び品質の向
上に大いに役立つ利点を有する。(Effect of the invention) In the through-hole part of the copper through-hole printed wiring board,
By using the hole-filling ink of the present invention, it is possible to easily achieve a high degree of flattening of through-hole portions, and when forming an etching resist layer, there is little displacement of the mask film during exposure. Even if the through-hole part is exposed by etching, the copper plating layer is protected from being attacked by the etching solution, improving the reliability of through-holes such as landless through-holes and small-diameter through-holes, and improving the reliability of high-density copper through-hole printed wiring boards. It has advantages that greatly help improve productivity and quality.
【図面の簡単な説明】
第1図は孔埋めインキを用いる銅スルーホールプリント
配線基板の製造法を示す工程流れ図、第2図A−Dはエ
ツチングレジスト層形成後の断面図及びスルーホール部
の平面図、第3図A−Hは従来の孔埋めインキを用いた
場合の加熱乾燥前後のスルーホール部の断面図、第4図
A−Cは本発明による孔埋めインキを用いた場合の加熱
乾燥後のスルーホール部の断面図である。
1 ・・・・・・絶縁基板
2 ・・・・・・銅めっき層
2′・・・・・・銅 箔
2′・・・・・・スルーホールエツジ部3 ・・・・・
・エツチングレジスト層4 ・・・・・・銅スルーホー
ル内孔埋めインキ4′ ・・・・・・銅めっき層上の孔
埋めインキ4′・・・・・・スルーホールエツジ部の孔
埋めインキ9・・・・・・空気層
10 ・・・・・・スルーホール用孔第
図
第
図
紫外線硬化型孔埋めインキ
ドライ
フ
イルムレジス
ト
第
図
熱乾燥型孔埋めインキ
熱乾燥型エラチンブレジス
トインキ
第
図
第
図
第
図
第3図C−2
第
図
第
図
第
図[Brief Description of the Drawings] Figure 1 is a process flow diagram showing a method for manufacturing a copper through-hole printed wiring board using hole-filling ink, and Figures 2A-D are cross-sectional views after forming an etching resist layer and the through-hole portion. A plan view, FIGS. 3A-H are cross-sectional views of the through-hole portion before and after heating and drying when conventional hole-filling ink is used, and FIGS. 4A-C are cross-sectional views of the through-hole section when using hole-filling ink according to the present invention. FIG. 3 is a cross-sectional view of the through-hole portion after drying. 1...Insulating substrate 2...Copper plating layer 2'...Copper foil 2'...Through hole edge portion 3...
・Etching resist layer 4...Ink for filling the inner hole of the copper through hole 4'...Filling ink on the copper plating layer 4'...Ink for filling the edge of the through hole 9 Air layer 10 Hole diagram for through holes Diagram Ultraviolet curing type hole filling ink Dry film resist Diagram Heat drying type hole filling ink Heat drying type Elatin resist ink No. Figure Figure Figure Figure 3 C-2 Figure Figure Figure Figure C-2 Figure Figure Figure Figure C-2 Figure Figure Figure Figure C-2
Claims (7)
液にて溶解除去可能な樹脂、溶剤、粉末状発泡剤の樹脂
複合体、及び必要に応じて不活性固体粉末を含む銅スル
ーホールプリント配線基板製造用の孔埋めインキ。(1) Manufacture of a copper through-hole printed wiring board containing a resin composite of a resin, a solvent, and a powdered foaming agent that is resistant to weakly alkaline aqueous solutions and can be dissolved and removed in strongly alkaline aqueous solutions, and if necessary, an inert solid powder. Hole-filling ink for.
変化率が10倍以下である請求項1に記載の銅スルーホ
ールプリント配線基板製造用の孔埋めインキ。(2) The hole-filling ink for manufacturing copper through-hole printed wiring boards according to claim 1, wherein the rate of volume change due to heating of the resin composite of the powdered foaming agent is 10 times or less.
液にて溶解除去可能な樹脂5〜90重量%、溶剤5〜5
0重量%、粉末状発泡剤の樹脂複合体0.1〜20重量
%、不活性固体粉末0〜80重量%を含む請求項1又は
2に記載の銅スルーホールプリント配線基板製造用の孔
埋めインキ。(3) Resin 5-90% by weight that has resistance to weakly alkaline aqueous solutions and can be dissolved and removed in strongly alkaline aqueous solutions, solvent 5-5%
3. Hole filling for manufacturing copper through-hole printed wiring boards according to claim 1 or 2, comprising: 0% by weight, 0.1-20% by weight of a resin composite of powdered foaming agent, and 0-80% by weight of an inert solid powder. ink.
液にて溶解除去可能な樹脂10〜60重量%、溶剤10
〜40重量%、粉末状発泡剤の樹脂複合体1〜10重量
%、不活性固体粉末20〜70重量%を含む請求項3に
記載の銅スルーホールプリント配線基板製造用の孔埋め
インキ。(4) 10 to 60% by weight of resin that has resistance to weakly alkaline aqueous solutions and can be dissolved and removed in strongly alkaline aqueous solutions; 10% by weight of solvent;
40% by weight, 1-10% by weight of a resin composite of powdered blowing agent, and 20-70% by weight of an inert solid powder.
液にて溶解除去可能な樹脂がフェノール類とアルデヒド
類との付加縮合体又はジハロアルカン類もしくはジエン
類との付加体又はパラヒドロキシスチレン樹脂から選択
されたものである請求項1〜4のいずれかに記載の銅ス
ルーホールプリント配線基板製造用の孔埋めインキ。(5) The resin that has resistance to weakly alkaline aqueous solutions and can be dissolved and removed in strongly alkaline aqueous solutions is selected from addition condensates of phenols and aldehydes, adducts with dihaloalkanes or dienes, or parahydroxystyrene resins. The hole-filling ink for manufacturing copper through-hole printed wiring boards according to any one of claims 1 to 4.
ミン、アゾジカルボンアミド、4,4′−オキシベンゼ
ンスルホニルヒドラジド、パラトルエンスルホニルヒド
ラジド、パラトルエンスルホニルアセトンヒドラゾン、
ヒドラゾジカルボンアミド、N,N′−ジメチル−N,
N′−ジニトロソテレフタルアミド、ジメチルジニトロ
テレフタルアミド、アゾビスイソブチロニトリル、ジア
ゾアミノベンゼン、アゾジカルボン酸バリウム、3,3
′−ジスルホンヒドラジドジフェニルスルホン、重炭酸
ソーダ、炭酸アンモニウム、重炭酸アンモニウム、カル
シウムアジド及びこれらの混合物から選択されたもので
ある請求項1〜5のいずれかに記載の銅スルーホールプ
リント配線基板製造用の孔埋めインキ。(6) Powdered blowing agent is dinitrosopentamethylenetetramine, azodicarbonamide, 4,4'-oxybenzenesulfonylhydrazide, paratoluenesulfonylhydrazide, paratoluenesulfonylacetone hydrazone,
hydrazodicarbonamide, N,N'-dimethyl-N,
N'-Dinitrosoterephthalamide, dimethyldinitroterephthalamide, azobisisobutyronitrile, diazoaminobenzene, barium azodicarboxylate, 3,3
The hole for producing copper through-hole printed wiring boards according to any one of claims 1 to 5, which is selected from '-disulfone hydrazide diphenyl sulfone, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, calcium azide and mixtures thereof. Filling ink.
シ樹脂、フェノール樹脂、ポリアミド樹脂、ポリエステ
ル樹脂及びポリウレタン樹脂から選択された網目状の熱
硬化性樹脂である請求項1〜6のいずれかに記載の銅ス
ルーホールプリント配線基板製造用の孔埋めインキ。(7) Any one of claims 1 to 6, wherein the resin in the resin composite of the powdered blowing agent is a reticulated thermosetting resin selected from epoxy resin, phenol resin, polyamide resin, polyester resin, and polyurethane resin. Hole-filling ink for producing copper through-hole printed wiring boards as described.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2168070A JPH0457866A (en) | 1990-06-26 | 1990-06-26 | Hole-filling ink for manufacturing copper through-hole printed wiring board |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2168070A JPH0457866A (en) | 1990-06-26 | 1990-06-26 | Hole-filling ink for manufacturing copper through-hole printed wiring board |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0457866A true JPH0457866A (en) | 1992-02-25 |
Family
ID=15861284
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2168070A Pending JPH0457866A (en) | 1990-06-26 | 1990-06-26 | Hole-filling ink for manufacturing copper through-hole printed wiring board |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0457866A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998013430A1 (en) * | 1996-09-24 | 1998-04-02 | Videojet Systems International, Inc. | Binder resins for ink compositions |
US6251175B1 (en) | 1998-08-06 | 2001-06-26 | Marconi Data Systems Inc. | Jet ink composition |
JP2009272431A (en) * | 2008-05-07 | 2009-11-19 | Taiyo Ink Mfg Ltd | Thermosetting resin composition for padding, combination unit of photo-curing and thermosetting resin composition for forming solder mask and printed wiring board |
CN104774499A (en) * | 2015-04-29 | 2015-07-15 | 韦利束 | Metal printing ink resistant to corrosion and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5713160A (en) * | 1980-06-30 | 1982-01-23 | Honda Motor Co Ltd | Corrosion resistant products consisting of aluminum |
JPS61212092A (en) * | 1985-03-18 | 1986-09-20 | サンワ化学工業株式会社 | Hole stopping ink for copper through hole printed wiring board |
-
1990
- 1990-06-26 JP JP2168070A patent/JPH0457866A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5713160A (en) * | 1980-06-30 | 1982-01-23 | Honda Motor Co Ltd | Corrosion resistant products consisting of aluminum |
JPS61212092A (en) * | 1985-03-18 | 1986-09-20 | サンワ化学工業株式会社 | Hole stopping ink for copper through hole printed wiring board |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998013430A1 (en) * | 1996-09-24 | 1998-04-02 | Videojet Systems International, Inc. | Binder resins for ink compositions |
US6251175B1 (en) | 1998-08-06 | 2001-06-26 | Marconi Data Systems Inc. | Jet ink composition |
JP2009272431A (en) * | 2008-05-07 | 2009-11-19 | Taiyo Ink Mfg Ltd | Thermosetting resin composition for padding, combination unit of photo-curing and thermosetting resin composition for forming solder mask and printed wiring board |
CN104774499A (en) * | 2015-04-29 | 2015-07-15 | 韦利束 | Metal printing ink resistant to corrosion and preparation method thereof |
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