EP0166327B1 - Procédé de fabrication de plaques pour circuits imprimés - Google Patents
Procédé de fabrication de plaques pour circuits imprimés Download PDFInfo
- Publication number
- EP0166327B1 EP0166327B1 EP85107381A EP85107381A EP0166327B1 EP 0166327 B1 EP0166327 B1 EP 0166327B1 EP 85107381 A EP85107381 A EP 85107381A EP 85107381 A EP85107381 A EP 85107381A EP 0166327 B1 EP0166327 B1 EP 0166327B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- baseboards
- activated
- cyclohexene
- way
- solution
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- -1 4-cyclohexene-1,2-dicarboxylic imide Chemical class 0.000 claims abstract description 12
- 239000012190 activator Substances 0.000 claims abstract description 11
- 239000011265 semifinished product Substances 0.000 claims abstract description 11
- 238000005530 etching Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 150000001993 dienes Chemical class 0.000 claims abstract description 3
- 238000009713 electroplating Methods 0.000 claims abstract description 3
- 150000002576 ketones Chemical class 0.000 claims abstract description 3
- 238000007772 electroless plating Methods 0.000 claims abstract 2
- 125000002524 organometallic group Chemical group 0.000 claims abstract 2
- 238000000926 separation method Methods 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 9
- 239000000243 solution Substances 0.000 description 23
- 239000010949 copper Substances 0.000 description 16
- 239000002585 base Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000001465 metallisation Methods 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- CIFFBTOJCKSRJY-UHFFFAOYSA-N 3α,4,7,7α-tetrahydro-1h-isoindole-1,3(2h)-dione Chemical compound C1C=CCC2C(=O)NC(=O)C21 CIFFBTOJCKSRJY-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000004922 lacquer Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000002318 adhesion promoter Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- SHOJXDKTYKFBRD-UHFFFAOYSA-N 4-Methyl-3-penten-2-one, 9CI Chemical compound CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- CVICEEPAFUYBJG-UHFFFAOYSA-N 5-chloro-2,2-difluoro-1,3-benzodioxole Chemical group C1=C(Cl)C=C2OC(F)(F)OC2=C1 CVICEEPAFUYBJG-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- HIDYYJFXCDZTHJ-UHFFFAOYSA-L acetonitrile;dichloropalladium Chemical compound CC#N.Cl[Pd]Cl HIDYYJFXCDZTHJ-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- MWOBKFYERIDQSZ-UHFFFAOYSA-N benzene;sodium Chemical compound [Na].C1=CC=CC=C1 MWOBKFYERIDQSZ-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 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 1
- 238000010438 heat treatment Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- WNSXUAGCWVZDQC-UHFFFAOYSA-N n-ethylbenzenesulfonamide Chemical compound CCNS(=O)(=O)C1=CC=CC=C1 WNSXUAGCWVZDQC-UHFFFAOYSA-N 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
Definitions
- the invention relates to a wet chemical process for the production of printed circuit boards.
- the deposition of adherent metal layers on the usual insulating base materials requires a complex pretreatment.
- the base plates must first be provided with an adhesion promoter layer and then treated with oxidizing liquid, preferably chromosulfuric acid, before the plates prepared in this way are activated, masked and metallized in commercially available metallization baths with ionic or colloidal noble metal solutions.
- this technique has the disadvantage that chromium ions which have been introduced poison the baths irreversibly and that the printed circuit boards obtained have unsatisfactory electrical properties.
- the method according to the invention has the advantage that a metal layer with a thickness of only a maximum of 10 ⁇ m, preferably 0.1-7 , 5 ⁇ m or - particularly preferably 0.1-5.0 ⁇ m - must be etched out, which results in considerable material savings.
- the palladium complexes are particularly preferred.
- novel process is advantageously carried out in such a way that base materials with the above. wetted organometallic compounds. This can be done primarily by spraying with a volatile organic solution of the activators mentioned or by dipping into these media.
- Alcohols such as C 2 H 5 OH and CH 3 0H or their mixtures with one another into consideration.
- the base materials treated in this way are then, if necessary swollen in a solvent, then sensitized and metallized over the entire area in a reductive metallization bath.
- the metal coating thus obtained is galvanically reinforced up to a maximum total thickness of 10 ⁇ m.
- the metallized base material also called “semi-finished product” is partially provided with a mask.
- resist layers photoresists, photoresists
- negative resists or “positive resists”
- positive resists are used to cover the semi-finished products. They are generally known (see, for example, Günther Hermann, “Printed Circuit Boards, Manufacturing and Pretreatment •, pp. 98-103 and 125-127).
- the unexposed parts are removed with a suitable solvent after the exposure, in the second case the exposed parts.
- a number of special resist systems can be used to produce reliefs for electronics or for microelectronics.
- the resist systems curable with the aid of UV radiation, electron radiation and laser radiation should be mentioned (cf. DE-A 2 007 267, DE-A 2 454 879 and DE-A 2 507 874).
- the relief mask can also be applied by screen printing, coating or stamping.
- Suitable substrates for the process according to the invention are plates, preferably plates made of glass fiber and glass mat reinforced epoxy resins provided with standard holes (see, for example, Kunststoff Handbuch, Prof. R. Vieweg, XI, pp. 180-246, Carl Hanser Verlag, Kunststoff (1971)) , fluorine-containing polymers (see, for example, reference p. 673-674) such as PTFE (polytetrafluoroethylene), thermosetting plastics such as phenol-formalin and / or melamine resins (see, for example, Prof. R. Vieweg "Plastics Manual" X, p.
- polypropylene polyethylene
- ABS acrylonitrile butadiene styrene
- polycondensates e.g. polycarbonates, aromatic and / or aliphatic polyamides, polyesters, aromatic and / or aliphatic polyamides or Polyamide imides and their mixture or cocondensates.
- the polymer plates In individual cases, the polymer plates must be swollen with a suitable swelling agent before metallization.
- solutions of a mixture of halides of elements of the 1st and / or 2nd main group of the periodic table with salts of weak inorganic bases and strong inorganic acids are used.
- Suitable halides of elements of the 1st and 2nd main group are in particular the chlorides; LiCl, BeCl 2 , MgCl 2 and CaCl 2 are preferred.
- Suitable salts of weak bases and strong acids are sulfates, nitrates and especially chlorides of metals of the 3rd and 4th main and subgroups as well as base metals of the 6th-8th Subgroup.
- FeCl 2, FEC1 3, TiCl 3, TiCl 4, BCI 3 and in particular AICI 3 are preferred.
- Suitable swelling agents and solvents are those as described in conventional manuals on polyamides (see, for example, “Die Polyamide von Hopff. Müller, Wegner, Springer-Verlag (1954), and“ Polymer Handbook ”by Brandrup et al. New York, Volume IV (1975) and «Vieweg / Müller Plastic Handbook; Volume IV (1966)).
- Examples include: low aliphatic and araliphatic alcohols, such as. B. methanol, ethanol, isopropanol, n-propanol, n-butanol, benzyl alcohol and phenylethyl alcohol. Methanol is particularly preferred.
- Dimethyl sulfoxide and amide group-containing solvents such as formamide and dimethylformamide are also suitable. Mixtures of these solvents can of course also be used.
- a particularly preferred swelling agent system is a solution of CaCl 2 / AICI 3 mixture in methanol.
- conventional polyamide plasticizers 0.2-10% by weight or 0.5-5% by weight, based on the total amount of liquid
- examples include benzenesulfonic acid monoethylamide, p-toluenesulfonic acid amide, dioxide diphenyl sulfone and dibenzyl alcohol.
- the “activation” and “acquiring” operations can be combined by dissolving the activator in the swelling agent and using this system.
- this variant is preferably carried out by immersing these polymers in an organic, preferably anhydrous, solution such as THF (tetrahydrofuran), benzene and toluene, which additionally contains an alkali organic compound with a solitary, contains capable of forming a pair of electrons capable of carbanion or carbcation.
- an organic, preferably anhydrous, solution such as THF (tetrahydrofuran), benzene and toluene, which additionally contains an alkali organic compound with a solitary, contains capable of forming a pair of electrons capable of carbanion or carbcation.
- THF tetrahydrofuran
- benzene and toluene which additionally contains an alkali organic compound with a solitary, contains capable of forming a pair of electrons capable of carbanion or carbcation.
- naphthalene sodium, naphthalene lithium, benzollite hium, benzene sodium, biphenyl, triphenyl and butyl lithium or sodium are particularly preferred.
- concentration of the alkali organic compounds should be 0.01 to 250, preferably 2.5-100, particularly preferably 5-75 g per liter of solvent.
- thermosets based on phenolic, epoxy and melamine resins which can also be used to produce base materials according to the invention, can of course be coated with an adhesion promoter (see, for example, G. Hermann, printed circuit boards, manufacture and preparation. Pp. 164-168, Eugen G. Lenze Verlag , Sauigau / Württ. (1978)), which contains a rubber-elastic component.
- an adhesion promoter see, for example, G. Hermann, printed circuit boards, manufacture and preparation. Pp. 164-168, Eugen G. Lenze Verlag , Sauigau / Württ. (1978)
- they can be dissolved in solvents or swelling agents customary for the ABS polymers (see, for example, “Polymer Handbook Brandrup et al. New York, Volume IV (1975)) or in oxidizing media are treated.
- the pretreated and activated base plates have to be sensitized by reduction.
- the reducing agents customary in electroplating such as hydrazine hydrate, formaldehyde, hypophosphite or boranes, can preferably be used for this purpose. Of course, other reducing agents are also possible.
- the reduction is preferably carried out in aqueous solution. However, other solvents such as alcohols, ethers, hydrocarbons can also be used. Of course, suspensions or slurries of the reducing agents can also be used.
- the surfaces sensitized in this way can be used directly for electroless metallization. However, it may also be necessary to rinse the surface of the reducing agent residues.
- a very particularly preferred embodiment of the method according to the invention consists in that the reduction in the metallization bath is carried out immediately with the reducing agent of the electroless metallization. This version represents a simplification of the electroless metallization that was previously not possible.
- This embodiment is very particularly suitable for the nickel baths containing amine borane or copper baths containing formalin, which are preferably used.
- the first is characterized in that the non-masked areas on the semi-finished product are removed with the etching solution. In this way, printed circuit boards with a relatively thin metal coating, namely a maximum of 10 ⁇ m, are obtained.
- the preferred procedure consists in galvanically strengthening the non-masked areas up to a maximum of 50 J.l.m and then optionally protecting them with a tin layer before the mask and the underlying thin layer layer are removed with the aid of an etching solution.
- the metal layers deposited using said method can also be developed in a grid-like manner using the differential etching method.
- Plastic plate made of polyamide-6 is activated for 5 minutes in a solution of 1 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride palladium (11) chloride in 1 1 CH 2 Cl 2 at room temperature (RT), dried and in a bath which contains, treated for 5 minutes at RT. The plate is then made up in a bath Sensitized for 5 min at RT, rinsed with distilled water and then copper-plated in a commercially available copper plating bath at 30 ° C. up to a metal layer of approx. 1 ⁇ m.
- the thin-layer plate produced in this way is covered with the aid of a screen printing varnish based on a styrene-butadiene copolymer, which has free comb-shaped webs of about 500 ⁇ m in width, and then in a bath which consists of exists, treated for 10 minutes.
- a plated-through circuit board with 500 ⁇ m wide and 4.0 ⁇ m thick conductor tracks is obtained.
- the metal coating adheres so well to the substrate surface that it cannot be removed from the polymer surface despite a 1-minute post-treatment at 265 ° C in a drying cabinet.
- a 200 x 200 x 1 mm commercial rubber-grafted polyamide 6 plate is provided with 0.2 mm holes in a bath of 1 liter.
- CH 2 C1 2 and 0.9 g mesityl oxide-palladium chloride activated in the course of 4 minutes at 18 ° C., dried, in a bath
- Example 2 treated at 20 ° C for 5 minutes, sensitized according to Example 1 and then copper-plated by chemical means in a commercially available copper plating bath.
- the thin-layer printed circuit board produced in this way is sprayed with a UV-curable lacquer based on oligomeric 1,4-polyisoprene (approx. 5% by weight in xylene) from Agfa Gevaert AG, Leverkusen) and then dried. After a week, the surface of the semi-finished product is covered with a photo mask and partially crosslinked with the help of UV radiation. The non-crosslinked prepolymer part is removed from the test specimen in methanol (very pure) after the mask has been removed. The thin-layer plate is then removed in a bath at 25 ° C developed pictorially.
- a plated-through circuit board with 40 ⁇ m wide and 7.5 ⁇ m thick conductor tracks is obtained.
- the peel strength of the metal pad measured according to DIN 53 494 is approx. 60 N / 25 mm and passes the 15 second solder bath test at 255 ° C.
- a 200 x 200 x 1 mm large commercially available polytetrafluoroethylene film is provided with standard holes and in a solution which consists of is prepared, pretreated for 5 minutes.
- the plate is then washed neutral with methanol and then in a bath which is made of
- 1,000 ml CC1 2 CHCI, treated at 30 ° C for 6 minutes and then dried.
- the plate activated in this way is in a bath which is made of exists at RT for 5 min. sensitized, washed and then nickel-plated in a standard nickel plating bath.
- test specimen After about two minutes, the test specimen turns silver-gray and after about 20 minutes an electrically highly conductive Ni coating is deposited, which is reinforced to 3.5 ⁇ m with galvanic silver.
- the thin-layer plate produced in this way is coated with a UV-curable resist lacquer, dried and then covered with a photomask or partially crosslinked with the aid of UV radiation.
- the non-crosslinked prepolymer portion is removed from the base material in a commercially available developer solution after removal of the mask.
- the plate is then post-treated in the metal etching solution specified in Example 1.
- a 200 x 300 mm aromatic polyimide film (Kapton (R) ) is provided with holes according to Example 1, in a solution which consists of 1.0 g of 4-cyclohexene-1,2-dicarboximide palladium chloride and 1 liter. CH 2 C1 2 is activated, sensitized according to Example 1, metallized and then the metal coating developed according to Example 2.
- a printed circuit board is obtained, the metal coating of which adheres so well to the substrate surface that it cannot be removed from the polymer surface despite a 1-minute aftertreatment in a commercial solder bath at 250 ° C.
- a 100 x 100 x 1 mm 40% mineral filler-reinforced polymer plate made of polyamide-6 is made in a bath from 0.8 g of 4-cyclohexene-1,2-dicarboxylic acid imide-palladium (II) chloride, 1 500 ml of methanol, 120 g CaC1 2 and 3 g AICI 3 adhesive activated at 30 ° C for 5 minutes.
- the plate is then sensitized in a bath consisting of 1 200 ml of ethanol, 24 ml of NH 3 solution (25%) and 500 ml of 2N-DMAB (dimethylamine borane) solution, washed for 5 minutes, in a commercially available wet-chemical copper plating bath an approx.
- the polymer-metal composite in methylene chloride is freed from the polymeric resist coating and 35 minutes in a Cu etching solution consisting of 100 ml HCl (37%), 30 ml H 2 0 2 (40%) and 1,000 ml H 2 0 treated.
- An electrical circuit board is obtained with continuous conductor tracks 200 ⁇ m wide and approx. 42 ⁇ m thick, consisting of approx. 5 4 m chemical and approx. 35 ⁇ m galvanic copper or approx. 1 ⁇ m galvanic tin.
- the metal coating adheres so well to the substrate surface that it cannot be removed from the polymer surface despite a two-hour aftertreatment at 160 ° C.
- a perforated polyamide plate is activated in accordance with Example 5 and a UV-curable resist film (LN ® Nylotron BASF AG) coated. Now the substrate surface is covered with a mask, partially cross-linked with the aid of UV radiation. The non-crosslinked prepolymer part is removed from the plate surface after removal of the mask by treatment with 1,1,1-trichloroethane.
- the test specimen according to Example 1 is then swollen in a methanolic solution, sensitized, rinsed with distilled water and then partially copper-coated in a commercially available copper plating bath at 60 ° C. up to a metal coating of approximately 17.5 ⁇ m.
- a finished printed circuit board is obtained, the copper layer of which adheres so well to the surface of the board that it cannot be removed from the board surface despite a one-day post-heating at 140 ° C.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Paper (AREA)
- Ultra Sonic Daignosis Equipment (AREA)
- Auxiliary Devices For Music (AREA)
- Luminescent Compositions (AREA)
- Electroplating Methods And Accessories (AREA)
- Control Of Electric Motors In General (AREA)
- Networks Using Active Elements (AREA)
- Emergency Protection Circuit Devices (AREA)
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT85107381T ATE39367T1 (de) | 1984-06-26 | 1985-06-14 | Verfahren zur herstellung von leiterplatten. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3423457 | 1984-06-26 | ||
DE19843423457 DE3423457A1 (de) | 1984-06-26 | 1984-06-26 | Verfahren zur herstellung von leiterplatten |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0166327A2 EP0166327A2 (fr) | 1986-01-02 |
EP0166327A3 EP0166327A3 (en) | 1986-10-08 |
EP0166327B1 true EP0166327B1 (fr) | 1988-12-21 |
Family
ID=6239138
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85107381A Expired EP0166327B1 (fr) | 1984-06-26 | 1985-06-14 | Procédé de fabrication de plaques pour circuits imprimés |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0166327B1 (fr) |
JP (1) | JPS6118195A (fr) |
AT (1) | ATE39367T1 (fr) |
DE (2) | DE3423457A1 (fr) |
ES (1) | ES8700538A1 (fr) |
FI (1) | FI852488L (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4576685A (en) * | 1985-04-23 | 1986-03-18 | Schering Ag | Process and apparatus for plating onto articles |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1696603A1 (de) * | 1967-01-03 | 1972-01-05 | Photocircuits Corp | Katalytische Materialien und Verfahren zu deren Herstellung |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA956294A (en) * | 1973-03-14 | 1974-10-15 | Stanley J. Whittaker | Rotary valve |
JPS5694690A (en) * | 1979-12-27 | 1981-07-31 | Asahi Chemical Ind | Method of manufacturing thick film fine pattern |
DE3148280A1 (de) * | 1981-12-05 | 1983-06-09 | Bayer Ag, 5090 Leverkusen | Verfahren zur aktivierung von substratoberflaechen fuer die stromlose metallisierung |
DE3324767A1 (de) * | 1983-07-08 | 1985-01-17 | Bayer Ag, 5090 Leverkusen | Verfahren zur aktivierung von substraten fuer die stromlose metallisierung |
-
1984
- 1984-06-26 DE DE19843423457 patent/DE3423457A1/de not_active Withdrawn
-
1985
- 1985-06-14 EP EP85107381A patent/EP0166327B1/fr not_active Expired
- 1985-06-14 DE DE8585107381T patent/DE3566905D1/de not_active Expired
- 1985-06-14 AT AT85107381T patent/ATE39367T1/de not_active IP Right Cessation
- 1985-06-24 FI FI852488A patent/FI852488L/fi not_active Application Discontinuation
- 1985-06-25 ES ES544533A patent/ES8700538A1/es not_active Expired
- 1985-06-26 JP JP60138051A patent/JPS6118195A/ja active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1696603A1 (de) * | 1967-01-03 | 1972-01-05 | Photocircuits Corp | Katalytische Materialien und Verfahren zu deren Herstellung |
Also Published As
Publication number | Publication date |
---|---|
JPS6118195A (ja) | 1986-01-27 |
FI852488L (fi) | 1985-12-27 |
EP0166327A2 (fr) | 1986-01-02 |
DE3423457A1 (de) | 1986-01-02 |
ATE39367T1 (de) | 1989-01-15 |
ES544533A0 (es) | 1986-10-16 |
EP0166327A3 (en) | 1986-10-08 |
DE3566905D1 (en) | 1989-01-26 |
FI852488A0 (fi) | 1985-06-24 |
ES8700538A1 (es) | 1986-10-16 |
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