EP0082438A1 - Process for the activation of surfaces for electroless metallization - Google Patents
Process for the activation of surfaces for electroless metallization Download PDFInfo
- Publication number
- EP0082438A1 EP0082438A1 EP82111461A EP82111461A EP0082438A1 EP 0082438 A1 EP0082438 A1 EP 0082438A1 EP 82111461 A EP82111461 A EP 82111461A EP 82111461 A EP82111461 A EP 82111461A EP 0082438 A1 EP0082438 A1 EP 0082438A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- palladium
- nickel
- minutes
- metallization
- solvent
- 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.)
- Granted
Links
- 238000001465 metallisation Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000004913 activation Effects 0.000 title claims description 7
- 230000008569 process Effects 0.000 title description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 21
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- -1 palladium (II) organic compound Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229920006305 unsaturated polyester Polymers 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 32
- 229910052759 nickel Inorganic materials 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000005062 Polybutadiene Substances 0.000 description 15
- 229920002857 polybutadiene Polymers 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 12
- 238000007747 plating Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000004816 latex Substances 0.000 description 10
- 229920000126 latex Polymers 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 229920000180 alkyd Polymers 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- HIDYYJFXCDZTHJ-UHFFFAOYSA-L acetonitrile;dichloropalladium Chemical compound CC#N.Cl[Pd]Cl HIDYYJFXCDZTHJ-UHFFFAOYSA-L 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000004922 lacquer Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 4
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HENYYBLMWDENHQ-UHFFFAOYSA-N benzonitrile palladium Chemical compound [Pd].N#CC1=CC=CC=C1 HENYYBLMWDENHQ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006289 polycarbonate film Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 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
- 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 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 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
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 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
- 229920001519 homopolymer Polymers 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 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
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001291 polyvinyl halide Polymers 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 210000003934 vacuole Anatomy 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910000634 wood's metal Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric 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 method for activating substrate surfaces for the purpose of chemical metallization.
- the polymer surface is changed so that caverns and vacuoles are formed.
- This is only possible with certain polymers, for example with 2-phase multicomponent grafts or copolymers, such as ABS polymers, impact-resistant polystyrene or 2-phase homopolymers, such as partially crystalline polypropylene.
- 2-phase multicomponent grafts or copolymers such as ABS polymers, impact-resistant polystyrene or 2-phase homopolymers, such as partially crystalline polypropylene.
- working with chromosulfuric acid or other oxidants is associated with a deterioration in the physical properties, for example the notched impact strength or the electrical surface resistance of the polymeric base material.
- the ionogenic palladium is reduced either in an acidic tin (II) chloride bath or by introducing tin (II) chloride into a strongly hydrochloric acid palladium (II) chloride solution.
- the excess protective colloid must be removed from the substrate surface so that a reduction in the metal ions, e.g. of copper, nickel, gold and cobalt in the metallization shading is possible through the catalytic action of active palladium centers on the substrate surface.
- the object of the present invention was to provide a new, gentle and process-technically simple method for activating substrate surfaces for the purpose of electroless metallization, with which even hard-to-metallize surfaces can be provided with a well-adhering metal coating.
- organometallic compounds of palladium are used, the organic part of which are oligomeric, prepolymeric or polymeric compounds which contain double bonds.
- the invention therefore relates to a method for activating substrate surfaces for the purpose of electroless metallization, the surface to be metallized, preferably without prior etching, being wetted with an organopalladium (II) compound homogeneously distributed in a solvent, in particular an organic solvent, the solvent removed and the organopalladium (II) compound adhering to the surface to be metallized is reduced, characterized in that the organic part of the organometallic compound is an oligomeric, prepolymeric or polymeric compound which contains double bonds.
- oligomer, prepolymer and polymer are known to the person skilled in the art. Together, they comprise a molecular weight range of approximately 150 to 1,000,000, preferably 200 to 500,000.
- Preferred organic compounds are homo- and copolymers of conjugated dienes, e.g. Styrene-butadiene copolymers, and unsaturated polyesters.
- the metal can be bound to the oligomer, prepolymer or polymer or to the corresponding monomer, which would be followed by the corresponding polymer reaction. It is also possible to carry out the polymer reaction and metal bonding in one operation.
- the oligomeric, prepolymeric or polymeric compounds have, in addition to the groups which bind the metal to the polymer, further functional groups which are capable of binding the organometallic compound to the substrate to be activated or of a further polymer reaction.
- groups which bind the metal to the polymer are carboxyl or ester groups.
- organometallic compounds used in accordance with the invention known low-molecular organometallic compounds with ligand exchange with the oligomers, prepolymers or polymers are reacted, or known organometallic compounds with ligand exchange with low-molecular compounds which are suitable for polymer production are reacted and the polymer reaction is then carried out.
- the organometallic compound can, for example, be dissolved or dispersed in the organic solvent, it can also be a rubbing of the organometallic compounds with the solvent.
- organometallic compound contains ligands which allow chemical fixation on the substrate surface, activation from the aqueous phase may also be possible.
- polar, protic and aprotic solvents such as methylene chloride, chloroform, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, acetone, methyl ethyl ketone, butanol, ethylene glycol and tetrahydrofuran are suitable as organic solvents.
- Suitable substrates for the process according to the invention are e.g. Steels, titanium, glass, quartz, ceramics, carbon, paper, polyethylene, polypropylene, ABS plastics, epoxy resins, polyesters and textile fabrics, threads and fibers made of polyamide, polyester, polyolefins, polyacrylonitrile, polyvinyl halides, cotton and wool, and mixtures thereof or from copolymers of the monomers mentioned.
- the organic solvent is removed.
- Low boiling solvents are preferred by evaporation, e.g. removed in vacuum.
- other methods such as extraction with a solvent in which the organometallic compounds are insoluble, are appropriate.
- the surfaces pretreated in this way must then be activated 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 there are others too Reducing agent 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 activated in this way can be used directly for electroless metallization. However, it may also be necessary to rinse the surfaces 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 has not been possible until now.
- This very simple embodiment only consists of the three work steps: immersing the substrate in the solution of the organometallic compound, evaporating the solvent and immersing the surfaces thus activated in the metallization bath (reduction and Metallization).
- This embodiment is particularly suitable for nickel baths containing amine borane or copper baths containing formalin.
- metallising baths with nickel salts, C obaltsalzen, copper salts, gold salts and silver salts, or their mixtures with one another or with iron salts.
- Such metallization baths are known in the electroless metallization art.
- oligomeric, prepolymeric and polymeric organic palladium compounds can be used to produce directly activated moldings, using conventional technologies. These moldings can then be subjected to the reduction and metallization.
- oligomeric, prepolymeric and polymeric organometallic compounds applied to substrates can of course be subjected to further reactions, for example crosslinking or grafting.
- the electrical resistance of the chemically deposited nickel layer is so low that the polypropylene foil washed after the chemical metallization is galvanically coated with copper of approximately 4.2 ⁇ m in thickness in a galvanic copper plating bath at 1.0 amps after 30 minutes.
- a glass plate (100 x 80 mm) is ent with methylene chloride greased and then immersed for 30 seconds in a solution of 7.2 g palladed polybutadiene with 7.1% by weight palladium (based on the dry polybutadiene mass) in 1 1 methylene chloride, after evaporation of the solvent at room temperature according to Example 1, nickel-plated. After a minute, the plate is covered with a fine black nickel layer.
- the nickel layer After about 15 minutes, the nickel layer has a thickness of 0.15 ⁇ m and can be switched and reinforced as a cathode in common galvanic metallization baths.
- a metallized piece of fabric with a coating of 9 g / m 2 nickel is obtained.
- a glass plate (100 x 100 mm) is sprayed with the above-mentioned prepolymer solution (blowing agent Frigen), after drying according to Example 1 nickel-plated for 9 minutes.
- a glass fiber reinforced epoxy resin plate (100 x 100 mm) is sprayed according to Example 12 with palladium-coated prepolymer solution, after drying the layer according to Example 1, nickel-plated in an alkaline nickel plating bath. After 9 minutes, a nickel layer 0.1 ⁇ m thick is measured.
- a 100 x 100 mm square of a woven fabric made of polyethylene terephthalate is sprayed according to Example 4 with palladed prepolymer solution (frigen as blowing agent) and, after the layer has dried, is nickel-plated according to Example 1. After just one minute, the fabric is covered with a fine layer of nickel. After 10 minutes the chemically deposited amount of nickel is 10 g / m 2 .
- Glass rods with a diameter of 8 mm and a length of 250 mm are coated with the above-mentioned palladed prepolymer solution by an immersion process, dried in a drying cabinet at 60 ° C. and then nickel-plated according to Example 1.
- the nickel layer After approx. 5 minutes the nickel layer has a thickness of approx. 0.2 ⁇ m.
- the rods are removed from the bath, rinsed with distilled water and reinforced as a cathode according to Example 1 in a galvanic copper plating bath at 1.0 amp. To 20 ⁇ m.
- a 250 x 250 mm square of a wooden plate is made sprayed with the prepolymer solution.
- the lacquer layer is dried for 12 hours at room temperature and nickel-plated according to Example 1.
- the electrical resistance of the chemical nickel layer is so low that the wood-metal composite material can be reinforced as a cathode in a galvanic nickel plating bath at 1.5 amps.
- Example 7 10 g of the alkyd resin used in Example 7 (60% in xylene) are mixed with 0.8 g of benzonitrile palladium dichloride in 20 ml of toluene at 30 ° C., then concentrated to 15 ml at room temperature and under a water jet vacuum.
- a glass-fiber-reinforced epoxy resin plate is partially coated with the palladium-coated prepolymer solution mentioned in the screen printing process, after which it is nickel-plated at 60 ° C. in a drying cabinet according to Example 1.
- Glass rods with a diameter of 3 mm and a length of 250 mm are coated with the palladed prepolymer solution according to Example 15 by an immersion process, dried in a drying cabinet at 80 ° C. in 4.5 hours, then nickel-plated according to Example 1. After a chemical metallization time of approx. 6 minutes, the rods are covered with a nickel layer.
- Example 16 The palladed prepolymer listed in Example 16 is printed on a glass fiber reinforced epoxy resin plate (150 x 50 mm) using the screen printing process, the prepolymer mask is cured in a drying cabinet at 50 ° C. for 8 hours and then nickel-plated according to Example 1.
- this printed circuit board is galvanically reinforced to 5 ⁇ m as the cathode in an acidic copper plating bath.
- the latex contains 31.5% by weight of solid with a 100% gel content and has a pH of 6.6 and an average particle diameter of 0.285 ⁇ m. Its swelling index in toluene is 5.0.
- Films (40 x 80 mm) are made from the palladed latex by casting on glass plates. The foils are annealed in a drying cabinet at 50 ° C. for 8 hours and then nickel-plated according to example 1.
- the electrical resistance of this chemical nickel layer is so low that the metallized metal-polymer composite material is reinforced to 15 ⁇ m in an acidic copper plating bath as the cathode.
- a 100 x 100 mm square of a 3 mm thick heat-resistant polycarbonate film is sprayed with a solution of 0.6 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride in 20 ml of n-butanol and 5 g of prepolymer solution according to Example 15, after evaporating the Solvent in the drying cabinet at 95 ° C for 10 minutes and then nickel-plated according to Example 1. After approx. 5 minutes the nickel layer has a thickness of approx. 0.2 ⁇ m.
- the sample is removed from the bath, carefully rinsed with distilled water, reinforced according to Example 1 at 1.2 amps with a 7.5 ⁇ m copper layer.
- a template for the production of printed circuits is placed on a 200 x 200 mm polyhydantoin film.
- the test specimen is sprayed with the coating solution (freezing as a blowing agent). After the solvent has evaporated, the stencil is removed from the film surface, the lacquer layer is cured in a drying cabinet at 50 ° C. in 5 hours and then nickel-plated according to Example 1.
- test specimen is removed from the metallization bath and the partial nickel coating in a galvanic copper plating bath is increased to 5 ⁇ m at 0.9 amp./dm 2 .
- lacquer (15% strength in xylene) based on 1,4-polyisoprene with diazole crosslinker are mixed with 0.4 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride palladium dichloride with stirring and nitrogen injection within one hour added in 5 ml of methylene chloride.
- a 25 x 80 mm, 1.5 mm thick glass fiber reinforced epoxy resin plate is coated with the above-mentioned lacquer by immersion, irradiated with a mercury lamp for 15 minutes after evaporation of the solvent and nickel-plated according to Example 1.
- the nickel coating is so thick that it can be reinforced in a galvanic copper plating bath.
- the underside of the carpet has a nickel layer.
- Isobutyl vinyl ether palladium dichloride is obtained in an analogous manner from the acetonitrile palladium dichloride and isobutyl vinyl ether, melting point: 57-60 ° C.
- a cetonitrile palladium dichloride is 5% by weight dissolved in methylene chloride, mixed with oligomeric polybutadiene, stirred for 30 minutes at room temperature and freed from solvent and acetonitrile in vacuo.
- a cetonitrile palladium dichloride is 5% by weight dissolved in methylene chloride. Butadiene is introduced and the solvent and acetonitrile are distilled off in vacuo.
Abstract
Eine schonende und verfahrenstechnisch einfache Methode zur Aktivierung von Substratoberflächen zum Zwecke der stromlosen Metallisierung besteht darin, daß man zur Aktivierung metallorganische Verbindungen von Elementen der 1. und 8. Nebengruppe des Periodensystems der Elemente verwendet, deren organischer Teil oligomere, präpolymere oder polymere Verbindungen sind, die Doppelbindungen enthalten.A gentle and procedurally simple method for activating substrate surfaces for the purpose of electroless metallization consists in using organometallic compounds of elements of the 1st and 8th subgroups of the periodic table of elements, the organic part of which are oligomeric, prepolymeric or polymeric compounds, which contain double bonds.
Description
Die Erfindung betrifft ein Verfahren zur Aktivierung von Substratoberflächen zum Zweck der chemischen Metallisierung.The invention relates to a method for activating substrate surfaces for the purpose of chemical metallization.
Es ist bekannt, daß polymere Werkstoffe vor dem chemischen und dem nachfolgenden galvanischen Metallisieren vorbehandelt werden müssen, R. Weiner, Kunststoff-Galvanisierung, Eugen G. Leuze Verlag, Saulgau/Württ. (1973). Dies sind im wesentlichen das Ätzen der Polymeroberfläche z.B. mit Chromschwefelsäure, das einfache und mehrfache Spülen mit Wasser, das Entgiften mit verdünnter Natriumbisulfitlösung, das weitere Spülen mit Wasser und die Behandlung der Substratoberfläche mit einem geeigneten Aktivierungsbad, beispielsweise einer Palladiumsalzlösung oder einem Palladiumsol.It is known that polymeric materials must be pretreated before chemical and subsequent galvanic metallization, R. Weiner, Plastic Galvanization, Eugen G. Leuze Verlag, Saulgau / Württ. (1973). This is essentially the etching of the polymer surface e.g. with chromic sulfuric acid, the single and multiple rinsing with water, the detoxification with dilute sodium bisulfite solution, the further rinsing with water and the treatment of the substrate surface with a suitable activation bath, for example a palladium salt solution or a palladium sol.
Bei der Ätzung wird die Polymeroberfläche so verändert, daß es zur Bildung von Kavernen und Vakuolen kommt. Dies ist nur bei bestimmten Polymeren möglich z.B. bei 2-Phasen-Mehrkomponenten-Pfropf- oder Copolymerisaten, wie ABS-Polymerisaten, schlagfestem Polystyrol oder 2-Phasen-Homopolymerisaten, wie teilkristallinem Polypropylen. Weiterhin ist das Arbeiten mit Chromschwefelsäure oder anderen Oxidantien mit einer Verschlechterung der physikalischen Eigenschaften, z.B. der Kerbschlagfestigkeit oder des elektrischen Oberflächenwiderstandes des polymeren Basismaterials, verbunden.During the etching, the polymer surface is changed so that caverns and vacuoles are formed. This is only possible with certain polymers, for example with 2-phase multicomponent grafts or copolymers, such as ABS polymers, impact-resistant polystyrene or 2-phase homopolymers, such as partially crystalline polypropylene. Furthermore, working with chromosulfuric acid or other oxidants is associated with a deterioration in the physical properties, for example the notched impact strength or the electrical surface resistance of the polymeric base material.
Darüber hinaus führt das in das Aktivierungs- und Metallisierungsbad eingeschleppte sechswertige Chrom zu einer Vergiftung der Bäder.In addition, the hexavalent chromium introduced into the activation and metallization bath leads to poisoning of the baths.
Die gleichen Nachteile stellen sich bei Verfahren ein, bei denen die Polymeroberflächen mittels eines starken gasförmigen Oxidationsmittels, z.B. heißem SO3-Dampf, chemisch verändert werden.The same disadvantages arise in processes in which the polymer surfaces are chemically changed by means of a strong gaseous oxidizing agent, for example hot SO 3 vapor.
Damit das an der Substratoberfläche fixierte ionogene Palladium eine katalytische Reduktion des Metallions im chemischen Metallisierungsbad ermöglicht, muß es zum Metall reduziert werden. Die Reduktion des ionogenen Palladiums erfolgt entweder in einem sauren Zinn (II)-chloridbad oder durch Einbringen von Zinn (II)-chlorid in eine stark salzsaure Palladium (II)-chlorid-Lösung.So that the ionic palladium fixed to the substrate surface enables a catalytic reduction of the metal ion in the chemical metallization bath, it must be reduced to the metal. The ionogenic palladium is reduced either in an acidic tin (II) chloride bath or by introducing tin (II) chloride into a strongly hydrochloric acid palladium (II) chloride solution.
Da nach der Reduktion des ionogenen Palladiums die Sub- stratoberfläche gewaschen werden muß, ist anzunehmen, daß dabei ein Gel aus Zinnhydroxid entsteht, was zur zusätzlichen Fixierung des Palladiums beiträgt. D a, after reduction of the ionogenic palladium S must be UB stratoberfläche washed, it is believed that this a gel of tin hydroxide is produced, which contributes to additional fixing of the palladium.
Bei dem nachfolgenden Arbeitsvprgang muß das überschüssige Schutzkolloid von der Substratoberfläche entfernt werden, damit eine Reduktion der Metallionen, z.B. von Kupfer, Nickel, Gold und Cobalt im Metallisierungshad durch katalytische Einwirkung von aktiven Palladiumzentren an der Substratoberfläche möglich ist.In the subsequent operation, the excess protective colloid must be removed from the substrate surface so that a reduction in the metal ions, e.g. of copper, nickel, gold and cobalt in the metallization shading is possible through the catalytic action of active palladium centers on the substrate surface.
Die bekannten Verfahren zur stromlosen Metallisierung von Werkstoffen bestehen somit aus verhältnismäßig vielen Verfahrensstufen und haben zudem den Nachteil, daß sie auf Substrate beschränkt sind, die wegen ihrer physikalischen Beschaffenheit oder des chemischen Aufbaues eine chemische oder physikalische Aufrauhung ermöglichen.The known methods for electroless metallization of materials thus consist of a relatively large number of process steps and also have the disadvantage that they are limited to substrates which, because of their physical nature or chemical structure, enable chemical or physical roughening.
Es ist weiterhin aus der US-PS 3 560 257 bekannt, Photolacken, Beschichtungen und polymeren Werkstoffen Verbindungen von Elementen der 1. und 8. Nebengruppe des Periodensystems der Elemente einzuverleiben.It is also known from US Pat. No. 3,560,257 to incorporate photoresists, coatings and polymeric materials into compounds of elements of the 1st and 8th subgroups of the Periodic Table of the Elements.
Dabei hat sich jedoch gezeigt, daß unter den dort genannten Bedingungen keine metallorganischen Verbindungen entstehen und daß lediglich die katalytische Eigenschaft des Palladium-(II)-chlorids genutzt wird.It has been shown, however, that no organometallic compounds are formed under the conditions mentioned there and that only the catalytic property of palladium (II) chloride is used.
Aufgabe der vorliegenden Erfindung war die Bereitstellung einer neuen, schonenden und verfahrenstechnisch einfachen Methode zur Aktivierung von Substratoberflächen zum Zwekke der stromlosen Metallisierung, mit der auch schwer zu metallisierende Oberfläche mit einem gut haftenden Metallüberzug versfehen werden können.The object of the present invention was to provide a new, gentle and process-technically simple method for activating substrate surfaces for the purpose of electroless metallization, with which even hard-to-metallize surfaces can be provided with a well-adhering metal coating.
Die Aufgabe wird dadurch gelöst daß man zur Aktivierung netallorganische Verbindungen des Palladiums verwendet, deren organischer Teil oligomere, präpolymere oder polymere Verbindungen sind, die Doppelbindungen enthalten.The object is achieved in that, for the activation, organometallic compounds of palladium are used, the organic part of which are oligomeric, prepolymeric or polymeric compounds which contain double bonds.
Die Erfindung betrifft daher ein Verfahren zum Aktivieren von Substratoberflächen zum Zwecke der stromlosen Metallisierung, wobei die zu metallisierende Oberfläche, vorzugsweise ohne vorheriges Ätzen, mit einer in einem Lösungsmittel, insbesondere einem organischen Lösungsmittel homogen verteilten Organopalladium-(II)-Verbindung benetzt, das Lösungsmittel entfernt und die an der zu metallisierenden Oberfläche haftende Organo- palladium-(II)-Verbindung reduziert wird, dadurch gekennzeichnet, daß der organische Teil der metallorganischen Verbindung eine oligomere, präpolymere oder polymere Verbindung ist, die Doppelbindungen enthält.The invention therefore relates to a method for activating substrate surfaces for the purpose of electroless metallization, the surface to be metallized, preferably without prior etching, being wetted with an organopalladium (II) compound homogeneously distributed in a solvent, in particular an organic solvent, the solvent removed and the organopalladium (II) compound adhering to the surface to be metallized is reduced, characterized in that the organic part of the organometallic compound is an oligomeric, prepolymeric or polymeric compound which contains double bonds.
Die Begriffe oligomer, präpolymer und polymer sind dem Fachmann bekannt. Sie umfassen zusammen einen Molekulargewichtsbereich von etwa 150 bis 1 000 000, vorzugsweise 200 bis 500 000.The terms oligomer, prepolymer and polymer are known to the person skilled in the art. Together, they comprise a molecular weight range of approximately 150 to 1,000,000, preferably 200 to 500,000.
Bevorzugte organische Verbindungen sind Homo- und Copolymerisate konjugierter Diene, z.B. Styrol-Butadien-Copolymerisate, und ungesättigte Polyester.Preferred organic compounds are homo- and copolymers of conjugated dienes, e.g. Styrene-butadiene copolymers, and unsaturated polyesters.
Diese Verbindungen gehen mit Palladium -Komplexe ein.These compounds go with palladium Complexes one.
Das Metall kann an das Oligomer, Präpolymer oder Palymer oder an das entsprechende Monomer, woran sich die entsprechende Polymerreaktion anschließen würde, gebunden werden. Es ist auch möglich Polymerreaktion und Metallbindung in einem Arbeitsgang durchzuführen.The metal can be bound to the oligomer, prepolymer or polymer or to the corresponding monomer, which would be followed by the corresponding polymer reaction. It is also possible to carry out the polymer reaction and metal bonding in one operation.
Es ist vorteilhaft, wenn die oligomeren, präpolymeren oder polymeren Verbindungen zusätzlich zu den Gruppen, die das Metall an das Polymer binden, weitere funktionelle Gruppen aufweisen, die zur Bindung der metallorganischen Verbindung an das zu aktivierende Substrat oder zur weiteren Polymerreaktion befähigt sind. Beispiele solcher Gruppen sind Carboxyl- oder Estergruppen.It is advantageous if the oligomeric, prepolymeric or polymeric compounds have, in addition to the groups which bind the metal to the polymer, further functional groups which are capable of binding the organometallic compound to the substrate to be activated or of a further polymer reaction. Examples of such groups are carboxyl or ester groups.
Zur Herstellung der erfindungsgemäß verwendeten metallorganischen Verbindungen setzt man bekannte niedermolekulare metallorganische Verbindungen unter Ligandenaustausch mit den Oligomeren, Präpolymeren oder Polymeren um oder man setzt bekannte metallorganische Verbindungen unter Ligandenaustausch mit niedermolekularen Verbindungen, die zur Polymerherstellung geeignet sind, um und führt dann die Polymerreaktion durch.To produce the organometallic compounds used in accordance with the invention, known low-molecular organometallic compounds with ligand exchange with the oligomers, prepolymers or polymers are reacted, or known organometallic compounds with ligand exchange with low-molecular compounds which are suitable for polymer production are reacted and the polymer reaction is then carried out.
Die organometallische Verbindung kann in dem organischen Lösungsmittel beispielsweise gelöst oder dispergiert sein, es kann sich auch um eine Anreibung der organometallischen Verbindungen mit dem Lösungsmittel handeln.The organometallic compound can, for example, be dissolved or dispersed in the organic solvent, it can also be a rubbing of the organometallic compounds with the solvent.
Wenn die organometallische Verbindung Liganden enthält, die eine chemische Fixierung auf der Substratoberfläche ermöglichen, kann eine Aktivierung auch aus wäßriger Phase möglich sein.If the organometallic compound contains ligands which allow chemical fixation on the substrate surface, activation from the aqueous phase may also be possible.
Ohne den Umfang der Erfindung einzuschränken, empfiehlt sich jedoch, bei der Durchführung des Verfahrens im technischen Maßstab folgende Bedingungen einzuhalten:
- 1. Die verwendeten metallorganischen Verbindungen sollten an der Luft und gegenüber Feuchtigkeit stabil sein. Sie sollten in organischen Lösungsmitteln gut löslich, in Wasser aber schwach löslich sein. Sie sollten außerdem mit gebräuchlichen Reduktionsmitteln zu einer bei der stromlosen Metallisierung katalytisch wirksamen Verbindung reduzierbar sein.
- 2. Die Lösungen der metallorganischen Verbindungen in organischen Lösungsmitteln sollten an der Luft und gegenüber Feuchtigkeit stabil sein.
- 3. Das organische Lösungsmittel sollte leicht entfernbar sein.
- 4. Bei der Reduktion der organometallischen Verbindung dürfen keine Liganden frei werden, die die Metallisierungsbäder vergiften.
- 5. Die reduzierten aktiven Keime sollten in wäßriger Lösung fest an der Oberfläche haften, um eine Zersetzung der Bäder durch eingeschlepptes Palladium zu verhindern.
- 1. The organometallic compounds used should be stable in air and moisture. They should be readily soluble in organic solvents, but slightly soluble in water. They should also be reducible with customary reducing agents to a compound which is catalytically active in the electroless metallization.
- 2. The solutions of the organometallic compounds in organic solvents should be stable to air and moisture.
- 3. The organic solvent should be easily removable.
- 4. When reducing the organometallic compound, no ligands that poison the metallization baths must be released.
- 5. The reduced active germs should adhere firmly to the surface in aqueous solution to prevent decomposition of the baths by palladium.
Das erfindungsgemäß neue Verfahren wird im allgemeinen folgendermaßen durchgeführt:
- Eine palladiumorganische Verbindung wird in einem organischen Lösungsmittel gelöst. Selbstverständlich können auch Mischungen von Verbindungen eingesetzt werden. Die Konzentration soll zwischen 0,01 g und 10 g pro Liter betragen, kann aber in besonderen Fällen auch darunter oder darüber liegen.
- An organic palladium compound is dissolved in an organic solvent. Mixtures of compounds can of course also be used. The concentration should be between 0.01 g and 10 g per liter, but in special cases it can also be below or above.
Als organische Lösungsmittel sind besonders polare, protische und aprotische Lösungsmittel wie Methylenchlorid, Chloroform, 1,1,1-Trichlorethan, Trichlorethylen, Perchlorethylen, Aceton, Methylethylketon, Butanol, Ethylenglykol und Tetrahydrofuran geeignet.In particular, polar, protic and aprotic solvents such as methylene chloride, chloroform, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, acetone, methyl ethyl ketone, butanol, ethylene glycol and tetrahydrofuran are suitable as organic solvents.
Selbstverständlich können auch Gemische obiger Lösungsmittel und Verschnitte mit anderen Lösungsmitteln, wie Benzin, Ligroin, Toluol, usw. verwendet werden. Mit diesen Lösungen werden bei dem erfindungsgemäßen Verfahren die Oberflächen der zu metallisierenden Substrate benetzt, wobei die Einwirkungsdauer vorzugsweise 1 Sekunde bis 10 Minuten beträgt. Besonders geeignet sind dazu Verfahren wie das Eintauchen des Substrats in die Lösungen oder das Besprühen von Substratoberflächen mit den Aktivierungslösungen. Selbstverständlich ist es bei dem neuen Verfahren auch möglich, die Aktivierungslösungen durch Stempeln oder durch Druckverfahren aufzubringen.Mixtures of the above solvents and blends with other solvents such as gasoline, ligroin, toluene, etc. can of course also be used. With the solutions according to the invention, the surfaces of the substrates to be metallized are wetted with these solutions, the duration of exposure preferably being Is 1 second to 10 minutes. Particularly suitable method such as immersion of the substrate in the solution or the spraying of substrate surfaces with the A are ktivierungslösungen. Of course, it is also possible with the new process to apply the activation solutions by stamping or by printing processes.
Als Substrate für das erfindungsgemäße Verfahren eignen sich z.B. Stähle, Titan, Glas, Quarz, Keramik, Kohlenstoff, Papier, Polyethylen, Polypropylen, ABS-Kunststoffe, Epoxydharze, Polyester und textile Flächengebilde, Fäden und Fasern aus Polyamid, Polyester, Polyolefinen, Polyacrylnitril, Polyvinylhalogeniden, Baumwolle und Wolle, sowie deren Mischungen oder aus Mischpolymerisaten der genannten Monomeren.Suitable substrates for the process according to the invention are e.g. Steels, titanium, glass, quartz, ceramics, carbon, paper, polyethylene, polypropylene, ABS plastics, epoxy resins, polyesters and textile fabrics, threads and fibers made of polyamide, polyester, polyolefins, polyacrylonitrile, polyvinyl halides, cotton and wool, and mixtures thereof or from copolymers of the monomers mentioned.
Nach der Benetzung wird das organische Lösungsmittel entfernt. Dabei werden niedrig siedene Lösungsmittel bevorzugt durch Verdampfen, z.B. im Vakuum entfernt. Bei höher siedenden Lösungsmitteln sind andere Verfahren, wie Extraktion mit einem Lösungsmittel, in dem die organometallischen Verbindungen unlöslich sind, angebracht.After wetting, the organic solvent is removed. Low boiling solvents are preferred by evaporation, e.g. removed in vacuum. For higher boiling solvents, other methods, such as extraction with a solvent in which the organometallic compounds are insoluble, are appropriate.
Die so vorbehandelten Oberflächen müssen anschließend durch Reduktion aktiviert werden. Dazu können bevorzugt die in der Galvanotechnik üblichen Reduktionsmittel, wie Hydrazinhydrat, Formaldehyd, Hypophosphit oder Borane verwendet werden. Natürlich sind auch andere Reduktionsmittel möglich. Bevorzugt wird die Reduktion in wässriger Lösung durchgeführt. Es sind aber auch andere Lösungsmittel wie Alkohole, Ether, Kohlenwasserstoffe einsetzbar. Selbstverständlich können auch Suspensionen oder Aufschlämmungen der Reduktionsmittel verwendet werden.The surfaces pretreated in this way must then be activated 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 there are others too Reducing agent 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.
Die so aktivierten Oberflächen können direkt zur stromlosen Metallisierung eingesetzt werden. Es kann aber auch erforderlich sein, die Oberflächen durch Spülen von den Reduktionsmittelresten zu reinigen.The surfaces activated in this way can be used directly for electroless metallization. However, it may also be necessary to rinse the surfaces of the reducing agent residues.
Eine ganz besonders bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, da3 die Reduktion im Metallisierungsbad gleich mit dem Reduktionsmittel der stromlosen Metallisierung durchgeführt wird. Diese Ausführung stellt eine bisher nicht mögliche Vereinfachung der stromlosen Metallisierung dar. Diese ganz einfache Ausführungsform besteht nur noch aus den drei Arbeitsgängen: Eintauchen des Substrates in die Lösung der metallorganischen Verbindung, Verdampfen des Lösungsmittels und Eintauchen der so aktivierten Oberflächen in das Metallisierungsbad (Reduktion und Metallisierung).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 has not been possible until now. This very simple embodiment only consists of the three work steps: immersing the substrate in the solution of the organometallic compound, evaporating the solvent and immersing the surfaces thus activated in the metallization bath (reduction and Metallization).
Diese Ausführungsform ist ganz besonders für aminboranhaltige Nickelbäder oder formalinhaltige Kupferbäder geeignet.This embodiment is particularly suitable for nickel baths containing amine borane or copper baths containing formalin.
Als in dem erfindungsgemäßen Verfahren einsetzbare Metallisierungsbäder kommen bevorzugt Bäder mit Nickelsalzen, Cobaltsalzen, Kupfersalzen, Gold- und Silbersalzen oder deren Gemische untereinander oder mit Eisensalzen in Betracht. Derartige Metallisierungsbäder sind in der Technik der stromlosen Metallisierung bekannt.As used in the inventive method can be used preferably metallising baths with nickel salts, C obaltsalzen, copper salts, gold salts and silver salts, or their mixtures with one another or with iron salts. Such metallization baths are known in the electroless metallization art.
Ein besonderer Vorteil der oligomeren, präpolymeren und polymeren palladiumorganischen Verbindungen besteht darin,daß aus ihnen direkt aktivierte Formkörper hergestellt werden können, wobei man sich üblicher Technologien bedient. Diese Formkörper können dann der Reduktion und Metallisierung unterzogen werden.A particular advantage of the oligomeric, prepolymeric and polymeric organic palladium compounds is that they can be used to produce directly activated moldings, using conventional technologies. These moldings can then be subjected to the reduction and metallization.
Die auf Substrate aufgebrachten oligomeren, präpolymeren und polymeren metallorganischen Verbindungen können selbstverständlich weiteren Reaktionen, beispielsweise Vernetzen oder Pfropfen unterzogen werden.The oligomeric, prepolymeric and polymeric organometallic compounds applied to substrates can of course be subjected to further reactions, for example crosslinking or grafting.
Das gleiche gilt für Formkörper, die aus den metallisierten Verbindungen selbst hergestellt worden sind.The same applies to moldings which have been produced from the metallized connections themselves.
Die vielfältigen Anwendungsmöglichkeiten metallisierter Gegenstände, die vor der Metallisierung nach dem erfindungsgemäßen Verfahren aktiviert wurden, sind dem auf Seite 1 genannten Buch von R. Weiner, Kunststoff-Galvanisierung beschrieben. Weitere Anwendungsmöglichkeiten ergeben sich aus den nachfolgenden Beispielen.The many possible uses of metallized objects that were activated before metallization by the process according to the invention are described in the book by R. Weiner, Plastic Galvanization mentioned on page 1. The following examples show further possible applications.
Eine Polypropylenfolie (100 x 80 mm) wird mit Methylenchlorid entfettet und anschließend 20 Sekunden in eine Lösung von 13 g palladiertem Polybutadien mit der mittleren Molmasse
Eine Glasplatte (100 x 80 mm) wird mit Methylenchlorid entfettet und anschließend 30 Sekunden in eine Lösung von 7,2 g palladiertem Polybutadien mit 7,1 Gew.-% Palladium (bezogen auf die trockene Polybutadienmasse) in 1 1 Methylenchlorid getaucht, nach dem Verdampfen des Lösungsmittels bei Raumtemperatur gemäß Beispiel 1 vernickelt. Bereits nach einer Minute ist die Platte mit einer feinen schwarzen Nickelschicht bedeckt.A glass plate (100 x 80 mm) is ent with methylene chloride greased and then immersed for 30 seconds in a solution of 7.2 g palladed polybutadiene with 7.1% by weight palladium (based on the dry polybutadiene mass) in 1 1 methylene chloride, after evaporation of the solvent at room temperature according to Example 1, nickel-plated. After a minute, the plate is covered with a fine black nickel layer.
Nach ca. 15 Minuten hat die Nickelschicht eine Dicke von 0,15 µm und kann in gängigen galvanischen Metallisierungsbädern als Kathode geschaltet und verstärkt werden.After about 15 minutes, the nickel layer has a thickness of 0.15 µm and can be switched and reinforced as a cathode in common galvanic metallization baths.
Ein 100 x 100 mm großes Quadrat eines Polyester/Baumwoll-Gewebes wird 30 Sekunden gemäß Beispiel 2 in eine Lösung von 7,2 g palladiertem Polybutadien mit der Molmasse
10 g lufttrocknendes dienhaltiges Alkydharz (60 %ig in Xylol) mit einem ölgehalt (berechnet als Triglycerid) von 48 % werden mit 0,75 g Acetonitrilpalladiumdichlorid in 20 ml Methylenchlorid bei Raumtemperatur versetzt und 20 Minuten gerührt.10 g of air-drying diene-containing alkyd resin (60% in xylene) with an oil content (calculated as triglyceride) of 48% are mixed with 0.75 g of acetonitrile palladium dichloride in 20 ml of methylene chloride at room temperature and stirred for 20 minutes.
Eine Glasplatte (100 x 100 mm) wird mit der oben angegebenen Präpolymerlösung besprüht (Treibmittel Frigen), nach der Trocknung gemäß Beispiel 1 9 Minuten vernickelt.A glass plate (100 x 100 mm) is sprayed with the above-mentioned prepolymer solution (blowing agent Frigen), after drying according to Example 1 nickel-plated for 9 minutes.
Auf der Substratoberfläche scheidet sich Nickel ab. Diese Schicht wird im galvanischen Metallisierungsbad gemäß Beispiel 1 auf eine Stärke von 15 µm verstärkt.Nickel deposits on the substrate surface. This layer is reinforced in the galvanic metallization bath according to Example 1 to a thickness of 15 microns.
Eine glasfaserverstärkte Epoxidharzplatte (100 x 100 mm) wird gemäß Beispiel 12 mit palladierter Präpolymerlösung besprüht, nach der Trocknung der Schicht gemäß Beispiel 1 in einem alkalischen Vernickelungsbad vernickelt. Nach 9 Minuten wird eine Nickelschicht von 0,1 µm Stärke gemessen.A glass fiber reinforced epoxy resin plate (100 x 100 mm) is sprayed according to Example 12 with palladium-coated prepolymer solution, after drying the layer according to Example 1, nickel-plated in an alkaline nickel plating bath. After 9 minutes, a nickel layer 0.1 µm thick is measured.
Ein 100 x 100 mm großes Quadrat eines Gewebes aus Polyethylenterephthalat wird gemäß Beispiel 4 mit palladierter Präpolymerlösung besprüht (Frigen als Treibmittel) und nach der Trocknung der Schicht gemäß Beispiel 1 vernickelt. Bereits nach einer Minute ist das Gewebe mit einer feinen Nickelschicht bedeckt. Nach 10 Minuten beträgt die chemisch abgeschiedene Nickelmenge 10 g/m 2.A 100 x 100 mm square of a woven fabric made of polyethylene terephthalate is sprayed according to Example 4 with palladed prepolymer solution (frigen as blowing agent) and, after the layer has dried, is nickel-plated according to Example 1. After just one minute, the fabric is covered with a fine layer of nickel. After 10 minutes the chemically deposited amount of nickel is 10 g / m 2 .
10 g lufttrocknendes Alkydharz (60 %ig in Xylol) mit einem ölgehalt (berechnet als Triglycerid) von 26 % werden bei Raumtemperatur in ca. einer Stunde mit 0,5 g Acetonitrilpalladiumdichlorid in 20 ml Methylenchlorid versetzt, anschließend bei Raumtemperatur und Wasserstrahlvakuum auf 15 ml eingeengt.10 g air-drying alkyd resin (60% in xylene) with an oil content (calculated as triglyceride) of 26% are mixed with 0.5 g acetonitrile palladium dichloride in 20 ml methylene chloride at room temperature in about one hour, then at room temperature and water jet vacuum to 15 ml constricted.
Glasstäbe mit einem Durchmesser von 8 mm und einer Länge von 250 mm werden durch ein Tauchverfahren mit der oben angegebenen palladierten Präpolymerlösung beschichtet, im Trockenschrank bei 60°C getrocknet und dann gemäß Beispiel 1 vernickelt.Glass rods with a diameter of 8 mm and a length of 250 mm are coated with the above-mentioned palladed prepolymer solution by an immersion process, dried in a drying cabinet at 60 ° C. and then nickel-plated according to Example 1.
Nach ca. 5 Minuten hat die Nickelschicht eine Dicke von ca. 0,2 µm. Die Stäbe werden dem Bad entnommen, mit destilliertem Wasser gespült und als Kathode gemäß Beispiel 1 in einen galvanischen Verkupferungsbad bei 1,0 Amp. auf 20 µm verstärkt.After approx. 5 minutes the nickel layer has a thickness of approx. 0.2 µm. The rods are removed from the bath, rinsed with distilled water and reinforced as a cathode according to Example 1 in a galvanic copper plating bath at 1.0 amp. To 20 μm.
10 g lufttrocknendes Alkydharz gemäß Beispiel 7 werden bei Raumtemperatur in ca. einer Stunde mit 0,6 g Butadienpalladiumdichlorid in 20 ml Methylenchlorid versetzt.10 g of air-drying alkyd resin according to Example 7 are mixed with 0.6 g of butadiene palladium dichloride in 20 ml of methylene chloride at room temperature in about one hour.
Ein 250 x 250 mm großes Quadrat einer Holzplatte wird mit der Präpolymerlösung besprüht. Die Lackschicht wird 12 Stunden bei Raumtemperatur getrocknet und gemäß Beispiel 1 vernickelt.A 250 x 250 mm square of a wooden plate is made sprayed with the prepolymer solution. The lacquer layer is dried for 12 hours at room temperature and nickel-plated according to Example 1.
Nach ca. 5 Minuten ist der elektrische Widerstand der chemischen Nickelschicht so gering, daß das Holz-Metall-Verbundmaterial als Kathode in einem galvanischen Vernickelungsbad bei 1,5 Amp. verstärkt werden kann.After about 5 minutes, the electrical resistance of the chemical nickel layer is so low that the wood-metal composite material can be reinforced as a cathode in a galvanic nickel plating bath at 1.5 amps.
10 g des in Beispiel 7 verwendeten Alkydharzes (60 %ig in Xylol) werden bei 30°C mit 0,8 g Benzonitrilpalladiumdichlorid in 20 ml Toluol versetzt, anschließend bei Raumtemperatur und unter Wasserstrahlvakuum auf 15 ml eingeengt. Eine glasfaserverstärkte Epoxidharzplatte wird im Siebdruckverfahren mit der oben aufgeführten palladierten Präpolymerlösung partiell beschichtet, nach der Trocknuhg bei 60°C im Trockenschrank gemäß Beispiel 1 vernickelt.10 g of the alkyd resin used in Example 7 (60% in xylene) are mixed with 0.8 g of benzonitrile palladium dichloride in 20 ml of toluene at 30 ° C., then concentrated to 15 ml at room temperature and under a water jet vacuum. A glass-fiber-reinforced epoxy resin plate is partially coated with the palladium-coated prepolymer solution mentioned in the screen printing process, after which it is nickel-plated at 60 ° C. in a drying cabinet according to Example 1.
Nach bereits 2 Minuten wird nur die Lackoberfläche selektiv mit einer feinen Nickelschicht bedeckt. Nach einer chemischen Metallisierungszeit von ca. 5 Minuten ist die Platte mit einer glänzenden Nickelauflage an den beschichteten Stellen versehen.After only 2 minutes, only the paint surface is selectively covered with a fine nickel layer. After a chemical metallization time of approx. 5 minutes, the plate is coated with a shiny nickel coating.
10 g lufttrocknendes Alkydharz (60 %ig in Xylol) mit 38 Gew.-% konjugiert-ungesättigten Fettsäuren, entsprechend einem ölgehalt (berechnet als Triglycerid) von 42 %, wird bei Raumtemperatur mit 1,0 g Butadienpalladiumdichlorid in 20 ml Methylenchlorid versetzt und 15 Mlinuten stehen gelassen.10 g of air-drying alkyd resin (60% in xylene) with 38% by weight of conjugated unsaturated fatty acids, correspondingly an oil content (calculated as triglyceride) of 42%, 1.0 g of butadiene palladium dichloride in 20 ml of methylene chloride is added at room temperature and the mixture is left to stand for 15 minutes.
Glasstäbe mit einem Durchmesser von 3 mm und einer Länge von 250 mm werden gemäß Beispiel 15 durch ein Tauchverfahren mit der palladierten Präpolymerlösung beschichtet, im Trockenschrank bei 80°C in 4,5 Stunden getrocknet, anschließend gemäß Beispiel 1 vernickelt. Nach einer chemischen Metallisierungszeit von ca. 6 Minuten sind die Stäbe mit einer Nickelschicht bedeckt.Glass rods with a diameter of 3 mm and a length of 250 mm are coated with the palladed prepolymer solution according to Example 15 by an immersion process, dried in a drying cabinet at 80 ° C. in 4.5 hours, then nickel-plated according to Example 1. After a chemical metallization time of approx. 6 minutes, the rods are covered with a nickel layer.
Das in Beispiel 16 aufgeführte palladierte Präpolymerisat wird auf eine glasfaserverstärkte Epoxidharzplatte (150 x 50 mm) im Siebdruckverfahren aufgedruckt, die Präpolymermaske bei 50°C 8h im Trockenschrank ausgehärtet und dann gemäß Beispiel 1 vernickelt.The palladed prepolymer listed in Example 16 is printed on a glass fiber reinforced epoxy resin plate (150 x 50 mm) using the screen printing process, the prepolymer mask is cured in a drying cabinet at 50 ° C. for 8 hours and then nickel-plated according to Example 1.
Nach 6 Minuten hat sich eine ca. 0,2 1m starke Nickelschicht abgeschieden.After 6 minutes an approximately 0.2 1m thick nickel layer has deposited.
Diese Leiterbahnplatte wird gemäß Beispiel 1 als Kathode in einem sauren Verkupferungsbad galvanisch auf 5 µm verstärkt.According to Example 1, this printed circuit board is galvanically reinforced to 5 µm as the cathode in an acidic copper plating bath.
0,25 g Benzonitrilpalladiumdichlorid werden in 60 ml Ethanol gelöst. Die Lösung wird bei Raumtemperatur mit 26 ml emulgatorfreiem Polybutadienlatex versetzt.0.25 g of benzonitrile palladium dichloride in 60 ml Ethanol dissolved. The solution is mixed with 26 ml of emulsifier-free polybutadiene latex at room temperature.
Der Latex enthält 31,5 Gew.-% Feststoff mit 100 %igem Gelgehalt und hat einen pH-Wert von 6,6 und einen mittleren Teilchendurchmesser von 0,285 µm. Sein Quellungsindex in Toluol ist 5,0.The latex contains 31.5% by weight of solid with a 100% gel content and has a pH of 6.6 and an average particle diameter of 0.285 μm. Its swelling index in toluene is 5.0.
Aus dem palladierten Latex werden Folien (40 x 80 mm) durch Gießen auf Glasplatten hergestellt. Die Folien werden bei 50°C 8 h im Trockenschrank getempert und dann gemäß Beispiel 1 vernickelt.Films (40 x 80 mm) are made from the palladed latex by casting on glass plates. The foils are annealed in a drying cabinet at 50 ° C. for 8 hours and then nickel-plated according to example 1.
Nach ca. 20 Minuten wird eine Nickelschicht von 0,15 µm erhalten.After about 20 minutes, a nickel layer of 0.15 µm is obtained.
0,7 g Acetonitrilpalladiumdichlorid werden in 60 ml Ethanol gelöst. Die Lösung wird bei Raumtemperatur mit 26 ml eines Polybutadienlatex gemischt. Der mittlere Teilchendurchmesser des vernetzten Polymerisates beträgt 0,260 µm. Der Feststoffgehalt des Latex beträgt 31,5 Gew.-% mit 98,7 % Gel. Der Quellungsindex in Toluol ist 8,0. Folien (40 x 50 mm), die aus dem palladierten Latex durch Gießen auf Glasplatten hergestellt werden, werden mit Hilfe einer Lichtquelle (λ = 254 nm) in einer Stunde vernetzt und dann gemäß Beispiel 1 vernickelt.0.7 g of acetonitrile palladium dichloride are dissolved in 60 ml of ethanol. The solution is mixed with 26 ml of a polybutadiene latex at room temperature. The average particle diameter of the crosslinked polymer is 0.260 μm. The solids content of the latex is 31.5% by weight with 98.7% gel. The swelling index in toluene is 8.0. Films (40 x 50 mm), which are produced from the palladed latex by casting on glass plates, are cross-linked in one hour using a light source (λ = 254 nm) and then nickel-plated according to Example 1.
Nach 4-6 Minuten erhält man eine glänzende, elektrisch leitende Nickelschicht.After 4-6 minutes you get a shiny, electrically conductive nickel layer.
0,8 g Isobutylvinyletherpalladiumdichlorid werden in 20 ml Dimethylformamid gelöst. Die Lösung wird bei Raumtemperatur zu 7,8 g Polybutadienlatex in 17 ml Wasser mit mittlerem Teilchendurchmesser von 0,181 µm und einem Gelgehalt von 100 % im Verlauf von 45 Minuten zugetropft. und 2 Stunden bei Raumtemperatur gerührt. Aus dem palladierten Latex werden Folien (40 x 50 x 10 mm) durch Gießen auf Glasplatten und Trocknen bei 35°C/ 6 Stunden im Trockenschrank hergestellt. Diese werden mit einer Lampe (λ = 254 nm) 60 Minuten belichtet und anschliessend gemäß Beispiel 1 vernickelt. Nach 45 Sekunden beginnt sich die Folie schwarz zu färben und nimmt im Verlaufe von 12 Minuten eine elektrisch leitende Nickelschicht an.0.8 g of isobutyl vinyl ether palladium dichloride are dissolved in 20 ml of dimethylformamide. The solution is added dropwise at room temperature to 7.8 g of polybutadiene latex in 17 ml of water with an average particle diameter of 0.181 μm and a gel content of 100% over the course of 45 minutes. and stirred for 2 hours at room temperature. Films (40 x 50 x 10 mm) are made from the palladed latex by pouring on glass plates and drying at 35 ° C / 6 hours in a drying cabinet. These are exposed to a lamp (λ = 254 nm) for 60 minutes and then nickel-plated according to Example 1. After 45 seconds, the film begins to turn black and takes on an electrically conductive nickel layer in the course of 12 minutes.
0,6 g 4-Cyclohexen-1,2-dicarbonsäursanhydridpalladium- dichlorid werden in 30 ml Methanol gelöst. Die Lösung wird bei 35°C zu einem enulgatorfreien Latex aus 8,82 g Polybutadien in 24,18 ml R2O mit mittlerem Teilchendurchmesser von 0,275 µm und einem Gelgehalt von 90,4 Gew.-% im Verlauf von 30 Minuten zugetropft und 45 Minuten gerührt.0.6 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride palladium dichloride are dissolved in 30 ml of methanol. The solution is added dropwise at 35 ° C. to an enulsifier-free latex composed of 8.82 g of polybutadiene in 24.18 ml of R 2 O with an average particle diameter of 0.275 μm and a gel content of 90.4% by weight over the course of 30 minutes, and 45 Minutes stirred.
Aus dem Latex werden Formstücke mit 23 mm Durchmesser und 1,8 mm Höhe durch Gießen in ein Becherglas und anschließendes Tempern bei 40°C im Trockenschrank hergestellt. Die Formstücke werden mit einer UV-Lampe ( = 366 nm) 90 Minuten belichtet und anschließend gemäß Beispiel 1 vernickelt.Shaped pieces with a diameter of 23 mm and a height of 1.8 mm are made from the latex by pouring them into a beaker and then tempering them at 40 ° C in a drying cabinet. The shaped pieces are exposed for 90 minutes with a UV lamp (= 366 nm) and then nickel-plated according to Example 1.
Nach 15 Minuten ist eine ca. 0,25 µm starke Nickelschicht abgeschieden.After 15 minutes, an approximately 0.25 µm thick nickel layer is deposited.
Der elektrische Widerstand dieser chemischen nickelschicht ist so gering, daß das metallisierte Metall-Polymer-Verbundmaterial in einem sauren Verkupferungsbad als Kathode auf 15 µm verstärkt wird.The electrical resistance of this chemical nickel layer is so low that the metallized metal-polymer composite material is reinforced to 15 μm in an acidic copper plating bath as the cathode.
Ein 100 x 100 mm großes Quadrat einer 3 mm starken wärmebeständigen Polycarbonatfolie wird mit einer Lösung von 0,6 g 4-Cyclohexen-1,2-dicarbonsäureanhydrid in 20 ml n-Butanol und 5 g Präpolymerlösung nach Beispiel 15 besprüht, nach dem Verdampfen des Lösungsmittels im Trockenschrank bei 95°C 10 Minuten ausgehärtet und anschließend gemäß Beispiel 1 vernickelt. Nach ca. 5 Minuten hat die Nickelschicht eine Stärke von ca. 0,2 µm. Die Probe wird dem Bad entnommen, mit destilliertem Wasser sorgfältig gespült, gemäß Beispiel 1 bei 1,2 Amp. mit einer 7,5 µm starken Kupferschicht verstärkt.A 100 x 100 mm square of a 3 mm thick heat-resistant polycarbonate film is sprayed with a solution of 0.6 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride in 20 ml of n-butanol and 5 g of prepolymer solution according to Example 15, after evaporating the Solvent in the drying cabinet at 95 ° C for 10 minutes and then nickel-plated according to Example 1. After approx. 5 minutes the nickel layer has a thickness of approx. 0.2 µm. The sample is removed from the bath, carefully rinsed with distilled water, reinforced according to Example 1 at 1.2 amps with a 7.5 μm copper layer.
40 ml 7,5 gew.-%ige chlorierte Polybutadienlösung in Toluol werden bei Raumtemperatur mit 5 g gemäß Beispiel 15 hergestellter Präpolymerlösung in 10 ml Methylethylketon versetzt. Der Lösung wird im Laufe von 20 Minuten 0,5 g 4-Cyclohexen-1,2-dicarbonsäureanhydridpalladiun- dichlorid in 5 ml Methylethylketon zugetropft. Eine sorgfältig gereinigte 1,5 mm starke Polycarbonatfolie (80 x 30 mm) wird kurz in die vorbereitete Beschichtungslösung getaucht, zum Aushärten und zum Verdampfen des Lösungsmittels im Trockenschrank 10 Minuten senkrecht aufgehängt und dann gemäß Beispiel 1 vernickelt. Nach 6 Minuten erhält man eine 0,150 µm starke Nickelauflage.40 ml of 7.5% by weight chlorinated polybutadiene solution in toluene are mixed with 5 g of prepolymer solution prepared according to Example 15 in 10 ml of methyl ethyl ketone at room temperature. 0.5 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride palladi-dichloride in 5 ml of methyl ethyl ketone is added dropwise to the solution in the course of 20 minutes. A carefully cleaned 1.5 mm thick polycarbonate film (80 x 30 mm) is briefly immersed in the prepared coating solution, suspended vertically for 10 minutes in the drying cabinet to harden and evaporate the solvent, and then nickel-plated according to Example 1. After 6 minutes, a 0.150 µm thick nickel coating is obtained.
10 g lufttrocknendes Alkydharz (60 %ig in Xylol) mit einem ölgehalt (berechnet als Triglycerid) von 26 % werden bei Raumtemperatur in 10 Minuten mit 0,5 g 1,4-Cyclohexen-1,2-dicarbonsäureanhydrid in 10 ml Methylethylketon versetzt.10 g of air-drying alkyd resin (60% in xylene) with an oil content (calculated as triglyceride) of 26% are mixed with 0.5 g of 1,4-cyclohexene-1,2-dicarboxylic acid anhydride in 10 ml of methyl ethyl ketone at room temperature in 10 minutes.
Auf eine 200 x 200 mm große-Polyhydantoinfolie wird eine Schablone zur Herstellung von gedruckten Schaltungen gelegt. Der Probekörper wird mit der Beschichtungslösung besprüht (Frigen als Treibmittel). Nach dem Verdampfen des Lösungsmittels wird die Folienoberfläche von der Schablone befreit, die Lackschicht im Trockenschrank in 5 Stunden bei 50°C ausgehärtet und dann gemäß Beispiel 1 vernickelt.A template for the production of printed circuits is placed on a 200 x 200 mm polyhydantoin film. The test specimen is sprayed with the coating solution (freezing as a blowing agent). After the solvent has evaporated, the stencil is removed from the film surface, the lacquer layer is cured in a drying cabinet at 50 ° C. in 5 hours and then nickel-plated according to Example 1.
Nach 15 Minuten wird der Probekörper dem Metallisierangsbad entnommen und die partielle Nickelauflage in einem galvanischen Verkupferungsbad auf 5 µm bei 0,9 Amp./dm2 verstärkt.After 15 minutes, the test specimen is removed from the metallization bath and the partial nickel coating in a galvanic copper plating bath is increased to 5 μm at 0.9 amp./dm 2 .
32,2 g Lack (15 %ig in Xylol) auf Basis von 1,4-Polyisopren mit Diazol-Vernetzer werden unter Rühren und Stickstoffeinleitung innerhalb einer Stunde bei Raumtemperatur mit 0,4 g 4-Cyclohexen-1,2-dicarbonsäureanhydrid- palladiumdichlorid in 5 ml Methylenchlorid versetzt.32.2 g of lacquer (15% strength in xylene) based on 1,4-polyisoprene with diazole crosslinker are mixed with 0.4 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride palladium dichloride with stirring and nitrogen injection within one hour added in 5 ml of methylene chloride.
Eine 25 x 80 mm große, 1,5 mm starke glasfaserverstärkte Epoxidharzplatte wird mit dem oben aufgeführten Lack im Tauchverfahren beschichtet, nach dem Verdampfen des Lösungsmittels mit einer Quecksilberlampe 15 Minuten bestrahlt und gemäß Beispiel 1 vernickelt.A 25 x 80 mm, 1.5 mm thick glass fiber reinforced epoxy resin plate is coated with the above-mentioned lacquer by immersion, irradiated with a mercury lamp for 15 minutes after evaporation of the solvent and nickel-plated according to Example 1.
Nach ca. 25 Minuten ist die Nickelauflage so stark, daß sie in einem galvanischen Verkupferungsbad verstärkt werden kann.After about 25 minutes, the nickel coating is so thick that it can be reinforced in a galvanic copper plating bath.
4 g Butadienpalladiumdichlorid werden in 100 ml trockenem Toluol mit 0,25 g Azodiisobuttersäurenitril unter Rühren bei 60°C und N2-Atmosphäre polymerisiert.4 g of butadiene palladium dichloride are polymerized in 100 ml of dry toluene with 0.25 g of azodiisobutyronitrile with stirring at 60 ° C. and in an N 2 atmosphere.
Nach 3 Stunden wird die Polymerisation abgebrochen und das Lösungsmittel im Vakuum bei 35°C abgezogen. Die klebrige Polymermasse wird mit 29 g technischem Polystyrol versetzt. Aus der Polymermischung wird in einer zylindrischen Kammer bei 100°C und 1 bar ein Preßling mit einer Stärke von ca. 2,0 mm und einem Durchmesser von 12,9 mm geformt. Dieser Formteil wird gemäß Beispiel 1 vernickelt. Nach ca. 6 Minuten hat die Nickelschicht eine Stärke von ca. 0,15 µm.After 3 hours, the polymerization is stopped and the solvent is removed in vacuo at 35 ° C. The sticky polymer mass is mixed with 29 g of technical polystyrene. A compact with a thickness of approximately 2.0 mm and a diameter of 12.9 mm is formed from the polymer mixture in a cylindrical chamber at 100 ° C. and 1 bar. This molded part is nickel-plated according to Example 1. After approx. 6 minutes the nickel layer has a thickness of approx. 0.15 µm.
Ein 12,5 x 16,5 cm großes Polyamid-Teppichbodenstück wird auf der Unterseite mit einer Lösung von 8,5 g palladiertem Polybutadien mit der mittleren Molmasse Mn = 1100 und 5,8 Gew.-% Palladium (bezogen auf trockene Polybutadienmasse) in 0,5 1 Methylenchlorid besprüht und anschließend in ein wäßriges alkalisches Verkupferungsbad, das 10 g CuSO4, 15 g Seignette-Salz und 20 ml 30 gew.-%ige Formaldehydlösung im Liter enthält und mit 40 gew.-%iger Natronlauge auf pH 12-13 eingestellt ist, getaucht.A 12.5 x 16.5 cm piece of polyamide carpet is covered on the underside with a solution of 8.5 g palladed polybutadiene with an average molecular weight M n = 1100 and 5.8% by weight palladium (based on dry polybutadiene mass) sprayed in 0.5 l of methylene chloride and then in an aqueous alkaline copper plating bath containing 10 g of CuSO 4 , 15 g of Seignette salt and 20 ml of 30% strength by weight formaldehyde solution in liters and with 40% strength by weight sodium hydroxide solution to pH 12-13 is set, submerged.
Bereits nach 4 Minuten weist die Teppichbodenunterseite eine Nickelschicht auf.After 4 minutes, the underside of the carpet has a nickel layer.
Die in den Beispielen verwendeten metallorganischen Verbindungen werden wie folgt hergestellt:
- 4-Cyclohexen-1,2-dicarbonsäureanhydrid-palladium(II)-chlorid:
- 4-Cyclohexen-1,2-dicarbonsäureanhydrid wird in der dreifachen Menge Dimethylformamid gelöst, in Verlaufe von 2
- 4-cyclohexene-1,2-dicarboxylic acid anhydride palladium (II) chloride:
- 4-Cyclohexene-1,2-dicarboxylic acid anhydride is dissolved in three times the amount of dimethylformamide, in the course of 2
Stunden mit der äquimolaren Menge Acetonitrilpalladiumdichlorid bei 40°C versetzt. Dimethylformamid und Acetonitril werden bei 45°C/25 mbar abdestilliert. Man erhält mit 90 %iger Ausbeute einen bräunlichen Feststoff vom Schmelzpunkt 53-54°C.Hours with the equimolar amount of acetonitrile palladium dichloride at 40 ° C. Dimethylformamide and acetonitrile are distilled off at 45 ° C / 25 mbar. A brownish solid with a melting point of 53-54 ° C. is obtained in 90% yield.
Isobutylvinyletherpalladiumdichlorid wird in analoger Weise aus dem Acetonitrilpalladiumdichlorid und Isobutylvinylether erhalten, Schmelzpunkt: 57-60°C.Isobutyl vinyl ether palladium dichloride is obtained in an analogous manner from the acetonitrile palladium dichloride and isobutyl vinyl ether, melting point: 57-60 ° C.
Acetonitrilpalladiumdichlorid wird 5 gew.-%ig in Methylenchlorid gelöst, mit oligomerem Polybutadien versetzt, 30 Minuten bei Raumtemperatur gerührt und im Vakuum von Lösungsmittel und Acetonitril befreit. A cetonitrile palladium dichloride is 5% by weight dissolved in methylene chloride, mixed with oligomeric polybutadiene, stirred for 30 minutes at room temperature and freed from solvent and acetonitrile in vacuo.
Acetonitrilpalladiumdichlorid wird 5 gew.-%ig in Methylenchlorid gelöst. Butadien wird eingeleitet und das Lösungsmittel und Acetonitril im Vakuum abdestilliert. A cetonitrile palladium dichloride is 5% by weight dissolved in methylene chloride. Butadiene is introduced and the solvent and acetonitrile are distilled off in vacuo.
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DE19813150985 DE3150985A1 (en) | 1981-12-23 | 1981-12-23 | METHOD FOR ACTIVATING SUBSTRATE SURFACES FOR ELECTRIC METALLIZATION |
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ID=6149500
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82111461A Expired EP0082438B1 (en) | 1981-12-23 | 1982-12-10 | Process for the activation of surfaces for electroless metallization |
Country Status (4)
Country | Link |
---|---|
US (2) | US4493861A (en) |
EP (1) | EP0082438B1 (en) |
JP (1) | JPS58113366A (en) |
DE (2) | DE3150985A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3419755A1 (en) * | 1984-05-26 | 1985-11-28 | Bayer Ag, 5090 Leverkusen | Chemical silvering bath |
EP0250867A1 (en) * | 1986-06-16 | 1988-01-07 | International Business Machines Corporation | Seeding process for electroless metal deposition |
DE3938710A1 (en) * | 1989-11-17 | 1991-05-23 | Schering Ag | COMPLEX CONNECTIONS WITH OLIGOMEREM TO POLYMERIC CHARACTER |
DE19941043A1 (en) * | 1999-08-28 | 2001-03-01 | Bosch Gmbh Robert | Bath for producing powdered materials, especially carbon powders contains an organic solvent to which is added a hydrophobic complex of a metal with organic ligands |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3242162A1 (en) * | 1982-11-13 | 1984-05-17 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING COMPOSITES |
DE3248778A1 (en) * | 1982-12-31 | 1984-07-12 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING METALLIZED POROESE SOLIDS |
US4719145A (en) * | 1983-09-28 | 1988-01-12 | Rohm And Haas Company | Catalytic process and systems |
PH23907A (en) * | 1983-09-28 | 1989-12-18 | Rohm & Haas | Catalytic process and systems |
DE3339856A1 (en) * | 1983-11-04 | 1985-05-15 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE ADHESIVE ACTIVATION OF POLYAMIDE SUBSTRATES FOR CURRENT METALLIZATION |
DE3339857A1 (en) * | 1983-11-04 | 1985-05-15 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRE-TREATING POLYAMIDE SUBSTRATES FOR CURRENT METALLIZATION |
DE3407114A1 (en) * | 1984-02-28 | 1985-09-05 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF CIRCUIT BOARDS |
DE3424065A1 (en) * | 1984-06-29 | 1986-01-09 | Bayer Ag, 5090 Leverkusen | METHOD FOR ACTIVATING SUBSTRATE SURFACES FOR ELECTRIC METALLIZATION |
JPS62149884A (en) * | 1985-12-24 | 1987-07-03 | Nippon Mining Co Ltd | Pretreatment for electroless copper plating |
JPH0694592B2 (en) * | 1986-04-22 | 1994-11-24 | 日産化学工業株式会社 | Electroless plating method |
US5182135A (en) * | 1986-08-12 | 1993-01-26 | Bayer Aktiengesellschaft | Process for improving the adherency of metallic coatings deposited without current on plastic surfaces |
US4910072A (en) * | 1986-11-07 | 1990-03-20 | Monsanto Company | Selective catalytic activation of polymeric films |
US5075037A (en) * | 1986-11-07 | 1991-12-24 | Monsanto Company | Selective catalytic activation of polymeric films |
JP2760984B2 (en) * | 1987-02-26 | 1998-06-04 | 株式会社東芝 | Insulated gate thyristor |
JPH01104782A (en) * | 1987-07-02 | 1989-04-21 | Fuji Photo Film Co Ltd | Catalytic material for electroless plating and metallized material using same |
DE3743780A1 (en) * | 1987-12-23 | 1989-07-06 | Bayer Ag | METHOD FOR IMPROVING THE ADHESIVITY OF CURRENTLY DEPOSITED METAL LAYERS ON POLYIMIDE SURFACES |
US5030742A (en) * | 1988-12-16 | 1991-07-09 | Ciba-Geigy Corporation | Ultrathin layers of palladium(O) complexes |
US5227223A (en) * | 1989-12-21 | 1993-07-13 | Monsanto Company | Fabricating metal articles from printed images |
US5279899A (en) * | 1992-03-17 | 1994-01-18 | Monsanto Company | Sulfonated polyamides |
US5517338A (en) * | 1992-10-20 | 1996-05-14 | Monsanto Company | Composite mirrors |
US5419954A (en) * | 1993-02-04 | 1995-05-30 | The Alpha Corporation | Composition including a catalytic metal-polymer complex and a method of manufacturing a laminate preform or a laminate which is catalytically effective for subsequent electroless metallization thereof |
DE4319759A1 (en) * | 1993-06-15 | 1994-12-22 | Bayer Ag | Powder mixtures for metallizing substrate surfaces |
US20040031404A1 (en) * | 2002-08-19 | 2004-02-19 | John Dixon | Seamless embossing shim |
US8465469B2 (en) * | 2002-09-12 | 2013-06-18 | Medtronic Vascular, Inc. | Reinforced catheter and methods of making |
CN1329554C (en) * | 2004-01-13 | 2007-08-01 | 长沙力元新材料股份有限公司 | Method for chemical plating metal for non-metal substrate surface and pretreatment system used thereof |
US20100003533A1 (en) * | 2006-10-23 | 2010-01-07 | Fujifilm Corporation | Metal-film-coated material and process for producing the same, metallic-pattern-bearing material and process for producing the same, composition for polymer layer formation, nitrile group-containing polymer and method of synthesizing the same, composition containing nitrile group-containing polymer, and laminate |
KR101385086B1 (en) * | 2010-05-04 | 2014-04-14 | 유니-픽셀 디스플레이스, 인코포레이티드 | Method of fabricating micro structured surfaces with electrically conductive patterns |
US8591636B2 (en) * | 2010-12-14 | 2013-11-26 | Rohm And Haas Electronics Materials Llc | Plating catalyst and method |
US8591637B2 (en) | 2010-12-14 | 2013-11-26 | Rohm And Haas Electronic Materials Llc | Plating catalyst and method |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3523824A (en) * | 1966-12-29 | 1970-08-11 | Ibm | Metallization of plastic materials |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL6713754A (en) * | 1965-08-13 | 1969-04-14 | ||
US3560257A (en) * | 1967-01-03 | 1971-02-02 | Kollmorgen Photocircuits | Metallization of insulating substrates |
US3488166A (en) * | 1967-01-13 | 1970-01-06 | Ibm | Method for activating plastics,subsequent metallization and article of manufacture resulting therefrom |
US3501332A (en) * | 1967-04-28 | 1970-03-17 | Shell Oil Co | Metal plating of plastics |
US3900320A (en) * | 1971-09-30 | 1975-08-19 | Bell & Howell Co | Activation method for electroless plating |
US3956041A (en) * | 1972-07-11 | 1976-05-11 | Kollmorgen Corporation | Transfer coating process for manufacture of printing circuits |
US3998602A (en) * | 1975-02-07 | 1976-12-21 | Carl Horowitz | Metal plating of polymeric substrates |
DE2727245C3 (en) * | 1977-06-16 | 1980-06-26 | Brintzinger, Hans, Prof. Dr., 7750 Konstanz | Polymer-bound cyclopentadienyl transition metal compounds and their ligand substitution derivatives, process for their preparation and their use as catalysts |
DE3025307A1 (en) * | 1980-07-04 | 1982-01-28 | Bayer Ag, 5090 Leverkusen | METHOD FOR ACTIVATING SURFACES FOR ELECTRIC METALLIZATION |
DE3148280A1 (en) * | 1981-12-05 | 1983-06-09 | Bayer Ag, 5090 Leverkusen | METHOD FOR ACTIVATING SUBSTRATE SURFACES FOR ELECTRIC METALLIZATION |
-
1981
- 1981-12-23 DE DE19813150985 patent/DE3150985A1/en not_active Withdrawn
-
1982
- 1982-12-10 EP EP82111461A patent/EP0082438B1/en not_active Expired
- 1982-12-10 DE DE8282111461T patent/DE3266873D1/en not_active Expired
- 1982-12-13 US US06/449,043 patent/US4493861A/en not_active Expired - Fee Related
- 1982-12-23 JP JP57225100A patent/JPS58113366A/en active Granted
-
1984
- 1984-10-25 US US06/664,668 patent/US4622411A/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3523824A (en) * | 1966-12-29 | 1970-08-11 | Ibm | Metallization of plastic materials |
Non-Patent Citations (2)
Title |
---|
IBM TECHNICAL DISCLOSURE BULLETIN, Band 11, Nr. 8, Januar 1969, Seite 1001, New York, USA * |
IBM TECHNICAL DISCLOSURE BULLETIN, Band 13, Nr. 5, Oktober 1970, Seite 1200, New York, USA * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3419755A1 (en) * | 1984-05-26 | 1985-11-28 | Bayer Ag, 5090 Leverkusen | Chemical silvering bath |
EP0250867A1 (en) * | 1986-06-16 | 1988-01-07 | International Business Machines Corporation | Seeding process for electroless metal deposition |
DE3938710A1 (en) * | 1989-11-17 | 1991-05-23 | Schering Ag | COMPLEX CONNECTIONS WITH OLIGOMEREM TO POLYMERIC CHARACTER |
DE19941043A1 (en) * | 1999-08-28 | 2001-03-01 | Bosch Gmbh Robert | Bath for producing powdered materials, especially carbon powders contains an organic solvent to which is added a hydrophobic complex of a metal with organic ligands |
DE19941043B4 (en) * | 1999-08-28 | 2004-04-29 | Robert Bosch Gmbh | Germination bath and method for germinating powdery materials, method for metallizing a germinated powdery material and method for producing metallically limited hollow bodies |
Also Published As
Publication number | Publication date |
---|---|
DE3266873D1 (en) | 1985-11-14 |
US4493861A (en) | 1985-01-15 |
US4622411A (en) | 1986-11-11 |
EP0082438B1 (en) | 1985-10-09 |
DE3150985A1 (en) | 1983-06-30 |
JPH026834B2 (en) | 1990-02-14 |
JPS58113366A (en) | 1983-07-06 |
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