EP0485839A2 - Couche de base pour métallisation - Google Patents
Couche de base pour métallisation Download PDFInfo
- Publication number
- EP0485839A2 EP0485839A2 EP91118731A EP91118731A EP0485839A2 EP 0485839 A2 EP0485839 A2 EP 0485839A2 EP 91118731 A EP91118731 A EP 91118731A EP 91118731 A EP91118731 A EP 91118731A EP 0485839 A2 EP0485839 A2 EP 0485839A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- primer
- weight
- parts
- primer according
- metallization
- 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 19
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 239000012766 organic filler Substances 0.000 claims description 3
- 230000001464 adherent effect Effects 0.000 claims description 2
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- 206010070834 Sensitisation Diseases 0.000 claims 1
- 229920003232 aliphatic polyester Polymers 0.000 claims 1
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 claims 1
- 229910003475 inorganic filler Inorganic materials 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 239000013110 organic ligand Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 230000008313 sensitization Effects 0.000 claims 1
- 230000001235 sensitizing effect Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 8
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 17
- -1 chrome sulfuric acids Chemical class 0.000 description 16
- 229920001228 polyisocyanate Polymers 0.000 description 15
- 239000005056 polyisocyanate Substances 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 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 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- LPCWMYHBLXLJJQ-SNAWJCMRSA-N (e)-hex-3-en-2-one Chemical compound CC\C=C\C(C)=O LPCWMYHBLXLJJQ-SNAWJCMRSA-N 0.000 description 1
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 1
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 description 1
- LPCWMYHBLXLJJQ-UHFFFAOYSA-N 3-Hexen-2-on Natural products CCC=CC(C)=O LPCWMYHBLXLJJQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical class C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical class OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 241001295925 Gegenes Species 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920006187 aquazol Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- VFGRALUHHHDIQI-UHFFFAOYSA-N butyl 2-hydroxyacetate Chemical compound CCCCOC(=O)CO VFGRALUHHHDIQI-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000001913 cellulose Chemical class 0.000 description 1
- 229920002678 cellulose Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 239000003245 coal Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920001567 vinyl ester resin Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical class [H]C([*])=C([H])[H] 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- polymeric materials must be pretreated before chemical and subsequent electroplating, e.g. by etching the polymer surface with polluting chrome sulfuric acids.
- EP-A 0 361 754 Pd-containing primers are proposed which require the additional use of chromosulfuric acid.
- the object of the present invention was therefore to develop an economical, universally applicable process for chemical metallization, with which material surfaces based on glasses, metals and in particular plastics can be provided with a well-adhering, wet-chemically deposited metal coating without prior etching with oxidants.
- substrate surfaces are coated with a special primer based on a polymeric organic film or matrix former which additionally contains an additive.
- the coating systems to be used at room temperature such as, for example, alkyd resins, unsaturated polyester resins, polyurethane resins, epoxy resins, modified fats and oils, polymers or copolymers based on vinyl chloride, vinyl ethers, vinyl esters, styrene, acrylic acid, acrylonitrile or Acrylic esters, cellulose derivatives, or the stoving enamels that crosslink at higher temperatures, such as polyurethanes made of hydroxyl-containing polyethers, polyesters or polyacrylates and capped polyisocyanates, Melamine resins from etherified melamine-formaldehyde resins and hydroxyl group-containing polyethers, polyesters or polyacrylates, epoxy resins from polyepoxides and polycarboxylic acids, carboxyl group-containing polyacrylates and carboxyl group-containing polyesters, stoving lacquers made from polyester, polyesterimides, polyesteramideimides, polyamideimides, polyamides, polyhydan
- auxiliaries and additives which may also be used, are described, for example, in DE-A 2 732 292, pages 21-24.
- the amount of film or matrix former used can be varied widely. As a rule, 3 to 30% by weight, preferably 4 to 20% by weight (based on the total formulation) are used.
- Additives b.) are organic and / or organometallic polymeric or prepolymeric compounds with a molecular weight of 100-1,000,000, preferably 500-20,000 with a total surface tension in the range of 45-65 mN / m, preferably 45-60 mN / m , particularly preferably 50-60 mN / m. Their amount can be varied widely between 0.1 and 15% by weight, based on the formulation, with 0.3-5% by weight being particularly preferred.
- polymers based on oxazolines such as polyethyloxazoline, which is produced, for example, by cationic polymerization from methyl tosylate and methyloxazoline, are suitable.
- Polymethyl, polypropyl and polybutyl oxazoline are also extremely suitable. Their amount can be varied widely between 0.1 and 15% by weight, based on the formulation, 0.3-5% by weight being particularly preferred.
- Examples include oligomeric polymethacrylic acid or its esters such as butyl, ethyl and methyl esters, polyamides based on adipic acid and hexamethylene diamine, polyethylene amines, amides, polyester types based on adipic acid, phthalic acid, butanediol, trimethylolpropane and polyacrylates such as polyethyl and polybutyl acrylate, polyalcohols such as polyvinyl alcohol or mixtures thereof. Polyester types and aliphatic polyamide types with a viscosity range of 10,000-35,000 cP at 20 ° C with a hydroxyl content of 5.5-0.15% or their isocyanate-modified derivatives are also suitable. Polyamines based on, for example, ethylene, propylene and butylene diamine are also suitable.
- organometallic compounds of the 1st or 8th subgroups of the periodic table in particular Pd, Pt, Au and Ag
- Organometallic compounds of palladium with olefins (dienes), with ⁇ , ⁇ -unsaturated carbonyl compounds, with crown ethers, with nitriles and with diketones such as pentadione-2,4 are particularly suitable.
- Butadiene palladium dichloride bisacetonitrile palladium dichloride, bisbenzonitrile palladium dichloride, 4-cyclohexene-1,2-dicarboxylic acid anhydride palladium dichloride, mesityl oxide palladium chloride, 3-heptene-2-one-palladium chloride, 5-methyl-3-hexadione chloride, 5-methyl-3-hexadiene chloride 4-palladium.
- O-valent complex compounds such as palladium (O) tetrakis (triphenylphosphine) are also suitable.
- Suitable ionic noble metals are salts such as halides, acetates, nitrates, carbonates, sulfates, sulfides and hydroxides, such as PdS, Na2PdCl4, Na2PdCN4, H2PtCl6, AgNO3, Ag2SO4, Ag2S.
- the amount of the noble metal can be varied widely in the range from 0.05 to 2.5% by weight, based on the overall formulation.
- the preferred amount of noble metal is 0.1-1.0% by weight.
- Suitable fillers d.) Are oxides of the elements Mn, Ti, Mg, Al, Bi, Cu, Ni, Sn, Zn and Si, as well as silicates, bentonites, talc and chalk. However, preference is given to using inorganic or organic fillers whose resistance is preferably between 0.01-10 ⁇ / cm.
- the particularly preferred filler is conductive carbon black. Mixtures of such inorganic or organic fillers are further preferred.
- the amount of the filler can be varied widely in the range from 0.5-35, but preferably 3-20, particularly preferably 5-15% by weight, based on the primer composition.
- Suitable solvents e.) In the primers according to the invention are substances known in printing or coating technology, such as aromatic and aliphatic hydrocarbons, for example toluene, xylene, gasoline, glycerol; Ketones, for example methyl ethyl ketone, cyclohexanone; Esters, for example butyl acetate, dioctyl phthalate, butyl glycolate; Glycol ethers, for example ethylene glycol monomethyl ether, diglyme, propylene glycol monomethyl ether; Esters of glycol ethers, for example ethylene glycol acetate, propylene glycol monomethyl ether acetate; Diacetone alcohol. Mixtures of these solvents and their blends with other solvents can of course also be used. The amounts used are 50-90% by weight, preferably 60-85% by weight.
- the primer according to the invention is generally prepared by mixing the constituents.
- the components can also be incorporated in separate steps.
- the primer can be applied to the plastic surfaces using the usual methods such as printing, stamping, dipping, brushing, knife coating and spraying.
- the layer thickness of the primer can be varied in the range of 0.1-200 ⁇ m, but preferably in the range of 5-30 ⁇ m.
- primers according to the invention does not require swelling adhesive treatment of the plastic. This prevents stress cracks from forming.
- Suitable substrates for the method according to the invention are workpieces based on inorganic glasses, metals and in particular plastics.
- Plastics such as those used in the electrical, electronics and household sectors are particularly preferred.
- ABS, PC (polycarbonate) or their mixtures and flame-retardant types such as Bayblend® FR-90, 1441, 1439 and 1448, polyamide, polyester types, PVC, polyethylene and polypropylene should be mentioned.
- Flameproofing of plastics is known.
- polybrominated bisphenols and halogenated benzylphosphonates are used.
- the surfaces modified in this way can then be sensitized by reduction.
- the reducing agents customary in electroplating such as hydrazine hydrate, formaldehyde, hypophosphite or boranes, can preferably be used for this purpose. Of course, other reducing agents are also possible.
- the reduction is preferably carried out in aqueous solution. However, other solvents such as alcohols, ethers, hydrocarbons can also be used. Of course, suspensions or slurries of the reducing agents can also be used.
- the surfaces activated in this way can be used directly for electroless metallization. However, it may also be necessary to clean the surfaces by rinsing off residual reducing agents.
- 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.
- This very simple embodiment only consists of the three work steps: immersing the substrate in the solution of the organic compound or applying or spraying on the primer, evaporating the solvent and immersing the surfaces activated in this way Metallization bath (reduction and metallization).
- This embodiment is particularly suitable for nickel baths containing amine borane or copper baths containing formalin.
- Metallization baths which can be used in the process according to the invention are preferably baths with nickel salts, cobalt salts, copper salts, gold and silver salts or mixtures thereof with one another or with iron salts. Such metallization baths are known in the electroless metallization art.
- the process according to the invention has the advantage that, even without previous oxidative etching and / or swelling or treatment with solvents widening the polymer chain of the substrate surface, an adherent metal deposition is made possible by the subsequent selective electroless metallization only with the aid of the primer surface.
- the new process thus enables material-saving and environmentally friendly, inexpensive, both full-surface and partial metal deposition on material surfaces.
- Materials metallized according to the new process are characterized by their excellent shielding against electromagnetic waves. These materials are used in the electrical, automotive, electronics and household sectors.
- the good mechanical properties of the polymeric base material are not adversely affected by the painting or metallization process.
- a 100 x 100 mm test plate made from a blend consisting of 60% of a polyester made of 4,4'-dihydroxydiphenyl-2,2-propane and carbonic acid and 40% acrylonitrile-butadiene-styrene copolymer with a Vicat temperature of approx. 90 ° C , was provided on one side with a 10 ⁇ m thick primer and dried at 80 ° C. in the course of 45 minutes.
- the primer consisted of 53.7 Parts by weight of polyurethane resin, 198 Parts by weight of solvent mixture consisting of toluene, diacetone alcohol and isopropanol (1: 1: 1); 14.7 Parts by weight of titanium dioxide; 5.4 Parts by weight of talc; 5.4 Parts by weight of chalk; 7.2 Parts by weight of carbon black; 20% in butyl acetate; 6.6 Parts by weight of polyester with 4.3% OH groups with a surface tension> 45 mN / m, 20% solution in MEK (methyl ethyl ketone) and DAA (diacetone alcohol) (1: 1); 9 Parts by weight of suspended silicate, 10% digestion in xylene and 0.35 Parts by weight of bisbenzonitrile palladium II dichloride.
- test plate was then treated in a reduction bath consisting of 10 g of dimethylamine borane and 1.0 g of NaOH in 1 liter of water at 30 ° C. and then at Room temperature copper-plated in a chemical copper bath for 30 minutes, washed with distilled water and then annealed at 80 ° C for 30 minutes. A 1.5 ⁇ m thick copper layer was formed.
- the metal coating also had a peel strength according to DIN 53 494 of 25 N / 25 mm.
- a polyphenylene oxide / polystyrene plate was made up with a primer 53.7 parts by weight Polyurethane resin 200 parts by weight Solvent mixture consisting of toluene, diacetone alcohol and isopropanol (1: 1: 1) 15 parts by weight Titanium dioxide 6 parts by weight talc 8 parts by weight Carbon black, 20% in butyl acetate 7 parts by weight Poly-2-ethyl-2-oxazoline, 20% solution in MEK 8 parts by weight Silica-based suspension agent, 10% digestion in xylene, 0.5 parts by weight 3-hexen-2-one palladium chloride, provided on one side and dried at 80 ° C for 45 minutes.
- Solvent mixture consisting of toluene, diacetone alcohol and isopropanol (1: 1: 1) 15 parts by weight Titanium dioxide 6 parts by weight talc 8 parts by weight Carbon black, 20% in butyl acetate 7 parts by weight Poly-2-ethyl-2-oxazoline, 20% solution in MEK 8 parts by weight
- the plate coated in this way was provided with a 2 ⁇ m thick copper layer in a chemical copper plating bath over the course of 45 minutes.
- This plate was well shielded from electromagnetic waves.
- a 100 x 100 mm ABS plate was made with a primer consisting of 50 parts by weight of a polyol component. 88.76 parts by weight a polyester polyol of molecular weight 2000 made from adipic acid, ethylene glycol and 1,4-dihydroxybutane (molar ratio of the diols 70:30) 8.0 parts by weight Ethylene glycol 0.5 parts by weight water 0.5 parts by weight Triethylenediamine 0.55 parts by weight a commercially available polysiloxane stabilizer 1.25 parts by weight Na2PdCl4 and 1.0 part by weight Tetrabutylammonium chloride, and 50 parts by weight of a polyisocyanate component 90.0 parts by weight an NCO prepolymer of 65.0 parts by weight of 4,4'-diisocyanate diphenylmethane and 38.0 parts by weight of the polyester polyol used in the polyol component 250.0 parts by weight Solvent mixture consisting of toluene, diacetone alcohol and isopropan
- a 100 x 150 mm test plate made of a polycarbonate was provided with an approximately 15 ⁇ m thick primer layer and dried at 65 ° C. in the course of 30 minutes.
- test plate was copper plated in a chemical copper plating bath over 30 minutes, washed with water and then dried at room temperature.
- a 2 ⁇ m thick copper layer had formed, which had a peel strength according to DIN 53 494 of 15 N / 25 mm.
- This metallized plate had excellent shielding against electromagnetic waves.
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Chemically Coating (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Details Of Measuring And Other Instruments (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4036591A DE4036591A1 (de) | 1990-11-16 | 1990-11-16 | Primer zum metallisieren von substratoberflaechen |
| DE4036591 | 1990-11-16 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0485839A2 true EP0485839A2 (fr) | 1992-05-20 |
| EP0485839A3 EP0485839A3 (en) | 1993-02-24 |
| EP0485839B1 EP0485839B1 (fr) | 1995-01-04 |
Family
ID=6418415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91118731A Expired - Lifetime EP0485839B1 (fr) | 1990-11-16 | 1991-11-04 | Couche de base pour métallisation |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5378268A (fr) |
| EP (1) | EP0485839B1 (fr) |
| JP (1) | JPH04365872A (fr) |
| CA (1) | CA2055352C (fr) |
| DE (2) | DE4036591A1 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999009794A1 (fr) * | 1997-08-20 | 1999-02-25 | Bayer Aktiengesellschaft | Fabrication de plaquettes de circuits imprimes tridimensionnelles |
| CN109694685A (zh) * | 2018-12-31 | 2019-04-30 | 苏州思德新材料科技有限公司 | 一种阻燃型单组份泡沫填缝剂及其制备方法 |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411795A (en) * | 1992-10-14 | 1995-05-02 | Monsanto Company | Electroless deposition of metal employing thermally stable carrier polymers |
| DE4319759A1 (de) * | 1993-06-15 | 1994-12-22 | Bayer Ag | Pulvermischungen zum Metallisieren von Substratoberflächen |
| DE19812880A1 (de) | 1998-03-24 | 1999-09-30 | Bayer Ag | Formteil und flexible Folie mit geschützter Leiterbahn und Verfahren zu ihrer Herstellung |
| JP2002001880A (ja) * | 2000-06-20 | 2002-01-08 | Inoac Corp | 導電性プラスチック成形品およびその製造方法 |
| DE10243132B4 (de) * | 2002-09-17 | 2006-09-14 | Biocer Entwicklungs Gmbh | Antiinfektiöse, biokompatible Titanoxid-Beschichtungen für Implantate sowie Verfahren zu deren Herstellung |
| US7255782B2 (en) * | 2004-04-30 | 2007-08-14 | Kenneth Crouse | Selective catalytic activation of non-conductive substrates |
| US20050241951A1 (en) * | 2004-04-30 | 2005-11-03 | Kenneth Crouse | Selective catalytic activation of non-conductive substrates |
| JP4859232B2 (ja) * | 2004-09-10 | 2012-01-25 | Ｊｘ日鉱日石金属株式会社 | 無電解めっき前処理剤及びフレキシブル基板用銅張り積層体 |
| GB0422386D0 (en) * | 2004-10-08 | 2004-11-10 | Qinetiq Ltd | Active filler particles in inks |
| JP2008007849A (ja) * | 2006-06-01 | 2008-01-17 | Nippon Paint Co Ltd | 無電解めっき用プライマー組成物及び無電解めっき方法 |
| US7909977B2 (en) * | 2008-03-27 | 2011-03-22 | Intel Corporation | Method of manufacturing a substrate for a microelectronic device, and substrate formed thereby |
| WO2010088606A1 (fr) * | 2009-01-30 | 2010-08-05 | E. I. Du Pont De Nemours And Company | Encres de jet d'encre avec densité optique améliorée |
| US9376591B2 (en) * | 2014-02-19 | 2016-06-28 | Golden Artist Colors, Inc. | Water color paint system |
| KR102573460B1 (ko) | 2017-08-28 | 2023-09-04 | 디에스엠 아이피 어셋츠 비.브이. | 불화된 폴리우레탄을 포함하는 합성 멤브레인 조성물 |
| US11643551B2 (en) * | 2017-08-28 | 2023-05-09 | Dsm Ip Assets B.V. | Synthetic membrane composition comprising a polyurethane and a polyoxazoline |
| CN114958169B (zh) * | 2022-05-11 | 2022-12-02 | 电子科技大学 | 一种用于制备图形化金属层的交联催化剂 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3560257A (en) * | 1967-01-03 | 1971-02-02 | Kollmorgen Photocircuits | Metallization of insulating substrates |
| EP0250867A1 (fr) * | 1986-06-16 | 1988-01-07 | International Business Machines Corporation | Procédé d'activation en vue d'un dépôt de métal par voie chimique |
| DE3814506A1 (de) * | 1988-04-29 | 1989-11-09 | Bayer Ag | Verfahren zum metallisieren von substratoberflaechen |
| EP0322641B1 (fr) * | 1987-12-23 | 1992-05-20 | Bayer Ag | Procédé relatif à l'adhérence des couches métalliques déposés par voie chimique sur des surfaces en polyimide |
| EP0256395B1 (fr) * | 1986-08-12 | 1992-07-01 | Bayer Ag | Procédé pour améliorer l'adhérence des couches de métaux déposées par voie chimique sur des surfaces en matière plastique |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3900320A (en) * | 1971-09-30 | 1975-08-19 | Bell & Howell Co | Activation method for electroless plating |
| US4017265A (en) * | 1972-02-15 | 1977-04-12 | Taylor David W | Ferromagnetic memory layer, methods of making and adhering it to substrates, magnetic tapes, and other products |
| DE2443488A1 (de) * | 1973-10-25 | 1975-04-30 | Akad Wissenschaften Ddr | Metallisierte koerper und verfahren zu deren herstellung |
| US4368281A (en) * | 1980-09-15 | 1983-01-11 | Amp Incorporated | Printed circuits |
| DE3148280A1 (de) * | 1981-12-05 | 1983-06-09 | Bayer Ag, 5090 Leverkusen | Verfahren zur aktivierung von substratoberflaechen fuer die stromlose metallisierung |
| US5053280A (en) * | 1988-09-20 | 1991-10-01 | Hitachi-Chemical Co., Ltd. | Adhesive composition for printed wiring boards with acrylonitrile-butadiene rubber having carboxyl groups and 20 ppm or less metal ionic impurities; an alkyl phenol resin; an epoxy resin; palladium catalyst, and coupling agent |
-
1990
- 1990-11-16 DE DE4036591A patent/DE4036591A1/de not_active Withdrawn
-
1991
- 1991-11-04 EP EP91118731A patent/EP0485839B1/fr not_active Expired - Lifetime
- 1991-11-04 DE DE59104146T patent/DE59104146D1/de not_active Expired - Fee Related
- 1991-11-07 US US07/788,957 patent/US5378268A/en not_active Expired - Lifetime
- 1991-11-12 JP JP3322376A patent/JPH04365872A/ja active Pending
- 1991-11-13 CA CA002055352A patent/CA2055352C/fr not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3560257A (en) * | 1967-01-03 | 1971-02-02 | Kollmorgen Photocircuits | Metallization of insulating substrates |
| EP0250867A1 (fr) * | 1986-06-16 | 1988-01-07 | International Business Machines Corporation | Procédé d'activation en vue d'un dépôt de métal par voie chimique |
| EP0256395B1 (fr) * | 1986-08-12 | 1992-07-01 | Bayer Ag | Procédé pour améliorer l'adhérence des couches de métaux déposées par voie chimique sur des surfaces en matière plastique |
| EP0322641B1 (fr) * | 1987-12-23 | 1992-05-20 | Bayer Ag | Procédé relatif à l'adhérence des couches métalliques déposés par voie chimique sur des surfaces en polyimide |
| DE3814506A1 (de) * | 1988-04-29 | 1989-11-09 | Bayer Ag | Verfahren zum metallisieren von substratoberflaechen |
Non-Patent Citations (2)
| Title |
|---|
| Römpps Chemie Lexikon, Band 1, 8. Auflage, 1979, Seiten 64-65 * |
| Römpps Chemie Lexikon, Band 4, 8. Auflage, 1985, Seiten 2866-2867 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999009794A1 (fr) * | 1997-08-20 | 1999-02-25 | Bayer Aktiengesellschaft | Fabrication de plaquettes de circuits imprimes tridimensionnelles |
| CN109694685A (zh) * | 2018-12-31 | 2019-04-30 | 苏州思德新材料科技有限公司 | 一种阻燃型单组份泡沫填缝剂及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US5378268A (en) | 1995-01-03 |
| DE4036591A1 (de) | 1992-05-21 |
| CA2055352A1 (fr) | 1992-05-17 |
| EP0485839A3 (en) | 1993-02-24 |
| CA2055352C (fr) | 1999-10-26 |
| JPH04365872A (ja) | 1992-12-17 |
| EP0485839B1 (fr) | 1995-01-04 |
| DE59104146D1 (de) | 1995-02-16 |
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