CN104364421B - Make the method for nonconductive plastic material surface metalation - Google Patents
Make the method for nonconductive plastic material surface metalation Download PDFInfo
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- CN104364421B CN104364421B CN201380029727.6A CN201380029727A CN104364421B CN 104364421 B CN104364421 B CN 104364421B CN 201380029727 A CN201380029727 A CN 201380029727A CN 104364421 B CN104364421 B CN 104364421B
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- 238000000034 method Methods 0.000 title claims abstract description 110
- 229920003023 plastic Polymers 0.000 title claims abstract description 53
- 239000004033 plastic Substances 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000006263 metalation reaction Methods 0.000 title claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005530 etching Methods 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims description 136
- 229910052751 metal Inorganic materials 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 47
- 239000000084 colloidal system Substances 0.000 claims description 31
- 229910052763 palladium Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 238000001465 metallisation Methods 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 14
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 13
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 229910000765 intermetallic Inorganic materials 0.000 claims description 11
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004425 Makrolon Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N hydroxylamine hydrochloride Substances Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 2
- WCYJQVALWQMJGE-UHFFFAOYSA-M hydroxylammonium chloride Chemical compound [Cl-].O[NH3+] WCYJQVALWQMJGE-UHFFFAOYSA-M 0.000 claims description 2
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical group O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims 2
- 150000003624 transition metals Chemical class 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 48
- 238000007747 plating Methods 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- 229910052759 nickel Inorganic materials 0.000 description 22
- 239000000853 adhesive Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 20
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 17
- 239000010949 copper Substances 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 229920001944 Plastisol Polymers 0.000 description 7
- -1 chlorate anions Chemical class 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 150000002940 palladium Chemical class 0.000 description 7
- 239000004999 plastisol Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- 239000011135 tin Substances 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920007019 PC/ABS Polymers 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000012212 insulator Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 150000002941 palladium compounds Chemical class 0.000 description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 229910000085 borane Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 235000017168 chlorine Nutrition 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
- 239000012286 potassium permanganate Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- 229910001436 Cr3+ Inorganic materials 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910010277 boron hydride Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000001309 chloro group Chemical class Cl* 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical group [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920006942 ABS/PC Polymers 0.000 description 1
- 101710190443 Acetyl-CoA carboxylase 1 Proteins 0.000 description 1
- 102100021334 Bcl-2-related protein A1 Human genes 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- TVWHTOUAJSGEKT-UHFFFAOYSA-N chlorine trioxide Chemical compound [O]Cl(=O)=O TVWHTOUAJSGEKT-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000454 electroless metal deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000009666 routine test Methods 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 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
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
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- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- 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
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
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- 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
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- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
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- 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
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- 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
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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- 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
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- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
Abstract
The present invention relates to make the method that nonconductive plastic material metallizes with not chromyl etching solution.Etching solution is based on the sulfuric acid solution for including chloranion source.After plastics are handled with etching solution, made by known method plastics metalizing.
Description
Invention field
The present invention relates to the pretreatment nonconductive plastic material surface before metallization, and it can be applied to wherein need plastic section
The dicoration of part or the difference industry of functional metal coating.Pretreatment is carried out in not chromyl solution.
Background of invention
The conventional method on pretreatment nonconductive plastic material surface before electroless metallising (mainly electroless nickel plating or copper facing)
Consist of：Surface is etched in chromyl solution, is then activated in the ion or colloidal solution of palladium compound, and
And reduced in sodium hypophosphite solution (in most cases) or in acid solution (the usual salt of palladium ion or colloid palladium particle
Acid) middle acceleration (adsorbing respectively on frosting).
For hydrophiling, it is necessary to etch non-conductive matrix surface during pre-treatment step so that surface method its
Its stage becomes hydrophilic in aqueous, while adsorbing the palladium salt of sufficient amount, and ensures coat of metal appropriate combination to non-conductive
Frosting.In order to trigger metal electroless deposition on plastics, activated, then reduction or acceleration.Then, by urging automatically
Change reaction progress metal electroless in metallization solution, wherein the metal deposited on the surface is as further depositing
Catalyst.This electroless mainly uses metallic nickel and copper.
Then, it can be electrolysed on the first metal layer or electrochemical plating.Can apply various metals, for example chromium, nickel, copper and
Other alloys of brass or aforementioned metal.
The major defect of conventional method is related to the carcinogenicity of chromic acid in etching solution.In addition, during electroless deposition step
The part of the metal of deposition, such as nickel, the also support that covering plastisol insulate, this causes in subsequent electrochemical metal plating
Solution metal loss, it is therefore undesirable.
The various methods for overcoming this problem are had pointed out in the prior art.
The A1 of U.S. Patent Application No. 2005/0199587, which is disclosed, a kind of is including the acid solution of 20-70g/l potassium permanganate
The method on middle etching nonconductive plastic material surface.Optimal KMnO in solution mentioned above4Concentration is close to 50g/l.It is less than in concentration
During 20g/l, solution is invalid, and upper limit of concentration is determined by the solubility of potassium permanganate.After etching, in the palladium salt solution comprising amine
Activation, and the further reduction treatment for example in boron hydride, hypophosphites or hydrazine solution.
However, the method has significant drawback.In the etch solution (it is recommended that about 50g/l, is carried under high permanganate concentration
48% volume phosphoric acid), it is decomposed quickly, especially in high temperature.It is recommended that temperature is 100 ℉, i.e., 37 DEG C.Experiment is it has been shown that warm herein
Degree, solution became invalid after 4 to 6 hours, i.e. frosting not hydrophiling, and some places are kept during metallizing
It is not plated, the adhesive force with plastics in plating zones is very weak.Need to adjust solution through conventional new peak manganate part, it is high
Manganate is not cheap.In addition, also generating insoluble permanganate catabolite, the surface metallized is polluted.
In addition, when being manganese dioxide with etch reaction products plating, the etching in permanganate solution makes support
Plastisol insulator surface is activated.The latter promotes palladium compound to be adsorbed on plastisol, and this tends to heavy in electroless metal
Product GOLD FROM PLATING SOLUTION categoryization.Generation manganese dioxide is the feature of the permanganate etch solution of any composition on the surface.Therefore, originally
The critically important purpose of invention is to avoid backbone metal, and avoids the metal loss in subsequent metalization level.
Lithuania number of patent application LT 2008-082 are directed to before metallization pre-process nonconductive plastic material surface.Its
Disclosed in a kind of pretreatment compositions, using 10-80 DEG C of temperature, in 13mol/L (about 75% volume) -17mol/L (about 90% bodies
Product) concentration sulfuric acid in 0,005-0,2M oxidizing agent solutions etch such as polyimides 1-2 minutes, wherein oxidant can be
KMnO4、HClO4、V2O5、KClO3.In chlorate anions (ClO3 -, M=83.5g/mol) in the case of, this is equivalent to 0.4-16.7g/l
Concentration.
An example is provided in the table 2 applied at this, example includes 7mol/L (about 50% volume) sulfuric acid and 0.2mol/L
(16.7g/L) chlorate anions.However, having shown the chlorate anions of such high concentration causes preprocessing solution fast decoupled, this, which does not conform to, needs
Will.
Invention description
Therefore, the present invention is based on problems with：So far also fail to be realized with Environmental security mode and be made up of nonconductive plastic material
Product metallization, and the metal level adhesive strength for having enough reliability of technology and then applying is enough.
It is therefore an object of the present invention to the etching solution on the nonconductive plastic material surface for pre-treatment preparations is found, these
It is nontoxic, but enough adhesive strengths is provided for the metal level applied on frosting.
This purpose is achieved by the following way：Using in the application can comprising 0.2 to 15.0g/l in 50-80% volume sulfuric acid
Molten chlorate (is based on KClO3, M=122.55, i.e. 0.0016mol/l to 0.12mol/l) etching solution etching frosting make
For the processing method of the frosting before electroless metallising, processing method is consisted of：With the inorganic acid with oxidant
Solution etches plastics, is activated by palladium salt solution, and by reducing or accelerating solution to handle.Etching is preferably in room temperature (15-28
DEG C, preferably 20-25 DEG C) carry out, but also can up to 40 DEG C or 50 DEG C higher temperature carry out, condition be solution stability by
Control.Preprocessing solution can optionally include up to 20g/l another oxidant, and it has the standard oxidation electricity more than chlorate anions
Position.
Etching period can be determined with matrix material and its alteration of form by routine test.It is general 1 and 20 minute it
Between, preferably no longer than 10 minutes.
Chloranion source can be any water soluble salt.Most-often used sodium chlorate and potassium chlorate.
In etching solution the concentration of chloranion be 0.0016mol/l to 0.12mol/l, or preferably of up to 0.03mol/
L is even more preferably up to 0.04mol/l.It is preferred that scope between 0.003mol/l and 0.08mol/l, or in 0.01mol/
Between l and 0.06mol/l or between 0.004mol/l and 0.04mol/l.
The concentration of sulfuric acid is even more excellent preferably between 55% volume and 70% volume between 50% volume and 80% volume
It is selected between 60% volume and 65% volume.
Optionally other acid can be used as comprising phosphoric acid in the etch solution.The concentration of phosphoric acid is generally 10% volume to 40% body
Product, preferably between 15% volume and 25% volume or 30% volume.When in addition using phosphoric acid, plating can be unexpectedly improved in addition
The adhesive force of metal level.
The mixture of phosphoric acid is particularly preferred between sulfuric acid and 20% volume and 30% volume between 60% volume and 65% volume.
The method on pretreated plastic surface includes before electroless metallising, is lost in the inorganic acid solution added with oxidant
Plastics are carved, are activated in palladium salt solution, and are handled in reducing or accelerating solution, it is characterised in that pass through 50-80% bodies in room temperature
The solution etching plastic table of 0.02-15.0g/l soluble chlorines hydrochlorate (for example, 0.5-5g/l soluble chlorines hydrochlorate) in product sulfuric acid
Face, and handled in addition in alkali hydroxide soln, then activated and molten with reduction/acceleration by palladium compound solution
Liquid processing.
Etching solution can optionally include 2 to 20g/l another oxidant, and it has the standard oxygen more than chloranion
Change current potential.
Alkali metal chlorate and sulfuric acid generation yellow compound, it is in H2SO4Standard oxidizing potential in solution medium is enough
Reacted in room temperature and frosting.Due to this reaction, frosting becomes hydrophilic, and adsorbs palladium compound with sufficient intensity.
Yellow reaction product between chlorate and sulfuric acid is the poisonous substance of palladium catalyst.During etching, the plasticising that it penetrates support is molten
Glue insulator surface layer, and prevention electroless deposition of metals on plastisol in electroless metallising solution, in nonconductive plastic material
The metallization processes occurred on surface are unaffected.
In 1 to 2g/l sodium chlorate or potassium chlorate and 5 to 10g/l second strong oxidizer (such as NaBiO3) dissolving when, etching
Property is kept for a couple of days in room temperature, and solution can be used in the case where not adjusting.If only including sodium chlorate/potassium chlorate in the solution, erosion
Carve the time (most long 24 hours) that property keeps much shorter.
Make its important difference for being different from the proposed method of permanganate etch be characterized in coating and plastics it
Between obtain very high adhesion value, usually more than 1.2 to 1.3kg/cm.Except the composition and etching period of etching solution are (to each
Composition has the optimal etch time) outside, these values additionally depend on the composition of activated solution.Generally, when using actual activated solution,
Obtained adhesion value is higher than those values obtained with colloidal activating solution.
It can be prepared as follows etching solution：
The 700ml concentrated sulfuric acids are made to be mixed with 300ml deionized waters.Cool down solution.Then 2g potassium chlorate and 10g perchloric acid are made
Sodium is dissolved in solution.Solution is ready to use.It is optional to be better than the second oxidant sodium perchlorate of potassium chloride.It increases composition
Useful life, but need not it obtain the well attached of subsequent metal plating layer.
When the amount for preparing water used in solution is compared with sulfuric acid more than 50% volume, chloranion and sulfuric acid molecule it
Between do not generate yellow plastic oxidized compound, therefore, 50% volume is preferably not to be exceeded in the water content of solution.
When the amount for preparing water used in solution is compared with sulfuric acid less than 20% volume, because sulfuric acid concentration is too high, in the etching phase
Between frosting decompose, therefore, there is no adhesive force between chemical nickel coating and plastics.
If the amount for being dissolved in the potassium chlorate of solution is less than 0.5g/l, etching process is time-consuming to be longer than 15 minutes, therefore, this dense
Degree is unacceptable.
It is considerable after minimum etching period (i.e. 2 to 3 minutes) if being dissolved in the amount of the potassium chlorate of solution more than 5.0g/l
Over etching is observed, this produces the adhesive strength of much weaker, and therefore, this high concentration cl hydrochlorate is also unacceptable.However, according to
Matrix material, the higher concentration for producing the highest 15g/l of enough adhesive force is also subjected to.
The purpose of the present invention is further realized by the following methods of the present invention：
Make the method for the nonconductive plastic material surface metalation of product, methods described includes following methods step：
A frosting) is etched with the above-mentioned etching solution comprising chloranion source, the chloranion source is obtained
0.0016 to 0.12mol/l chloranion concentration in 50-80% volume sulfuric acid；
B) with the solution processing frosting of metallic colloid or metallic compound, the metal is selected from periodic table of elements I
The metal of transition group and periodic table of elements VIII transition groups；And
C) metallization of plastic surface is made with metallization solution；
It will be appreciated that in the context of the present invention, product refers to be made up or with least one of at least one nonconductive plastic material
Plant the product of at least one layer of covering in nonconductive plastic material.Therefore, product has the surface of at least one nonconductive plastic material.Ying Liao
Solution, in the context of the present invention, frosting means these described surfaces of product.
The method and step of the present invention, but need not be with immediately order to provide that order is carried out.Other method and steps can be carried out, and
And cleaning step can be additionally carried out in all cases between the steps, preferably use water.
Frosting is made up of at least one nonconductive plastic material.In one embodiment of the invention, it is at least one
Nonconductive plastic material be selected from acrylonitrile-butadiene-styrene copolymer (Acrylonitrile Butadiene-Styrene copolymer), polyamide (PA), makrolon (PC),
With Acrylonitrile Butadiene-Styrene copolymer and the mixture of at least one other polymer.
In a preferred embodiment of the invention, nonconductive plastic material is Acrylonitrile Butadiene-Styrene copolymer or Acrylonitrile Butadiene-Styrene copolymer and at least one
Plant the mixture of other polymer.At least one other polymer is more preferably makrolon (PC), and this represents particularly preferred
ABS/PC mixtures.
Etching solution of the present invention is preferably free of any chromium or chromium compound, and etching solution is both free of chromium (III) ion, also not
Containing chromium (VI) ion.Therefore, etching solution of the present invention is free of chromium or chromium compound, and etching solution is free of chromium (III) ion and chromium
(VI) ion.
In another preferred embodiment of the present invention, in method and step A) and B) between carry out method additionally below
Step：
A i) frosting is handled in the solution including alkaline solution.
Other method and step A i) it is also referred to as neutralisation treatment.Any alkaline source, the aqueous solution of sodium hydroxide can be used
It is preferred.
The present invention another for selecting embodiment in, in method and step A) and B) between carry out method additionally below
Step：
A i) handle plastic table in comprising the solution for chloranion and the reducing agent of the second optional oxidant
Face.
Other method and step A i) it is also referred to as reduction treatment.This reduction treatment reduces the chlorine for being attached to frosting
Acid ion and the second optional oxidant, and promote to remove these ions.Reducing agent is selected from hydroxylammonium sulfate, hydroxylammonium chloride
And hydrogen peroxide.
The method of the present invention further comprises method and step B), wherein frosting metallic colloid or metallic compound
Solution processing.
The metal of metallic colloid or metallic compound is selected from the periodic table of elements (PTE) I transition groups and PTE VIII transition
The metal of race.
The metal of PTE VIII transition groups is selected from the mixture of palladium, platinum, iridium, rhodium and two or more these metals.
The metal of PTE I transition groups is selected from gold, silver and the mixture of these metals.
Preferred metal in metallic colloid is palladium.Metallic colloid protective colloid-stabilisedization.Protective colloid is selected from gold
Belong to protective colloid, organic protective colloid and other protective colloids.It is preferred that being used as metal coating colloid with tin ion.Have
Machine protective colloid is selected from polyvinyl alcohol, polyvinylpyrrolidone and gelatin, preferably polyvinyl alcohol.
In a preferred embodiment of the invention, method and step B) in metallic colloid solution be with palladium/tin glue
The activator solution of body.This colloidal solution is obtained from palladium salt, tin (II) salt and inorganic acid.It is preferred that palladium salt be palladium bichloride.It is excellent
Tin (II) salt of choosing is stannic chloride (II).Inorganic acid can be made up of hydrochloric acid or sulfuric acid, preferably hydrochloric acid.Colloidal solution by by
Stannic chloride (II) makes palladium bichloride be reduced into palladium to generate.It is complete that palladium bichloride, which changes into colloid, and therefore, colloidal solution no longer contains
Any palladium bichloride.The concentration of palladium is based on Pd2+For 5mg/l-100mg/l, more preferably preferably 20mg/l-50mg/l, 30mg/l-
45mg/l.The concentration of stannic chloride (II) is based on Sn2+For 0.5g/l-10g/l, more preferably preferably 1g/l-5g/l, 2g/l-4g/l.Salt
The concentration of acid is 100ml/l -300ml/l (37% weight HCl).In addition, palladium/tin colloid solution also includes tin (IV) ion, tin
(IV) ion is generated by tin (II) ionic oxide formation.In method and step B) during colloidal solution temperature be 20 DEG C -50 DEG C, preferably
35℃-45℃.It is 0.5min-10min, more preferably preferably 2min-5min, 3min- using the processing time of activator solution
5min。
In another embodiment of the present invention, in method and step B) in, replace metal with the solution of metallic compound
Colloid.The solution of metallic compound used is the solution comprising acid and metal salt.Metal in metal salt by one or more with
Upper listed PTE I and VIII transition groups metal composition.Metal salt can be palladium salt, preferably palladium bichloride, palladium sulfate or acetic acid
Palladium, or silver salt, preferably silver acetate.Acid is preferably hydrochloric acid.Or, it is possible to use metal complex, such as palladium complex salt, for example
Palladium-aminopyridine complex salts.Method and step B) in metallic compound deposited with the concentration based on metal 40mg/l to 80mg/l
.The solution of metallic compound can be used in 25 DEG C to 70 DEG C temperature, preferably at 25 DEG C.Utilize the processing of metal compound solution
Time is 0.5min -10min, more preferably preferably 2min -6min, 3min -5min.
In method and step A) and B) between can carry out method and step additionally below：
A ii) frosting is handled in acidic aqueous solution.
It is preferred that in method and step A i) and B) between carry out method and step A ii).In the method for the invention, if in side
Method step A i) protective cradle afterwards, then more preferably in protective cradle and method and step B) between carry out method and step A ii).
In method and step A ii) in processing frosting be also referred to as preceding dipping, acidic aqueous solution is used as preceding dipping solution.Before
Dipping solution have and method and step B) in colloidal solution identical constitute, but in colloid and its protective colloid be not present gold
Category.In method and step B) it is middle using in the case of palladium/tin colloid solution, if colloidal solution equally includes hydrochloric acid, preceding dipping
Solution exclusively includes hydrochloric acid.For preceding dipping, dipping solution is just enough before environment temperature briefly immerses.Do not clean plastics
Surface, in preceding dipping solution handle after, they are further directly used into method and step B) colloidal solution handle.
In method and step B) when including handling frosting with colloidal metal solution, preferably carry out method and step A ii).
Can be in method and step B) include carrying out method and step A ii when handling frosting with metal compound solution).
In method and step B) after middle metallic colloid or metallic compound processing frosting, it can be cleaned.
In another embodiment of the present invention, in method and step B) and C) between carry out additionally below method step
Suddenly：
B i) frosting is handled in acidic aqueous solution, and
B ii) make frosting electroless metallising in metallization solution.
Embodiment is shown schematically in table 1.
| Method and step | Composition | Time | Temperature |
| A) etch | Table 2 | 4-6min | 22℃ |
| A i) neutralize | 10g/l NaOH | 4min | 20℃ |
| A ii) preceding dipping | Hydrochloric acid, about 10% weight | 1min | 20℃ |
| B) activate | Palladium/tin colloid in hydrochloric acid solution | 3-6min | 20-45℃ |
| B i) accelerate | Sulfuric acid (5%) | 2-6min | 40-50℃ |
| B ii) electroless metal deposition | Electronation nickel plating or copper facing | 6-20min | 30-50℃ |
| C) metal deposit | For example, Cu electroplating or nickel plating | 15-70min | 20-35℃ |
Table 1：Plastics metalizing embodiment
When product will be metallized by electroless metallising method, i.e., the first metal layer will be by being applied to modeling without method for electrically
When expecting surface, these other method and step B i are utilized) and B ii).
If method and step B) in activation carried out with metallic colloid, in order to from frosting remove colloidal solution in
Colloid composition such as protective colloid, in method and step B i) in accelerator solution handle frosting.If in method
Step B) in colloid in colloidal solution be palladium/tin colloid, then accelerator solution preferably used for acid the aqueous solution.For example, sour
Selected from sulfuric acid, hydrochloric acid, citric acid and tetrafluoro boric acid.In the case of palladium/tin colloid, accelerator solution helps to remove as protection
The tin compound of property colloid.
Or, in method and step B) in replace metallic colloid to be used for when activating with the solution of metallic compound, in method
Step B i) middle progress reducing agent processing.Then, if the solution of metallic compound is the hydrochloric acid solution or silver salt of palladium bichloride
During acid solution, the reductant solution used for this purpose includes hydrochloric acid and stannic chloride (II).Reductant solution also can be comprising another
A kind of reducing agent, such as NaH2PO2Or borine or boron hydride, such as alkali metal borine or alkaline-earth metal borine or dimethylamino
Base borine.It is preferred that using NaH in reductant solution2PO2。
In method and step B i) in reductant solution accelerate or handle after, frosting can be cleaned first.
In method and step B i) and optional one or more cleaning steps after, carry out method and step B ii), wherein making modeling
Expect surface electroless metallising.For example, completing electroless nickel plating with conventional nickel bath, the nickel bath especially includes nickel sulfate, is used as reduction
The hypophosphites (for example, sodium hypophosphite) and organic complexing agent and pH adjusting agent (for example, buffer) of agent.Reducing agent used can be same
Sample is the mixture of dimethyl amino borane or hypophosphites and dimethyl amino borane.
Or, electroless copper can be carried out with electroless copper bath, electroless copper bath generally comprises mantoquita, for example, copper sulphate or secondary phosphorus
Sour copper；And reducing agent, such as formaldehyde or hypophosphites (such as alkali metal or ammonium salt) or hypophosphorous acid；And it is another or a variety of
Complexing agent, such as tartaric acid；And pH adjusting agent, such as sodium hydroxide.
Then, in order to obtain feature or decorative surface, the surface electrolyzing gold that electric conductivity is so provided can further be made
Categoryization.
The step C of the method for the present invention) it is to make metallization of plastic surface with metallization solution.Method and step C) in metal
Change can be electrolysed progress.For electrolytic metal chemical, can with any required metal deposit bath for example deposition nickel, copper, silver, gold, tin,
Zinc, iron, lead or their alloy.These deposition baths are familiar with by those skilled in the art.The bath of Watts nickel is typically used as bright nickel
Bath, this bath includes nickel sulfate, nickel chloride and boric acid, is also used as additive comprising saccharin.The reality for the composition bathed as bright copper
Example includes copper sulphate, sulfuric acid, sodium chloride and organosulfur compound, and wherein sulphur is in low-oxidation-state, such as organic sulfur compound or two
Sulfide, is used as additive.
Method and step C) in the effect of metallization of plastic surface be frosting metal deposition, metal, which is selected from, to be used to deposit
The metal listed above of bath.
In another embodiment of the present invention, in method and step C) method and step additionally below is carried out afterwards：
C i) metallized frosting is stored at elevated temperatures.
As wherein with metal by the idioelectric all electro-plating methods of wet chemical method plating, metal level is being applied
Afterwards, the adhesive strength between metal and plastic substrate increases in the first stage.In room temperature, this process was completed after about 3 days.This can
Substantially speeded up by storing at elevated temperatures.This process is completed after about 1 hour at 80 DEG C.It is assumed that initial low adhesive strength
The thin water layer for forming electrostatic force by the interface between metal and non-conductive matrix and prevention is produced.
Therefore, method of the invention can apply the splendid adhesive strength of metal level with good process reliability and then
Realize the nonconductive plastic material surface metalation of product.The adhesive strength for being administered to the metal level of frosting reaches up to 2.7N/
Mm (being approximately equivalent to 2.7kg/cm, 1kg/cm=0.98N/mm) or higher value.Therefore, the adhesive strength reached is also far above
The intensity reached after frosting (see embodiment 2 and 3) can be etched according to prior art chromatosulfuric acid.
In general, commercial Application needs the adhesion value more than 0.8N/mm, and the thing for wanting plating non-complex to be molded
Body.In general, the adhesive force of deposit is higher, and stability is better.
In addition, not only flat frosting is metallized by the method for the present invention with high-adhesion, and uneven shaping
Frosting, such as spray head, also are provided with uniform strong adhesion metal coating.
Frosting is handled preferably in conventional impregnation methods by the method for the present invention, by by product successively wherein
Solution is immersed in the container handled respectively to carry out.In the case, support can be secured the article to or be contained in drum
To immerse solution.It is preferred fixed to support.Or, for example, by being placed on disk, and it is logical with horizontal direction continuous conveying
Cross equipment, also can in so-called conveying equipment treatment articles.
Effective embodiment
Effective embodiment as described below is intended to explain the present invention.
Embodiment 1
According to the A1 of U.S. Patent Application No. 2005/0199587,50g/l KMnO are being included445% volume phosphoric acid solution
In 37 DEG C in 5min (for ABS) or 15min (for PC/ABS) during, or with 0.5 to 5.0g/l KClO3And add
Have in 50 to 80% volume sulfuric acid solutions of oxidant at 20 DEG C during 1 to 12min, etch ABS (acrylonitrile-butadienes-benzene
Ethylene copolymer) and PC/ABS (mixture of 45% makrolon and 55% acrylonitrile-butadiene-styrene copolymer).Etching
Afterwards, plastics are submerged to 1 to 2min, then in the true solution of palladium compound in the room temperature comprising 10g/l NaOH and in solution
(colloidal solution is special for DOW Chemical Company's (" DOW ") for (5min, 20 DEG C) or colloidal solution (2min, 35 DEG C)
Solution) middle activation.PdCl in true solution2Concentration is 0.1g/l, and pH value of solution is 2.7.After being activated in true Pd solution, make plastics
In the solution of pH 9 comprising 20g/l sodium hypophosphites 5min is kept at 60 DEG C.After being activated in special colloidal solution, DOW is utilized
Special acceleration solution handles plastics 2min at 40 DEG C.Then, plastics nickel plating is made with DOW Niposit-PM nickel plating process.Coating
Quality is according to many factors evaluation, such as the plastisol of the frosting of complete or incomplete plating, plating or non-plating is exhausted
The adhesive strength of edge support and electroless nickel and plastics.In order to evaluate adhesive force, thicken Ni coating in the bath of electrochemical copper, and measure
Intensity (kg/cm) needed for peeling off the wide bars of 1cm from plastics.For ABS test specimens, the etching period in permanganate solution is
5min, is 15min to PC/ABS test specimens.For all test specimens, the etching period in solution of chlorate is 5min.For metal
The plastics pretreatment condition of change and the result of metallization (electroless nickel plating) are shown down in table 2 below.
Table 2
* (remaining is activated in ion activation solution) is activated in special DOW colloidal solution.
Test specimen 1 to 4 shows that in the case of based on permanganate etch, the plastisol insulator of support is by electroless nickel
Part plating, and in the case where being etched based on chlorate, insulator keeps clean.In addition, for ion and colloidal activating
In the case of the chlorate etching of both solution, the adhesion value between Ni coating and ABS is significantly higher.
Identical result is observed in the case of PC/ABS (test specimen 5 to 8) electroless nickel plating：In chlorate engraving method,
Plastisol insulator not plating, and adhesion value is significantly higher, especially when using ion activation solution.
As the KClO in etching solution3When concentration is less than 0.5g/l, ABS is not by plated with electroless nickel, or not exclusively plating
(test specimen 9).In KClO3When concentration is more than 5g/l (test specimen 10), the over etching after etching 5min, therefore, coating adhesion value
Significantly lower (being not enough to be used for practical application).In the KClO more than suggestion3During concentration value, class also is obtained to PC/ABS metallization
Like result (test specimen 11 and 12).
H in the etch solution2SO4In the case that concentration is less than 50% volume, etchant is not effective enough, therefore, plastics root
This is not by plated with electroless nickel, or not exclusively plating (test specimen 13).In H2SO4When concentration is higher than 80% volume (test specimen 14), occur
Adhesive force between plastics over etching, and chemical nickel coating and plastics is not enough.
Embodiment 2
ABS plastic (Novodur P2MC, purchased from Ineos) circular base disk with 7cm diameters is fixed to stainless steel
On silk.Then, as provided in table 4, matrix is undergone 4 minutes in the different pretreatments etching solution that 22 DEG C of temperature immerse the present invention
(method order is shown in table 3).Then, underwater cleaning matrix is being flowed about 1 minute.In subsequent cleaning, neutralize (method and step A
I) hydrochloric acid solutions of 300ml/l 36% (method and step A ii)) and are briefly immersed) after, based on palladium colloid (Adhemax
Aktivator NA, purchased from Atotech, 100ppm palladiums) colloidal activating dose in 40 DEG C of activated matrix, 3 minutes (method and steps
B))。
After subsequent cleaning, palladium removing particle containment vessel being removed at 40 DEG C 3 minutes, (Adhemax ACC1 accelerators, are purchased from
Atotech, method and step B i)).Then make matrix at 45 DEG C (Adhemax LFS, are obtained within 10 minutes without nickel plating under foreign current
From Atotech, method and step B ii)), cleaning, and in room temperature in 3.5A/dm2(Cupracid HT, are derived within 70 minutes for copper facing
Atotech, method and step C)).After cleaning, by plate in 70 DEG C of storages 60 minutes (method and step C i)).Then, width is cut out with knife
The plastic substrate bar of about 1cm metallization is spent, metal level is pulled away from plastics (ASTM B with Tensile Tester (being purchased from Instron)
533 1985,2009 again through).Obtain adhesive strength as shown in table 4.
Table 3：The order of method and step in embodiment 2
Table 4：According to the adhesive strength of the copper/nickel dam on different ABS mixtures of embodiment 2
From table 4 it became apparent that, by combining careful selection perchlorate concentration with sulfuric acid, can obtain very high attached
Force value.Test specimen 1 shows, the low concentration (ClO equivalent to 0.0016mol/l as 0.2g/l potassium chlorate3 -Concentration) foot
To obtain excellent adhesive force.Maximum is obtained in about 1.5g/l potassium chlorate scopes.Then, observable adhesive strength declines.Should
It is noted that being compared with being etched in the solution for only including sulfuric acid, composition (table 4, test specimen 9 comprising sulfuric acid and phosphate mixture
To 16) generally showing higher adhesion value in identical chloranion concentration, therefore particularly preferably.
Claims (14)
1. making the method for the nonconductive plastic material surface metalation of product, it the described method comprises the following steps：
A) frosting is etched with aqueous etching solution；
B the frosting) is handled with the solution of metallic colloid or metallic compound, the metal is selected from periodic table of elements I
Group 4 transition metal and periodic table of elements group VIII transition metal；And
C) metallization of plastic surface is made with metallization solution；
It is characterized in that the etching solution, which is included, obtains 0.01 to the chloranion source of 0.08mol/L chloranion concentration
With 50-80% volume sulfuric acid, wherein the etching solution be free of chromium III ions and chromium VI ions.
2. the method for claim 1, it is characterised in that in method and step A) in chloranion source in etching solution be selected from chlorine
Sour sodium and potassium chlorate.
3. the method for claim 1, it is characterised in that chloranion concentration is 0.01mol/L-0.06mol/L.
4. the method for claim 1, it is characterised in that chloranion concentration is 0.01mol/L-0.04mol/L.
5. the method for claim 1, it is characterised in that sulfate ion concentration is the volume of 60% volume -70%.
6. the method for claim 1, it is characterised in that second oxidation of the etching solution further comprising 2 to 20g/L amount
Agent, second oxidant has the standard oxidizing potential more than chloranion.
7. the method for claim 1, it is characterised in that the etching solution further includes phosphoric acid.
8. the method for claim 7, it is characterised in that phosphoric acid concentration is the volume of 10% volume -30%.
9. the method for claim 1, it is characterised in that method and step B) in metal be palladium.
10. the method for claim 1, it is characterised in that the frosting is made up of at least one nonconductive plastic material, and institute
State at least one nonconductive plastic material and be selected from acrylonitrile-butadiene-styrene copolymer, polyamide, makrolon and acrylic nitrile-butadiene
The mixture of diene-styrene copolymer and at least one other polymer.
11. the method for claim 1, it is characterised in that in method and step A) and B) between carry out method and step additionally below：
A i) frosting is handled in comprising the solution for the reducing agent of chloranion.
12. the method for claim 11, it is characterised in that the reducing agent is selected from hydroxylammonium sulfate, hydroxylammonium chloride and hydrogen peroxide.
13. the method for claim 1, it is characterised in that in method and step A) and B) between carry out method and step additionally below：
A i) frosting is handled in the solution containing the nertralizer comprising hydroxyl ion source.
14. the method for any one of preceding claims, it is characterised in that in method and step B) and C) between carry out additionally below
Method and step：
B i) frosting is handled in acidic aqueous solution, and
B ii) make the frosting electroless metallising in metallization solution.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| LT2012042A LT5997B (en) | 2012-06-05 | 2012-06-05 | Process for preparing plastics surfaces prior to their chemical metallization |
| LT2012042 | 2012-06-05 | ||
| PCT/EP2013/061568 WO2013182590A1 (en) | 2012-06-05 | 2013-06-05 | Process for metallizing nonconductive plastic surfaces |
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| CN104364421B true CN104364421B (en) | 2017-07-21 |
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| US (1) | US20150129540A1 (en) |
| EP (1) | EP2855731B1 (en) |
| JP (1) | JP6180518B2 (en) |
| KR (1) | KR102130947B1 (en) |
| CN (1) | CN104364421B (en) |
| BR (1) | BR112014029353B1 (en) |
| CA (1) | CA2875323C (en) |
| ES (1) | ES2575001T3 (en) |
| LT (1) | LT5997B (en) |
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| LT6070B (en) | 2012-12-07 | 2014-09-25 | Atotech Deutschland Gmbh | Preparation of plastic surface for chemical metallization process |
| US10920321B2 (en) | 2014-05-30 | 2021-02-16 | Uab Rekin International | Chrome-free adhesion pre-treatment for plastics |
| US9506150B2 (en) | 2014-10-13 | 2016-11-29 | Rohm And Haas Electronic Materials Llc | Metallization inhibitors for plastisol coated plating tools |
| EP3181726A1 (en) | 2015-12-18 | 2017-06-21 | ATOTECH Deutschland GmbH | Etching solution for treating nonconductive plastic surfaces and process for etching nonconductive plastic surfaces |
| US20200087791A1 (en) * | 2017-06-01 | 2020-03-19 | Jcu Corporation | Multi-stage resin surface etching method, and plating method on resin using same |
| FR3074808B1 (en) | 2017-12-13 | 2020-05-29 | Maxence RENAUD | GALVANOPLASTY TOOLS |
| CN108624907A (en) * | 2018-04-26 | 2018-10-09 | 复旦大学 | Nonmetal basal body efficient catalytic electrode and preparation method thereof |
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2012
- 2012-06-05 LT LT2012042A patent/LT5997B/en unknown
-
2013
- 2013-06-05 PT PT137275954T patent/PT2855731E/en unknown
- 2013-06-05 CA CA2875323A patent/CA2875323C/en active Active
- 2013-06-05 KR KR1020147034195A patent/KR102130947B1/en active IP Right Grant
- 2013-06-05 ES ES13727595.4T patent/ES2575001T3/en active Active
- 2013-06-05 BR BR112014029353-8A patent/BR112014029353B1/en active IP Right Grant
- 2013-06-05 CN CN201380029727.6A patent/CN104364421B/en active Active
- 2013-06-05 US US14/399,987 patent/US20150129540A1/en not_active Abandoned
- 2013-06-05 JP JP2015515506A patent/JP6180518B2/en active Active
- 2013-06-05 WO PCT/EP2013/061568 patent/WO2013182590A1/en active Application Filing
- 2013-06-05 PL PL13727595.4T patent/PL2855731T3/en unknown
- 2013-06-05 EP EP13727595.4A patent/EP2855731B1/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4919768A (en) * | 1989-09-22 | 1990-04-24 | Shipley Company Inc. | Electroplating process |
| US5160600A (en) * | 1990-03-05 | 1992-11-03 | Patel Gordhanbai N | Chromic acid free etching of polymers for electroless plating |
| CN1508287A (en) * | 2002-12-18 | 2004-06-30 | Method for activating substrate for plating on plastic | |
| LT2008082A (en) * | 2008-10-28 | 2010-05-25 | Chemijos Institutas | Process for etching polyimide and other plastics |
| CN102409320A (en) * | 2011-11-29 | 2012-04-11 | 沈阳工业大学 | Electroplating pretreatment method for acrylonitrile butadiene styrene (ABS) plastic surface |
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| BR112014029353B1 (en) | 2021-04-20 |
| CA2875323A1 (en) | 2013-12-12 |
| LT5997B (en) | 2014-02-25 |
| BR112014029353A2 (en) | 2017-06-27 |
| KR102130947B1 (en) | 2020-07-08 |
| EP2855731B1 (en) | 2016-03-23 |
| JP6180518B2 (en) | 2017-08-16 |
| KR20150024327A (en) | 2015-03-06 |
| ES2575001T3 (en) | 2016-06-23 |
| CN104364421A (en) | 2015-02-18 |
| PL2855731T3 (en) | 2016-09-30 |
| PT2855731E (en) | 2016-06-15 |
| US20150129540A1 (en) | 2015-05-14 |
| WO2013182590A1 (en) | 2013-12-12 |
| CA2875323C (en) | 2020-08-25 |
| JP2015518924A (en) | 2015-07-06 |
| EP2855731A1 (en) | 2015-04-08 |
| LT2012042A (en) | 2013-12-27 |
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