CN101654564B - Plastic composition and surface selective metallization process thereof - Google Patents
Plastic composition and surface selective metallization process thereof Download PDFInfo
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- CN101654564B CN101654564B CN2008101419873A CN200810141987A CN101654564B CN 101654564 B CN101654564 B CN 101654564B CN 2008101419873 A CN2008101419873 A CN 2008101419873A CN 200810141987 A CN200810141987 A CN 200810141987A CN 101654564 B CN101654564 B CN 101654564B
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- plastics composite
- photocatalyst
- plastic composition
- plating
- metallization process
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- 229920003023 plastic Polymers 0.000 title claims abstract description 87
- 239000004033 plastic Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 68
- 230000008569 process Effects 0.000 title claims abstract description 25
- 238000001465 metallisation Methods 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 238000007747 plating Methods 0.000 claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims description 64
- -1 cation salt Chemical class 0.000 claims description 31
- 238000000608 laser ablation Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000007772 electroless plating Methods 0.000 claims description 13
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 7
- 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 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 5
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 4
- 241000931526 Acer campestre Species 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910013641 LiNbO 3 Inorganic materials 0.000 claims description 2
- 229910017640 MgSb Inorganic materials 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004962 Polyamide-imide Substances 0.000 claims description 2
- 239000004693 Polybenzimidazole Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 229910002367 SrTiO Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229920013662 Zylonite Polymers 0.000 claims description 2
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 claims description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 claims description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002312 polyamide-imide Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 2
- 229920003987 resole Polymers 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 9
- 239000002923 metal particle Substances 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 2
- 238000010329 laser etching Methods 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 230000005855 radiation Effects 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 238000002203 pretreatment Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 238000005253 cladding Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 229920006351 engineering plastic Polymers 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 102220542295 39S ribosomal protein L15, mitochondrial_R95E_mutation Human genes 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- OSBSXTGABLIDRX-UHFFFAOYSA-N 5-methylidenecyclohexa-1,3-diene Chemical compound C=C1CC=CC=C1 OSBSXTGABLIDRX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BVLZACQMNXCBES-UHFFFAOYSA-N butanoic acid;silver Chemical compound [Ag].CCCC(O)=O BVLZACQMNXCBES-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000010330 laser marking Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method 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
- FTNNQMMAOFBTNJ-UHFFFAOYSA-M silver;formate Chemical compound [Ag+].[O-]C=O FTNNQMMAOFBTNJ-UHFFFAOYSA-M 0.000 description 1
- CYLMOXYXYHNGHZ-UHFFFAOYSA-M silver;propanoate Chemical compound [Ag+].CCC([O-])=O CYLMOXYXYHNGHZ-UHFFFAOYSA-M 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 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 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- C23C18/22—Roughening, e.g. by etching
Abstract
The invention provides a plastic composition and a surface selective metallization process thereof. The plastic composition comprises a high molecular polymer and a photocatalyst, wherein the mass ratio of the polymer to the photocatalyst is 1 to 100. The surface selective metallization process of the plastic composition comprises the following steps: performing laser etching on the surface of the plastic composition; putting the plastic composition after the laser etching into an aqueous solution containing a metal ion salt and a cavity sacrificial agent to perform photocatalysis reduction reaction so as to obtain a plastic composition with nanometer metal particles on the surface; and finally performing metal chemical plating. By adopting the plastic composition and the surface selective metallization process of the plastic composition, the bonding force of a plating layer and the chemical plating precision are very high.
Description
[technical field]
The present invention relates to a kind of plastics composite and surface selective metallization process thereof.
[background technology]
Traditional electron trade, main chemistry and the photochemical method of relying on of the circuit of information industry preparation in these methods wiring process in the early stage, must could be accomplished through multiple working procedures such as plate, exposure, development and etchings.Along with developing rapidly of electronic industry, to the time of product design and development, price, the small-scale production ability is all had higher requirement.Operation is too much, the shortcoming of excessive cycle and traditional technology demonstrates.
Therefore, the laser direct-writing technology in the electronic industry is arisen at the historic moment.A kind of laser direct forming (Laser Direct Structuring-LDS) technology has been invented by LPKF D. O. O.; The plastics that employing is added with certain non-conductive organo-metallic mixture are raw material; Directly be incident upon laser beam on the moulding surface, the part of illuminated mistake can be carried out the electroless deposition metal.Plastic component need not process special alligatoring, sensitization, activation treatment in this technology, directly after laser radiation, can carry out electroless plating, and technical process is short, simple to operate, produces flexibility greatly, live width, line-spacing precision height.But employing LDS technology must be with the plastics with LDS performance; These plastics include certain non-conductive organo-metallic mixture; And when carrying out the laser radiation plastic component, have only the surface to need the position of electroless plating activation to take place through laser radiation, activation does not take place in other positions without laser radiation; Therefore the organo-metallic mixture in the activation plastics does not obtain utilizing, and causes very big waste.
A kind of laser induced selective chemical plating method is disclosed among the CN1772949A; This method adopts Vinylpyrrolidone polymer/silver colloid to be coated on the matrix; Carry out the selectivity radiation with Ultra-Violet Laser; Silver ions in the colloidal silver of radiation areas is reduced into metallic silver corpuscle and embeds in the matrix, is cleaned without the colloidal silver of radiation areas, implements electroless plating then and can obtain the patterned chemical plating of micron order on the matrix.But adopt this method to carry out selective chemical plating, relate to silver-colored pollution problem.Because the Silver Nitrate that uses in this patent, silver formate, silver acetate, silver propionate, butyric acid silver decompose under the sun exposure and the situation of being heated easily; Therefore in actual mechanical process; Cause the silver in non-laser radiation zone to pollute easily,, also be difficult to remove fully even clean; Behind electroless copper, the non-laser radiation of matrix surface zone also has part coating; In addition, through the mode of painting polyethylene pyrrolidone/silver colloid, adopt laser radiation that silver particles is embedded in the matrix then, binding force of cladding material is relatively poor during last electroless plating.
[summary of the invention]
The present invention is directed to the deficiency of prior art, proposed a kind of plastics composite and surface selective metallization process thereof.
The invention provides a kind of plastics composite, comprise high molecular polymer, photocatalyst, wherein the mass ratio of high molecular polymer, photocatalyst is 1～100.
The present invention also provides a kind of plastics composite surface selective metallization process method provided by the present invention, comprises following steps:
(a) laser ablation plastics composite surface; Plastics composite behind the laser ablation is placed the aqueous solution that contains metal cation salt and hole sacrifice agent; Under the light source irradiation; In the exposed part generation metals ion photo catalytic reduction reaction that laser ablation causes, make the plastics composite surface that the selective deposition metallics take place;
(b) plastics composite that the selective deposition metallics takes place is carried out electroless plating, obtain plating piece.
Of the present invention being contemplated that: the plastics composite that contains high molecular polymer and photocatalyst is under laser irradiation condition; The regional instantaneous temperature of laser radiation is very high; Be higher than the plastics composite second-order transition temperature; High molecular polymer softening sinking of moment in the plastics composite, the emersion from high molecular polymer that the photocatalyst in the plastics composite is then relative comes, and makes that the part photocatalyst in the plastics composite exposes out; Then the plastics composite behind the laser ablation is put into the aqueous solution that contains metal cation salt, hole sacrifice agent; Under can the light source irradiation condition of exciting light catalyzer; The photocatalyst that is exposed to the plastics composite surface can obtain the nano level metal particle with the reduction of solution metal ion; Carry out the metallochemistry plating at last.
Adopt plastics composite provided by the present invention and surface selective metallization process thereof, following advantage compared with prior art arranged:
(1) photocatalyst is distributed in plastics composite inside, exposes the part photocatalyst under the laser irradiation condition, depositing nano metallics and carry out electroless plating on this surface, and binding force of cladding material is high;
(2) during selective metallization process, only at the photocatalyst surface depositing nano metallics that exposes out, be that electroless plating is carried out in the active site then with the nano metal particles, precision is very high.
[embodiment]
The invention provides a kind of plastics composite, comprise high molecular polymer, photocatalyst, wherein the mass ratio of high molecular polymer, photocatalyst is 1～100.
According to plastics composite provided by the present invention, wherein said high molecular polymer is the various high molecular polymer that is used for the plastics field known in those skilled in the art.Among the present invention, said high molecular polymer comprises Vilaterm, Vestolen PP 7052, PS, SE, polymethylmethacrylate, polyethylene terephthalate, gathers para Toluic Acid's butanediol ester, polymeric amide, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyimide, polyamide-imide, polybenzimidazole, urethane, polypyrrole, Polythiophene, polyaniline, gather methylene-benzene, styrene-acrylonitrile interpolymer, resol, urea-formaldehyde resin, polyoxymethylene, polyetheretherketone, polyetherketone, polyethersulfone, polyphenylene sulfide, chlorinatedpolyethylene, styrene-butadiene-styrene block polymer, styrene-ethylene-butadiene-styrene block polymer, tetrafluoroethylene, epoxy resin, polyoxymethylene, ppe, polysulfones, FM, cellulose acetate butyrate, zylonite, zellglas, urea formaldehyde, melamino-formaldehyde, melamine urea-formaldehyde, polyethersulfone, PPSU, gather amino span and come acid amides, gather in the triazine one or more.All preferably adopt ABS in the embodiment of the invention, but be not limited to this.
Said photocatalyst is various one type of material that under the exciting of photon, can play katalysis.Common photocatalyst has titanium oxide (TiO2), zinc oxide (ZnO), White tin oxide (SnO2), ZIRCONIUM DIOXIDE 99.5 (ZrO2), Cadmium Sulfide multiple oxide compound sulfide semiconductors such as (CdS).Among the present invention, said photocatalyst is selected from TiO
2, Cu
2O, Fe
2O
3, ZnO, ZnS, Nb
2O
5, MoO
3, CdS, In
2O
3, SnO
2, Ta
2O
5, WO
3, Bi
2O
3, BaTiO
3, SrTiO
3, CaTiO
3, MgTiO
3, PbTiO
3, BaSnO
3, CaSnO
3, InSnO
3, CaSnO
3, NiSnO
3, PbSnO
3, LiNbO
3, KNbO
3, BaSb
2O
6, PbSb
2O
6, MgSb
2O
6, NaTaO
3, KTaO
3, Ba
5Ta
4O
15, Ca
6Bi
6O
15, in the sodium wolframate, potassium wolframate, lithium molybdate, Sodium orthomolybdate, ammonium molybdate, zinc molybdate, calcium molybdate one or more.All preferably adopt titanium oxide in the embodiment of the invention, but be not limited to this.
The present invention also provides a kind of said plastics composite surface selective metallization process method, comprises following steps:
(a) laser ablation plastics composite surface; Plastics composite behind the laser ablation is placed the aqueous solution that contains metal cation salt and hole sacrifice agent; Under the light source irradiation; In the exposed part generation metals ion photo catalytic reduction reaction that laser ablation causes, make the plastics composite surface that the selective deposition metallics take place;
(b) plastics composite that the selective deposition metallics takes place is carried out electroless plating, obtain plating piece.
According to method provided by the present invention; Wherein said laser ablation is: the plastics composite base material is positioned under the laser shines; Because the regional instantaneous temperature of laser radiation is very high, is higher than the plastics composite second-order transition temperature, the high molecular polymer softening sinking of moment in the plastics composite; The emersion from high molecular polymer that photocatalyst in the plastics composite is then relative comes, and makes that the part photocatalyst in the plastics composite exposes out.And without the zone of laser radiation, the no considerable change in surface.Thereby through after the laser radiation, plastics composite substrate surface selectivity is distributed with photocatalyst.
Wherein, the condition of said laser ablation is conventionally known to one of skill in the art: mark electric current 0～24A, and frequency 1～60KHz, middle time-delay 0～30ms fills spacing >=0.01mm, etching time 1～60s.The optical maser wavelength that said laser ablation adopted is 200～1064nm, all is preferably 1064nm in the embodiment of the invention, but is not limited to this.
To pass through the plastics composite of laser ablation and put into the aqueous solution that contains metal cation salt and hole sacrifice agent, metals ion issues third contact of a total solar or lunar eclipse catalytic reduction reaction at illumination condition, the photocatalyst surface metal refining particle that is exposing.
Wherein, the metal that said metal cation salt adopted comprises one or more among Cu, Au, Ni, Co, Fe, Zn, Pd, Pt, Ru, Rh, Re, Os, the Ir.
Said hole sacrifice agent is claimed organic electronic donor again, is to be used for catching one type of material that photohole impels carrier separation, improves photocatalysis efficiency.Among the present invention, said hole sacrifice agent is selected from one or more in methyl alcohol, sulphite, the organic dye.Wherein, Said organic dye is the known various dyestuffs of art technology, like N3, N719, N621, N712, N749, Z235, N773, N790, N820, N823, N845, N886, N945, K8, K9, K19, K23, K27, K29, K51, K60, K66, K69, K73, K77, Z316, Z907, Z910.
According to method provided by the present invention, the mass ratio of wherein said metal cation salt and hole sacrifice agent is 0.1～100.
Said photocatalyst makes the electronics in the molecular orbital(MO) leave valence band (Valence band) under the irradiate light of certain wavelength and transits to conduction band (conduction band); Generate electron-hole pair; Said metals ion obtains the reaction of electronics generation photo catalytic reduction; Said hole sacrifice agent provides electronics, eliminates the hole.Among the present invention, the main emission wavelength of the light source that the reaction of the photo catalytic reduction of said metals ion is adopted is 180～1000nm.
Through the photo catalytic reduction reaction, metallics is deposited on photocatalyst surface.With said metallics is the active site, carries out conventional chemical plating, get final product required plating piece.Said electroless plating technology is conventionally known to one of skill in the art, is preferably the metal plating that reductibility is not better than metallics.Among the embodiment provided by the present invention, all preferred electroless copper, but be not limited to this.
Said metallics is a nano level, and median size is 10～100nm.
Among the present invention, said plastics composite is carried out also need carrying out pre-treatment before the laser ablation.Said pre-treatment, its technology is conventionally known to one of skill in the art.The present invention does not have particular requirement to the method for pre-treatment, and generally speaking, pre-treatment comprises carries out oil removing and alligatoring successively with the plastics composite substrate surface.
Oil removing in the said pre-treatment, purpose are to remove the grease of plastics composite substrate surface and oxide compound thereof.The method of oil removing is a whole bag of tricks known in those skilled in the art.Adopt among the present invention: the plastics composite base material is dipped to contains NaOH1mol.L
-1, Na
2CO
31mol.L
-1, sodium laurylsulfonate 0.1mol.L
-1Solution in 5～10min, solution temperature is 50～60 ℃.Take out the back water and clean, be dipped to 1mol.L
-1Phosphoric acid solution in 5～10min, take out water then and clean.
Alligatoring in the said pre-treatment, purpose are to make the plastics composite surface produce spongy micropore hole and hydrophilicity, satisfy the requirement of metal plating bonding force intensity.The method of alligatoring is a whole bag of tricks known in those skilled in the art.Adopt among the present invention: with containing chromic anhydride, sulfuric acid, CrCl
36H
2Solution soaking plastics composite base material 10～15min of O, solution temperature is 60～70 ℃, takes out the back water and cleans.Also can adopt and contain NaOH, KMnO
4Solution soaking plastics composite base material 10～15min, solution temperature is 60～70 ℃.Under 40～50 ℃, embathe 5～8min then with Hydrogen chloride.Taking out the back water cleans.
Among the present invention, the not special restriction of the washing step in said oil removing and the coarsening process, washing times is cleaned as long as the treatment solution of plastics composite substrate surface fully removed, and under the preferable case, the washing times that after said oil removing, carries out is 1～3 time; The washing times that after said alligatoring, carries out is 4～6 times.The used water of washing step is various water of the prior art, and like municipal tap water, deionized water, zero(ppm) water, pure water or their mixture, the present invention is preferably deionized water.
According to method provided by the present invention, before electroless plating, also need to clean to soaking the plastics composite base material that contains the metal cation salt and the hole sacrifice agent aqueous solution.Said cleaning is conventionally known to one of skill in the art, and the present invention does not have particular requirement, does not give unnecessary details at this.
Among the present invention, non-laser radiation region surface does not have photocatalyst, can the metal refining particle, also can not produce metal plating, thereby the electroless plating precision is very high.
Below specify plastics composite provided by the present invention and surface selective metallization process thereof through specific embodiment.Following embodiment only is used to further specify the present invention, rather than limits scope of the present invention.
[embodiment 1]
Present embodiment is used to explain plastics composite provided by the invention and surface selective metallization process thereof.
(1) preparation of plastics composite: (Dongguan C2950) with the 1kg titania powder, mixes with prosperous engineering plastics ltd to take by weighing the 1kgABS plastic grain; Use extrusion machine (Nanjing New Times dynamo-electric industry and trade ltd; XSD-35) push, (sea day plastics machinery ltd HTF60W1) injects to adopt injection moulding machine then; Obtain the ABS plastic compsn base material of 4.5cm * 14.5cm, be designated as ABS-I.
(2) pretreatment of base material: the ABS-I that step (1) is made puts into and contains NaOH1mol.L
-1, Na
2CO
31mol.L
-1, 0.1mol.L
-1In the solution of sodium lauryl sulphate, embathe 10min under 50 ℃, take out the back and uses washed with de-ionized water, put into phosphoric acid 1mol.L then
-1Solution in embathe 10min, use washed with de-ionized water after the taking-up.ABS-I after cleaning put into contain H
2SO
4200ml.L
-1, CrO
34mol.L
-1, CrCl
36H
2O0.02mol.L
-1Solution in, solution temperature is 70 ℃, soak time 10min.Use washed with de-ionized water after the taking-up.
(3) solution preparation: in 200ml water, add 3.2g copper sulfate, 2ml formaldehyde, 6gEDTA
.2Na, the 4g Seignette salt, and use NaOH to regulate pH value to be 12.5,50 ℃ of following constant temperature water baths, to obtain chemical plating bath; Take by weighing the cupric nitrate of 3g and the methyl alcohol of 20mL (AR level), add deionized water and be mixed with 200ml metals ion-hole sacrifice agent aqueous solution.
(4) laser ablation: with vertically being affixed on the glass wall after the ABS-I drying after the cleaning of step (2) gained.(Taide, Shenzhen laser Science and Technology Ltd. DPY-M50) carries out etching to ABS-I, and optical maser wavelength is 1064nm, certain power 50W to use the Taide laser marking machine.Etching condition: mark electric current 13.0A, frequency 5KHZ, step-length 4unit, middle time-delay 100 μ s fill spacing 0.05mm, etching time 10s.
(5) photo catalytic reduction reaction: the ABS-I that will pass through step (4) puts into metals ion-hole sacrifice agent aqueous solution of (3) being prepared; Place ultraviolet high voltage mercury lamp (Shenzhen Bo Lida Electro-optical Technology, INC. (US) 62 Martin Road, Concord, Massachusetts 017; Wavelength 365nm) irradiation down, irradiation time is 10min.
(6) electroless copper: the ABS-I that will pass through the photo catalytic reduction reaction puts into the 100mL deionized water and cleans; After the taking-up, put into the chemical plating bath that step (3) prepared and carry out electroless copper, 50 ℃ of constant temperature water baths take out behind the 15min, promptly obtain plating piece A1.
[embodiment 2]
Present embodiment is used to explain plastics composite provided by the invention and surface selective metallization process thereof.
Adopt with embodiment 1 identical method the plating of selective metal chemistry is carried out on plastics composite base material ABS-I surface; Difference is: (Dongguan is with prosperous engineering plastics ltd, C2950) with the 20g titania powder to take by weighing the 2kgABS plastic grain in the step (1).The ABS plastic compsn base material for preparing is designated as ABS-II.
Obtain plating piece according to the method described above, be designated as A2.
[embodiment 3]
Present embodiment is used to explain plastics composite provided by the invention and surface selective metallization process thereof.
Adopt with embodiment 1 identical method the plating of selective metal chemistry is carried out on plastics composite base material ABS-I surface; Difference is: (Science and Technology Ltd. of HTC is pacified by the Shenzhen with ir lamp in the step (5); PHILIPS infrared lamp IN R95E; Wavelength 850nm) uv lamp that is adopted in the alternative embodiment 1, irradiation time are 10min.
Obtain plating piece according to the method described above, be designated as A3.
[embodiment 4]
Present embodiment is used to explain plastics composite provided by the invention and surface selective metallization process thereof.
Adopt with embodiment 2 identical methods the plating of selective metal chemistry is carried out on plastics composite base material ABS-II surface; Difference is: (Science and Technology Ltd. of HTC is pacified by the Shenzhen with ir lamp in the step (5); PHILIPS infrared lamp IN R95E; Wavelength 850nm) uv lamp that is adopted in the alternative embodiment 2, irradiation time are 10min.
The gained plating piece is designated as A4 according to the method described above.
[embodiment 5]
Present embodiment is used to explain plastics composite provided by the invention and surface selective metallization process thereof.
Adopt with embodiment 1 identical method the plating of selective metal chemistry is carried out on plastics composite base material ABS-I surface; Difference is: in the step (3); Take by weighing the cupric nitrate in the Palladous chloride alternative embodiment 1 of 2g, be mixed with metals ion-hole sacrifice agent aqueous solution.
Obtain plating piece according to the method described above, be designated as A5.
[embodiment 6]
Present embodiment is used to explain plastics composite provided by the invention and surface selective metallization process thereof.
Adopt with embodiment 2 identical methods the plating of selective metal chemistry is carried out on plastics composite base material ABS-II surface; Difference is: in the step (3); Take by weighing the cupric nitrate in the Palladous chloride alternative embodiment 2 of 2g, be mixed with metals ion-hole sacrifice agent aqueous solution.
Obtain plating piece according to the method described above, be designated as A6.
[embodiment 7]
Present embodiment is used to explain plastics composite provided by the invention and surface selective metallization process thereof.
Adopt with embodiment 1 identical method the plating of selective metal chemistry is carried out on plastics composite base material ABS-I surface; Difference is: in the step (3); Take by weighing the methyl alcohol of the 20mL in the 20mg organic dye N3 alternative embodiment 1, add metals ion-hole sacrifice agent aqueous solution that deionized water is mixed with 200mL.
Obtain plating piece according to the method described above, be designated as A7.
[embodiment 8]
Present embodiment is used to explain plastics composite provided by the invention and surface selective metallization process thereof.
Adopt with embodiment 2 identical methods the plating of selective metal chemistry is carried out on plastics composite base material ABS-II surface; Difference is: in the step (3); Take by weighing the methyl alcohol of the 20mL in the 20mg organic dye N3 alternative embodiment 2, add metals ion-hole sacrifice agent aqueous solution that deionized water is mixed with 200mL.
Obtain plating piece according to the method described above, be designated as A8.
[Comparative Examples 1]
Adopt with embodiment 1 in identical method the selective metal chemistry carried out on plastic basis material surface commonly used in the prior art plate; Difference is: in the step (1); (Dongguan is with prosperous engineering plastics ltd directly to take by weighing the 2kgABS plastic grain; C2950) replace 1kgABS plastic grain and 1kg titania powder among the embodiment 1, be compression molded into the ABS engineering plastics base material of 4.5cm * 14.5cm, be designated as ABS-III.Adopt with embodiment 1 identical method ABS-III is carried out pre-treatment, laser ablation, photo catalytic reduction reaction and electroless copper step, the gained plating piece is designated as D1.
[Comparative Examples 2]
Disclosed technical scheme is carried out the plating of selective metal chemistry to the plastic basis material surface among the employing CN1772949A.
Adopt the ABS engineering plastics base material ABS-III of preparation in the Comparative Examples 1, adopt then and ABS-III is carried out pre-treatment with embodiment 1 identical method.
Take by weighing the 0.10g Silver Nitrate, add in the 10ml ethanol, after 20 ℃ of following stirring and dissolving, add the 0.2g Vinylpyrrolidone polymer again, continue under 20 ℃, to be stirred to whole dissolvings, obtain Vinylpyrrolidone polymer/silver colloid; (Sheng Hua Chemical Industry Science Co., Ltd in Guangzhou 1110N/1112N) is uniformly coated on gained Vinylpyrrolidone polymer/silver colloid through on the ABS-III after the pre-treatment, dries naturally to adopt spin coater.
Adopt and the ABS-III that has been coated with Vinylpyrrolidone polymer/silver colloid is carried out radiation of Ultra-Violet Laser selectivity and electroless copper with embodiment 1 identical method.The gained plating piece is designated as D2.
Performance test:
The test of sample binding force of cladding material, be called for short cross-hatching:
Adopting the disclosed method of GB9286-88 that embodiment 1～8 and Comparative Examples 1～2 gained plating piece A1～A8 are carried out bonding force with D1～D2 tests: Sample A 1～A8 and D1～D2 are applied on the model; After waiting to parch; Employing have 6 facets multitool sheet cutting unit draw the parallel pulling 3～4cm of lattice tstr (German BYK company, 511 series), the cutting knife gap is 1mm; Six road cut channels are arranged, should cut and wear paint film; It is vertical with the former to use the same method then, cut channel six roads; Form many lattices like this.Stick on the grid and draw back rapidly from diagonal brush 5 times or with adhesive tape with soft brush,, and compare definite binding force of cladding material level with the cutting surface of 4 times of lens examinations test coatings.0 grade of sticking power the best generally surpasses 2 grades and just thinks that in protective system sticking power does not reach requirement.
0 grade of cut edge is level and smooth fully, and none lattice comes off;
1 grade has a little slice separates in otch infall coating, and the lattice district is influenced obviously to be no more than 5% but draw;
2 grades of notching edges or infall coating shedding be obviously greater than 5%, but influencedly be not more than 15%;
3 grades of coatings come off with big fragment along the edge section or all, between 15%～35%.
Experimental result is as shown in table 1 below.
Table 1
| Sample | Binding force of cladding material (/ level) |
| A1 | 0 |
| A2 | 1 |
| A3 | 1 |
| A4 | 1 |
| A5 | 0 |
| A6 | 1 |
| A7 | 2 |
| A8 | 2 |
| D1 | No coating |
| D2 | 3 |
Can find out that from the test result of table 1 embodiment 1～8 relatively finds out with Comparative Examples 1～2, adopt the binding force of cladding material of the plating piece that technical scheme provided by the present invention obtains obviously to be superior to prior art.
Can find out relatively that from embodiment 1～6 and the result of embodiment 7～8 adopting preferred version provided by the present invention is that the mass ratio of metal cation salt and hole sacrifice agent is, resulting binding force of cladding material height at 0.1～100 o'clock.
Find in the Comparative Examples 1,, do not have the deposition of nano metal, the basic coating that formed not during electroless plating owing to there is not the existence of photocatalyst through the comparative experiments result; The plating piece that obtains in the Comparative Examples 2 except that the zone of laser ablation has the coating, also has coating to exist without the zone of laser ablation, does not satisfy the requirement of circuit board pattern.Because before and after the laser ablation, even at room temperature, silver salt also is prone to see light, decomposes, make laser not etch areas receive silver and pollute, cause the plating piece precision very poor at last.And adopt plating piece A1～A8 among the embodiment 1～8 that technical scheme provided by the present invention obtains; Because laser not etch areas surface does not have the existence of photocatalyst; The deposition that does not have nano metal particles, so the plating piece picture on surface is clear clearly demarcated behind the electroless copper, precision is very high.
Claims (9)
1. plastics composite surface selective metallization process method comprises following steps:
(a) laser ablation plastics composite surface; Plastics composite behind the laser ablation is placed the aqueous solution that contains metal cation salt and hole sacrifice agent; Under the light source irradiation; In the exposed part generation metals ion photo catalytic reduction reaction that laser ablation causes, make the plastics composite surface that the selective deposition metallics take place;
(b) plastics composite that the selective deposition metallics takes place is carried out electroless plating, obtain plating piece;
Said plastics composite comprises high molecular polymer, photocatalyst, and wherein the mass ratio of high molecular polymer, photocatalyst is 1～100.
2. method according to claim 1 is characterized in that: said high molecular polymer comprises Vilaterm, Vestolen PP 7052, PS, SE, polymethylmethacrylate, polyethylene terephthalate, gathers para Toluic Acid's butanediol ester, polymeric amide, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyimide, polyamide-imide, polybenzimidazole, urethane, polypyrrole, Polythiophene, polyaniline, styrene-acrylonitrile interpolymer, resol, urea-formaldehyde resin, polyoxymethylene, polyetheretherketone, polyetherketone, polyphenylene sulfide, chlorinatedpolyethylene, styrene-butadiene-styrene block polymer, styrene-ethylene-butadiene-styrene block polymer, tetrafluoroethylene, epoxy resin, ppe, polysulfones, FM, cellulose acetate butyrate, zylonite, zellglas, urea formaldehyde, melamino-formaldehyde, melamine urea-formaldehyde, gather amino span and come acid amides, gather in the triazine one or more.
3. method according to claim 1 is characterized in that: said photocatalyst comprises TiO
2, Cu
2O, Fe
2O
3, ZnO, ZnS, Nb
2O
5, MoO
3, CdS, In
2O
3, SnO
2, Ta
2O
5, WO
3, Bi
2O
3, BaTiO
3, SrTiO
3, CaTiO
3, MgTiO
3, PbTiO
3, BaSnO
3, CaSnO
3, InSnO
3, NiSnO
3, PbSnO
3, LiNbO
3, KNbO
3, BaSb
2O
6, PbSb
2O
6, MgSb
2O
6, NaTaO
3, KTaO
3, Ba
5Ta
4O
15, Ca
6Bi
6O
15, in the sodium wolframate, potassium wolframate, lithium molybdate, Sodium orthomolybdate, ammonium molybdate, zinc molybdate, calcium molybdate one or more.
4. method according to claim 1, wherein the optical maser wavelength that adopted of the said laser ablation of (a) step is 200～1064nm.
5. method according to claim 1, wherein the light source master emission wavelength that adopted of the said photo catalytic reduction of (a) step is 180～1000nm.
6. method according to claim 1, the metal that wherein said metal cation salt adopted comprises one or more among Cu, Au, Ni, Co, Fe, Zn, Pd, Pt, Ru, Rh, Re, Os, the Ir.
7. method according to claim 1, wherein the said hole of (a) step sacrifice agent is selected from one or more in methyl alcohol, sulphite, the organic dye.
8. method according to claim 1, wherein in the said solution of (a) step, the mass ratio of metal cation salt and hole sacrifice agent is 0.1～100.
9. method according to claim 1 is characterized in that: the median size of said metallics is 10～100nm.
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| PCT/CN2009/073466 WO2010022641A1 (en) | 2008-08-23 | 2009-08-24 | Plastic composition and method of selective metallization on the surface thereof |
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