CN101490310B - Process for metallization of plastic surfaces - Google Patents
Process for metallization of plastic surfaces Download PDFInfo
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- CN101490310B CN101490310B CN2007800273670A CN200780027367A CN101490310B CN 101490310 B CN101490310 B CN 101490310B CN 2007800273670 A CN2007800273670 A CN 2007800273670A CN 200780027367 A CN200780027367 A CN 200780027367A CN 101490310 B CN101490310 B CN 101490310B
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- Prior art keywords
- frosting
- liquid
- metallising
- catalyst
- compound
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- 238000000034 method Methods 0.000 title claims abstract description 83
- 229920003023 plastic Polymers 0.000 title claims abstract description 31
- 239000004033 plastic Substances 0.000 title claims abstract description 31
- 238000001465 metallisation Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 3
- 150000007522 mineralic acids Chemical class 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 79
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 48
- 229910052763 palladium Inorganic materials 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 230000004913 activation Effects 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- 229920002521 macromolecule Polymers 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 10
- 239000011707 mineral Substances 0.000 claims description 10
- -1 ethylenediamines compound Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 238000007772 electroless plating Methods 0.000 claims description 5
- 230000002708 enhancing effect Effects 0.000 claims description 5
- 238000009713 electroplating Methods 0.000 claims description 4
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000010970 precious metal Substances 0.000 claims description 2
- 238000007747 plating Methods 0.000 abstract description 60
- 238000000151 deposition Methods 0.000 abstract description 33
- 230000008021 deposition Effects 0.000 abstract description 33
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 238000005530 etching Methods 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract 3
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 42
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 41
- 239000000243 solution Substances 0.000 description 23
- 230000000274 adsorptive effect Effects 0.000 description 21
- 229910052759 nickel Inorganic materials 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012286 potassium permanganate Substances 0.000 description 11
- 238000007598 dipping method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000004417 polycarbonate Substances 0.000 description 8
- 229920000515 polycarbonate Polymers 0.000 description 8
- 229920007019 PC/ABS Polymers 0.000 description 6
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 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 6
- 229920000083 poly(allylamine) Polymers 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229920001207 Noryl Polymers 0.000 description 5
- 239000004727 Noryl Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229940045713 antineoplastic alkylating drug ethylene imines Drugs 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005649 polyetherethersulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention aims at providing a practical process for chrome-free metallization of plastic surfaces by which a plating film adhering tightly to the surface of a plastics part can be formed and which is free from the deposition on a jig. A process for the metallization of plastic surfaces which is characterized by treating a plastics part with an etching fluid containing both a permanganate and an inorganic acid, treating the resulting plastics part with a potentiator fluid for the impartment of a catalyst which contains a compound exhibiting selective adsorption to functional groups exposed on the surface of the plastics part, imparting a catalyst to the treated plastics part with a catalyst imparting fluid, and then subjecting the resulting plastics part to metal plating.
Description
Technical field
The present invention relates to the method for metallising of frosting, in more detail, relate to a kind of in the plating operation not can clamping by the chucking surface of plated article on deposition plating (coating), but only on frosting, form the method for plated film with high tack.
Background technology
Past, to acronitrile-butadiene-styrene (ABS) resin, when polycarbonate/acrylonitrile butadiene styrene frostings such as (PC/ABS) is implemented metalized by plating, in order to improve the tack between frosting and the plated film, be known that the etching processing method that before plating is handled, makes the frosting roughening with chromic acid and vitriolic mixed solution.
Yet, in above-mentioned etch processes, use deleterious 6 valency chromium, and under the high temperature more than 60 ℃, carry out operation, therefore, the operating environment variation, and its wastewater treatment must be noted that also this is the problem that exists.In addition, in the plating process that after above-mentioned etch processes, carries out, when carrying out plating on the frosting that is difficult to deposition plating at PC/ABS etc. or when carrying out direct plating on the ADSORPTION OF GOLD metal catalyst that is being called as direct plating, in order to increase the absorption of catalyst metal, must regulate processing, and, on chucking surface, also tend to deposition plating by carrying out this processing.Therefore,, must change anchor clamps, having the problem of the non-constant of operation transferring to when electroplating from regulate handling.
Owing to there are these problems, therefore, be desirable to provide a kind of etching reagent that can replace chromic acid and vitriolic mixed solution, for example, according to reports, mixed solution with permanganate and phosphoric acid replaces these etching reagents to carry out etch processes, then handles etc. with ionized catalyst liquid, implements the Chrome-free plating technic (patent documentation 1) of plating then.
Yet, in above-mentioned technology, use ionized catalyst liquid to handle, though the adsorptive capacity of catalyst metal on frosting increased, but catalyst metal also is adsorbed onto on the coatingsurface of anchor clamps, therefore, meeting while deposition plating on frosting and chucking surface in plating process subsequently, this is the problem that exists.In addition, in this technology,, therefore also there is the problem that lacks practicality owing to be used for catalyst metal reductive reductive agent natural decomposition.Patent documentation 1:WO2005/094394 brochure
Summary of the invention
Invent problem to be solved
Therefore, problem of the present invention is, provide a kind of and in the metallization of plastic surface technology of Chrome-free, can form the plated film that fully adheres to frosting, and method for metallising that can the frosting that the practicality of deposition plating is high on anchor clamps.Be used to solve the means of problem
The inventor etc. have carried out meticulous research in order to solve above-mentioned problem, found that, the etch processes liquid that contains permanganate etc. by use is handled frosting, and then give enhancing liquid with the catalyzer that contains specific compound and handle, just can so that, give in the processing at catalyzer subsequently, catalyst metal optionally is adsorbed on the frosting, and its adsorptive capacity is increased.And then, after above-mentioned catalyzer is given processing, then carry out plating when handling, can realize the plating that fully adheres to frosting, and, can be on the anchor clamps coatingsurface deposition plating, so far finished the present invention.
Promptly, the invention provides a kind of method for metallising of frosting, it is characterized in that, with the etch processes liquid that contains permanganate and mineral acid plastics are handled, then, to plastics through above-mentioned processing, give and strengthen liquid and handle with containing the catalyzer that the functional group of exposing on this frosting is had a compound of selecting adsorptivity, and then, give catalyzer with catalyst-imparting treatment solution to given the enhancing plastics that liquid was handled by above-mentioned catalyzer, then, the above-mentioned plastics of having given catalyzer are implemented metal deposition.The invention effect
According to the method for metallising of frosting of the present invention, the plating that can fully adhere at frosting, and also plated film can not deposit on the anchor clamps, is the high method of practicality therefore.In addition, according to the method for metallising of frosting of the present invention, owing to can increase the adsorptive capacity of catalyst metal on frosting, therefore, also can similarly carry out plating being not easy according in the past method to make on the plastics of catalyst metal absorption.
Therefore, the method for metallising of frosting of the present invention is the good method as the metallization of plastic surface technology of Chrome-free.
Description of drawings
Fig. 1 is the result (1: the ABS resin surface, 2 of no etch processes: use the ABS resin surface, 3 after the etch processes liquid that contains chromic acid is handled: the ABS resin surface after handling with the etch processes liquid that contains permanganic acid) with fourier-transform infrared spectrophotometric determination ABS resin surface.
Embodiment
In the method for metallising of frosting of the present invention (hereinafter referred to as " the inventive method "), plastics as the metallization object, there is not particular restriction, for example can enumerate acronitrile-butadiene-styrene (ABS), polycarbonate/acrylonitrile butadiene styrene (PC/ABS), vinyl cyanide styrene-acrylate (ASA), silicone based compounded rubber-acrylonitrile-styrene (SAS), modified polyphenylene ether resin (Noryl
TM), the multipolymer of polypropylene, polycarbonate (PC), vinyl cyanide vinylbenzene, poly-acetic ester, polystyrene, polymeric amide, aromatic polyamide, polyethylene, polyetherketone, polyethylene terephthalate, polybutylene terephthalate, polysulfones, polyether ethersulfone, polyetherimide, Noryl, polyphenylene sulfide, polymeric amide, polyimide, Resins, epoxy, liquid crystalline polymers etc. and above-mentioned each polymkeric substance etc.In the methods of the invention, especially preferably metallization is implemented on the surface of ABS and PC/ABS.
In the methods of the invention, at first, above-mentioned frosting is handled with the etch processes liquid that contains permanganate and mineral acid.Do not have particular restriction as the permanganate that is contained in this etch processes liquid, for example can utilize the metal-salt of permanganic acid such as potassium permanganate, sodium permanganate.The concentration of this permanganate in etch processes liquid is more than the 0.0005mol/L, to be preferably 0.005～0.5mol/L.On the other hand, do not have particular restriction as the mineral acid that is contained in the etch processes liquid, for example can enumerate, at least a kind of the mineral acid of selecting from phosphoric acid, sulfuric acid and nitric acid is preferably phosphoric acid.The concentration of these mineral acids in etch processes liquid is more than the 2mol/L, to be preferably 6～12mol/L.For frosting being handled with above-mentioned etch processes liquid, be 0～50 ℃ as long as make the liquid temperature, be preferably 25～40 ℃, with plastics therein dip treating 1～30 minute, got final product in preferred 5～15 minutes.By handling with this etch processes liquid, just can make the functional group on the frosting, be in particular hydrophilic functional groups such as hydroxyl, carboxyl and expose.
Then, to having carried out the frosting of above-mentioned etch processes, use a kind of contain to give for the catalyzer that has a compound of selecting adsorptivity (below be referred to as " selecting the adsorptivity compound ") in the functional group of exposing on the frosting by above-mentioned processing strengthen liquid and handle.Give the selection adsorptivity compound that is contained in the enhancing liquid as this catalyzer, so long as above-mentioned functional group is had the compound of selection adsorptivity, just there is not particular restriction, for example can enumerate, contain the compound of nitrogen-atoms, the compound that contains 3 above nitrogen-atoms or molecular weight at the compound more than 100, preferably contain 3 above nitrogen-atoms and molecular weight at the compound more than 100.As this concrete example of selecting the adsorptivity compound, can enumerate ethylenediamines compounds (but except quadrol) such as ethylidene triamine, Triethylenetetramine (TETA); Epomin
TMSP-003, Epomin
TMSP-012, Epomin
TMSP-200 the aziridine type macromolecular compounds such as (by Nippon Shokubai Co., Ltd's systems); PAA-03, PAA-D41-HCl propylamine macromolecular compounds such as (by Nitto Boseiki Co., Ltd.'s systems); , PAS-92, PAS-M-1, PAS-880 diallylamine family macromolecule compounds such as (by Nitto Boseiki Co., Ltd.'s systems); PVAM-0570-B vinyl-amine family macromolecule compounds such as (Mitsubishi chemical Co., Ltd's systems).These are selected in the adsorptivity compound, special optimal ethylene imines family macromolecule compound, propylamine macromolecular compound and diallylamine family macromolecule compound.These select the adsorptivity compound to give the concentration that strengthens in the liquid at catalyzer is more than the 10mg/L, to be preferably 100～1000mg/L.In addition, this catalyzer is given enhancing liquid and preferably with for example sodium hydroxide, sulfuric acid etc. its pH value is adjusted to 5～12, preferred 8～10.To strengthen liquid above-mentioned frosting handled in order to give with this catalyzer, as long as making the liquid temperature is 0～70 ℃, be preferably 25～35 ℃, with plastics therein dip treating 1～20 minute, got final product in preferred 2～3 minutes.
Then, give catalyzer with catalyst-imparting treatment solution to the frosting of giving enhancement process through above-mentioned catalyzer.This catalyst-imparting treatment solution does not just have particular restriction so long as generally can use in the catalyzer of plating process is given, preferably contain precious metal, more preferably contains palladium, especially preferably contains palladium/tin colloid mixture catalyst solution.For these catalyzer are imparted on the frosting, as long as making the liquid temperature of catalyst-imparting treatment solution is 10～60 ℃, be preferably 20～50 ℃, with plastics therein dip treating 1～20 minute, got final product in preferred 2～5 minutes.
Then, for the frosting of so having given catalyzer, carry out the metallization of frosting by chemical metal-plated or Metal plating metal depositions such as (directly platings).
When the metallization of frosting adopts no electrolytic metal to plate, with catalyst-imparting treatment solution after it gives catalyzer, also can be further with containing hydrochloric acid or vitriolic activation treatment liquid is handled.Hydrochloric acid in this activation treatment liquid or vitriolic concentration are more than the 0.5mol/L, to be preferably 1～4mol/L.For frosting being handled with these activation treatment liquid, be 0～60 ℃ as long as make the liquid temperature of activation treatment liquid, be preferably 30～45 ℃, with plastics therein dip treating 1～20 minute, got final product in preferred 2～5 minutes.
Then, to giving the plastics of processing, activation treatment, carry out chemical metal-plated and handle through above-mentioned catalyzer.The chemistry metal-plated is handled and can be adopted chemical metal plating liquids such as known electroless nickel plating solution, electroless plating copper liquid, electroless plating cobalt liquid, carries out according to ordinary method.Particularly, frosting is being carried out plating when handling with electroless nickel plating solution, if with plastics be 8～10 in the pH value, the liquid temperature is dip treating 5～15 minutes in 30～50 ℃ the electroless nickel plating solution.
In addition, when adopting Metal plating (directly plating) when making metallization of plastic surface, with catalyst-imparting treatment solution after it gives catalyzer, and then, also can be with more than the pH7 that contains cupric ion, preferably the activation treatment liquid more than the pH12 be handled.The source of the cupric ion that is contained in this activation treatment liquid does not have particular restriction, can enumerate for example copper sulfate.For frosting being handled with activation treatment liquid, as long as making the liquid temperature of activation treatment liquid is 0～60 ℃, be preferably 30～50 ℃, with plastics therein dip treating 1～20 minute, got final product in preferred 2～50 minutes.
Then, give through above-mentioned catalyzer, the plastics of activation treatment, be impregnated in the general copper electroplating bath such as copper sulfate bath, as long as in common condition, 1～5A/dm for example
2Under handle and got final product in 2～10 minutes.
In addition, can also be according to purpose, as described above frosting is implemented metal depositions such as electroless plating or Metal plating and on the metallized frosting, further implemented various plating such as electro-coppering or electronickelling.Embodiment
Embodiment and comparative example below are shown, are described more specifically the present invention.But the present invention is not subjected to any qualification of these records.
The surface modification treatment of reference example 1 frosting: the ABS resin (UMG ABS Ltd.'s system) of using 50 * 100 * 3mm is flooded them 10 minutes in 35 ℃ etch processes liquid of the phosphoric acid of potassium permanganate that contains 0.01mol/L and 7.5mol/L as sample.In addition, as a comparison, above-mentioned sample was flooded 10 minutes in the etch processes liquid that contains 65 ℃ of 3.5mol/L chromic trioxide and 3.6mol/L vitriolic.Use fourier-transform infrared spectrophotometer (FT/IR 6100FV type (Japanese beam split Co., Ltd. system)), the surface of each ABS resin after adopting 1 secondary reflection ATR method to dipping is analyzed.It the results are shown in Fig. 1.
Can confirm that the surface of being contained the ABS resin that the etch processes liquid of permanganic acid handled is at 3340cm
-1Near have peak from hydroxyl and carboxyl.On the other hand, can confirm, without the surface of the ABS resin of etch processes not from the peak of hydroxyl and carboxyl.In addition, can confirm that the surface of being contained the ABS resin that the etch processes liquid of chromic acid handled is not almost from the peak of hydroxyl and carboxyl.
The making of embodiment 1 electroless plated film: the ABS resin (UMG ABS Ltd.'s system) of using 50 * 100 * 3mm is flooded them 10 minutes in 35 ℃ etch processes liquid of the phosphoric acid of potassium permanganate that contains 0.01mol/l and 7.5mol/l as sample.Then, with it by (polyallylamine: pH value Nitto Boseiki Co., Ltd.'s system) is adjusted to 10 30 ℃ catalyzer that form and gives and strengthened in the liquid dipping 2 minutes with the PAA-03 of 200mg/l with sodium hydroxide.And then, with its in the hydrochloric acid of 1.2mol/l, at room temperature flood 1 minute after, in 35 ℃ the palladium/tin colloid mixture catalyst solution of the hydrochloric acid that contains the CT-580 of 10ml/l (Co., Ltd. of weak former excellent Gilat system) and 2.5mol/l, flooded 4 minutes again, so on ABS resin, give catalyzer.Then, it was flooded 4 minutes in 35 ℃ activation treatment liquid of the hydrochloric acid that contains 1.2mol/l, make catalyst activation.Then, dipping is 10 minutes in pH8.8,35 ℃ electroless nickel plating solution ENI LEX NI-5 (Co., Ltd. of weak former excellent Gilat system), implements electroless nickel plating on ABS resin, makes thickness reach 0.5 μ m.Then, in the acid activity solution that contains the V-345 of 150g/l (Co., Ltd. of weak former excellent Gilat system), at room temperature flooded 1 minute.Then, it is bathed in (Watts bath), at 2V/dm at 45 ℃ the watt that contains 0.75mol/l single nickel salt, 0.4mol/l nickelous chloride and 0.55mol/l boric acid
2Under flooded 3 minutes.And then, it was flooded 1 minute in the copper substitutional solution of the vitriolic room temperature that contains the PDC of 10ml/l (Co., Ltd. of weak former excellent Gilat system) and 0.5mol/l, carry out the copper displacement.Then, with among its copper sulfate bath EP-30 of 25 ℃ (Co., Ltd. of weak former excellent Gilat system), at 3A/dm at the chlorine of sulfuric acid that contains the copper sulfate of 0.9mol/l, 0.55mol/l and 0.0017mol/l
2Under flooded 40 minutes, on ABS resin, implement electro-coppering, make thickness reach 20 μ m.Then, it was annealed 1 hour down at 70 ℃.
The making (1) of comparative example 1 electroless plated film: in the operation of embodiment 1, strengthen in the liquid 2 minutes the processing of dipping except not carrying out giving at catalyzer, all the other all similarly implement electroless nickel plating on ABS resin.
The making (2) of comparative example 2 electroless plated films: the ABS resin (UMG ABS Ltd.'s system) of using 50 * 100 * 3mm is flooded them 10 minutes in 35 ℃ etch processes liquid of the phosphoric acid of potassium permanganate that contains 0.01mol/l and 7.5mol/l as sample.Then, it was flooded 4 minutes in 50 ℃ catalyst solution of the Palladous chloride that contains 0.0024mol/l, so on ABS resin, give catalyzer.Then, it was flooded 4 minutes in 35 ℃ the activation treatment liquid that contains the PC-66H of 10ml/l (Co., Ltd. of weak former excellent Gilat system), make catalyst activation.Then, implement electroless nickel plating and the identical processing of subsequent handling thereof with embodiment 1.
The making (3) of comparative example 3 electroless plated films: in the operation of comparative example 2, except dipping in 50 ℃ catalyst solution of the palladous sulfate of 2-aminopyridine that contains 0.0019mol/l and 0.00094mol/l replaced containing 50 ℃ the catalyst solution of Palladous chloride of 0.0024mol/l in 4 minutes, all the other all similarly implemented electroless nickel plating on ABS resin.
The electroless nickel plating film that test example 1 visual valuation obtains in the foregoing description 1 and comparative example 1～3 is in the deposition on the ABS resin, deposition on the anchor clamps coating.In addition, as following, measure palladium adsorptive capacity and adhesion strength on the ABS resin.These the results are shown in table 1.
＜measuring method〉adsorptive capacity of palladium catalyst: after the palladium ion that adsorbs on the ABS resin surface reduces and handles, with chloroazotic acid palladium is dissolved, use high frequency plasma apparatus for analyzing luminosity ICPS-7510 (Shimadzu Scisakusho Ltd's system), measure the adsorptive capacity of palladium by measuring this solution absorbency.Adhesion strength is measured: according to JIS H8630 appendix 6, after forming the copper electroplating film of about 20 μ m on the ABS resin surface, annealed 1 hour down at 70 ℃, use tensile-strength tester AGS-H500N (Shimadzu Scisakusho Ltd's system) to measure adhesion strength then.
Table 1
| ? | The deposition of electroless plated film | Deposition on the anchor clamps coating | Adsorptive capacity (the mg/dm of palladium catalyst 2) | Adhesion strength (kgf/cm) |
| | Well | Do not have | 0.108? | 1.4? |
| Comparative example 1 | Not sedimentary part is arranged | Do not have | 0.025? | -? |
| Comparative example 2 | Well | Have | 0.063? | 1.4? |
| Comparative example 3 | Well | Have | 0.082? | 1.4? |
-: survey not come out
Among the embodiment 1, the adsorptive capacity of palladium catalyst increases, and the deposition and the adhesion strength of electroless plated film are good.And in this operation, plated film can not deposit on the anchor clamps coating.On the other hand, in comparative example 1, though plated film can not deposit on the anchor clamps, the adsorptive capacity of palladium on ABS resin is few, exists plated film not deposit thereon part.In addition, in comparative example 2 and comparative example 3, though the adsorptive capacity of palladium on ABS resin is abundant, plated film also deposits on the anchor clamps coating simultaneously.
The direct plating of embodiment 2 on ABS resin: the ABS resin (UMG ABS Ltd.'s system) of using 50 * 100 * 3mm is flooded them 10 minutes in containing 35 ℃ etch processes liquid of 0.01mol/l potassium permanganate and 7.5mol/l phosphoric acid as sample.Then, with it by (polyallylamine: pH value Nitto Boseiki Co., Ltd.'s system) is adjusted to 10 30 ℃ catalyzer that form and gives and strengthened in the liquid dipping 2 minutes with the PAA-03 of 200mg/l with sodium hydroxide, then, with it in the hydrochloric acid of 1.2mol/l, at room temperature flooded 1 minute.Then, it was flooded 4 minutes in 35 ℃ the activator that contains the D-POPACT of 25ml/l (Co., Ltd. of weak former excellent Gilat system), 1.2mol/l hydrochloric acid and 1.7mol/l sodium-chlor.Then, 45 ℃ the metal plating bath of the D-POPMEB (Co., Ltd. of weak former excellent Gilat system) that contains the D-POPMEA of 100ml/l (Co., Ltd. of weak former excellent Gilat system) and 100ml/l (metallizer, metallizer) in dipping 3 minutes.At last, containing 25 ℃ EP-30 (copper sulfate bath of 0.9mol/l copper sulfate, 0.55mol/l sulfuric acid and 0.017mol/l hydrochloric acid; Co., Ltd. of weak former excellent Gilat system) dipping is 10 minutes in, in energising initial stage low pressure starting (carried out under 0.5V in initial 30 seconds, carried out under 1.0V, and finally carried out under 1.5V in 30 seconds subsequently), implements directly plating thus on ABS resin.
The result who directly plates on ABS resin in energising 5 minutes, also do not have deposition plating on the anchor clamps coating, and plated film can cover entire sample with following.In addition, the adhesion strength with the test example 1 same plated film of measuring is 0.8kgf/cm.
The making of embodiment 3 electroless plated films on various resins: except using various resins (ABS, PC/ABS (containing PC 65%), ASA, SAS, PC (UMG ABS Ltd.'s system), Noryl (trade(brand)name, modified polyphenylene ether resin, General Electric's system), polypropylene (Japanese polychem Co., Ltd. system)) as beyond the sample, all the other implement electroless nickel plating similarly to Example 1 on each resin.
The making of comparative example 4 electroless plated films on various resins: use various resins (ABS, PC/ABS (containing PC 65%), ASA, SAS, PC (UMG ABS Ltd.'s system), Noryl (General Electric's system), polypropylene (Japanese polychem Co., Ltd. system)), it to be flooded 10 minutes in the etching solution that contains 65 ℃ of 3.5mol/l chromic trioxide and 3.6mol/l vitriolic as sample.Then, will flood 2 minutes in 25 ℃ the reduced liquid of its ENILEXRD (Co., Ltd. of weak former excellent Gilat system) at hydrochloric acid that contains 0.5mol/l and 10ml/l.And then, to salt acid dipping (preimpregnation) and the identical processing of subsequent handling thereof of the 1.2mol/l that grants embodiment 1 in fact.
The electroless plated film that obtains in test example 2 visual valuation the foregoing descriptions 3 and the comparative example 4 is in the deposition on the various resins, deposition on the anchor clamps coating.In addition, similarly be determined at the adhesion strength of the electroless plated film that obtains on the various resins with test example 1.These the results are shown in table 2.
Table 2
-: survey not come out
Any electroless plated film that obtains among the embodiment 3 can both cover on the resin everywhere with following fully, can obtain and the equal above adhesion strength of comparative example 4 (chromic acid etch process).In addition, in embodiment 3, when on any resin, carrying out electroless plating, can be on the anchor clamps coating yet deposition plating.On the other hand, there is not deposition part thereon in comparative example 4 (chromic acid etch process) on Noryl, acrylic resin, and on the PC resin deposition plating not fully.
Embodiment 4 catalyzer are given the effect that strengthens liquid: in the operation of embodiment 1, except catalyzer is given strengthen liquid effective constituent by PAA-03 (polyallylamine; Nitto Boseiki Co., Ltd.'s system) replaces with composition or the Adeka Hope that puts down in writing in the following table 4
TM, Adeka Tole
TM, Adeka Pluronic
TM(being Asahi Denka Kogyo K. K's system), Energy Call
TM(Lion Corporation's system) in addition, all the other all similarly implement electroless nickel plating on ABS resin.Similarly estimate the electroless nickel plating film that obtains in the deposition on the ABS resin, deposition on the anchor clamps coating with test example 1.In addition, similarly measure palladium adsorptive capacity on the ABS resin with test example 1.These the results are shown in table 3.
If use ethylenediamines compound, the aziridine type macromolecular compound, propylamine macromolecular compound, diallylamine family macromolecule compound, vinyl-amine family macromolecule compound to give the effective constituent that strengthens liquid as catalyzer, then any situation all can make the palladium adsorptive capacity increase and can obtain not sedimentary good coated film deposition on anchor clamps.In contrast, use the compounds such as monoethanolamine, quadrol, glycine, taurine, aminoothyl mercaptan that have a compound of 2 following nitrogen-atoms as 1 intramolecularly then not observe the increase of palladium adsorptive capacity.In addition, especially, use Adeka Hope as aniorfic surfactant
TM, EnergyCall
TM, do not observe the effect that the palladium adsorptive capacity increases yet.In addition, use is as the Adeka Tole of nonionic surface active agent
TM, Adeka Pluronic
TM, the palladium adsorptive capacity does not increase, and appears at sedimentary phenomenon on the anchor clamps coating.
The effect of the mineral acid in the embodiment 5 etch processes liquid: in the operation of embodiment 1, except the composition with etch processes liquid replaced with the composition of record in the following table 5, all the other all similarly implemented electroless nickel plating on ABS resin.Similarly estimate the deposition of electroless nickel plating film on ABS resin that obtains with test example 1.These the results are shown in table 5.In addition, adopt following belt stripping test to measure the adhesion strength of the electroless nickel plating film that obtains.
＜measuring method〉with the finger internal surface scotch tape (CT24:Nichiban Co., Ltd. system) is fitted on the sample surfaces behind the electroless nickel plating, then, adhesive tape is peeled off by 90 ° of angles tops.After scotch tape peeled off, whether the Visual Confirmation plated film was peeled off with adhesive tape.
Table 5
| The composition of etch processes liquid | The deposition of electroless plated film | Belt stripping test |
| Potassium permanganate | Not sedimentary part is arranged | Observe and peel off |
| Phosphoric acid | Not sedimentary part is arranged | Observe and peel off |
| Potassium permanganate+phosphoric acid | Do not have | Nothing is peeled off |
| Potassium permanganate+sulfuric acid | Do not have | Nothing is peeled off |
| Potassium permanganate+nitric acid | Do not have | Nothing is peeled off |
For the mixing solutions of potassium permanganate and mineral acid, arbitrary solution can both make coated film deposition good, and adhesion strength is also high, and can make belt stripping test become clear (cleared).On the other hand, for the solution that only contains the single composition of potassium permanganate or phosphoric acid respectively, frosting almost can not get modification, therefore, exists not deposit part when electroless nickel plating subsequently.In addition, the adhesion strength of the part of formation plated film is also low, can simply it be peeled off with adhesive tape.
Embodiment 6 contains the effect that catalyzer is given the pH value of water solution that strengthens liquid: in the operation of embodiment 1, be adjusted to the value of putting down in writing in the following table 6 except using sodium hydroxide and sulfuric acid to give the pH value that strengthens liquid with catalyzer, all the other all similarly implement electroless nickel plating on ABS resin.Similarly estimate the electroless nickel plating that obtains in deposition on the ABS resin and the deposition on the anchor clamps coating with test example 1.In addition, similarly measure palladium adsorptive capacity on the ABS resin with test example 1.These results are shown in table 6 in the lump.
Table 6
| Catalyzer is given the pH value that strengthens liquid | The deposition of electroless plated film | Deposition on the anchor clamps coating | Adsorptive capacity (the mg/dm of palladium catalyst 2)? |
| 5.0? | Well | Do not have | 0.045? |
| 6.0? | Well | Do not have | 0.061? |
| 7.0? | Well | Do not have | 0.063? |
| 8.0? | Well | Do not have | 0.073? |
| 9.0? | Well | Do not have | 0.094? |
| 10.0? | Well | Do not have | 0.108? |
| 11.0? | Well | Do not have | 0.116? |
| 12.0? | Well | Do not have | 0.102? |
| Do not use catalyzer to give the processing that strengthens liquid | Not sedimentary part is arranged | Do not have | 0.025? |
It is 5.0～12.0 that catalyzer is given the pH value that strengthens liquid, and plated film can not deposit on anchor clamps, and observes the effect that the palladium adsorptive capacity increases.
Embodiment 7 catalyzer are given the effect of the concentration that strengthens liquid: in the operation of embodiment 1, give the polyallylamine that strengthens the effective constituent in the liquid (PAA-03: concentration Nitto Boseiki Co., Ltd.'s system) is adjusted to the value of record in the table 7, and all the other all similarly implement electroless nickel plating on ABS resin except belonging to catalyzer.Similarly estimate the electroless nickel plating film that obtains in deposition on the ABS resin and the deposition on the anchor clamps coating with test example 1.In addition, similarly measure palladium adsorptive capacity on the ABS resin with test example 1.These results are shown in table 7 in the lump.
Table 7
| Catalyzer is given the concentration that strengthens polyallylamine in the liquid | Deposition on the anchor clamps coating | Adsorptive capacity (the mg/dm of palladium catalyst 2) |
| 10mg/L? | Do not have | 0.066? |
| 100mg/L? | Do not have | 0.098? |
| 1g/L? | Do not have | 0.119? |
| 10g/L? | Do not have | 0.098? |
| Do not use catalyzer to give the processing that strengthens liquid | Do not have | 0.025? |
As seen, with the concentration of polyallylamine irrelevant, have an effect that is suppressed at the deposition on the anchor clamps coating and the palladium adsorptive capacity is increased.Industrial applicibility
The method for metallising of frosting of the present invention be a kind of can frosting form the plated film fully adhere to and also can be on anchor clamps the high method of the practicality of deposition plating. In addition, method of the present invention can increase catalyst metals in the adsorbance of frosting, therefore, also can be not easy similarly to carry out plating on the plastics that catalyst metals is adsorbed according to previous methods.
Therefore, the inventive method can be used as the metallization process of the frosting of Chrome-free.
Claims (15)
1. the method for metallising of frosting; It is characterized in that; With the etch processes liquid that contains permanganate and inorganic acid plastics are processed; Then; To the plastics through above-mentioned processing; Give and strengthen liquid and process with containing the catalyst that the functional group of exposing on this frosting is had a compound of Selective adsorption; And then; Give catalyst with catalyst-imparting treatment solution to given the enhancing plastics that liquid was processed by above-mentioned catalyst; Then; The above-mentioned plastics of having given catalyst are implemented metal deposition
Described catalyzer give strengthen contain in the liquid, to the functional group of exposing on the frosting have the compound of selecting adsorptivity be contain 3 above nitrogen-atoms, molecular weight is 100 above compounds,
Described catalyst-imparting treatment solution contains precious metal.
2. the method for metallising of the described frosting of claim 1, wherein, the mineral acid that contains in the etch processes liquid is to be selected from least a kind of mineral acid in phosphoric acid, sulfuric acid and the nitric acid.
3. the method for metallising of the described frosting of claim 1 wherein, uses 0 ℃～50 ℃ etch processes liquid to carry out etch processes.
4. the method for metallising of the described frosting of claim 1, wherein, the concentration of the permanganate in the etch processes liquid is more than the 0.0005mol/L.
5. the method for metallising of the described frosting of claim 1, wherein, the concentration of the mineral acid in the etch processes liquid is more than the 2mol/L.
6. the method for metallising of the described frosting of claim 1, wherein, catalyzer give strengthen in the liquid, to the functional group of exposing on the frosting have select adsorptivity, to contain 3 above nitrogen-atoms, molecular weight be that compound concentrations more than 100 is more than the 10mg/L.
7. the method for metallising of the described frosting of claim 1, wherein, it is 5～12 that catalyzer is given the pH value that strengthens liquid.
8. the method for metallising of the described frosting of claim 1, wherein, metal-plated is an electroless plating.
9. the method for metallising of the described frosting of claim 1, wherein, catalyst-imparting treatment solution is the solution that contains palladium.
10. the method for metallising of the described frosting of claim 1, wherein, catalyst-imparting treatment solution is palladium/tin colloid mixture catalyst solution.
11. the method for metallising of the described frosting of claim 1 wherein, is included in catalyst-imparting treatment solution and gives after the catalyzer, with containing the operation that hydrochloric acid or vitriolic activation treatment liquid are handled.
12. the method for metallising of the described frosting of claim 11, wherein, hydrochloric acid in the activation treatment liquid or vitriolic concentration are more than the 0.5mol/L.
13. the method for metallising of the described frosting of claim 1, wherein, metal-plated is for electroplating.
14. the method for metallising of the described frosting of claim 1 wherein, after giving catalyzer with catalyst-imparting treatment solution, is handled with the above activation treatment liquid of the pH7 that contains cupric ion again.
15. the method for metallising of the described frosting of claim 1, wherein, to the functional group of exposing on the frosting have select adsorptivity, to contain 3 above nitrogen-atoms, molecular weight be that compound more than 100 is selected from ethylenediamines compound, the aziridine type macromolecular compound, propylamine macromolecular compound, diallylamine family macromolecule compound and the vinyl-amine family macromolecule compound except that quadrol.
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| PCT/JP2007/060332 WO2008012984A1 (en) | 2006-07-27 | 2007-05-21 | Process for metallization of plastic surfaces |
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| KR101284479B1 (en) * | 2011-06-30 | 2013-07-16 | 영남대학교 산학협력단 | Plating method of Acrylonitrile-Butadiene-Styrene copolymer using manganate salt as etchant |
| DE102011111294B4 (en) * | 2011-08-26 | 2018-12-20 | Atotech Deutschland Gmbh | Process for the treatment of plastic substrates and apparatus for the regeneration of a treatment solution |
| CN102409320B (en) * | 2011-11-29 | 2015-02-25 | 沈阳工业大学 | Electroplating pretreatment method for acrylonitrile butadiene styrene (ABS) plastic surface |
| JP5742701B2 (en) * | 2011-12-14 | 2015-07-01 | トヨタ自動車株式会社 | Electroless plating method |
| KR101410395B1 (en) * | 2013-01-17 | 2014-06-20 | 한진화학(주) | Method for plating an antenna according to double injection molding |
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| CN1508287A (en) * | 2002-12-18 | 2004-06-30 | Method for activating substrate for plating on plastic | |
| CN1715444A (en) * | 2004-05-27 | 2006-01-04 | 恩通公司 | Method for metallizing plastic surfaces |
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| TW200811311A (en) | 2008-03-01 |
| JP4275157B2 (en) | 2009-06-10 |
| JP2008031513A (en) | 2008-02-14 |
| WO2008012984A1 (en) | 2008-01-31 |
| CN101490310A (en) | 2009-07-22 |
| KR20090036123A (en) | 2009-04-13 |
| KR101365970B1 (en) | 2014-02-21 |
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