US3684572A - Electroless nickel plating process for nonconductors - Google Patents
Electroless nickel plating process for nonconductors Download PDFInfo
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- US3684572A US3684572A US3684572DA US3684572A US 3684572 A US3684572 A US 3684572A US 3684572D A US3684572D A US 3684572DA US 3684572 A US3684572 A US 3684572A
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- nonconductor
- electroless nickel
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- 238000000034 method Methods 0.000 title abstract description 29
- 239000000615 nonconductor Substances 0.000 title abstract description 21
- 238000007747 plating Methods 0.000 title abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 65
- 229910052759 nickel Inorganic materials 0.000 title description 33
- 239000004094 surface-active agent Substances 0.000 abstract description 52
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- 150000001412 amines Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 80
- 239000003054 catalyst Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 18
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 16
- 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 15
- 239000004743 Polypropylene Substances 0.000 description 13
- 229920001155 polypropylene Polymers 0.000 description 13
- 125000003277 amino group Chemical group 0.000 description 9
- 238000005530 etching Methods 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002940 palladium Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000006177 alkyl benzyl group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- WLCFKPHMRNPAFZ-UHFFFAOYSA-M didodecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC WLCFKPHMRNPAFZ-UHFFFAOYSA-M 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OQUFOZNPBIIJTN-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium Chemical compound [Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OQUFOZNPBIIJTN-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- JELVGRRIFONCCE-UHFFFAOYSA-N benzyl-ethyl-dimethylazanium cyclohexyl sulfamate Chemical compound NS(=O)(=O)OC1CCCCC1.CC[N+](C)(C)CC1=CC=CC=C1 JELVGRRIFONCCE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229960000228 cetalkonium chloride Drugs 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/208—Multistep pretreatment with use of metal first
-
- 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
- C23C18/26—Roughening, e.g. by etching using organic liquids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
Definitions
- This invention relates to an electroless metal plating process for a nonconductor and more particularly to a process wherein a uniform metal coating is obtained on the surface of a nonconductor by treatment of the surface with a solution of aquaternary amine surfactant during the process.
- the nonconductor surface is not completely covered with a uniform coating of metaLThere may be voids or discontinuities in the metal coating on the nonconductor. Further, the metal coating may be rough rather than smooth and the thickness of the coating variable.
- cellent surfacecoverage of a nonconductor has been of the nonconductor during the processwith a solution of a quaternary amine surfactant where one radical is an alkyl having from about 10 to'about 20 carbon atoms and a second radical is an alkyl having about 10 to about 20 carbon atoms, benzyl or an alkyl benzyl radical.
- a nonconductor is treated with a dilute solution of a quaternary amine surfactant, after etching and before catalyzing.
- useful surfactants include N-alkyl (C1240%, C -50%, ammonium chloride such as Hyamine 3500 (Rohm and Haas C03, Philadelphia, Pennsylvania), n-alkyl (C -C dimethyl ethylbenzyl ammonium cyclohexyl sulfamate such as Onyxide 172 (Onyx Chemical 00., Jersey City, N.J.), dilauryl dimethyl ammonium chloride such as Aliquat 204 (General Mills, Kankakee, 111.), cetyl dimethyl benzyl ammonium chloride such as Ammonyx T (Onyx Chemical 00., Jersey City, N.J.).
- the above surfactants are used to prepare dilute aqueous solutions containing from about 0.01 to about 0.1% by volume of active surfactant. These surfactant solutions can then be used to treatthe surface of the nonconductor after etching and before cat alyzing in the electroless plating process. Or they may be used in other steps of the process.
- Advantages of the process of this invention include faster deposition of metal, more uniform deposition of metal, reduced operating temperatures in the oxidizing solution bath and electroless nickel bath. Further, use of the surfactant solution does not appear to adversely affect other steps in the process. Life tests on a plating line did not show any evidence of contamination or other adverse effects that might be attributed to the surfactant solution or its use.
- the surfactant can also be dissolved in the reducing solution and the resulting solution of surfactant and reducing agent can be used as the reducing solution.
- a surfactant solution after etching and before catalyzing the surface can be omitted when a solufurther improvements in plating results can be obtained using both a surfactant solution and a reducing solution containing a surfactant and reducing agent in this process.
- a nonconductor surface for example, polypropylene (PP), acrylonitrile-butadienestyrene (ABS) or other polymeric material
- PP polypropylene
- ABS acrylonitrile-butadienestyrene
- the surface is first etched or conditioned, usually by immersion in an oxidizing solution to make the surface hYdI'OPhiIlC-*U.S. Pat. 3,471,313, Saubestre et al., patented Oct. 7, 1969 discloses numerous oxidizing solutions useful for this purpose. There are also numerous commercial oxidizing solutions offered under proprietary names for this purpose.
- a typical catalyst solution has the following composition:
- catalyst solution A has been used to catalyze ABS and PP surfaces for metalizing.
- the catalyst solution can be the palladium catalyst solu- Water to make 1 1.
- the substrate surface is rinsed with water and then immersed in an electroless *metal plating bath;
- Typical electroless metal plating baths have the following compositions: I
- Electroless nickel bath A G./l. Nickel sulfate hexahydrate 31.3 Sodium acetate 3 Citric acid Sodium hypophosphite monohydrate 20 Water to make 1 1.
- Electroless nickel bath B G./l. Nickel sulfate hexahydrate 26.3 Ammonium chloride 53.5 Sodium hypophosphite monohydrate 21.2
- Electroless nickel bath B is from U.S. Pat. 3,488,166, Kovac et al., patented Jan. 6, 1970. There are also numerous commercial electroless nickel baths offered under proprietary names for this use.
- one of the above quaternary amine surfactants can be dissolved in the above reducing solution and used in conjunction with the surfactant solution in the above described process or the surfactant solution omitted from the process and the solution of surfactant and reducing agent used alone.
- nickel While the common practice is to refer to the deposits from the above hypophosphite containing electroless nickel bath as nickel, it is well known that the deposits are really a nickel phosphorus alloy.
- nickel as used herein is understood to refer to this nickel phosing examples. These examples are given merely to illus- I ing sense. All references to temperature are F. unless otlierwiseindi ated. t
- EXAMPLE 1 To demonstrate the increased rate of metal deposition and the greater uniformity of the metal deposit obtained by the use of these quaternary amine surfactants in the process of metallizing nonconductors, a number of pieces of injection molded acrylonitrile-butadiene-styrene (ABS) and polypropylene (PP) polymers which had been etched were metalized with and without the use of the surfactants and after 45 seconds immersion in the electroless nickel metalizing bath, the pieces wereremoved and the percent of thesurface of the nonconductor which was covered by the electroless nickel deposit was determined by visualobservation.
- ABS injection molded acrylonitrile-butadiene-styrene
- PP polypropylene
- Sequence 1 I Catalyst solution A, room temperature, 2 min. Reducingg solution, room temperature, 1min. Nickel bath A or B, room temperature, 45 sec.
- Sequence 2 Surfactant solution, room temperature, 2 min. Catalyst solution A, room temperature, 2 min. Reducing solution, room temperature, 1 min. Nickel bath A or B, room temperature, 45 sec.
- surfactant solution is shown in the sequence above, the solution was prepared by dissolving sufiicient commercial quaternary amine surfactant in water to obtain a solution containing the percent by volume of active surfactant which is shown in the column under this heading in Tables 1 and 2.
- this solution was prepared by adding an equivalent amount of the same surfactant to the reducingsolution as was used to prepare the surfactant solution.
- Ammonyx T the solution can be prepared more easily if the surfactant is first dissolved using 1 volume to 2 volumes of ethanol and then added to either the reducing solution or to water to make up the surfactant solution.
- Sequences 1 and 2 were used to plate ABS polymers and sequences 3 and 4 were used to plate PP polymers.
- Table lv shows the percentage of the surface covered with nickel when nickel bath A was used to metalize the surface of the polymer as Well as the type and concentration of surfactant-used, the plating sequence used and the polymer which was metalized.
- Table 2 shows'the same information for those examples where nickel bath -B was used tometalize the surface of the polymer.
- Hyamjne 3500 A 0.05% by volume surfactant solution of Hyamjne 3500 was used in conjunction with a commercial system for plating polypropylene to plate injection molded PP chips and plaques. The sequence used to plate these parts was as follows:
- Etching solution 175-185 F., 10-15 min.
- Surfactant solution room temperature, 1-3 min.
- Catalyst solution room temperature, 1-2 min.
- Reducing solution room temperature, 1 min.
- Catalyst solution room temperature, 1 min.
- Electroless nickel bath 70-85 -F., 6 min.
- step (e) 5. The process of claim 1 wherein from 0.0 1 to 0.1% by volume of the surfactant used in step (a) is also added to the reducing solution in step (e).
Abstract
THE USE OF A QUATERNARY AMINE SURFACTANT SOLUTION IN AN ELECTROLESS METAL PLATING PROCESS PRODUCES A UNIFORM COATING ON A NONCONDUCTOR SURFACE AND EXCELLENT SURFACE COVERAGE.
Description
United states Patent omce 3,684,572 Patented Aug. 15, 1972 6 Claims ABSTRACT OF THE DISCLOSURE The use of a quaternary amine surfactant solution in an electroless metal plating process produces a uniform coating on a nonconductor surface and excellent surface coverage.
BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to an electroless metal plating process for a nonconductor and more particularly to a process wherein a uniform metal coating is obtained on the surface of a nonconductor by treatment of the surface with a solution of aquaternary amine surfactant during the process.
(2) Description of the prior art In the process of metalizing a nonconductor surface such as polypropylene; acrylonitrile-butadiene-styrene or other plastics, the surface is first etched or conditioned usually by immersion in an oxidizing solution to make the surface hydrophilic. After the oxidizing treatment, the surface is then rinsed with water to remove excess oxidizing solution and then immersed in a catalyst solution. After treatment with the catalyst" solution, the surface is rinsed with water to remove excess catalyst solution and then immersed in a reducing solution to reduce the catalyst to metallic form after which the surface is rinsed with water and immersed in anelectroless metal plating bath to metalize the part. '1
Frequently, it is found that the nonconductor surface is not completely covered with a uniform coating of metaLThere may be voids or discontinuities in the metal coating on the nonconductor. Further, the metal coating may be rough rather than smooth and the thickness of the coating variable.
S MM R F THE I NVEN TION An electroless metal plating process, which gives exfound. The process produces uniform metal coating on a part molded from a nonconductor such; as polypropylene (PP), acrylonitrile-butadiene-styrene (ABS) or the like. Improved results are attributed to treatment of the surface I tion of surfactant and reducing agent is used. However,
cellent surfacecoverage of a nonconductor has been of the nonconductor during the processwith a solution of a quaternary amine surfactant where one radical is an alkyl having from about 10 to'about 20 carbon atoms and a second radical is an alkyl having about 10 to about 20 carbon atoms, benzyl or an alkyl benzyl radical.
It is an object of this invention to provide a surfactant solution for improving the coverage of a nonconductor when plated by an electroless nickel plating process. Another object of this invention is to provide an electroless plating process. A further object is toprovide an improved electroless plating process wherein the surface of the nonconductor is treated with a quaternary amine surfactant after etching and before catalyzing the surface to obtain a uniform metal coating. A further object is to provide uniform coverage of nonconductor surface with meta1. Other objects will become apparent fromthe detailed description given hereinafter. It is intended that this description and specific examples merely indicate preferred embodiments and are not given to limit this invention since various changes and modifications within the scope of this invention will become apparent to those skilled in the art. 7.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The surface of a nonconductor is treated with a dilute solution of a quaternary amine surfactant, after etching and before catalyzing. Useful surfactants include N-alkyl (C1240%, C -50%, ammonium chloride such as Hyamine 3500 (Rohm and Haas C03, Philadelphia, Pennsylvania), n-alkyl (C -C dimethyl ethylbenzyl ammonium cyclohexyl sulfamate such as Onyxide 172 (Onyx Chemical 00., Jersey City, N.J.), dilauryl dimethyl ammonium chloride such as Aliquat 204 (General Mills, Kankakee, 111.), cetyl dimethyl benzyl ammonium chloride such as Ammonyx T (Onyx Chemical 00., Jersey City, N.J.). The above surfactants are used to prepare dilute aqueous solutions containing from about 0.01 to about 0.1% by volume of active surfactant. These surfactant solutions can then be used to treatthe surface of the nonconductor after etching and before cat alyzing in the electroless plating process. Or they may be used in other steps of the process.
Advantages of the process of this invention include faster deposition of metal, more uniform deposition of metal, reduced operating temperatures in the oxidizing solution bath and electroless nickel bath. Further, use of the surfactant solution does not appear to adversely affect other steps in the process. Life tests on a plating line did not show any evidence of contamination or other adverse effects that might be attributed to the surfactant solution or its use. The surfactant can also be dissolved in the reducing solution and the resulting solution of surfactant and reducing agent can be used as the reducing solution. If desired, use of a surfactant solution after etching and before catalyzing the surface can be omitted when a solufurther improvements in plating results can be obtained using both a surfactant solution and a reducing solution containing a surfactant and reducing agent in this process.
In the process of metalizing :a nonconductor surface, for example, polypropylene (PP), acrylonitrile-butadienestyrene (ABS) or other polymeric material, the surface is first etched or conditioned, usually by immersion in an oxidizing solution to make the surface hYdI'OPhiIlC-*U.S. Pat. 3,471,313, Saubestre et al., patented Oct. 7, 1969 discloses numerous oxidizing solutions useful for this purpose. There are also numerous commercial oxidizing solutions offered under proprietary names for this purpose.
After thorough rinsing with water, the surface of the substrate is then immersed in one of the dilute solutions of cationic surfactants described above and then rinsed thoroughly with water. The substrate surface is then catalyzed by being immersed in a catalyst solution of a catalytic metal ion usually palladium ions obtained by dissolving a palladium salt in a solution of acid. Various concentrations of a palladium salt and hydrochloric acid can be used. A typical catalyst solution has the following composition:
Palladium chloride-01 g./l.-0.3 g./l. Hydrochloric acid-d0 ml./1.50 ml./l. Water to make 1 1.
(Reference: Goldie, William, Metallic Coating of Plastics, Middlesex, England: Electrochemical Publications Limited, 1968, pp. 39-52.) The following solution designated as catalyst solution A has been used to catalyze ABS and PP surfaces for metalizing.
3 Catalyst solution A G,./l. Palladium chloride 0.2 Hydrochloric acid 0.2
Water to make 1 l.
The catalyst solution can be the palladium catalyst solu- Water to make 1 1.
After removal from the reducing solution, the substrate surface is rinsed with water and then immersed in an electroless *metal plating bath;
Typical electroless metal plating baths have the following compositions: I
Electroless nickel bath A G./l. Nickel sulfate hexahydrate 31.3 Sodium acetate 3 Citric acid Sodium hypophosphite monohydrate 20 Water to make 1 1.
For use at a temperature of 75 to 85 F. and a pH of 8.5 to 8.7.
Electroless nickel bath B G./l. Nickel sulfate hexahydrate 26.3 Ammonium chloride 53.5 Sodium hypophosphite monohydrate 21.2
Water to make 1 1.
For use at room temperature, pH adjusted to 9 with NaOH.
Electroless nickel bath B is from U.S. Pat. 3,488,166, Kovac et al., patented Jan. 6, 1970. There are also numerous commercial electroless nickel baths offered under proprietary names for this use.
If desired, from about 0.01 to about 1.0% by weight of one of the above quaternary amine surfactants can be dissolved in the above reducing solution and used in conjunction with the surfactant solution in the above described process or the surfactant solution omitted from the process and the solution of surfactant and reducing agent used alone.
The ease with which extruded or molded plastic nonconductor surfaces are metalized varies from part to part or even from batch to batch. Reasons for this variation are not really known but have been attributed to variations such as mold design, gate size, mold temperature, melt temperature, etc. These variations are readily overcome by use of the process of this invention.
While the common practice is to refer to the deposits from the above hypophosphite containing electroless nickel bath as nickel, it is well known that the deposits are really a nickel phosphorus alloy. The term nickel as used herein is understood to refer to this nickel phosing examples. These examples are given merely to illus- I ing sense. All references to temperature are F. unless otlierwiseindi ated. t
EXAMPLE 1 To demonstrate the increased rate of metal deposition and the greater uniformity of the metal deposit obtained by the use of these quaternary amine surfactants in the process of metallizing nonconductors, a number of pieces of injection molded acrylonitrile-butadiene-styrene (ABS) and polypropylene (PP) polymers which had been etched were metalized with and without the use of the surfactants and after 45 seconds immersion in the electroless nickel metalizing bath, the pieces wereremoved and the percent of thesurface of the nonconductor which was covered by the electroless nickel deposit was determined by visualobservation.
After etching in a chromic acid-sulfuric acid etching solution, the followingsequences were used to metalize the surfaces. These sequences show type of solution used in treatment, temperature of treatment and time period of treatment. Surfaces of the pieces were rinsed with water between each step in the sequences.
Sequence 1 I Catalyst solution A, room temperature, 2 min. Reducingg solution, room temperature, 1min. Nickel bath A or B, room temperature, 45 sec.
Sequence 2 Surfactant solution, room temperature, 2 min. Catalyst solution A, room temperature, 2 min. Reducing solution, room temperature, 1 min. Nickel bath A or B, room temperature, 45 sec.
Sequence 3 Catalyst solution A, room temperature, 2 min. Reducing solution, room temperature, 1 min. Catalyst solution A, room temperature, 1 min. Reducing'solution, room temperature, 1 min. Nickel bath A or B, room temperature, 45 sec.
Sequence 4 Surfactant solution, room temperature, 2 min.
Where surfactant solution is shown in the sequence above, the solution was prepared by dissolving sufiicient commercial quaternary amine surfactant in water to obtain a solution containing the percent by volume of active surfactant which is shown in the column under this heading in Tables 1 and 2. In sequence 4, where use of reducing solution and surfactant is shown, this solution was prepared by adding an equivalent amount of the same surfactant to the reducingsolution as was used to prepare the surfactant solution. When Ammonyx T is used, the solution can be prepared more easily if the surfactant is first dissolved using 1 volume to 2 volumes of ethanol and then added to either the reducing solution or to water to make up the surfactant solution. Sequences 1 and 2 were used to plate ABS polymers and sequences 3 and 4 were used to plate PP polymers. Table lvshows the percentage of the surface covered with nickel when nickel bath A was used to metalize the surface of the polymer as Well as the type and concentration of surfactant-used, the plating sequence used and the polymer which was metalized. Table 2 shows'the same information for those examples where nickel bath -B was used tometalize the surface of the polymer.
TABLE 1.PERCENT OF SURFACE COVERED WITH ELECTROLESS NICKEL DEPOSIT AFTER 45 SEC. WHEN NICKEL BATH A WAS USED TO METALIZE THE SURFACE Percent by Percent of volume of Metalizing surface active sequence covered Surfactant used surfactant used Polymer with metal 1 ABS 5 2 ABS 100 1 ABS None 2 ABS 100 3 PP None 1 ABS 1O 2 ABS 100 1 ABS 2 ABS 9O 1 ABS 10 2 ABS 90 TABLE 2.PERCENT OF SURFACE COVERED WITH ELECTROLESS NICKEL DEPOSIT AFTER 45 Sec. WHEN NICKEL BATH B WAS USED TO METAL'IZE THE SURFACE The quaternary amne surfactant solutions listed below were used in conjunction with a commercial system for plating on ABS plastic to plate ABS panels. The following plating sequence was used:
Etching solution, 135-145 F., 6 min.
Surfactant solution, room temperature, 1-3 min.
Catalyst solution, 140 F., 1-3 min.
Reducing solution, room temperature, '1-2 min. Electroless nickel bath, 70-85 F., 1 min.
Surfaces of the panels were rinsed with water between each step in the sequence. When the surfactant solution step was omitted, only 10% of the surface was covered with nickel. When the surfactant step was included in the sequence, the following results were obtained:
Percent of Percent by s cc volume of covered with active nickel in Surfactant used surfactant 1 min.
Onyxide 172 0. 8 100 Ammonyx T 0. 25 80-95 Hyamine 3500- 0. 05 95-100 Aliquat 240 0. 75 95 EXAMPLE 3 A 0.05% by volume surfactant solution of Hyamjne 3500 was used in conjunction with a commercial system for plating polypropylene to plate injection molded PP chips and plaques. The sequence used to plate these parts was as follows:
Etching solution, 175-185 F., 10-15 min. Surfactant solution, room temperature, 1-3 min. Catalyst solution, room temperature, 1-2 min. Reducing solution, room temperature, 1 min. Catalyst solution, room temperature, 1 min. Electroless nickel bath, 70-85 -F., 6 min.
Surfaces of the parts were rinsed with water between each step in the sequence. When the surfactant solution was omitted from the above sequence, the nickel deposit did not completely cover the surface of the plastic and parts were unsuitable for subsequent electroplating. When the surfactant solution was included in the above sequence, the surface of plastic parts was completely covered with electroless nickel and the parts were suitable for subsequent electroplating.
What is claimed is:
1. In an electroless nickel plating process for a nonconductor wherein the noncondnctor substrate surface is oxidized to convert the surface to a hydrophilic state followed by water rinsing, the process which then comprises the steps of:
(a) treating the surface in an aqueous surfactant solution comprising from 0.01 to 0.1% by volume of a quaternary amine surfactant where one radical is an alkyl having from about 10 to about 20 carbon atoms and a second radical is selected from the group consisting of an alkyl having from about-10 to about 20 carbon atoms, benzyl and an alkyl benzyl radical, then (b) rinsing the surface with water to remove excess surfactant solution, thereafter (c) treating the surface in a palladium salt catalyst solution, then (d) .rinsing the surface with water to remove excess catalyst solution, thereafter (e) treating the surface in a reducing solution, thereafter (f rinsing the surface to remove excess reducing solution, and then (g) treating the surface in an electroless nickel plating bath to deposit nickel from the bath onto the surface.
2. The process of claim 1 wherein the noncondnctor is a polypropylene polymeric material.
3. The process of claim 1 wherein the noncondnctor is an acrylonitrile-butadiene-styrene polymeric material.
4. The process of claim 1 wherein the noncondnctor is immersed in an electroless nickel plating bath at a temperature of about 65 to about F.
5. The process of claim 1 wherein from 0.0 1 to 0.1% by volume of the surfactant used in step (a) is also added to the reducing solution in step (e).
6. The process of claim 1 wherein from 0.01 to 0.1% by volume of the surfactant used in step (a) is added to the reducing solution in step (e) and steps (a) and (b) are omitted.
References Cited UNITED STATES PATENTS 3,563,784 2/1971 Innes et al. 117--160 X 3,561,995 2/1971 Wu et al. 11747 3,095,373 6/196'3 'Blomfield 117-47 X 3,556,882 1/ 1971 Fishman et al 117-47 X 2,555,883 6/1951 Harvey et al.
3,338,726 8/ 1967 Berzins 106-1 3,485,643 12/ 1969 Zeblisky et a1 117-47 X 3,515,563 6/1970 Hodoley et al 117-'47 X 3,442,683 5/ 1969' Lenoble et al. 1 17160 X 3,437,507 4/1969 Jensen 117-1'6O X 3,467,540 9/ 1969 Schick ll7--2l3 X RALPH S. KENDALL, Primary Examiner.
C. WESTON, Assistant Examiner US. Cl. X.R.
117- 47 R, R, 213; 260--567.6 R
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US5456970A | 1970-07-13 | 1970-07-13 |
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US3684572D Expired - Lifetime US3684572A (en) | 1970-07-13 | 1970-07-13 | Electroless nickel plating process for nonconductors |
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Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3881049A (en) * | 1971-12-08 | 1975-04-29 | Kalle Ag | Process for depositing copper layers on shaped articles of a polyimide |
US3914126A (en) * | 1973-02-12 | 1975-10-21 | Xerox Corp | Nickel oxide interlayers for photoconductive elements |
DE2634232A1 (en) * | 1976-07-30 | 1978-02-02 | Licentia Gmbh | Thin film resistors using electroless nickel-phosphorus layer - obtd. from aq. bath providing very low temp. coefft. of resistance |
US4478883A (en) * | 1982-07-14 | 1984-10-23 | International Business Machines Corporation | Conditioning of a substrate for electroless direct bond plating in holes and on surfaces of a substrate |
US4639380A (en) * | 1985-05-06 | 1987-01-27 | International Business Machines Corporation | Process for preparing a substrate for subsequent electroless deposition of a metal |
EP0213542A1 (en) * | 1985-08-23 | 1987-03-11 | Schering Aktiengesellschaft | Conditioning agent for the treatment of basic materials |
US4720400A (en) * | 1983-03-18 | 1988-01-19 | W. L. Gore & Associates, Inc. | Microporous metal-plated polytetrafluoroethylene articles and method of manufacture |
US4910072A (en) * | 1986-11-07 | 1990-03-20 | Monsanto Company | Selective catalytic activation of polymeric films |
US4940609A (en) * | 1987-12-23 | 1990-07-10 | Basf Aktiengesellschaft | Polymeric conditioner for pretreating nonmetallic surfaces for chemical metallization |
US4997680A (en) * | 1987-12-23 | 1991-03-05 | Basf Aktiengesellschaft | Polymeric conditioner for pretreating nonmetallic surfaces for chemical metallization |
US5039550A (en) * | 1990-01-23 | 1991-08-13 | The United States Of America As Represented By The Secretary Of Commerce | Colloidal processing method for coating ceramic reinforcing agents |
US5075037A (en) * | 1986-11-07 | 1991-12-24 | Monsanto Company | Selective catalytic activation of polymeric films |
US6468672B1 (en) | 2000-06-29 | 2002-10-22 | Lacks Enterprises, Inc. | Decorative chrome electroplate on plastics |
US20040058071A1 (en) * | 2002-09-24 | 2004-03-25 | International Business Machines Corporation | Colloidal seed formation for printed circuit board metallization |
US20050218487A1 (en) * | 2004-03-30 | 2005-10-06 | Satoshi Kimura | Method for manufacturing wiring substrate and method for manufacturing electronic device |
US20060086620A1 (en) * | 2004-10-21 | 2006-04-27 | Chase Lee A | Textured decorative plating on plastic components |
US20120073978A1 (en) * | 2009-06-08 | 2012-03-29 | Basf Se | Use of ionic liquids for the pretreatment of surfaces of plastics for metallization |
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1970
- 1970-07-13 US US3684572D patent/US3684572A/en not_active Expired - Lifetime
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3881049A (en) * | 1971-12-08 | 1975-04-29 | Kalle Ag | Process for depositing copper layers on shaped articles of a polyimide |
US3914126A (en) * | 1973-02-12 | 1975-10-21 | Xerox Corp | Nickel oxide interlayers for photoconductive elements |
DE2634232A1 (en) * | 1976-07-30 | 1978-02-02 | Licentia Gmbh | Thin film resistors using electroless nickel-phosphorus layer - obtd. from aq. bath providing very low temp. coefft. of resistance |
US4478883A (en) * | 1982-07-14 | 1984-10-23 | International Business Machines Corporation | Conditioning of a substrate for electroless direct bond plating in holes and on surfaces of a substrate |
US4720400A (en) * | 1983-03-18 | 1988-01-19 | W. L. Gore & Associates, Inc. | Microporous metal-plated polytetrafluoroethylene articles and method of manufacture |
US4639380A (en) * | 1985-05-06 | 1987-01-27 | International Business Machines Corporation | Process for preparing a substrate for subsequent electroless deposition of a metal |
AT394213B (en) * | 1985-08-23 | 1992-02-25 | Schering Ag | CONDITIONING OF BASE MATERIALS |
EP0213542A1 (en) * | 1985-08-23 | 1987-03-11 | Schering Aktiengesellschaft | Conditioning agent for the treatment of basic materials |
US4910072A (en) * | 1986-11-07 | 1990-03-20 | Monsanto Company | Selective catalytic activation of polymeric films |
US5075037A (en) * | 1986-11-07 | 1991-12-24 | Monsanto Company | Selective catalytic activation of polymeric films |
US4940609A (en) * | 1987-12-23 | 1990-07-10 | Basf Aktiengesellschaft | Polymeric conditioner for pretreating nonmetallic surfaces for chemical metallization |
US4997680A (en) * | 1987-12-23 | 1991-03-05 | Basf Aktiengesellschaft | Polymeric conditioner for pretreating nonmetallic surfaces for chemical metallization |
US5039550A (en) * | 1990-01-23 | 1991-08-13 | The United States Of America As Represented By The Secretary Of Commerce | Colloidal processing method for coating ceramic reinforcing agents |
US6468672B1 (en) | 2000-06-29 | 2002-10-22 | Lacks Enterprises, Inc. | Decorative chrome electroplate on plastics |
US20040058071A1 (en) * | 2002-09-24 | 2004-03-25 | International Business Machines Corporation | Colloidal seed formation for printed circuit board metallization |
US6852152B2 (en) | 2002-09-24 | 2005-02-08 | International Business Machines Corporation | Colloidal seed formulation for printed circuit board metallization |
US20050042383A1 (en) * | 2002-09-24 | 2005-02-24 | International Business Machines Corporation | Colloidal seed formation for printed circuit board metallization |
US20050218487A1 (en) * | 2004-03-30 | 2005-10-06 | Satoshi Kimura | Method for manufacturing wiring substrate and method for manufacturing electronic device |
US7305761B2 (en) * | 2004-03-30 | 2007-12-11 | Seiko Epson Corporation | Method for manufacturing wiring substrate |
US20060086620A1 (en) * | 2004-10-21 | 2006-04-27 | Chase Lee A | Textured decorative plating on plastic components |
US20120073978A1 (en) * | 2009-06-08 | 2012-03-29 | Basf Se | Use of ionic liquids for the pretreatment of surfaces of plastics for metallization |
US9090966B2 (en) * | 2009-06-08 | 2015-07-28 | Basf Se | Use of ionic liquids for the pretreatment of surfaces of plastics for metallization |
US20140054788A1 (en) * | 2011-03-08 | 2014-02-27 | Japan Science And Technology Agency | Method for fabricating nanogap electrodes, nanogap electrodes array, and nanodevice with the same |
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