US3793159A - Electroplating plastics - Google Patents

Electroplating plastics Download PDF

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Publication number
US3793159A
US3793159A US00250585A US3793159DA US3793159A US 3793159 A US3793159 A US 3793159A US 00250585 A US00250585 A US 00250585A US 3793159D A US3793159D A US 3793159DA US 3793159 A US3793159 A US 3793159A
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United States
Prior art keywords
surfactant
solution
volume
ethyleneoxy
electroplating
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US00250585A
Inventor
J Wells
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Phillips Petroleum Co
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Phillips Petroleum Co
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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
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate

Definitions

  • this invention relates to an improvement in a process for electroplating plastics containing a siliceous filler in which the plastic is conditioned and plated in an electroless process.
  • the method of the present invention is an improvement of that process and is applicable to the plastics, and can be carried out employing the conditions, the procedural steps and the reagents defined therein.
  • the mineral-filled plastic is conditioned by employing an acid chromate etch and an HP treatment, the sequence of the steps not being critical. Thereafter, the plastic is water rinsed or acid rinsed and is then contacted with one or more sensitizing solutions and activating solutions, these frequently including stannous chloride and palladium ammonium chloride solutions, respectively, whose purpose is to seed the plastic surface. Thereafter, the plastic is contacted with one or more plating solutions.
  • the method of this invention relates to the water I rinse or acid rinse referred to above. Since, as has been said, the acid chromate and the Hf treatment are sequentially interchangeable, it will be assumed for the in which R is an alkyl radical containing eight to 12 carbon atomsexemplifiegb octy l nonyl and dodecyl radicals and R' is hydrogen or R, and n has a value ranging from about 2 to 30, thus the number of repeating ethylene oxide units ranges from 1 to 29.
  • octylphenoxypoly(ethyleneoxy)ethanol octylphenoxypoly(ethyleneoxy)ethanol, nonylphenoxypoly(ethyleneoxy)ethanol, dodecylphenoxypoly(ethyleneoxy)ethanol, and 2,4-dioctylphenoxypoly(ethyleneoxy)ethanol.
  • nonylphenoxypoly(ethyleneoxy)ethanol in which n ranges from about 9 to 10, available commercially as Igepal CO-630 from General Aniline and Film Corp.
  • the method of this invention can be employed by using either an aqueous solution wash followed by an acid solution wash in which either or both solutions comprises the surfactant, or by using a single aqueous solution comprising an acid and the surfactant.
  • the surfactant is effective in improving the process regardless of whether it is employed in conjunction with an 5 acid wash.
  • the acid bath be employed since the use of a bath containing an acid similar to that contained in the activator solution to which the plastic is subsequently subjected reduces dilution of the latter. Accordingly, no water rinse is employed after the acid bath containing the surfactant, the plastic being introduced from the acid bath directly into the activator.
  • the surfactant is effective when employed in amounts of a minimum of about 5 parts per million by volume, and greater, preferably in amounts between about 8 and about 150 ppm.
  • the plastic is maintained in contact with the solution containing the surfactant for a period sufficient to insure complete contact, this period being that generally employed in similar rinsing operations.
  • the method of this invention is illustrated by the following data in which molded plastic plastes comprising mineral-filled polypropylene, previously identically processed, were introduced into various aqueous solutions as defined below.
  • a nonionic surfactant was employed, this surfactant being nonylphenoxypoly(ethyleneoxy)ethanol in which n is a nominal 9 to 10.
  • the rinsed plates were plated with several layers of metal as described in the aforementioned patent under substantially identical conditions with the following results:
  • a method of electroplating a plastic surface which comprises:
  • said surfactant is thanol in which the alkyl radical contains from eight to 5 12 carbon atoms and the number of units of ethylene oxide in said surfactant is within the range of from contained in said aqueous solution in an amount within the range of from about 8 to about 150 parts by volume about 1 to per million parts by volume of said solution.

Abstract

In an electroless process for electroplating plastics containing a siliceous filler, a wash solution containing a nonionic surfactant is employed to remove the chromium from the plastic subsequent to the acid chromate etch and before electroplating.

Description

United States Patent Wells Feb. 19, 1974 [5 ELECTROPLATING PLAST ICS 3,663,377 5/1972 Khelghatian....- 204 30 [75] Inventor: Johnny L- wells, Bartlesvine, Okla. 3,620,804 ll/l 97l Baur 204/30 [73] Assignee: Phillips Petroleum Company,
B tl ill Okla Primary ExaminerT. Tufariello [22] Filed: May 5, 1972 [21] Appl. No.: 250,585 ABSTRACT Cl 7/47 A, 204/20 In an electroless process for electroplating plastics [51] Int. Cl C23b 5/60, 844d 1/092 containing 3 siliceous filler, a wash solution containing Field of Search 117/47 A a nonionic surfactant is employed to remove the chromium from the plastic subsequent to the acid chro- [56] References Cited mate etch and before electroplating.
UNITED STATES PATENTS 5/1971 Grunwald 106/265 7 Claims, N0 Drawings 1 ELECTROPLATING PLASTICS This invention relates to the electroplating of plastics.
In one of its more specific aspects, this invention relates to an improvement in a process for electroplating plastics containing a siliceous filler in which the plastic is conditioned and plated in an electroless process.
The electroplating of plastics is well known. One such process is that described in U.S. Pat. No. 3,567,594 to Wells, the disclosure of which is incorporated herein by reference.
The method of the present invention is an improvement of that process and is applicable to the plastics, and can be carried out employing the conditions, the procedural steps and the reagents defined therein.
In one aspect of that process, the mineral-filled plastic is conditioned by employing an acid chromate etch and an HP treatment, the sequence of the steps not being critical. Thereafter, the plastic is water rinsed or acid rinsed and is then contacted with one or more sensitizing solutions and activating solutions, these frequently including stannous chloride and palladium ammonium chloride solutions, respectively, whose purpose is to seed the plastic surface. Thereafter, the plastic is contacted with one or more plating solutions.
The method of this invention relates to the water I rinse or acid rinse referred to above. Since, as has been said, the acid chromate and the Hf treatment are sequentially interchangeable, it will be assumed for the in which R is an alkyl radical containing eight to 12 carbon atomsexemplifiegb octy l nonyl and dodecyl radicals and R' is hydrogen or R, and n has a value ranging from about 2 to 30, thus the number of repeating ethylene oxide units ranges from 1 to 29.
Among those compounds which can be employed are octylphenoxypoly(ethyleneoxy)ethanol, nonylphenoxypoly(ethyleneoxy)ethanol, dodecylphenoxypoly(ethyleneoxy)ethanol, and 2,4-dioctylphenoxypoly(ethyleneoxy)ethanol.
Among the preferred surfactants is nonylphenoxypoly(ethyleneoxy)ethanol in which n ranges from about 9 to 10, available commercially as Igepal CO-630 from General Aniline and Film Corp.
The method of this invention can be employed by using either an aqueous solution wash followed by an acid solution wash in which either or both solutions comprises the surfactant, or by using a single aqueous solution comprising an acid and the surfactant. The surfactant is effective in improving the process regardless of whether it is employed in conjunction with an 5 acid wash. However, it is preferred that the acid bath be employed since the use of a bath containing an acid similar to that contained in the activator solution to which the plastic is subsequently subjected reduces dilution of the latter. Accordingly, no water rinse is employed after the acid bath containing the surfactant, the plastic being introduced from the acid bath directly into the activator.
The surfactant is effective when employed in amounts of a minimum of about 5 parts per million by volume, and greater, preferably in amounts between about 8 and about 150 ppm. The plastic is maintained in contact with the solution containing the surfactant for a period sufficient to insure complete contact, this period being that generally employed in similar rinsing operations.
The method of this invention is illustrated by the following data in which molded plastic plastes comprising mineral-filled polypropylene, previously identically processed, were introduced into various aqueous solutions as defined below. A nonionic surfactant was employed, this surfactant being nonylphenoxypoly(ethyleneoxy)ethanol in which n is a nominal 9 to 10. The rinsed plates were plated with several layers of metal as described in the aforementioned patent under substantially identical conditions with the following results:
Electroplating Results 3 5 Concentration in Aqeuous Solution HCI, Vol. Surfactant & Surface Metal Adhesion,
Conc., ppm Plated lb./in.
O 0 Less than I Not determined 25 0 40 Not determined These data indicate the operability of the surfactants defined in the method of this invention in aqueous solution with or without the presence of the mineral acid, in the concentrations defined.
It will be evident from the foregoing that various modifications can be made to the method of this invention. Such are considered, however, to be within the scope thereof.
What is claimed is:
l. A method of electroplating a plastic surface which comprises:
a. preparing said plastic surface by contacting said surface with an acid chromate etching solution and a hydrogen fluoride treatment; b. rinsing the contacted surface with an aqueous solution comprising a nonionic surfactant and hydrogen chloride; c. then sensitizing the rinsed surface with a solution comprising stannous chloride and palladium chloride; and,
d. electroplating the sensitized surface. 2. The method of claim 1 in which said contacted surface is rinsed in an aqueous solution consisting essentially of hydrochloric acid and a mono-dialkyl substicontained in said aqueous solution in an amount of at tute p yp y( y y)et least about 5 parts by volume per million parts by vol- 3. The method of claim 1' in which said surfactant is me f Said solution mono'dialkyl substituted phenoxypolethyleneoxy)e' 6. The method of claim 5 in which said surfactant is thanol in which the alkyl radical contains from eight to 5 12 carbon atoms and the number of units of ethylene oxide in said surfactant is within the range of from contained in said aqueous solution in an amount within the range of from about 8 to about 150 parts by volume about 1 to per million parts by volume of said solution.
4. The method of claim 1 in which said surfactant is The method of claim 1 in which said Solution nonylphenoxypoly(ethyleneoxy)ethanol containing tains hydrochloric acid in an amount of about 25 perabout 8 to 9 repeating units of ethylene oxide. cent by volume.
5. The method of claim 1 in which said surfactant is UNITED sTATEs PATENT OFFICE Patent No. 3,793, 59
, Johnny L. Wells error appears in the above-identified patent and that said It is certified that ted as shown below:
Letters Patent are hereby correc Column 3, line 8, after "to insert about Signed and sealed this 9th day of July 1974 (SEAL) Attest:
McCOY GIBSON, JR. C. MARSHALII DANN Attestlng Officer Commissioner of Patents

Claims (6)

  1. 2. The method of claim 1 in which said contacted surface is rinsed in an aqueous solution consisting essentially of hydrochloric acid and a mono-dialkyl substituted phenoxypoly(ethyleneoxy)ethanol.
  2. 3. The method of claim 1 in which said surfactant is mono-dialkyl substituted phenoxypoly(ethyleneoxy)ethanol in which the alkyl radical contains from eight to 12 carbon atoms and the number of units of ethylene oxide in said surfactant is within the range of from about 1 to 29.
  3. 4. The method of claim 1 in which said surfactant is nonylphenoxypoly(ethyleneoxy)ethanol containing about 8 to 9 repeating units of ethylene oxide.
  4. 5. The method of claim 1 in which said surfactant is contained in said aqueous solution in an amount of at least about 5 parts by volume per million parts by volume of said solution.
  5. 6. The method of claim 5 in which said surfactant is contained in said aqueous solution in an amount within the range of from about 8 to about 150 parts by volume per million parts by volume of said solution.
  6. 7. The method of claim 1 in which said solution contains hydrochloric acid in an amount of about 25 percent by volume.
US00250585A 1972-05-05 1972-05-05 Electroplating plastics Expired - Lifetime US3793159A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935081A (en) * 1973-08-14 1976-01-27 Phillips Petroleum Company Density control for electroplatable polymer compositions
US4552626A (en) * 1984-11-19 1985-11-12 Michael Landney, Jr. Metal plating of polyamide thermoplastics
EP0398019A1 (en) * 1989-05-08 1990-11-22 International Business Machines Corporation Direct electroplating of through-holes
WO1991008325A1 (en) * 1989-12-04 1991-06-13 Schering Aktiengesellschaft Process for direct galvanic metallisation
US5681443A (en) * 1992-07-01 1997-10-28 Gould Electronics Inc. Method for forming printed circuits
CN109852954A (en) * 2019-01-29 2019-06-07 上海交通大学 A kind of method of polymeric film surface growth nanometer metal palladium particle

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3579365A (en) * 1967-06-14 1971-05-18 Macdermid Inc Compositions for and methods of improving adhesion of plated metal on plastic substrates
US3620804A (en) * 1969-01-22 1971-11-16 Borg Warner Metal plating of thermoplastics
US3663377A (en) * 1970-05-08 1972-05-16 Habet M Khelghatian Electroplatable polyolefins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3579365A (en) * 1967-06-14 1971-05-18 Macdermid Inc Compositions for and methods of improving adhesion of plated metal on plastic substrates
US3620804A (en) * 1969-01-22 1971-11-16 Borg Warner Metal plating of thermoplastics
US3663377A (en) * 1970-05-08 1972-05-16 Habet M Khelghatian Electroplatable polyolefins

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935081A (en) * 1973-08-14 1976-01-27 Phillips Petroleum Company Density control for electroplatable polymer compositions
US4552626A (en) * 1984-11-19 1985-11-12 Michael Landney, Jr. Metal plating of polyamide thermoplastics
EP0398019A1 (en) * 1989-05-08 1990-11-22 International Business Machines Corporation Direct electroplating of through-holes
WO1991008325A1 (en) * 1989-12-04 1991-06-13 Schering Aktiengesellschaft Process for direct galvanic metallisation
US5681443A (en) * 1992-07-01 1997-10-28 Gould Electronics Inc. Method for forming printed circuits
US5685970A (en) * 1992-07-01 1997-11-11 Gould Electronics Inc. Method and apparatus for sequentially metalized polymeric films and products made thereby
US5716502A (en) * 1992-07-01 1998-02-10 Gould Electronics Inc. Method and apparatus for sequentially metalizing polymeric films and products made thereby
US5944965A (en) * 1992-07-01 1999-08-31 Gould Electronics Inc. Method and apparatus for sequentially metalizing polymeric films and products made thereby
US6224722B1 (en) 1992-07-01 2001-05-01 Gould Electronics Inc. Method and apparatus for sequentially metalizing polymeric films and products made thereby
CN109852954A (en) * 2019-01-29 2019-06-07 上海交通大学 A kind of method of polymeric film surface growth nanometer metal palladium particle

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