US3905877A - Process for electroplating polyoxymethylene - Google Patents

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
• • 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
  • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
  • C23C18/2033—Heat
• • 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
  • C23C18/28—Sensitising or activating
  • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
  • Y10T428/12556—Organic component

Definitions

• ABSTRACT An improved process for electroplating polyoxymeth' ylene is provided wherein shaped articles of polyoxymethylene are treated with pyridine preferably by immersion techniques prior to subjecting the shaped article to surface treatment with an acid etching agent.
• the present invention relates to a process for electroplating shaped structures of polyacetal polymeric material and, more particularly, is directed to a novel improved process for electroplating articles of polyoxymethylene.
• 3,5 54,880 discloses a process for electroplating an article of polyoxymethylene which comprises first subjecting the article to a surface preparation treatment by immersing the article in an acid agent such as orthophosphoric acid thereby to etch the surface of the article.
• the acid-etched article is thereafter treated as by an immersion technique with a basic solution such as sodium hydroxide.
• the thus treated article is then subjected to the conventional electroplating technique which entails the sequential steps of treating the article with sensitizing agents and activating agents followed by depositing an electroless plating of, for example, copper on the article and thereafter electroplating the article in a conventional electroplating bath.
• a drawback and continuing problem encountered heretofore as regards the electroplating of polyoxymethylene articles has been the inability to obtain plated articles wherein the metal plating is firmly bonded to the sur face of the plastic article. Oftentimes, the metal coating on the plastic object will exhibit undesirable blistering when the plated plastic object is subjected to a thermal cycle of heating and cooling, and the plastic objects often exhibit undesirable surface cracks which are be lieved to be induced by the acid etchant.
• the principal object of the present invention is to provide an improved process for electroplating shaped articles and objects of polyacetal resins such as polyoxymethylene that are characterized by more firmly adhered metal coatings and substantially free of the above-mentioned drawbacks.
• THE INVENTION there is provided in a process for electroplating a shaped article of polyoxymethylene by the sequential steps of etching the surface of said article with an acid etching agent such as orthophosphoric acid, neutralizing the etched surface of said article with a basic solution such as sodium hydroxide, treating said article with a noble metal catalyst such as palladium, depositing by electroless plating a metal coating such as nickel on said article, and depositing by electroplating a metal coating such as nickel, copper or chrome on said electroless plated article, the improvement which comprises treating said article with pyridine before etching the surface of said article.
• an acid etching agent such as orthophosphoric acid
• a basic solution such as sodium hydroxide
• a noble metal catalyst such as palladium
• depositing by electroless plating a metal coating such as nickel on said article
• depositing by electroplating a metal coating such as nickel, copper or chrome on said electroless plated article
• the salient feature of the present invention is the discovery that subjecting polyoxymethylene shaped articles to a treatment with pyridine prior to the conventional pre-treatment with acid etchants and catalysts (for electroless deposition) prior to the electroless plating and the electroplating thereof results in superior plated polyoxymethylene shaped articles characterized by a unique surface topography after etching and a more uniformly etched surface, fewer acid-etchant induced surface cracks, and unexpected and surprising adhesion of the metal coating characterized by superior resistance to blistering of the metal coating.
• the improved process of the present invention may be practiced by treating the shaped articles of polyoxymethylene with pyridine. This is preferably done by immersing the polyoxymethylene article in the pyridine.
• the pyridine utilized for the treatment may be a solution entirely of pyridene or an aqueous solution of pyridine containing up to about 7.5 percent by volume of water.
• the polyoxymethylene article is subjected to a preplate process and an electroplating process similar to that described in the aforementioned U.S. Pat. No. 3,554,880.
• plaque samples were immersed for 2 minutes into an alkaline cleaner solution comprising 6 oz. of Metex S1651 (MacDermid, Inc.., Waterbury, Connecticut) per gallon of distilled water maintained at 84C. and thereafter rinsed for 2 minutes with water at room temperature.
• an alkaline cleaner solution comprising 6 oz. of Metex S1651 (MacDermid, Inc.., Waterbury, Connecticut) per gallon of distilled water maintained at 84C. and thereafter rinsed for 2 minutes with water at room temperature.
• the cleaned plaque samples were next immersed for 5 minutes in a solution of 30% pyridine and distilled water maintained at 60C., followed by a l minute rinse with water at room temperature.
• the pyridine-treated plaque samples were next immersed for two minutes in a solution of distilled water containing 83% by volume of 85% by weight orthophosphoric acid maintained at 70C., followed by a one minute rinse with water at room temperature.
• the acid etched plaque samples were next immersed for 6 minutes in a distilled water solution containing 12% by weight sodium hydroxide maintained at 104C.
• the base-neutralized plaque samples were next immersed for 10 minutes in a distilled water solution con taining 1% by volume of acetic acid maintained at C.
• the surface treated polyoxymethylene plaque samples were next subjected to electroless nickel plating in the following manner: (1) the plaques were first immersed for 2 minutes in a preactivator bath (maintained at room temperature) consisting of a solution of distilled water containing 1% by volume of MACuplex Preactivator PA-3 (MacDermid, Dermid, Inc., Waterbury, Connecticut), followed by a one minute rinse water at room temperature, (2) the plaques were next immersed for 2 minutes in a palladium activator bath (maintained at room temperature) consisting of a solution of distilled water containing by volume of MACuplex Activator D-34 (MacDermid, Inc., Waterbury, Connecticut) and 20% by volume of HCI, followed by a 1 minute rinse with water at room tempera- 1O ture, (3) the plaques were next immersed for one minute in an accelerator bath (maintained at 50C.) consisting of an aqueous solution of distilled water containing 5% by volume of MACuplex D-45 Accelerator (MacD
• polyoxymethylene plaque samples were evaluated for surface cracks; these samples were prepared in accordance with the procedure described above except that the electroless nickel plating was conducted for 5 minutes instead of' 10 minutes, in order to obtain a thinner layer of electroless nickel to facilitate evaluation for surface cracks.
• the summation of the length of the cracks induced on the surface of the plaque samples also is presented in Table 1 below under the column ZCL.
• the electroless nickel plated plaque samples were next electroplated by subjecting the plaques to the sequential steps of the eleetroplate sequence set forth in the table below; the plaques were immersed sequentially into each treating bath of the composition identified in the table below by immersing the plaques under the conditions also set forth in the table:
• the nickel-strike was deposited by immersing the plaque samples into the Watts type nickel plating bath operating at a current density of about l5 amps/sq. ft. for up to about 2 minutes after which the current density of the hath was l'fliSLftl to about 30 amps/sq. ft.

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• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Chemically Coating (AREA)

Abstract

Description

Claims (2)

Priority Applications (1)

Applications Claiming Priority (1)

Publications (1)

Family

ID=23759815

Family Applications (1)

Country Status (1)

Cited By (5)

Citations (7)

• 1974
  • 1974-02-19 US US443204A patent/US3905877A/en not_active Expired - Lifetime

Patent Citations (7)

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