US3686016A - Conditioning of propylene polymers for electroless plating - Google Patents

Conditioning of propylene polymers for electroless plating Download PDF

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US3686016A
US3686016A US3686016DA US3686016A US 3686016 A US3686016 A US 3686016A US 3686016D A US3686016D A US 3686016DA US 3686016 A US3686016 A US 3686016A
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amine
acid
conditioning
propylene
propylene polymers
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Eileen Maguire
Leon A Kadison
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Crown City Plating Co
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Crown City Plating Co
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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
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/26—Roughening, e.g. by etching using organic liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, 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
    • C23C18/285—Sensitising or activating with tin based compound or composition
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to electroless plating of propylene polymers, such as polypropylene, and more particularly to improving the bond strength between an electroless deposited metal coating and the polymer substrate.
  • Propylene polymers like most plastics, are electrically non-conductive. It has, however, been sought to achieve a good metal bond to the surface of propylene polymers by an initial plating operation, known as electroless plating.
  • This procedure generally consists of conditioning the surface of the plastic article for plating by etching with a strong oxidizing acid, seeding the surface by contact with a noble metal salt solution, e.g., a palladium chloride solution, then immersing the seeded surface in an auto-catalytic electroless solution where an initial coating of a conductive metal, e.g., copper and nickel, is established by chemical deposition.
  • the metal coating formed acts as a bus which allows a thicker metal coating to be built up electrolytically.
  • Adhesion is further optimized by employing as the strong oxidizing acid the solution containing chromic acid and trivalent chromium ions and by immersing the electrolessly plated substrate in a dilute aqueous anionic or non ionic ⁇ surfactant solution prior to normal aging to prevent the drying out of absorbed salts and oxidation of the electrolessly deposited layer.
  • DRAWING Attached drawing contains schematic representation of the preferred procedure followed in preparing a propylene polymer for electroless plating.
  • the bond strength of metals electrolessly deposited on propylene polymer substrates is remarkably improved by preceding etching with a strong oxidizing acid with contact with certain secondary and/ or tertiary amines.
  • the propylene polymers treated in accordance with the practice of this invention include homopolymers of propylene and interpolymers of propylene with one or more ethylenically unsaturated monomers such as ethylene and butene, and including among others, the so-called platable grades of polypropylene.
  • the amine pre-etch conditioners of this invention are compounds having the general structure wherein R1 and AR2 are alkyl groups containin-g from one to about four carbon atoms and the total number of carbon atoms provided by R1 and R2 is between two and eight, preferably about four to about six, and wherein R3 is hydrogen or a hydrocarbyl group.
  • the nature of the two alkyl groups of the amines used to condition the surfaces of propylene polymers for electroless plating appears important, the nature of the third group attached to the amine does not appear to be critical. It may, as indicated, be hydrogen or a hydrocarbon radical such as straight chain, branched chain, saturated or unsaturated aliphatic, cycloaliphatic, aromatic and the like. What appears to be important, however, is that a certain balance be reached between the two functional alkyl groups of the amine such that good wetting contact exists between the amine conditioner and the surface of the propylene polymer.
  • amines which may be used as conditioners for the surface propylene polymers there may be mentioned diethyl amine, dipropyl amine, diisopropyl, dibutyl amine, diisobutyl amine, trimethyl amines, tripropyl amine, triisopropyl amine, tributyl amine, triisobutyl amine, N-methylbutyl amine, N- ethylbutyl amine, N,Ndiethyl ethylenediamine, N,Ndi methylaniliue, N,Ndiethylaniline, diethylamino phenol, diethylamino benzaldehyde, N,Ndiethyl cyclohexylamine, and the like, as well as mixtures thereof.
  • the preferred amine conditioner is N,Ndiethylaniline.
  • the secondary and tertiary amines of this invention may be used as such they also may be diluted with organic solvents, which play no part as conditioners in conditioning the surface of the propylene polymers for electroless plating.
  • the conditioners are used full strength.
  • the temperature at which the propylene polymers are conditioned using secondary and tertiary amines of this invention is not narrowly critical. They may range from about 90 F. up to the softening point of the propylene polymer or the boiling point of the conditioner, whichever is lower. We have generally found, however, that conditioning is favored by higher temperatures and it is preferred to use amines which are relatively nonvolatile in the temperature range of from about 90 to about 170 F.
  • the amount of contact between the propylene polymer and the amine conditioners of this invention will vary somewhat depending on the nature of the polymer as well as the temperature at which it is conditioned. Conditioning times will generally range up to about l minutes, with shorter times being employed for the socalled platable grades of polypropylene and the longer conditioning times employed for the propylene polymers which will not, under normal conditions accept an electrolessly deposited plate even after conditioning with a strong acid.
  • propylene polymers conditioned with the amines of this invention are adapted for an electroless plating operation, to obtain optimum results it is preferred to follow the procedure schematically shown in the drawing.
  • the article is first conditioned by contact with the amine for a desired period of time, then rinsed with water, preferably de-ionized water, and passed directly to the strong oxidizing acid etchant. It is preferred to wash the article for a short period of time, generally from about to about 120 seconds, with an acid, such as 80% sulfuric acid, to quench the etch and initiate deglazing of the polymer surface.
  • water preferably de-ionized water
  • an acid such as 80% sulfuric acid
  • the article is rinsed in water again, preferably de-ionized water, and passed on to a strong oxidizing acid etch.
  • a strong oxidizing acid etch any of the known oxidizing acid solutions may be employed, it is preferred to use a pure chromic acid etch.
  • the chromic acid etch used contains from about 8.5 to about 10.5 lbs. of chromic acid per gallon of solution, which is above the normal solubility of chromic acid in water. Higher solubility, however, is achieved by the presence of trivalent chromium, which is formed in the reduction of the hexavalent chromium during oxidation of the polymer surface.
  • An initial solution of high chromic acid content may be conveniently obtained by the addition of oxalic acid to a chromic acid solution to form trivalent chromium ions followed by the addition of chromium trioxide to the resultant solution to form an oxidizing acid of the desired hexavalent chromium assay.
  • the etch with the strong oxidizing acid is generally at a temperature from about 110 F. to distortion temperature of the propylene polymer, preferably from about 110 to about 200 F., and more preferably from about 150 to about 185 F. Residence times ranging from about 5 to about 10 minutes, depending upon the nature of the propylene polymer treated, are generally employed.
  • the article After etching with the strong oxidizing acid, the article is then passed on to a spray rinse where any of the remaining acid is forcibly washed from its surface.
  • an alkaline cleanser which is free of silicates.
  • This cleanser is preferably mild and free of caustics.
  • the cleanser is generally maintained at 4 temperatures from about to about 130 F. and the residence time of the article is from about 3 to about 5 minutes.
  • the article may now be passed on to any of the electroless plating operations, employing either copper or nickel.
  • the conditioned article may be immersed in a solution of stannous chloride-hydrochloric acid to sensitize the plastic surface by absorption of stannous ions.
  • a noble metal salt @.g., palladium chloride
  • the noble metal film on the article surface then acts as a catalyst in the electroless metal bath into which the activated article is passed.
  • electroless copper and nickel formulations may be used.
  • electroless copper formulations essentially consist of a soluble cupric salt, such as copper sulfate; a complexing agent for the cupric ion, such as Rochelle salt; and alkali hydroxide for adjustment of pH; a carbonate radical as a buffer; and a reducing agent for the cupric ion, such as formaldehyde.
  • a soluble cupric salt such as copper sulfate
  • a complexing agent for the cupric ion such as Rochelle salt
  • alkali hydroxide for adjustment of pH
  • carbonate radical as a buffer
  • a reducing agent for the cupric ion such as formaldehyde
  • the article may be electrolytically plated by conventional means with copper, nickel, gold, silver, chromium and the like to provide the desired finish on the article.
  • the amine conditioned article may be passed after a water rinse directly to the oxidizing acid and thereafter directly to the electroless plating step, it has been observed that exercising care in thoroughly cleansing the article after each conditioning step has a cumulative beneficial effect on improving overall adhesion.
  • the deposited metal coating will be uniform and the bond strength of both electrolessly deposited copper and nickel to the surface will be unusually high independent of the electroless deposition technique employed. Moreover, high bond strengths, often above 25 lbs/inch, are achieved without undermining or adversely affecting the resin integrity. During standard destruct peel tests it has been determined that failure is mainlyat the resin-metal interface and there is little or no removal of plastic from the substrate with the metal.
  • peel strengths were determined by pulling a one-inch strip of the deposited metal at an angle of 90 to the propylene polymer surface using a Dillon pull tester.
  • Example 1 Using the procedure set forth above and as illustrated by the drawing, a plaque fabricated from a propylene polymer was conditioned for electroless copper plating by first immersing the plaque in a dipropyl amine bath maintained at a temperature of F. for 15 minutes. Fol lowing immersion the plaque was acid rinsed by immersion in 80% sulfuric acid bath for 90 seconds and then etched in a chromic acid bath maintained at F. for 6 minutes. After electroless plating, a copper plate was built up electrolytically to a thickness of about 4 mils. It was found that the plate had an average bond strength of 2 7 lbs. per inch when adjusted to a plate thickness of 4 mils.
  • Example 2 The procedure of Example 1 was repeated except that the dipropyl amine bath was maintained at a temperature between 100-118 F.
  • the resultant plate had an average bond strength of 15 lbs. per inch.
  • Example 3 The procedure of Example 1 was repeated except a mixture of sulfuric and chromic acids were used instead of a chromic acid as the etch.
  • the resultant copper plate had a bond strength of 12 lbs. per inch.
  • Example 4 Following the procedure set forth in Example 1, a propylene polymer was etched in an amine mixture containing about 86.5 percent by Weight dipropyl amine and 13.5 percent by weight N,Ndiethyl aniline. The mixture of amines was maintained at 150 F. and conditioning time was 15 minutes. After a 90 second acid dip, the plaque was etched for 7 minutes in an etch comprising a major amount of chromic acid and a minor amount of sulfuric acid. The resultant plate had a bond strength of 20 lbs. per inch.
  • Example 5 The procedure of Example 1 was repeated except that N,Ndiethyl aniline was used as the conditioner and conditioning was carried out at a temperature of 170 F. Average bond strength of the copper to the plaque was 22.25 lbs. per inch.
  • Example 6 The procedure of Example 1 was repeated except dibutyl amine was used as the conditioner and conditioning temperature was between 105 and 110 F. A good bond of copper to the conditioned and etched propylene polymer was obtained.
  • a process for electrolessly plating propylene polymers which includes the step of contacting the propylene polymer surface with a strong oxidizing acid to promote adhesion of the metal to the propylene polymer, the improvement which comprises conditioning the polymer surface prior to contact with the oxidizing acid by contact with at least one amine having the structure wherein R1 and R2 are alkyl groups containing from 1 to about 4 carbon atoms and provide a total of from 2 to 8 carbon atoms and R3 is hydrogen or a hydrocarbon radical.
  • process for electrolessly plating propylene polymers which includes the step of contacting the propylene polymer surface with a strong oxidizing acid to promote adhesion of the metal to the propylene polymer, the improvement which comprises conditioning the polymer surface prior to contact with the oxidizing acid by contact with at least one amine selected from the group consisting of dipropyl amine, dibutyl amine and N,Ndiethy1 aniline.
  • a process as claimed in claim 10 in which the amine conditioned propylene polymer is washed with an acid for a period of time from 30 to 120 seconds.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemically Coating (AREA)
US3686016D 1970-08-19 1970-08-19 Conditioning of propylene polymers for electroless plating Expired - Lifetime US3686016A (en)

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US6502470A 1970-08-19 1970-08-19
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3779840A (en) * 1968-10-03 1973-12-18 Dow Chemical Co Lamination of olefin polymer to various substrates
US3791848A (en) * 1972-05-19 1974-02-12 Western Electric Co A method of improving the adherence of a metal deposit to a polyimide surface
US3905877A (en) * 1974-02-19 1975-09-16 Du Pont Process for electroplating polyoxymethylene
US4148945A (en) * 1974-02-04 1979-04-10 The Dow Chemical Company Process of metal plating on plastics
US6077913A (en) * 1998-03-26 2000-06-20 Beholz Technology, L.L.C. Process for producing paintable polymeric articles
US6100343A (en) * 1998-11-03 2000-08-08 Beholz Technology, L.L.C. Process for producing paintable polymeric articles
US7901603B1 (en) 2004-06-21 2011-03-08 Lars Guenter Beholz Process for producing adhesive polymeric articles from expanded foam materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2149427B (en) * 1983-11-09 1987-12-02 Nippon Paint Co Ltd Surface treatment of aluminium materials

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3779840A (en) * 1968-10-03 1973-12-18 Dow Chemical Co Lamination of olefin polymer to various substrates
US3791848A (en) * 1972-05-19 1974-02-12 Western Electric Co A method of improving the adherence of a metal deposit to a polyimide surface
US4148945A (en) * 1974-02-04 1979-04-10 The Dow Chemical Company Process of metal plating on plastics
US3905877A (en) * 1974-02-19 1975-09-16 Du Pont Process for electroplating polyoxymethylene
US6077913A (en) * 1998-03-26 2000-06-20 Beholz Technology, L.L.C. Process for producing paintable polymeric articles
US6100343A (en) * 1998-11-03 2000-08-08 Beholz Technology, L.L.C. Process for producing paintable polymeric articles
US7901603B1 (en) 2004-06-21 2011-03-08 Lars Guenter Beholz Process for producing adhesive polymeric articles from expanded foam materials

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FR2166439A5 (enExample) 1973-08-17
GB1317849A (en) 1973-05-23

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