US3639153A - Process of modifying a hydrohalogen polymer surface - Google Patents

Process of modifying a hydrohalogen polymer surface Download PDF

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Publication number
US3639153A
US3639153A US3639153DA US3639153A US 3639153 A US3639153 A US 3639153A US 3639153D A US3639153D A US 3639153DA US 3639153 A US3639153 A US 3639153A
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Prior art keywords
polymer
hydrohalogen
alkoxide
activated
alkali metal
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English (en)
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Terry Bill Waggoner
Edgar John Seyb Jr
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M&T Chemicals Inc
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M&T Chemicals Inc
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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
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • 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
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
    • 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

Definitions

  • hydrohalogen polymer Surface which comprises contacting a um Cl (373C 3/02 hydrohalogen polymer surface with an alkali metal alltoxide [58] w 8 H8 MOR wherein M is an alkali metal and R is an alkyl group 1 R, 61, thereby forming an alkoxide-activated surface and contacting said alkoxide-activated surface with an oxidizing agent ⁇ 56]
  • This invention relates to the modification of plastic surfaces. More particularly, it relates to the modification of the surface of a hydrohalogen-containing polymer to render it receptive to a deposited metal plate.
  • the process of the present invention for modifying a hydrohalogen polymer surface may comprise contacting the hydrohalogen polymer surface with an alkali metal alkoxide MOR wherein M is an alkali metal and R is an alkyl group thereby forming an alkoxide activated surface.
  • the hydrohalogen polymer surfaces which may be treated in practice of this invention may include those having, in the polymer, at least one group.
  • X may be a halogen atom selected from the group consisting of fluorine, chlorine, bromine, and iodine.
  • X may be an active halogen atom selected from the group consisting of chlorine and bromine.
  • X may be chlorine.
  • the hydrohalogen polymer surfaces may preferably be chlorine-containing polymers and preferably polymers of vinyl chloride or vinylidene chloride. They may be homopolymers of polyvinyl chloride, of polyvinylidene chloride, or of polyvinyl dichloride. They may be copolymers of these compositions with other ethylenically unsaturated monomers.
  • Ethylenically unsaturated monomers are compounds which contain polymerizable carbon-to-carbon double bonds and may include acrylates such as acrylic acid, ethyl acrylate, acrylonitrile, etc.; vinyls such as styrenes, vinyl acetate, etc; maleates such as maleic acid, maleic anhydride, maleate esters, etc.
  • the preferred hydrohalogen-containing polymer may be polyvinyl chloride.
  • the polymer may be treated in practice of this invention in the form of bodies, sheets, rods, etc., of polymer. It may also be possible to treat surface layers of polymer on other basis materials, e.g., a body of methyl methacrylate bearing a surface layer of polyvinyl chloride, etc.
  • a hydrohalogen polymer such as e.g., a polyvinyl chloride, polyvinylidene chloride, polyvinyl dichloride, polychlorostyrene, etc.
  • a hydrohalogen polymer such as e.g., a polyvinyl chloride, polyvinylidene chloride, polyvinyl dichloride, polychlorostyrene, etc.
  • the alkali metal alkoxidcs which may be cm pluyctl may be those having the formula MOR wherein M is an x l c l alkali metal and R is an alkyl group.
  • M may be potassium, sodium, lithium, and preferably sodium.
  • R may be methyl, ethyl, npropyl, i-propyl, n-butyl, i-butyl, s-butyl, n-amyl, nhexyl, i-hexyl, n-heptyl, n-octyl, 2-ethyl liexyl, nonyls, decyls, dodecyls, etc.
  • R may be an alkyl group having one to 12 carbon atoms and most preferably one to eight carbon atoms.
  • Typical illustrative alkoxides MOR which may be employed may include:
  • the preferred alkoxide may include the ethoxides and propoxides and preferably sodium ethoxide and sodium ipropoxide.
  • the alkoxides may be dissolved in alcohol ROH and preferably the corresponding alcohol.
  • Preferably sodium ethoxide may be made by adding sodium: metal to an excess of absolute ethanol and the resulting solution used as preparedcontaining an excess of ethanol in which the solid sodium ethoxide is very soluble.
  • Contact between the hydrohalogen polymer surface and the alkoxide may be effected preferably by dipping the polymer surface into a body of the alkoxide in solution. Temperature during contact may be 2l06 C., preferably 5588 C,, more preferably 60-77 C. Contact time may be 3-5 minutes to 70-8O hours, preferably 5-300 minutes, most preferably 1045 minutes. The temperature and times may be varied. lllustrative temperatures and times may be as set forth in table I.
  • the surface may become activated. In some cases there may be no apparent visual change in the surface although in other cases, the surface may visually appear slightly modified.
  • the surface may be referred to as an alkoxide-activated surface.
  • the novel product so prepared may comprise a basis material bearing a hydrohalogen surface including at least one-CH-CX group, wherein X is a halogen, at least a portion of which has been alkoxide activated.
  • This novel product may be particularly characterized by its chemical reactivity, and particularly by its ready ability to be oxidized, to accept donor atoms from other molecules, etc.
  • the alkoxide-activated surface of the hydrohalogen polymer material may be contacted with an oxidizing agent of sufficient strength to convert an olefinic double bond to the corresponding aldehyde, ketone, or carboxyl group.
  • Typical oxidizing agents may include oxygen, potassium permanganate (in aqueous solution) KMnO chromic acid (in aqueous solution), organic peracids (such as perbenzoic acid, peracetic acid, etc.), inorganic peroxides (such as hydrogen peroxide), etc.
  • Oxidation may be carried out at temperatures from ambient room temperature (typically l5-20 C.) to the melting point of the plastic. Preferably, temperatures of from about 55-77 C. are employed.
  • the alkoxide-activated surface is generally contacted with the oxidizing agent at temperatures of from about 66-77 C., for times 2-3 seconds to 2-3 hours. Longer contact times may be employed if desired on certain hydrohalogen polymers [e.g., poly(vinylidene chloride)], but it is preferable to use contact times of only a few minutes, especially with hydrohalogen resins such as polyvinyl chloride.
  • hydrohalogen polymers e.g., poly(vinylidene chloride)
  • the product so-prepared may comprise a basis material bearing a hydrohalogen surface including at least one Cl-lCX- group, wherein X halogen, at least a portion of which has been alkoxide activated and the oxygen activated e.g., oxidized.
  • This novel product may be characterized by the presence on the polymer surface of polar (i.e., more strongly polar than before) groups including hydroxyl, aldehyde, ketone, earboxyl, etc.
  • This novel product may be particularly characterized by its chemical reactivity, and particularly by its ready ability to receive a chemically deposited plate metal.
  • the oxygen-activated polymer surface (obtained by contact with alkali metal alkoxide and subsequent treatment with an oxidizing agent) may be electrolessly plated as by chemical plating.
  • Electroless plating includes maintaining the surface in contact with a medium containing in solution the metal to be electrolessly plated and a reducing agent capable of reducing the metal to be plated to its zero-valent form.
  • Metals which may be chemically or electrolessly deposited on the activated plastic substrate include e.g., nickel, silver, cobalt, copper, gold, etc.
  • metallic nickel is deposited by chemical reduction on the oxygen-activated polymer surface.
  • the oxygen-activated polymer surface may be rinsed with water, contacted with aqueous solution of stannous chloride (prepared by combining 50 g./l. of SnCl '2H and 100 g./l. of concentrated hydrochloric acid) at 20 C. for about 1 minute.
  • the polymer may then be rinsed with water and contacted for one minute with aqueous palladium dichloride PdCl (0.2 g./l. of PdCl and containing 5 g./l. of concentrated hydrochloric acid).
  • the polymer surface may again be rinsed with water and then immersed for about 5-l0 minutes (depending upon the thickness of nickel plate desired) in a chemical plating bath (pH approximately 4.5, temperature about 72 C.) containing 50 g./l. of NiCl -6H O, l0 g./l. of NaH PO -H O, and g./l. of Na C H O -2H O.
  • the nickel-plated polymer surface may be removed from the bath and rinsed.
  • the plated polymer surface may be subsequently electroplated (e.g., with copper, nickel, chromium, etc.) or may be used directly without further plating.
  • the alkoxide-activated polyvinyl chloride surface may be removed, rinsed in cold running water for a few seconds, and then placed in l,000 parts of a chromic acid-sulfuric acid solution containing g./l. of CrO and 500 g./l. of H 50, at about 66 C. for approximately 20 minutes.
  • the surface of the polymer may become wetted after being in the oxidizing bath for only about 30 seconds (indicating that the surface had been oxygen activated upon contact).
  • the polymer may be removed, rinsed, immersed in stannous chloride solution (50 g./l. of SnCl -2H 0 and 100 g./l. of concentrated HCl for 1 minute, at room temperature, removed, rinsed in H O, immersed in palladium dichloride PdCl solution (0.2 g./l. of PdCl and 5 g./l. of concentrated hydrochloric acid) at room temperature, removed and placed in a chemical nickel plating bath at 71 C. (containing 50 g./l.
  • NiCl 'GH O NiCl 'GH O
  • l0 g./l. of sodium citrate 21-1 l0 g./l. of sodium citrate 21-1 0, and 10 g./l. of NaH PO -H O
  • the nickelplated polymer may be removed, rinsed, and a 0.003 cm. thickness of dull copper electrolytically deposited on the nickel-plated surface.
  • the polymer may then be removed from the bath and plated with an additional 0.0075 mm. of bright nickel.
  • the plated panel may be subjected to a standard thermocycle rest which comprises heating the plated polymer for 60-70 minutes'at 96 C., then at room temperature (27-32 C.) for about 10 minutes, and then cooling to about l0 C. for 60-70 minutes.
  • This cycle when repeated three times for each plated article, may be termed a standard thermocycle test. No blistering, peeling, or lifting of the metal from the panel was observed after completion of the standard thermocycle test.
  • PVDC Polyvinyldichloride
  • S Polyvinylidenechloride
  • the method of modifying a hydrohalogen polymer surface which comprises contacting the [hydrohalogen polymer surface with an alkali metal alkoxide MOR wherein M is an alkali metal and R is an alkyl group having one to l2 carbon atoms thereby forming an alkoxide-activated surface with chromic acid thereby forming an oxygen-activated alkoxideactivated surface.

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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)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Chemically Coating (AREA)
US3639153D 1966-08-25 1966-08-25 Process of modifying a hydrohalogen polymer surface Expired - Lifetime US3639153A (en)

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US57495466A 1966-08-25 1966-08-25

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US (1) US3639153A (de)
CH (1) CH502395A (de)
DE (1) DE1694642A1 (de)
ES (1) ES344336A1 (de)
GB (1) GB1178585A (de)
NL (1) NL6711678A (de)
SE (1) SE333286B (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853589A (en) * 1970-11-09 1974-12-10 Ici Ltd Metal deposition process
USRE29039E (en) * 1969-11-26 1976-11-16 Imperial Chemical Industries Limited Metal deposition process
JPS52107070A (en) * 1976-03-04 1977-09-08 Mitsubishi Gas Chemical Co Method of roughing surface of epoxy resin
JPS53142472A (en) * 1977-05-18 1978-12-12 Mitsubishi Gas Chem Co Inc Roughening of synthetic resin
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

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2943937A (en) * 1956-06-12 1960-07-05 Eastman Kodak Co Surface conditioning and subbing of oriented linear polyester photographic film support
US3067078A (en) * 1960-07-28 1962-12-04 Us Stoneware Co Treatment of polymeric fluorine-containing resins and resulting products
US3142581A (en) * 1961-09-18 1964-07-28 Ibm Method of treating polyester polymer materials to improve their adhesion characteristics
US3167491A (en) * 1960-07-29 1965-01-26 Plasitron Corp Polyfluorinated ethylene polymermetal article and method
US3370974A (en) * 1965-10-20 1968-02-27 Ivan C. Hepfer Electroless plating on non-conductive materials
US3392035A (en) * 1963-09-02 1968-07-09 Torigai Eiichi Method and bath for chemically plating copper

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2943937A (en) * 1956-06-12 1960-07-05 Eastman Kodak Co Surface conditioning and subbing of oriented linear polyester photographic film support
US3067078A (en) * 1960-07-28 1962-12-04 Us Stoneware Co Treatment of polymeric fluorine-containing resins and resulting products
US3167491A (en) * 1960-07-29 1965-01-26 Plasitron Corp Polyfluorinated ethylene polymermetal article and method
US3142581A (en) * 1961-09-18 1964-07-28 Ibm Method of treating polyester polymer materials to improve their adhesion characteristics
US3392035A (en) * 1963-09-02 1968-07-09 Torigai Eiichi Method and bath for chemically plating copper
US3370974A (en) * 1965-10-20 1968-02-27 Ivan C. Hepfer Electroless plating on non-conductive materials

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE29039E (en) * 1969-11-26 1976-11-16 Imperial Chemical Industries Limited Metal deposition process
US3853589A (en) * 1970-11-09 1974-12-10 Ici Ltd Metal deposition process
JPS52107070A (en) * 1976-03-04 1977-09-08 Mitsubishi Gas Chemical Co Method of roughing surface of epoxy resin
JPS53142472A (en) * 1977-05-18 1978-12-12 Mitsubishi Gas Chem Co Inc Roughening of synthetic resin
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

Also Published As

Publication number Publication date
CH502395A (de) 1971-01-31
DE1694642A1 (de) 1971-08-05
ES344336A1 (es) 1968-12-01
GB1178585A (en) 1970-01-21
SE333286B (sv) 1971-03-08
NL6711678A (de) 1968-02-26

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