[go: up one dir, main page]

WO1993004215A1 - Emulsions catalytiques utilisees dans un procede de depot sans courant - Google Patents

Emulsions catalytiques utilisees dans un procede de depot sans courant Download PDF

Info

Publication number
WO1993004215A1
WO1993004215A1 PCT/US1992/006395 US9206395W WO9304215A1 WO 1993004215 A1 WO1993004215 A1 WO 1993004215A1 US 9206395 W US9206395 W US 9206395W WO 9304215 A1 WO9304215 A1 WO 9304215A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
water
emulsion
polymer
catalytic
Prior art date
Application number
PCT/US1992/006395
Other languages
English (en)
Inventor
James Delvin Gabbert
Edward Francis Tokas
Original Assignee
Monsanto Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Monsanto Company filed Critical Monsanto Company
Publication of WO1993004215A1 publication Critical patent/WO1993004215A1/fr

Links

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

Definitions

  • CATA YTIC EMULSIONS FOR ELECTROLESS DEPOSITION Disclosed herein are catalytic emulsions, catalytic polymeric films prepared from such emulsions, and metal coated articles, including metal- coated textile materials, where the metal is electrolessly deposited onto catalytic polymeric films prepared by such emulsions. Also disclosed are methods of preparing and using such catalytic emulsions, films and articles.
  • Metal-coated textile articles are useful for a variety of electromagnetic radiation shielding applications, e.g. wall coverings, gaskets, composite housings, protective clothing, and the like.
  • the shielding performance of such metal-coated textile materials is influenced by adhesion and electrical conductivity of the metal coating, especially the long term durability of such properties in common environments, e.g. metal-oxidizing environments of high humidity, rain, fog or salt spray or laundering.
  • Such metal-coated articles are advantageously produced by electroless deposition onto a catalytic coating on such articles. Morgan et al. in U.S. Patent 4,910,072,
  • Such aqueous catalytic solutions are environmentally advantageous for preparing polymeric films that catalyze the electroless deposition of metals because the organic solvents typically used in prior art formulations is replaced by water. Maintaining adhesion of catalytic material on the substrate is of considerable importance since loosely adhered catalytic material, e.g. palladium, can be washed from the surface in the agitation of the plating bath causing depletion of the metal value of the plating bath as uncontrolled metal deposition occurs, resulting in what is commonly referred to as a "crashed" bath. Vaughn teaches the use of crosslinking agents, e.g. dialdehydes, with water- soluble polymers to provide more stable, catalytic, polymer coatings. See also U.S. Patents 3,615,471; 3,719,490 and 3,779,758 for other disclosures of crosslinked catalytic coatings of water-soluble polymers.
  • crosslinking agents e.g. dialdehydes
  • a disadvantage of coatings of water-soluble polymers, including crosslinked water soluble polymers, is that high pH plating baths and/or incomplete crosslinking and/or failure to wash away deliberately uncrosslinked polymer coating can cause undesired transfer of catalytic metal into a plating bath causing the plating bath to crash, i.e. undergo an uncontrolled metal reduction and deposition throughout the plating bath.
  • An object of this invention is to provide catalytic coatings of essentially water-insoluble polymers to minimize the opportunity for complexes of catalytic metal and polymer to solubilize into a plating bath with attendant crashing of a plating solution.
  • a further object is to provide essentially water insoluble polymeric coatings that catalyze the electroless deposition of metal that is highly adherent, even after severe environmental exposure such as laundering in the case of metal-coated textiles.
  • metal coatings having enhanced adhesion can be electrolessly deposited onto articles coated with a catalytic, crosslinked polymeric film prepared from aqueous, catalyst emulsions.
  • a catalytic, crosslinked polymeric film prepared from aqueous, catalyst emulsions is exceptionally adhesive, electr,olessly-deposited metal coatings, e.g. on textile materials.
  • Another aspect of this invention is crosslinked, polymeric coatings which can catalyze the electroless deposition of such adherent metal.
  • aqueous catalytic emulsions which comprise (a) water, (b) surfactant-stabilized particles of a crosslinkable, water-insoluble polymer dispersed as an emulsion in said water, (c) a water soluble compound of a Group 8 metal, and (d) a crosslinking agent.
  • Still other aspects of this invention are methods of preparing catalytic, crosslinked polymeric coatings and abrasion-resistant metal coatings.
  • the figure is a reference scale for metal adhesion ratings based on the amount of metal removed by a layer of adhesive tape after standardized rubbing under a fixed load.
  • emulsion means a suspension in a liquid of small particles or globules of a polymer where coagulation of the suspended polymer particles is prevented by the presence of surfactant, e.g. a synthetic latex of polystyrene, poly(vinylchloride) or polybutadiene in water.
  • surfactant e.g. a synthetic latex of polystyrene, poly(vinylchloride) or polybutadiene in water.
  • Coherent polymeric films of the polymer are provided by removing the liquid medium, e.g. by evaporation of water.
  • aqueous solution refers to solutions consisting essentially of water and low levels of organic solvents, e.g. as solubilizing agents for catalytic metal compounds.
  • Copper Bath-A refers to an agitated electroless plating solution comprising about 8 g/1 formaldehyde, about 4 g/1 copper, and about 0.12 M ethylenediaminetetraacetic acid (EDTA) which is maintained at pH 11.5-12.5 and about 35 °C.
  • Copper Bath-B refers to an agitated electroless plating solution comprising about 5 g/1 formaldehyde, about 1.5 g/1 copper, 5.5 g/1 of sodium hydroxide and about 0.05 M EDTA (sodium salt) which is maintained at about 20-25 °C.
  • EDTA sodium salt
  • catalytically inert refers to films of polymer and catalytic metal compounds having surfaces onto which metal is not effectively deposited from standard electroless plating solutions such as a Copper Bath.
  • catalytically activatable refers to catalytically inert films comprising polymer and a compound of a catalytic metal which can be made catalytic, e.g.
  • heat can be provided to the polymer film by exposing selected areas to heat transfer fluid, e.g. hot air, or coherent electromagnetic radiation such as from a laser, electron beam radiation, etc., which can be adsorbed generating sufficient heat to allow activation.
  • heat transfer fluid e.g. hot air, or coherent electromagnetic radiation such as from a laser, electron beam radiation, etc., which can be adsorbed generating sufficient heat to allow activation.
  • Abrasion resistance of textile fabrics is commonly determined using an A.A.T.C.C. Crockmeter Model CM1 (obtained from Atlas Electric Devices Company, Chicago, Illinois) which comprises a sandpaper-surfaced suoport for holding in position a piece of textile fabric located within a open-topped bracket.
  • Abrasion resistance is characterized by measuring the weight loss of the fabric caused by abrasion from the reciprocating rubbing of an acrylic finger back and forth over the fabric surface; the acrylic finger is mounted under the end of a reciprocating arm.
  • the "durability test method" used to characterize the durability of metal-coated textile fabrics of this invention is performed using a modified Crockmeter where the acrylic finger is provided with a 9.5 mm (3/8 inch) diameter, flat bottomed tip under a 2 kilogram load.
  • the loaded finger effects 50 reciprocating rubbings (i.e. 25 cycles) on the surface of 2 layers of adhesive tape (HighlandTM 6200 permanent mending tape from 3-M Company) applied to a metal-coated textile fabric. After the double layer of adhesive tape is rubbed on the metal coating, the tapes are pulled from the fabric and compared against standards set forth in the Figure of Metal Adhesion Ratings to determine the amount of metal removed from the textile by the tape.
  • a "5 RATING"- applies to a sample of very durable metal-coated textile where metal adhesion to the textile is so good that only a very slight amount of metal is removed by the adhesive tape after rubbing according to this durability test method; a "4 RATING” applies where more metal is removed so that the outline of the path of the acrylic finger is barely visible; a “3 RATING” applies where sufficient metal is removed so that a distinct outline of the finger's path is clearly visible; a “2 RATING” applies where the rubbed pathway is completely filled in with metal; and a "1 RATING” applies where the path filled and metal is adhered to areas of the tape outside of the path of the finger.
  • Samples rating substantially better than 5 are designated as "5+”; and samples rating substantially worse than 1 are rated as “1-”.
  • This invention provides emulsions which are useful for providing catalytically activated film comprising a crosslinked polymer and catalytic metal of Group 8, which can catalyze the electroless deposition of metal that is of superior adhesion and durability even after laundering.
  • this invention also provides strongly adherent metal-coated articles comprising metal electrolessly deposited on areas of an article coated with a catalytic, crosslinked polymer and Group 8 metal.
  • Such strongly adherent metal coatings exhibit a Metal Adhesion Rating of at least 4, preferably 5.
  • Preferred adherent metal coated articles of this invention are textile articles, e.g.
  • Preferred metal coated textile articles are sufficiently durable so as to maintain a Metal Adhesion Rating of at least 3, preferably 4, and more preferably 5 even after the article is washed for 5 minutes in 20-30 ° C water containing 1.8 g/1 laundry detergent.
  • the aqueous, catalyst emulsions of this invention are adapted for forming crosslinked, polymeric coatings which can catalyze the electroless deposition of metal.
  • Such emulsions comprising (a) water, (b) surfactant-stabilized particles of a crosslinkable, water-insoluble polymer dispersed as an emulsion in said water, (c) a water soluble compound of a Group 8 metal, and (d) a crosslinking agent.
  • the surfactant-stabilized particles can comprise a variety of crosslinkable, water-insoluble polymers, preferably having a glass transition temperature less than about 200 °C, more preferably less than 100 °C.
  • Such water- insoluble polymers can include thermoplastics or rubbers.
  • thermoplastic polymers include vinyl polymers such as poly(vinylchloride) , poly(acrylates) , poly(vinylacetate) , poly(methacrylates) , polystyrene and copolymers such as poly(vinylacetate/ethylene) , poly(vinylchloride/vinylacetate) , poly(vinylacetate/ acrylate) and mixtures of such polymers and/or copolymers.
  • Useful synthetic rubbers include polybutadiene and polybutylacrylate and copolymers of butadiene and vinyl monomers such as poly(butadiene/styrene) , poly(butadiene/ acrylonitrile) and mixtures of such polymers and/or copolymers, including mixtures with thermoplastic polymers and/or copolymers.
  • At least a portion of the polymers used in the emulsions of this invention will have one or more reactive groups to facilitate crosslinking.
  • such reactive groups can comprise unsaturation, e.g. in the backbone or on branches.
  • reactive groups can be inherent in the polymer or grafted onto the polymer; such reactive groups can be hydroxyl groups, carboxylic acid groups, vinyl groups, ester groups and amine groups.
  • Suspended particles of water-insoluble polymer are maintained in the emulsion, e.g. inhibited against coagulation by the use of a surfactant, e.g. a cationic, anionic or neutral charged molecule, oligo er or polymer.
  • Preferred surfactants which are compatible with many water insoluble polymers are neutral polymeric surfactants such as polyoxy- ethylenes.
  • the emulsions of this invention also comprise a crosslinking agent which can initiate or participate in a crosslinking reaction.
  • Initiating crosslinking agents can include free radical initiators, e.g. for crosslinking vinyl groups of polybutadiene.
  • Participating crosslinking agents can be monomers, oligomers or polymers having two or more reactive groups which can reactively combine with the reactive groups of the polymer.
  • the cross linking agent can be inherent in the polymer or dispersed or dissolved in the polymer particles or dissolved or dispersed in the water medium of the emulsion. Depending on the nature of the reactive group of the polymer, an appropriate crosslinking agent can readily be selected by those skilled in the polymer coatings arts.
  • a useful inherently crosslinkable polymer is carboxy-modified polyvinyl chloride.
  • Useful crosslinking agents for use with other polymers include acrylamide, methyolacrylamide, dialdehydes, polyols, polyalkoxides, etc.
  • the emulsions of this invention also comprise a water-soluble compound of a catalytic metal, for instance a metal of Group 8 of the Periodic Table of Elements, i.e. iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, osmium and platinum.
  • a catalytic metal for instance a metal of Group 8 of the Periodic Table of Elements, i.e. iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, osmium and platinum.
  • Preferred Group 8 metals are the noble catalytic metals, i.e. ruthenium, rhodium, palladium, iridium and platinum.
  • the most preferred metal used in emulsions according to this invention is palladium.
  • Such catalytic metals are desirably employed as water soluble compounds, e.g.
  • ligands such as acetonitrile, acetone, acetate, chloride or nitrate.
  • a metal solubilizing agent selected from the group consisting of ammonia, primary amines, secondary a ines, tertiary amines and inorganic hydroxides.
  • the metal can be provide in solution as a complex of an water miscible organic ligand where there is molecular interaction, e.g. coordinate bonding, between nucleophilic groups on the organic ligand the metal atom.
  • complex as used herein also refers to the intermolecular bonding between the catalytic metal and nucleophilic groups of the polymeric species in the films of the invention.
  • the polymer can be present at high levels, e.g. about 50 percent solids, or at low levels, e.g. less than about 10 percent by weight of the emulsion, preferably not more than 2 percent by weight. In more preferred emulsions the polymer will advantageously comprise not more than 1 percent by weight of the emulsion or less.
  • the emulsions of this invention can comprise polymer and Group 8 metal in the weight ratio of polymer to metal between 100:1 and 1:1, preferably about 10:1 to 2:1.
  • the Group 8 metal is present in a low level, e.g. less than 5 percent by weight of the emulsion or lower, e.g. less than about 1 percent.
  • the emulsions according to this invention are adapted to forming dry films which can be crosslinked, e.g. preferably thermally, to provide stable catalytic polymeric films that can catalyze electroless deposition, e.g. of copper from a Copper Bath.
  • the emulsions are adapted to forming catalytically inert polymeric films which can be activated, preferably thermally, to catalyze electroless deposition.
  • catalytically inert films can be simultaneously thermally crosslinked and activated at moderate temperatures, e.g. by exposure to heat at less than 200 °C.
  • Catalytic, crosslinked polymeric coatings can be prepared by depositing on a substrate a film of aqueous emulsion according to this invention, i.e. an aqueous emulsion comprising surfactant-stabilized particles of a crosslinkable, water-insoluble polymer dispersed as an emulsion, a water soluble compound of a Group 8 metal, and a crosslinking agent.
  • aqueous emulsion comprising surfactant-stabilized particles of a crosslinkable, water-insoluble polymer dispersed as an emulsion, a water soluble compound of a Group 8 metal, and a crosslinking agent.
  • the choice of method for applying the aqueous emulsions to provide catalytic films depends on the nature of the substrate and the metallized layer desired.
  • catalytically inert films can be provided by dipping the textile substrate into an aqueous solution and letting the solution drip off or passing the textile through squeeze rolls to remove excess solution.
  • the water can be evaporated by letting the wet coated substrate stand in air or be facilitated by placing the textile material in a warm air stream.
  • the aqueous solution can be applied by roller, doctor blade, spray and such to provide large area coverage of a wet film which can be dried to a catalytically inert film by allowing the water to evaporate.
  • Fine patterns can be applied to film substrates by printing techniques, e.g.
  • drying is an important step in the practice of this invention regardless of the nature of the substrate. Evaporation can be advantageously facilitated by exposing the wet film to evaporation conditions, e.g. vacuum or warm air flow, either of which provides an environment having a partial pressure of water low enough to expedite evaporation. Although not necessary it is often desirable to employ moderate evaporation conditions to avoid boiling of water from the wet emulsion film surface. In most cases this can be assured by maintaining the forming film at a temperature less than 95 ⁇ C. In many cases it is desirable that drying is effected at a temperature less than 80 ⁇ C, say less than about 60 "C.
  • evaporation conditions e.g. vacuum or warm air flow, either of which provides an environment having a partial pressure of water low enough to expedite evaporation.
  • moderate evaporation conditions to avoid boiling of water from the wet emulsion film surface. In most cases this can be assured by maintaining the forming film at a temperature less than 95 ⁇ C. In
  • drying the wet emulsion film at low or moderate temperature will form an uncrosslinked precursor film unless the crosslinking agent is thermally activated at such drying temperatures.
  • the film can be treated to effect crosslinking, e.g. exposure to actinic radiation or heat such as at a temperature above 100 °C for sufficient time to crosslink said polymer.
  • drying will be effected to produce precursor films which will be catalytically inert and uncrosslinked.
  • the catalytically inert and uncrosslinked films can be simultaneously activated and crosslinked by the same treatment, e.g.
  • the metal coated articles of this invention comprise a layer of electrolessly deposited metal on a catalytic layer of crosslinked polymer and Group 8 metal.
  • Such articles can comprise molded articles where the metal layer provides shielding against electromagnetic radiation, e.g. for electronic equipment housings, or environmental resistance, e.g. for automotive trim or fixtures.
  • Other articles can comprise printed circuits on rigid polymeric substrates or on flexible polymeric films.
  • An especially preferred aspect of this invention provides metal coated textile materials, e.g. woven, non-woven, knitted or needle-punched fabrics, threads, yarns, chopped fiber sliver or monofilament tow and the like.
  • the substrate of the metal coated articles can comprise any of a variety of materials including inorganic materials such as metals, metal oxides, stone, ceramics, glass, quartz, alumina, carbon and graphite; organic polymers including organic thermoset polymers such as epoxy and phenolic resins and thermoplastic polymers such as polyamides, polyaramides, polyesters, polyolefins, polycarbonates, polysulfones, styrenics, and cellulosics; and natural materials such as wood.
  • the substrate can comprise natural fibers such as cellulosics, synthetic fibers of acrylic, nylon, polyester, polyaramide, inorganic fibers such as glass, quartz, graphite and the like.
  • the metal- coated textile materials of this invention are especially useful in electromagnetic radiation shielding applications.
  • copper-coated nylon non-woven fabric according to this invention exhibited greater than 60 dB attenuation in near field shielding of radiation between 100 and 800 megahertz.
  • Metal-coated nylon non-woven fabric according to this invention comprising a first layer of copper and a second layer of tin exhibited far field shielding effectiveness of greater than 60 dB for radiation up to 10 gigahertz.
  • Metal coatings of this invention exhibiting enhanced adhesion will also experience substantially less degradation of shielding performance after severe environmental exposure, e.g. as simulated by laundering, as compared to metal coatings applied by prior art catalytic polymeric surfaces.
  • Metal coatings on the articles of this invention can comprise any of a variety of the metals which can be deposited electrolessly from aqueous solutions onto palladium catalyzed surfaces, e.g. copper, nickel, cobalt, silver, palladium , platinum, etc.
  • a multilayered metal coating e.g. a first electrolessly deposited layer of copper or nickel and one or more subsequent layers applied electrolessly, electrolytically or by replacement, e.g. in the case of silver.
  • the subsequent layer can comprise copper, nickel, zinc, cobalt, gold, silver, zinc, platinum, palladium, iridium, etc.
  • EXAMPLE 1 This example illustrates the preparation and use of a catalytic emulsion of this invention and its use in providing durable metal coatings.
  • a palladium solution was prepared by mixing 2.1 g of palladium acetate suspended in 50 ml of water with 2.4 g of a 70% aqueous solution of ethylamine. The suspension was stirred for about 30 minutes to dissolve the palladium salt followed by the addition of 2 ml of a 25 % aqueous solution of Triton X-100 polyoxyethylene surfactant and 150 ml of water to provide 205 ml of palladium solution. The surfactant serves to prevent the palladium salt for coagulating the latex.
  • the palladium solution was added to 8.6 g of a heat curing nitrile rubber latex (Hycar ® 1572X64 polybutadiene/ acrylonitrile latex, 47.3% solids from B.F.Goodrich Company, Cleveland, Ohio) diluted to 700 ml water, followed by 95 ml of rinse water from the palladium solution container, providing 1000 ml of catalyst emulsion, containing 0.1 weight precent palladium and 0.4 weight percent polymer.
  • a heat curing nitrile rubber latex Hycar ® 1572X64 polybutadiene/ acrylonitrile latex, 47.3% solids from B.F.Goodrich Company, Cleveland, Ohio
  • a plainweave polyester fabric was dipped in the catalytic emulsion, squeezed dry to remove excess emulsion and dried in room temperature air to provide a catalytically inert, uncrosslinked polymer coated fabric which was heated for 15 minutes in 180 "C air to effect crosslinking and catalyst activation.
  • the crosslinked, catalytically activated polymer-coated fabric was immersed in Copper Bath-B to provide a strongly adherent copper coating.
  • the copper-coated fabric ' exhibited a metal adhesion rating of 5 when tested according to the modified Crockmeter abrasion test.
  • the fabric was laundered in a commercial household washing machine for 5 minutes using 1.8 g/1 of ERA brand laundery detergent (from Procter & Gamble) in 20-25 °C water, rinsed and dried, and retested for adhesion; the fabric had a metal adhesion rating of 4.
  • EXAMPLE 4 This example illustrates the application of emulsions of this invention for providing electrolessly deposited metal on flat film substrates.
  • a high solids catalytic emulsion was prepared by adding an aqueous solution of ammonia and palladium acetate to an aqueous latex (50.5% solids) of a heat curing copolymer of polyvinyl chloride/vinyl acetate (Geon ® 590X20 phosphate ester plasticized vinyl chloride copolymer from the B.F. Goodrich Company) to provide an high solids (49%) catalytic emulsion containing 20 weight percent polymer and about 1 weight percent palladium.
  • the high solids catalytic emulsion was diluted with 231 ml of waer and 0.8 ml of 25% Triton X-100 surfactant to provide a catalytic emulsion of about 5% solids.
  • Each of the catalytic emulsions i.e. 49% solids and 5% solids, was coated on a polyethylene terephthalate (PET) film substrate using a NO. 5 draw bar; the wet emulsions were dried and cured in a air oven at 160 °C, then immersed in a Copper Bath-A providing a strongly adhering copper coatings.
  • PET polyethylene terephthalate

Landscapes

  • 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)
  • Catalysts (AREA)
  • Chemically Coating (AREA)

Abstract

Des émulsions catalytiques aqueuses, conçues pour produire des revêtements polymères réticulés susceptibles de catalyser le dépôt sans courant d'un métal, comprennent (a) de l'eau, (b) des particules, stabilisées par un agent tensioactif, d'un polymère réticulable et insoluble dans l'eau, dispersé dans l'eau sous forme d'émulsion, (c) un composé soluble dans l'eau d'un métal du Groupe 8, et (d) un agent de réticulation. De telles émulsions sont conçues pour produire des feuilles sèches et inertes d'un point de vue catalytique, qui peuvent simultanément subir une réticulation thermique et être activées pour catalyser le dépôt sans courant de métaux à forte adhérence tels que le cuivre, le nickel et l'argent. Les polymères réticulables comprennent du polybutadiène ainsi que des copolymères de butadiène, du poly(vinylchlorure), du poly(méthacrylate) du poly(alkylméthacrylate) et du poly(vinylacétate).
PCT/US1992/006395 1991-08-15 1992-07-30 Emulsions catalytiques utilisees dans un procede de depot sans courant WO1993004215A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US74625491A 1991-08-15 1991-08-15
US746,254 1991-08-15

Publications (1)

Publication Number Publication Date
WO1993004215A1 true WO1993004215A1 (fr) 1993-03-04

Family

ID=25000061

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/006395 WO1993004215A1 (fr) 1991-08-15 1992-07-30 Emulsions catalytiques utilisees dans un procede de depot sans courant

Country Status (3)

Country Link
AU (1) AU2431892A (fr)
MX (1) MX9204757A (fr)
WO (1) WO1993004215A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006111451A1 (fr) * 2005-04-20 2006-10-26 Agfa-Gevaert Procede d'impression par contact de motifs de catalyseurs formes par depot non electrique
WO2008012518A1 (fr) * 2006-07-25 2008-01-31 W.L. Gore And Associates (U.K.) Limited Tissu contenant des fibres recouvertes de métal

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0327057A1 (fr) * 1988-02-01 1989-08-09 TEXMET S.p.A. Procédé pour métalliser les matériaux fibreux
US4910072A (en) * 1986-11-07 1990-03-20 Monsanto Company Selective catalytic activation of polymeric films

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4910072A (en) * 1986-11-07 1990-03-20 Monsanto Company Selective catalytic activation of polymeric films
EP0327057A1 (fr) * 1988-02-01 1989-08-09 TEXMET S.p.A. Procédé pour métalliser les matériaux fibreux

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006111451A1 (fr) * 2005-04-20 2006-10-26 Agfa-Gevaert Procede d'impression par contact de motifs de catalyseurs formes par depot non electrique
WO2008012518A1 (fr) * 2006-07-25 2008-01-31 W.L. Gore And Associates (U.K.) Limited Tissu contenant des fibres recouvertes de métal

Also Published As

Publication number Publication date
MX9204757A (es) 1993-04-01
AU2431892A (en) 1993-03-16

Similar Documents

Publication Publication Date Title
KR950000014B1 (ko) 금속피복을 위한 수용성 촉매 폴리머 필름
US5411795A (en) Electroless deposition of metal employing thermally stable carrier polymers
US5082734A (en) Catalytic, water-soluble polymeric films for metal coatings
EP0271466B1 (fr) Activation catalytique sélective de pellicules en matière plastique
US4493861A (en) Process for activating substrate surfaces for currentless metallization
US4201825A (en) Metallized textile material
JP5236919B2 (ja) 撥水または撥油性仕上げ処理層
JPS58104170A (ja) 無電解めっき方法
CA1169720A (fr) Methode d'activation de surfaces pour la metallisation sans courant
JP2716505B2 (ja) 繊維状材料の金属化法
US2676896A (en) Treatment of textile materials with antistatic material product obtained thereby
US3833457A (en) Polymeric complex composite
US5279899A (en) Sulfonated polyamides
JPS6227192B2 (fr)
WO1993004215A1 (fr) Emulsions catalytiques utilisees dans un procede de depot sans courant
JPH0762311B2 (ja) 金属被覆繊維の製造方法
JPH10500734A (ja) 金属無電解デポジション用の触媒性架橋ポリマーフィルム
CN1153227A (zh) 因金属涂层而有催化性的水溶性聚合物薄膜
JPS60254515A (ja) 導電性高分子材料
CN1155591A (zh) 因金属涂层而有催化性的水溶性聚合物薄膜
JPH0583664B2 (fr)
JPS6328975A (ja) 金属被覆繊維布帛の製造方法
JPS6155803A (ja) 耐久性を有する導電性高分子材料
JPS6381705A (ja) 耐久性良好な導電性高分子材料
TH5909B (th) กรรมวิธีและเครื่องอุปกรณ์สำหรับการผลิตสิ่งทอแบบไม่ถักสานที่ถูกประทับลวดลายพิมพ์

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA JP KR RU

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA