WO1991015610A1 - Methode de preparation de revetements de fluorocarbone amorphe - Google Patents

Methode de preparation de revetements de fluorocarbone amorphe Download PDF

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Publication number
WO1991015610A1
WO1991015610A1 PCT/US1990/006696 US9006696W WO9115610A1 WO 1991015610 A1 WO1991015610 A1 WO 1991015610A1 US 9006696 W US9006696 W US 9006696W WO 9115610 A1 WO9115610 A1 WO 9115610A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethylenic
fluorinated
copolymer
coating
substrate
Prior art date
Application number
PCT/US1990/006696
Other languages
English (en)
Inventor
Richard Swisher
James Andrew Phipps
Douglas Ray Pelleymounter
James Leroy Grieser
Original Assignee
Sheldahl, Inc.
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 Sheldahl, Inc. filed Critical Sheldahl, Inc.
Publication of WO1991015610A1 publication Critical patent/WO1991015610A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2506/00—Halogenated polymers
    • B05D2506/10—Fluorinated polymers

Definitions

  • the present invention relates generally to an improved system for preparing highly adherent/coherent coatings of high molecular weight amorphous fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copoly ers upon substrate surfaces, and more specifically to a method for pre-conditioning the substrate surface for acceptance of a coating of castable high molecular weight amorphous fluorinated copolymer layers, specifically fluorinated copolymers consisting of fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer, having molecular weights ranging from between about 230,000 and 500,000.
  • fluorocarbon polymers of relatively lower molecular weight and consisting essentially of tetrafluoroethylene have been utilized in a wide variety of applications. Specifically, these polymers have been available in solid or powder form, for use in preparing molded and/or extruded articles as well as films and coatings. For example, the polymer has also been available in aqueous dispersion form for the preparation of non-stick coatings as well as in certain applications requiring surfaces with low friction. Because of its relatively low coefficient of friction, the material has further been utilized as a finish for multi-filament filaments and/or fibers.
  • One of the primary applications of fluorocarbon polymers has been in the formation of finishes and/or films for cookware to provide non ⁇ stick surfaces for food preparation.
  • the material can be hot-pressed into sheets to form useful objects. Because of the unusual physical properties of this high molecular weight amorphous fluorinated copolymer material, adhesion of the castable materials has presented problems in finding techniques for application primarily because of the unavailability of suitable techniques for achieving adhesion to substrate surfaces.
  • One particularly valuable property of the material is its dielectric constant, with the material having been found to possess the lowest dielectric constant of plastics, particularly at gigahertz frequencies.
  • a method which provides a means for laying down a castable film of amorphous fluorinated copolymer consisting essentially of evaporatively depositing an initial or primer layer of this high molecular weight fluorinated (ethylenic- cyclo oxyaliphatic substituted ethylenic) copolymer and thereafter applying one or more relatively thick layers of this same material onto the primer layer.
  • the second application is undertaken with the amorphous fluorinated copolymer in liquid solution and/or dispersion form, and it is in this form that the castable film develops good adhesion to the surface upon which it is deposited.
  • an initial or primary layer of high molecular weight fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer is applied to the substrate upon which the castable coating is to be formed.
  • the initial or primer film is applied to the surface of the substrate by vacuum deposition techniques, with such techniques having been found to provide films with good adhesive as well as cohesive properties.
  • a coating of the castable film of high molecular weight amorphous fluorinated copolymer consisting of fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer is applied or otherwise cast thereover.
  • Application techniques for the liquid forms include brushing, spraying, dipping and spinning.
  • the coating formed by the residue possesses the unusual physical and electrical properties of the high molecular weight amorphous fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer material, and in addition may be deposited as a relatively thick layer onto the surface of the substrate.
  • These coatings which may be cured with only room temperature or low heat requirements, may have thicknesses ranging up to and over .25 millimeters. It has also been found that the coatings, when cast into thin-film form, are substantially pinhole-free, and will achieve this property without requiring sintering.
  • the castable fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer material which is utilized in accordance with the present invention is available in particulate or granular form.
  • the molecular weight of the amorphous fluorinated copolymer ranges from between about 230,000 and 500,000, and as such, possesses a property of forming stable solutions which can be used to form desirable coatings.
  • the material possesses solubility of up to between about 3% and 5% in certain liquid fluorocarbons, with certain forms of the high molecular weight amorphous material possessing a solubility limit of up to about 12% in such solvents.
  • the technique of the present invention widens the scope of use of the material, since it renders it possible to form relatively thick coatings of this material with the desirable adhesive and cohesive properties.
  • the material can be loaded with finely powdered silica, with such materials drying so as to form filled coatings.
  • a substrate of aluminum metal measuring 3" x 2" x 1/16" was placed within a vacuum chamber along with a boat containing a charge of 8 grams of amorphous fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer solids having a molecular weight of about 230,000.
  • the chamber was evacuated to 10" 5 TORR and the boat heated to a temperature sufficiently high to commence evaporative deposition, with the contents of the boat being disposed in appropriate line-of-sight disposition with respect to the substrate being coated. After a period of 5 minutes, the boat was permitted to cool and the evacuated chamber permitted to return to atmosphere.
  • the source was warmed up slowly for a period of about 8 minutes prior to deposition.
  • the 5-minute interval indicated is the time utilized for the deposition operation only, with a deposit rate of approximately 11 A° per second being achieved.
  • the substrate received a coating of approximately 3,325 A°, which was found to be highly receptive to a second applied coating of high molecular weight fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer in dissolved solids form.
  • amorphous fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer solids dissolved in a liquid fluorocarbon mixture were applied, by eye-dropper brush application, upon the surface of the previously deposited film.
  • the coating was permitted to air-dry and the resultant composite coating was both coherent and adherent to the aluminum metal surface, and was found to have a uniform adherent and coherent structure with a thickness of approximately 2-5 mils.
  • the samples prepared on the aluminum substrate have been tested through temperature cycles extending between -65° C. to 250° C. for a total of ten cycles, with a 4-minute ramp-up and ramp-down time. No loss of adhesion was experienced, nor was any change in optical properties observed.
  • Example II The process of Example I was repeated with a substrate of aluminum foil (2.5 mils thick) with comparable results.
  • EXAMPLE III A substrate of stainless steel metal measuring 3" x 2" x 1/16" was placed within a vacuum chamber along with a boat containing a charge of 8 grams of amorphous fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer solids having a molecular weight of between about 230,000 and 500,000.
  • the chamber was evacuated to 10 "*5 TORR and the source heated as in Example I, with the contents of the boat being disposed in appropriate sight disposition with respect to the substrate being coated. After a deposition period of 5 minutes, the boat was permitted to cool and the evacuated chamber permitted to return to atmosphere.
  • the substrate received a coating of approximately
  • a substrate of polyimide film having a 2,000 A° film of aluminum applied thereon was utilized as a substrate.
  • the aluminum metal is coated pursuant to the process parameters set forth in Example I with reasonable results. In this particular arrangement, however, multiple pass coatings for the liquid formulations should provide benefits for reducing stresses in the finished product.
  • Fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer having molecular weights ranging from between about 230,000 and 500,000 are commercially available. These materials are available from E. I. DuPont de Nemours Co. of Wilmington, Delaware under the code name "Teflon AF Amorphous Fluoropolymer 2400" and "A-1600".
  • the fluorocarbon solvent in which the fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer dissolves is also commercially available, and is available from Minnesota Mining and Manufacturing Co., of St. Paul, Minnesota under the code name "FC-75". This fluorocarbon is in liquid form at normal atmospheric conditions, and is believed to comprise essentially a perfluorocarbon.
  • the liquid solutions containing the amorphous fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer in accordance with the present invention may be loaded with powdered silica or other filler.
  • powdered silica specifically up to about 50% by weight of powdered silica based upon amorphous fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer solids, a film is formed having high resistance to decomposure upon exposure to atmospheres containing quantities of atomic oxygen.
  • a minimum thickness of evaporated primer has been found to be about 1500 A°, with this thickness being utilized to achieve good bonding with the substrate and the liquid/amorphous fluorinated (ethylenic-cyclo oxyaliphatic substituted ethylenic) copolymer solid mixtures.
  • Standard bell-jar glow discharge pre-treatment may be utilized if desired, to provide improved adhesion results.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Une méthode de préparation d'un revêtement de fluorocarbone amorphe moulable sur la surface d'un substrat comprend les étapes consistant: à déposer initialement un film d'un fluorocarbone d'une épaisseur d'environ 1.500 à 50.000 A°; à appliquer ensuite un second revêtement comme couche de couverture sur le film initial. Le film initial et le revêtement moulable sont tous deux composés d'un copolymère (éthylénique à substitution éthylénique-cyclo oxyaliphatique) fluoré amorphe ayant un poids moléculaire se situant entre environ 230.000 et 500.000.
PCT/US1990/006696 1990-04-10 1990-11-15 Methode de preparation de revetements de fluorocarbone amorphe WO1991015610A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US50672090A 1990-04-10 1990-04-10
US506,720 1990-04-10

Publications (1)

Publication Number Publication Date
WO1991015610A1 true WO1991015610A1 (fr) 1991-10-17

Family

ID=24015747

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1990/006696 WO1991015610A1 (fr) 1990-04-10 1990-11-15 Methode de preparation de revetements de fluorocarbone amorphe

Country Status (2)

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EP (1) EP0524174A4 (fr)
WO (1) WO1991015610A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996031571A1 (fr) * 1995-04-06 1996-10-10 Catalina Coatings, Inc. Revetement anti-adherent obtenu par metallisation par evaporation sous vide d'un compose d'acrylate fluore ou de silicone, et procede de production
US6150024A (en) * 1997-11-25 2000-11-21 Rexam Release, Inc. Acrylate release compositions and sheet materials having a release coating formed of the same
EP1449861A2 (fr) * 1999-03-16 2004-08-25 E.I. du Pont de Nemours and Company Couches fluoropolymeres faiblement reflechissantes destinees aux lentilles et dispositifs plastiques
US9630206B2 (en) 2005-05-12 2017-04-25 Innovatech, Llc Electrosurgical electrode and method of manufacturing same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4016125A (en) * 1975-07-21 1977-04-05 E. I. Du Pont De Nemours And Co. Fluoropolymer coating compositions having improved adhesion
US4863762A (en) * 1987-03-31 1989-09-05 Central Glass Company, Limited Method of forming coating film of fluororesin by physical vapor deposition
US4883716A (en) * 1988-08-01 1989-11-28 Chemical Fabrics Corporation Method for manufacture of cast fluoropolymer-containing films at high productivity

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5838707A (ja) * 1981-08-20 1983-03-07 イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− パ−フルオロ−２，２−ジメチル−１，３−ジオキソ−ルの無定形共重合体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4016125A (en) * 1975-07-21 1977-04-05 E. I. Du Pont De Nemours And Co. Fluoropolymer coating compositions having improved adhesion
US4863762A (en) * 1987-03-31 1989-09-05 Central Glass Company, Limited Method of forming coating film of fluororesin by physical vapor deposition
US4883716A (en) * 1988-08-01 1989-11-28 Chemical Fabrics Corporation Method for manufacture of cast fluoropolymer-containing films at high productivity

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0524174A4 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996031571A1 (fr) * 1995-04-06 1996-10-10 Catalina Coatings, Inc. Revetement anti-adherent obtenu par metallisation par evaporation sous vide d'un compose d'acrylate fluore ou de silicone, et procede de production
US5811183A (en) * 1995-04-06 1998-09-22 Shaw; David G. Acrylate polymer release coated sheet materials and method of production thereof
US5945174A (en) * 1995-04-06 1999-08-31 Delta V Technologies, Inc. Acrylate polymer release coated sheet materials and method of production thereof
US6150024A (en) * 1997-11-25 2000-11-21 Rexam Release, Inc. Acrylate release compositions and sheet materials having a release coating formed of the same
EP1449861A2 (fr) * 1999-03-16 2004-08-25 E.I. du Pont de Nemours and Company Couches fluoropolymeres faiblement reflechissantes destinees aux lentilles et dispositifs plastiques
EP1449861A3 (fr) * 1999-03-16 2004-11-10 E.I. du Pont de Nemours and Company couches fluoropolymeres faiblement reflechissantes destinees aux lentilles et dispositifs plastiques
US7297398B2 (en) 1999-03-16 2007-11-20 E.I. Du Pont De Nemours And Company Fluoropolymer low reflecting layers for plastic lenses and devices
US9630206B2 (en) 2005-05-12 2017-04-25 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
US10463420B2 (en) 2005-05-12 2019-11-05 Innovatech Llc Electrosurgical electrode and method of manufacturing same
US11246645B2 (en) 2005-05-12 2022-02-15 Innovatech, Llc Electrosurgical electrode and method of manufacturing same

Also Published As

Publication number Publication date
EP0524174A1 (fr) 1993-01-27
EP0524174A4 (en) 1993-07-21

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