Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2001-07-13
2002-09-17
Niland, Patrick D. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C156S243000, C156S281000, C156S306300, C427S412400, C427S385500, C427S372200, C428S036600, C428S421000, C428S422000, C428S520000, C428S522000, C524S252000, C523S200000, C523S218000, C523S219000
Reexamination Certificate
active
06451925
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to compositions for bonding fluoropolymers to non-fluorinated polymers, multilayer adhesive articles comprising a fluoropolymer and a substantially non-fluorinated material, and methods of making such articles.
Fluorine-containing polymers (that is, fluoropolymers or fluorinated polymers), are an important class of polymers that include, for example, fluoroelastomers and fluoroplastics. Among this broad polymer class are polymers of high thermal stability, polymers of extreme toughness, and polymers exhibiting usefulness along a broad spectrum of temperatures. Many of these polymers also are almost totally insoluble in a wide variety of organic solvents; see, for example, F. W. Billmeyer,
Textbook of Polymer Science,
3rd ed., pp. 398-403, John Wiley & Sons, New York (1984).
Fluoroelastomers, particularly the copolymers of vinylidene fluoride with other ethylenically unsaturated halogenated monomers such as hexafluoropropylene find particular utility in high temperature applications, such as in seal gaskets and linings. See, for example, Brullo, R. A., “Fluoroelastomer Rubber for Automotive Applications,”
Automotive Elastomer
&
Design,
June 1985; “Fluoroelastomers Seal Up Automotive Future,”
Materials Engineering
, October 1988; and “Fluorinated Elastomers,” Kirk-Othmer,
Encyclopedia of Chemical Technology,
3rd ed., Vol. 8, pp. 500-515, John Wiley & Sons, New York (1979).
Fluoroplastics, particularly polychlorotrifluoroethylene, polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, and poly(vinylidene fluoride), have numerous electrical, mechanical, and chemical applications. Fluoroplastics are useful, for example, as wire coatings, electrical components, seals, and in solid and lined pipes and piezoelectric detectors. See, for example, “Organic Fluorine Compounds,” Kirk-Othmer,
Encyclopedia of Chemical Technology,
Vol. 11, pp. 20, 21, 32, 33, 40, 41, 48, 50, 52, 62, 70, and 71, John Wiley & Sons, New York (1980).
Multi-layer constructions containing a fluorinated polymer enjoy wide industrial application. Multi-layer fluoropolymer constructions find utility in, for example, fuel line hoses and related containers and in retroreflective sheeting materials. Increased concerns with evaporative fuel standards give rise to a need for fuel system components that have increased barrier properties to minimize the permeation of fuel vapors through automotive components including fuel filler lines, fuel supply lines, fuel tanks, and other components of the engine's fuel system control system. Various types of constructions have been proposed to address these concerns. In general, the most successful of these are co-extruded multi-layer constructions.
Multi-layer compositions comprising a fluorinated polymer layer and a polyamide or polyolefin layer are known. U.S. Pat. No. 4,933,090 (Krevor), for example, discloses laminate tubular articles that can comprise layers of fluorocarbon elastomers, and PCT Publication WO 93/14933 discloses a laminar film structure comprising a polyimide and a fluoropolymer. The use of fluorinated polymers in retroreflective sheeting also is known. U.S. Pat. Nos. 3,551,025 (Bingham et al.) and 4,348,312 (Tung), for example, describe products that include glass microspheres, and PCT Publications WO 95/11466 and WO 95/11464 describe products containing retroreflective cube corner arrays.
A variety of methods can be used to increase the adhesion between a fluorinated polymer layer and a polyamide or polyolefin layer. An adhesive layer can, for example, be added between the two polymer layers. U.S. Pat. No. 5,047,287 (Horiuchi et al.) discloses a diaphragm, suitable for use in automotive applications, that comprises a base fabric having bonded to at least one surface a fluororubber layer by an adhesive that includes an acrylonitrile-butadiene or acrylonitrile-isoprene rubber having an amino group.
Surface treatment of one or both of the layers sometimes is employed to aid bonding. Some, for example, have taught treating fluoropolymer layers with charged gaseous atmosphere and applying subsequently a layer of a second material, for example a thermoplastic polyamide.
Blends of the fluoropolymer and the dissimilar layer themselves are in some cases employed as an intermediate layer to help bond the two layers together. European Patent Application No. 0523644 (Kawashima et al.) discloses a plastic laminate having a polyamide resin surface layer and a fluororesin surface layer. The reference recognizes the difficulties encountered when making laminates having a polyamide layer and a fluororesin layer because of the incompatibility of the two materials. The laminate of the reference is prepared by use of an intermediate layer composed of a blend of an aliphatic polyamide resin with a fluorine-containing graft copolymer.
SUMMARY OF THE INVENTION
In one aspect, the invention provides a composition comprising a mixture of melt processable substantially non-fluorinated polymer, primary or secondary di- or polyamine, and onium catalyst.
In another aspect, the invention provides an article comprising a first layer comprising fluoropolymer, and a second layer bonded to the first layer comprising a mixture of: melt processable substantially non-fluorinated polymer, primary or secondary di- or polyamine, and onium catalyst. In another aspect, the invention provides a method of bonding fluoropolymer to substantially non-fluorinated polymer comprising the steps of: providing a bonding composition comprising a mixture of melt processable substantially non-fluorinated polymer, primary or secondary di- or polyamine, and onium catalyst; providing fluoropolymer; and forming a multi-layer article by contacting a first layer comprising the substantially non-fluorinated polymer with a second layer comprising the fluoropolymer.
Some of the advantages of the articles of the invention include lower cost, chemical resistance, and resistance to marking or dirt and grime, for example for signage. The compositions of the invention provide improved adhesion to fluoropolymers while using smaller quantities of polyamines than compositions not containing an onium catalyst.
DETAILED DESCRIPTION OF THE INVENTION
Fluoropolymer materials useful in the present invention include those fluoropolymers broadly categorized structurally into three basic classes. A first class includes those fluorinated polymers, copolymers, terpolymers, etc., comprising interpolymerized units derived from vinylidene fluoride or vinyl fluoride (sometimes referred to as “VF
2
” or “VDF” and VF respectively). Preferably fluoropolymer materials of this first class comprise at least 3 percent by weight of interpolymerized units derived from VF
2
or VF. Such polymers may be homopolymers of VF
2
or VF or copolymers of VF
2
or VF and other ethylenically unsaturated monomers. Copolymers of VF
2
or VF and other ethylenically unsaturated monomers are examples of fluoropolymers.
VF
2
and VF-containing polymers and copolymers can be made by well-known conventional means, for example, by free-radical polymerization of VF
2
with or without other ethylenically-unsaturated monomers. The preparation of colloidal aqueous dispersions of such polymers and copolymers is described, for example, in U.S. Pat. No. 4,335,238 (Moore et al.). It follows the customary process for copolymerizing fluorinated olefins in colloidal aqueous dispersions, which is carried out in the presence of water-soluble initiators that produce free radicals, such as, for example, ammonium or alkali metal persulfates or alkali metal permanganates, and in the presence of emulsifiers, such as, in particular, the ammonium or alkali metal salts of perfluorooctanoic acid.
Useful fluorine-containing monomers for copolymerization with VF
2
or VF include hexafluoropropylene (“HFP”), tetrafluoroethylene (“TFE”), chlorotrifluoroethylene (“CTFE”), 2-chloropentafluoro-propene, perfluoroalkyl vinyl ethers, for example, CF
3
OCF═CF
2
or CF
3
CF
2
OCF═CF
2
, 1-hydropentafluoropr
Bardell Scott A.
Niland Patrick D.
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