Adhesive bonding and miscellaneous chemical manufacture – Methods – Surface bonding and/or assembly therefor
Reexamination Certificate
2000-09-28
2003-11-18
Knable, Geoffrey L. (Department: 1733)
Adhesive bonding and miscellaneous chemical manufacture
Methods
Surface bonding and/or assembly therefor
C156S309300
Reexamination Certificate
active
06649005
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to multi-layer constructions comprising a fluoropolymer and a substantially non-fluorinated polymeric material as well as to methods of producing same. In another aspect, this invention relates to methods of improving the adhesion between a fluoropolymer and other dissimilar materials, including polyurethanes. In yet another aspect, the invention relates to bonding compositions useful to adhere two dissimilar materials together.
BACKGROUND OF THE INVENTION
Fluorine-containing polymers (i.e., 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 exhibiting chemical (and solvent) resistance, and polymers displaying 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 retroflective sheeting materials. Increased concerns with fuel evaporation 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 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 (LaCourt) 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 and 4,348,312, for example, describe products that include glass microspheres, and PCT 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 discloses a diaphragm, suitable for use in automotive applications, that comprises a base fabric having a fluororubber layer bonded to at least one surface 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 also sometimes is employed to aid bonding. Some, for example, have taught treating fluoropolymer layers with charged gaseous atmosphere (e.g., corona treatment) and subsequently applying a layer of a second material, for example a thermoplastic polyamide. E.g., European Patent Applications 0185590 (Ueno et al.) and 0551094 (Krause et al.) and U.S. Pat. Nos. 4,933,060 (Prohaska et al.) and 5,170,011 (Martucci).
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 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.
The addition of a di- or polyamine as an auxiliary bonding agent to a “tie” layer that comprises the dissimilar, non-fluorinated polymer also has been suggested to increase the degree of chemical bonding between the fluoropolymer and the non-fluorinated layer. Such methods generally employ those fluoropolymers and non-fluorinated polymers having some measure of reactivity with the di- or polyamine to achieve an acceptable level of adhesion. Many non-fluorinated polymers that are reactive with a di- or polyamine can, however, exhibit a significant change in physical properties by the amine reaction when employed to construct such tie layers; polyurethanes, for example, can suffer a significant degradation in melt viscosity in the presence of even a minimal amount of a di- or polyamine, leading to a viscosity differential between the tie-layer it comprises and the other layers that can make it prohibitively difficult to co-process the multiple layers. Another significant drawback to the use of such tie layers lies in the presence of the di- or polyamine itself. The di- or polyamine also can be a difficult material to handle directly in any process, and any method that decreases or eliminates the necessity of direct contact with a di- or polyamine presents a substantial benefit to the art.
SUMMARY OF THE INVENTION
Briefly, in one aspect, this invention provides a method of bonding fluoropolymer to substantially non-fluorinated polymeric material, the method comprising the steps of:
(a) providing an amide group-containing substantially non-fluorinated polymer;
(b) treating the substantially non-fluorinated polymer with a suitable organic or inorganic base to form a base-treated, substantially non-fluorinated polymeric material;
(c) providing a fluoropolymer; and
(d) forming a multi-layer article comprising a substantially non-fluorinated layer made of the base-treated, substantially non-fluorinated polymeric material in contact with a fluorinated layer made of the fluoropolymer and exposing the multi-layer article to temperature and pressure conditions sufficient to bond the layers.
In other aspects, the present invention provides multi-layer constructions, including retroreflective sheeting, adhesive articles, and fuel line hoses and related components, comprising multi-layer articles made according to the above-described methods.
In another aspect the invention provides a bonding composition useful to adhere two dissimilar materials to one another, said composition comprising substantially non-fluorinated polymeric material that comprises base-treated amide group-containing substantially non-fluorinated polymer.
In practice of the invention, the use of a base-treated, amide group-containing polymer to comprise a “tie” layer provides a mechanism for bonding a wide array of s
Jing Naiyong
Nam Sehyun
Pham Trang
3M Innovative Properties Company
Bardell Scott A.
Knable Geoffrey L.
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