Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
  • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of 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; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31536—Including interfacial reaction product of adjacent layers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
  • Y10T428/31544—Addition polymer is perhalogenated
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31645—Next to addition polymer from unsaturated monomers
  • Y10T428/31649—Ester, halide or nitrile of addition polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31678—Of metal
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31678—Of metal
  • Y10T428/31692—Next to addition polymer from unsaturated monomers
  • Y10T428/31699—Ester, halide or nitrile of addition polymer

Definitions

• This invention relates to methods and compositions for bonding a fluoropolymer to a substrate.
• Fluorine-containing polymers are a commercially useful class of materials. Fluoropolymers include, for example, crosslinked fluoroelastomers and semi-crystalline or glassy fluoropolymers. Fluoropolymers are generally of high thermal stability and are particularly useful at high temperatures. They may also exhibit extreme toughness and flexibility at very low temperatures. Many of these fluoropolymers are almost totally insoluble in a wide variety of solvents and are generally chemically resistant. Some have extremely low dielectric loss and high dielectric strength, and may have unique non-adhesive and low friction properties.
• Fluoroelastomers particularly the copolymers of vinylidene fluoride with other ethylenically unsaturated halogenated monomers such as hexafluoropropylene, have particular utility in high temperature applications such as seals, gaskets, and linings. Multi-layer constructions containing a fluoropolymer enjoy wide industrial application.
• Adhesion between the layers of a multi-layered article may need to meet various performance standards depending on the use of the finished article.
• Various methods have been proposed to address this problem.
• One approach is to use an adhesive layer or tie layer between the fluoropolymer layer and the second polymer layer.
• fluoropolymer layer treatments for the fluoropolymer layer, including the use of powerful reducing agents (e,g., sodium naphthalide) and corona discharge, have also been employed to enhance adhesion.
• powerful reducing agents e,g., sodium naphthalide
• corona discharge treatments for the fluoropolymer layer, including the use of powerful reducing agents (e,g., sodium naphthalide) and corona discharge, have also been employed to enhance adhesion.
• reducing agents e,g., sodium naphthalide
• corona discharge corona discharge
• a multi-layer structure includes a fluoropolymer bonded to a substrate.
• the structure is prepared by exposing a bonding composition to actinic radiation, such as ultraviolet radiation, with optional heating, pressure, or combination thereof, to form the bond.
• actinic radiation such as ultraviolet radiation
• the bonding composition includes a light-absorbing compound and an electron donor.
• the bonding composition may be free of adhesive materials.
• a method of bonding a fluoropolymer to a substrate includes providing a bonding composition between a fluoropolymer and a substrate, and exposing the bonding composition to actinic radiation.
• a method of bonding a fluoropolymer to a substrate includes providing a first substrate including a bonding composition, contacting the treated surface of the first substrate with a surface of a second substrate, and exposing the bonding composition to actinic radiation.
• the method may include applying heat, pressure, or a combination thereof, to form the bond.
• Each of the first substrate and the second substrate independently, includes a matrix material.
• the matrix material can be a metal, a glass, an organic-inorganic composite, a fluoropolymer, and a non-fluorinated polymer with the proviso that at least one of the first substrate and the second substrate is a fluoropolymer.
• the bonding composition may be provided between the fluoropolymer and the substrate in different ways.
• a surface of the fluoropolymer may be treated with the bonding composition and the treated surface of the fluoropolymer may be contacted with a surface of the substrate, or a surface of the substrate may be treated with the bonding composition and the treated surface of the substrate may be contacted with a surface of the fluoropolymer.
• a mixture of the fluoropolymer and the bonding composition may be extruded and a surface of the extruded mixture may be contacted with a surface of the substrate.
• the substrate or the fluoropolymer may be cast from solution or polymerized from a monomer.
• a composite article includes a fluoropolymer having a surface, a substrate having a surface, and a bonding composition interposed between the surface of the fluoropolymer and the surface of the substrate.
• a treated fluoropolymer substrate suitable for bonding to a polymeric substrate includes a surface exposed to a combination of a light-absorbing compound and an electron donor and actinic radiation.
• a laminated article including a fluoropolymer is bonded to a substrate by a bonding composition including a light-absorbing compound and an electron donor exposed to actinic radiation.
• a composition in another aspect, includes a fluoroalkylamine, such as a 2,2,2- trifluoroethylamine.
• the bonding composition includes a light-absorbing compound and an electron donor.
• the light-absorbing compound may be an ammonium compound, a phosphonium compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound, or combinations thereof.
• the ammonium compound or phosphonium compound may include a benzyl moiety.
• the electron donor may be an amine, a phosphine, a thioether, or combinations thereof.
• the amine may be a primary amine, an amino-substituted organosilane, or combinations thereof.
• the amine may be a mono-, di- or tri-alkylamine.
• the alkylamine can be a fluoroalkylamine.
• the amino-substituted organosilane may have a hydrolyzable substituent.
• the bonding composition may include a vinylsilane. The bonding composition may be exposed to actin
• the fluoropolymer may be a perfluorinated polymer or a partially fluorinated polymer.
• the substrate may include an inorganic substrate, such as a metal and a glass, or an organic substrate, such as a non-fluorinated polymer or fluoropolymer, or an organic-inorganic composite.
• Bonded multi-layer materials may have combined physical and chemical properties possessed by both fluoropolymers and non-fluorinated polymers, resulting in less expensive, well-performing articles.
• the fluoropolymer component may be used in automotive hose and container constructions, anti-soiling films, low energy surface PSA tapes and coatings for aircraft.
• the bonding process is a mild photochemical lamination that may promote adhesion between a fluoropolymer and a substrate.
• the bonding composition may be used to form a composite article having a fluoropolymer cladding on a conductive and lustrous metal to protect it from corrosion, a fluoropolymer cladding on glass fibers to enhance their physical strength and chemical resistance for telecommunication, or a fluoropolymer layer bonded to a hydrocarbon substrate in a multi-layer materials.
• FIG. 1 is a cross-sectional view of a multi-layer article.
• a fluoropolymer layer may be bonded on one surface of a substrate to form, for example, a laminate.
• the laminate may contain two or more layers. Referring to Fig. 1, the laminate 10 includes fluoropolymer layer 20 and the substrate 30. Bonding composition 40 contacts the interface between fluoropolymer layer 20 and substrate 30. Actinic radiation applied to the bonding composition promotes bonding between fluoropolymer layer 20 and substrate 30.
• the bonding composition includes a light-absorbing compound and an electron donor.
• the bonding composition may include a solvent to facilitate applying a coating of the composition to a surface of the fluoropolymers or the substrate, or both.
• the solvent may be removed, for example, by drying, prior to contacting the substrate and fluoropolymers surfaces.
• Any solvent, if used may be a fluorinated solvent, for example, a fluorinated solvent having at least one fluorinated moiety. Fluorinated solvents may be effective at promoting wetting of the bonding composition onto either substrate.
• Preferred fluorinated solvents include, for example, hexafluoroxylene, hexafluorobenzene, and the like.
• Actinic radiation is electromagnetic radiation having a wavelength capable of affecting bonding between the fluoropolymer and the substrate in the presence of the bonding composition.
• the actinic radiation has an intensity at a wavelength capable of affecting bonding within a reasonable amount of time.
• the actinic radiation may have a wavelength between 190 nm and 700 nm, preferably between 200 nm and 400 nm, more preferably between 205 nm and
• 320 nm even more preferably between 210 nm and 290 nm, and even more preferably between 240 nm and 260 nm.
• the actinic radiation has a wavelength that is absorbed by the light-absorbing compound.
• the light-absorbing compound may have an absorbing moiety capable of being excited by the actinic radiation, such as, for example, a benzyl moiety or other aromatic moiety.
• the light- absorbing compound may be an ammonium compound, a phosphine, a phosphonium compound, an aromatic hydrocarbon compound, a thioether compound, an ether compound, a phenolic compound, a sulfonium compound, a sulfoxonium compound, an iodonium compound, an arsonium compound, or combinations thereof.
• Examples include triphenylphosphine, benzyltriphenylphosphonium chloride, benzyltributylammonium chloride, an arylammonium salt, tetraphenylarsonium chloride, diphenyl sulfide, biphenyl, 4,4'-dihydroxybiphenyl and triarylsulfonium chloride.
• Other examples of light-absorbing compounds are described, e.g., in Fukushi, U.S. Patent No. 5,658,671, "Fluoroelastomer Coating Composition," hereby incorporated by reference.
• the light-absorbing compound may have a molar absorptivity of at least 100, preferably at least 500, more preferably at least 1,500, even more preferably at least 5,000 at a wavelength when exposed to actinic radiation.
• the light- absorbing compound may include individual components that do not significantly absorb actinic radiation in a purified state, but absorbs light when the components are combined.
• a component of the composite may form a charge-transfer complex with the donor, fluoropolymer, substrate or other added ingredient, resulting in a compound that absorbs actinic radiation.
• the electron donor is a compound capable of reducing the excited state of the light- absorbing compound.
• the electron donor may be an amine, a phosphine, a thiol, a thioether, phenol, thiophenol, phenolate, thiophenolate or combinations thereof.
• the amine may be a primary amine, such as an alkylamine, e.g., a monoalkylamine, a dialkylamine, or a trialkylamine, such as a fluoroalkylamine.
• the electron donor may be polymerizable, for example, a polymerizable amine such as an aminoalkene or a vinylaniline.
• the amine may be an amino-substituted organosilane.
• the amino-substituted organosilane may have a hydrolyzable substituent; for example, it may be a trialkoxysilane.
• the amino- substituted organosilane may have the formula R ⁇ N-L-SiXX'X" where each of R 1 and R 2 , independently, is H, C 1-12 alkyl, Cl-12 alkenyl, Cl-12 alkynyl, or aryl, and L is a divalent straight chain Cl-12 alkylene, C3-8 cycloalkylene, 3-8 membered ring heterocycloalkylene, Cl-12 alkenylene, C3-8 cycloalkenylene, 3-8 membered ring heterocycloalkenylene, arylene, or heteroarylene.
• L is optionally substituted with Cl-4 alkyl, C2-4 alkenyl, C2-4 alkynyl, Cl-4 alkoxy, hydroxyl, halo, carboxyl, amino, nitro, cyano, C3-6 cycloalkyl, 3-6 membered heterocycloalkyl, aryl, 5-6 membered ring heteroaryl, Cl-4 alkylcarbonyloxy, Cl-4 alkyloxycarbonyl, Cl-4 alkylcarbonyl, formyl, Cl-4 alky lcarbony lam ino, or Cl-4 aminocarbonyl.
• L is further optionally interrupted by -O-, -S-, - N(Rc)-, -N(Rc)-C(0)-, -N(Rc)-C(0)-O-, -O-C(0)-N(Rc)-, -N(Rc)-C(O)-N(Rd)-, -O-C(O)-, - C(O)-0-, or -0-C(0)-0-.
• Each of Re and Rd independently, is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, hydroxylalkyl, hydroxyl, or haloalkyl.
• Each of X, X' and X" is a Cl-18 alkyl, halogen, Cl-8 alkoxy, Cl-8 alkylcarbonyloxy, or amino group.
• the amino-substituted organosilane has a hydro lyzable substituent, at least one of X, X', and X" is not alkyl. Further, any two of X, X' and X" may be joined through a covalent bond.
• the amino group may be an alkylamino group.
• the bonding composition may include other additives, for example, a vinylsilane, such as an alkoxyvinylsilane, polyhydroxy aromatic compounds, or a thermosetting resin such as an epoxy resin, a urethane resin, a urea resin, or an acrylate resin.
• a vinylsilane such as an alkoxyvinylsilane, polyhydroxy aromatic compounds
• a thermosetting resin such as an epoxy resin, a urethane resin, a urea resin, or an acrylate resin.
• the fluoropolymer may be a perfluorinated polymer or a partially fluorinated polymer.
• the fluoropolymer may be either melt-processible such as in the case of a terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THVTM), a tetrafluoroethylene-hexafluoropropene copolymer (FEP), and other melt-processible fluoroplastics, or may be non-melt processable such as in the case of polytetrafluoroethylene (PTFE), modified PTFE copolymers, such as a copolymer of TFE and low levels of fluorinated vinyl ethers and fluoroelastomers.
• Fluoroelastomers may be processed before they are cured by injection or compression molding or other methods normally associated with thermoplastics. Fluoroelastomers after curing or crosslinking may not be not able to be further
• Fluoroelastomers may also be coated out of solvent in their uncross linked form. Fluoropolymers may also be coated from an aqueous dispersion form.
• the fluoropolymer may be FEP, a tetrafluoroethylene-perfluoropropyl vinyl ether copolymer (PFA), perfluoroelastomer, or mixtures thereof.
• the fluoropolymer is a material that is capable of being extruded or solvent coated.
• Such fluoropolymers typically are fluoroplastics that have melting temperatures ranging from about 100 to about 330°C, more preferably from about 150 to about 270°C.
• Preferred fluoroplastics include interpolymerized units derived from VDF and fluoroethylene and may further include interpolymerized units derived from other fluorine-containing monomers, non- fluorine-containing monomers, or a combination thereof.
• suitable non-fluorine-containing monomers include olefin monomers such as ethylene, propylene, and the like.
• VDF-containing fluoropolymer may be prepared using emulsion polymerization techniques as described, e.g., in Sulzbach et al., U.S. Patent No. 4,338,237 or Grootaert, U.S. Patent No. 5,285,002, hereby incorporated by reference.
• Useful commercially available VDF- containing fluoroplastics include, for example, DyneonTM THVTM 200, THVTM 400, THVTM 500G, THVTM 61 OX fluoropolymers (available from Dyneon LLC, St. Paul, MN), KYNARTM
• a particularly useful fluoropolymer includes interpolymerized units derived from at least TFE and VDF in which the amount of VDF is at least 0.1% by weight, but less than 20% by weight.
• the amount of VDF ranges from 3-15%) by weight, more preferably from 10-15% by weight.
• the substrate may include an inorganic substrate, such as a metal or an inorganic glass, or an organic substrate, such as a fluoropolymer or a non-fluorinated polymer.
• the substrate may be an organic-inorganic composite.
• the metal may be copper or stainless steel.
• the inorganic glass may be a silicate.
• the non-fluorinated polymer may be a polyamide, a polyolefin, a polyurethane, a polyester, a polyimide, a polyimide, a polystyrene, a polycarbonate, a polyketone, a polyurea, a polyacrylate, and a polymethylmethacrylate, or a mixture thereof.
• the non-fluorinated polymer may be a non-fluorinated elastomer, such as acrylonitrile butadiene (NBR), butadiene rubber, chlorinated and chlorosulfonated polyethylene, chloroprene, ethylene-propylene monomer (EPM) rubber, ethylene-propylene-diene monomer (EPDM) rubber, epichlorohydrin (ECO) rubber, polyisobutylene, polyisoprene, polysulfide, polyurethane, silicone rubber, blends of polyvinyl chloride and NBR, styrene butadiene (SBR) rubber, ethylene-acrylate copolymer rubber, and ethylene-vinyl acetate rubber.
• Suitable ethylene-vinyl acetate copolymers include ELVAXTM available from E.I DuPont de Nemours Co., Wilmington, DE.
• Polyamides useful as the non-fluorinated polymer are generally commercially available.
• polyamides such as any of the well-known nylons are available from a number of sources.
• Particularly preferred polyamides are nylon-6, nylon-6,6, nylon-11, and nylon-12. It should be noted that the selection of a particular polyamide material should be based upon the physical requirements of the particular application for the multi-layer article. For example, nylon-6 and nylon-6,6 offer better heat resistance properties than nylon-11 and nylon-12, whereas nylon-11 and nylon-12 offer better chemical resistance properties.
• nylon-6, 12, nylon-6,9, nylon-4, nylon-4,2, nylon-4,6, nylon-7, and nylon-8 may be used, as well as ring-containing polyamides such as nylon-6,T and nylon-6, 1.
• Suitable nylons include VESTAMIDTM L2140, a nylon-12 available from Creanova, Inc. of Somerset, NJ.
• Polyether-containing polyamides, such as PEBAXTM polyamides (Atochem North America, Philadelphia, PA), may also be used.
• Useful polyurethane polymers include aliphatic, cycloaliphatic, aromatic, and polycyclic polyurethanes. These polyurethanes are typically produced by reaction of a polyfunctional isocyanate with a polyol according to well-known reaction mechanisms.
• Useful diisocyanates for employment in the production of a polyurethane include dicyclohexylmethane-4,4'- diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexyl diisocyanate, and diphenylmethane diisocyanate. Combinations of one or more polyfunctional isocyanates may also be used.
• Useful polyols include polypentyleneadipate glycol, polytetramethylene ether glycol, polyethylene glycol, polycaprolactone diol, poly-l,2-butylene oxide glycol, and combinations thereof.
• Chain extenders such as butanediol or hexandiol may also be used in the reaction.
• Useful polyolefin polymers include homopolymers of ethylene, propylene, and the like, as well as copolymers of these monomers with, for example, acrylic monomers and other ethylenically unsaturated monomers such as vinyl acetate and higher alpha-olefins. Such polymers and copolymers may be prepared by conventional free radical polymerization or catalysis of such ethylenically unsaturated monomers. The degree of crystallinity of the polymer may vary.
• the polymer may, for example, be a semi-crystalline high density polyethylene or may be an elastomeric copolymer of ethylene and propylene.
• Carboxyl, anhydride, or imide functionalities may be incorporated into the polymer by polymerizing or copolymerizing functional monomers such as acrylic acid or maleic anhydride, or by modifying the polymer after polymerization, e.g., by grafting, by oxidation, or by forming ionomers.
• functional monomers such as acrylic acid or maleic anhydride
• Examples include acid modified ethylene acrylate copolymers, anhydride modified ethylene vinyl acetate copolymers, anhydride modified polyethylene polymers, and anhydride modified polypropylene polymers.
• Such polymers and copolymers generally are commercially available, for example, as ENGAGETM (Dow-DuPont Elastomers, Wilmington, DE) or EXACTTM (ExxonMobil, Linden, NJ).
• anhydride modified polyethylene polymers are commercially available from E.I. DuPont de Nemours & Co., Wilmington, DE, under the trade designation BYNELTM
• Useful polyacrylates and polymethacrylates include polymers of acrylic acid, methyl acrylate, ethyl acrylate, acrylamide, methacrylic acid, methyl methacrylate, ethyl methacrylate, and the like.
• An example of a polymethacrylate is EMACTM (Chevron Chemical Co., Houston, TX).
• Useful polycarbonate polymers include aliphatic polycarbonates such as polyester carbonates, polyether carbonates, and bisphenol A-derived polycarbonates, and the like.
• Useful polyimide polymers include polyimide polymers made from the anhydride of pyromellitic acid and 4,4'-diaminodiphenyl ether available from E.I. DuPont de Nemours and Company under the tradename KAPTONTM. Variations include KAPTONTM H, KAPTONTM E and KAPTONTM V, among others.
• non-fluorinated polymers include polyesters, polycarbonates, polyketones, and polyureas.
• Commercially available examples of such polymers include SELARTM polyester (E.I. DuPont de Nemours & Co., Wilmington, DE), LEXANTM polycarbonate (General Electric, Pittsfield, MA), KADELTM polyketone (Amoco,
• elastomers include NIPOLTM 1052 NBR (Zeon Chemical, Louisville, KY), HYDRINTM C2000 epichlorohydrin-ethylene oxide rubber (Zeon Chemical, Louisville, KY), HYPALONTM 48 chlorosulfonated polyethylene rubber (E.I. DuPont de Nemours & Co., Wilmington, DE), NORDELTM EPDM (R.T. Vanderbilt Co., Inc., Norwalk,
• the substrate may include a second fluoropolymer.
• the substrate may have one or more surface polar functionality present thereon to enhance bonding, such as, for example, an amino, carboxyl and hydroxyl functionality.
• the bonding composition may be deposited on a surface of the fluoropolymer, the substrate or both.
• the bonding composition may be incorporated into the fluoropolymer, the substrate, or both, such that when the surfaces contact each other, the bonding composition contacts the fluoropolymer and the substrate simultaneously.
• the bonding composition may be incorporated into the fluoropolymer or the substrate by melt mixing or extruding a mixture including the bonding composition.
• the bonding composition may be applied to a surface of the fluoropolymer or substrate by a process such as, for example, spray coating, curtain coating, immersion coating, dip coating, flood coating, and the like.
• the fluoropolymer and substrate may contact each other under pressure, with optional heating, to form a precursor that is subsequently exposed to actinic radiation.
• more than one fluoropolymer layer may contact more than one surface of the substrate.
• two substrates may contact two surfaces of a fluoropolymer.
• Each of the fluoropolymer and the substrate independently, may be provided as a film or as a molded or shaped article.
• the fluoropolymer or the substrate is substantially transmissive to the actinic radiation.
• the fluoropolymer is bonded to the substrate by exposing the bonding composition to actinic radiation.
• the bonding composition may be exposed to actinic radiation through the fluoropolymer, through the substrate, or both.
• the exposure to actinic radiation may be before the substrate contacts the fluoropolymer.
• the exposure to actinic radiation may occur after the substrate and fluoropolymer contact each other.
• exposure to actinic radiation occurs simultaneously upon contacting the substrate and the fluoropolymer.
• Suitable sources of actinic radiation include arc lamps, such as xenon-arc lamps, mercury arc lamps (including low and medium pressure mercury arc lamps), fluorescent blacklights, microwave-driven lamps, such as those sold by Fusion UV Systems of Rockville, MD (including H-type and D-type bulbs), lasers and the like. Lamps that emit enriched amounts of ultraviolet or blue light, such as, for example, low pressure mercury (e.g., germicidal) lamps, are preferred.
• Suitable heat sources include, but are not limited to, ovens, heated rollers, heated presses, infrared radiation sources, flame, and the like.
• Suitable pressure sources are well known and include presses, nip rollers, and the like.
• wt%> means weight percent based on total weight.
• THVTM 500 refers to a terpolymer of TFE/HFP/VDF, having a melt temperature of 165°C
• THVTM 400 refers to a terpolymer of TFE/HFP/VDF, having a melt temperature of 150°C
• THVTM 200 refers to a terpolymer of TFE/HFP/VDF, having a melt temperature of 120°C
• FEP refers to FEP X6307 which is a copolymer of tetrafluorethylene and hexafluoropropylene, 85/15 by weight
• HTE is a terpolymer of hexafluoropropylene, teterafluoroethylene and ethylene, all available from Dyneon, L.L.C.
• PVDF-HV refers to "PVDF 1 1010" which is a tradename for a copolymer of hexafluoropropylene and vinylidene fluoride having a melting point of 160°C
• PVDF-CV refers to SOLEFTM PVDF-CV which is a copolymer of chlorotrifluoroethylene and vinylidene fluoride, both commercially available from Soltex Polymer Corp. of Houston, TX.
• BYNELTM 3101 is an acid modified ethylene-vinyl acetate copolymer
• ELVAXTM 450 is an ethylene-vinyl acetate copolymer havingl ⁇ wt% vinyl acetate and a Vicat softening temperature of 61°C
• polyimide refers to KaptonTM lOOHN film, all commercially available from E.I. du Pont de Nemours of Wilmington DE.
• EMACTM 2202T is a copolymer of ethylene and methyl acrylate, 80/20 by weight available from Chevron Chemical Co. of Houston, TX.
• VESTAMIDTM L2140 refers to nylon 12 having a Vicat softening point of 140°C commercially available from Creanova, Inc. of Somerset, NJ.
• Copper-coated polyimide refers to KaptonTM lOOHN film that has been metallized with copper.
• Gold-coated polyimide refers to KaptonTM 100HN film that has been metallized with gold.
• Polycarbonate film refers to polyethylene terephthalate film of about 10 mils (0.25 mm) thickness.
• Polymer films (i.e., substrates) were prepared by placing polymer granules indicated in Tables 1 A and IB were placed between two sheets of polytetrafluoroethylene having a thickness of 0.38 mm and softening them for 2-3 minutes at 200°C. Subsequently, the softened materials were pressed for about 5 to 10 seconds between two heated platens of a Wabash hydraulic press (Wabash Metal Products Company, Inc., Hydraulic Division, Wabash, IN) and immediately transferred to a cold Wabash hydraulic press at 13-15°C and 2-4 psi (0.014 - 0.028 MPas). After cooling to room temperature in the cold press, round-shaped films of polymer having a thickness of 1.5 mm were obtained.
• Wabash hydraulic press Wabash Metal Products Company, Inc., Hydraulic Division, Wabash, IN
• the films produced in this manner were thin smooth films of 0.08 to 0.15 mm in thickness.
• the substrate films thus prepared were cut to dimensions of approximately 2.5 cm by 5 cm for use in lamination.
• Bonding composition (BC 1) was prepared by mixing 0.2 g allylamine and 0.1 g benzyltriphenylphosphonium chloride in 2 g methanol.
• a second bonding composition (BC 2) was prepared by mixing 0.2 g allylamine and 0.1 g triphenylphosphine in 2 g methanol. All the above chemicals were available from Sigma- Aldrich Chemical Co, Milwaukee, Wl.
• the cut film was flood-coated with the bonding composition. It was not necessary to dry the bonding composition before forming the bond.
• Samples were prepared by contacting a fluoropolymer film surface with the bonding composition-coated substrate surface to form a laminate precursor. Comparative samples were prepared by omitting the bonding composition.
• the laminate precursor was then placed vertically in the center of a 254 nm photoreactor (Rayonet chamber reactor, model RPR-100 equipped with sixteen low pressure mercury bulbs available from The Southern New England Ultraviolet, Inc. of New Haven, CT. These samples were irradiated for periods of time indicated in Tables 1A and IB.
• Peel strength was used to determine the degree of bonding. Peel strength was determined in accordance with ASTM D-1876 (T-peel test). An InstronTM model 1125 tester, available from Instron Corp, Canton, MA set at a 4 inch (10.2 cm) per minute crosshead speed was used as the test device. The peel strength was calculated as the average load measured during the peel test. The measured peel strength is shown in Tables 1 A and IB. Comparative experiments showed that no adhesion between substrates and fluoropolymer films was observed prior to irradiation with the bonding composition present.
• Example 2 Glass microscope slides and stainless steel panels (1 inch (2.54 cm) by 2 inch (5.08 cm) pieces were cleaned with acetone. A surface of the glass or steel substrate was coated with a bonding composition, and a piece of fluoropolymer film was subsequently laminated onto the coated substrate in a good surface contact. A strip of silicone liner was inserted along the short edge between the substrate surface and the fluoropolymer film to provide tabs for the peel test. The laminated sample was positioned vertically in the center of a 254 nm photoreactor as described in Example 1 and irradiated for a period of time as shown in Tables 1 A and IB. The measured peel strength is shown in Tables 1 A and IB.
• Laminate Comparative BC l BC 2 BC 3 Adhesion Irrad. Adhesion Irrad. Adhesion Irrad. Adhesion time time Time
• Example 1 The procedure of Example 1 was followed using the bonding composition (BC) and comparative compositions (COMP) listed in Tables 2A and 2B, except that cut fluoropolymer film was coated with the bonding composition or comparative compositions. Subsequently, a second fluoropolymer film was placed on the bonding composition to form a laminate precursor. The precursor was then placed vertically in the center of a 254 nm photoreactor (Rayonet chamber reactor, model RPR- 100 equipped with sixteen low pressure mercury bulbs. Samples were irradiated for periods of time indicated in Tables 3A-4. After irradiation, the two pieces of fluoropolymer films were peeled apart and individually laminated to bonding substrates to form the final multiplayer articles.
• BC bonding composition
• COMP comparative compositions
• a strip of a silicon liner was inserted about 0.6 cm into the space between the layers along the short edge for peel testing.
• the article was hot pressed at 200°C for 2 minutes and immediately transferred to a cold Wabash hydraulic press 13-15°C. After cooling to room temperature in the cold press, the sample was ready for peel testing.
• composition Ingredients
• BC6 Tetraphenylarsonium chloride (0.05g) + ethylenediamine (0.2g) + acetonitrile (2.0g)
• BC1 1 Tetraphenylphosphonium chloride (O.lg) + allylamine (0.2g) + acetonitrile (2.0g)
• composition Ingredients

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