WO2001096487A2 - Feuille de materiau contenant du fluor pouvant adherer, feuille de materiau contenant du fluor adhesive, et procede et structure d'adherence d'une feuille de materiau contenant du fluor - Google Patents

Feuille de materiau contenant du fluor pouvant adherer, feuille de materiau contenant du fluor adhesive, et procede et structure d'adherence d'une feuille de materiau contenant du fluor Download PDF

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Publication number
WO2001096487A2
WO2001096487A2 PCT/US2001/018344 US0118344W WO0196487A2 WO 2001096487 A2 WO2001096487 A2 WO 2001096487A2 US 0118344 W US0118344 W US 0118344W WO 0196487 A2 WO0196487 A2 WO 0196487A2
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Prior art keywords
fluorine
adhesive
containing material
material sheet
layer
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PCT/US2001/018344
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English (en)
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WO2001096487A3 (fr
Inventor
Toshihiro Suwa
Keizo Yamanaka
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3M Innovative Properties Company
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Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Priority to EP01946132A priority Critical patent/EP1290070A2/fr
Priority to US10/258,937 priority patent/US20040091713A1/en
Priority to BR0111499-9A priority patent/BR0111499A/pt
Publication of WO2001096487A2 publication Critical patent/WO2001096487A2/fr
Publication of WO2001096487A3 publication Critical patent/WO2001096487A3/fr
Priority to HK03105007.7A priority patent/HK1054399A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2300/102—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/22—Presence of unspecified polymer
    • C09J2400/226—Presence of unspecified polymer in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/006—Presence of halogenated polymer in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C09J2433/003—Presence of (meth)acrylic polymer in the primer coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • C09J2475/003—Presence of polyurethane in the primer coating

Definitions

  • the present invention relates to an adhe able fluorine-containing material sheet, an adhesive fluorine-containing material sheet, an adhering method of a fluorine-containing material sheet, and an adhesion structure.
  • Fluorine-containing materials such as DyneonTM THV (terpolymer of tetrafiuoroethylene, hexafluoropropylene and vinylidene fluoride, produced by Dyneon) and PVDF (polyvinylidene fluoride) have excellent properties which hydrocarbon-based material cannot possess, and occupy a very important position in industry.
  • the fluorine-containing materials are suitable as a surface protective material of a billboard, a reflector, a solar cell or the like, particularly for outdoor uses, because of their specific properties such as good chemical stability, excellent weatherability and high thermal stability.
  • the fluorine-containing material may be used solely as a part by inserting it or fixing it with screws or the like, however, the fluorine-containing material is generally expensive and therefore, mostly used as a composite material improved in the function by combining it with other materials (lamination or covering). These composite materials are expected of uses, for example, a substitute film for finish coating or a protective film of billboards.
  • the fluorine-containing material inherently has a low surface energy, therefore, suffers from extremely poor adhesion to a dissimilar material, for example, an adhesive or a pressure sensitive adhesive. To overcome this problem, various methods have been heretofore investigated for improving the adhesive property.
  • 3-163182 of Yagi et al. discloses effectiveness of an IPN-style adhesive comprising an acryl polymer and a fluoropolymer, which is obtained by dissolving a fluorine-containing monomer in an acryl monomer and curing the blend;
  • Japanese Unexamined Patent Publication (Kokai) No. 61-31411 of Usami et al. discloses effectiveness of an adhesive obtained by mixing an acryl monomer or oligomer and a fluoropolymer, which are relatively good in the compatibility therebetween;
  • U.S. Patent No. 5,482,991 of Kumar et al. discloses effectiveness of an acrylic pressure sensitive adhesive having acrylsiloxane fluoride.
  • European Patent EP-0523644 of Kawashima et al. proposes to improve the adhesive property by combining a fluoropolymer and a polyamide resin.
  • One industrially useful application example is Denka DX film of Denka described in Japanese Unexamined Patent Publication (Kokai) No. 2-28239. This is a film manufactured fundamentally by the melt-coextrusion of two layers different in the mixing ratio.
  • a pressure sensitive adhesive is coated on the inner layer with a larger amount of the PMMA (polymethylmethacrylate) component and having a higher polarity.
  • an adherability- imparting layer i.e., particularly a primer layer by the irradiation of an electron beam.
  • conventional techniques relating to the formation of a primer layer are described below.
  • irradiation of an electron beam causes crosslinking of a polymer such as polyethylene and thereby the heat resistance is improved.
  • Modern Fluoropolvmers. edited by John Scheirs, John Wiley & Sons, New York (1997) describes this.
  • Maku-uchi et al J. Poly. Sci. Poly. Chem. Ed., 14, 617 - 625 (1976) suggests that when PNDF is irradiated with an electron beam, radicals are generated and form a crosslinked structure.
  • Japanese Unexamined Patent Publication No. 2-209928 of L. Sidney at al. and also their publication at an international meeting (Proceedings of Rad Tech Asia '91, Osaka, Japan (April 15 - 18, 1991)) suggest that a fluororubber is crosslinked with a polyfunctional acrylate such as trimethylpropane acrylate (TMPTA) upon irradiation of an electric beam and that the TMPTA polymer is grafted to the main chain of a copolymer of vinylidene fluoride and hexafluoropropylene.
  • TMPTA trimethylpropane acrylate
  • U.S. Patent No. 5,266,400 of Yarusso et al. discloses a method of reducing the acceleration voltage for crosslinking a rubber-based pressure sensitive adhesive on paper (cellulose), polypropylene or polytetrafluoroethylene which are prone to degrade by an electron beam. However, if the acceleration voltage is increased to such a level that an electron beam acts on the substrate, the substrate degrades.
  • U.S. Patent No. 5,209,971 of Babu et al. discloses a technique of irradiating an electron beam on a polyolefin-based pressure sensitive adhesive to crosslink the pressure sensitive adhesive, thereby improving the cohesion and heat resistance.
  • Example 8 shows in Example 8 that when a PTFE (polytetrafluoroethylene) sheet was immersed in an acryl monomer and a ⁇ -ray was applied thereto for 3 days, an acrylonitrile polymer was grafted to the surface of the PTFE sheet and thereby tackyness was generated on the surface.
  • the polyacrylonitrile by itself has a Tg of about 100°C and this is not effective as a pressure sensitive adhesive.
  • Japanese Unexamined Patent Publication (Kokai) No. 3-250034 proposes "a method for forming a fluorine-containing polymer layer on a plastic substrate, comprising applying onto a plastic substrate a coating solution obtained by adding an oligomer or polymer to a polyfluorinated group-containing monomer and irradiating thereon an electron beam".
  • an oligomer dissolved or dispersed in an monomer
  • this monomer solution is coated on the surface of a plastic, and an electron beam of from 5 to 200 kGy is irradiated thereon to polymerize and cure the monomer.
  • This invention is characterized in that a thin polymer film comprising a polyfluoride group is formed within a short time on the surface of a plastic and the film is free of a freon solvent and has good adhesive property.
  • the polymer surface for example, the portion very close (50 to 10,OO ⁇ A) to the surface of PTFE is treated with a low energy electron beam (from 100 to 10,000 eN) in a high vacuum (10 "8 Torr) to remove fluorine from the carbon-fluorine bond on the substrate surface and convert the bond into a carbon-carbon or carbon-oxygen bond, thereby improving the adhesive properties to various materials.
  • the treated film can be bonded to the brass, copper or steel surface using an ordinary adhesive.
  • U.S. Patent No. 4,533,566 of J. Evans et al. proposes to improve the adhesive property by irradiating an electron beam on a polyester film as a substrate for a silicone release liner.
  • This patent relates to the production of a release liner and discloses a method for bonding a silicone thin layer onto a flexible polyester film. More specifically, while allowing a polyester film to move in an atmosphere having an oxygen concentration of 500 ppm or less, preferably 40 ppm or less, the polyester film is exposed to an electron beam of at least 20 kGy, preferably from 20 to 200 kGy, more preferably from 50 to 100 kGy, whereby a thin silicon layer is formed on the film surface.
  • Toray have filed a series of inventions using a fluororesin film as the substrate.
  • Japanese Unexamined Patent Publication (Kokai) No. 10-58617 discloses a repairing sheet comprising a fluororesin film having provided on one surface thereof an antifouling layer and on another surface thereof a pressure sensitive adhesive layer.
  • the adhesion between the fluororesin film and the antifouling layer or pressure sensitive adhesive layer is accelerated by a surface treatment of the fluororesin film or undercoating therebetween.
  • an ultraviolet ray absorbing layer is provided between the fluororesin film and the pressure sensitive adhesive layer and a crosslinking agent is added to the ultraviolet ray absorbing layer, the crosslinking can be attained by heating or exposure to ultraviolet ray or electron beam.
  • Japanese Unexamined Patent publication (Kokai) No. 4-146129 describes a technique of forming a resin coated metal by heat-fusing a fluorine-containing resin film having a printing layer formed of an ink resin composition on the surface of a metal, wherein the ink resin composition comprises an energy line-curable resin, hi this technique, the printing layer is merely printed on a part of the fluorine-containing resin film and the fluorme-containing resin film is heat-fused onto the metal film. Furthermore, the fluorine-containing resin film is heat-fused to the metal substrate but not bonded thereto using an adhesive.
  • Japanese Unexamined Patent Publication (Kokai) No. 5-8353 describes a resin tube suitable for fuel piping of a vehicle, in which a resin tube having a polyamide resin outer layer and a fluororesin inner layer is exposed to radiation to cause crosslinking and thereby introduce a crosslinked structure.
  • This is a double extruded resin product and differs from the adhesive sheet of the present invention.
  • the present invention has been made in order to solve the above-described problems and relates to an adherable fluorine-containing material sheet formed without using a surface treatment or a special adhesive.
  • the present invention also relates to an adhesive fluorine-containing material sheet, a method of adhering a fluorine-containing material sheet, and an adhesion structure, using the adherable fluorine-containing material sheet.
  • the present inventors have previously disclosed a pressure-sensitive adhesive sheet comprising a substrate which is an electron-beam non-degradable fluorine-containing material sheet, and a pressure sensitive adhesive layer provided on the outer surface of the substrate with or without an intermediate layer therebetween, wherein the fluorine- containing material sheet has a chemical bond with the pressure sensitive adhesive layer or intermediate layer directly contacting with the fluorine-containing material sheet and the chemical bond is formed by the irradiation of an electron beam at least on the fluorine- containing material sheet (Japanese Patent Application No. 11-189081).
  • an adherable fluorine-containing material sheet where an adherability-imparting layer is provided on the surface of an electron-beam non-degradable fluorine-containing material sheet and a chemical bond formed by irradiating an electron beam at least on the fluorine-material sheet is present between the fluorine-containing material sheet and the adherability-imparting layer, is effective for the adhesion to an adherend using other adhesives including epoxy, hot melt, and acrylic adhesives.
  • the present invention has been accomplished based on this finding.
  • the adherable fluorine-containing material sheet of the present invention is fundamentally an adherable fluorine-containing material sheet obtained by coating or stacking an adherability-imparting material (e.g., a hot-melt of monomer, syrup, oligomer or polymer, or a polymerization product solution or aqueous dispersion) on a fluorine- containing substrate sheet and irradiating thereon an electron beam to form an adherability-imparting layer capable of adhering using a non-pressure sensitive adhesive.
  • an adherability-imparting material e.g., a hot-melt of monomer, syrup, oligomer or polymer, or a polymerization product solution or aqueous dispersion
  • the adherability-imparting material component is polymerized (crosslinked) and a radical of the molecule of the adherability-imparting material reacts with a radical of the substrate molecule, so that a strong chemical bonding can be formed between two layers which are originally very low in the adhesive property and the substrate sheet can also be crosslinked.
  • the thus-obtained adherability-imparting layer on the fluorine-containing material sheet exhibits good adherability with an ordinary adhesive, accordingly, the fluorine-containing material sheet can be successfully adhered to an adherend using an ordinary adhesive.
  • the structure of the adherable fluorine-containing material sheet of the present invention is advantageous in that although an adlierability-imparting layer is formed on a fluorine-containing material sheet, use of an adhesive layer between two layers or a specific surface treatment of the fluorine-containing material required in conventional techniques can be completely dispensed with.
  • the crosslinking of the substrate sheet may be made according to the intensity of the electron beam, for example, the substrate sheet as a whole may be crosslinked or only a portion of the substrate in the vicinity of the interface with the adherability-imparting material may be crosslinked, though some materials undergo degradation of the molecular bonds by an electron beam and prudence is necessary in this point.
  • an adhesive fluorine-containing material sheet and an adhering method of a fluorine-containing material sheet which use the above- described adherable fluorine-containing material sheet, and the resulting adhesion structure are also provided.
  • An adherable fluorine-containing material sheet comprising an electron- beam non-degradable fluorine-containing material sheet having on the surface thereof an adherability-imparting layer, wherein a chemical bond is present between the fluorine- containing material sheet and the adlierability-imparting layer and the chemical bond is formed by the irradiation of an electron beam at least on the fluorine-containing material sheet.
  • An adhesive fluorine-containing material sheet comprising an adherable fluorine-containing material sheet described in (1) to (6) and a non-pressure sensitive adhesive layer formed on the surface of the adherability-imparting layer.
  • a method for adhering a fluorine-containing material sheet comprising adhering an adherable fluorine-containing material sheet described in (1) to (6) to an adherend by applying an adhesive onto the surface of the adherable fluorine-containing material sheet and/or the adherend or applying an adhesive therebetween.
  • Fig. 1 An example of a fluorme-containing material substrate on one side of which an adherability-imparting layer is formed.
  • Fig. 2 An example of a fluorine-containing material substrate, on both sides of which an adherability-imparting layer is fo ⁇ ned.
  • Fig. 3 An example of a fluorine-containing material substrate having on the surface of the subsfrate a primer layer, on which a hot-melt adliesive layer is formed.
  • Fig. 4 An example of a fluorine-containing material substrate having on the surface of the substrate a primer layer, on which an elastic layer is formed.
  • Fig. 5 An example of adhering an adherability-imparted fluorine-containing material sheet of the present invention onto an adherend.
  • the fluorine material (namely, fluorine-containing material or fluorinated material) for use as the substrate of the adherable fluorine-containing sheet of the present invention may be, for example, a homopolymer or copolymer of carbon fluoride, a blend thereof or a blend with a non-fluorine material.
  • HFP hexafluoropropylene
  • TFE tetrafluoroethylene
  • VDF vinylidene fluoride
  • NF vinyl fluoride
  • CTFE chlorotrifluoroethylene
  • fluorine-containing diolefin examples include perfluorodiallyl ether and perfluoro-l,3-butadiene.
  • the fluorine-containing monomer may be copolymerized with a fluorine-free terminal unsaturated monoolefm copolymer such as ethylene or propylene. In the polymer mixture, the fluorine-containing monomer preferably accounts for at least 50 wt% of the entire monomer.
  • the fluorme-containing monomer may be copolymerized with iodine- or bromine-containing curing site monomer to prepare a peroxide curable polymer.
  • curing site monomers examples include a terminal unsaturated monoolefm having from 2 to 4 carbon atoms such as bromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene and 4-bromo- 3,3,4,4-tetrafluorobutene-l .
  • a homopolymer or copolymer of these fluorinated carbons or a mixture or crosslinked product thereof with another polymer may also be used.
  • fluoropolymer examples include polymers and copolymers such as polyvinylidene fluoride (PNDF), polyvinyl fluoride (PNF), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetrafluoroethylene-ethylene-propylene copolymer, tetrafluoroethylene-ethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene-heptafluoropentene copolymer, tetrafluoroetliylene-ethylene-(perfluorobutyl)ethylene copolymer, tetrafluoroethylene-ethylene-hexafluoropropylene copolymer, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-propylene-vinylidene fluoride
  • PNDF
  • a graft, block or blend polymer of these polymers may also be used and examples thereof include a graft polymer obtained by grafting chlorotrifluoroethylene-vinylidene fluoride copolymer to vinylidene fluoride copolymer, and a block polymer of tetrafluoroethylene-ethylene copolymer with vinylidene fluoride-hexafluoropropylene copolymer.
  • Halar chlorotrifluoroethylene-ethylene copolymer (Allied Corp.)
  • Aflon COP tetrafluoroethylene-ethylene-based copolymer (Asahi Glass) Cefral Soft vinylidene fluoride-based graft polymer (Central Glass)
  • Daiel T-530 hexafluoropropylene-vinylidene fluoride- based block copolymer Daikin
  • ⁇ eoflonEP-610 tetrafluoroethylene-ethylene-based copolymer (Daikin) Aflas 150E tetrafluoroethylene-propylene-based copolymer (Asahi Glass) Aflas 200 tetrafluoroethylene-propylene-vinylidene fluoride copolymer (Asahi Glass) Teflon PFA tetrafluoroethylene-perfluoropropyl vinyl ether copolymer (E.I. Du Pont) Tedlar polyvinyl fluoride (E.I. Du Pont)
  • the fluorine-containing material constituting the substrate of the adherable fluorine-containing material sheet of the present invention contains fluorine and, therefore, is excellent in the chemical resistance, heat resistance, mechanical properties and electrical properties.
  • the fluorine must be contained in an amount of at least 10 wt%, preferably 30 wt% or more, more preferably 40 wt% or more of the material.
  • the fluorine may be contained even in an amount of 50 wt% or more and maximally 76 wt%.
  • the substrate of the fluorine-containing material sheet of the present invention is preferably cross-linkable under the irradiation of an electron beam.
  • the acceleration voltage or linear density of the electron beam must be controlled low such that the electron beam does not transmit and degredate not only the irradiated surface area but also the whole bulk, and particular account is also necessary for the irradiation time.
  • polytetrafluoroethylene is a polymer which degrades under irradiation of an electron beam, and not preferred in the present invention.
  • a modified polytetrafluoroethylene which is improved in the degradability may be suitably used.
  • an electron-beam degradable material may be used in combination with an electron-beam non-degradable or electron-beam crosslinkable material because the film formed of such a combination is not damaged by the irradiation of an electron beam or under such conditions.
  • the thickness of the substrate of the adherable fluorine-containing material sheet of the present invention is not particularly limited, hi the case of a protective sheet made of polyvinyl chloride, some commercially available products has a thickness of 5 mm or those called as "film" having a thickness of less than hundreds of ⁇ m may also be used. In general, the thickness of the substrate is from about 50 to 1,000 ⁇ m.
  • the application is not limited and may be a sheet, an adhesive tape, a graphic film, an insulating sheet or the like. Various additives such as colorants (pigments and dyes), fillers, UN-absorbers may be added to the fluorine-containing material if desired.
  • the adherability-imparting material for use in the adherable fluorine-containing material sheet of the present invention is not particularly limited and any may be used as long as it is a material which can form a chemical bond with the fluorine-containing material sheet upon irradiation of an electron beam and at the same time which can adhere by an adhesive.
  • the component constituting the adherability-imparting material may be a hydrocarbon-based (e.g., acrylate-based, urethane-based) or rubber-based compound.
  • a hydrocarbon-based e.g., acrylate-based, urethane-based
  • rubber-based compound e.g., butylene-based, polystyrene-based
  • polyolefin-based, silicone-based and fluorine-containing compounds which are generally low in the adherability may also be used because an adhesive corresponding thereto can be used.
  • the substrate for use in the present invention is a fluorine-containing material having excellent chemical resistance and superior weatherability, therefore, the adherability-imparting material preferably has the same property in some cases and to this purpose, a silicone-based, fluorine-containing or polyolefin-based compound is used.
  • the adherability-imparting material may also be blended with a crosslinking agent, an oligomer or a polymer, or may be formed by the polymerization of a sole adherability-imparting material monomer.
  • the adherability- imparting composition is preferably formed using an electron beam sensitive monomer, oligomer, polymer or crosslinking agent because bonding between the substrate and the pressure sensitive adhesive is accelerated by the irradiation of an electron beam and moreover, the adherability-imparting material is improved in the shear holding force or heat resistance.
  • the adherability-imparting layer of the adherability-imparted fluorine-containing material sheet may be made of various materials, for example, a primer layer formed of a material having high wettability to an adhesive, an elastic layer formed of a urethane or acrylic rubber material for imparting elasticity to the fluorine-containing material sheet, a monochromatic solid layer, a printing layer having letters and a background or image, or a backing layer (suitably an acryl layer or urethane layer) for ensuring the handleability as a film while reducing the thickness of the fluorine-containing material so as to achieve the low cost, but this is not particularly limited.
  • the surface of the fluorine-containing material substrate may be primed with a material having high wettability to an adliesive.
  • the primer is preferably of acrylates and vinyl compounds that are electron beam curable.
  • monofunctional acrylates including acrylic acid, ethyl acrylate, butyl acrylate, 2- ethylhexyl acrylate, isooctyl acrylate, methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, isobornyl acrylate, methoxypolyethyleneglycol acrylate, morpholine acrylate, phenoxyethyl acrylate, vinyl acetate and N-vinylpyrrolidone, and polyfunctional acrylates including tryallyl isocyanurate, butanediol diacrylate, pentaerythritol triacrylate, polyethyleneglycol diacrylate and urethane acrylate can be preferably used. These acrylates may be used alone or two or more of them may be combined.
  • the primer layer is advantageous in that, for example, a very thin primer layer can be cured by an electron beam to cause an interface reaction at a high line speed and taken up to provide an adherability-imparted fluorine-containing sheet having a necessary minimum thickness.
  • the thickness of the primer layer is not particularly limited and maybe, for example, 100 ⁇ m or less, suitably 50 ⁇ m or less.
  • the primer layer is preferably thinner and in this meaning, the thickness is preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the elastic layer formed of a urethane material, an acrylic rubber material, silicone elastmer material, elastomeric epoxy material, or a foaming material is used as the adlierability-imparting layer for the following purposes.
  • the thickness of the fluorine- containing material surface layer having durability can be reduced to realize the low cost while not impairing the handleability as a film.
  • the curved face conformability application performance to a curved face
  • the stability or durability against abrupt change of temperatures can be improved.
  • an elastic layer when present under the substrate, it can serve as a protective film having effects of preventing or reducing scratches generated upon colliding of a pebble or rubbing with a hard material from reaching the material protected, or preventing or reducing the fluorine-containing film itself from flawing.
  • Printing Layer examples of the printing layer include a monochromatic solid layer or a printing layer comprising a letter/an image and a background. For example, at the time of re- coating with an ordinary coating material, the coating is applied after the surface is polished or cleaned with a solvent, however, such a process is not necessary or can be shortened in the case where a fluorine-containing film having high weatherability has a printing layer and coloring or printing is made thereon.
  • coloring is sometimes required.
  • the coloring also varies depending on the case, for example, coloring for preventing viewing of the background (masking) or translucent coloring may be required, or a logo mark or company name may be printed on the protective film itself.
  • a backing later is provided between the fluorine-containing material surface layer and an adhesive layer.
  • Suitable examples thereof include an acryl layer, a urethane layer and a soft vinyl layer.
  • the adherability-imparting material may further contain, if desired, various additives in a small amount, such as a pigment, a dye, a plasticizer, a filler, a stabilizer, a UN-absorbent, an antioxidant, a leveling agent, a surface active agent and a process oil.
  • various additives such as a pigment, a dye, a plasticizer, a filler, a stabilizer, a UN-absorbent, an antioxidant, a leveling agent, a surface active agent and a process oil.
  • the adherability-imparting material for use in the present invention may be any of a solventless-type material (e.g., syrup, hot-melt of oligomer or polymer), an organic solvent-type material and a water dispersion-type material (e.g., emulsion, suspension).
  • the number of these adherability-imparting layers is not limited and for example, a structure such as fluorine-containing material substrate/primer layer, fluorine-containing material substrate/primer layer/elastic layer or fluorine-containing material substrate/primer layer/colored layer (printing layer) may be employed.
  • the present invention is characterized in that since the fluorine-containing material substrate is low in the adhesion to an adherend, the fluorine-containing material substrate is chemically bonded (adhered) to the adherability-imparting layer directly contacting therewith by the irradiation of an electron beam.
  • the method for coating the adherability-imparting material for use in the present invention on a fluorine-containing material substrate is not particularly limited.
  • a solvent type coating method where the solvent is dried after the coating or a solventless type coating method may be used.
  • the solvent for use in the solvent type (usually, polymer solution) coating ethyl acetate, methyl ethyl ketone or a mixed solvent thereof is commonly and widely used.
  • the adherability-imparting material (monomer, syrup, oligomer, polymer or a mixture thereof) may be directly coated without a solvent or may be coated by a spray or the like. Particularly in the case of a polymer, hot-melt coating may also be used.
  • a fluorine-containing surface active agent such as hydroxyl group, carboxyl group or ether group
  • a fluorocarbon having a functional group such as hydroxyl group, carboxyl group or ether group
  • a fluorocarbon having a functional group such as hydroxyl group, carboxyl group or ether group
  • perfluoropolyether diol for example, perfluoropolyether diol (Dynamar FC-2202, produced by 3M)
  • the wettability may also be improved by adding a photoinitiator to a monomer which forms the adherability-imparting material, controlling the exposure of the mixture to an ulfraviolet ray such that increase in the molecular weight or viscosity is limited to a syrup state, and coating the syrup on a substrate.
  • the adherability-imparted fluorine-containing material sheet of the present invention is characterized in that a chemical bond is formed between the fluorine- containing material subsfrate and the adherability-imparting layer by the irradiation of an electron beam.
  • a fluorine-containing material when a fluorine-containing material is used as the substrate, the bonding force between the substrate and the adhesive layer is insufficient because the adhesive has no adhesive property to the fluorine- containing material substrate.
  • a special treatment e.g., metal sodium treatment, alkali treatment
  • a special intermediate bonding layer a layer formed of a material having adhesive property to a fluorine-containing material and also to an adhesive
  • the performance e.g., adhesive strength, transparency
  • the profitability are difficult to attain at the same time.
  • adherability-imparting material also generates radicals upon irradiation of an electron beam, mutual bonding between the substrate and the adherability-imparting material is facilitated. There arises no problem with respect to the. adhesion between the thus-formed adherability-imparting layer and the adhesive layer.
  • an electron beam must be irradiated at least on interface between the fluorine-containing material substrate and the adherability-imparting layer.
  • the electron beam is preferably irradiated both on the fluorine-containing material substrate and the adherability-imparting layer formed thereon because this is simple and the bonding force is higher.
  • a crosslinking structure can be introduced into the polymer of the fluorine-containing material substrate. .
  • the bonding is different from the structure obtained when a chemical bond is formed by other methods such as metal sodium treatment or alkali treatment.
  • the adherability- imparted fluorine-containing sheet of the present invention is characterized by having such a structure derived from an electron beam irradiation.
  • the surface of the fluorine-containing material substrate is not subjected to a surface treatment such as metal sodium treatment or corona discharging.
  • the surface of a fluorine-containing material substrate subjected to a surface treatment such as metal sodium treatment has traces of the surface treatment such as metal sodium treatment, however, the present invention is free of such traces.
  • the surface of the fluorine-containing material substrate is discolored to brown or black.
  • the fluorine-containing material sheet cannot be transparent.
  • the present invention at the time when an adherability-imparting material is coated on the surface of a fluorine-containing material substrate and bonded thereto by the irradiation of an electron beam, polymerization or cross- linking of the adherability-imparting material can simultaneously proceed by the irradiation. Therefore, the present invention is advantageous as compared with conventional techniques in that a special process for forming a bond between the fluorine-containing material substrate and the adlierability-imparting layer needs not be additionally provided. Furthermore, since the fluorine-containing substrate can also be crosslinked by the irradiation of an electron beam, the chemical resistance and heat resistance of the substrate can be further improved.
  • the electron beam may be irradiated either from the adherability-imparting layer side or from the substrate side.
  • the conditions for the irradiation of an electron beam may be sufficient if radicals are generated on the substrate surface in contact with the adlierability-imparting layer.
  • the conditions vary depending on the kind and thickness of the fluorine-containing material subsfrate or the adherability-imparting material, however, it is suitably 10 keN or more, 30 kGy or more. More preferably it is from 50 to 200 keN, 30 to 1,000 kGy.
  • a chemical bonding can also be formed between the fluorine-containing material subsfrate and the adherability- imparting layer by irradiating an electron beam on the substrate to generate radicals on the substrate surface and immediately thereafter coating an adherability-imparting layer on the substrate surface.
  • the intensity of the chemical bond formed is slightly reduced.
  • an interface adhesive strength sufficiently tolerable in practice can be attained even by irradiating EB, immediately followed by coating an acrylate syrup thereon in an ordinary atmosphere (oxygen concentration: about 20%) and curing it by an ultraviolet ray.
  • the intensity of the chemical bond formed between the fluorine-containing material substrate and the adherability-imparting layer according to the present invention can be evaluated by an adhesion peeling test of the adherability-imparted fluorine- containing material sheet obtained. A specific method is described later in the Examples.
  • an adherability-imparting layer is formed on the surface of a fluorine-containing material substrate having poor adherability, therefore, the fluorine-containing material sheet can be easily adhered to the surface of an adherend' in the same manner as in the adhering method using an ordinary non-pressure sensitive adhesive but without using a special method.
  • an adhesive is applied to either one or both of the surface of the adherability-imparting layer of the adherability-imparted fluorine-containing material sheet and the surface of an adherend or between the adherability-imparting layer of the adherability-imparted fluorine-containing material sheet and an adherend, and then the fluorine-containing material sheet and the adherend are tightly contacted or attached by pressure, whereby the fluorine-containing material sheet can be adhered to the adherend.
  • the hot-melt adhesive means an adhesive mainly comprising a thermoplastic resin and having a solid content of 100%, which is solid at room temperature.
  • the hot-melt adhesive is usually heat-melted in a coater called an applicator, and coated in the melted state on an adherend. After the attachment by pressure, when the melted resin is cooled, the adhesion is completed.
  • a hot-melt adhesive may be temporarily adhered by previously fusing or coating it on the surface of the adherability-imparting layer to prepare an adhesive fluorine-containing material sheet which is used for the adhesion.
  • the hot-melt adhesive does not contain water or a solvent and can dispense with a drying time and a drying apparatus, so that the adhesion can be completed by the attachment under pressure for a short period of time after the application of the adhesive. Furthermore, unlike the pressure-sensitive adhesive sheet, the hot-melt adhesive does not exhibit adhesive property before the heat-melting, therefore, the storage is easy and the storage stability is excellent.
  • thermoplastic resin ethylene-vinyl acetate copolymer (EVA), polyethylene, atactic polypropylene (APP), ethylene-ethyl acrylate copolymer (EEA), polyamide and polyester.
  • EVA ethylene-vinyl acetate copolymer
  • APP atactic polypropylene
  • EOA ethylene-ethyl acrylate copolymer
  • polyamide polyamide
  • tackifier which can be used include rosin, rosin derivatives, pinene-type resin and hydrocarbon resin (petroleum resin).
  • the wax is used for lowering the melt viscosity of the adhesive or controlling the physical properties such as open time, softening point, hardness, hot tackyness and blocking.
  • the application method (use method) of the hot-melt adhesive slightly varies mainly depending on the shape thereof, namely between the bulk hot melt and the film hot melt.
  • a hot-melt adhesive formed into a pellet or a bar is heated and liquefied in an applicator having various sizes and coated on a material to be adhered (adherend) like a dot or line or coated by a spray like a spider web, and another adherend is superposed thereon before the hot-melt adhesive is cooled to set.
  • the hot-melt adhesive is usually cooled to set within a few minutes, therefore, at that time, a sufficiently high strength can be obtained.
  • the adhesion is not attained by the heat-melting but a hot-melt adhesive previously formed into a film is placed between two (or two sheets of) adherends which are intended to adhere, and these are passed through a hot press or heating rollers to liquefy the hot melt between the adherends and thereby complete the adhesion.
  • This method is effective in the case where the material to be adhered is in the film form or the entire surface of an adherend is intended to adhere.
  • the adherend itself is heated, therefore, the method must be employed by taking account of the relationship between the heat resistance of the adherend and the temperature where the hot melt is liquefied, hi particular, for adherends having low heat resistance or for uses where the dimensional change by the heat is inliibited, an adhesive capable of being liquefied at a low temperature, such as low melt series (produced by 3M), is effective.
  • the hot-melt adhesive also include rubber-based hot melts and for the main component thereof, a styrene-based elastomer such as SIS (styrene-isoprene-styrene copolymer), SBS (styrene-butadiene-styrene copolymer) and SEBS (styrene-ethylene-butene-styrene copolymer) or an olefin-based elastomer is usually used in many cases. Also in this rubber-based hot melt, a tackifier or a wax is mixed. Further, the hot-melt adhesive may be a moisture curable hot melt (predominantly a urethane-based hot melt). This is different from the ordinary hot-melt adhesive in the point that the adhesive strength increases with the elapse of time, namely, as the curing reaction proceeds due to- moisture, but the use method thereof is fundamentally the same as the ordinary hot-melt adhesive.
  • SIS
  • curable Adhesive includes a thermosetting adhesive, an ambient temperature- curable adhesive and an UN-curable adhesive.
  • the commonly used curable adhesive is an epoxy resin-type adhesive.
  • the epoxy resin-type adhesive is roughly classified into a thermosetting adhesive and an ambient temperature-curable adhesive.
  • the thermosetting adhesive is heat-cured at a high temperature (usually 80°C or more), therefore, the crosslinking structure is liable to be dense and the cured product is generally favored with high strength, superior heat resistance and excellent resistance against chemicals.
  • the ambient temperature-curable adhesive is an adhesive used by mixing an epoxy-based main agent with a curing agent such as amine or mercaptan and thereafter curing it at an ambient temperature. This is advantageous in that a heating apparatus is not necessary and the curing can be performed outdoors. Even in the case of the ambient temperature-curable adhesive, when it is heat- cured, the curing may be completed within a short time or the curing reaction may be accelerated.
  • the main component is generally an acryl-type, silicone-type or epoxy-type adhesive.
  • the acryl-type adhesive is roughly classified into, other than the photocurable type, an anaerobic polymerization type in which the reaction starts under insulation of an air, a primer type, a two-liquid mixing type and a microcapsule type, and these can also be used. Rubber-Based Adhesive
  • the rubber-based adhesive include a hot-melt-type adhesive (described above) and an aerosol-type adhesive (described later).
  • an adhesive obtained by dissolving a rubber in a solvent is used in many cases.
  • the rubber include various rubbers such as natural rubber, SBR (styrene-butadiene rubber), NBR (nitrile rubber), chloroprene rubber, butyl rubber, polysulfide-based synthetic rubber, acrylic rubber, urethane rubber and silicon rubber.
  • derivatives e.g., chloride rubber, sulfide rubber, maleic acid rubber
  • graft copolymer or block copolymer rubbers may be used.
  • the rubber is widely used because the rubber in general well adheres to many materials and the initial adhesive strength thereof is large. In many cases, the rubber is dissolved in an organic solvent and the resulting rubber solution is coated or sprayed on an adherend. The rubber is sometimes used as a water dispersion-type latex and this is described later. To the rubber-based adhesive, a tackifier, a vulcanizing agent and an antioxidant are usually added.
  • the aqueous adhesive in the present invention, a water dispersion-type adliesive, includes a long known natural rubber-based latex.
  • a synthetic rubber-based latex is used in many cases. Examples of the synthetic rubber-based latex which is predominantly used include SBR (styrene-butadiene rubber), NBR (nitrile rubber), CR (chloroprene rubber), IR (isoprene rubber) and acrylic rubber.
  • the aqueous adliesive is advantageous in that the working environment can be improved (free of dangers of fire or poisoning) because an organic solvent is not contained, the working process is easy because the medium is water, and the adhesive can be used in a higher concentration as compared with the solvent-type adhesive because this is a dispersion type adhesive.
  • a crosslinking agent, a crosslinking accelerator, a tackifier and a thickener are generally added in many cases.
  • Aerosol Adhesive The aerosol-type adhesive is generally prepared by dissolving or dispersing a rubber-based adhesive, namely rubber, in a solution and filling it into a spray can together with a propellant. In some cases, the adhesive is jetted out like spraying by a hand pump without using a propellant.
  • the composition itself of the adhesive is the same as that of the solvent-type adhesive or the aqueous adhesive. Others
  • An instantaneous adhesive (cyanoacrylate-base) can also be very suitably used. (Adliesive Fluorine-Containing Material Sheet) hi the adhering method using the adherable fluorine-containing material sheet of the present invention, as .
  • the fluorine-containing material sheet is adhered to an adherend using an adhesive such as a hot-melt adhesive and this may be performed not only by a method of applying the adhesive to the fluorine-containing material sheet first at the adhering but also by a method of temporarily adhering an adhesive layer such as a hot-melt adhesive by previously fusing or coating it on the surface of the adherability- imparting layer of the adherable fluorine-containing material sheet of the present invention to prepare an adhesive fluorine-containing material sheet, applying the prepared adhesive fluorine-containing material sheet to an adherend and heating these at an appropriate stage to complete the adhesion.
  • an adhesive such as a hot-melt adhesive
  • the present invention also include an adhesive fluorine-containing material sheet obtained by temporarily adhering an adhesive to the surface of the adherability-imparting layer of the adherable fluorine-containing material sheet.
  • Examples of the adhesive which can be suitable used for the adhesive fluorine- containing material sheet include, in addition to a hot-melt adhesive, an acryl-type adhesive, a rubber-based adhesive, an emulsion-type adhesive and an instantaneous adhesive.
  • Fig. 1 shows an example where an adlierability-imparting layer 2 is formed on a fluorine-containing material substrate 1.
  • Fig. 2 shows an example where adherability-imparting layers 2 and 3 are formed on both surfaces of a fluorine-containing material substrate 1.
  • the adherability-imparting layer maybe provided on both surfaces of the fluorine-containing material substrate.
  • Fig. 3 shows an example where a primer layer 4 is formed as the adherability- imparting layer on the surface of a fluorine-containing material substrate 1 and a hot-melt adhesive layer 5 is temporarily adhered thereon (an example of the adhesive fluorine- containing material sheet).
  • Fig. 4 shows an example where a primer layer 4 is formed on a fluorine-containing material substrate 1 and a layer 6 such as an elastic layer, a printing layer or a backing layer is formed thereon.
  • the printing layer or backing layer 6 may be formed directly on the fluorine-containing material substrate 1 without forming the primer layer 4.
  • the adherability-imparted fluorine-containing material sheet of the present invention is characterized in that the bonding between the fluorine-containing material substrate 1 and the layer directly contacting therewith is chemical bonding caused by the irradiation of an electron beam.
  • Other layers may also be chemically bonded by the irradiation of an electron beam.
  • Fig. 5 shows an example where adhering to an adherend is performed using the adlierability-imparted fluorine-containing material sheet of the present invention.
  • the adherend 6 is an example of a glass or plastic plate in which surface contamination should be avoided.
  • the adherability-imparted fluorine-containing material sheet 7 on which a hot-melt adhesive 8 is coated in an applicator (not shown) is attached by pressure to the adherend while the hot-melt adhesive 8 is in the melted state, then, the hot-melt adhesive 8 is cooled within a few seconds, thereby completing the adhesion.
  • Carbon fluoride substrate films used in Examples and Comparative Examples are shown in Table 1 below.
  • THV is a TFE-HFP-VDF terpolymer (TFE is tetrafluoroethylene, HFP is hexafluoropropylene and VDF is vinylidene fluoride), PVDF is polyvinylidene fluoride, ETFE is an ethylene-TFE copolymer and m-PTFE is a modified polytetrafluoroethylene;
  • PVDF and E-TFE were molded by heat pressing to manufacture films
  • PTFE was a commercially available film
  • m-PTFE was subjected to ram molding and then skiving to prepare a film
  • THV500 film was prepared from a T-die extruder
  • the electron beam was irradiated from the release sheet side in a nitrogen atmosphere (oxygen concentration: about 50 ppm) at normal temperature under the conditions such that the acceleration voltage was from 150 to 250 kN, the dose was from 50 to 200 kGy, and the line speed was from 2 to 5 m/min.
  • the apparatus used was System 7824 manufactured by Energy Science, hie.
  • an adherability-imparting layer originally having low adhesive property was adhered to a fluorine film (THN film or PVDF film) by the irradiation of an electron beam.
  • the adherability-imparting layer was an elastic material such as urethane and acrylate elastomer, a blend of isobornyl acrylate or butyl acrylate and an acrylic acid, which is polymerized to form a primer layer or an anchor layer, or a coating material or ink.
  • coloring is applied on the layer (elastic material, primer layer or coating material), therefore, this possibility was examined here.
  • Adherend (Fluorine-Containing Material Sheef) THV500 film (manufactured using a T-die extruder, thickness: about 200 ⁇ m) or
  • PVDF film commercially available film, thickness: about 260 ⁇ m.
  • Urethane acrylate (M-1310, produced by Toa-Gosei Kagaku K.K., crosslinked type because this is bifunctional) as a urethane-based material, and 2-methoxyethyl acrylate (produced by Wako Junyaku Kogyo K.K.) as an acrylic rubber-type material were used. Since the 2-methoxyethyl acrylate is monofunctional, in a case, a crosslinking agent was also added thereto.
  • the urethane acrylate as having a high viscosity at an ambient temperature was hot-melt coated on a fluorine film at about 80°C to a thickness of about 200 ⁇ m.
  • a solvent diluent or a surface active agent may also be added.
  • the methoxyethyl acrylate as having a low viscosity at an ambient temperature was increased in the viscosity up to the level of ensuring good coating by adding a slight amount (0.01% or 0.5%) of a photoinitiator and then irradiating an ultraviolet ray.
  • a surface active agent may be added. Thereafter, in some Examples, a crosslinking agent (KAYARAD HDD A, produced by Nippon Kayaku K.K.) was added.
  • the coating thickness was controlled to about 200 ⁇ m. After the coating, the surface was protected by a transparent silicone release liner and then an electron beam (Examples) or an ultraviolet ray (Comparative Examples) was irradiated to cure the layer material.
  • the compositions are shown in Table 2.
  • UV ray-curable ink (UN FIL ink No. 190, produced by Teikoku Ink Seizo K.K.), a line in a width of about 300 ⁇ m was drawn and cured by an electron beam (Examples) or an ultraviolet ray (Comparative Examples).
  • Example 9 MEA + 0.01 % of photoinitiator THV
  • Example 10 MEA + 0.01% of photoinitiator PVDF
  • Comparative Example 9 Acrylic rubber layer was dissolved in the solvent.
  • Example 10 No particular change Comparative Example 10 Acrylic rubber layer was dissolved in the solvent.
  • Example 11 No particular change Comparative Example 11 Acrylic rubber layer was peeled off and suspended in the solvent.
  • Example 12 No particular change Comparative Example 12 Acrylic rubber layer was peeled off and suspended in the solvent.
  • Example 13 No particular change Comparative Example 13 Acrylic rubber layer was peeled off and suspended in the solvent.
  • Example 14 No particular change Comparative Example 14 Acrylic rubber layer was peeled off and suspended in the solvent.
  • Example 15 No particular change Comparative Example 15 Coating material was dissolved in the solvent.
  • Example 16 No particular change Comparative Example 16 Coating material was dissolved in the solvent.
  • the structure of the tested sheet is a four layer structure of fluorine-containing material film/electron beam curable material (primer layer)/adhesive/adherend.
  • the adhesives used were an epoxy resin adhesive, ultraviolet ray curable adhesive and hot melt adhesive. In all the cases, the adhesion of the fluorine-containing material film was significantly improved by the present invention.
  • a syrup of a prepolymer of BA and AA in various formulations was coated as the adherability-imparting layer to various thicknesses. From the primer layer side, an electron beam was applied at various doses to polymerize the primer layer and bond the primer layer and the substrate.
  • the thus-treated sheets and untreated sheets for comparison each was adhered to a glass plate using an epoxy resin adhesive (Scotch- Weld DP- 100 Plus clear, manufactured by 3M).
  • the thickness of the adhesive was about 30 ⁇ m.
  • Example 17 ETFE 100 BA AA (90/10) 5 14.5
  • Example 19 TFM-1700 100 BA/AA (75/25) 70 14.5
  • Example 20 TFM-1700 100 BA/AA (75/25) 5 10.5
  • the adhesion was performed in the same manner as above except for using an UV-curable adhesive (Scotch-Grip LC-2101, manufactured by 3M) in place of the epoxy resin adhesive, and the peel strength was measured in the same manner.
  • the thickness of the adhesive was about 30 ⁇ m.
  • the formulation of the primer layer was IOA/AA (90/10), the thickness of the coating was about 5 ⁇ m, and the electron beam intensity was 100 kGy.
  • Example 23 ETFE 100 BA/AA 5 2.3 (90/10)
  • Example 25 TFM-1700 100 BA/AA 5 9.5 (75/25)

Abstract

La présente invention concerne une feuille de matériau contenant du fluor pouvant adhérer, une feuille de matériau contenant du fluor adhésive, un procédé d'adhérence d'une feuille de matériau contenant du fluor, et une structure d'adhérence. Une couche facilitant l'adhérence est déposée sur la surface d'un matériau non dégradable à faisceau d'électrons contenant du fluor, formant une liaison chimique par irradiation du faisceau d'électrons.
PCT/US2001/018344 2000-06-09 2001-06-07 Feuille de materiau contenant du fluor pouvant adherer, feuille de materiau contenant du fluor adhesive, et procede et structure d'adherence d'une feuille de materiau contenant du fluor WO2001096487A2 (fr)

Priority Applications (4)

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EP01946132A EP1290070A2 (fr) 2000-06-09 2001-06-07 Feuille de materiau contenant du fluor pouvant adherer, feuille de materiau contenant du fluor adhesive, et procede et structure d'adherence d'une feuille de materiau contenant du fluor
US10/258,937 US20040091713A1 (en) 2000-06-09 2001-06-07 Adherable fluorine-containing material sheet, adhesive fluorine-containing material sheet, and adhering method and adhesion structure of fluorine-containing material sheet
BR0111499-9A BR0111499A (pt) 2000-06-09 2001-06-07 Folha de material contendo flúor aderìvel, método para aderir uma folha de material contendo flúor, e, estrutura de adesão de uma folha de material contendo flúor
HK03105007.7A HK1054399A1 (zh) 2000-06-09 2003-07-10 可黏性含氟片材，具有黏性的含氟片材以及黏附方法和含氟片材的黏附結構

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JP2000-179397 2000-06-09
JP2000179397A JP2002001886A (ja) 2000-06-09 2000-06-09 被接着可能フッ素系材料シート、接着性フッ素系材料シート、フッ素系材料シートの接着方法および接着構造

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WO2017117510A1 (fr) * 2015-12-30 2017-07-06 Saint-Gobain Performance Plastics Corporation Tube composite et son procédé de fabrication et d'utilisation

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JP2002001886A (ja) 2002-01-08
WO2001096487A3 (fr) 2002-06-13
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BR0111499A (pt) 2003-07-22
HK1054399A1 (zh) 2003-11-28
KR20040030172A (ko) 2004-04-09

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