EP1311381A1 - Procede de preparation d'un article multicouches possedant une couche de plastique fluore et une couche d'elastomere - Google Patents

Procede de preparation d'un article multicouches possedant une couche de plastique fluore et une couche d'elastomere

Info

Publication number
EP1311381A1
EP1311381A1 EP01959657A EP01959657A EP1311381A1 EP 1311381 A1 EP1311381 A1 EP 1311381A1 EP 01959657 A EP01959657 A EP 01959657A EP 01959657 A EP01959657 A EP 01959657A EP 1311381 A1 EP1311381 A1 EP 1311381A1
Authority
EP
European Patent Office
Prior art keywords
layer
fluoroplastic
process according
article
elastomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01959657A
Other languages
German (de)
English (en)
Inventor
Tatsuo Fukushi
Robert E. Kolb
Craig R. Hoff
Steven J. Wellner
Attila Molnar
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of EP1311381A1 publication Critical patent/EP1311381A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0013—Extrusion moulding in several steps, i.e. components merging outside the die
    • B29C48/0015—Extrusion moulding in several steps, i.e. components merging outside the die producing hollow articles having components brought in contact outside the extrusion die
    • B29C48/0016—Extrusion moulding in several steps, i.e. components merging outside the die producing hollow articles having components brought in contact outside the extrusion die using a plurality of extrusion dies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/06—Rod-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/154—Coating solid articles, i.e. non-hollow articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/304—Extrusion nozzles or dies specially adapted for bringing together components, e.g. melts within the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer

Definitions

  • This invention relates to preparing multi-layer articles having a fluoroplastic layer and an elastomer layer.
  • Fluorine-containing polymers are a commercially useful class of materials. Fluoropolymers include, for example, crosslinked fluoroelastomers and semi-crystalline or glassy fluoroplastics. Fluoroplastics 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 fluoroplastics 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. See, e.g., F.W. Billmeyer, Textbook of Polymer Science, 3d ed., pp. 398-403, John Wiley & Sons, New York (1984).
  • Fluoroelastomers particularly the copolymers of vinylidene fluoride with other ethylenically unsaturated halogenated monomers such as hexafluoropropylene, have particular utility in high temperature applications such as seals, gaskets, and linings. See, e.g., R.A. Brullo, "Fluoroelastomer Rubber for Automotive Applications,” Automotive Elastomer & Design, June 1985; “Fluoroelastomer Seal Up Automotive Future,” Materials Engineering, October 1988; and W.M. Grootaert et al., "Fluorocarbon Elastomers,” Kirk-Othmer, Encyclopedia of Chemical Technology, vol. 8, pp. 990-1005 (4 th ed., John Wiley & Sons, 1993).
  • Multi-layer constructions containing a fluoropolymer enjoy wide industrial application. Such constructions find utility, for example, in fuel line hoses and related containers and hoses or gaskets in the chemical processing field. Increased concerns with evaporative fuel standards give rise to a need for fuel system components that have increased barrier properties to minimize the permeation of fuel or fuel vapors through automotive components such as fuel filler lines, fuel supply lines, fuel tanks, and other components of the engine's fuel or vapor recovery systems. Various types of tubing have been proposed to address these concerns.
  • 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.
  • fluoropolymers containing interpolymerized units derived from vinylidene fluoride exposure of the fluoropolymer to a dehydrofluorinating agent such as a base has been used, as well as polyamine reagents applied to the fluoropolymer surface or incorporated within the fluoropolymer itself.
  • the invention relates to a method for enhancing the bond strength between a fluoroplastic layer and an elastomer layer of a multi-layer article.
  • the elastomer may be a fluoroelastomer or a non-fluorinated elastomer.
  • a fluoroplastic composition that includes interpolymerized units derived from vinylidene fluoride (VDF) is applied to the surface of a precursor article that includes a curable elastomer layer, preferably by extrusion coating the composition in molten form through a crosshead die, to form a fluoroplastic layer.
  • VDF vinylidene fluoride
  • the composition is applied directly to the surface of the elastomer layer.
  • the curable elastomer layer Prior to application of the fluoroplastic composition, the curable elastomer layer is thermally insulated to prevent it from undergoing substantial heating.
  • thermal insulation is achieved by equipping the die with a sleeve located at least partially within the upstream end of the die that receives and thermally insulates the curable elastomer layer prior to application of the fluoroplastic composition.
  • the fluoroplastic layer is heated and the curable elastomer layer is cured (preferably thermally cured).
  • the elastomer cure occurs separately from and subsequent to heating of the fluoroplastic layer.
  • the combination of thermally insulating the curable elastomer layer prior to application of the fluoroplastic composition and heating the fluoroplastic layer following application of the fluoroplastic composition results in formation of a strong bond between the fluoroplastic and elastomer layers upon cure, even in the absence of adhesion aids such as surface treatments, separate adhesive layers, and the like. For example, bond strengths of at least 15 N/cm, can be achieved.
  • Multi-layer articles prepared according to this method can be provided in a wide variety of shapes, including sheets, films, containers, hoses, tubes, and the like.
  • the articles are especially useful wherever chemical resistance and/or barrier properties are necessary. Examples of specific uses for the articles include their use in rigid and flexible retroreflective sheets, adhesive articles such as adhesive tapes, paint replacement films, drag reduction films, fuel line and filler neck hoses, exhaust handling hoses, fuel tanks, and the like.
  • the articles are also useful in chemical handling and processing applications, and as wire and cable coatings or jackets.
  • FIG. 1 is a schematic drawing of a process for making a multi-layered article according to the invention.
  • FIG. 1 there is shown one embodiment of a process for preparing a multilayer article featuring a fluoroplastic layer bonded to an elastomer layer.
  • An extruder 20 extrudes a curable elastomer composition through a die 21 to form a length of tubing 22 having a curable elastomer layer.
  • a second extruder 23 located downstream of extruder 20 and equipped with a crosshead die 25 coats a layer of molten fluoroplastic onto the surface of the curable elastomer layer.
  • the absence of substantial heating prior to application of the fluoroplastic contributes to the development, upon cure, of a strong bond between the fluoroplastic and elastomer layers.
  • the resulting multi-layer article 27 Following extrusion coating, the resulting multi-layer article 27, featuring a fluoroplastic layer deposited on a curable elastomer layer, enters a tubular heater 28 that heats the fluoroplastic layer.
  • a useful tubular heater is a radiant heater.
  • heat is transferred from heater 28 to the fluoroplastic layer, and then transferred inwardly from the fluoroplastic layer to the curable elastomer layer. It is believed that this heating step contributes to the development, upon cure, of a strong bond between the fluoroplastic and elastomer layers.
  • the multi-layer article may be cooled, e.g., by immersion in a cooling bath 29.
  • the elastomer layer may be cured either in heater 28, or, more preferably, in a separate step under pressure and higher temperature either before or after immersion in cooling bath 29.
  • it may be desirable to cool the article in bath 29, cut it into appropriately sized pieces, and then heat the individual pieces under pressure, e.g., in an autoclave, to cure the curable elastomer layer.
  • the fluoroplastic preferably is a material that is capable of being extrusion coated. Such fluoropolastics typically have melting temperatures ranging from about 100 to about 330°C, more preferably from about 150 to about 270°C.
  • the fluoroplastic includes interpolymerized units derived from VDF and may further include interpolymerized units derived from other fluorine-containing monomers, non-fluorine-containing monomers, or a combination thereof.
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • CTFE chlorotrifluoroethylene
  • 3- chloropentafluoropropene examples include tetrafluoroethylene (TFE), hexafluoropropylene (
  • VDF-containing fluoroplastics examples include olefin monomers such as ethylene, propylene, and the like.
  • the VDF-containing fluoroplastics may be prepared using emulsion polymerization techniques as described, e.g., in Sulzbach et al, U.S. 4,338,237, hereby incorporated by reference.
  • Useful commercially available VDF-containing fluoroplastics include, for example, THV 200, THV 400, THV 500G, THV 61 OX fluoropolymers (available from Dyneon LLC, St.
  • a particularly useful fluoroplastic 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 curable elastomer may be a fluoroelastomer or a non-fluorinated elastomer.
  • suitable fluoroelastomers include VDF-HFP copolymers, VDF-HFP-TFE terpolymers, TFE-propylene copolymers, and the like.
  • non-fluorinated elastomers examples include 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.
  • NBR acrylonitrile butadiene
  • EPM ethylene-propylene monomer
  • EPDM ethylene-propylene-diene monomer
  • ECO epichlorohydrin
  • SBR styrene butadiene
  • SBR styrene butadiene
  • 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, CT), VamacTM ethylene-acrylate elastomer (E.I. DuPont de Nemours & Co.
  • a curing agent is preferably blended with the curable elastomer to facilitate cure.
  • useful curing agents include imidazolines, diamines, internal salts of diamines, thioureas, and polyphenol curing agents as discussed in U.S. 4,287,322 (Worm), incorporated herein by reference. Such agents are particularly useful for epichlorohydrin compositions. Other examples, particularly useful in the curing of nitrile rubber-containing compositions, include peroxide compounds and sulfur-containing compounds.
  • examples of useful curing agents include polyols in combination with organo-onium salts (e.g., organo-ammonium, organo- phosphonium, and organo-sulfonium salts). Specific examples are described, e.g., in Fukushi, U.S. 5,658,671, "Fluoroelastomer Coating Composition," hereby incorporated by reference. Diamines and peroxides are also useful.
  • organo-onium salts e.g., organo-ammonium, organo- phosphonium, and organo-sulfonium salts.
  • the multi-layer article may contain additional polymer layers as well.
  • suitable polymer layers include non-fluorinated polymers such as polyamides, polyimides, polyurethanes, polyolefms, polystyrenes, polyesters, polycarbonates, polyketones, polyureas, polyacrylates, and polymethylmethacrylates. Adhesion between a fluorothermoplastic layer, a fluoroelastomer layer and an elastomer layer can be improved by step curing the three extruded layers in which the elastomer layer is an outside layer, the fluoroplastic layer is a middle layer and the fluoroelastomer layer is an inside layer.
  • a particularly useful construction for fuel applications features a relatively thin layer of the fluoroplastic that acts as a barrier layer bonded on one face to a relatively thick layer of non-fluorinated polymer that acts as a coverstock, and on the opposite face to a relatively thin elastomer layer (e.g., a fluoroelastomer or a non-fluorinated elastomer) that performs a sealing function.
  • the coverstock provides the article with structural integrity.
  • reinforcing aids such as fibers, mesh, and/or a wire screen may be incorporated in the multi-layer article, e.g., as separate layers or as part of an existing layer.
  • any or all of the individual layers of the multi-layer article may further include one or more additives.
  • useful additives include pigments, plasticizers, tackifiers, fillers, electrically conductive materials (e.g., of the type described in U.S. 5,552,199), electrically insulating materials, stabilizers, antioxidants, lubricants, processing aids, impact modifiers, viscosity modifiers, and combinations thereof.
  • electrically conductive materials e.g., of the type described in U.S. 5,552,199
  • electrically insulating materials e.g., of the type described in U.S. 5,552,199
  • stabilizers e.g., antioxidants, lubricants
  • processing aids e.g., impact modifiers, viscosity modifiers, and combinations thereof.
  • impact modifiers e.g., viscosity modifiers, and combinations thereof.
  • viscosity modifiers e.g., viscosity modifiers, and combinations thereof.
  • the article may be subjected to additional heat, pressure, or both, following cure.
  • Another way of increasing the bond strength between the layers is to treat the surface of one or more of the layers prior to forming the multi-layered articles.
  • Such surface treatments may consist of a solution treatment using a solvent. If the solvent contains a base, e.g., l,8-diaza[5.4.0]bicyclo undec-7-ene (DBU), treatment of the fluoropolymer will result in some degree of dehydrofluorination. Such dehydrofluorination may be beneficial to promote adhesion to subsequently applied materials. This is particularly true when the subsequently applied material contains any agent that is reactive to sites of unsaturation.
  • a base e.g., l,8-diaza[5.4.0]bicyclo undec-7-ene (DBU)
  • surface treatments include charged atmosphere treatments such as corona discharge treatment or plasma treatment. Electron beam treatment is also useful. Interlayer adhesion may also be enhanced using an agent such as an aliphatic di- or polyamine.
  • the amine can be of any molecular weight that, when used, will result in an improvement in the adhesive bond strength between the layers of the multi-layer article.
  • a particularly useful polyamine is polyallylamine having a molecular weight greater than about 1,000, as measured by gel permeation chromatography.
  • An example of a useful commercially available polyamine is polyallyl amine having a molecular weight of about 3,000 available fromNitto Boseki Co., Ltd.
  • the amine may be incorporated into one or more of the layers of the multi-layer article prior to forming the article using conventional means such as melt-mixing.
  • the amine may be applied to a surface of one or more of the layers using conventional coating methods such as spray coating, curtain coating, immersion coating, dip coating, and the like.
  • the elastomer was a fluoroelastomer prepared by combining the following ingredients: 100 parts Dyneon FE-5830Q fluoroelastomer (commercially available from Dyneon LLC, St. Paul, MN); 13 parts N-762 carbon black (commercially available from Cabot Corp., Alpharetta, GA); 6 parts calcium hydroxide HP (commercially available from C.P. Hall, Chicago, IL); 3 parts magnesium oxide (commercially available from Morton International, Danvers, MA, under the designation "ElastomagTM 170"); and 6 parts calcium oxide HP (commercially available from C.P.
  • Dyneon FE-5830Q fluoroelastomer commercially available from Dyneon LLC, St. Paul, MN
  • 13 parts N-762 carbon black commercially available from Cabot Corp., Alpharetta, GA
  • 6 parts calcium hydroxide HP commercially available from C.P. Hall, Chicago, IL
  • 3 parts magnesium oxide commercially available from Morton International, Danvers, MA, under
  • Example 1 A cross-head die equipped with a polytetrafluoroethylene (PTFE) sleeve was used to coat a molten fluoroplastic composition onto the surface of the fluoroelastomer tube.
  • the fluoroplastic was a TFE-HFP-VDF terpolymer featuring 76 wt.% TFE, 11 wt.% HFP, and 13 wt.% VDF.
  • the fluoroplastic had a melt flow index of 7 and a melting point of 233°C.
  • the PTFE sleeve prevented heating of the fluoroelastomer surface prior to application of the fluoroplastic.
  • the resulting multi-layer article was passed through a 15.2 cm long tubular heater set at 220°C (the surface temperature of the fluoroplastic was 140°C) to heat the article prior to cooling. Once cooled, the article was cut into smaller samples that were then placed on a steel mandrel and thermally cured at a temperature of 160°C and a pressure of 0.4 MPa for 60 minutes using steam in an autoclave. Following cure, the samples were removed from the autoclave and cooled to room temperature.
  • the peel adhesion of the cured samples was evaluated by making a cut in each sample to separate a 7 mm wide strip of the fluoroplastic outer layer from the fluoroelastomer core in order to provide a tab for adhesion testing.
  • the thickness of the fluoroplastic layer was 0.3 mm.
  • An Instron® Model 1125 tester, available from Instron Corp., set at a 100 mm/min. crosshead speed was used as the test device. Peel strength between the fluoroplastic and fluoroelastomer layers was measured in accordance with ASTM D 1876 (T-Peel Test) with the exception that the peel angle was 90 degrees. The results of two samples were averaged. The average value is reported in Table 1.
  • Example 1 The procedure of Example 1 was followed except that the fluoroplastic was a TFE- HFP-VDF terpolymer commercially available from Dyneon LLC, St. Paul, MN under the designation "THV-500". The results of the peel adhesion test are reported in Table 1. Comparative Example C-l
  • Example 1 The procedure of Example 1 was followed except that the PTFE sleeve was not used. The results of the peel adhesion test are reported in Table 1.
  • Example 1 The procedure of Example 1 was followed except that the heater was not used. The results of the peel adhesion test are reported in Table 1.
  • Example 1 The procedure of Example 1 was followed except that neither the PTFE sleeve nor the heater was used. The results of the peel adhesion test are reported in Table 1.
  • a multi-layer tube includes an inner layer of a fluoroelastomer, an intermediate layer of a fluorothermoplastic barrier layer, and an outer layer of an elastomer or rubber or thermoplastic elastomer.
  • Example 3 a cross-head die with a PTFE sleeve was used to coat THV-500 onto an extruded fluoroelastomer tube, which has an outer diameter of 16 mm with 1 mm thick wall.
  • the sleeve prevented heating of the surface of the fluoroelastomer.
  • the fluoroelastomer compound formulation for making the tube is shown in Table 2.
  • the resulting multi-layer article was passed through a 15.2 cm long tubular heater set at 220°C (the surface temperature of the fluoroplastic was 140°C) to heat the article prior to cooling.
  • the fluoroplastic coated fluoroelastomer tube was cooled and then the tube was covered with ethylene-epichlorohydrin rubber (ECO) rubber, which had a wall thickness of 2 mm.
  • ECO ethylene-epichlorohydrin rubber
  • the article was cut into curing samples. The samples were cured at 143°C and 0.28 MPa for 30 minutes by steam in an autoclave with a steel mandrel and then cured at 154°C and 0.41 MPa for 30 minute. Following the cure, the samples were removed from the autoclave and cooled to room temperature.
  • the peel adhesion of the cured samples was evaluated by making a cut to separate a 25.4 mm wide strip of the fluoroplastic layer from the fluoroelastomer and ECO layer from the fluoroplastic in order to provide tabs to test the adhesion between the layers via a peel test.
  • the thickness of fluoroplastic layer was 0.3 mm.
  • An Instron® Model 1125 tester, available from Instron Corp., set at a 100 mm/mm crosshead speed was used as the test device. Peel strength or adhesion was measured on the two strips in accordance with ASTM D 1876 (T- Peel Test). The results of the two samples were averaged the test results are summarized in Table 3.
  • Example 4 the sample was prepared and tested as in Example 3 except that the first curing condition was 146°C and 0.3 MPa for 30 minutes.
  • the test result is svimmarized in Table 3.
  • Comparative Example C-4 In Comparative Example C-l, the sample was prepared and tested as in Example 3 except that the sample was cured at 143°C and 0.28 MPa for 60 minutes without applying the second curing condition. The test result is summarized in Table 3.
  • Example C-5 the sample was prepared and tested as in Example 3 except that the sample was cured at 154°C and 0.41 MPa for 30 minutes without applying the second curing condition.
  • the test result is summarized in Table 3.
  • Fig. 1 illustrates the preparation of a multi-layer article in the form of a tube
  • Fig. 1 illustrates the use of extruders to prepare the curable elastomer layer and fluoroplastic layers
  • other polymer processing techniques may be used.
  • the curable elastomer and fluoroplastic compositions can be prepared in the form of sheets and then laminated together, so long as measures are taken to thermally insulate the curable elastomer prior to application of the fluoroplastic.
  • Fig. 1 illustrates the use of a tubular heater for radiantly heating the fluoroplastic layer
  • other heating methods could be used.
  • fluoroplastic layers containing, e.g., metal particles induction heating could be used.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un procédé permettant d'augmenter la résistance d'adhésion entre une couche de plastique fluoré contenant du fluorure de vinylidène et une couche d'élastomère d'un article multicouches. Une composition de plastique fluoré contenant du fluorure de vinylidène est appliquée sur la surface d'un article précurseur qui comprend une couche d'élastomère durcissable afin de former une couche de plastique fluoré. Avant l'application de la composition de plastique fluoré, l'isolation thermique de la couche d'élastomère durcissable est réalisée pour empêcher que cette dernière ne soit soumise à un chauffage important. Après l'application, la couche de plastique fluoré est chauffée et la couche d'élastomère durcissable est traitée (par ex. soumise à un traitement thermique). De préférence, le traitement de l'élastomère a lieu séparément du chauffage de la couche plastique fluoré et ultérieurement à ce dernier. L'isolement thermique de la couche d'élastomère durcissable avant application de la composition de plastique fluoré associé au chauffage de la couche de plastique fluoré après application de la composition de plastique fluoré a pour résultat dans la formation une forte adhésion entre les couches de plastique fluoré et d'élastomère après traitement.
EP01959657A 2000-08-23 2001-08-08 Procede de preparation d'un article multicouches possedant une couche de plastique fluore et une couche d'elastomere Withdrawn EP1311381A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US64473100A 2000-08-23 2000-08-23
US644731 2000-08-23
PCT/US2001/024867 WO2002016112A1 (fr) 2000-08-23 2001-08-08 Procede de preparation d'un article multicouches possedant une couche de plastique fluore et une couche d'elastomere

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EP1311381A1 true EP1311381A1 (fr) 2003-05-21

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EP (1) EP1311381A1 (fr)
JP (1) JP2004506548A (fr)
KR (1) KR100773306B1 (fr)
CN (1) CN1220578C (fr)
AU (2) AU2001225857A1 (fr)
CA (1) CA2418110A1 (fr)
RU (1) RU2286878C2 (fr)
WO (2) WO2002016111A1 (fr)

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Publication number Publication date
WO2002016112A1 (fr) 2002-02-28
AU2001225857A1 (en) 2002-03-04
KR100773306B1 (ko) 2007-11-06
RU2286878C2 (ru) 2006-11-10
KR20030027057A (ko) 2003-04-03
CN1447743A (zh) 2003-10-08
AU2001281188A1 (en) 2002-03-04
CA2418110A1 (fr) 2002-02-28
CN1220578C (zh) 2005-09-28
JP2004506548A (ja) 2004-03-04
WO2002016111A1 (fr) 2002-02-28

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