EP0888403A1 - Laminate - Google Patents

Laminate

Info

Publication number
EP0888403A1
EP0888403A1 EP97915373A EP97915373A EP0888403A1 EP 0888403 A1 EP0888403 A1 EP 0888403A1 EP 97915373 A EP97915373 A EP 97915373A EP 97915373 A EP97915373 A EP 97915373A EP 0888403 A1 EP0888403 A1 EP 0888403A1
Authority
EP
European Patent Office
Prior art keywords
layer
rubber
adhesion promoter
fluoropolymer
laminate
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Withdrawn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
EP97915373A
Other languages
German (de)
French (fr)
Inventor
Hermann Blädel
Gerd Grossmann
Michael Dadalas
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.)
Dyneon GmbH
Original Assignee
Dyneon GmbH
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 Dyneon GmbH filed Critical Dyneon GmbH
Publication of EP0888403A1 publication Critical patent/EP0888403A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber 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
    • 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
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2327/00—Polyvinylhalogenides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • Moldings and coatings made of natural and synthetic rubber are widely used in technology.
  • a disadvantage of these materials is the relatively low resistance to aggressive chemicals, especially at higher temperatures.
  • fluorothermoplastics in particular copolymers of tetrafluoroethylene with such amounts of comonomers that the product can be processed from the melt, for this purpose. But even these copolymers, which are closer to elastomers in their properties, do not adhere to rubbers.
  • adhesion promoter a preparation made from the rubber and a thermoplastic or elastic fluoropolymer with a melting point ⁇ 250 ° C., hereinafter referred to as "adhesion promoter"
  • the invention thus relates to a composition consisting essentially of a rubber and an adhesion promoter made of a thermoplastic or elastomeric fluoropolymer with a melting point ⁇ 250 "C.
  • the adhesion promoter is a terpolymer made from tetrafluoroethylene, hexafluoropropene and vinylidene fluoride or from tetrafluoroethylene, hexafluoropropene and Ethylene or a copolymer of tetrafluoroethylene and propene.
  • terpolymers of tetrafluoroethylene, hexfluoropropene and vinylidene fluoride have thermoplastic properties if they contain more than about 35% by weight of tetrafluoroethylene.
  • Such terpolymers are known, for example, from US Pat. No. 4,335,238 and US Pat
  • Suitable terpolymers contain from about 40 to about 60 percent by weight tetrafluoroethylene, from about 10 to about 40 percent by weight hexafluoropropene and from about 10 to about 40 percent by weight vinylidene fluoride.
  • Terpolymers of tetrafluoroethylene, hexafluoropropene and ethyne are known, for example, from GB-A-1 355 595 and US-A-3 817 951.
  • Copolymers of tetrafluoroethylene and propene are known from WO-A-96/18665.
  • composition according to the invention therefore combines on the one hand with rubber and on the other hand with (a layer of) the adhesion promoter.
  • the adhesion promoter in turn combines with layers of other fluoropolymers.
  • the most diverse laminates can be produced in this way, the layers made of rubber and fluoropolymers and thus combine the properties of these two material classes.
  • Adesion promoters Mixtures of copolymers of the same type or copolymers composed of different monomers can be used as adhesion promoters. Uniform adhesion promoters are advantageously used.
  • One aspect of the invention relates to a laminate that contains a layer of an adhesion promoter and a rubber.
  • a laminate can be constructed, for example, as follows: a) an upper layer consisting essentially of an adhesion promoter, and b) said layer consisting essentially of a mixture of a rubber and adhesion promoter.
  • Layer a) can adjoin a layer made of a fluoropolymer, that is to say that such a laminate constitutes an intermediate product for composite bodies.
  • This intermediate product can adjoin layer b) with one or more rubber layers which are or are connected by vulcanization.
  • the invention further relates to laminates in which both outer sides consist of a fluoropolymer, so that there is only a chewing action in the interior.
  • the amount of adhesion promoter in layer b) can vary within wide limits and is usually in the range from 10 to 70% by weight, preferably 20 to 50% by weight.
  • rubber i.e. in addition to natural rubber, the usual synthetic rubbers based on butadiene, butadiene-acrylonitrile, butadiene-styrene, chloroprene, isoprene, isobutene, ethylene-propylene, ethylene-vinyl acetate, acrylate and epichlorohydrin , as well as butyl, chlorobutyl, bromobutyl, polysulfide, urethane, fluorine or silicone rubbers, chlorinated and chlorosulfonated polyethylene and hydrogenated acrylonitrile-butadiene rubber.
  • the laminates according to the invention can be produced by mixing a rubber with the adhesion promoter or incorporating one component into the other, for example by kneading, whereupon a flat or spatial structure is produced from this mixture, vulcanizing it, optionally with a layer of rubber is what is applied to at least one layer of adhesion promoter and fixed.
  • the coupling agent can be in the form of a powder, in the form of a film, melt or as a liquid preparation, for example as a solution or dispersion, in accordance with customary methods Methods are applied. Such methods include spraying, pouring or knife coating, which are mastered by a person skilled in the art in accordance with the usual specialist knowledge.
  • the laminates obtained in this way combine the advantages of the fluoropolymer outer layer, in particular the chemical and thermal insensitivity and the non-stick properties, with the resilience and thus mechanical insensitivity of the rubber sub-layer or intermediate rubber layer.
  • Such laminates can be used for many purposes since, for example, more or less rigid layers made of fluoropolymers can now be provided with an elastic rubber back.
  • Such laminates can therefore in chemical apparatus construction as well as in
  • Automotive industry sealing technology, used in expansion joints, hoses and filler neck.
  • a mixture of 80% rubber mixture and 20% terpolymer is produced and vulcanized in several layers.
  • the layers show very good adhesion.
  • a mixture according to Example 1 is processed into a layer and vulcanized with a layer consisting only of the rubber mixture.
  • the layer shows very good adhesion after vulcanization, that is to say the layer containing the terpolymer gives very good adhesion to the layer made of the rubber mixture.
  • the laminate obtained in this way can be processed with the layer containing the terpolymer in a separate step with an adhesion promoter layer.
  • the terpolymer is only sieved onto a layer of the rubber mixture, then a layer of the rubber mixture is placed over it and the composite is vulcanized, there is no adhesion.
  • a laminate is produced, that is to say a composite of which one layer contains the terpolymer.
  • the terpolymer is sieved onto this layer in a thin layer and sintered by heating.
  • the top layer of the terpolymer adheres excellently to the composite.
  • a composite is produced according to Example 5 and a solution of the terpolymer in methyl ethyl ketone is applied to the layer containing the terpolymer and the solvent is evaporated.
  • a film of a second terpolymer of the following composition is applied to the lacquer layer thus obtained: 57% tetrafluoroethylene units, 30% hexafluoropropene units and 13% ethylene units and vulcanized. A bond with good adhesion is obtained.
  • a mixture of 50% rubber mixture and 50% of the second terpolymer mentioned in Example 6 is prepared, a layer is prepared therefrom, this is combined on one side with a rubber layer and on the other side with the film mentioned in Example 6. Vulcanization gives a bond with good adhesion.
  • a layer is produced from 30% rubber mixture and 70% of the second terpolymer mentioned in Example 6 and is connected on one side to a rubber layer and on the other side to the film mentioned in Example 6. A bond with good adhesion is obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Flat structures of rubber and fluorine polymer layers may be produced if a mixture of a rubber and a thermoplastic or elastomeric fluorine polymer with a melting point < 250 °C is used as the adhesive layer.

Description

Beschreibung description
SchichtstoffLaminate
Formkörper und Überzüge aus natürlichem und synthetischem Kautschuk sind in der Technik weit verbreitet. Ein Nachteil dieser Werkstoffe ist die relativ geringe Beständigkeit gegen aggressive Chemikalien, insbesondere bei höheren Temperaturen. Es hat deshalb nicht an Versuchen gefehlt, Kautschuk mit den sehr viel resistenteren Fluorpolymeren zu beschichten. Diese Versuche scheiterten jedoch, weil die üblichen Kleb- und Vulkanisierverfahren keine hinreichend feste Bindung zu dem Fluorpolymer ermöglichen.Moldings and coatings made of natural and synthetic rubber are widely used in technology. A disadvantage of these materials is the relatively low resistance to aggressive chemicals, especially at higher temperatures. There has been no shortage of attempts to coat rubber with the much more resistant fluoropolymers. However, these attempts failed because the usual adhesive and vulcanization processes do not allow a sufficiently firm bond to the fluoropolymer.
Es hat auch nicht an Versuchen gefehlt,There was no lack of attempts either
Fluorthermoplaste, insbesondere Copolymere des Tetrafluorethylens mit solchen Mengen an Comonomeren, daß das Produkt aus der Schmelze verarbeitbar ist, für diesen Zweck einzusetzen. Aber auch diese in ihren Eigenschaften den Elastomeren näherkommenden Copolymeren haften nicht auf Kautschuken.Use fluorothermoplastics, in particular copolymers of tetrafluoroethylene with such amounts of comonomers that the product can be processed from the melt, for this purpose. But even these copolymers, which are closer to elastomers in their properties, do not adhere to rubbers.
Überraschenderweise wurde nun gefunden, daß eine vorzügliche Haftung zwischen Kautschuken und Fluorpolymeren dann hergestellt werden kann, wenn eine Zubereitung aus dem Kautschuk und einem thermoplastischen oder elastischen Fluorpolymer mit einem Schmelzpunkt < 250 °C, im folgenden "Haftvermittler", als Haftschicht eingesetzt wird. Die Erfindung betrifft somit eine Zusammensetzung, bestehend im wesentlichen aus einem Kautschuk und einem Haftvermittler aus einem thermoplastischen oder elastomeren Fluorpolymer mit einem Schmelzpunkt < 250 "C. In bevorzugten Zusammensetzungen ist der Haftvermittler ein Terpolymer aus Tetrafluorethylen, Hexafluorpropen und Vinylidenfluorid oder aus Tetrafluorethylen, Hexafluorpropen und Ethyien oder ein Copolymer aus Tetrafluorethylen und Propen.Surprisingly, it has now been found that excellent adhesion between rubbers and fluoropolymers can be produced if a preparation made from the rubber and a thermoplastic or elastic fluoropolymer with a melting point <250 ° C., hereinafter referred to as "adhesion promoter", is used as the adhesive layer. The invention thus relates to a composition consisting essentially of a rubber and an adhesion promoter made of a thermoplastic or elastomeric fluoropolymer with a melting point <250 "C. In preferred compositions, the adhesion promoter is a terpolymer made from tetrafluoroethylene, hexafluoropropene and vinylidene fluoride or from tetrafluoroethylene, hexafluoropropene and Ethylene or a copolymer of tetrafluoroethylene and propene.
Die Terpolymeren aus Tetrafluorethylen, Hexfluorpropen und Vinylidenfluorid haben dann thermoplastische Eigenschaften, wenn sie mehr als etwa 35 Gew.-% Tetrafluorethylen enthalten. Solche Terpolymeren sind beispielsweise aus der US-A-4 335 238 und derThe terpolymers of tetrafluoroethylene, hexfluoropropene and vinylidene fluoride have thermoplastic properties if they contain more than about 35% by weight of tetrafluoroethylene. Such terpolymers are known, for example, from US Pat. No. 4,335,238 and US Pat
DE-A-26 35 402 (AU-A-76/16635) bekannt. Geeignete Terpolymere enthalten etwa 40 bis etwa 60 Gew.-% Tetrafluorethylen, etwa 10 bis etwa 40 Gew.-% Hexafluorpropen und etwa 10 bis etwa 40 Gew.-% Vinylidenfluorid.DE-A-26 35 402 (AU-A-76/16635) known. Suitable terpolymers contain from about 40 to about 60 percent by weight tetrafluoroethylene, from about 10 to about 40 percent by weight hexafluoropropene and from about 10 to about 40 percent by weight vinylidene fluoride.
Terpolymere aus Tetrafluorethylen, Hexafluorpropen und Ethyien sind beispielsweise bekannt aus GB-A-1 355 595 und US-A-3 817 951.Terpolymers of tetrafluoroethylene, hexafluoropropene and ethyne are known, for example, from GB-A-1 355 595 and US-A-3 817 951.
Copolymere aus Tetrafluorethylen und Propen sind aus WO-A-96/18665 bekannt.Copolymers of tetrafluoroethylene and propene are known from WO-A-96/18665.
Die erfindungsgemäße Zusammensetzung verbindet sich also einerseits mit Kautschuk und andererseits mit (einer Schicht aus) dem Haftvermittler. Der Haftvermittler verbindet sich seinerseits mit Schichten aus anderen Fluorpolymeren. Es lassen sich so die verschiedenartigsten Schichtstoffe erzeugen, die Lagen aus Kautschuk und Fluorpolymeren enthalten und so die Eigenschaften dieser beiden Werkstoffklassen verbinden.The composition according to the invention therefore combines on the one hand with rubber and on the other hand with (a layer of) the adhesion promoter. The adhesion promoter in turn combines with layers of other fluoropolymers. The most diverse laminates can be produced in this way, the layers made of rubber and fluoropolymers and thus combine the properties of these two material classes.
Als Haftvermittler können Mischungen von Copolymeren des gleichen Typs oder aus unterschiedlichen Monomeren zusammengesetzte Copolymere eingesetzt werden. Vorteilhaft verwendet man einheitliche Haftvermittler.Mixtures of copolymers of the same type or copolymers composed of different monomers can be used as adhesion promoters. Uniform adhesion promoters are advantageously used.
Ein Aspekt der Erfindung bezieht sich auf einen Schichtstoff, der eine Schicht aus einem Haftvermittler und einem Kautschuk enthält. Ein solcher Schichtstoff kann zum Beispiel wie folgt aufgebaut sein: a) eine Oberschicht, bestehend im wesentlichen aus Haftvermittler, und b) die genannte Schicht, bestehend im wesentlichen aus einer Mischung aus einem Kautschuk und Haftvermittler.One aspect of the invention relates to a laminate that contains a layer of an adhesion promoter and a rubber. Such a laminate can be constructed, for example, as follows: a) an upper layer consisting essentially of an adhesion promoter, and b) said layer consisting essentially of a mixture of a rubber and adhesion promoter.
Die Schicht a) kann an eine Schicht aus einem Fluorpolymeren angrenzen, das heißt, ein solcher Schichtstoff stellt ein Zwischenprodukt für Verbundkörper dar. Dieses Zwischenprodukt kann mit der Schicht b) an eine oder mehrere Kautschuklagen angrenzen, die durch Vulkanisieren verbunden ist beziehungsweise sind.Layer a) can adjoin a layer made of a fluoropolymer, that is to say that such a laminate constitutes an intermediate product for composite bodies. This intermediate product can adjoin layer b) with one or more rubber layers which are or are connected by vulcanization.
Die Erfindung bezieht sich weiterhin auf Schichtstoffe, bei denen beide Außenseiten aus einem Fluorpolymer bestehen, so daß nur im Inneren eine Kauschuklage vorliegt.The invention further relates to laminates in which both outer sides consist of a fluoropolymer, so that there is only a chewing action in the interior.
Weitere Ausgestaltungen dieses Prinzips kann der Fachmann nach den jeweiligen Anforderungen erstellen, je nachdem, ob beispielsweise das als Haftvermittler bezeichnete Fluorpolymer den Anforderungen an die Außenseite entspricht oder ob ein anderes Fluorpolymer als Außenseite eingesetzt werden soll.The person skilled in the art can create further configurations of this principle according to the respective requirements, depending on whether, for example, that as an adhesion promoter designated fluoropolymer meets the requirements on the outside or whether another fluoropolymer should be used as the outside.
Die Menge an Haftvermittler in der Schicht b) kann in weiten Grenzen schwanken und liegt üblicherweise im Bereich von 10 bis 70 Gew.-%, vorzugsweise 20 bis 50 Gew.-%.The amount of adhesion promoter in layer b) can vary within wide limits and is usually in the range from 10 to 70% by weight, preferably 20 to 50% by weight.
Als Kautschuk kommen - wie erwähnt - natürliche und synthetische Kautschukarten in Betracht, also neben Naturgummi die üblichen synthetischen Kautschuke auf Basis Butadien, Butadien-Acrylnitril, Butadien-Styrol, Chloropren, Isopren, Isobuten, Ethylen-Propylen, Ethylen-Vinylacetat, Acrylat und Epichlorhydrin, sowie Butyl-, Chlorbutyl-, Brombutyl-, Polysulfid-, Urethan-, Fluor- oder Silicon-Kautschuke, chloriertes und chlorsulfoniertes Polyethylen sowie hydrierter Acrylnitril-Butadien-Kautschuk.As mentioned, natural and synthetic types of rubber come into consideration as rubber, i.e. in addition to natural rubber, the usual synthetic rubbers based on butadiene, butadiene-acrylonitrile, butadiene-styrene, chloroprene, isoprene, isobutene, ethylene-propylene, ethylene-vinyl acetate, acrylate and epichlorohydrin , as well as butyl, chlorobutyl, bromobutyl, polysulfide, urethane, fluorine or silicone rubbers, chlorinated and chlorosulfonated polyethylene and hydrogenated acrylonitrile-butadiene rubber.
Die erfindungsgemäßen Schichtstoffe können dadurch hergestellt werden, daß ein Kautschuk mit dem Haftvermittler vermischt beziehungsweise eine Komponente in die andere eingearbeitet wird, beispielsweise durch Einkneten, worauf aus dieser Mischung ein Flächen- oder Raumgebilde hergestellt wird, dieses, gegebenenfalls mit einer Lage aus Kautschuk, vulkanisiert wird, worauf auf mindestens eine Schicht Haftvermittler aufgetragen und fixiert wird.The laminates according to the invention can be produced by mixing a rubber with the adhesion promoter or incorporating one component into the other, for example by kneading, whereupon a flat or spatial structure is produced from this mixture, vulcanizing it, optionally with a layer of rubber is what is applied to at least one layer of adhesion promoter and fixed.
Der Haftvermittler kann als Pulver, in Form einer Folie, Schmelze oder als Flüssigzubereitung, zum Beispiel als Lösung oder Dispersion, nach üblichen Methoden aufgebracht werden. Solche Methoden umfassen das Sprühen, Gießen oder Rakeln, die vom Fachmann entsprechend dem üblichen Fachwissen beherrscht werden.The coupling agent can be in the form of a powder, in the form of a film, melt or as a liquid preparation, for example as a solution or dispersion, in accordance with customary methods Methods are applied. Such methods include spraying, pouring or knife coating, which are mastered by a person skilled in the art in accordance with the usual specialist knowledge.
Auch die weiteren Verarbeitungsschritte des so erhaltenen Gebildes sind dem Fachmann vertraut, der die Bedingungen im einzelnen den besonderen Gegebenheiten anpaßt.The skilled worker is also familiar with the further processing steps of the structure thus obtained, and he adapts the conditions in detail to the particular circumstances.
Die so erhaltenen Schichtstoffe vereinen die Vorteile der Fluorpolymer-Außenschicht, also insbesondere der chemischen und thermischen Unempfindlichkeit und der Antihafteigenschaften, mit der Nachgiebigkeit und damit mechanischen Unempfindlichkeit der Kautschukunter- beziehungsweise Kautschukzwischenschicht. Derartige Schichtstoffe sind für viele Zwecke einsetzbar, da beispielsweise mehr oder weniger starre Schichten aus Fluorpolymeren nun mit einem elastischem Gummirücken versehen werden können. Solche Schichtstoffe können deshalb im chemischen Apparatebau sowie in derThe laminates obtained in this way combine the advantages of the fluoropolymer outer layer, in particular the chemical and thermal insensitivity and the non-stick properties, with the resilience and thus mechanical insensitivity of the rubber sub-layer or intermediate rubber layer. Such laminates can be used for many purposes since, for example, more or less rigid layers made of fluoropolymers can now be provided with an elastic rubber back. Such laminates can therefore in chemical apparatus construction as well as in
Automobilindustrie, Dichtungstechnik, in Kompensatoren, Schläuchen und Füllstutzen Verwendung finden.Automotive industry, sealing technology, used in expansion joints, hoses and filler neck.
Die Erfindung wird in den folgenden Beispielen noch näher erläutert.The invention is explained in more detail in the following examples.
BeispieleExamples
Im folgenden beziehen sich alle Prozentgaben aufIn the following, all percentages refer to
Gewichtsprozent, sofern keine anderen Angaben gemacht sind. Es wurden folgende Materialien eingesetzt: a) Ein Terpolymer mit der ZusammensetzungWeight percent, unless other information is given. The following materials were used: a) A terpolymer with the composition
42 % Tetrafluorethylen-, 20 % Hexafluorpropen- und 38 % Vinylidenfluorid-Einheiten und b) eine Buty1kautschukmischung, bestehend aus42% tetrafluoroethylene, 20% hexafluoropropene and 38% vinylidene fluoride units and b) a butyl rubber mixture consisting of
100 Teilen Kautschuk, 100 Teilen Ruß und 100 Teilen Füllstoff (im wesentlichen Kaolin) . Der Kautschuk ist benzinlöslich und wird bei 143 'C vulkanisiert.100 parts of rubber, 100 parts of carbon black and 100 parts of filler (essentially kaolin). The rubber is soluble in petrol and is vulcanized at 143 ° C.
Beispiel 1example 1
Es wird eine Mischung aus 80 % Kautschukmischung und 20 % Terpolymer hergestellt und in mehreren Schichten vulkanisiert. Die Schichten zeigen eine sehr gute Haftung.A mixture of 80% rubber mixture and 20% terpolymer is produced and vulcanized in several layers. The layers show very good adhesion.
Beispiel 2Example 2
Eine Mischung entsprechend Beispiel 1 wird zu einer Schicht verarbeitet und mit einer Schicht vulkanisiert, die nur aus der Kautschukmischung bestehen. Auch hier zeigt nach dem Vulkanisieren die Schicht eine sehr gute Haftung, das heißt, die das Terpolymer enthaltende Schicht vermittelt gegenüber der Schicht aus der Kautschukmischung eine sehr gute Haftung.A mixture according to Example 1 is processed into a layer and vulcanized with a layer consisting only of the rubber mixture. Here, too, the layer shows very good adhesion after vulcanization, that is to say the layer containing the terpolymer gives very good adhesion to the layer made of the rubber mixture.
Der so erhaltene Schichtstoff kann mit der das Terpolymer enthaltenden Schicht in einem getrennten Schritt mit einer Haftvermittlerschicht verarbeitet werden. KontrollbeispielThe laminate obtained in this way can be processed with the layer containing the terpolymer in a separate step with an adhesion promoter layer. Control example
Wird auf eine Schicht aus der Kautschukmischung das Terpolymer nur aufgesiebt, dann eine Schicht aus der Kautschukmischung darübergelegt und der Verbund vulkanisiert, so ergibt sich keine Haftung.If the terpolymer is only sieved onto a layer of the rubber mixture, then a layer of the rubber mixture is placed over it and the composite is vulcanized, there is no adhesion.
Beispiel 3Example 3
Man stellt eine Mischung aus gleichen Teilen Terpolymer und Kautschukmischung her und verfährt entsprechend Beispiel 2. Es ergibt sich eine sehr gute Haftung.A mixture of equal parts of terpolymer and rubber mixture is produced and the procedure of Example 2 is followed. The adhesion is very good.
Beispiel 4Example 4
Entsprechend Beispiel 2, aber mit der Mischung gemäß Beispiel 3, wird ein Schichtstoff hergestellt, also ein Verbund, von dem eine Schicht das Terpolymer enthält. Auf diese Schicht wird in dünner Lage das Terpolymer aufgesiebt und durch Erhitzen gesintert. Die Deckschicht aus dem Terpolymer haftet ausgezeichnet auf dem Verbund.According to example 2, but with the mixture according to example 3, a laminate is produced, that is to say a composite of which one layer contains the terpolymer. The terpolymer is sieved onto this layer in a thin layer and sintered by heating. The top layer of the terpolymer adheres excellently to the composite.
Beispiel 5Example 5
Eine Schicht aus 70 % Terpolymer und 30 % Kautschukmischung wird vulkanisiert und nach Aufrauhen der Oberflache mit einer Schicht aus der Kautschukmischung vulkanisiert. Man erhält einen Verbund mit guter Haftung. Beispiel 6A layer of 70% terpolymer and 30% rubber mixture is vulcanized and, after roughening the surface, vulcanized with a layer of the rubber mixture. A bond with good adhesion is obtained. Example 6
Man stellt einen Verbund nach Beispiel 5 her und bringt auf die das Terpolymer enthaltende Schicht eine Lösung des Terpolymers in Methyl-ethyl-keton auf und verdampft das Lösemittel. Auf die so erhaltene Lackschicht bringt man eine Folie aus einem zweiten Terpolymer der folgenden Zusammensetzung auf: 57 % Tetrafluorethylen-Einheiten, 30 % Hexafluorpropen-Einheiten und 13 % Ethylen-Einheiten und vulkanisiert. Man erhält einen Verbund mit guter Haftung.A composite is produced according to Example 5 and a solution of the terpolymer in methyl ethyl ketone is applied to the layer containing the terpolymer and the solvent is evaporated. A film of a second terpolymer of the following composition is applied to the lacquer layer thus obtained: 57% tetrafluoroethylene units, 30% hexafluoropropene units and 13% ethylene units and vulcanized. A bond with good adhesion is obtained.
Beispiel 7Example 7
Man stellt eine Mischung aus 50 % Kautschukmischung und 50 % des in Beispiel 6 genannten zweiten Terpolymers her, bereitet daraus eine Schicht, bringt diese auf der einen Seite mit einer Kautschukschicht und auf der anderen Seite mit der in Beispiel 6 genannten Folie zusammen. Durch Vulkanisieren erhält man einen Verbund mit guter Haftung.A mixture of 50% rubber mixture and 50% of the second terpolymer mentioned in Example 6 is prepared, a layer is prepared therefrom, this is combined on one side with a rubber layer and on the other side with the film mentioned in Example 6. Vulcanization gives a bond with good adhesion.
Beispiel 8Example 8
Man stellt eine Schicht aus 30 % Kautschukmischung und 70 % des in Beispiel 6 genannten zweiten Terpolymers her und verbindet diese auf der einen Seite mit einer Kautschukschicht und auf der anderen Seite mit der in Beispiel 6 genannten Folie. Man erhält einen Verbund mit guter Haftung. A layer is produced from 30% rubber mixture and 70% of the second terpolymer mentioned in Example 6 and is connected on one side to a rubber layer and on the other side to the film mentioned in Example 6. A bond with good adhesion is obtained.

Claims

Ansprüche Expectations
1. Zusammensetzung, bestehend im wesentlichen aus einem Kautschuk und einem Haftvermittler aus einem thermoplastischen oder elastomeren Fluorpolymer mit einem Schmelzpunkt < 250 'C.1. Composition consisting essentially of a rubber and an adhesion promoter made of a thermoplastic or elastomeric fluoropolymer with a melting point <250 'C.
2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Fluorpolymer ein Copolymer mit Einheiten des Tetrafluorethylens, Hexafluorpropens und Vinylidenfluorids, des Tetrafluorethylens, Hexafluorpropens und Ethylens oder des Tetrafluorethylens und Propens ist.2. Composition according to claim 1, characterized in that the fluoropolymer is a copolymer with units of tetrafluoroethylene, hexafluoropropene and vinylidene fluoride, tetrafluoroethylene, hexafluoropropene and ethylene or tetrafluoroethylene and propene.
Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß der Gehalt an Haftvermittler 10 bis 70 Gew.-%, vorzugsweise 20 bis 50 Gew.-%, beträgt.Composition according to Claim 1, characterized in that the content of adhesion promoter is 10 to 70% by weight, preferably 20 to 50% by weight.
Schichtstoff, enthaltend eine Schicht aus einer Zusammensetzung nach Anspruch 1.Laminate containing a layer of a composition according to claim 1.
5. Schichtstoff nach Anspruch 4, bei dem die Schicht mit einer Lage aus Kautschuk verbunden ist.5. Laminate according to claim 4, wherein the layer is connected to a layer of rubber.
6. Schichtstoff nach Anspruch 4, bei dem die Schicht mit einer Lage aus Haftvermittler verbunden ist.6. Laminate according to claim 4, wherein the layer is connected to a layer of adhesion promoter.
7. Schichtstoff, bestehend im wesentlichen aus einer Kautschuklage, die auf beiden Seiten mit einer Schicht nach Anspruch 4 verbunden ist, wobei gegebenenfalls eine oder beide der äußeren Schichten mit einer Lage aus Haftvermittler und von diesen gegebenenfalls eine oder beide Haftvermittler mit einer weiteren Lage aus einem weiteren Fluorpolymeren verbunden sind.7. Laminate consisting essentially of a rubber layer, which is connected on both sides to a layer according to claim 4, wherein optionally one or both of the outer layers with a layer of adhesion promoter and of if appropriate, one or both of these adhesion promoters are connected to a further layer of a further fluoropolymer.
Schichtstoff nach Anspruch 4, bei dem die Schicht auf der einen Seite mit einer Kautschuklage und auf der anderen Seite mit einer Lage aus Haftvermittler verbunden ist, welche gegebenenfalls mit einer Lage aus einem weiteren Fluorpolymer verbunden ist.Laminate according to Claim 4, in which the layer is connected on one side to a rubber layer and on the other side to a layer of adhesion promoter, which is optionally connected to a layer of a further fluoropolymer.
9. Verfahren zur Herstellung eines Schichtstoffs, dadurch gekennzeichnet, daß man einen Haftvermittler aus einem thermoplastischen oder elastischen Fluorpolymer mit einem Schmelzpunkt < 250 "C mit einem Kautschuk vermischt, aus der9. A process for producing a laminate, characterized in that an adhesion promoter made of a thermoplastic or elastic fluoropolymer with a melting point <250 ° C. is mixed with a rubber from which
Mischung ein Flächengebilde oder einen Raumkörper herstellt, diese gegebenenfalls mit einer weiteren Kautschuklage vulkanisiert, auf das so erhaltene Gebilde auf mindestens einer Seite, die den Haftermittler enthält, Haftvermittler aufträgt, diese aufgebrachte Schicht thermisch fixiert und gegebenenfalls auf die genannte(n) Haftvermittlerschicht(en) (je) eine weitere Fluorpolymerschicht aufbringt und fixiert.Mixture produces a flat structure or a three-dimensional structure, optionally vulcanized with a further rubber layer, applies adhesion promoter to the structure thus obtained on at least one side which contains the adhesion promoter, thermally fixed this applied layer and, if appropriate, to the said adhesion promoter layer (s) ) (each) applies and fixes another fluoropolymer layer.
10. Verwendung der Zusammensetzung nach den Ansprüchen 1 bis 3 zum Verbinden von Kautschuk und dem Haftvermittler sowie gegebenenfalls einem Fluorpolymer oder zum Verbinden von Kautschukschichten.10. Use of the composition according to claims 1 to 3 for connecting rubber and the adhesion promoter and optionally a fluoropolymer or for connecting rubber layers.
11. Verwendung der Schichtstoffe nach den Ansprüchen 4 bis 8 beziehungsweise der nach Anspruch 9 erhaltenen Schichtstoffe im chemischen Apparatebau. 11. Use of the laminates according to claims 4 to 8 or of the laminates obtained according to claim 9 in chemical apparatus engineering.
EP97915373A 1996-03-22 1997-03-15 Laminate Withdrawn EP0888403A1 (en)

Applications Claiming Priority (3)

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DE19611311 1996-03-22
DE19611311A DE19611311A1 (en) 1996-03-22 1996-03-22 Laminate
PCT/EP1997/001319 WO1997035917A1 (en) 1996-03-22 1997-03-15 Laminate

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KR (1) KR20000004928A (en)
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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6960377B2 (en) * 1998-05-01 2005-11-01 Dayco Products, Llc Fuel hose and its production
US6203873B1 (en) * 1998-05-22 2001-03-20 Dayco Products, Inc. Blends of fluoroelastomer interpolymers with thermo fluoroplastic interpolymers and the use of such blends in hoses
US20070218233A1 (en) * 1998-05-22 2007-09-20 Jeremy Duke Fuel impermeable, fuel resistant hose having improved high temperature resistant characteristics
US9390031B2 (en) * 2005-12-30 2016-07-12 Intel Corporation Page coloring to associate memory pages with programs
US10162694B2 (en) 2015-12-21 2018-12-25 Intel Corporation Hardware apparatuses and methods for memory corruption detection

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS535354B1 (en) * 1971-07-06 1978-02-25
US3817951A (en) * 1972-11-20 1974-06-18 Pennwalt Corp Low-modulus thermoplastic ethylene-tetrafluoroethylene-hexafluoropropene terpolymers
JPS5244889A (en) * 1975-10-07 1977-04-08 Bridgestone Corp Thermostable rubber laminates
JPS5940109B2 (en) * 1978-10-06 1984-09-28 ダイキン工業株式会社 Laminate and laminate forming method
US4335238A (en) * 1980-10-06 1982-06-15 E. I. Du Pont De Nemours And Company Fluoropolymer hexafluoropropene, tetrafluorethene and 1,1-difluoroethene
JPS6123638A (en) * 1984-07-11 1986-02-01 Central Glass Co Ltd Crosslinked fluororesin
DE3668722D1 (en) * 1985-06-26 1990-03-08 Toshiba Kawasaki Kk MAGNETIC CORE AND PRODUCTION METHOD.
US4828923A (en) * 1987-04-10 1989-05-09 Nippon Zeon Co., Ltd. Rubber laminates of fluororubber and nitrile rubber
JP2583442B2 (en) * 1987-08-14 1997-02-19 日本ゼオン株式会社 Manufacturing method of rubber laminate
JP2612748B2 (en) * 1987-10-30 1997-05-21 日本合成ゴム株式会社 Crosslinkable rubber composition and crosslinked rubber product
JPH01159245A (en) * 1987-12-16 1989-06-22 Tokai Rubber Ind Ltd Rubber hose
GB8813250D0 (en) * 1988-06-04 1988-07-06 Scapa Group Plc Coated textile materials
JP2583444B2 (en) * 1988-06-23 1997-02-19 日本ゼオン株式会社 Manufacturing method of rubber laminate
EP0428158A3 (en) * 1989-11-14 1992-03-18 Daikin Industries, Limited Curable polymer composition and packing material comprising the same
DE4224559A1 (en) * 1992-07-24 1994-01-27 Bayer Ag Combinations of polyorganosiloxanes and double bond-containing fluororubbers through Si-H addition
IT1269295B (en) * 1994-03-07 1997-03-26 Dow Corning MIXTURES BASED ON FLUOROSILICONIC ELASTOMERS AND POLYMERS OF VINYLIDENE FLUORIDE
US5480930A (en) * 1994-08-18 1996-01-02 Dow Corning Corporation Fluorocarbon rubbers modified by silicone resins
US5623038A (en) * 1994-12-14 1997-04-22 Minnesota Mining And Manufacturing Company Fluorine-containing polymers and preparation thereof
US5898051A (en) * 1996-01-31 1999-04-27 Central Glass Company, Limited Elastic fluorohydrocarbon resin-based polymer blend with graft copolymers of rubbers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9735917A1 *

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KR20000004928A (en) 2000-01-25
BR9708329A (en) 1999-08-03
US6048940A (en) 2000-04-11
JP2000507293A (en) 2000-06-13
WO1997035917A1 (en) 1997-10-02
CN1214063A (en) 1999-04-14
CA2249427A1 (en) 1997-10-02
ZA972432B (en) 1997-09-22
AU2288097A (en) 1997-10-17

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