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WO1998001500A1 - Produit en caoutchouc vulcanise - Google Patents

Produit en caoutchouc vulcanise Download PDF

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Publication number
WO1998001500A1
WO1998001500A1 PCT/NL1997/000361 NL9700361W WO9801500A1 WO 1998001500 A1 WO1998001500 A1 WO 1998001500A1 NL 9700361 W NL9700361 W NL 9700361W WO 9801500 A1 WO9801500 A1 WO 9801500A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
tpe
functional
rubber product
product according
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.)
Ceased
Application number
PCT/NL1997/000361
Other languages
English (en)
Inventor
Michael Henri Koch
Alexander Wilhelmus Maria Anna Jaspers
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.)
Koninklijke DSM NV
Original Assignee
DSM NV
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
Priority claimed from NL1003517A external-priority patent/NL1003517C2/nl
Priority claimed from NL1004246A external-priority patent/NL1004246C2/nl
Application filed by DSM NV filed Critical DSM NV
Priority to AU32774/97A priority Critical patent/AU3277497A/en
Publication of WO1998001500A1 publication Critical patent/WO1998001500A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • B32B25/18—Layered products comprising a layer of natural or synthetic rubber comprising butyl or halobutyl rubber
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • 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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/72—Cured, e.g. vulcanised, cross-linked
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/02—Temperature
    • 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
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the invention relates to a vulcanized rubber product as well as to a process for the manufacture of such a rubber product.
  • the disadvantage is that such products cannot easily be joined to each other. Fusion welding is difficult and results in a low adhesion. Adding a polyolefin (for example polyethylene) to the rubber compound (i.e. the rubber composition before it is vulcanized) results in some improvement, but the adhesion strength is still inadequate.
  • the invention now offers a solution to this problem and is characterized in that the vulcanized rubber product consists of a bonded combination of the rubber and a thermoplastic elastomer (TPE), the rubber as well as the TPE comprising a functional polymeric compound, which compounds are reactive with each other. This results in rubber products with a strong bond between the component parts (the rubber and the TPE). Rubber products for which the invention offers a solution are for instance products consisting of rubber bonded to rubber (such as multilayer systems - or laminates - or corner sections) and e.g. overmoulds of rubber with a TPE.
  • TPE thermoplastic elastomer
  • one of the component parts is a vulcanized rubber.
  • a rubber is understood in this invention a hydrocarbon rubber, such as natural rubber (NR), butyl rubber (whether or not halogenated or crosslinked with e.g. divinylbenzene) , styrene-butadiene rubber (SBR), nitr ile-butadiene rubber (NBR) (both also in their hydrogenated form, viz.
  • NR natural rubber
  • butyl rubber whether or not halogenated or crosslinked with e.g. divinylbenzene
  • SBR styrene-butadiene rubber
  • NBR nitr ile-butadiene rubber
  • EPDM a rubber composed of ethylene, an ⁇ -olefin (in particular propylene) and optionally a diene as third monomer (mostly dicyclopentadiene and in particular ethylidene norbornene) ) , and others.
  • An enumeration of suitable rubbers can be found in . Hofmann's Rubber Technology Handbook, Hanser Verlag, Kunststoff 1989.
  • the invention in particular relates to a rubber product on the basis of EPDM.
  • the rubber can contain the additives that are commonly used for these rubbers, such as extender oil, carbon black, pigments, stabilizers and the like. The person skilled in the art will be familiar with these additives.
  • the rubber has been vulcanized with agents that are likewise known to the person skilled in the art, for instance by means of sulphur (compounds), peroxides, phenolic resins and the like.
  • thermoplastic elastomer is a product which combines the flexibility of a rubber with the strength and the processability of a thermoplast.
  • the TPE according to the invention has been chosen from the group comprising the styrene-based TPEs (STPEs) and the rubber/thermoplast blends, which include the thermoplastic elastomeric polyolefins (TPOEBs) and the thermoplastic elastomeric vulcanizates (TPOEVs).
  • Styrene-based thermoplastic elastomers are polymers which consist of polymer chains with a polydiene central block and polystyrene terminal blocks (also called SBCs, styrene block copolymers).
  • SBCs polystyrene terminal blocks
  • the diene block gives the polymer its elastomeric properties, while the polystyrene blocks constitute the thermoplastic phase.
  • the polydiene block is composed of butadiene units, so that the resulting TPE is an SBS (styrene-butadiene-styrene polymer).
  • SBS styrene-butadiene-styrene polymer
  • the styrene-based TPE preferably is a hydrogenated polymer, i.e. a polymer in which at least part of the aliphatic unsaturation has been hydrogenated.
  • SEBS polymers styrene- ethylene/butylene-styrene
  • thermoplastic polyolefin elastomers thermoplastic polyolefin elastomers
  • TPOEBs thermoplastic polyolefin and a hydrocarbon rubber
  • TPOEVs thermoplastic - A -
  • TPOERs or reactor thermoplastic polyolefin elastomers, which are the product of a copolymer izat ion of an elastomer segment on a thermoplastic crystalline polyolefin.
  • the difference between categories 1) and 2) on the one hand, and category 3) on the other therefore lies in the fact that the former categories comprise blends and the latter category comprises copolymers.
  • the morphology is that of a crystalline polyolefin as a continuous matrix in which the elastomer is distributed, whether or not partially crosslinked, as a dispersed phase.
  • the rubber component can also be at least partially vulcanized; since the rubber component is already anchored to the polyolefin component, this is not strictly necessary.
  • 'TPOE' here and in the following is understood to refer to a combination of a crystalline polyolefin (such as polyethylene and by preference polypropylene, homopolymer ic as well as copolymeric) and a rubber which is dispersed in it and, in the case of a TPOEV, is at least partially vulcanized.
  • the rubber in the TPOE can be any hydrocarbon rubber, of the type as has also been described under A) above ('The rubber').
  • suitable rubber for the TPOE can therefore be mentioned: natural rubber, butyl rubber (whether or not halogenated or crosslinked), SBR, NBR (both hydrogenated or non-hydrogenated) and EPDM.
  • the rubber in the TPOE preferably is an EPDM or a butyl rubber since these contribute to a particular improvement of the physical properties of the rubber product to be obtained with it.
  • the degree of vulcanization of the rubber in a TPOEV is preferably high (i.e. the proportion of extractable rubber is preferably lower than 15%, more preferably lower than 5%, as determined by extraction with boiling xylene).
  • a hydroxy-functional polymer is present in the TPE or in the rubber.
  • a polymer is a halogenated or non-halogenated phenolic or resolic resin (such as for instance marketed by Schenactady under the designations SP 1045 and SP 1055).
  • the hydroxy-functional polymer is a polyol (such as for instance polyethylene glycol). Natural hydroxy-functional polymers (such as for instance cellulose and lignin) can also be used.
  • Such a hydroxy-functional polymer has to be reactive with a second functional polymer that is present in the other phase (i.e. if the first functional polymer is in the rubber, then the second functional polymer must be present in the TPE).
  • the second functional polymer is then preferably a carboxylic acid functional or carboxylic anhydride functional polymer.
  • Such a polymer is preferably based on a polyolefin and more preferably on a polyethylene, a polypropylene or an ethene/ ⁇ -olefin copolymer (such as for instance EPDM) .
  • one of the functional polymeric compounds is an amine, epoxy or aldehyde functional polymer.
  • the functional polymeric compounds to be used should possess such a functionality that the functionality of the compound that is present in the TPE is reactive with the functionality of the compound that is present in the rubber.
  • gearing of the polarities of the rubber and the TPE can contribute to an improved adhesion.
  • the functionalities in the rubber and in the TPE can be present in different forms. They can be present in the form of a separate, functional polymer which has been added to the rubber or to the TPE.
  • the functionality can also have been obtained by modification of the rubber or the TPE with a functional group, for instance by grafting the rubber or the TPE with e.g. a maleic anhydride (resulting in an anhydride functional polymer) or through an oxygen treatment
  • the invention is also applicable in the situation where the rubber is also a thermoplastic elastomer and where, moreover, the adhesion behaviour of the starting products is inadequate. In that case as well the application of functional polymeric, mutually reactive compounds is the indicated option.
  • the invention also relates to a process for the manufacture of rubber products on the basis of a vulcanized rubber and a thermoplastic elastomer.
  • the process is characterized in that the rubber and the TPE, which each contain a functional polymer that are reactive with each other, are bonded to each other under the influence of pressure and/or temperature. Ways to effectuate such a bond are injecting a molten TPE against a vulcanized rubber object (such as a profile) or coextruding of the rubber and the TPE.
  • the invention is suitable in particular for a process for the manufacture of a rubber profile, in which process rubber profiles are placed in a mould and the space between the profiles is filled up by injecting the TPE. This applies more in particular to profiles in corner bond. It is of course an additional option to cover the rubber profiles themselves with the TPE, so that the product obtained is a profile whose exterior consists entirely of the TPE.
  • the functional polymers should have a weight average molecular weight of at least 500, more preferably at least 1500. This will prevent excessive mobility of the functional polymers in the rubber or the TPE, which would result in the loss of their function in for instance a rubber profile or laminate.
  • the functional groups of the respective functional polymers in the rubber or the TPE should be present in an amount of 0.01-15 wt.%; the amount of functional polymer in the TPE or the rubber is of course dependent on the proportion of functional groups in the functional polymers.
  • the invention also relates to a (process for the manufacture of a) laminate consisting of a layer of rubber which for instance by means of coextrusion is / has been provided with a second TPE-based layer, the rubber layer and the TPE layer both containing a functional polymeric compound, in such a way that the two polymeric compounds are reactive with each other.
  • a first functional polymeric compound is present in the rubber, while a second functional compound that is reactive with it is present in the TPE.
  • the rubber contains a phenolic or resolic resin and the TPE phase a carboxylic acid functional or carboxylic anhydride functional polymer, the latter preferably derived from a polyolefin, more preferably derived from a polyethylene or polypropylene.
  • the temperature has to be sufficiently high for the intended reaction between the functional groups to take place, and on the other hand low enough to avoid, for instance, thermal damage to the rubber and the TPE.
  • the temperature by preference lies between 60 and 260°C, more preferably between 110 and 225°C.
  • Application of pressure also promotes the interaction between the rubber and the TPE and thereby the adhesion. It is not always required for the TPE and/or the rubber as a whole to have said temperature. Since the bonding is limited to the interface of the TPE and the rubber, it is also an option to ensure that the contact surfaces have said temperature. Such a surface temperature can be reached for instance by means of infrared irradiation. A microwave is also applicable.
  • the invention is widely applicable; it can be used for the manufacture of door profiles or tubes, involving the bonding of a TPE layer on or on top of a rubber layer, for bonding of roofings on the basis of rubber, for the manufacture of overmouldings.
  • a rubber composition on the basis of an EPDM rubber (Keltan® 4802 from DSM) was mixed with 5 and 10 parts of phenolic resin (SP 1045) per 100 parts of rubber (phr) and additionally vulcanized using a sulphur vulcanization system; a TPE (Sarlink® 4165) was mixed with 5 and 12 parts of a maleic anhydride modified PE (Yparex® 8102 from DSM).
  • the TPEs thus obtained were injected, at 250°C, on the EPDM vulcanizates thus obtained, which had been placed in a mould.
  • the mould temperature was 95°C in all cases.
  • the tensile strength of the samples thus obtained was determined by means of a tensile test on a tensile test bar consisting half of the TPE and half of the rubber. For the purpose of comparison the same test was repeated on a product made of rubber and TPE to which the above-mentioned components had not been added.

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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

L'invention concerne un produit en caoutchouc vulcanisé et elle est caractérisée en ce que ce produit consiste en une combinaison liée d'un caoutchouc vulcanisé et d'un élastomère thermoplastique, le caoutchouc et l'élastomère comprenant chacun un composé polymère fonctionnel, lesquels composés réagissent l'un avec l'autre. L'invention concerne également un procédé de fabrication de tels produits en caoutchouc.
PCT/NL1997/000361 1996-07-05 1997-06-26 Produit en caoutchouc vulcanise Ceased WO1998001500A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU32774/97A AU3277497A (en) 1996-07-05 1997-06-26 Vulcanized rubber product

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
NL1003517 1996-07-05
NL1003517A NL1003517C2 (nl) 1996-07-05 1996-07-05 Rubber-profielen.
NL1004246A NL1004246C2 (nl) 1996-10-10 1996-10-10 Gevulcaniseerd rubberprodukt.
NL1004246 1996-10-10
US3267496P 1996-12-09 1996-12-09
US60/032,674 1996-12-09

Publications (1)

Publication Number Publication Date
WO1998001500A1 true WO1998001500A1 (fr) 1998-01-15

Family

ID=27351136

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1997/000361 Ceased WO1998001500A1 (fr) 1996-07-05 1997-06-26 Produit en caoutchouc vulcanise

Country Status (2)

Country Link
AU (1) AU3277497A (fr)
WO (1) WO1998001500A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998058528A3 (fr) * 1997-10-09 1999-04-01 Dsm Nv Appareil et procede de coextrusion de matieres a des temperatures differentes
WO2008000493A1 (fr) * 2006-06-29 2008-01-03 Dsm Ip Assets B.V. Adhésion de structures polymériques

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3306438A1 (de) * 1983-02-24 1984-08-30 Phoenix Ag, 2100 Hamburg Klebstoff fuer artikel auf basis epdm
EP0206689A2 (fr) * 1985-06-15 1986-12-30 Mitsubishi Petrochemical Co., Ltd. Laminés d'un polymère thermoplastique d'hydrocarbure halogéné
EP0413912A1 (fr) * 1989-08-23 1991-02-27 Alkor Gmbh Kunststoffe Feuille mono ou multicouche en matière plastique, procédé de préparation et utilisation
EP0550346A1 (fr) * 1991-12-31 1993-07-07 Elf Atochem S.A. Procédé de préparation de matériau composite formé d'un élastomère vulcanisé associe à un élastomère thermoplastique à séquences polyamides; et matériau composite ainsi constitué
WO1994013164A1 (fr) * 1992-12-10 1994-06-23 Nike International Ltd. Liaison caoutchouc-matiere plastique concernant des chaussures
EP0607085A1 (fr) * 1993-01-13 1994-07-20 Elf Atochem S.A. Article tubulaire composite formé d'un élastomère vulcanisé associé à un élastomère thermoplastique à séquences polyamide, notamment tuyau à essence et procédé de préparation d'un tel article
WO1995000331A1 (fr) * 1993-06-28 1995-01-05 Elf Atochem S.A. Structure composite comprenant un elastomere et un polymere thermoplastique, procede de preparation et objet contenant celle-ci
EP0636473A1 (fr) * 1993-07-28 1995-02-01 Alkor Gmbh Kunststoffe Film emboutissable, procédé pour sa fabrication et son utilisation
EP0656388A1 (fr) * 1993-11-26 1995-06-07 Elf Atochem S.A. Alliages de thermoplastique et caoutchouc adhérents sur des thermoplastiques
EP0682060A1 (fr) * 1994-05-06 1995-11-15 Elf Atochem S.A. Matériaux comprenant un élastomère vulcanisé associé à un élastomère thermoplastique
EP0732384A2 (fr) * 1995-01-12 1996-09-18 Hutchinson Produit composite en élastomère et en thermoplastique, et ses procédés de fabrication

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3306438A1 (de) * 1983-02-24 1984-08-30 Phoenix Ag, 2100 Hamburg Klebstoff fuer artikel auf basis epdm
EP0206689A2 (fr) * 1985-06-15 1986-12-30 Mitsubishi Petrochemical Co., Ltd. Laminés d'un polymère thermoplastique d'hydrocarbure halogéné
EP0413912A1 (fr) * 1989-08-23 1991-02-27 Alkor Gmbh Kunststoffe Feuille mono ou multicouche en matière plastique, procédé de préparation et utilisation
EP0550346A1 (fr) * 1991-12-31 1993-07-07 Elf Atochem S.A. Procédé de préparation de matériau composite formé d'un élastomère vulcanisé associe à un élastomère thermoplastique à séquences polyamides; et matériau composite ainsi constitué
WO1994013164A1 (fr) * 1992-12-10 1994-06-23 Nike International Ltd. Liaison caoutchouc-matiere plastique concernant des chaussures
EP0607085A1 (fr) * 1993-01-13 1994-07-20 Elf Atochem S.A. Article tubulaire composite formé d'un élastomère vulcanisé associé à un élastomère thermoplastique à séquences polyamide, notamment tuyau à essence et procédé de préparation d'un tel article
WO1995000331A1 (fr) * 1993-06-28 1995-01-05 Elf Atochem S.A. Structure composite comprenant un elastomere et un polymere thermoplastique, procede de preparation et objet contenant celle-ci
EP0636473A1 (fr) * 1993-07-28 1995-02-01 Alkor Gmbh Kunststoffe Film emboutissable, procédé pour sa fabrication et son utilisation
EP0656388A1 (fr) * 1993-11-26 1995-06-07 Elf Atochem S.A. Alliages de thermoplastique et caoutchouc adhérents sur des thermoplastiques
EP0682060A1 (fr) * 1994-05-06 1995-11-15 Elf Atochem S.A. Matériaux comprenant un élastomère vulcanisé associé à un élastomère thermoplastique
EP0732384A2 (fr) * 1995-01-12 1996-09-18 Hutchinson Produit composite en élastomère et en thermoplastique, et ses procédés de fabrication

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998058528A3 (fr) * 1997-10-09 1999-04-01 Dsm Nv Appareil et procede de coextrusion de matieres a des temperatures differentes
WO2008000493A1 (fr) * 2006-06-29 2008-01-03 Dsm Ip Assets B.V. Adhésion de structures polymériques

Also Published As

Publication number Publication date
AU3277497A (en) 1998-02-02

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