EP1802451A2 - Tpe/pp/reinforcement multilayer tube - Google Patents

Tpe/pp/reinforcement multilayer tube

Info

Publication number
EP1802451A2
EP1802451A2 EP05804711A EP05804711A EP1802451A2 EP 1802451 A2 EP1802451 A2 EP 1802451A2 EP 05804711 A EP05804711 A EP 05804711A EP 05804711 A EP05804711 A EP 05804711A EP 1802451 A2 EP1802451 A2 EP 1802451A2
Authority
EP
European Patent Office
Prior art keywords
layer
tube according
tube
polypropylene
styrene
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Withdrawn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
EP05804711A
Other languages
German (de)
French (fr)
Inventor
Johann Dabouineau
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.)
Nobel Plastiques SA
Original Assignee
Nobel Plastiques SA
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 Nobel Plastiques SA filed Critical Nobel Plastiques SA
Publication of EP1802451A2 publication Critical patent/EP1802451A2/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Withdrawn legal-status Critical Current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
    • 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
    • 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
    • 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
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • F16L11/045—Hoses, i.e. flexible pipes made of rubber or flexible plastics with four or more layers without reinforcement
    • 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
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
    • Y10T428/1393—Multilayer [continuous layer]

Definitions

  • the present invention relates to a multi-duct tube that can be used in particular as a pipe for transporting fluid in a cooling circuit of a thermal engine of a motor vehicle.
  • An object of the invention is to provide a tube structure for obtaining a better compromise between the various constraints mentioned above.
  • a multilayer tube comprising from inside to outside:
  • thermoplastic elastomer compatible with polypropylene
  • intermediate polypropylene layer in direct contact with the inner layer
  • the polypropylene layer provides essentially a barrier function vis-à-vis the cooling fluid.
  • the thermoplastic elastomer layer also provides a barrier function that allows it to se ⁇ conder the polypropylene layer.
  • the inner layer made of thermoplastic elastomer has a good resistance to cracking so that it prevents the fluid transported from being brought into contact with the intermediate layer for a relatively long period of time, allowing the layer intermediate to maintain its barrier properties vis-à-vis the fluid transported.
  • the inner layer thus protects the polypropy ⁇ lene of the intermediate layer of the aggression due to the cooling fluid and also allows the connection of the tube to tips type fir teeth.
  • thermoplastic elastomer also has a property of natural adhesion to polypropylene (there is interpenetration at the macromolecular level of polypropylene and thermoplastic elastomer) up to relatively high temperatures (above beyond 15O 0 C). There is thus a synergy between the inner layer and the intermediate layer which allows good performance of the tube.
  • the outer layer strengthens the tube mechanically by giving it good resistance to temperature and pressure.
  • the tube according to the invention comprises from inside to outside:
  • the inner layer 1 comprises a thermoplastic elastomer material (TPE).
  • TPE thermoplastic elastomer material
  • thermoplastic elastomer material is an olefinic thermo ⁇ plastic elastomer (TPE-O) that is not vulcanized here.
  • the olefinic thermoplastic elastomer material comprises a majority phase of polyolefin and a minor phase based one elastomer dispersed in the main phase.
  • the olefinic thermoplastic elastomer material used is for example one of those produced by the company MULTIBASE under the reference MULTIBASE.
  • the thermoplastic elastomer material used can be vulcanized (TPV) or not and comprises ethylene-propylene-diene monomer (EPDM).
  • the material used in this case is a mixture of polypropylene and ethylene-propylene-diene monomer (PP / EPDM) such as those produced by AES under the references SANTOPRENE 101-64A, 101-73A, 101-80A, 101-87A, 201-64A, 201-73A, 201-80A, 201-87A.
  • thermoplastic elastomer material is a thermoplastic styrene elastomer (TPE-S) comprising here a polypropylene base in which is dispersed styrene-butadiene-styrene (SBS) or styrene-ethylene-butadiene- styrene (SEBS).
  • TPE-S thermoplastic styrene elastomer
  • SBS dispersed styrene-butadiene-styrene
  • SEBS styrene-ethylene-butadiene- styrene
  • the inner layer 1 has a good resistance to the cooling fluid and a low permeability to this fluid.
  • the inner layer 1 has the advantage of being deformable which allows it to perform a function sealing during a connection of the tube with an em ⁇ end for example fir-type tooth.
  • the inner layer 1 preferably has a stabilized grade with respect to the thermal aging in air by incorporating, for example, antioxidants therein.
  • the intermediate layer 2 is made of polypropylene (PP) such as that of grade EPD60R (heat stabilized and protected against oxidation and aging with hydrolysis) produced by the company " DEGUSSA " under the references SX8100 or SX8100sw, or that produced by the company SOLVAY ENGINEERED POLYMERS under the reference SEQUEL 1420 or ELTEX PHL 102 Engineered Polyolefin, or else that produced by the company BAMBERGER POLYMERS under the reference BAPOLENE Grade PP 4012.
  • PP polypropylene
  • the materials of the inner layer 1 and the intermediate layer 2 have mutual adhesion properties. This is particularly interesting because this adhesion prevents (or at least limit) between these layers a recondensation of fluid vapors that could cross the inner layer and be blocked by the intermediate layer. Such a recondensation au ⁇ would create bubbles likely to degrade the cohesion of the tube and affect its resistance including mechanical.
  • the binder layer 3 is based on maleic anhydride grafted polyolefin (PO-g-AM) such as those produced by the company MITSUI CHEMICALS under the references Admer QB 520, QF 550 E, QB 510 E, QF 551 E, AT 843 E, AT 1190 E, AT 1657 E or AT 1658 E; or by EQUISTAR under the references PLEXAR PX 6002 or PX 6006.
  • PO-g-AM maleic anhydride grafted polyolefin
  • the outer layer 4 is made of polyamide 6- 12 (PA 6-12) such as that produced under the references: VESTAMID DX 9304 or DX 9303 or X 7099 by the company HULS; GRILON CAE 6 or CR9 NAT 6361 by MEMS-GRIVORY; ASHLENE 982 by the company ASHLEY POLYMERS; COMTUF 608 by the company COMALLOY; ZYTEL 151 L NCOlO or EFE 4168 by the company DUPONT DE NEMOURS.
  • Polyamide 6-12 gives the tube a relatively high resistance to pressure and temperature.
  • the outer layer comprises a major phase of polyphenylene sulfone (PPS).
  • the material used is a mixture of polyphenylene sulphone with an impact modifying agent such as that produced by CHEVRON PHILIPS under the references ' XTEL XE 3200 or 3400.
  • the material used is a mixture of polyphenylene sulfone and polyamide such as that produced by the same company under the reference XTEL, XK series.
  • the inner layer has a thickness of 0.20 mm
  • the intermediate layer has a thickness of 0.20 mm
  • the binder layer has a thickness between 0.05 and 0.10 mm
  • the outer layer has a thickness of 0.90 mm (the values indicated are orders of magnitude).
  • the permeability of the tube is even lower than the thicknesses are important.
  • the different layers are for example coextruded.
  • the cooling must not be too fast, so as to obtain a crystallinity rate sufficient to limit the per ⁇ meability of the tube to the desired value. Extrusion per ⁇ puts a relatively slow cooling, from the outside to the inside.
  • the tube can be smooth or ringed.
  • the in ⁇ dull layer 1 protects the intermediate layer 2 stress-cracking in particular.
  • thermoplastic elastomers polypropylene, binder and polyamide (in particular polyamide 12, although this has a lower maximum temperature of use than the
  • the binder layer may be of a material other than that described, especially when the outer reinforcing layer itself is of a material different from that described.

Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

The invention concerns a multilayer tube comprising from inside outwards: an inner thermoplastic elastomer layer (1) compatible with polypropylene, and intermediate polypropylene layer (2) in direct contact with the inner layer, an outer reinforcing layer (4).

Description

Tube multicouche TPE/PP/renfort Multilayer tube TPE / PP / reinforcement
La présente invention concerne un tube multicou¬ che utilisable notamment comme canalisation de transport de fluide dans un circuit de refroidissement d'un moteur thermique d'un véhicule automobile.The present invention relates to a multi-duct tube that can be used in particular as a pipe for transporting fluid in a cooling circuit of a thermal engine of a motor vehicle.
Il existe de nombreuses structures de tube desti¬ nées au transport de fluide de refroidissement. Le choix des matériaux formant les couches desdites structures ré¬ sulte d'un compromis entre la tenue au fluide transporté, la perméabilité à ce fluide, la résistance mécanique et le coût du tube.There are many tube structures desti¬ ned for the transport of coolant. The choice of the materials forming the layers of said structures re¬ is a compromise between the resistance to the fluid transported, the permeability to the fluid, the mechanical strength and the cost of the tube.
Ce compromis est particulièrement délicat à trou¬ ver lorsque le tube est soumis à des températures élevées typiquement supérieures a 1500C II a été envisagé un tube comportant une couche en polyamide et une couche en élastomère thermoplastique rendues compatibles entre elles. Toutefois, dans un tel tube, la température élevée entraîne une rupture des liaisons covalentes entre l'anhydride maléique et les fonctions amides du polyamide ou toute autre fonction permettant de rendre les deux couches compatibles. En ou¬ tre, ces liaisons covalentes sont très sensibles aux agressions chimiques du fluide transporté qui peut provo¬ quer un délaminage des couches. On connaît par ailleurs des tubes en élastomère thermoplastique. Ces tubes sont cependant onéreux et pré¬ sentent une perméabilité relativement élevée.This compromise is particularly difficult to find when the tube is subjected to high temperatures typically greater than 150 ° C. It has been envisaged a tube comprising a polyamide layer and a thermoplastic elastomer layer made compatible with each other. However, in such a tube, the high temperature leads to a rupture of the covalent bonds between the maleic anhydride and the amide functions of the polyamide or any other function making the two layers compatible. In addition, these covalent bonds are very sensitive to the chemical attack of the transported fluid which can provoke delamination of the layers. Thermoplastic elastomer tubes are also known. These tubes are however expensive and pre¬ feel a relatively high permeability.
Un but de l'invention est de fournir une struc¬ ture de tube permettant l'obtention d'un meilleur σompro- mis entre les différentes contraintes énoncées ci-dessus.An object of the invention is to provide a tube structure for obtaining a better compromise between the various constraints mentioned above.
A cet effet, on prévoit, selon l'invention, un tube multicouche comportant de l'intérieur vers l'exté¬ rieur :For this purpose, according to the invention, there is provided a multilayer tube comprising from inside to outside:
- une couche interne en élastomère thermoplasti- que compatible avec le polypropylène, - une couche intermédiaire en polypropylène en contact direct avec la couche interne,an inner layer of thermoplastic elastomer compatible with polypropylene, an intermediate polypropylene layer in direct contact with the inner layer,
- une couche externe de renfort.an outer reinforcing layer.
La couche de polypropylène assure pour l'essen- tiel une fonction barrière vis-à-vis du fluide de refroi¬ dissement. La couche d'élastomère thermoplastigue assure également une fonction barrière qui lui permet de se¬ conder la couche de polypropylène. Du fait de sa sou¬ plesse, la couche interne en élastomère thermoplastique présente une bonne résistance à la fissuration de sorte qu'elle empêche la mise en contact du fluide transporté avec la couche intermédiaire pendant une durée relative¬ ment importante, permettant à la couche intermédiaire de conserver ses propriétés barrière vis-à-vis du fluide transporté. La couche interne protège ainsi le polypropy¬ lène de la couche intermédiaire des agressions dues au fluide de refroidissement et permet en outre la connexion du tube à des embouts de type en dents de sapin. L'élas¬ tomère thermoplastique présente en outre une propriété d'adhérence naturelle sur le polypropylène (il y a une interpénétration au niveau macromoléculaire du polypropy¬ lène et de l'élastomère thermoplastique) jusqu'à des tem¬ pératures relativement importantes (au-delà de 15O0C) . Il existe ainsi une synergie entre la couche interne et la couche intermédiaire qui autorise de bonnes performances du tube. La couche externe renforce le tube mécaniquement en lui conférant une bonne résistance à la température et à la pression.The polypropylene layer provides essentially a barrier function vis-à-vis the cooling fluid. The thermoplastic elastomer layer also provides a barrier function that allows it to se¬ conder the polypropylene layer. Because of its flexibility, the inner layer made of thermoplastic elastomer has a good resistance to cracking so that it prevents the fluid transported from being brought into contact with the intermediate layer for a relatively long period of time, allowing the layer intermediate to maintain its barrier properties vis-à-vis the fluid transported. The inner layer thus protects the polypropy¬ lene of the intermediate layer of the aggression due to the cooling fluid and also allows the connection of the tube to tips type fir teeth. The thermoplastic elastomer also has a property of natural adhesion to polypropylene (there is interpenetration at the macromolecular level of polypropylene and thermoplastic elastomer) up to relatively high temperatures (above beyond 15O 0 C). There is thus a synergy between the inner layer and the intermediate layer which allows good performance of the tube. The outer layer strengthens the tube mechanically by giving it good resistance to temperature and pressure.
D'autres caractéristiques et avantages de 1 ' in- vention ressortiront à la lecture de la description qui suit d'un mode de réalisation particulier non limitatif de 1 ' invention.Other features and advantages of the invention will become apparent from reading the following description of a particular non-limiting embodiment of the invention.
Il sera fait référence à la figure unique annexée représentant en coupe transversale un tube conforme à l'invention. Le tube conforme a 1 ' invention comprend de 1 ' in¬ térieur vers 1 'extérieur :Reference will be made to the attached single figure showing in cross section a tube according to the invention. The tube according to the invention comprises from inside to outside:
- une couche interne 1,an inner layer 1,
- une couche intermédiaire 2, - une couche de liant 3,an intermediate layer 2, a binder layer 3,
- une couche externe 4 de renfort.an outer layer 4 of reinforcement.
La couche interne 1 comprend un matériau élasto- mère thermoplastique (TPE) .The inner layer 1 comprises a thermoplastic elastomer material (TPE).
Le matériau thermoplastique élastomère est selon une première version de l'invention un élastomère thermo¬ plastique oléfinique (TPE-O) ici non vulcanisé.According to a first version of the invention, the thermoplastic elastomer material is an olefinic thermo¬ plastic elastomer (TPE-O) that is not vulcanized here.
Le matériau élastomère thermoplastique oléfinique comprend une phase majoritaire de polyoléfine et une phase minoritaire à base d1élastomère dispersé dans la phase majoritaire. Le matériau élastomère thermoplastique oléfinique employé est par exemple un de ceux produits par la société MULTIBASE sous la référence MULTIBASE.The olefinic thermoplastic elastomer material comprises a majority phase of polyolefin and a minor phase based one elastomer dispersed in the main phase. The olefinic thermoplastic elastomer material used is for example one of those produced by the company MULTIBASE under the reference MULTIBASE.
Selon une deuxième version, le matériau élasto¬ mère thermoplastique utilisé peut être vulcanisé (TPV) ou non et comprend de 1 'éthylène-propylène-diène monomère (EPDM) . Le matériau utilisé en l'espèce est un mélange de polypropylène et d'éthylène-propylène-diène monomère (PP/EPDM) tel que ceux produits par la société AES sous les références SANTOPRENE 101-64A, 101-73A, 101-80A, 101- 87A, 201-64A, 201-73A, 201-80A,201-87A.According to a second version, the thermoplastic elastomer material used can be vulcanized (TPV) or not and comprises ethylene-propylene-diene monomer (EPDM). The material used in this case is a mixture of polypropylene and ethylene-propylene-diene monomer (PP / EPDM) such as those produced by AES under the references SANTOPRENE 101-64A, 101-73A, 101-80A, 101-87A, 201-64A, 201-73A, 201-80A, 201-87A.
Selon une troisième version, le matériau élasto¬ mère thermoplastique est un élastomère thermoplastique styrénique (TPE-S) comportant ici une base de polypropy¬ lène dans laquelle est dispersé du styrène-butadiène- styrène (SBS) ou du styrène-éthylène-butadiène-styrène (SEBS) .According to a third version, the thermoplastic elastomer material is a thermoplastic styrene elastomer (TPE-S) comprising here a polypropylene base in which is dispersed styrene-butadiene-styrene (SBS) or styrene-ethylene-butadiene- styrene (SEBS).
La couche interne 1 présente une bonne résistance au fluide de refroidissement et une faible perméabilité à ce fluide. La couche interne 1 présente l'avantage d'être déformable ce qui lui permet d'assurer une fonction d'étanchéité lors d'un raccordement du tube avec un em¬ bout par exemple de type dent de sapin. La couche interne 1 a de préférence un grade stabilisé vis à vis du vieil¬ lissement thermique à l'air en y incorporant par exemple des anti-oxydants.The inner layer 1 has a good resistance to the cooling fluid and a low permeability to this fluid. The inner layer 1 has the advantage of being deformable which allows it to perform a function sealing during a connection of the tube with an em¬ end for example fir-type tooth. The inner layer 1 preferably has a stabilized grade with respect to the thermal aging in air by incorporating, for example, antioxidants therein.
La couche intermédiaire 2 est réalisée en poly- propylêne (PP) tel que celui de grade EPD60R (stabilisé à la chaleur et protégé vis à vis de l'oxydation et du vieillissement à l'hydrolyse) produit par la société "" " DEGUSSA sous les références SX8100 ou SX8100sw ; ou celui produit par la société SOLVAY ENGINEERED POLYMERS sous la référence SEQUEL 1420 ou ELTEX PHL 102 Engineered Polyo- lefin ; ou bien encore celui produit par la société BAMBERGER POLYMERS sous la référence BAPOLENE Grade PP 4012.The intermediate layer 2 is made of polypropylene (PP) such as that of grade EPD60R (heat stabilized and protected against oxidation and aging with hydrolysis) produced by the company " DEGUSSA " under the references SX8100 or SX8100sw, or that produced by the company SOLVAY ENGINEERED POLYMERS under the reference SEQUEL 1420 or ELTEX PHL 102 Engineered Polyolefin, or else that produced by the company BAMBERGER POLYMERS under the reference BAPOLENE Grade PP 4012.
Les matériaux de la couche interne 1 et de la couche intermédiaire 2 présentent des propriétés d'adhé¬ rence mutuelle. Ceci est particulièrement intéressant car cette adhérence empêche (ou tout au moins limite) entre ces couches une recondensation de vapeurs de fluides qui auraient pu traverser la couche interne et être bloquées par la couche intermédiaire. Une telle recondensation au¬ rait créé des bulles risquant de dégrader la cohésion du tube et d'affecter sa résistance notamment mécanique. La couche de liant 3 est à base de polyoléfine greffée anhydride maléique (PO-g-AM) telle que celles produites par la société MITSUI CHEMICALS sous les réfé¬ rences Admer QB 520, QF 550 E, QB 510 E, QF 551 E, AT 843 E, AT 1190 E, AT 1657 E ou AT 1658 E ; ou par la société EQUISTAR sous les références PLEXAR PX 6002 ou PX 6006.The materials of the inner layer 1 and the intermediate layer 2 have mutual adhesion properties. This is particularly interesting because this adhesion prevents (or at least limit) between these layers a recondensation of fluid vapors that could cross the inner layer and be blocked by the intermediate layer. Such a recondensation au¬ would create bubbles likely to degrade the cohesion of the tube and affect its resistance including mechanical. The binder layer 3 is based on maleic anhydride grafted polyolefin (PO-g-AM) such as those produced by the company MITSUI CHEMICALS under the references Admer QB 520, QF 550 E, QB 510 E, QF 551 E, AT 843 E, AT 1190 E, AT 1657 E or AT 1658 E; or by EQUISTAR under the references PLEXAR PX 6002 or PX 6006.
La couche externe 4 est réalisée en polyamide 6- 12 (PA 6-12) tel que celui produit sous les références : VESTAMID DX 9304 ou DX 9303 ou X 7099 par la société HULS ; GRILON CAE 6 ou CR9 NAT 6361 par la société MEMS- GRIVORY ; ASHLENE 982 par la société ASHLEY POLYMERS ; COMTUF 608 par la Société COMALLOY ; ZYTEL 151 L NCOlO ou EFE 4168 par la société DUPONT DE NEMOURS. Le polyamide 6-12 confère au tube une résistance à la pression et à la température relativement importante. En variante, la couche externe comprend une phase majoritaire de polyphénylêne sulfone (PPS) . Selon une première version, le matériau utilisé est un mélange de polyphénylêne sulfone avec un agent modifiant choc tel que celui produit par la société CHEVRON PHILIPS sous les références 'XTEL XE 3200 ou 3400. Selon une deuxième ver¬ sion, le matériau utilisé est un mélange de polyphénylêne sulfone et de polyamide tel que celui produit par cette même société sous la référence XTEL, série XK.The outer layer 4 is made of polyamide 6- 12 (PA 6-12) such as that produced under the references: VESTAMID DX 9304 or DX 9303 or X 7099 by the company HULS; GRILON CAE 6 or CR9 NAT 6361 by MEMS-GRIVORY; ASHLENE 982 by the company ASHLEY POLYMERS; COMTUF 608 by the company COMALLOY; ZYTEL 151 L NCOlO or EFE 4168 by the company DUPONT DE NEMOURS. Polyamide 6-12 gives the tube a relatively high resistance to pressure and temperature. Alternatively, the outer layer comprises a major phase of polyphenylene sulfone (PPS). According to a first version, the material used is a mixture of polyphenylene sulphone with an impact modifying agent such as that produced by CHEVRON PHILIPS under the references ' XTEL XE 3200 or 3400. According to a second version, the material used is a mixture of polyphenylene sulfone and polyamide such as that produced by the same company under the reference XTEL, XK series.
A titre d'exemple, pour un diamètre interne du tube égal à 27 mm, la couche interne a une épaisseur de 0,20 mm, la couche intermédiaire a une épaisseur de 0,20 mm, la couche de liant a une épaisseur comprise entre 0,05 et 0,10 mm, et la couche externe a une épaisseur de 0,90 mm (les valeurs indiquées sont des ordres de gran- deurs) . La perméabilité du tube est d'autant plus faible que les épaisseurs sont importantes.By way of example, for an internal diameter of the tube equal to 27 mm, the inner layer has a thickness of 0.20 mm, the intermediate layer has a thickness of 0.20 mm, the binder layer has a thickness between 0.05 and 0.10 mm, and the outer layer has a thickness of 0.90 mm (the values indicated are orders of magnitude). The permeability of the tube is even lower than the thicknesses are important.
Les différentes couches sont par exemple co- extrudées.The different layers are for example coextruded.
Lors de la fabrication du tube, le refroidisse- ment ne doit pas être trop rapide, de manière à obtenir un taux de cristallinitë suffisant pour limiter la per¬ méabilité du tube à la valeur souhaitée. L'extrusion per¬ met un refroidissement relativement lent, de l'extérieur vers l'intérieur. Le tube peut être lisse ou annelé.During the manufacture of the tube, the cooling must not be too fast, so as to obtain a crystallinity rate sufficient to limit the per¬ meability of the tube to the desired value. Extrusion per¬ puts a relatively slow cooling, from the outside to the inside. The tube can be smooth or ringed.
Lorsque le tube est un tube annelé, la couche in¬ terne 1 protège la couche intermédiaire 2 du stress- cracking en particulier.When the tube is a corrugated tube, the in¬ dull layer 1 protects the intermediate layer 2 stress-cracking in particular.
Bien entendu, l'invention n'est pas limitée au mode de réalisation décrit et on peut y apporter des va- riantes de réalisation sans sortir du cadre de l'inven¬ tion tel que défini par les revendications.Of course, the invention is not limited to the embodiment described and it is possible to provide embodiments without departing from the scope of the invention as defined by the claims.
En particulier, sont utilisables d'autres élasto- mères thermoplastiques, polypropylène, liant et polyamide (notamment du polyamide 12 bien que celui-ci présente une température maximale d'utilisation inférieure à celle duIn particular, it is possible to use other thermoplastic elastomers, polypropylene, binder and polyamide (in particular polyamide 12, although this has a lower maximum temperature of use than the
PA 6-12) .PA 6-12).
La couche de liant peut être en un autre matériau -- - que celui- décrit, notamment- lorsque la couche externe de renfort est elle-même en un matériau différent de celui décrit.The binder layer may be of a material other than that described, especially when the outer reinforcing layer itself is of a material different from that described.
En outre, on peut choisir une couche externe de renfort en un matériau ayant des propriétés d'adhérence naturelles avec la couche intermédiaire en polypropylène. II n'est' alors pas utile d'intercaler entre ces couches une couche de liant si la cohésion des couches procurée par l'adhérence naturelle est suffisante au regard de l'application envisagée. In addition, it is possible to choose an outer reinforcing layer of a material having natural adhesion properties with the polypropylene interlayer. It is therefore not necessary to interpose between these layers a binder layer if the cohesion of the layers provided by the natural adhesion is sufficient for the intended application.

Claims

REVENDICATIONS
1. Tube multicouche comportant de l'intérieur vers 1 'extérieur :1. Multilayer tube with from inside to outside:
- une couche interne en élastomère thermoplasti- que (1) compatible avec le polypropylêne,an inner thermoplastic elastomer layer (1) compatible with the polypropylene,
- une couche intermédiaire en polypropylêne (2) en contact direct avec la couche interne,an intermediate layer of polypropylene (2) in direct contact with the inner layer,
- une couche externe de renfort (4) .an outer reinforcing layer (4).
2-. Tube selon la revendication 1, -caractérisé en ce que la couche externe (4) est en polyamide.2-. Tube according to claim 1, characterized in that the outer layer (4) is made of polyamide.
3. Tube selon la revendication 2, caractérisé en ce que la couche externe (4) est en polyamide 6-12.3. Tube according to claim 2, characterized in that the outer layer (4) is polyamide 6-12.
4. Tube selon la revendication 1, caractérisé en ce que la couche externe (4) comporte une phase majori- taire de polyphénylène sulfone.4. Tube according to claim 1, characterized in that the outer layer (4) comprises a major phase of polyphenylene sulfone.
5. Tube selon la revendication 1, caractérisé en ce qu'il comprend une couche de liant (3) en polyoléfine greffée anhydride maléique.5. Tube according to claim 1, characterized in that it comprises a binder layer (3) polyolefin grafted maleic anhydride.
6. Tube selon la revendication 1, caractérisé en ce que la couche interne (1) est en un élastomère thermo¬ plastique vulcanisé.6. Tube according to claim 1, characterized in that the inner layer (1) is a vulcanized thermo¬ plastic elastomer.
7. Tube selon la revendication 1, caractérisé en ce que la couche interne (1) est en un élastomère thermo¬ plastique oléfinique. 7. Tube according to claim 1, characterized in that the inner layer (1) is an olefinic thermo¬ plastic elastomer.
8. Tube selon la revendication 1, caractérisé en ce que la couche interne (1) est en un élastomère thermo¬ plastique styrènique,8. Tube according to claim 1, characterized in that the inner layer (1) is a thermoplastic styrene elastomer,
9. Tube selon la revendication 8, caractérisé en ce que l'élastomère thermoplastique styrènique comprend une base de polypropylêne dans laquelle est dispersé du styrène-butadiène-styrène.9. Tube according to claim 8, characterized in that the thermoplastic styrene elastomer comprises a polypropylene base in which is dispersed styrene-butadiene-styrene.
10. Tube selon la revendication 8, caractérisé en ce que l'élastomère thermoplastique styrènique comprend une base de polypropylêne dans laquelle est dispersé du styrène-éthylène-butadiène-styrène. 10. Tube according to claim 8, characterized in that the thermoplastic styrene elastomer comprises a polypropylene base in which is dispersed styrene-ethylene-butadiene-styrene.
EP05804711A 2004-10-19 2005-10-19 Tpe/pp/reinforcement multilayer tube Withdrawn EP1802451A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0411064A FR2876765B1 (en) 2004-10-19 2004-10-19 MULTILAYER TUBE TPE / PP / REINFORCEMENT
PCT/FR2005/002593 WO2006042966A2 (en) 2004-10-19 2005-10-19 Tpe/pp/reinforcement multilayer tube

Publications (1)

Publication Number Publication Date
EP1802451A2 true EP1802451A2 (en) 2007-07-04

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US (1) US20080187701A1 (en)
EP (1) EP1802451A2 (en)
JP (1) JP2008516814A (en)
BR (1) BRPI0517101A (en)
CA (1) CA2584042A1 (en)
FR (1) FR2876765B1 (en)
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WO (1) WO2006042966A2 (en)

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RU2457388C2 (en) * 2010-10-07 2012-07-27 Общество с ограниченной ответственностью "Группа ПОЛИМЕРТЕПЛО" (ООО "Группа ПОЛИМЕРТЕПЛО") Multilayer reinforced polymer pipe and pipe system for water transportation
KR20150036587A (en) * 2012-07-26 2015-04-07 생-고뱅 퍼포먼스 플라스틱스 코포레이션 Multilayer flexible tube
EP3613578B1 (en) * 2018-08-21 2021-04-07 TI Automotive (Fuldabrück) GmbH Multilayer motor vehicle temperature control pipe
US20220097276A1 (en) * 2020-09-29 2022-03-31 Cooper Standard Automotive, Inc. Composition of a multi-layer tube with a polyamide outer layer and process for making
CN114213750B (en) * 2021-12-08 2023-09-19 万华化学（宁波）有限公司 Multilayer pipeline

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JP2997831B2 (en) * 1993-09-06 2000-01-11 グンゼ株式会社 Laminate
JP2000506462A (en) * 1996-03-21 2000-05-30 ゼンゲバルト フェアパックンゲン ゲーエムベーハー Multilayer film, method of manufacturing the same, and method of using the same
ATE332335T1 (en) * 2001-11-23 2006-07-15 Arkema VULCANIZED ELASTOMER TUBE WITH POLYAMIDE AND EVOH BARRIER LAYERS
FR2858038B1 (en) * 2003-07-23 2006-09-01 Nobel Plastiques MULTILAYER DRIVE HAVING INTERNAL LAYER OF POLYMER BASED ON SUBSTITUTED PENTENE MONOMER
JP3938169B2 (en) * 2003-09-30 2007-06-27 東海ゴム工業株式会社 Automotive fuel hose

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Also Published As

Publication number Publication date
WO2006042966A3 (en) 2007-04-05
FR2876765A1 (en) 2006-04-21
BRPI0517101A (en) 2008-09-30
JP2008516814A (en) 2008-05-22
US20080187701A1 (en) 2008-08-07
MX2007004456A (en) 2007-08-08
WO2006042966A2 (en) 2006-04-27
FR2876765B1 (en) 2007-01-19
CA2584042A1 (en) 2006-04-27

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