EP0461453A1 - Method of bonding the components of a ski - Google Patents

Method of bonding the components of a ski Download PDF

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Publication number
EP0461453A1
EP0461453A1 EP91108572A EP91108572A EP0461453A1 EP 0461453 A1 EP0461453 A1 EP 0461453A1 EP 91108572 A EP91108572 A EP 91108572A EP 91108572 A EP91108572 A EP 91108572A EP 0461453 A1 EP0461453 A1 EP 0461453A1
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Prior art keywords
film
bonding
polyamide
ski
process according
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EP91108572A
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German (de)
French (fr)
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EP0461453B1 (en
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Gilles Recher
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Salomon SAS
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Salomon SAS
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    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63C—SKATES; SKIS; ROLLER SKATES; DESIGN OR LAYOUT OF COURTS, RINKS OR THE LIKE
    • A63C5/00—Skis or snowboards
    • A63C5/12—Making thereof; Selection of particular materials

Definitions

  • the present invention relates to films suitable for bonding, thermoplastics composed of a mixture of thermoplastic elastomer (TPE) based on polyamide and modified olefin copolymer, as well as the method of bonding elements of the structure d 'a ski using said thermoplastic films.
  • TPE thermoplastic elastomer
  • thermoplastic films there are in particular "hot melts" films.
  • adhesives described in application FR 2 523 143, and the composition of which contains copolymers based on ethylene (at least 35% by weight) and at least one vinyl ester and containing from 0.5 to 20 % of a copolyetheresteramide.
  • thermoplastic polymer mainly consist of a thermoplastic polymer and an adhesion promoter such as a silane or an epoxy resin.
  • the object of the present invention is to provide a film of new composition, suitable for bonding, having improved adhesion properties and which can be applied to a wider range of materials.
  • Another object of the invention is to improve the thermal resistance of the bonding of the laminate thus formed.
  • the present invention therefore relates to thermoplastic films or sheets, suitable for bonding, composed of a mixture of thermoplastic elastomer (s) (TPE) based on polyamide and of a modified olefin copolymer consisting of at least two different olefin monomers; said mixture being such that the thermoplastic elastomer (s) therein represent (s) at least 50% and preferably at least 60% of the total weight.
  • TPE thermoplastic elastomer
  • s thermoplastic elastomer
  • thermoplastic or TPE elastomers based on polyamide can be random or block copolymers.
  • copolymers are formed by the random sequence of the various constituents (monomers and / or prepolymers) while the block copolymers or blocks preferred by the applicant, are formed from blocks having a certain chain length of their various constituents.
  • the polyamide-based copolymers according to the invention are either polyesteramides or polyetheramides.
  • the number-average molecular mass of these polyamide blocks is generally between 500 and 10,000 and more particularly between 600 and 5,000.
  • the polyamide blocks of the polyetheresteramides are preferably formed from aliphatic polyamides and / or from amorphous polyamide or from copolyamide resulting from polycondensation of their monomers.
  • the number average molecular weight of the polyethers is generally between 200 and 6000 and more particularly between 600 and 3000.
  • the polyether blocks most often consist of polytetramethylene glycol (PTMG), polyethylene glycol (PEG) and / or polypropylene glycol (PPG).
  • PTMG polytetramethylene glycol
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • the inherent viscosity of polyetheresteramides is advantageously between 0.8 and 2.05. It is measured in metacresol at 20 ° C with an initial concentration of 0.5 g of polymer per 100 g of metacresol.
  • the polyetheresteramides can be formed from 5 to 85% by weight of polyether, from 95 to 15% by weight of polyamide, and preferably from 30 to 85% by weight of polyether and from 70 to 15% by weight of polyamide.
  • polyetheresteramides preferred by the applicant are those whose polyamide sequences are essentially made up of PA-11, 12 and / or 12.12 and when a composition having antistatic properties is sought, polyetheresteramides whose polyether blocks are essentially used are preferably used made of polyethylene glycol (PEG).
  • PEG polyethylene glycol
  • the second compound used in the composition of the film is a modified olefin copolymer made up of at least two different olefin monomers.
  • the olefins represent at least 50% and preferably at least 60% of the total weight of the copolymer, it being understood that the copolymers can be polymerized in a statistical or sequenced fashion and have a linear or branched structure, for the polyolefins modified according to the invention.
  • copolymers which are particularly preferred by the applicant, mention will be made most particularly of the copolymers of ethylene and of propylene grafted with a carboxylic acid or anhydrous carboxylic acid or an acid salt.
  • the unsaturated dicarboxylic acids will be chosen more particularly, such as maleic, fumaric, itaconic acid for example.
  • the anhydrous and salts chosen are those corresponding to the acids mentioned, of course.
  • the films or sheets particularly preferred by the applicant consist of a mixture of polyetheresteramide at least 50% by weight (preferably 60%) and of ethylene propylene copolymer containing 0.1 to 2% by weight of maleic anhydride graft.
  • compositions of the films described above it is possible to incorporate various other constituents such as fillers, pigments or dyes, various additives.
  • fillers By way of example of fillers, mention may be made of glass fibers, carbon fibers, aramid fibers, talc, silica, kaolin, glass beads and fibers, ceramics, metallic fillers, metal salts and oxides. , such as aluminum powder, calcium and manganese carbonates, ferrite powder, titanium oxide.
  • fillers in general, up to 50% and preferably up to 40% by weight of fillers can be incorporated relative to the compositions of thermoplastic elastomer (s) and of modified olefin copolymer.
  • additives mention may be made of anti-UV agents, release agents, impact modifiers.
  • the films or sheets according to the invention are obtained according to any known extrusion process such as extrusion-calendering flat, extrusion-plaxing, extrusion-blowing, the extrusion temperature generally being between 190 and 250 ° C.
  • film is reserved for objects of planar section whose thickness is less than 250 microns and the term “sheet” for objects of greater thickness and up to several mm, but in all this which follows, and for reasons of simplification, one or the other of the terms may be used to designate films and sheets simultaneously.
  • the films according to the invention can be used as such but can also be used in the manufacture of multilayer films obtained for example by co-extrusion, hot lamination.
  • Single-layer films are particularly suitable for bonding to fabrics and non-woven materials, for coating natural or synthetic fibers, and foam.
  • These films can be bonded to rigid parts and in particular to metal parts (such as cables, sheets) as well as to synthetic materials preferably based on, covered or impregnated with epoxy resin (s) and / or polyester (s) and / or polyurethane (s).
  • the manufacturing process for these composite materials generally takes place in two stages: The co-extrusion of the bi-layer film is first carried out and then it is hot-glued on the side of the composition layer according to the invention, on the support of synthetic material for example, by hot forming or thermoforming.
  • These composite materials can be decorated using the sublimable ink transfer printing method and in particular according to the methods described in patent application FR 2 596 286.
  • the decoration of these materials can also be carried out using other techniques such as screen printing, painting or varnishing, hot transfer, pad printing, inkjet, laser marking.
  • the composite materials made up of the two-layer film described above and of a support impregnated with epoxy resin (s) and / or polyester and / or polyurethane possibly decorated are particularly suitable for the production of ski tops, windsurfing, skateboarding, surfboard, boat hulls, decorative panels for automobile bodywork, noise or thermal insulation laminates.
  • Monolayer films can also serve as co-extrusion binder for multilayer films allowing adhesion of layers whose bonding is difficult or even impossible.
  • films of composition according to the invention as co-extrusion binder of a film based on polycarbonate (PC) on the one hand and of a film based on copolymer ethylene and vinyl alcohol (EVOH) on the other hand.
  • PC polycarbonate
  • EVOH copolymer ethylene and vinyl alcohol
  • the present invention also relates to the method of manufacturing a ski used in winter sports and more particularly to the bonding of elements of the structure of a ski, and to a ski obtained by this method.
  • thermosetting adhesive of the epoxy, polyester or polyurethane foam type, for example.
  • this adhesive must be compatible with all the elements to be assembled.
  • binders are generally not sufficient to adhere all the materials that one wishes to use in the composition of a ski. To obtain adhesion to certain materials, it is therefore proposed to use the thermoplastic bonding films of the invention.
  • This composite structure manufacturing process comprising a step of assembling at least a first element and a second element by the action of a layer of resin glue or foam between the joining surfaces of the two elements is characterized by the fact that at least between the adhesive layer and the joining surface of the first element is interposed a thermoplastic adhesive film of the invention.
  • the method of the invention allows the assembly of a first element 1 and a second element 2, according to their respective junction surfaces 3 and 4, by means of 'a layer of glue 5 interposed between said junction surfaces 3 and 4.
  • the second element 2 is assumed to be compatible with the glue 5, that is to say that the glue 5 has good adhesion on the second element 2.
  • the first element 1 is made of a material which may not have good compatibility with the adhesive 5, that is to say that the adhesive 5 does not have good adhesion on the junction surface. 3 of the first element 1.
  • the first element 1 not having a good adhesion power with the adhesive 5, one interposes between the layer of adhesive 5 and the junction surface 3 of the first element 1 a film 6 composed of a mixture of the invention, that is to say a mixture of thermoplastic elastomer (s) based on polyamide and of modified olefin copolymer; said mixture being such that the thermoplastic elastomer (s) therein represents at least 50% of the total weight of the mixture as defined before.
  • a mixture of the invention that is to say a mixture of thermoplastic elastomer (s) based on polyamide and of modified olefin copolymer; said mixture being such that the thermoplastic elastomer (s) therein represents at least 50% of the total weight of the mixture as defined before.
  • FIGS. 1 to 4 a first possibility, represented in FIGS. 1 to 4, consists in coating the joining surface 4 of the second element 2 with an adhesive 5, as shown in FIG. 3, before assembly by pressing the adhesive layer 5 against the film 6 and obtaining the assembly shown in FIG. 4.
  • a second way of ensuring the joining between the film and the second element 2 can be provided in the case where the second element 2 comprises a junction surface 4 based on thermosetting resin which is not entirely crosslinked.
  • the second element 2 may be a reinforcing element pre-impregnated with resin. It is then possible to apply the junction surface 4 of the second element 2 directly against the film 6, and, by heating, the not entirely crosslinked resin of the second element 2 itself ensures the bonding function, the adhesion being obtained by complementing crosslinking of said resin.
  • the resins generally used are epoxy resins, or polyesters or polyurethane.
  • a film 6 based on polyetheresteramide at least 50%, preferably 60% by weight, and of maleized ethylene propylene copolymer (EPR) can advantageously be used.
  • This embodiment allows, for example, to ensure the bonding by an epoxy adhesive, a polyester or polyurethane adhesive of a first element 1, the junction surface of which is made of one of the following materials: polyamide, polyethylene, polyethylene terephthalate, polybutadiene terephthalate, polypropylene, treated aluminum, aluminum alloy or steel.
  • a film 6 of the invention allows the bonding of a first element 1 consisting of a polyamide film 11 for example by an adhesive 5 made of epoxy resin on a support 2.
  • Element 1 can advantageously be used as an upper element for decorating and protecting a ski, for example.
  • the support 2 can be a mechanical reinforcing element consisting of a reinforcing textile web woven or not made of glass fiber, carbon, aramid or other, or even a metallic reinforcing element of steel, aluminum or a alloy.
  • the assembly is carried out in successive stages: during a first stage illustrated in FIGS. 1 and 2, assembly is carried out by calendering or hot pressing, or co-extrusion , the film 6 on the junction surface 3 of the first element 1 having a lack of adhesion with the adhesive 5; the temperature must be raised to the softening point of the film; during a second step, the adhesive 5 is applied to the junction surface 4 of the second element 2, as shown in Figure 6; during a third step, the layers formed by the adhesive 5 and the film 6 are applied against one another, carrying out the assembly as shown in FIG. 4.
  • a third embodiment of the invention represented by FIG. 7 consists in assembling elements of the structure of a ski 1 and 2 by injection of a thermosetting foam 5 of polyurethane and expandable type. Since the foam 5 is not compatible with all of the elements to be assembled, adhesion is therefore ensured by the interposition of a bonding film 6 between the foam and the element to be bonded. Thus, a first element 1 of ski structure, a bonding film 6 and then a second element 2 are placed beforehand in a mold 8. Then, the polyurethane foam 5 is injected which, after its expansion and then hardening phase, adheres perfectly to the bonding film 6 and to the first element 1.
  • the heat released by the exothermic reaction is generally sufficient to bring the bonding film to its softening point and to cause bonding on the structural element.
  • a calorific supplement after or during the molding operation.
  • the tubular casing 61 has the advantage of ensuring the impermeability to any overflow of the foam.
  • a fabric / film complex is first produced in a machine for laminating at least one layer of fabrics, and of a film according to the invention, and optionally of a layer of foam.
  • the complex thus produced is placed in a mold and a thermosetting type foam, preferably polyurethane, is injected.
  • the "in situ" expansion reaction of the constituents of the foam causes adhesion to the complex.
  • the extrusion temperature is between 200 and 220 ° C and the extruder flow rate is fixed at 30 kg / h.
  • the composition obtained in the form of rods with an average particle size equal to approximately 3 mm has a Melt Index (MI) of 1.31 measured at 190 ° C. under a load of 2.16 kg according to standard ASTM D1238.
  • the maleized EPR used contains 70% ethylene. Its total anhydride level is between 1.08 and 1.5% and its Melt Index (measured at 230 ° C under a load of 10 kg) is equal to 9.
  • composition I is extruded.
  • the extrusion conditions are as follows: - extrusion temperature: 184 ° C / 206 ° C / 215 ° C - channel temperature: 231 ° C / 236 ° C - die temperature: 228 ° C / 236 ° C
  • the screw speed is 80 rpm and the drawing speed is 20 m / min.
  • a film of thickness equal to approximately 50 ⁇ m is obtained.
  • composition II is compounded consisting of 70 parts of polyetheresteramide (A2) and 30 parts of EPR m (B1).
  • composition II is extruded under conditions identical to those described in I.
  • composition III is composed consisting of 90 parts of polyetheresteramide (A2) and 10 parts of EPR m (B2).
  • the EPR m (B2) used contains 50% ethylene. Its total anhydride level is equal to 1.26% and its Melt Index (measured at 230 ° C under a load of 2.16 kg) is equal to 3.
  • the Shore D hardness (5s) of III measured according to ISO standard 868, is equal to 60.6.
  • the tensile breaking stress measured according to standard ASTM D638, is equal to 20.9 MPa.
  • the modulus of elasticity in flexion at 20 ° C measured according to standard ASTM D790, is equal to 357 MPa.
  • the tear resistance measured according to ISO standard 34 (tear parallel to injection) is equal to 147.4 kN / m.
  • composition III is extruded under the same conditions as those described in I.

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  • Laminated Bodies (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Golf Clubs (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a method of bonding the structural components of a ski, consisting in assembling at least a first element (1) and a second element (2) by the action of a layer of adhesive bonding material (5), of resin or of foam, interposing at least between the layer of adhesive bonding material (5) and the junction surface of the first component (1) a thermoplastic film (6), suitable for bonding, composed of a mixture of one or more thermoplastic elastomer(s) based on polyamide and of an olefin copolymer consisting of at least two different olefin monomers. The mixture is such that the thermoplastic elastomer(s) represents (represent) at least 50 % and preferably at least 60 % of the total weight of the mixture. <IMAGE>

Description

La présente invention a pour objet des films aptes au collage, thermoplastiques composés d'un mélange d'élastomère thermoplastique (TPE) à base de polyamide et de copolymère d'oléfines modifié, ainsi que le procédé de collage d'éléments de la structure d'un ski utilisant lesdits films thermoplastiques.The present invention relates to films suitable for bonding, thermoplastics composed of a mixture of thermoplastic elastomer (TPE) based on polyamide and modified olefin copolymer, as well as the method of bonding elements of the structure d 'a ski using said thermoplastic films.

Dans les films thermoplastiques, on rencontre notamment les films "hot melts". On peut citer les adhésifs décrits dans la demande FR 2 523 143, et dont la composition contient des copolymères à base d'éthylène (au moins 35 % en poids) et d'au moins un ester vinylique et contenant de 0,5 à 20 % d'un copolyétheresteramide.In thermoplastic films, there are in particular "hot melts" films. Mention may be made of the adhesives described in application FR 2 523 143, and the composition of which contains copolymers based on ethylene (at least 35% by weight) and at least one vinyl ester and containing from 0.5 to 20 % of a copolyetheresteramide.

Dans la demande de brevet européenne n° 312 968, on a décrit l'utilisation de films de collage "hot melt" pour l'assemblage d'éléments de la structure d'un ski. Ces films sont principalement constitués d'un polymère thermoplastique et d'un promoteur d'adhésion tel qu'un silane ou une résine époxyde.In European patent application No. 312 968, the use of "hot melt" bonding films has been described for the assembly of elements of the structure of a ski. These films mainly consist of a thermoplastic polymer and an adhesion promoter such as a silane or an epoxy resin.

La présente invention a pour objet de proposer un film de composition nouvelle, apte au collage, présentant des propriétés d'adhésion amélioriées et pouvant s'appliquer à une plus large gamme de matériaux.The object of the present invention is to provide a film of new composition, suitable for bonding, having improved adhesion properties and which can be applied to a wider range of materials.

Un autre objet de l'invention est d'améliorer la tenue thermique du collage du laminé ainsi formé.Another object of the invention is to improve the thermal resistance of the bonding of the laminate thus formed.

Enfin, les films de l'invention sont d'un coût de fabrication et de mise en oeuvre plus économique que ceux actuellement connus.Finally, the films of the invention are more costly to manufacture and use than those currently known.

La présente invention concerne donc, des films ou feuilles thermoplastiques, aptes au collage, composés d'un mélange d'élastomère(s) thermoplastique(s) (TPE) à base de polyamide et d'un copolymère d'oléfines modifié constitué d'au moins deux monomères différents d'oléfines ; ledit mélange étant tel que le(s) élastomère(s) thermoplastiques(s) y représente(nt) au moins 50% et de préférence au moins 60% du poids total.The present invention therefore relates to thermoplastic films or sheets, suitable for bonding, composed of a mixture of thermoplastic elastomer (s) (TPE) based on polyamide and of a modified olefin copolymer consisting of at least two different olefin monomers; said mixture being such that the thermoplastic elastomer (s) therein represent (s) at least 50% and preferably at least 60% of the total weight.

Les élastomères thermoplastiques ou TPE à base de polyamide peuvent être des copolymères statistiques ou séquencés.The thermoplastic or TPE elastomers based on polyamide can be random or block copolymers.

Les copolymères sont formés par l'enchaînement aléatoire des divers constituants (monomères et/ou prépolymères) tandis que les copolymères séquencés ou blocs préférés par la demanderesse, sont formés à partir de blocs présentant une certaine longueur de chaîne de leurs divers constituants.The copolymers are formed by the random sequence of the various constituents (monomers and / or prepolymers) while the block copolymers or blocks preferred by the applicant, are formed from blocks having a certain chain length of their various constituents.

Les copolymères à base de polyamide selon l'invention sont soit des polyesteramides soit des polyétheramides.The polyamide-based copolymers according to the invention are either polyesteramides or polyetheramides.

Les polyétheramides séquencés ou polyéther bloc amides peuvent notamment résulter de la copolycondensation de séquences polyamides à extrémités réactives avec des séquences polyéthers à extrémités réactives, telles que, entre autre :

  • a) Séquences polyamides à bouts de chaînes diamines avec des séquences polyoxalkylènes à bouts de chaînes dicarboxliques.
  • b) Séquences polyamides à bouts de chaînes dicarboxyliques avec des séquences polyoxyalkykènes à bouts de chaînes diamines obtenues par cyanoéthylation et hydrogénation de séquences polyoxyalkylènes alpha, oméga, dihydroxylées aliphatiques appelées polyétherdiols.
  • c) Séquences polyamides à bouts de chaînes dicarboxyliques avec des polyétherdiols, appelés polyétheresteramides particulièrement préférés par la demanderesse.
The block polyetheramides or polyether block amides can in particular result from the copolycondensation of polyamide sequences with reactive ends with polyether sequences with reactive ends, such as, inter alia:
  • a) Polyamide sequences at the ends of diamine chains with polyoxalkylene sequences at the ends of dicarboxylic chains.
  • b) Polyamide sequences at the ends of dicarboxylic chains with polyoxyalkykene sequences at the ends of diamine chains obtained by cyanoethylation and hydrogenation of alpha, omega, dihydroxylated aliphatic sequences called polyetherdiols.
  • c) Polyamide sequences at the ends of dicarboxylic chains with polyetherdiols, called polyetheresteramides which are particularly preferred by the applicant.

La composition et la fabrication de tels polyétheresteramides ont été décrites dans les brevets français n° 2 273 021 et 2 401 947 dont le contenu s'ajoute à la présente description.The composition and manufacture of such polyetheresteramides have been described in French patents No. 2,273,021 and 2,401,947, the content of which is added to the present description.

La masse moléculaire moyenne en nombre de ces séquences polyamides est généralement comprise entre 500 et 10 000 et plus particulièrement entre 600 et 5 000. Les séquences polyamides des polyétheresteramides sont formées de préférence de polyamides aliphatique et/ou de polyamide amorphe ou de copolyamide résultant de la polycondensation de leurs monomères.The number-average molecular mass of these polyamide blocks is generally between 500 and 10,000 and more particularly between 600 and 5,000. The polyamide blocks of the polyetheresteramides are preferably formed from aliphatic polyamides and / or from amorphous polyamide or from copolyamide resulting from polycondensation of their monomers.

La masse moléculaire moyenne en nombre des polyéthers est comprise généralement entre 200 et 6000 et plus particulièrement entre 600 et 3000.The number average molecular weight of the polyethers is generally between 200 and 6000 and more particularly between 600 and 3000.

Les séquences polyéthers consistent le plus souvent en polytétraméthylène glycol (PTMG), polyéthylène glycol (PEG) et/ou de polypropylène glycol (PPG).The polyether blocks most often consist of polytetramethylene glycol (PTMG), polyethylene glycol (PEG) and / or polypropylene glycol (PPG).

La viscosité inhérente des polyétheresteramides est avantageusement comprise entre 0,8 et 2,05. Elle est mesurée dans le métacrésol à 20°C avec une concentration initiale de 0,5 g de polymère pour 100 g de métacrésol.The inherent viscosity of polyetheresteramides is advantageously between 0.8 and 2.05. It is measured in metacresol at 20 ° C with an initial concentration of 0.5 g of polymer per 100 g of metacresol.

Les polyétheresteramides peuvent être formés de 5 à 85 % en poids de polyéther, de 95 à 15 % en poids de polyamide, et de préférence de 30 à 85 % en poids de polyéther et de 70 à 15 % en poids de polyamide.The polyetheresteramides can be formed from 5 to 85% by weight of polyether, from 95 to 15% by weight of polyamide, and preferably from 30 to 85% by weight of polyether and from 70 to 15% by weight of polyamide.

Les polyétheresteramides préférés par la demanderesse sont ceux dont les séquences polyamides sont essentiellement consitutées de PA-11, 12 et/ou 12.12 et lorsque l'on recherche une composition ayant des propriétés antistatiques, on utilise de préférence des polyetheresteramides dont les séquences polyéthers sont essentiellement constituées de polyéthylène glycol (PEG).The polyetheresteramides preferred by the applicant are those whose polyamide sequences are essentially made up of PA-11, 12 and / or 12.12 and when a composition having antistatic properties is sought, polyetheresteramides whose polyether blocks are essentially used are preferably used made of polyethylene glycol (PEG).

Le second composé entrant dans la composition du film est un copolymère d'oléfines modifié constitué d'au moins deux monomères différents d'oléfines .The second compound used in the composition of the film is a modified olefin copolymer made up of at least two different olefin monomers.

Les oléfines représentent au moins 50 % et de préférence au moins 60 % du poids total du copolymère, étant entendu que les copolymères peuvent être polymérisés de façon statistique ou séquencée et présenter une structure linéaire ou ramifiée, pour les polyoléfines modifiées selon l'invention.The olefins represent at least 50% and preferably at least 60% of the total weight of the copolymer, it being understood that the copolymers can be polymerized in a statistical or sequenced fashion and have a linear or branched structure, for the polyolefins modified according to the invention.

Parmi les copolymères particulièrement préférés par la demanderesse, on citera tout particulièrement les copolymères d'éthylène et de propylène greffés par un acide carboxylique ou anhydre d'acide carboxylique ou un sel d'acide.Among the copolymers which are particularly preferred by the applicant, mention will be made most particularly of the copolymers of ethylene and of propylene grafted with a carboxylic acid or anhydrous carboxylic acid or an acid salt.

Parmi les acides, on choisira plus particulièrement les acides dicarboxyliques insaturés, tels que l'acide maléique, fumarique, itaconique par exemple. Les anhydres et sels choisis sont ceux correspondant aux acides cités bien entendu.Among the acids, the unsaturated dicarboxylic acids will be chosen more particularly, such as maleic, fumaric, itaconic acid for example. The anhydrous and salts chosen are those corresponding to the acids mentioned, of course.

On citera également parmi ces copolymères : les éthylène/propylène/diène maléisés (EPDM).Among these copolymers, mention will also be made of: ethylene / propylene / maleic diene (EPDM).

Les films ou feuilles particulièrement préférés par la demanderesse sont constitués d'un mélange de polyétheresteramide à au moins 50 % en poids (de préférence 60 %) et de copolymère d'éthylène propylène contenant 0,1 à 2 % en poids d'anhydre maléique greffé.The films or sheets particularly preferred by the applicant consist of a mixture of polyetheresteramide at least 50% by weight (preferably 60%) and of ethylene propylene copolymer containing 0.1 to 2% by weight of maleic anhydride graft.

Aux compositions des films décrits ci-dessus, on peut incorporer divers autres constituants tels que des charges, des pigments ou colorants, divers additifs.In the compositions of the films described above, it is possible to incorporate various other constituents such as fillers, pigments or dyes, various additives.

A titre d'exemple de charges, on peut citer les fibres de verre, de carbone, aramide, le talc, la silice, le kaolin, les billes et fibres de verre, les céramiques, les charges métalliques, les sels et les oxydes métalliques, tels que poudre d'aluminium, carbonates de calcium et de manganèse, poudre de ferrite, oxyde de titane.By way of example of fillers, mention may be made of glass fibers, carbon fibers, aramid fibers, talc, silica, kaolin, glass beads and fibers, ceramics, metallic fillers, metal salts and oxides. , such as aluminum powder, calcium and manganese carbonates, ferrite powder, titanium oxide.

En général, on peut incorporer jusqu'à 50 % et de préférence jusqu'à 40 % en poids de charges par rapport aux compositions d'élastomère(s) thermoplastique(s) et de copolymère d'oléfines modifié.In general, up to 50% and preferably up to 40% by weight of fillers can be incorporated relative to the compositions of thermoplastic elastomer (s) and of modified olefin copolymer.

A titre d'exemple d'additifs, on peut citer des agents anti-UV, des agents démoulants, des modifiants choc.By way of example of additives, mention may be made of anti-UV agents, release agents, impact modifiers.

Les films ou feuilles selon l'invention sont obtenus selon tout procédé d'extrusion connu tel que l'extrusion-calandrage à plat, l'extrusion-plaxage, l'extrusion-soufflage, la température d'extrusion étant en général comprise entre 190 et 250°C.The films or sheets according to the invention are obtained according to any known extrusion process such as extrusion-calendering flat, extrusion-plaxing, extrusion-blowing, the extrusion temperature generally being between 190 and 250 ° C.

Selon Modern Plastics Enclopedia, on réserve le terme "film" à des objets de section plane dont l'épaisseur est inférieure à 250 microns et le terme "feuille" à des objets d'épaisseur supérieure et pouvant atteindre plusieurs mm, mais dans tout ce qui suit, et pour des raisons de simplification, on pourra utiliser l'un ou l'autre des termes pour désigner simultanément films et feuilles.According to Modern Plastics Enclopedia, the term "film" is reserved for objects of planar section whose thickness is less than 250 microns and the term "sheet" for objects of greater thickness and up to several mm, but in all this which follows, and for reasons of simplification, one or the other of the terms may be used to designate films and sheets simultaneously.

Les films selon l'invention peuvent être utilisés tels quels mais peuvent également intervenir dans la fabrication de films multicouches obtenus par exemple par co-extrusion, contre-collage à chaud.The films according to the invention can be used as such but can also be used in the manufacture of multilayer films obtained for example by co-extrusion, hot lamination.

Les films mono-couche sont particulièrement aptes au collage sur tissus et matériaux non tissés, au revêtement de fibres naturelles ou synthétiques, de mousse.Single-layer films are particularly suitable for bonding to fabrics and non-woven materials, for coating natural or synthetic fibers, and foam.

Les films multicouches particulièrement préférés par la demanderesse comprennent :

  • une couche de polyamide aliphatique (tel que PA-6, PA-6.6, PA-11,PA-12, PA-12.12), de polyamide amorphe d'élastomère thermoplastique à base de polyamide et/ou de copolymère d'éthylène et d'alcool vinylique (EVOH)
  • un film selon l'invention.
The multilayer films particularly preferred by the applicant include:
  • a layer of aliphatic polyamide (such as PA-6, PA-6.6, PA-11, PA-12, PA-12.12), of amorphous polyamide of thermoplastic elastomer based on polyamide and / or copolymer of ethylene and d vinyl alcohol (EVOH)
  • a film according to the invention.

Ces films peuvent être collés sur des pièces rigides et notamment sur des pièces métalliques (telles que des câbles, tôles) ainsi que sur des matériaux synthétiques de préférence à base de, recouverts ou imprégnés de résine(s) époxyde(s) et/ou polyester(s) et/ou polyuréthane(s).These films can be bonded to rigid parts and in particular to metal parts (such as cables, sheets) as well as to synthetic materials preferably based on, covered or impregnated with epoxy resin (s) and / or polyester (s) and / or polyurethane (s).

Le procédé de fabrication de ces matériaux composites se déroule en général en deux étapes :
   On procède d'abord à la co-extrusion du film bi-couche puis on le colle à chaud du côté de la couche de composition selon l'invention, sur le support en matière synthétique par exemple, par formage à chaud ou thermoformage.The manufacturing process for these composite materials generally takes place in two stages:
The co-extrusion of the bi-layer film is first carried out and then it is hot-glued on the side of the composition layer according to the invention, on the support of synthetic material for example, by hot forming or thermoforming.

Ces matériaux composites peuvent être décorés selon la méthode d'impression de transfert d'encres sublimables et notamment selon les procédés décrits dans la demande de brevet FR 2 596 286. La décoration de ces matériaux peut également être mise en oeuvre selon d'autres techniques telles que par sérigraphie, peinture ou vernissage, transfert à chaud, tampographie, jet d'encre, marquage laser.These composite materials can be decorated using the sublimable ink transfer printing method and in particular according to the methods described in patent application FR 2 596 286. The decoration of these materials can also be carried out using other techniques such as screen printing, painting or varnishing, hot transfer, pad printing, inkjet, laser marking.

Les matériaux composites constitués du film bi-couche décrit ci-dessus et d'un support imprégné de résine(s) époxyde(s) et/ou polyester et/ou polyuréthane éventuellement décorés sont particulièrement adaptés pour la réalisation de dessus de ski, de planche à voile, à roulettes, planche de surf, coques de bateau, panneaux de décoration pour bas de carrosserie automobile, laminés anti-bruit ou d'isolation thermique.The composite materials made up of the two-layer film described above and of a support impregnated with epoxy resin (s) and / or polyester and / or polyurethane possibly decorated are particularly suitable for the production of ski tops, windsurfing, skateboarding, surfboard, boat hulls, decorative panels for automobile bodywork, noise or thermal insulation laminates.

Les films mono-couches peuvent également servir de liant de co-extrusion pour films multicouches permettant de faire adhérer des couches dont le collage est difficile voire impossible.Monolayer films can also serve as co-extrusion binder for multilayer films allowing adhesion of layers whose bonding is difficult or even impossible.

A titre d'exemple, on peut citer l'utilisation de films de composition selon l'invention comme liant de co-extrusion d'un film à base de polycarbonate (PC) d'une part et d'un film à base de copolymère d'éthylène et d'alcool vinylique (EVOH) d'autre part.By way of example, mention may be made of the use of films of composition according to the invention as co-extrusion binder of a film based on polycarbonate (PC) on the one hand and of a film based on copolymer ethylene and vinyl alcohol (EVOH) on the other hand.

La présente invention concerne également le procédé de fabrication d'un ski utilisé en sports d'hiver et plus particulièrement au collage d'éléments de la structure d'un ski, et à un ski obtenu selon ce procédé.The present invention also relates to the method of manufacturing a ski used in winter sports and more particularly to the bonding of elements of the structure of a ski, and to a ski obtained by this method.

Le caractère composite d'une structure de ski conduit à réaliser le ski par assemblage de plusieurs éléments préalablement enduits ou imprégnés d'une colle thermodurcissable de type époxyde, polyester ou d'une mousse polyuréthane par exemple. Naturellement, cette colle doit être compatible avec tous les éléments à assembler. Ces liants ne suffisent généralement pas à faire adhérer tous les matériaux que l'on souhaite utiliser dans la composition d'un ski. Pour obtenir l'adhérence sur certains matériaux, on se propose donc d'utiliser les films de collage thermoplastiques de l'invention.The composite nature of a ski structure leads to skiing by assembling several elements previously coated or impregnated with a thermosetting adhesive of the epoxy, polyester or polyurethane foam type, for example. Naturally, this adhesive must be compatible with all the elements to be assembled. These binders are generally not sufficient to adhere all the materials that one wishes to use in the composition of a ski. To obtain adhesion to certain materials, it is therefore proposed to use the thermoplastic bonding films of the invention.

Ce procédé de fabrication à structure composite comprenant une étape d'assemblage d'au moins un premier élément et un second élément par action d'une couche de colle de résine ou de mousse entre les surfaces de jonction des deux éléments se caractérise par le fait que l'on interpose au moins entre la couche de colle et la surface de jonction du premier élément un film de collage thermoplastique de l'invention.This composite structure manufacturing process comprising a step of assembling at least a first element and a second element by the action of a layer of resin glue or foam between the joining surfaces of the two elements is characterized by the fact that at least between the adhesive layer and the joining surface of the first element is interposed a thermoplastic adhesive film of the invention.

D'autres objets, caractéristiques et avantages ressortiront de la description des modes de réalisation particuliers, faite en relation avec les figures jointes, parmi lesquelles :

  • les figures 1 à 4 illustrent un procédé d'assemblage par collage selon un premier mode de réalisation de l'invention ;
  • les figures 5 à 6 illustrent un procédé d'assemblage par collage selon un second mode de réalisation de l'invention ;
  • les figures 7 et 8 illustrent un procédé d'assemblage par collage selon un autre mode de réalisation.
Other objects, characteristics and advantages will emerge from the description of the particular embodiments, made in relation to the attached figures, among which:
  • Figures 1 to 4 illustrate a bonding method according to a first embodiment of the invention;
  • Figures 5 to 6 illustrate a method of assembly by gluing according to a second embodiment of the invention;
  • Figures 7 and 8 illustrate a method of assembly by gluing according to another embodiment.

Dans le mode de réalisation représenté sur les figures 1 à 4, le procédé de l'invention permet l'assemblage d'un premier élément 1 et d'un second élément 2, selon leurs surfaces de jonction respective 3 et 4, au moyen d'une couche de colle 5 interposée entre lesdites surfaces de jonction 3 et 4. Le second élément 2 est supposé compatible avec la colle 5, c'est-à-dire que la colle 5 présente un bon pouvoir d'adhésion sur le second élément 2. Par contre, le premier élément 1 est en une matière pouvant ne pas présenter une bonne compatibilité avec la colle 5, c'est-à-dire que la colle 5 ne présente pas un bon pouvoir d'adhésion sur la surface de jonction 3 du premier élément 1.In the embodiment shown in Figures 1 to 4, the method of the invention allows the assembly of a first element 1 and a second element 2, according to their respective junction surfaces 3 and 4, by means of 'a layer of glue 5 interposed between said junction surfaces 3 and 4. The second element 2 is assumed to be compatible with the glue 5, that is to say that the glue 5 has good adhesion on the second element 2. On the other hand, the first element 1 is made of a material which may not have good compatibility with the adhesive 5, that is to say that the adhesive 5 does not have good adhesion on the junction surface. 3 of the first element 1.

Pour permettre l'assemblage du premier élément 1 avec le second élément 2, le premier élément 1 n'ayant pas un bon pouvoir d'adhérence avec la colle 5, on interpose entre la couche de colle 5 et la surface de jonction 3 du premier élément 1 un film 6 composé d'un mélange de l'invention, c'est-à-dire un mélange d'élastomère(s) thermoplastique(s) à base de polyamide et de copolymère d'oléfines modifié ; ledit mélange étant tel que le(s) élastomère(s) thermoplastique(s) y représente au moins 50% du poids total du mélange tel que défini avant.To allow the assembly of the first element 1 with the second element 2, the first element 1 not having a good adhesion power with the adhesive 5, one interposes between the layer of adhesive 5 and the junction surface 3 of the first element 1 a film 6 composed of a mixture of the invention, that is to say a mixture of thermoplastic elastomer (s) based on polyamide and of modified olefin copolymer; said mixture being such that the thermoplastic elastomer (s) therein represents at least 50% of the total weight of the mixture as defined before.

En ce qui concerne la présence de la colle 5, une première possibilité, représentée sur les figures 1 à 4, consiste à enduire la surface de jonction 4 du second élément 2 d'une colle 5, comme le représente la figure 3, avant assemblage par pressage de la couche de colle 5 contre le film 6 et obtention de l'ensemble représenté sur la figure 4.As regards the presence of the adhesive 5, a first possibility, represented in FIGS. 1 to 4, consists in coating the joining surface 4 of the second element 2 with an adhesive 5, as shown in FIG. 3, before assembly by pressing the adhesive layer 5 against the film 6 and obtaining the assembly shown in FIG. 4.

Une seconde façon d'assurer la solidarisation entre le film et le second élément 2 peut être prévue dans le cas où le second élément 2 comporte une surface de jonction 4 à base de résine thermodurcissable non-entièrement réticulée. Il peut s'agir, dans ce cas particulier, d'un élément de renfort pré-imprégné de résine. On peut alors appliquer la surface de jonction 4 du second élément 2 directement contre le film 6, et, par chauffage, la résine non entièrement réticulée du second élément 2 assure elle-même la fonction de collage, l'adhésion étant obtenue par complément de réticulation de ladite résine.A second way of ensuring the joining between the film and the second element 2 can be provided in the case where the second element 2 comprises a junction surface 4 based on thermosetting resin which is not entirely crosslinked. In this particular case, it may be a reinforcing element pre-impregnated with resin. It is then possible to apply the junction surface 4 of the second element 2 directly against the film 6, and, by heating, the not entirely crosslinked resin of the second element 2 itself ensures the bonding function, the adhesion being obtained by complementing crosslinking of said resin.

Les résines généralement utilisées sont des résines époxydes, ou polyesters ou polyuréthane.The resins generally used are epoxy resins, or polyesters or polyurethane.

On peut avantageusement utiliser un film 6 à base de polyétheresteramide à au moins 50 %, de préférence 60% en poids, et de copolymère d'éthylène propylène (EPR) maléisé.A film 6 based on polyetheresteramide at least 50%, preferably 60% by weight, and of maleized ethylene propylene copolymer (EPR) can advantageously be used.

Ce mode de réalisation permet, par exemple, d'assurer le collage par une colle époxyde, une colle polyester ou polyuréthane d'un premier élément 1 dont la surface de jonction est constituée de l'un des matériaux suivants : polyamide, polyéthylène, polyéthylène téréphtalate, polybutadiène téréphtalate, polypropylène, aluminium traité, alliage d'aluminium ou acier.This embodiment allows, for example, to ensure the bonding by an epoxy adhesive, a polyester or polyurethane adhesive of a first element 1, the junction surface of which is made of one of the following materials: polyamide, polyethylene, polyethylene terephthalate, polybutadiene terephthalate, polypropylene, treated aluminum, aluminum alloy or steel.

A titre d'exemple, l'utilisation d'un film 6 de l'invention permet le collage d'un premier élément 1 constitué d'un film en polyamide 11 par exemple par une colle 5 en résine époxyde sur un support 2. L'élément 1 peut avantageusement être utilisé comme élément supérieur de décoration et de protection d'un ski par exemple. Dans ce cas particulier, le support 2 peut être un élément de renfort mécanique constitué d'une nappe textile de renfort tissée ou non en fibre de verre, carbone, aramide ou autre, ou encore un élément de renfort métallique en acier, aluminium ou un alliage.By way of example, the use of a film 6 of the invention allows the bonding of a first element 1 consisting of a polyamide film 11 for example by an adhesive 5 made of epoxy resin on a support 2. Element 1 can advantageously be used as an upper element for decorating and protecting a ski, for example. In this particular case, the support 2 can be a mechanical reinforcing element consisting of a reinforcing textile web woven or not made of glass fiber, carbon, aramid or other, or even a metallic reinforcing element of steel, aluminum or a alloy.

Dans le mode de réalisation représenté sur les figures 1 à 4, l'assemblage s'effectue par étapes successives : au cours d'une première étape illustrée par les figures 1 et 2 on assemble par calandrage ou pressage à chaud, ou co-extrusion, le film 6 sur la surface de jonction 3 du premier élément 1 présentant un défaut d'adhérence avec la colle 5 ; la température doit être élevée au niveau du point de ramolissement du film ; au cours d'une seconde étape, on applique la colle 5 sur la surface de jonction 4 du second élément 2, comme le représente la figure 6 ; au cours d'une troisième étape, on applique l'une contre l'autre les couches constituées par la colle 5 et le film 6, réalisant l'assemblage tel que représenté sur la figure 4.In the embodiment represented in FIGS. 1 to 4, the assembly is carried out in successive stages: during a first stage illustrated in FIGS. 1 and 2, assembly is carried out by calendering or hot pressing, or co-extrusion , the film 6 on the junction surface 3 of the first element 1 having a lack of adhesion with the adhesive 5; the temperature must be raised to the softening point of the film; during a second step, the adhesive 5 is applied to the junction surface 4 of the second element 2, as shown in Figure 6; during a third step, the layers formed by the adhesive 5 and the film 6 are applied against one another, carrying out the assembly as shown in FIG. 4.

Dans le mode de réalisation représenté sur les figures 5 et 6, on dispose tous les éléments dans un moule, c'est-à-dire dans l'ordre : le premier élément 1, le film 6, la couche de colle 5, le second élément 2 ; par pressage à chaud, on applique tous les éléments les uns sur les autres, et on réalise l'assemblage en une étape. La température de l'ensemble doit également être élevée au niveau du point de ramollissement du film.In the embodiment shown in FIGS. 5 and 6, all the elements are placed in a mold, that is to say in order: the first element 1, the film 6, the layer of adhesive 5, the second element 2; by hot pressing, all the elements are applied to each other, and the assembly is carried out in one step. The temperature of the assembly must also be raised to the level of the softening point of the film.

Un troisième mode de réalisation de l'invention représenté par la figure 7 consiste à assembler des éléments de la structure d'un ski 1 et 2 par injection d'une mousse thermodurcissable 5 de type polyuréthane et expansible. La mousse 5 n'étant pas compatible avec tous les éléments à assembler, on assure donc l'adhésion par l'interposition d'un film de collage 6 entre la mousse et l'élément à coller. Ainsi, on dispose préalablement un premier élément 1 de structure de ski, un film de collage 6 puis un second élément 2 dans un moule 8. Puis, on injecte la mousse 5 de polyuréthane qui, après sa phase d'expansion puis de durcissement, adhère parfaitement au film de collage 6 et au premier élément 1. La chaleur dégagée par la réaction d'exothermie suffit généralement à porter le film de collage à son point de ramolissement et à entraîner le collage sur l'élément de structure. Mais l'on peut, bien entendu, apporter un complément calorifique après ou pendant l'opération de moulage. Bien entendu, on peut envisager de la même façon la disposition d'un film de collage 6 selon l'invention entre la mousse 5 et le second élément 2 lorsque celui-ci ne représente également aucun pouvoir d'adhésion ou un faible pouvoir d'adhésion avec la mousse. Dans ce cas, on peut prévoir que le film se présente sous la forme particulière d'une enveloppe tubulaire 61 dans laquelle est injectée la mousse 5, comme le montre la figure 8. L'enveloppe tubulaire 61 a pour avantage d'assurer l'imperméabilité à un éventuel débordement de la mousse.A third embodiment of the invention represented by FIG. 7 consists in assembling elements of the structure of a ski 1 and 2 by injection of a thermosetting foam 5 of polyurethane and expandable type. Since the foam 5 is not compatible with all of the elements to be assembled, adhesion is therefore ensured by the interposition of a bonding film 6 between the foam and the element to be bonded. Thus, a first element 1 of ski structure, a bonding film 6 and then a second element 2 are placed beforehand in a mold 8. Then, the polyurethane foam 5 is injected which, after its expansion and then hardening phase, adheres perfectly to the bonding film 6 and to the first element 1. The heat released by the exothermic reaction is generally sufficient to bring the bonding film to its softening point and to cause bonding on the structural element. However, it is of course possible to add a calorific supplement after or during the molding operation. Of course, it is possible to envisage in the same way the arrangement of a bonding film 6 according to the invention between the foam 5 and the second element 2 when the latter also represents no adhesion power or a low adhesion power. adhesion with foam. In this case, provision can be made for the film to be in the particular form of a tubular casing 61 into which the foam 5 is injected, as shown in FIG. 8. The tubular casing 61 has the advantage of ensuring the impermeability to any overflow of the foam.

On comprendra que la présente invention n'est pas limitée aux modes de réalisation particuliers qui ont été explicitement décrits et que son étendue comprend les divers procédés de collage d'éléments dans d'autres applications couvrant d'autres domaines tels que ceux de l'équipement automobile, des laminés anti-bruits ou d'isolation thermique, des semelles de chaussures, des combinaisons isothermiques, etc...It will be understood that the present invention is not limited to the particular embodiments which have been explicitly described and that its scope includes the various methods of bonding elements in other applications covering other fields such as those of automotive equipment, anti-noise or thermal insulation laminates, shoe soles, wetsuits, etc.

A titre d'exemple, on peut citer l'application de l'utilisation de ces films de collage à la réalisation de produits en mousse recouverts de tissus selon la technique connue du "Foam baking". On réalise dans un premier temps un complexe tissu/film en machine de lamination d'au moins une couche de tissus, et d'un film selon l'invention, et éventuellement d'une couche de mousse. On dispose le complexe ainsi réalisé dans un moule et l'on injecte une mousse de type thermodurcissable de préférence polyuréthane. La réaction d'expansion "in situ" des constituants de la mousse provoque l'adhésion sur le complexe.By way of example, mention may be made of the application of the use of these bonding films to the production of foam products covered with fabrics according to the known technique of "Foam baking". A fabric / film complex is first produced in a machine for laminating at least one layer of fabrics, and of a film according to the invention, and optionally of a layer of foam. The complex thus produced is placed in a mold and a thermosetting type foam, preferably polyurethane, is injected. The "in situ" expansion reaction of the constituents of the foam causes adhesion to the complex.

Les exemples suivants illustrent l'invention sans toutefois la limiter :
   Sauf indication contraire dans tout ce qui suit, les proportions des constituants sont données en poids.The following examples illustrate the invention without however limiting it:
Unless otherwise indicated in all that follows, the proportions of the constituents are given by weight.

Exemple IExample I

Dans une extrudeuse mono-vis dont la vitesse de la vis est réglée à 33 trs/mn, on compounde 80 parties de polyétheresteramide (A₁) et 20 parties de copolymère d'éthylène et de polypropylène maléisé (B₁).In a single-screw extruder whose screw speed is set at 33 rpm, 80 parts of polyetheresteramide (A₁) and 20 parts of ethylene copolymer and maleized polypropylene (B₁) are compounded.

La température d'extrusion est comprise entre 200 et 220°C et le débit de l'extrudeuse est fixé à 30 kg/h.The extrusion temperature is between 200 and 220 ° C and the extruder flow rate is fixed at 30 kg / h.

En sortie de filière, la composition obtenue sous forme de joncs de granulométrie moyenne égale à environ 3 mm a un Melt Index (MI) de 1,31 mesuré à 190°C sous une charge de 2,16 kg selon la norme ASTM D1238.At the outlet of the die, the composition obtained in the form of rods with an average particle size equal to approximately 3 mm has a Melt Index (MI) of 1.31 measured at 190 ° C. under a load of 2.16 kg according to standard ASTM D1238.

Le polyétheresteramide (A₁) utilisé est constitué de 88 % de séquences de PA-12 (Mn = 1 000) et de 12 % de séquences de PTMG (Mn = 1 000).The polyetheresteramide (A₁) used consists of 88% of PA-12 sequences ( Mn = 1000) and 12% PTMG sequences ( Mn = 1000).

L'EPR maléisé utilisé contient 70 % d'éthylène. Son taux d'anhydride total est compris entre 1,08 et 1,5 % et son Melt Index (mesuré à 230°C sous une charge de 10 kg) est égal à 9.The maleized EPR used contains 70% ethylene. Its total anhydride level is between 1.08 and 1.5% and its Melt Index (measured at 230 ° C under a load of 10 kg) is equal to 9.

On procède ensuite à l'extrusion d'un film de composition I.Next, a film of composition I is extruded.

Les conditions d'extrusion sont les suivantes : - température d'extrusion : 184°C/206°C/215°C - température des canaux : 231°C/236°C - température filière : 228°C/236°C
La vitesse de la vis est de 80 trs/mn et la vitesse de tirage est de 20 m/mn.
En sortie de filière, on obtient un film d'épaisseur égale à environ 50 µm.The extrusion conditions are as follows: - extrusion temperature: 184 ° C / 206 ° C / 215 ° C - channel temperature: 231 ° C / 236 ° C - die temperature: 228 ° C / 236 ° C
The screw speed is 80 rpm and the drawing speed is 20 m / min.
At the outlet of the die, a film of thickness equal to approximately 50 μm is obtained.

Exemple IIExample II

Dans les mêmes conditions qu'en I, on compounde une composition II constituée de 70 parties de polyétheresteramide (A₂) et de 30 parties d'EPR m (B₁).Under the same conditions as in I, a composition II is compounded consisting of 70 parts of polyetheresteramide (A₂) and 30 parts of EPR m (B₁).

Le polyétheresteramide B₂ est constitué de 88 % de séquences de PA-12 (Mn = 5 000) et de 12 % de séquences de PTMG (Mn =650).Polyetheresteramide B₂ consists of 88% of PA-12 sequences ( Mn = 5,000) and 12% PTMG sequences ( Mn = 650).

On procède ensuite à l'extrusion d'un film de composition II dans des conditions identiques à celles décrites en I.Next, a film of composition II is extruded under conditions identical to those described in I.

Exemple IIIExample III

Dans les mêmes conditions qu'en I, on compounde une composition III constituée de 90 parties de polyétheresteramide (A₂) et de 10 parties d'EPR m (B₂).Under the same conditions as in I, a composition III is composed consisting of 90 parts of polyetheresteramide (A₂) and 10 parts of EPR m (B₂).

L'EPR m (B₂) utilisé contient 50 % d'éthylène. Son taux d'anhydride total est égal à 1,26 % et son Melt Index (mesuré à 230°C sous une charge de 2,16 kg) est égal à 3.The EPR m (B₂) used contains 50% ethylene. Its total anhydride level is equal to 1.26% and its Melt Index (measured at 230 ° C under a load of 2.16 kg) is equal to 3.

La dureté Shore D (5s) de III, mesurée selon la norme ISO 868, est égale à 60,6.The Shore D hardness (5s) of III, measured according to ISO standard 868, is equal to 60.6.

La contrainte à la rupture en traction, mesurée selon la norme ASTM D638, est égale à 20,9 MPa.The tensile breaking stress, measured according to standard ASTM D638, is equal to 20.9 MPa.

Le module d'élasticité en flexion à 20°C, mesuré selon la norme ASTM D790, est égal à 357 MPa.The modulus of elasticity in flexion at 20 ° C, measured according to standard ASTM D790, is equal to 357 MPa.

La résistance à la déchirure, mesurée selon la norme ISO 34, (déchirure parallèle à l'injection) est égale à 147,4 kN/m.The tear resistance, measured according to ISO standard 34 (tear parallel to injection) is equal to 147.4 kN / m.

On procède ensuite à l'extrusion d'un film de composition III dans les mêmes conditions que celles décrites en I.Next, a film of composition III is extruded under the same conditions as those described in I.

Claims (15)

Procédé de collage d'éléments de la structure d'un ski comprenant une étape d'assemblage d'au moins un premier élément (1) et un second élément (2) par action d'une couche de colle, de résine ou d'une mousse (5) entre les surfaces de jonction (3,4) des deux éléments, caractérisé en ce que l'on interpose au moins entre la couche de colle (5) et la surface de jonction (3) du premier élément (1) un film thermoplastique (6) apte au collage, composé d'un mélange d'élastomère(s) thermoplastique(s) à base de polyamide et d'un copolymère d'éthylène et de propylène greffé ; ledit mélange étant tel que le(s) élastomère(s) thermoplastiques(s) représente(nt) au moins 50 %, et de préférence au moins 60% du poids total du mélange.Method for bonding elements of the structure of a ski comprising a step of assembling at least a first element (1) and a second element (2) by the action of a layer of glue, resin or a foam (5) between the junction surfaces (3,4) of the two elements, characterized in that at least between the adhesive layer (5) and the junction surface (3) of the first element (1) ) a thermoplastic film (6) suitable for bonding, composed of a mixture of thermoplastic elastomer (s) based on polyamide and of a grafted ethylene and propylene copolymer; said mixture being such that the thermoplastic elastomer (s) represents (s) at least 50%, and preferably at least 60% of the total weight of the mixture. Procédé selon la revendication 1, caractérisé en ce que le copolymère d'éthylène et de propylène est greffé par un acide carboxylique, un anhydre d'acide ou un sel.Process according to claim 1, characterized in that the copolymer of ethylene and propylene is grafted with a carboxylic acid, an acid anhydride or a salt. Procédé selon la revendication 1 ou 2, caractérisé en ce que le copolymère d'oléfines est un EPDM.Process according to claim 1 or 2, characterized in that the olefin copolymer is an EPDM. Procédé selon la revendication 1, caractérisé en ce que le(s) élastomères thermoplastiques(s) à base de polyamide est un copolymère statistique ou séquencé.Method according to claim 1, characterized in that the thermoplastic elastomer (s) based on polyamide is a random or block copolymer. Procédé selon la revendication 4, caractérisé en ce que le copolymère séquencé est un polyétherestéramide dans lequel les séquences polyamides ont une masse moléculaire moyenne comprise entre 500 et 10 000, et plus particulièrement 600 et 5 000, et les polyéthers ont une masse moléculaire moyenne comprise également entre 200 et 6 000 et plus particulièrement 600 et 3 000.Process according to Claim 4, characterized in that the block copolymer is a polyetheresteramide in which the polyamide blocks have an average molecular weight of between 500 and 10,000, and more particularly 600 and 5,000, and the polyethers have an average molecular weight of also between 200 and 6,000 and more particularly 600 and 3,000. Procédé selon la revendication 2, caractérisé en ce que le copolymère d'éthylène et propylène contient 0,1 à 2 % en poids d'anhydre maléique greffé.Process according to Claim 2, characterized in that the ethylene-propylene copolymer contains 0.1 to 2% by weight of grafted maleic anhydride. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le film (6) contient des charges, des pigments, colorants ou des additifs.Method according to any one of the preceding claims, characterized in that the film (6) contains fillers, pigments, dyes or additives. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'on utilise une colle (5) thermodurcissable époxyde et/ou polyester et/ou polyuréthane.Method according to any one of the preceding claims, characterized in that an epoxy and / or polyester and / or polyurethane thermosetting adhesive (5) is used. Procédé selon la revendication 8, caractérisé en ce que la colle (5) et le second élément (2) constituent un ensemble pré-imprégné non-entièrement réticulé.Method according to claim 8, characterized in that the adhesive (5) and the second element (2) constitute a prepreg assembly which is not entirely crosslinked. Procédé selon la revendication 7 ou 8, caractérisé en ce que la surface de jonction (3) du premier élément (1) est constitué des matériaux suivants : polyamide, polyéthylène, polyéthylène téréphtalate, polybutadiène téréphtalate, polypropylène, aluminium traité, alliage d'aluminium ou acier.Method according to claim 7 or 8, characterized in that the joining surface (3) of the first element (1) consists of the following materials: polyamide, polyethylene, polyethylene terephthalate, polybutadiene terephthalate, polypropylene, treated aluminum, aluminum alloy or steel. Procédé selon la revendication 10,. caractérisé en ce que le premier élément (1) est un film de polyamide 11.The method of claim 10 ,. characterized in that the first element (1) is a polyamide 11 film. Procédé selon la revendication 11, caractérisé en ce que le premier élément (1) constitue l'élément supérieur de décoration et de protection d'un ski.Method according to claim 11, characterized in that the first element (1) constitutes the upper element for decorating and protecting a ski. Procédé selon la revendication 11, caractérisé en ce que l'élément 1 et le film (6) sont réalisés en une seule étape par coextrusion.Method according to claim 11, characterized in that the element 1 and the film (6) are produced in a single step by coextrusion. Procédé selon les revendications 1 à 7, caractérisé en ce que l'étape d'assemblage consiste à : - disposer préalablement le premier élément (1), le film de collage (6) puis le second élément (2) dans un moule (8), - puis à injecter une mousse de polyuréthane expansible (5) qui, après sa phase d'expansion, puis de durcissement, adhère parfaitement au film de collage (6) et au premier élément (1). Process according to Claims 1 to 7, characterized in that the assembly step consists in: - first place the first element (1), the bonding film (6) then the second element (2) in a mold (8), - Then injecting an expandable polyurethane foam (5) which, after its expansion phase, then hardening, adheres perfectly to the bonding film (6) and to the first element (1). Ski obtenu à partir du procédé de collage selon les revendications 1 à 14.Ski obtained from the bonding process according to claims 1 to 14.
EP91108572A 1990-06-14 1991-05-27 Method of bonding the components of a ski Expired - Lifetime EP0461453B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9007600 1990-06-14
FR9007600A FR2663237B1 (en) 1990-06-14 1990-06-14 METHOD FOR GLUING ELEMENTS OF THE STRUCTURE OF A SKI.

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EP0461453A1 true EP0461453A1 (en) 1991-12-18
EP0461453B1 EP0461453B1 (en) 1994-08-17

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EP91108572A Expired - Lifetime EP0461453B1 (en) 1990-06-14 1991-05-27 Method of bonding the components of a ski

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EP (1) EP0461453B1 (en)
JP (1) JPH04231985A (en)
AT (1) ATE109993T1 (en)
DE (1) DE69103479T2 (en)
FR (1) FR2663237B1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2720289A1 (en) * 1994-05-31 1995-12-01 Gaillon Ski with transparent upper surface with decoration underneath
FR2740384A1 (en) * 1995-10-27 1997-04-30 Indec Thermoplastic laminations used for ornamental finishes and protection
FR2740385A1 (en) * 1995-10-27 1997-04-30 Indec Thermoplastic lamination useful for washing machine ornamental finish
US9504292B2 (en) 2013-04-02 2016-11-29 Nike, Inc. Method of bonding PEBA plastic composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10236959B4 (en) * 2002-08-13 2004-10-07 Leonhard Kurz Gmbh & Co. Kg Multi-layer film for the construction of skis

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3003537A1 (en) * 1979-02-01 1980-08-14 Rost & Co H Laminar construction ski - has intermediate plastics layer rendered adhesive only on heating
FR2553290A1 (en) * 1983-10-13 1985-04-19 Arntz Optibelt Kg Method for manufacturing a ski of stratified structure
US4690856A (en) * 1984-12-27 1987-09-01 Ube Industries, Inc. Metal polyamide adhesive laminates

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3003537A1 (en) * 1979-02-01 1980-08-14 Rost & Co H Laminar construction ski - has intermediate plastics layer rendered adhesive only on heating
FR2553290A1 (en) * 1983-10-13 1985-04-19 Arntz Optibelt Kg Method for manufacturing a ski of stratified structure
US4690856A (en) * 1984-12-27 1987-09-01 Ube Industries, Inc. Metal polyamide adhesive laminates

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2720289A1 (en) * 1994-05-31 1995-12-01 Gaillon Ski with transparent upper surface with decoration underneath
FR2740384A1 (en) * 1995-10-27 1997-04-30 Indec Thermoplastic laminations used for ornamental finishes and protection
FR2740385A1 (en) * 1995-10-27 1997-04-30 Indec Thermoplastic lamination useful for washing machine ornamental finish
US9504292B2 (en) 2013-04-02 2016-11-29 Nike, Inc. Method of bonding PEBA plastic composition

Also Published As

Publication number Publication date
FR2663237A1 (en) 1991-12-20
DE69103479D1 (en) 1994-09-22
DE69103479T2 (en) 1995-01-05
ATE109993T1 (en) 1994-09-15
JPH04231985A (en) 1992-08-20
FR2663237B1 (en) 1993-02-12
EP0461453B1 (en) 1994-08-17

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