EP0461453B1 - Verfahren zum Verbinden der Bestandteile eines skis - Google Patents

Verfahren zum Verbinden der Bestandteile eines skis Download PDF

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Publication number
EP0461453B1
EP0461453B1 EP91108572A EP91108572A EP0461453B1 EP 0461453 B1 EP0461453 B1 EP 0461453B1 EP 91108572 A EP91108572 A EP 91108572A EP 91108572 A EP91108572 A EP 91108572A EP 0461453 B1 EP0461453 B1 EP 0461453B1
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EP
European Patent Office
Prior art keywords
film
adhesive
copolymer
ski
polyamide
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Expired - Lifetime
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EP91108572A
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English (en)
French (fr)
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EP0461453A1 (de
Inventor
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 capable of bonding, thermoplastics composed of a mixture of thermoplastic elastomer (TPE) based on polyamide and of 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 composition comprises 100 parts by weight of a polyamide component and 0.1 to 5 parts of an amino-silane, said polymer component comprising 50 to 99.5% by weight of a polyamide and 0.5 to 50% by weight. weight of a modified polyolefin.
  • the polyamide is an aliphatic or semi-aromatic polyamide.
  • Document DE 30 03 537 relates to a ski made up of an assembly of layers which comprises at least one layer of thermoplastic material which has a layer of adhesive on each face.
  • the adhesive layer mainly consists of a polyamide and / or a copolymer of polyethylene and / or of a thermoplastic polyester and / or of a polyurethane and / or of a copolyester.
  • the adhesive layer can be handled at room temperature and exerts its adhesion properties only when hot.
  • 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 poly (ether (s) block amides) or polyether block amides and of a modified olefin copolymer consisting of at least two different olefin monomers said mixture being such that the polyether (s) amide block represents therein (s) at least 50% and preferably at least 60% of the total weight.
  • 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 in which the polyamide blocks are essentially made up of PA-11, 12 and / or 12.12 and when a composition having antistatic properties is sought, polyetheresteramides are preferably used in which the polyether blocks are essentially 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 there may be mentioned 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 they are 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 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-reduction or thermal insulation laminates.
  • Monolayer films can also serve as a 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 glue 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.
  • 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 adhesive or foam between the joining surfaces of the two elements is characterized by the fact that at least between the adhesive layer and the junction 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 joining 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 securing between the film and the second element 2 can be provided in the case where the second element 2 has 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).
  • EPR maleized ethylene propylene copolymer
  • 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 may be a mechanical reinforcement element consisting of a textile reinforcement ply woven or not made of glass fiber, carbon, aramid or the like, or even a metallic reinforcement 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 should 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 constituted by the adhesive 5 and the film 6 are applied against each other, 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 screw speed is 80 rpm and the drawing speed is 20 m / min.
  • 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 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 bending 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.

Landscapes

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

Claims (14)

  1. Verfahren zum Kleben von Elementen des Aufbaus eines Ski, das einen Schritt des Zusammenfügens von zumindest einem ersten Element (1) und einem zweiten Element (2) durch Wirkung einer Schicht aus Klebstoff, Harz oder einem Schaum (5) zwischen den Verbindungsoberflächen (3, 4) der beiden Elemente aufweist, dadurch gekennzeichnet, daß man zumindest zwischen die Klebstoffschicht (5) und die Verbindungsoberfläche (3) des ersten Elementes (1) eine thermoplastische Schicht (6) zwischenlegt, die zum Kleben geeignet ist, zusammengesetzt aus einer Mischung von Polyetherblockamiden oder aneinandergereihten Polyetheramiden und einem modifizierten Copolymer aus Olefinen, das zumindest aus zwei unterschiedlichen Monomeren aus Olefinen gebildet ist; wobei die Mischung derart ist, daß die Polyetherblockamide zumindest 50% ausmachen, und vorzugsweise zumindest 60% des Gesamtgewichtes der Mischung.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß das Copolymer aus Olefinen ein Copolymer aus Ethylen und aus einem durch eine Carbonsäure, einem Säureanhydrid oder einem Salz-veredelten Propylen ist.
  3. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß das Copolymer aus Olefinen ein EPDM ist.
  4. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das aneinandergereihte Copolymer ein Polyetheresteramid ist, in dem die Polyamidfolgen eine mittlere Molekularmasse haben, die zwischen 500 und 10.000 und insbesondere zwischen 600 und 5.000 liegt, und daß die Polyether eine mittlere Molekularmasse haben, die gleichfalls zwischen 200 und 6.000 und insbesondere 600 und 3.000 liegt.
  5. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß das Copolymer aus Ethylen und Propylen 0,1 bis 2 Gew-% eines veredelten Maleinsäureanhydrids enhält.
  6. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Schicht (6) Füllmittel, Pigmente, Farbstoffe oder Additive enthält.
  7. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man einen wärmehärtbaren Klebstoff (5) aus Epoxid und/oder Polyester und/oder Polyurethan verwendet.
  8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß der Klebstoff (5) und das zweite Element (2) eine vorimprägnierte, nicht vollständig ausgehärtete Einheit bilden.
  9. Verfahren gemäß Anspruch 7 oder 8, dadurch gekennzeichnet, daß die Verbindungsoberfläche (3) des ersten Elementes (1) aus den folgenden Materialien gebildet ist: Polyamide, Polyethylene, Polyethylenterephtalate, Polybutadienterephtalate, Polypropylen, behandeltes Aluminium, eine Aluminumlegierung oder Stahl.
  10. Verfahren gemäß Anspruch 9, dadurch gekennzeichnet, daß das erste Element (1) eine Polyamidschicht (11) ist.
  11. Verfahren gemäß Anspruch 10, dadurch gekennzeichnet, daß das erste Element (1) das obere Element der Dekorierung und des Schutzes eines Ski bildet.
  12. Verfahren gemäß Anspruch 9, 10 oder 11, dadurch gekennzeichnet, daß das Element (1) und die Schicht (6) in einem einzigen Schritt durch Koextrusion hergestellt sind.
  13. Verfahren gemäß den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß der Schritt des Zusammenfügens besteht aus:
    - zuvor Anordnen des ersten Elementes (1), der Klebstoffschicht (6) und dann des zweiten Elementes (2) in einer Form (8),
    - danach Injizieren eines ausdehnbaren Polyurethanschaumes (5), der nach seiner Ausdehnungsphase, und nach dem Aushärten, perfekt auf der Klebstoffschicht (6) und dem ersten Element (1) anhaftet.
  14. Ski, der durch das Verfahren zum Kleben gemäß den Ansprüchen 1 bis 13 erhalten worden ist.
EP91108572A 1990-06-14 1991-05-27 Verfahren zum Verbinden der Bestandteile eines skis Expired - Lifetime EP0461453B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9007600 1990-06-14
FR9007600A FR2663237B1 (fr) 1990-06-14 1990-06-14 Procede de collage d'elements de la structure d'un ski.

Publications (2)

Publication Number Publication Date
EP0461453A1 EP0461453A1 (de) 1991-12-18
EP0461453B1 true EP0461453B1 (de) 1994-08-17

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EP91108572A Expired - Lifetime EP0461453B1 (de) 1990-06-14 1991-05-27 Verfahren zum Verbinden der Bestandteile eines skis

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

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2720289B1 (fr) * 1994-05-31 1996-08-23 Gaillon Ski ou similaire.
FR2740385B1 (fr) * 1995-10-27 1998-01-16 Indec Stratifie, notamment de decoration d'un substrat, et article obtenu a partir d'un substrat incluant ledit stratifie, leurs procedes de fabrication et procede de decoration en faisant application
FR2740384B1 (fr) * 1995-10-27 1998-01-16 Indec Stratifies de decoration de substrats et procede de decoration en faisant application
DE10236959B4 (de) * 2002-08-13 2004-10-07 Leonhard Kurz Gmbh & Co. Kg Mehrschichtfolie für den Bau von Skiern
US9504292B2 (en) 2013-04-02 2016-11-29 Nike, Inc. Method of bonding PEBA plastic composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT360392B (de) * 1979-02-01 1980-01-12 Rost & Co H Aus schichten zusammengesetzter ski und verfahren zu seiner herstellung
CH662952A5 (de) * 1983-10-13 1987-11-13 Arntz Optibelt Kg Verfahren zur herstellung eines sandwichartig aufgebauten skibrettes.
JPS61152782A (ja) * 1984-12-27 1986-07-11 Ube Ind Ltd ポリアミド系接着剤組成物および積層物

Also Published As

Publication number Publication date
JPH04231985A (ja) 1992-08-20
FR2663237A1 (fr) 1991-12-20
ATE109993T1 (de) 1994-09-15
DE69103479T2 (de) 1995-01-05
FR2663237B1 (fr) 1993-02-12
EP0461453A1 (de) 1991-12-18
DE69103479D1 (de) 1994-09-22

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