EP0459347B1 - Ski und Skikomponenten - Google Patents

Ski und Skikomponenten Download PDF

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Publication number
EP0459347B1
EP0459347B1 EP91108573A EP91108573A EP0459347B1 EP 0459347 B1 EP0459347 B1 EP 0459347B1 EP 91108573 A EP91108573 A EP 91108573A EP 91108573 A EP91108573 A EP 91108573A EP 0459347 B1 EP0459347 B1 EP 0459347B1
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EP
European Patent Office
Prior art keywords
ski according
ski
layer
composition
polyamide
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Expired - Lifetime
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EP91108573A
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English (en)
French (fr)
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EP0459347A1 (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
    • A63C5/122—Selection of particular materials for damping purposes, e.g. rubber or the like
    • 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
    • A63C5/003—Structure, covering or decoration of the upper ski surface
    • 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
    • A63C5/04—Structure of the surface thereof
    • A63C5/052—Structure of the surface thereof of the tips or rear ends

Definitions

  • the present invention relates to skis intended to be used on snow and in particular elements used in the constitution of skis. These elements have the particularity of being a composition of thermoplastic elastomer (s) (TPE) based on polyamide and modified polyolefin (s).
  • TPE thermoplastic elastomer
  • s polyamide
  • modified polyolefin s
  • compositions containing ethylene-based copolymers (at least 35% by weight) and at least one vinyl ester and containing from 0.5 to 20% of are described.
  • a copolyetheresteramide which can be used as hot-melt adhesives.
  • the object of the invention is mainly to produce a ski, certain elements of which, due to their composition, have high mechanical and aging properties, an excellent ability for molding, bonding and decoration.
  • thermoplastic or TPE elastomers based on polyamide can be random or block copolymers.
  • Random polyamide-based 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 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 of aliphatic polyamide and / or of amorphous polyamide or of 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, and 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 sequences consist essentially of PA-11, 12 and / or 12.12 and when a composition having antistatic properties is sought, preferably uses polyetheresteramides, the polyether blocks of which essentially consist of polyethylene glycol (PEG).
  • PEG polyethylene glycol
  • the polyolefin-based copolymers can be polymerized statistically or sequentially and have a linear or branched structure, for the polyolefins modified according to the invention.
  • compositions described above various other constituents can be incorporated, such as fillers, pigments or dyes, various additives.
  • fillers examples include glass fibers, carbon fibers, aramids, 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 modified polyolefin (s) proper.
  • additives there may be mentioned anti-UV agents, release agents, impact modifiers.
  • compositions can in particular be prepared by compounding; the constituents, most often in the form of granules with an average diameter of less than 5 mm, are mixed in the molten state in general in a kneader at a temperature between 190 and 250 ° C.
  • compositions according to the invention can be used in very diverse forms (molded or extruded parts, films, sheets, fibers) alone or for the production of complex or composite objects: molded parts, coextruded films.
  • the molded or extruded parts can be obtained according to known molding and extrusion techniques, the processing temperatures being generally similar to those of the compounding of the constituents of the compositions according to the invention ( ⁇ 20 ° C in general).
  • the elements used in the composition of the ski include in particular the films or sheets of bonding from the compositions. They can be obtained according to any known extrusion process such as flat extrusion-calendering, extrusion-plastering, 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 "m and the term” sheet "for objects of greater thickness and up to several mm, but in all what follows and for reasons of simplification, one or the other of the terms may be used to designate films and sheets simultaneously.
  • the films obtained from the compositions can be used as such but can also be used in the manufacture of multilayer films obtained for example by co-extrusion, hot lamination.
  • the manufacturing process for these composite materials can take place in 2 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 by screen printing, painting or varnishing, hot transfer, pad printing, inkjet, laser marking, it being understood that the decoration techniques can be applied to the compositions according to the invention in any form (film, molded parts, fibers ”).
  • These films can be bonded to rigid parts of the ski and in particular to metal parts serving as reinforcement (such as cables, sheets) or on wooden parts as well as on synthetic materials preferably based on, covered or impregnated with epoxy resin (s) and / or polyester (s).
  • the composite materials made up of the two-layer film described above and of a support impregnated with epoxy resin (s) and / or polyester (s), and / or polyurethane (s), possibly decorated, are particularly suitable for the production of ski tops according to the invention.
  • compositions in the form of single-layer films can also serve as co-extrusion binder for multilayer films making it possible to adhere 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
  • a ski generally consists of the assembly of several elements independently performing the necessary functions such as mechanical strength, protection, sliding, etc.
  • modern skis generally have an assembly bringing together the so-called “mechanical” elements which are in particular a core 3, lower and upper mechanical reinforcement elements 4, squares 5 and a sole 1, or sliding surface and an upper assembly of decoration and protection 2 consisting of one or more layers extending or not laterally along the edges of the ski.
  • “mechanical” elements which are in particular a core 3, lower and upper mechanical reinforcement elements 4, squares 5 and a sole 1, or sliding surface and an upper assembly of decoration and protection 2 consisting of one or more layers extending or not laterally along the edges of the ski.
  • FIG. 2 illustrates a specific example of application to an upper decorative and protective element 2 of the compositions according to the invention.
  • this element consists of an upper layer 21 of polyamide 11 or 12 or of a polyetherblocamide, resistant to UV rays, to hot creep, and easily sublimable and to a lower layer 22 consisting of a composition. from that described above.
  • the bilayer can advantageously be produced by coextrusion or hot plaxing for example. It is then hot bonded to the upper reinforcement impregnated with an epoxy resin and / or polyester, and / or polyurethane shown in FIG. 1.
  • the operating conditions and the adhesion results are those given in Examples I to Following VII:
  • composition (IV) obtained is then co-extruded with PA-11 and then bonded to an epoxy support under the same conditions as in I.1.
  • the co-extrusion conditions are as follows: - extrusion temperatures: EVOH 200 ° C / 220 ° C / 235 ° C from III 200 ° C / 210 ° C / 220 ° C / 230 ° C - industry temperature 220 ° C - grille temperature 50 ° C / 35 ° C / 50 ° C
  • Maleized EVA B7 contains 14% vinyl acetate and 0.35% maleic anhydride. Its melting temperature is equal to 94 ° C and its Vicat point to 71 ° C.
  • Composition VII obtained is then used as a co-extrusion binder between EVOH and crystal polycarbon.
  • the EVOH used has the same characteristics as that of Example VI.
  • the crystal polycarbonate used is sold by General Electric Company, under the brand LEXAN 154.
  • the coextrusion conditions are as follows: - extrusion temperatures: EVOH 190 ° C / 200 ° C / 205 ° C / 210 ° from VII 185 ° C / 190 ° C / 190 ° C / 190 ° C - crystal PC temperature 270 ° C / 275 ° C / 270 ° C / 270 ° C - die temperature 250 ° C - grille temperature 45 ° C / 50 ° C / 50 ° C
  • the film of the invention in the case of injected skiing, it is advantageous to use the film of the invention as a bonding film and more particularly, in the form of a tubular envelope 6 as shown in FIG. 3.
  • the structured elements of the ski are placed in a mold and a thermosetting foam is injected inside the tubular envelope.
  • the expansion of the foam in the envelope creates the compaction of the ski elements, including in particular reinforcements 4.
  • the expansion reaction is accompanied by an exothermic reaction which is generally sufficient to achieve the adhesion of the film on compacted elements.
  • composition according to the invention also allows the production of added molded parts such as the heel tips 7 or the spatulas 8. These parts are generally molded and can be loaded with fiberglass for example. They can be removably mounted on the ski body, in particular for the tip 8, as shown in FIG. 4.
  • FIG. 5 illustrates a nonlimiting embodiment of the invention where the damping elements 9 of the composition of the invention are located laterally between the lateral faces of the core 3 and the inclined lateral faces of the top of the ski 2.

Landscapes

  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Claims (16)

  1. Ski, der aus einer Zusammenfügung von mehreren Elementen gebildet ist, insbesondere einer unteren Gleitoberfläche (1), einer oberen Dekorationseinheit (2), einem Kern (3), internen mechanischen Verstärkungselementen (4), unteren Kantenleisten (5), dadurch gekennzeichnet, daß zumindest ein Element dieser Zusammenfügung teilweise zumindest aus einer Zusammensetzung gebildet ist, die aufweist:
    zumindest ein thermoplastisches Elastomer auf der Basis von Polyamid,
    zumindest ein modifiziertes Polyolefin, das aus statistischen oder aufeinanderfolgenden Copolymeren auf der Basis von Polyolefin ausgewählt ist, aufweisend:
    - zumindest ein Comonomer, das aus den Vinylestern von gesättigter Karbonsäure, ungesättigten Mono- und Dikarbonsäuren, ihren Estern, Salzen, Dikarbonsäureanhydriden, gesättigt oder nicht, ausgewählt ist;
    wobei das Olefin zumindest 50% und vorzugsweise 60% des Gesamtgewichts des Copolymeres auf der Basis von Polyolfin darstellt.
  2. Ski, der aus einer Zusammenfügung von mehreren Elementen gebildet ist, insbesondere aus einer unteren Gleitoberfläche (1), einer oberen Dekorationseinheit (2), einem Kern (3), internen mechanischen Verstärkungselementen (4), unteren Kantenleisten (5), dadurch gekennzeichnet, daß zumindest ein Element dieser Zusammenfügung zum Teil zumindest aus einer Zusammensetzung gebildet ist, die aufweist:
    zumindest ein thermoplastisches Elastomer auf der Basis von Polyamid,
    zumindest ein modifiziertes Polyolefin, das aus den Blockcopolymeren auf der Basis von Styrol ausgewählt ist, die 0,2 bis 0,8 Gewichtsprozent an Maleinsäureanhydrid aufweisen.
  3. Ski gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß das (die) thermoplastische(n) Elastomer(e) zumindest 50% und vorzugsweise zumindest 60% des Gesamtgewichtes des (der) thermoplastischen Elastomers (Elastomere) und des (der) modifizierten Polyolefins (Polyolefine) aufweist.
  4. Ski gemäß Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß das thermoplastische Elastomer auf der Basis von Polyamid ein Polyetheramid und vorzugsweise ein Polyetheresteramid ist.
  5. Ski gemäß Anspruch 1, dadurch gekennzeichnet, daß das modifizierte Polyolefin ausgewählt ist aus:
    den Copolymeren aus Ethylen und maleisiertem oder nichtmaleisiertem Vinylacetat,
    den Copolymeren aus Ethylen und (Meth)acrylsäure,
    Copolymeren aus Ethylen, Vinylacetat und evtl. (Meth)acrylsäure und/oder Alkyl-(Meth)acrylat.
  6. Ski gemäß Anspruch 2, dadurch gekennzeichnet, daß das modifizierte Polyolefin gewählt ist aus:
    den maleisierten SBS, SIS und SEBS.
  7. Ski gemäß Anspruch 1, dadurch gekennzeichnet, daß das modifizierte Polyolefin ein Copolymer aus Ethylen, aus Alkyl-(Meth)acrylat und vorzugsweise Maleinsäureanhydrid ist.
  8. Ski gemäß Anspruch 7, dadurch gekennzeichnet, daß das Alkylacrylat ein Ethylacrylat ist.
  9. Ski gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Zusammensetzungen Additive und/oder. Pigmente oder Farbstoffe, und/oder bis zu 50 und vorzugsweise bis zu 40 Gewichtsprozent an Füllmitteln enthalten bzgl. dem (den) thermoplastischen Elastomer(en) auf der Basis von Polyamid und dem (den) modifizierten Polyolefin(en).
  10. Ski gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Element, das zumindest teilweise aus der Zusammensetzung der Mischung gebildet ist, ein einschichtiger oder vielschichtiger Film ist, der zum Kleben geeignet ist.
  11. Ski gemäß Anspruch 10, dadurch gekennzeichnet, daß der einschichtige oder vielschichtige Film heiß auf einen mit Epoxidharz(en) und/oder Polyester(n) und/oder Polyurethan(en) imprägnierten Träger geklebt ist.
  12. Ski gemäß Anspruch 11, dadurch gekennzeichnet, daß das Element ein zweischichtiger Film (2) ist, der aus einer Schicht aus aliphatischem Polyamid (21) zusammengesetzt ist, auf der eine Schicht der Zusammensetzung der Mischung (22) haftet.
  13. Ski gemäß Anspruch 12, dadurch gekennzeichnet, daß das Element ein zweischichtiger Film (2) ist, der aus einer Schicht aus Polyether-Blockamid (21) zusammengesetzt ist, auf der eine Schicht der Zusammensetzung der Mischung (22) haftet.
  14. Ski gemäß einem der Ansprüche 12 bis 13, dadurch gekennzeichnet, daß die Doppel-Schicht das obere Dekorations- und Schutzelement (2) bildet.
  15. Ski gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Element der Zusammensetzung der Mischung ein zusammengesetztes, geformtes Teil, wie zum Beispiel ein Skiende-Ansatzstück (7) oder eine Skispitze (8) ist.
  16. Ski gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das Element der Zusammensetzung der Mischung ein internes Dämpfungselement (9) ist.
EP91108573A 1990-06-01 1991-05-27 Ski und Skikomponenten Expired - Lifetime EP0459347B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9007044 1990-06-01
FR9007044A FR2662611B1 (fr) 1990-06-01 1990-06-01 Ski et elements de ski.

Publications (2)

Publication Number Publication Date
EP0459347A1 EP0459347A1 (de) 1991-12-04
EP0459347B1 true EP0459347B1 (de) 1994-09-21

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EP91108573A Expired - Lifetime EP0459347B1 (de) 1990-06-01 1991-05-27 Ski und Skikomponenten

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EP (1) EP0459347B1 (de)
JP (1) JPH04231083A (de)
AT (1) ATE111757T1 (de)
DE (1) DE69104120T2 (de)
FR (1) FR2662611B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1352934A1 (de) 2002-04-08 2003-10-15 Atofina Mit Polyamiden beschichtete Metalloberflächen

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2683733B1 (fr) * 1991-11-19 1994-03-18 Rossignol Sa Skis Ski en forme, de section non rectangulaire.
FR2685214B1 (fr) * 1991-12-19 1995-05-19 Rossignol Sa Embout de spatule de ski.
FR2685215B1 (fr) * 1991-12-19 1994-10-21 Rossignol Sa Embout de spatule de ski.
FR2687925B1 (fr) * 1992-02-27 1994-05-06 Salomon Sa Procede de fabrication d'un ski et ski obtenu par ce procede.
FR2694890B1 (fr) * 1992-08-24 1994-10-14 Rossignol Sa Ski comportant un corps et au moins un embout, spatule et/ou talon réalisé indépendamment, et procédé de fabrication d'un tel ski.
FR2694889B1 (fr) * 1992-08-24 1994-10-14 Rossignol Sa Ski comportant un corps et au moins un embout, spatule et/ou talon réalisé indépendamment, et procédé de fabrication d'un tel ski.
EP0768911A1 (de) * 1992-09-15 1997-04-23 Hagan Yamaha Sport Ges.M.B.H. Ski, insbesondere alpin- oder langlaufski
US5848800A (en) * 1993-06-09 1998-12-15 Kastle Aktiengesellschaft Ski
US5544908A (en) * 1994-05-06 1996-08-13 K-2 Corporation Thermoplastic composite ski and method of manufacture
DE29519867U1 (de) * 1995-12-14 1997-01-23 Ems-Inventa AG, Zürich Oberbelag für Skier/Snowboards
DE102005007663A1 (de) * 2005-02-19 2006-08-24 Degussa Ag Transparente, dekorierbare mehrschichtige Folie
CN102906211B (zh) * 2010-07-23 2014-11-05 大自达电线股份有限公司 导电性粘合剂组合物及导电性粘合膜
FR2983416B1 (fr) * 2011-12-05 2015-02-20 Rossignol Sa Planche de glisse
JP6361352B2 (ja) * 2013-08-12 2018-07-25 宇部興産株式会社 ポリアミドエラストマー組成物、及びそれを用いた成形体

Family Cites Families (7)

* 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
JPH0647260B2 (ja) * 1985-07-30 1994-06-22 三菱油化株式会社 複合成形体
JP2618626B2 (ja) * 1985-10-09 1997-06-11 住友化学工業株式会社 熱可塑性樹脂組成物の製造方法
FR2596286B1 (fr) * 1986-03-26 1989-10-06 Rossignol Sa Ski a decor protege
JPH0686533B2 (ja) * 1986-09-22 1994-11-02 三井・デユポンポリケミカル株式会社 エチレン系樹脂成形品
JPS63191857A (ja) * 1987-02-04 1988-08-09 Showa Denko Kk ポリアミド樹脂組成物
FR2626778B1 (fr) * 1988-02-09 1990-07-13 Atochem Nouvelles semelles de ski, leur procede de fabrication et skis equipes de ces semelles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1352934A1 (de) 2002-04-08 2003-10-15 Atofina Mit Polyamiden beschichtete Metalloberflächen

Also Published As

Publication number Publication date
FR2662611A1 (fr) 1991-12-06
ATE111757T1 (de) 1994-10-15
DE69104120D1 (de) 1994-10-27
FR2662611B1 (fr) 1992-08-07
EP0459347A1 (de) 1991-12-04
DE69104120T2 (de) 1995-01-19
JPH04231083A (ja) 1992-08-19

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