EP0328439A1 - Soles of ski, process for their fabrication, and skis equiped with these soles - Google Patents

Soles of ski, process for their fabrication, and skis equiped with these soles Download PDF

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Publication number
EP0328439A1
EP0328439A1 EP19890400297 EP89400297A EP0328439A1 EP 0328439 A1 EP0328439 A1 EP 0328439A1 EP 19890400297 EP19890400297 EP 19890400297 EP 89400297 A EP89400297 A EP 89400297A EP 0328439 A1 EP0328439 A1 EP 0328439A1
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EP
European Patent Office
Prior art keywords
ski
sole according
ski sole
polyetheresteramide
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP19890400297
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German (de)
French (fr)
Inventor
Michel Vuachet
Jean-Marie Huet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Elf Atochem SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Elf Atochem SA filed Critical Elf Atochem SA
Publication of EP0328439A1 publication Critical patent/EP0328439A1/en
Ceased legal-status Critical Current

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Classifications

    • 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
    • A63C5/044—Structure of the surface thereof of the running sole
    • 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
    • A63C5/056—Materials for the running sole
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide

Definitions

  • the present invention relates to a ski sole, that is to say the lower part of the ski in contact with the snow and on which the ski and the skier rests.
  • the ski sole according to the invention has an excellent ability to absorb waxes and retain them durably.
  • the ski soles are generally in the form of a sheet or a film with a thickness of between 0.5 and 2 mm. They are made of polyolefinic plastic and preferably based on high density polyethylene (HDPE), and / or high molecular weight (number average molecular weight between 150,000 and 450,000) which can be measured by gel permeation chromatography. .
  • HDPE high density polyethylene
  • high molecular weight number average molecular weight between 150,000 and 450,000
  • HDPE of very high molecular weight (number average molecular weight of between 300,000 and 8,000,000) is also used to manufacture high competition ski soles. These soles are obtained by sintering, a much more expensive technique than extrusion.
  • the ski sole, object of the present invention comprises a sheet or film of thermoplastic polymer material based on an intimate mixture of one or more polyolefins and one or more polyetheresteramides.
  • the properties that such a ski sole has are, in particular: - an excellent ability to absorb waxes and retain them in a sustainable way, - a very good slip due to a low coefficient of friction, - good resistance to impact and abrasion, - good bonding ability on the draft of the ski, - a particularly good dye affinity as well as antistatic properties at low temperature, - a transparency or translucency such that one can quite clearly distinguish the draft of the ski through the sole possibly coated with various inscriptions such as drawings, marks ...
  • the ski sole according to the invention consists of a thermoplastic polymer material based on one or more polyolefins and one or more polyetheresteramides, and which may contain various additives, fillers, etc.
  • polyetheresteramides is intended to mean both the random polyetheresteramides (that is to say formed by the random sequence of the various monomer components) and the block polyetheresteramides, that is to say formed from blocks having a certain length of chain. their various constituents.
  • Polyetheresteramides are the product of the copolycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, inter alia: . polyamide sequences for dicarboxylic chain ends with polyetherdiol sequences.
  • 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 polyamide 6, 6.6, 6.12, 11 or 12 (PA- 6, PA-6.6, PA-6.12, PA-11, PA-12) or of copolyamides resulting from the 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 preferably consist of polytetramethylene glycol (PTMG), polypropylene glycol (PPG), or polyethylene glycol (PEG).
  • PTMG polytetramethylene glycol
  • PPG polypropylene glycol
  • PEG polyethylene glycol
  • the inherent viscosity of polyetheresteramides is advantageously between 0.8 and 2.05.
  • the inherent viscosity is measured in metacresol at 20 ° C with an initial concentration of 0.5 g per 100 g of metacresol. It is expressed in dlg ⁇ 1.
  • the polyetheresteramides according to the invention 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 80% by weight of polyether and from 70 to 20% by weight polyamide.
  • the polyolefin (s) used for the ski sole, object of the present invention consist of polypropylene (PP), polyethylene (PE), their mixtures or copolymers, but is preferably polyethylene.
  • the polyolefin (s) are of high molecular weight.
  • the number average molecular weight of the preferred polyolefins can be between 100,000 and 500,000, and preferably between 150,000 and 400,000.
  • the mixture of thermoplastic polymer material constituting the ski sole of the invention may contain from 50 to 99% by weight of polyolefin (s) and from 50 to 1% by weight of polyetheresteramide (s) and preferably it contains from 60 90% by weight of polyolefin (s) and 40 to 10% of polyetheresteramide (s).
  • the mixture may optionally contain, for example, up to 70% of organic or inorganic, fibrous or pulverulent fillers.
  • fillers examples include silica, titanium oxide, glass fibers, carbon fibers.
  • the mixture can also contain various additives such as anti-UV agents, release agents, impact modifiers, waxes ...
  • an emulsifying agent it is possible to choose, for example, maleized polypropylene.
  • emulsifier In general, 1 to 5% by weight of emulsifier is incorporated into the mixture.
  • the presence of an emulsifying agent is not necessary. However, it is particularly recommended when the proportion of polyetheresteramide in the mixture is greater than or equal to 20% by weight.
  • the manufacture of the ski soles according to the invention and in particular the shaping of a sheet or film of the mixture described above can be carried out according to any known extrusion process. Before extruding the actual mixture, it is also necessary to intimately mix said constituents of the sole.
  • the preferred extrusion techniques are either extrusion-plastering or extrusion-calendering flat.
  • a sheet or film of the mixture described above is thus obtained with a thickness of between 0.5 and 2 mm, and preferably between 0.9 and 1.4 mm.
  • a variant of the ski sole manufacturing method according to the invention consists in incorporating into the mixture constituting the sole all or part of the waxes before extrusion. A more or less self-waxed sole is thus obtained, that is to say that the waxing of the ski provided with its sole will no longer be necessary.
  • the self-waxing technique has the following advantages: - the sole can absorb a larger amount of wax. - the waxes being integrated into the structure of the sole, they are permanently maintained in this structure and the ski is waxed once and for all.
  • farts we mean both gliding waxes, used more specifically for downhill skis and retaining farts, more specifically used for cross-country skis.
  • the so-called sliding waxes generally have the main function of improving the sliding of the ski on snow by significantly reducing the coefficient of friction of said sole.
  • So-called retaining farts mainly have an anti-kickback function: snow crystals can penetrate the surface layer of wax and they thus give the sole the anchoring properties necessary for good support of the ski on snow, preventing it to slide in a direction not desired by the skier.
  • the bonding of the sole to the ski blank can be done according to a known method. For example, one can operate by flaming: the film or sheet is heated and applied with pressure on the ski blank.
  • the present invention also applies advantageously to the production and use of a sheet or film based on one or more polyetheresteramides and one or more polyolefins as described above as a sliding surface for objects whose function is to slide on a liquid or solid surface such as water, snow, grass ...
  • HDPE high density polyethylene
  • PTMG polyether sequences
  • the granules of the constituents described in 1.A are mechanically mixed.
  • the mixture thus obtained is then introduced into a single-screw extruder whose speed of rotation of the screw is 100 revolutions / min.
  • the assembly is brought to a temperature between 225 and 230 ° C.
  • HDPE alone is extruded under the same conditions as above in order to obtain a continuous sheet 1.2 mm thick and 105 mm wide (SAMPLE 2).
  • connection angle ⁇ made by a drop of standard liquid deposited on a side kept horizontal of the sheets of SAMPLES 1 and 2.
  • connection angle The method of measuring the connection angle is described in the article by W.D. WARKINS, The Physical Chemistry of Surface Films, p 41. Reinhold Pub. Corp. 1952.
  • connection angle measurements are carried out successively at 25 ° C on both sides of the samples.
  • the standard liquids used are: - diodomethane, ⁇ -bromonaphthalene (slightly polar liquids) - water, formamide (polar liquids)
  • a drop of 1 to 5 ⁇ l of standard liquid is placed on the horizontal side of the sheet.
  • connection angle ⁇ made by the drop with the horizontal surface on which it was deposited.
  • SAMPLING 1 Mixture of HDPE and polyetheresteramide
  • SAMPLING 2 HDPE alone
  • the polar contribution is equal to 6.7 m Nm ⁇ 1 for SAMPLE 1 while it is zero for SAMPLE 2.
  • the whole is brought to 230 ° C., the speed of rotation of the screw is 150 rpm and the flow rate of the material is 17 kg / h.
  • Granules are obtained which are extruded under conditions identical to those of EXAMPLE 1 in order to obtain a continuous sheet 1.2 mm thick and 105 mm wide.
  • HDPE alone is extruded (the characteristics of which are those described in 2.A) under the same conditions in order to obtain a continuous sheet of HDPE 1.2 mm thick and 105 mm wide.
  • the sheets thus produced are capable of being bonded to a ski blank and the ski thus produced can then undergo waxing.

Abstract

The present application relates to ski soles with improved wax absorption in a durable manner, a process for their fabrication and skis equipped with these soles. …<??>These soles consist of a sheet or of a film in thermoplastic polymer material based on an intimate mixture of one or more polyolefins and of one or more polyether ester amides.

Description

La présente invention concerne une semelle de ski c'est-à-dire la partie inférieure du ski en contact avec la neige et sur laquelle repose le ski ainsi que le skieur.The present invention relates to a ski sole, that is to say the lower part of the ski in contact with the snow and on which the ski and the skier rests.

La semelle de ski selon l'invention présente une excellente apti­tude à absorber les farts et à les retenir durablement.The ski sole according to the invention has an excellent ability to absorb waxes and retain them durably.

Les semelles de ski se présentent en général sous forme d'une feuille ou d'un film d'épaisseur comprise entre 0,5 et 2 mm. Elles sont en matière plastique polyoléfinique et préférentiellement à base de polyéthylène de haute densité (PEHD), et/ou de haute masse moléculaire (masse moléculaire moyenne en nombre comprise entre 150.000 et 450.000) que l'on peut mesurer par chromatographie par perméation de gel.The ski soles are generally in the form of a sheet or a film with a thickness of between 0.5 and 2 mm. They are made of polyolefinic plastic and preferably based on high density polyethylene (HDPE), and / or high molecular weight (number average molecular weight between 150,000 and 450,000) which can be measured by gel permeation chromatography. .

De telles semelles sont réalisées selon une technique d'extrusion classique. Or les propriétés de résistance aux chocs, l'affinité tinc­toriale et la faculté à absorber les farts (corps gras de type paraf­fine) ne sont pas très satisfaisantes voire même insuffisantes pour les besoins spécifiques d'une semelle de ski.Such soles are produced according to a conventional extrusion technique. However, the impact resistance properties, the dye affinity and the ability to absorb waxes (paraffin-type fatty substances) are not very satisfactory or even insufficient for the specific needs of a ski sole.

C'est pourquoi on a tenté d'améliorer les qualités spécifiques des polyéthylènes des semelles de ski en modifiant leur structure soit par incorporation d'additifs soit par traitement avec un agent favorisant la porosité des PEHD.This is why we have tried to improve the specific qualities of the polyethylenes of ski soles by modifying their structure either by incorporating additives or by treatment with an agent promoting the porosity of HDPE.

Dans le brevet américain publié sous le n°3.075.948, on a décrit le greffage d'une polyoléfine (et notamment d'un polyéthylène) avec un silane.In the American patent published under No. 3,075,948, the grafting of a polyolefin (and in particular of a polyethylene) with a silane has been described.

Dans le brevet français publié sous le n°2.478.877, on a proposé de rectifier la surface de glisse en incorporant au PEHD une substance soluble dans des liquides non aqueux avant extrusion puis mise en forme de feuille ou de film.In the French patent published under No. 2,478,877, it has been proposed to rectify the sliding surface by incorporating into HDPE a substance soluble in non-aqueous liquids before extrusion then shaping into a sheet or film.

On utilise également du PEHD de très haute masse moléculaire (masse moléculaire moyenne en nombre comprise entre 300.000 et 8.000.000) pour fabriquer des semelles de ski de haute compétition. Ces semelles sont obtenues par frittage, technique beaucoup plus onéreuse que l'extrusion.HDPE of very high molecular weight (number average molecular weight of between 300,000 and 8,000,000) is also used to manufacture high competition ski soles. These soles are obtained by sintering, a much more expensive technique than extrusion.

Dans le brevet autrichien publié sous le n°332.273, on a décrit un procédé d'obtention d'une semelle de ski en PEHD fritté.In the Austrian patent published under No. 332,273, a process has been described for obtaining a sintered HDPE ski sole.

La semelle de ski, objet de la présente invention, comprend une feuille ou un film en matière polymère thermoplastique à base d'un mélange intime de une ou plusieurs polyoléfines et de un ou plusieurs polyétheresteramides.The ski sole, object of the present invention, comprises a sheet or film of thermoplastic polymer material based on an intimate mixture of one or more polyolefins and one or more polyetheresteramides.

Les propriétés que possède une telle semelle de ski sont, notam­ment :
- une excellente faculté à absorber les farts et à les retenir de façon durable,
- un glissement de très bonne qualité dû à un bas coefficient de frottement,
- une bonne résistance aux chocs et à l'abrasion,
- une bonne aptitude au collage sur l'ébauche du ski,
- une affinité tinctoriale particulièrement bonne ainsi que des propriétés d'antistatisme à basse température,
- une transparence ou une translucidité telle que l'on peut distin­guer tout à fait clairement l'ébauche du ski à travers la semelle éventuellement revêtue d'inscriptions diverses telles que dessins, marques...The properties that such a ski sole has are, in particular:
- an excellent ability to absorb waxes and retain them in a sustainable way,
- a very good slip due to a low coefficient of friction,
- good resistance to impact and abrasion,
- good bonding ability on the draft of the ski,
- a particularly good dye affinity as well as antistatic properties at low temperature,
- a transparency or translucency such that one can quite clearly distinguish the draft of the ski through the sole possibly coated with various inscriptions such as drawings, marks ...

Comme indiqué plus haut, la semelle de ski selon l'invention est constituée d'un matériau polymère thermoplastique à base d'une ou plusieurs polyoléfines et d'un ou plusieurs polyétheresteramides, et pouvant contenir divers additifs, charges...As indicated above, the ski sole according to the invention consists of a thermoplastic polymer material based on one or more polyolefins and one or more polyetheresteramides, and which may contain various additives, fillers, etc.

Par polyétheresteramides, on entend aussi bien les polyétherestera­mides statistiques (c'est-à-dire formés par l'enchaînement aléatoire des divers constituants monomères) que les polyétheresteramides séquencés c'est-à-dire formés de blocs présentant une certaine longueur de chaîne de leurs divers constituants.The term “polyetheresteramides” is intended to mean both the random polyetheresteramides (that is to say formed by the random sequence of the various monomer components) and the block polyetheresteramides, that is to say formed from blocks having a certain length of chain. their various constituents.

Les polyétheresteramides sont le produit de la copolycondensation de séquences polyamides à extrémités réactives avec des séquences polyé­thers à extrémités réactives, telles que entre autres :
. séquences polyamides à fins de chaîne dicarboxyliques avec des séquence polyétherdiols.Polyetheresteramides are the product of the copolycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, inter alia:
. polyamide sequences for dicarboxylic chain ends with polyetherdiol sequences.

De tels produits ont été décrits par exemple dans les brevets français n°74 18913 et 77 26678 dont le contenu doit être ajouté à la présente description.Such products have been described for example in French patents No. 74 18913 and 77 26678, the content of which must be 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 polyamide 6, 6.6, 6.12, 11 ou 12 (PA-6, PA-6.6, PA-6.12, PA-11, PA-12) ou de copolyamides 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 polyamide 6, 6.6, 6.12, 11 or 12 (PA- 6, PA-6.6, PA-6.12, PA-11, PA-12) or of copolyamides resulting from the polycondensation of their monomers.

La masse moléculaire moyenne en nombre des polyéthers est comprise généralement entre 200 et 6 000 et plus particulièrement entre 600 et 3 000.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 de préférence en polytétramé­thylène glycol (PTMG), polypropylène glycol (PPG), ou polyéthylène glycol (PEG).The polyether blocks preferably consist of polytetramethylene glycol (PTMG), polypropylene glycol (PPG), or polyethylene glycol (PEG).

La viscosité inhérente des polyétheresteramides est avantageusement comprise entre 0,8 et 2,05.The inherent viscosity of polyetheresteramides is advantageously between 0.8 and 2.05.

La viscosité inhérente est mesurée dans le métacrésol à 20°C avec une concentration initiale de 0,5 g pour 100 g de métacrésol. Elle est exprimée en dlg⁻¹.The inherent viscosity is measured in metacresol at 20 ° C with an initial concentration of 0.5 g per 100 g of metacresol. It is expressed in dlg⁻¹.

Les polyétheresteramides selon l'invention peuvent être formés de 5 à 85 % en poids de polyéther, et de 95 à 15 % en poids de polyamide, et de préférence de 30 à 80 % en poids de polyéther et de 70 à 20 % en poids de polyamide.The polyetheresteramides according to the invention 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 80% by weight of polyether and from 70 to 20% by weight polyamide.

La ou les polyoléfines utilisées pour la semelle de ski, objet de la présente invention consistent en polypropylène (PP), polyéthylène (PE), leurs mélanges ou copolymères, mais est de préférence le polyéthy­lène.The polyolefin (s) used for the ski sole, object of the present invention consist of polypropylene (PP), polyethylene (PE), their mixtures or copolymers, but is preferably polyethylene.

Suivant un mode de réalisation préféré de l'invention, la ou les polyoléfine(s) sont de masse moléculaire élevée.According to a preferred embodiment of the invention, the polyolefin (s) are of high molecular weight.

La masse moléculaire moyenne en nombre des polyoléfines préférées peut être comprise entre 100 000 et 500 000, et de préférence entre 150 000 et 400 000.The number average molecular weight of the preferred polyolefins can be between 100,000 and 500,000, and preferably between 150,000 and 400,000.

Le mélange de matériau polymère thermoplastique constituant la semelle de ski de l'invention peut contenir de 50 à 99 % en poids de polyoléfine(s) et de 50 à 1 % en poids de polyétheresteramide(s) et de préférence, il contient de 60 à 90 % en poids de polyoléfine(s) et de 40 à 10 % de polyétheresteramide(s).The mixture of thermoplastic polymer material constituting the ski sole of the invention may contain from 50 to 99% by weight of polyolefin (s) and from 50 to 1% by weight of polyetheresteramide (s) and preferably it contains from 60 90% by weight of polyolefin (s) and 40 to 10% of polyetheresteramide (s).

Le mélange peut éventuellement contenir par exemple jusqu'à 70 % de charges organiques ou minérales, fibreuses ou pulvérulentes.The mixture may optionally contain, for example, up to 70% of organic or inorganic, fibrous or pulverulent fillers.

Des mélanges similaires ont été décrits dans le brevet français publié sous le n° 2 519 012.Similar mixtures have been described in the French patent published under No. 2,519,012.

A titre d'exemple de charges, on peut citer notamment la silice, l'oxyde de titane, les fibres de verre, de carbone.Examples of fillers that may be mentioned include silica, titanium oxide, glass fibers, carbon fibers.

Le mélange peut également contenir divers additifs tels que agents anti-UV, agents démoulants, modifiants choc, farts...The mixture can also contain various additives such as anti-UV agents, release agents, impact modifiers, waxes ...

Pour améliorer la compatibilité des différents constituants du mélange, on peut en outre incorporer un agent émulgateur.To improve the compatibility of the various constituents of the mixture, it is also possible to incorporate an emulsifying agent.

Comme agent émulgateur, on peut choisir par exemple le polypropy­lène maléisé.As an emulsifying agent, it is possible to choose, for example, maleized polypropylene.

En général, on incorpore au mélange de 1 à 5 % en poids d'agent émulgateur.In general, 1 to 5% by weight of emulsifier is incorporated into the mixture.

La présence d'agent émulgateur n'est pas nécessaire. Cependant, elle est particulièrement recommandée lorsque la proportion de polyéthe­resteramide dans le mélange est supérieure ou égale à 20 % en poids.The presence of an emulsifying agent is not necessary. However, it is particularly recommended when the proportion of polyetheresteramide in the mixture is greater than or equal to 20% by weight.

La fabrication des semelles de ski selon l'invention et en particu­lier la mise en forme de feuille ou de film du mélange décrit ci-dessus peut s'effectuer selon tout procédé d'extrusion connu. Avant l'extrusion du mélange proprement dite, il est en outre nécessaire de mélanger intimement lesdits constituants de la semelle.The manufacture of the ski soles according to the invention and in particular the shaping of a sheet or film of the mixture described above can be carried out according to any known extrusion process. Before extruding the actual mixture, it is also necessary to intimately mix said constituents of the sole.

Il est possible d'opérer par mélange mécanique des constituants de la semelle avant introduction dans la trémie de l'extrudeuse.It is possible to operate by mechanical mixing of the constituents of the sole before introduction into the extruder hopper.

On peut également mélanger les matières premières constituant le mélange intime décrit précédemment sous forme pulvérulente ou granulaire et ensuite traiter le mélange à l'état fondu dans une extrudeuse mono-­ou double vis, ou dans un appareil de malaxage ou dans un appareil de calandrage. Cette technique assure une meilleure homogénéité du mélange.One can also mix the raw materials constituting the intimate mixture described above in powder or granular form and then treat the mixture in the molten state in a single or twin screw extruder, or in a kneading machine or in a calendering machine. This technique ensures better homogeneity of the mixture.

Une fois les constituants de la semelle intimement mélangés, ou peut procéder à l'extrusion proprement dite. On peut utiliser tout type d'extrudeuse mono ou double vis.Once the constituents of the sole are thoroughly mixed, or can proceed to the actual extrusion. Any type of single or twin screw extruder can be used.

Les techniques d'extrusion préférées sont soit l'extrusion-plaxage, soit l'extrusion-calandrage à plat.The preferred extrusion techniques are either extrusion-plastering or extrusion-calendering flat.

On obtient ainsi une feuille ou un film du mélange décrit précédem­ment d'épaisseur comprise entre 0,5 et 2 mm, et de préférence comprise entre 0,9 et 1,4 mm.A sheet or film of the mixture described above is thus obtained with a thickness of between 0.5 and 2 mm, and preferably between 0.9 and 1.4 mm.

Une variante du procédé de fabrication de semelle de ski selon l'invention consiste à incorporer au mélange constituant la semelle tout ou partie des farts avant l'extrusion. On obtient ainsi une semelle plus ou moins auto-fartée c'est-à-dire que le fartage du ski muni de sa semelle ne sera plus nécessaire.A variant of the ski sole manufacturing method according to the invention consists in incorporating into the mixture constituting the sole all or part of the waxes before extrusion. A more or less self-waxed sole is thus obtained, that is to say that the waxing of the ski provided with its sole will no longer be necessary.

La technique de l'auto-fartage présente les avantages suivants :
- la semelle peut absorber une plus grande quantité de farts.
- les farts étant intégrés à la structure de la semelle, ils sont maintenus de façon permanente à cette structure et le ski est farté une fois pour toutes.The self-waxing technique has the following advantages:
- the sole can absorb a larger amount of wax.
- the waxes being integrated into the structure of the sole, they are permanently maintained in this structure and the ski is waxed once and for all.

Sous la dénomination farts, on entend à la fois les farts de glisse, utilisés plus spécifiquement pour les skis de descente et les farts de retenue, plus spécifiquement employés pour les skis de fond.Under the name farts, we mean both gliding waxes, used more specifically for downhill skis and retaining farts, more specifically used for cross-country skis.

Les farts dits de glisse ont en général pour fonction principale d'améliorer le glissement du ski sur la neige en diminuant de façon non négligeable le coefficient de frottement de ladite semelle.The so-called sliding waxes generally have the main function of improving the sliding of the ski on snow by significantly reducing the coefficient of friction of said sole.

Les farts dits de retenue ont principalement une fonction anti-­recul : les cristaux de neige peuvent pénétrer dans la couche superfi­cielle de fart et ils donnent ainsi à la semelle les propriétés d'an­crage nécessaire à un bon maintien du ski sur la neige, lui évitant de glisser dans un sens non désiré par le skieur.So-called retaining farts mainly have an anti-kickback function: snow crystals can penetrate the surface layer of wax and they thus give the sole the anchoring properties necessary for good support of the ski on snow, preventing it to slide in a direction not desired by the skier.

Le collage de la semelle sur l'ébauche de ski peut se faire selon un procédé connu. A titre d'exemple, on peut opérer par flammage : on chauffe le film ou la feuille et on l'applique avec une pression sur l'ébauche de ski.The bonding of the sole to the ski blank can be done according to a known method. For example, one can operate by flaming: the film or sheet is heated and applied with pressure on the ski blank.

La présente invention s'applique également de façon avantageuse à la réalisation et à l'utilisation d'une feuille ou un film à base d'un ou plusieurs polyétheresteramides et d'une ou plusieurs polyoléfines tel que décrits précédemment comme surface de glissement d'objets ayant pour fonction de glisser sur une surface liquide ou solide telle que eau, neige, herbe...The present invention also applies advantageously to the production and use of a sheet or film based on one or more polyetheresteramides and one or more polyolefins as described above as a sliding surface for objects whose function is to slide on a liquid or solid surface such as water, snow, grass ...

A titre d'exemple de tels objets, on peut citer la luge, le trai­neau, la planche à voile, la planche de surf. Les exemples suivants illustrent l'invention sans toutefois la limiter.By way of example of such objects, mention may be made of sledging, sledding, windsurfing, surfboards. The following examples illustrate the invention without, however, limiting it.

EXEMPLE 1EXAMPLE 1 A - CONSTITUANTSA - CONSTITUENTS

La composition de la semelle de ski comprend en poids : - polyéthylène haute densité (PEHD) 90 parts (copolymère éthylène-butène contenant 2 à 3 % de butène de Mn = 150 000) - polyétheresteramide 10 parts (résultant de la copolycondensation de séquences PA-12 de Mn = 600 et de séquences polyéthers (PTMG) de Mn = 2000). The composition of the ski sole includes by weight: - high density polyethylene (HDPE) 90 parts (ethylene-butene copolymer containing 2 to 3% butene of M n = 150,000) - polyetheresteramide 10 parts (resulting from the copolycondensation of PA-12 sequences of M n = 600 and polyether sequences (PTMG) of M n = 2000).

B - MISE EN OEUVREB - IMPLEMENTATION

On procède au mélange mécanique des granulés des constituants décrits en 1.A. On introduit ensuite le mélange ainsi obtenu dans une extrudeuse mono vis dont la vitesse de rotation de la vis est de 100 tours/mn. Dans l'extrudeuse, l'ensemble est porté à une température comprise entre 225 et 230° C.The granules of the constituents described in 1.A are mechanically mixed. The mixture thus obtained is then introduced into a single-screw extruder whose speed of rotation of the screw is 100 revolutions / min. In the extruder, the assembly is brought to a temperature between 225 and 230 ° C.

On obtient en sortie de filière, une feuille continue de 1,2 mm d'épaisseur et de 105 mm de largeur(ECHANTILLON 1).At the outlet of the die, a continuous sheet 1.2 mm thick and 105 mm wide is obtained (SAMPLE 1).

A titre de comparaison, on extrude du PEHD seul dans les mêmes conditions que ci-dessus afin d'obtenir une feuille continue de 1,2 mm d'épaisseur et de 105 mm de largeur (ECHANTILLON 2).By way of comparison, HDPE alone is extruded under the same conditions as above in order to obtain a continuous sheet 1.2 mm thick and 105 mm wide (SAMPLE 2).

Pour connaître les caractéristiques des feuilles des ECHANTILLONS 1 et 2, on détermine l'énergie superficielle libre γs des surfaces des feuilles des ECHANTILLONS 1 et 2 ainsi que ses 2 composantes : γs d et γs p.To know the characteristics of the leaves of SAMPLES 1 and 2, we determine the free surface energy γ s of the surfaces of the leaves of SAMPLES 1 and 2 as well as its 2 components: γ s d and γ s p .

L'énergie superficielle libre de la surface d'un solide est la somme de la composante γs d (contribution des forces dispersives de London) et de la composante γs p (contribution des forces non disper­sives : forces polaires et autres forces) γs = γs d + γs p.The free surface energy of the surface of a solid is the sum of the component γ s d (contribution of London dispersive forces) and the component γ s p (contribution of non-dispersive forces: polar forces and other forces) γ s = γ s d + γ s p .

Pour cela, on mesure l'angle de raccordement ϑ que fait une goutte de liquide standard déposée sur une face maintenue horizontale des feuilles des ECHANTILLONS 1 et 2.For this, we measure the connection angle ϑ made by a drop of standard liquid deposited on a side kept horizontal of the sheets of SAMPLES 1 and 2.

La méthode de mesure de l'angle de raccordement est exposée dans l'article de W.D. WARKINS, The Physical Chemistry of Surface Films, p 41. Reinhold Pub. Corp. 1952.The method of measuring the connection angle is described in the article by W.D. WARKINS, The Physical Chemistry of Surface Films, p 41. Reinhold Pub. Corp. 1952.

Les mesures d'angles de raccordement sont effectuées à 25° C successivement sur les 2 faces des échantillons.The connection angle measurements are carried out successively at 25 ° C on both sides of the samples.

Les liquides standards utilisés sont :
- le diodométhane, l'α-bromonaphtalène (liquides peu polaires)
- l'eau, le formamide (liquides polaires)The standard liquids used are:
- diodomethane, α-bromonaphthalene (slightly polar liquids)
- water, formamide (polar liquids)

On dépose une goutte de 1 à 5 µl de liquide standard sur la face maintenue horizontale de la feuille.A drop of 1 to 5 µl of standard liquid is placed on the horizontal side of the sheet.

30 secondes à 2 minutes après dépôt de la goutte sur la surface horizontale de la feuille, on mesure l'angle de raccordement ϑ que fait la goutte avec la surface horizontale sur laquelle elle a été déposée.30 seconds to 2 minutes after depositing the drop on the horizontal surface of the sheet, we measure the connection angle ϑ made by the drop with the horizontal surface on which it was deposited.

Une fois l'angle de raccordement mesuré, on utilise la méthode de W. RABEL - Farbe and Lack - 77 Jahrg - n° 10 - 997-1006-1971 pour calculer γs d, γs p et γs.Once the connection angle has been measured, we use the method of W. RABEL - Farbe and Lack - 77 Jahrg - n ° 10 - 997-1006-1971 to calculate γ s d , γ s p and γ s .

Les résultats sont réunis dans le Tableau I. γs d, γs p et γs sont exprimées en m N.m⁻¹. La précision des mesures est de ± 1 m N.m⁻¹.The results are collated in Table I. γ s d , γ s p and γ s are expressed in m Nm⁻¹. The accuracy of the measurements is ± 1 m Nm⁻¹.

On ne note pas de différence significative entre les 2 faces des ECHANTILLONS 1 et 2.There is no significant difference between the 2 faces of SAMPLES 1 and 2.

Les caractéristiques physiques des ECHANTILLONS 1 et 2 sont très différentes : l'ECHANTILLON 1 (mélange de PEHD et de polyéthereste­ramide) présente une énergie superficielle libre de 39 % supérieure à celle de l'ECHANTILLON 2 (PEHD seul). La contribution polaire est égale à 6,7 m N.m⁻¹ pour l'ECHANTILLON 1 alors qu'elle est nulle pour l'ECHAN­TILLON 2. TABLEAU I Energie superficielle libre γS (mN.m⁻¹) Contribution dispersive γS d (mN.m⁻¹) Contribution polaire γS p (mN.m⁻¹) ENCHANTILLON 1 45,4 38,7 6,7 ENCHANTILLON 2 32,7 32,7 0 The physical characteristics of SAMPLES 1 and 2 are very different: SAMPLING 1 (mixture of HDPE and polyetheresteramide) has a free surface energy of 39% greater than that of SAMPLING 2 (HDPE alone). The polar contribution is equal to 6.7 m Nm⁻¹ for SAMPLE 1 while it is zero for SAMPLE 2. TABLE I Free surface energy γ S (mN.m⁻¹) Dispersive contribution γ S d (mN.m⁻¹) Polar contribution γ S p (mN.m⁻¹) SAMPLE 1 45.4 38.7 6.7 SAMPLE 2 32.7 32.7 0

EXEMPLE 2EXAMPLE 2 A - CONSTITUANTSA - CONSTITUENTS

La composition de la semelle comprend en poids : - PEHD 80 parts (homopolymère de propylène de Mn = 300 000) - polyétheresteramide 20 parts (obtenu par copolycondensation de-séquences PA - 12 de Mn = 850 et de séquences polyéthers (PTMG) de Mn = 2000.) The composition of the sole includes by weight: - HDPE 80 parts (propylene homopolymer of Mn = 300,000) - polyetheresteramide 20 parts (obtained by copolycondensation of PA-12 sequences of Mn = 850 and polyether sequences (PTMG) of Mn = 2000.)

B - MISE EN OEUVREB - IMPLEMENTATION

Dans une extrudeuse double vis WERNER PFLEIDERER de type ZSK 30, on mélange à l'état fondu la composition décrite en A.In a WERNER PFLEIDERER ZSK 30 twin screw extruder, the composition described in A is mixed in the molten state.

L'ensemble est porté à 230° C, la vitesse de rotation de la vis est de 150 tours/mn et le débit de la matière est de 17 kg/h.The whole is brought to 230 ° C., the speed of rotation of the screw is 150 rpm and the flow rate of the material is 17 kg / h.

On obtient des granulés que l'on extrude dans des conditions identiques à celles de l'EXEMPLE 1 afin d'obtenir une feuille continue de 1,2 mm d'épaisseur et de 105 mm de largeur.Granules are obtained which are extruded under conditions identical to those of EXAMPLE 1 in order to obtain a continuous sheet 1.2 mm thick and 105 mm wide.

A titre comparatif, on extrude du PEHD seul (dont les caracté­ristiques sont celles décrites en 2.A) dans les mêmes conditions afin d'obtenir une feuille continue de PEHD de 1,2 mm d'épaisseur et de 105 mm de largeur.By way of comparison, HDPE alone is extruded (the characteristics of which are those described in 2.A) under the same conditions in order to obtain a continuous sheet of HDPE 1.2 mm thick and 105 mm wide.

Les feuilles ainsi réalisées sont aptes à être collées sur une ébauche de ski et le ski ainsi réalisé peut alors subir un fartage.The sheets thus produced are capable of being bonded to a ski blank and the ski thus produced can then undergo waxing.

EXEMPLE 3EXAMPLE 3

Au mélange de PEHD et de polyétheresteramide réalisé à l'état fondu et décrit l'EXEMPLE 2, on ajoute quelques parties en poids de fart du commerce. On extrude ce mélange ainsi obtenu dans les mêmes condi­tions qu'en 2.B.To the mixture of HDPE and polyetheresteramide produced in the molten state and described in EXAMPLE 2, a few parts by weight of commercial wax are added. This mixture thus obtained is extruded under the same conditions as in 2.B.

On obtient une feuille continue dite "auto-fartée" que l'on peut coller sur l'ébauche de ski.We obtain a continuous sheet called "self-waxed" that can be glued on the ski blank.

Selon la quantité de fart introduite comme ci-dessus dans la structure de la semelle, un fartage ultérieur peut ne pas être néces­saire.Depending on the amount of wax introduced as above into the sole structure, subsequent waxing may not be necessary.

Claims (17)

1. Semelle de ski comprenant une feuille ou un film en matière polymère thermoplastique, caractérisée en ce que ladite matière polymère thermoplastique est à base d'un mélange intime d'une ou plusieurs polyoléfines et d'un ou plusieurs polyétheresteramides.1. Ski sole comprising a sheet or film of thermoplastic polymer material, characterized in that said thermoplastic polymer material is based on an intimate mixture of one or more polyolefins and one or more polyetheresteramides. 2. Semelle de ski selon la revendication 1, caractérisée en ce que le ou les polyétheresteramides sont des polyétheresteramides statis­tiques.2. Ski sole according to claim 1, characterized in that the polyetheresteramide (s) are random polyetheresteramide (s). 3. Semelle de ski selon la revendication 1, caractérisée en ce que le ou les polyétheresteramides consistent en les produits de la copoly-­condensation de séquences polyamides à extrémités réactives avec des séquences polyéthers à extrémités réactives, telles que :
. séquences polyamides à fins de chaîne dicarboxyliques avec des séquences polyétherdiols.3. Ski sole according to claim 1, characterized in that the polyetheresteramide (s) consist of the products of the copoly-condensation of polyamide sequences with reactive ends with polyether sequences with reactive ends, such as:
. polyamide sequences for dicarboxylic chain ends with polyetherdiol sequences. 4. Semelle de ski selon la revendication 3 caractérisée en ce que les séquences polyamides des polyétheresteramides sont formées de préférence de polyamide 6, 11, 6.6, 6.12, ou 12 (PA-6, PA-11, PA-6.6, PA-6.12, PA-12- ou de copolyamide résultant de la copolycondensation de leurs monomères.4. Ski sole according to claim 3 characterized in that the polyamide sequences of the polyetheresteramides are preferably formed of polyamide 6, 11, 6.6, 6.12, or 12 (PA-6, PA-11, PA-6.6, PA-6.12 , PA-12- or copolyamide resulting from the copolycondensation of their monomers. 5. Semelle de ski selon l'une quelconque des revendications 3 ou 4 caractérisée en ce que la masse moléculaire moyenne en nombre de ces séquences polyamides est comprise entre 500 et 10 000 et plus particu­lièrement entre 600 et 5 000.5. Ski sole according to any one of claims 3 or 4 characterized in that the number-average molecular mass of these polyamide sequences is between 500 and 10,000 and more particularly between 600 and 5,000. 6. Semelle de ski selon l'une quelconque des revendications 1 à 5 caractérisée en ce que les séquences polyéthers consistent en polytétra­méthylène glycol (PTMG), polypropylène glycol (PPG) ou polyéthylène glycol (PEG).6. Ski sole according to any one of claims 1 to 5 characterized in that the polyether sequences consist of polytetramethylene glycol (PTMG), polypropylene glycol (PPG) or polyethylene glycol (PEG). 7. Semelle de ski selon l'une quelconque des revendications 1 à 6, caractérisée en ce que la masse moléculaire moyenne en nombre des polyéthers est comprise entre 200 et 6 000 et plus particulièrement entre 600 et 3 000.7. Ski sole according to any one of claims 1 to 6, characterized in that the number-average molecular weight of the polyethers is between 200 and 6000 and more particularly between 600 and 3000. 8. Semelle de ski selon l'une quelconque des revendications 1 à 7, caractérisée en ce que le polyétheresteramide précité est formé de 5 à 85 % et plus particulièrement de 30 à 80 % de polyéther et de 95 à 15 % et de préférence 70 à 20 % de polyamide.8. Ski sole according to any one of claims 1 to 7, characterized in that the aforementioned polyetheresteramide is formed from 5 to 85% and more particularly from 30 to 80% of polyether and from 95 to 15% and preferably 70 20% polyamide. 9. Semelle de ski selon l'une quelconque des revendications 1 à 8, caractérisée en ce que la ou les polyoléfines consistent en polypropy­lène, polyéthylène, leurs mélanges ou leurs copolymères.9. Ski sole according to any one of claims 1 to 8, characterized in that the polyolefin (s) consist of polypropylene, polyethylene, their blends or their copolymers. 10. Semelle de ski selon l'une quelconque des revendications 1 à 9 caractérisée en ce que la polyoléfine est un polyéthylène de haute densité et de masse moléculaire moyenne en nombre comprise entre 100 000 et 500.000, et de préférence compris entre 150.000 et 400.000.10. Ski sole according to any one of claims 1 to 9 characterized in that the polyolefin is a high density polyethylene and of number average molecular weight between 100,000 and 500,000, and preferably between 150,000 and 400,000. 11. Semelle de ski selon l'une quelconque des revendications 1 à 10, caractérisée en ce que ledit mélange est formé de 50 à 99 % en poids de polyoléfine(s) et de 50 à 1 % en poids de polyétheresteramide(s).11. Ski sole according to any one of claims 1 to 10, characterized in that said mixture is formed from 50 to 99% by weight of polyolefin (s) and from 50 to 1% by weight of polyetheresteramide (s). 12. Semelle de ski selon l'une quelconque des revendications 1 à 10, caractérisée en ce que ledit mélange est formé de 60 à 90 % en poids de polyoléfine et de 40 à 10 % en poids de polyétheresteramide.12. Ski sole according to any one of claims 1 to 10, characterized in that said mixture is formed from 60 to 90% by weight of polyolefin and from 40 to 10% by weight of polyetheresteramide. 13. Semelle de ski selon l'une quelconque des revendications 1 à 12 caractérisée en ce qu'elle contient une charge organique ou minérale, fibreuse ou pulvérulente et/ou des additifs tels que agents anti-UV, agents démoulants, des agents émulgateurs.13. Ski sole according to any one of claims 1 to 12 characterized in that it contains an organic or inorganic, fibrous or pulverulent filler and / or additives such as anti-UV agents, release agents, emulsifying agents. 14. Semelle de ski, selon l'une quelconque des revendications 1 à 13, caractérisée en ce qu'on incorpore au mélange constituant la semelle tout ou partie des farts avant son extrusion et sa mise en forme de film ou de feuille.14. Ski sole according to any one of claims 1 to 13, characterized in that all or part of the waxes are incorporated into the mixture constituting the sole before it is extruded and shaped into film or sheet. 15. Procédé de fabrication d'une semelle de ski définie dans l'une quelconque des revendications 1 à 14, caractérisé en ce qu'on réalise préalablement un mélange intime des constituants de la semelle ; puis on extrude ledit mélange sous forme d'une feuille ou d'un film.15. A method of manufacturing a ski sole defined in any one of claims 1 to 14, characterized in that an intimate mixture of the constituents of the sole is previously produced; then said mixture is extruded in the form of a sheet or a film. 16. Ski dont la partie inférieure ou semelle est telle que définie dans l'une quelconque des revendications 1 à 13.16. Ski whose lower part or sole is as defined in any one of claims 1 to 13. 17. Surface assurant le glissement d'objet servant à glisser sur une surface liquide ou solide constituée d'un film, d'une feuille ayant des caractéristiques identiques à celles de la semelle de ski définie dans l'une quelconque des revendications 1 à 13.17. Surface ensuring the sliding of an object used to slide on a liquid or solid surface consisting of a film, of a sheet having characteristics identical to those of the ski sole defined in any one of claims 1 to 13 .
EP19890400297 1988-02-09 1989-02-02 Soles of ski, process for their fabrication, and skis equiped with these soles Ceased EP0328439A1 (en)

Applications Claiming Priority (2)

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FR8801519A FR2626778B1 (en) 1988-02-09 1988-02-09 NEW SKI SOLES, THEIR MANUFACTURING PROCESS AND SKIS EQUIPPED WITH SUCH SOLE
FR8801519 1988-02-09

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EP0459862A1 (en) * 1990-06-01 1991-12-04 Elf Atochem S.A. Compositions of thermoplastic elastomers based on polyamides and modified polyolefins, moulded or extruded articles, films and composite materials produced therefrom
EP0461966A1 (en) * 1990-06-14 1991-12-18 Elf Atochem S.A. Thermoplastic elastomeric films based on polyamide and modified copolyolefine(s), apt for glueing composite materials obtained therewith
FR2697440A1 (en) * 1992-10-30 1994-05-06 Salomon Sa Ski with upper decorative sub assembly - made of alloy of polyamide and polyolefin with compatibiliser provides high resistance to deterioration with good printing characteristics
US5348804A (en) * 1990-06-01 1994-09-20 Salomon S.A. Ski structure obtained from a polyamide based thermoplastic elastomer and grafted copolyolefin based film adapted for adhesion
US5506310A (en) * 1990-06-14 1996-04-09 Elf Atochem S.A. Adhesive film composition
WO2006069706A1 (en) * 2004-12-23 2006-07-06 Florian Felix Sliding coating for winter sports equipment
EP2110164A1 (en) * 2008-04-16 2009-10-21 ATOMIC Austria GmbH Running sole material for winter sport device
CN101090757B (en) * 2004-12-23 2010-10-06 弗洛里安·费利克斯 Sliding coating for winter sports equipment, preparation method and winter sports device
EP2353670A3 (en) * 2010-02-05 2013-05-15 Zai AG Snowglide board

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US6588772B2 (en) * 2000-12-28 2003-07-08 The Burton Corporation Sintered sheet plastic material and gliding board base material
DE10305088B4 (en) * 2003-02-07 2005-03-24 Xaver Hoffmann Winter sports equipment with sliding coating

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0459862A1 (en) * 1990-06-01 1991-12-04 Elf Atochem S.A. Compositions of thermoplastic elastomers based on polyamides and modified polyolefins, moulded or extruded articles, films and composite materials produced therefrom
US5348804A (en) * 1990-06-01 1994-09-20 Salomon S.A. Ski structure obtained from a polyamide based thermoplastic elastomer and grafted copolyolefin based film adapted for adhesion
EP0461966A1 (en) * 1990-06-14 1991-12-18 Elf Atochem S.A. Thermoplastic elastomeric films based on polyamide and modified copolyolefine(s), apt for glueing composite materials obtained therewith
FR2663339A1 (en) * 1990-06-14 1991-12-20 Atochem THERMOPLASTIC ELASTOMERIC (S) FILMS BASED ON POLYAMIDE AND COPOLYOLEFIN (S) MODIFIED FOR BONDING, COMPOSITE MATERIALS OBTAINED FROM SAID FILMS.
US5506310A (en) * 1990-06-14 1996-04-09 Elf Atochem S.A. Adhesive film composition
FR2697440A1 (en) * 1992-10-30 1994-05-06 Salomon Sa Ski with upper decorative sub assembly - made of alloy of polyamide and polyolefin with compatibiliser provides high resistance to deterioration with good printing characteristics
WO2006069706A1 (en) * 2004-12-23 2006-07-06 Florian Felix Sliding coating for winter sports equipment
CN101090757B (en) * 2004-12-23 2010-10-06 弗洛里安·费利克斯 Sliding coating for winter sports equipment, preparation method and winter sports device
EP2110164A1 (en) * 2008-04-16 2009-10-21 ATOMIC Austria GmbH Running sole material for winter sport device
EP2353670A3 (en) * 2010-02-05 2013-05-15 Zai AG Snowglide board

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KR890012680A (en) 1989-09-18

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