WO2020021038A1 - Snowshoe sole - Google Patents

Snowshoe sole Download PDF

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Publication number
WO2020021038A1
WO2020021038A1 PCT/EP2019/070106 EP2019070106W WO2020021038A1 WO 2020021038 A1 WO2020021038 A1 WO 2020021038A1 EP 2019070106 W EP2019070106 W EP 2019070106W WO 2020021038 A1 WO2020021038 A1 WO 2020021038A1
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WO
WIPO (PCT)
Prior art keywords
oils
phr
sole according
sole
snowshoe
Prior art date
Application number
PCT/EP2019/070106
Other languages
French (fr)
Inventor
Bozena Voge
Philippe Souyri
Original Assignee
Compagnie Generale Des Etablissements Michelin
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 Compagnie Generale Des Etablissements Michelin filed Critical Compagnie Generale Des Etablissements Michelin
Priority to CA3102707A priority Critical patent/CA3102707A1/en
Priority to EP19742769.3A priority patent/EP3826737A1/en
Publication of WO2020021038A1 publication Critical patent/WO2020021038A1/en

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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
    • A63C13/00—Snow shoes
    • A63C13/005—Frames therefor

Definitions

  • the present invention relates to snowshoe soles.
  • Snowshoes have been known for many years. They were originally designed to allow people to move on soils covered with a large amount of snow. They are also very widespread in the Nordic countries, frequently affected by heavy snowfall. However, these extreme conditions less and less reflect the reality of the current use of snowshoes. Indeed, nowadays, they are mainly used in a "sport and leisure" setting by hikers. The followers are of very varied levels, from the beginner to the expert hiker, the requirements of each level are very different. This heterogeneity forces manufacturers to constantly develop new products to best meet various expectations. There are therefore today several product lines, each with specific advantages. But manufacturers are still looking for innovative solutions that can provide greater comfort and increased dynamic performance.
  • snowshoes consist of a sieve, a front spatula, a rear portion and a fixing system. This basic configuration makes it easy to move on snow due to its increased lift, avoiding sinking into the snow.
  • snowshoe architecture Different types have been developed to allow an easy approach, with an unrolled foot making walking easier and more natural. So in order to always improve user comfort when snowshoeing, the ergonomics of snowshoes have been improved along various development axes.
  • One of these axes includes grip for use specifically on snowshoe ice using elastomer soles provided with indentations and / or studs.
  • the document WO9506502 describes a snowshoe formed from a semi-flexible platform comprising connecting means for binding a user shoe to the platform.
  • the platform is molded in a semi-flexible plastic which can flex with the shoe, such as for example thermoplastic polyurethane.
  • the hardness of the platform is between 50 and 90 Shore D at around 18 ° c. This characteristic makes it a slightly flexible racket but insufficient to obtain real comfort during the unrolling of the foot.
  • the underside of the platform is formed with indentations and / or protrusions to increase traction when using snowshoes.
  • the circular recesses each contain an oval recess oriented according to their location on the lower side.
  • the semi-flexible plastic material as well as the indentations make it possible to increase the grip rate of the rackets, which remains however perfectible.
  • the document FR2743501 describes a walking racket, in particular on snow, consisting of a substantially flat platform, provided with reversible fastening members for the user's foot to said platform, made of cellular elastomer.
  • This racket is light, rigid but with a certain elasticity and with good grip.
  • the underside has studs formed by molding, distributed as a function of the distribution of the load in use. These characteristics allow the user to have a more comfortable racket than conventional rackets and also to have better grip thanks to the distribution of the studs.
  • the grip provided by the elastomer studs and their distribution do not give optimal grip to the racket.
  • the front part of the racket forces the user to lift the foot more than usual, which can lead to premature fatigue.
  • the Applicant has discovered that by adding to the basic structure of the snowshoe initially intended to come into contact with the ground, a sole which will be in contact with the ground, produced using a specific rubber composition. , the snowshoe surprisingly improved its grip properties.
  • the subject of the invention is therefore a snowshoe sole comprising a rubber composition based on at least one majority isoprene elastomer, a reinforcing inorganic filler, a plasticizer and a crosslinking system.
  • the plasticizer of the composition has a Tg less than or equal to 20 ° C.
  • the plasticizer of the composition is chosen from plasticizing oils and their mixtures.
  • the plasticizing oils are chosen from the group consisting of naphthenic oils, paraffinic oils, MES oils (Medium Extracted Solvated), TDAE oils (Treated Distillate Aromatic Extracts), RAE oils (Residual Aromatic Extract oils), TRAE oils (Treated Residual Aromatic Extract) and SRAE oils (Safety Residual Aromatic Extract oils), mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulfonate plasticizers and mixtures of these compounds .
  • the level of plasticizer in the composition is greater than or equal to 5 parts per hundred parts of elastomers, phr, preferably it ranges from 5 to 50 phr, more preferably from 10 to 40 phr and even more preferably from 25 at 40 pce.
  • the level of isoprene elastomer of the composition ranges from 60 to 100 phr, preferably from 70 to 100 phr, more preferably from 80 to 100 phr.
  • the level of reinforcing inorganic filler of the composition ranges from 10 to 60 phr, preferably from 30 to 55 phr; the reinforcing inorganic filler preferably being silica.
  • the invention also relates to a snowshoe comprising a sole as described above.
  • the invention also relates to a snowshoe comprising a basic structure of non-rubber material forming a shoe zone and a lift zone and in which the lift zone comprises a lateral overhang on each side of the shoe zone, said zone of bearing extends towards the rear of the shoe zone to form a rear spatula and forms a front portion of the racket opposite the rear spatula, the contact face of the basic structure comprising a sole as described previously.
  • the present invention relates to a snowshoe sole comprising a rubber composition based on at least one majority isoprene elastomer, a reinforcing inorganic filler, a plasticizer and a crosslinking system.
  • composition based on is meant a composition comprising the mixture and / or the in situ reaction product of the various constituents used, some of these constituents being able to react and / or being intended to react with each other, less partially, during the different manufacturing phases of the composition; the composition thus being able to be in the fully or partially crosslinked state or in the non-crosslinked state.
  • any range of values designated by the expression “between a and b” represents the range of values going from more than a to less than b (ie limits a and b excluded) while any range of values designated by the expression “from a to b” signifies the range of values ranging from a to b (that is to say including the strict limits a and b).
  • the expression “part by weight per hundred parts by weight of elastomer” (or phr) it is to be understood in the sense of the present invention, the part, by mass per hundred parts by mass of elastomer.
  • a majority compound it is understood within the meaning of the present invention, that this compound is predominant among the compounds of the same type in the composition, that is to say that it is that which represents the greatest amount by mass among compounds of the same type.
  • a majority elastomer is the elastomer representing the largest mass relative to the total mass of the elastomers in the composition.
  • a so-called majority charge is that representing the largest mass among the charges of the composition.
  • the majority elastomer represents more than half of the mass of the elastomers.
  • the compounds comprising carbon mentioned in the description can be of fossil origin or bio-based. In the latter case, they can be, partially or totally, from biomass or obtained from renewable raw materials from biomass. Are concerned in particular polymers, plasticizers, fillers, etc.
  • iene elastomer or indistinctly rubber, whether natural or synthetic, must be understood in known manner an elastomer consisting at least in part (ie, a homopolymer or a copolymer) of diene monomer units (monomers carrying two carbon-carbon double bonds, conjugated or not).
  • diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”.
  • essentially unsaturated means a diene elastomer derived at least in part from conjugated diene monomers, having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (% by moles); This is how diene elastomers such as butyl rubbers or copolymers of dienes and of alpha-olefins of the EPDM type do not enter into the preceding definition and can be qualified in particular as “essentially saturated” diene elastomers (content of motifs of diene origin weak or very weak, always less than 15%).
  • iene elastomer capable of being used in the compositions in accordance with the invention is particularly understood to mean: (a) - any homopolymer of a diene monomer, conjugated or not, having from 4 to 18 carbon atoms;
  • the other monomer can be ethylene, an olefin or a diene, conjugated or not.
  • conjugated dienes having from 4 to 12 carbon atoms are suitable, in particular 1,3-dienes, such as in particular 1,3-butadiene and isoprene.
  • olefins suitable are vinyl aromatic compounds having 8 to 20 carbon atoms and aliphatic ⁇ -monoolefins having 3 to 12 carbon atoms.
  • vinyl aromatic compounds examples include styrene, ortho-, meta-, para-methylstyrene, the commercial "vinyl-toluene” mixture, para-tert-butylstyrene.
  • aliphatic ⁇ -monoolefins suitable in particular are acyclic aliphatic ⁇ -monoolefins having 3 to 18 carbon atoms.
  • the diene elastomer is chosen from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene copolymers, isoprene copolymers, and mixtures of these. elastomers.
  • the butadiene copolymers are particularly chosen from the group consisting of butadiene-styrene copolymers (SBR).
  • isoprene elastomer is understood in known manner an isoprene homopolymer or copolymer, in other words a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), different isoprene copolymers and mixtures of these elastomers.
  • NR natural rubber
  • IR synthetic polyisoprenes
  • isoprene copolymers mention will be made in particular of isobutene-isoprene (butyl rubber - IIR), isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene copolymers (SBIR).
  • This isoprene elastomer is preferably natural rubber or a synthetic cis-1,4 polyisoprene; among these synthetic polyisoprenes, polyisoprenes are preferably used having a rate (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%.
  • diene elastomer a person skilled in the art of tires will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b ) above.
  • the diene elastomer can be modified, that is to say either coupled and / or star-shaped, or functionalized, or coupled and / or star-shaped and simultaneously functionalized.
  • the diene elastomer can be coupled and / or star-shaped, for example by means of a silicon or tin atom which links the elastomer chains together.
  • the diene elastomer can be simultaneously or alternately functionalized and comprise at least one functional group.
  • functional group is meant a group comprising at least one heteroatom chosen from Si, N, S, O, P.
  • Particularly suitable as functional groups are those comprising at least one function such as: silanol, an alkoxysilane, a primary amine , secondary or tertiary, cyclic or not, a thiol, an epoxide.
  • the rubber composition of the invention may contain a single diene elastomer or a mixture of several diene elastomers.
  • the level of isoprene elastomer ranges from 60 to 100 phr, preferably from 70 to 100 phr, more preferably from 80 to 100 phr.
  • the composition also comprises one or more elastomers chosen from the group consisting of polybutadienes (BR), butadiene copolymers and mixtures of these elastomers.
  • BR polybutadienes
  • the composition comprises a level of 0 to 40 phr of these elastomers, preferably of 0 to 30 phr more preferably of 0 to 20 phr.
  • filler is meant here any type of filler, whether it is reinforcing or whether it is non-reinforcing or inert.
  • the rubber composition of the invention comprises at least one reinforcing filler.
  • Any type of reinforcing filler can be used, known for its capacity to reinforce a rubber composition which can be used in particular for the manufacture of tires, for example an organic filler such as carbon black, an inorganic filler such as silica or else a mixture of these two types of charges.
  • carbon blacks all carbon blacks are suitable, in particular the blacks conventionally used in tires or their treads.
  • the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series grades ASTM D-1765-2017
  • these carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a support for some of the rubber additives used.
  • the carbon blacks could for example already be incorporated into the diene elastomer, in particular isoprene, in the form of a masterbatch (see for example applications WO97 / 36724-A2 or WO99 / 16600-A1).
  • reinforcing inorganic filler should be understood here any inorganic or mineral filler, whatever its color and its origin (natural or synthetic), also called “white” filler, “clear” filler or even “non-black” filler As opposed to carbon black, capable of reinforcing on its own, without other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires.
  • certain reinforcing inorganic fillers can be characterized in particular by the presence of hydroxyl groups (-OH) on their surface.
  • inorganic fillers in particular mineral fillers of the siliceous type, preferably silica (Si02) or of the aluminous type, in particular alumina (A1203), are suitable.
  • the silica used can be any reinforcing silica known to those skilled in the art, in particular any precipitated or pyrogenic silica having a BET specific surface as well as a CTAB specific surface both of which are less than 450 m 2 / g, preferably included in a range ranging from 30 to 400 m2 / g, in particular from 60 to 300 m2 / g.
  • any type of precipitated silica can be used, in particular highly dispersible precipitated silicas (called “HDS” for “highly dispersible” or “highly dispersible silica”).
  • HDS highly dispersible precipitated silicas
  • These precipitated silicas, highly dispersible or not, are well known to those skilled in the art. Mention may be made, for example, of the silicas described in applications W003 / 016215-A1 and W003 / 016387-A1.
  • non-HDS silica the following commercial silicas can be used: "Ultrasil ® VN2GR”, “Ultrasil ® VN3GR” from Evonik, silica, "Hi-Sil EZl20G (-D)”, “ Hi-Sil EZl60G (-D) “,” Hi-Sil EZ200G (- D) “,” Hi-Sil 243LD “,” Hi-Sil 210 ",” Hi-Sil HDP 320G “from PPG.
  • reinforcing inorganic filler is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of silicas as described above.
  • a reinforcing filler of another nature could be used, since this reinforcing filler of another nature would be covered with an inorganic layer.
  • silica or else would have on its surface functional sites, in particular hydroxyls, requiring the use of a coupling agent to establish the connection between this reinforcing filler and the diene elastomer.
  • a coupling agent to establish the connection between this reinforcing filler and the diene elastomer.
  • carbon blacks partially or entirely covered with silica or carbon blacks modified with silica, such as, without limitation, fillers of the “Ecoblack®” type from the series CRX2000 ”or from the“ CRX4000 ”series from Cabot Corporation.
  • the rate of total reinforcing filler is included in a range from 10 to 100 phr, more preferably from 10 to 60 phr, more preferably from 20 to 60 phr; and even more preferably from 30 to 55 pce.
  • the reinforcing filler is mainly an inorganic reinforcing filler (preferably silica), that is to say that it comprises more than 50% (> 50%) by weight of an inorganic reinforcing filler such as silica relative to the total weight of the reinforcing filler.
  • the reinforcing filler also comprises carbon black.
  • the carbon black is used at a rate less than or equal to 20 phr, more preferably less than or equal to 10 phr and even more preferably the composition does not contain carbon black.
  • the BET surface area is determined by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society” (Vol. 60, page 309, February 1938) , and more precisely according to a method adapted from standard NF ISO 5794-1, appendix E of June 2010 [multi-point volumetric method (5 points) - gas: nitrogen - degassing under vacuum: one hour at 160 ° C - relative pressure range w / in: 0.05 to 0.2]
  • CT AB For inorganic fillers such as silica for example, the values of specific surface CT AB were determined according to standard NF ISO 5794-1, appendix G of June 2010. The process is based on the adsorption of CTAB (bromide of N -hexadecyl-N, N, N-trimethylammonium) on the "external" surface of the reinforcing filler.
  • the specific surface area STSA is determined according to standard ASTM D6556-2016.
  • an at least bifunctional coupling agent intended to ensure a sufficient connection, of chemical nature and / or physical, between the inorganic charge (surface of its particles) and the diene elastomer.
  • organosilanes or polyorganosiloxanes which are at least bifunctional are used.
  • bifunctional is meant a compound having a first functional group capable of interacting with the inorganic charge and a second functional group capable of interacting with the diene elastomer.
  • such a bifunctional compound can comprise a first functional group comprising a silicon atom, the said first functional group being capable of interacting with the hydroxyl groups of an inorganic charge and a second functional group comprising a sulfur atom, the so-called second functional group capable of interacting with the diene elastomer.
  • the organosilanes are chosen from the group consisting of polysulfurized organosilanes (symmetrical or asymmetrical) such as bis tetrasulfide (3-triethoxysilylpropyl), in short TESPT marketed under the name "Si69” by the company Evonik or bis disulfide - (triethoxysilylpropyle), abbreviated as TESPD marketed under the name “Si75” by the company Evonik, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, such as “NXT-Silane” sold by the company Momentive. More preferably, the organosilane is a polysulfurized organosilane.
  • the content of coupling agent in the composition of the invention is advantageously less than or equal to 20 phr, it being understood that it is generally desirable to use as little as possible.
  • the level of coupling agent represents from 0.5% to 15% by weight relative to the amount of reinforcing inorganic filler. Its rate is preferably included in a range from 0.5 to 12 phr, more preferably included in a range ranging from 3 to 10 phr. This rate is easily adjusted by a person skilled in the art according to the rate of reinforcing inorganic filler used in the composition.
  • composition of the invention may also comprise an additional filler such as an inert filler, for example, a semi-reinforcing filler such as graphite or a mixture of these two types of filler.
  • an additional filler such as an inert filler, for example, a semi-reinforcing filler such as graphite or a mixture of these two types of filler.
  • the composition does not include any additional filler.
  • the composition according to the invention comprises at least one plasticizer.
  • this plasticizer can be preferably chosen from hydrocarbon resins of high glass transition temperature (Tg), plasticizing oils, and their mixtures.
  • Tg glass transition temperature
  • the plasticizer is chosen from plasticizing oils and their mixtures.
  • a high Tg hydrocarbon resin is by definition a solid at room temperature and pressure (20 ° C, 1 atm), while a plasticizer oil is liquid at room temperature and a low Tg hydrocarbon resin is viscous at room temperature.
  • the Tg is measured according to standard ASTM D3418 (1999).
  • the total level of plasticizers in the composition is greater than or equal to 5 phr, preferably it ranges from 5 to 50 phr, preferably from 10 to 40 phr, and even more preferably from 25 to 40 phr. Below 5 phr, the targeted technical effect may prove to be insufficient, while beyond the upper limit, the desired compromise in properties for the rubber composition considered is no longer achieved.
  • the plasticizer mainly comprises plasticizing oils or their mixtures.
  • the plasticizer consists of one or more plasticizing oils or their mixture.
  • the level of plasticizing oils is greater than or equal to 5 phr, preferably greater it ranges from 5 to 50 phr, preferably from 10 to 40 phr, and even more preferably from 25 to 40 phr.
  • the plasticizer can also contain an extension oil (or plasticizing oil) liquid at 20 ° C, called "low Tg", that is to say which by definition has a Tg below 20 ° C, preferably lower at 40 ° C.
  • low Tg an extension oil (or plasticizing oil) liquid at 20 ° C
  • extension oil whether of an aromatic or non-aromatic nature known for its plasticizing properties with regard to elastomers, can be used.
  • these oils more or less viscous, are liquids (that is to say, substances having the capacity to eventually take the form of their container), by difference especially with high Tg hydrocarbon resins which are by nature solid at room temperature.
  • plasticizing oils chosen from the group consisting of naphthenic oils (low or high viscosity, in particular hydrogenated or not), paraffinic oils, MES oils (Medium Extracted Solvated), TDAE oils (Treated Distillate Aromatic Extracts), RAE (Residual Aromatic Extract oils), TRAE (Treated Residual Aromatic Extract) oils and SRAE (Safety) oils Residual Aromatic Extract oils), mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulfonate plasticizers and mixtures of these compounds.
  • the liquid plasticizer is a petroleum oil, preferably non-aromatic.
  • a liquid plasticizer is qualified as non-aromatic when it has a content of polycyclic aromatic compounds, determined with the extract in DMSO according to the IP 346 method, of less than 3% by weight, relative to the total weight of the plasticizer.
  • a liquid plasticizing agent may be used chosen from the group consisting of MES oils, TDAE oils, naphthenic oils (low or high viscosity, in particular hydrogenated or not), paraffinic oils and mixtures of these oils.
  • RAE oils, TRAE oils and SRAE oils or mixtures of these oils, which contain low contents of polycyclic compounds, are also suitable as petroleum oil.
  • Liquid polymers resulting from the polymerization of olefins or dienes such as polybutenes, polydienes, in particular polybutadienes, polyisoprenes (also known under the name "LIR") or copolymers of butadiene, are also suitable as plasticizing oil. isoprene, or the copolymers of butadiene or isoprene and styrene or mixtures of these liquid polymers.
  • the number-average molar mass of such liquid polymers is preferably within a range from 500 g / mol to 50,000 g / mol, preferably from 1,000 g / mol to 10,000 g / mol.
  • the "RICON" products from SARTOMER.
  • the crosslinking system can be any type of system known to those skilled in the art in the field of rubber compositions. It can in particular be based on sulfur, and / or peroxide and / or bismaleimides.
  • the crosslinking system is based on sulfur, this is called a vulcanization system.
  • the sulfur can be provided in any form, in particular in the form of molecular sulfur, or of a sulfur donor.
  • At least one vulcanization accelerator is also preferably present, and, optionally, also preferentially, various known vulcanization activators can be used such as zinc oxide, stearic acid or equivalent compound such as stearic acid salts and salts. of transition metals, guanidine derivatives (in particular diphenylguanidine), or also known vulcanization retardants.
  • Sulfur is used at a preferential rate of between 0.5 and 12 phr, in particular between 1 and 10 phr.
  • the vulcanization accelerator is used at a preferential rate of between 0.5 and 10 phr, more preferably of between 0.5 and 5.0 phr.
  • Any compound capable of acting as an accelerator for vulcanization of diene elastomers in the presence of sulfur in particular accelerators of the thiazole type and their derivatives, accelerators of the sulfenamide, thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthate type can be used as accelerator.
  • Examples of such accelerators include the following compounds: 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (“CBS”), N, N-dicyclohexyl- 2-benzothiazyle sulfenamide (“DCBS”), N-ter-butyl-2-benzothiazyle sulfenamide (“TBBS”), N-ter-butyl-2-benzothiazyle sulfenimide (“TBSI”), tetrabenzylthiuram disulfide (“TBZTD”) , zinc dibenzyldithiocarbamate (“ZBEC”) and mixtures of these compounds. Miscellaneous additives.
  • MBTS 2-mercaptobenzothiazyl disulfide
  • CBS N-cyclohexyl-2-benzothiazyl sulfenamide
  • DCBS N-dicyclohexy
  • the rubber compositions in accordance with the invention may also comprise all or part of the usual additives and processing agents known to those skilled in the art and usually used in rubber compositions, such as for example pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants.
  • additives and processing agents known to those skilled in the art and usually used in rubber compositions, such as for example pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants.
  • the rubber compositions of the invention are produced in suitable mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first working phase or thermo-mechanical kneading (sometimes called a phase "non-productive") on a suitable mixer (for example "Banbury” type mixer) at high temperature, up to a maximum temperature of between 10 ° C and 200 ° C, preferably between 135 ° C and 185 ° C, followed by a second mechanical working phase (sometimes called a "productive" phase) at a lower temperature, typically below 120 ° C, for example between 40 ° C and 100 ° C, the finishing phase during which is incorporated the crosslinking or vulcanization system.
  • a first working phase or thermo-mechanical kneading (sometimes called a phase "non-productive") on a suitable mixer (for example "Banbury” type mixer) at high temperature, up to a maximum temperature of between 10 ° C and 200 ° C, preferably between 135 ° C
  • the final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for characterization in the laboratory, or still extruded in the form of a semi-finished (or profiled) rubber usable as a snowshoe sole.
  • the crosslinking of the composition can be carried out in a manner known to a person skilled in the art, for example at a temperature between 130 ° C. and 200 ° C., under pressure.
  • a sole for snowshoe according to the invention as described above, can be glued or adhered to the basic structure of a snowshoe, which is intended to come into contact with the ground.
  • the shape of the sole can be adapted to the basic structure of the snowshoe and can form a plurality of disjoint elements.
  • such a sole can be adapted to a snowshoe as described in patent applications FR 17/71369 or FR 17/71370, as illustrated in the single figure which is a schematic perspective representation of the snowshoe. snow.
  • Such a snowshoe 1 comprises a basic structure comprises a basic structure of non-rubber material forming a shoe zone 2 and a lift zone and in which the lift zone comprises a lateral overhang on each side of the shoe zone 2, said lift zone extends towards the rear of the shoe zone 2 to form a rear spatula 3 and forms a front portion 4 of the racket opposite the rear spatula 3, the contact face of the structure base comprising a sole 5 according to the invention arranged on all or part of said contact face.
  • This sole 5 comprises a plurality of tread elements 51 of rubber material are arranged over all or part of said foot area.
  • This sole can be glued, as indicated above, to the basic structure or produced by molding or overmolding.
  • tread with a rubber material according to the invention gives significantly better performance in grip on snow compared to the many other snowshoes tested.

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Abstract

The invention relates to a snowshoe sole comprising a rubber composition based on at least a predominant isoprene elastomer, a reinforcing inorganic filler, a plasticiser, and a crosslinking system.

Description

La présente invention se rapporte à des semelles de raquettes à neige.  The present invention relates to snowshoe soles.
Les raquettes à neige sont des objets connus depuis de nombreuses années. Elles ont été initialement conçues afin de permettre aux personnes de se déplacer sur des sols recouverts d’une grande quantité de neige. Elles sont en outre très répandues dans les pays nordiques, fréquemment touchés par de fortes chutes de neige. Cependant, ces conditions extrêmes reflètent de moins en moins la réalité de l’utilisation actuelle des raquettes. En effet, de nos jours, elles sont surtout utilisées dans un cadre « sport et loisirs » par des randonneurs. Les adeptes étant de niveaux très variés, en partant de l’amateur débutant jusqu’au randonneur expert, les exigences de chacun des niveaux sont très différentes. Cette hétérogénéité oblige les fabricants à développer sans cesse de nouveaux produits pour répondre au mieux aux diverses attentes. On retrouve donc aujourd’hui plusieurs gammes de produits, présentant chacune des avantages spécifiques. Mais les fabricants restent à la recherche de solutions innovantes susceptibles d’apporter un plus grand confort, et des performances dynamiques en hausse. Snowshoes have been known for many years. They were originally designed to allow people to move on soils covered with a large amount of snow. They are also very widespread in the Nordic countries, frequently affected by heavy snowfall. However, these extreme conditions less and less reflect the reality of the current use of snowshoes. Indeed, nowadays, they are mainly used in a "sport and leisure" setting by hikers. The followers are of very varied levels, from the beginner to the expert hiker, the requirements of each level are very different. This heterogeneity forces manufacturers to constantly develop new products to best meet various expectations. There are therefore today several product lines, each with specific advantages. But manufacturers are still looking for innovative solutions that can provide greater comfort and increased dynamic performance.
De manière générale, les raquettes à neige sont composées d’un tamis, d’une spatule avant, d’une portion arrière et d’un système de fixation. Cette configuration de base permet de se déplacer facilement sur la neige du fait d’une portance accrue, évitant de s’enfoncer dans la neige. Generally speaking, snowshoes consist of a sieve, a front spatula, a rear portion and a fixing system. This basic configuration makes it easy to move on snow due to its increased lift, avoiding sinking into the snow.
Différents types d’architecture de raquettes à neige ont été développées afin de permettre une démarche aisée, avec un déroulé du pied facilitant la marche en la rendant plus naturelle. Ainsi afin toujours d’améliorer le confort des utilisateurs lors de la marche en raquette à neige, l’ergonomie des raquettes a été améliorée selon divers axes de développement. Un de ces axes comprend l’adhérence pour une utilisation spécifiquement sur la glace des raquettes grâce à des semelles en élastomères munies d’indentations et/ou de plots. Different types of snowshoe architecture have been developed to allow an easy approach, with an unrolled foot making walking easier and more natural. So in order to always improve user comfort when snowshoeing, the ergonomics of snowshoes have been improved along various development axes. One of these axes includes grip for use specifically on snowshoe ice using elastomer soles provided with indentations and / or studs.
Par exemple, le document W09506502 décrit une raquette à neige formée d'une plate- forme semi-flexible comprenant des moyens de liaison pour lier une chaussure d’utilisateur à la plate-forme. La plate-forme est moulée dans une matière plastique semi- flexible qui peut fléchir avec la chaussure, comme par exemple du polyuréthane thermoplastique. La dureté de la plate-forme est comprise entre 50 et 90 Shore D à environ l8°c. Cette caractéristique en fait une raquette légèrement flexible mais insuffisamment pour obtenir un réel confort lors du déroulé du pied. Par ailleurs, la face inférieure de la plate-forme est formée avec des indentations et/ou des saillies pour augmenter la traction lors de l’utilisation des raquettes. Les évidements circulaires contiennent chacun une creusure ovale orientée en fonction de leur emplacement sur la face inférieure. La matière plastique semi-flexible ainsi que les indentations permettent d’augmenter le taux d’adhérence des raquettes, qui reste toutefois perfectible. For example, the document WO9506502 describes a snowshoe formed from a semi-flexible platform comprising connecting means for binding a user shoe to the platform. The platform is molded in a semi-flexible plastic which can flex with the shoe, such as for example thermoplastic polyurethane. The hardness of the platform is between 50 and 90 Shore D at around 18 ° c. This characteristic makes it a slightly flexible racket but insufficient to obtain real comfort during the unrolling of the foot. Furthermore, the underside of the platform is formed with indentations and / or protrusions to increase traction when using snowshoes. The circular recesses each contain an oval recess oriented according to their location on the lower side. The semi-flexible plastic material as well as the indentations make it possible to increase the grip rate of the rackets, which remains however perfectible.
Le document FR2743501 décrit une raquette de marche, notamment sur neige, constituée d’une plate-forme sensiblement plane, munie d’organes de solidarisation réversible du pied de l’utilisateur à ladite plate-forme, réalisée en élastomère cellulaire. Cette raquette est légère, rigide mais avec une certaine élasticité et avec une bonne adhérence. La face inférieure comporte des plots constitués par moulage, répartis en fonction de la répartition de la charge en utilisation. Ces caractéristiques permettent à l’utilisateur d’avoir une raquette plus confortable que les raquettes classiques et également d’avoir une meilleure adhérence grâce à la répartition des plots. Cependant, l’adhérence fournie par les plots en élastomère et leur répartition ne confèrent pas une accroche optimale à la raquette. De plus, la partie avant de la raquette oblige l’utilisateur à lever le pied plus que d’ordinaire ce qui peut entraîner une fatigue prématurée. The document FR2743501 describes a walking racket, in particular on snow, consisting of a substantially flat platform, provided with reversible fastening members for the user's foot to said platform, made of cellular elastomer. This racket is light, rigid but with a certain elasticity and with good grip. The underside has studs formed by molding, distributed as a function of the distribution of the load in use. These characteristics allow the user to have a more comfortable racket than conventional rackets and also to have better grip thanks to the distribution of the studs. However, the grip provided by the elastomer studs and their distribution do not give optimal grip to the racket. In addition, the front part of the racket forces the user to lift the foot more than usual, which can lead to premature fatigue.
La demanderesse a découvert qu’en ajoutant à la structure de base de la raquette à neige destinée initialement à entrer en contact avec le sol, une semelle qui sera en contact avec le sol, réalisée à l’aide d’une composition de caoutchouc spécifique, la raquette à neige améliorait de façon surprenante ses propriétés d’adhérence. The Applicant has discovered that by adding to the basic structure of the snowshoe initially intended to come into contact with the ground, a sole which will be in contact with the ground, produced using a specific rubber composition. , the snowshoe surprisingly improved its grip properties.
L’invention a ainsi pour objet une semelle de raquette à neige comprenant une composition de caoutchouc à base d’au moins un élastomère isoprénique majoritaire, une charge inorganique renforçante, un plastifiant et un système de réticulation. The subject of the invention is therefore a snowshoe sole comprising a rubber composition based on at least one majority isoprene elastomer, a reinforcing inorganic filler, a plasticizer and a crosslinking system.
De préférence, le plastifiant de la composition possède un Tg inférieure ou égale à 20°C. Preferably, the plasticizer of the composition has a Tg less than or equal to 20 ° C.
Plus préférentiellement, le plastifiant de la composition est choisi parmi les huiles plastifiantes et leurs mélanges. More preferably, the plasticizer of the composition is chosen from plasticizing oils and their mixtures.
En particulier, les huiles plastifiantes sont choisies dans le groupe constitué par les huiles naphténiques, les huiles paraffiniques, les huiles MES (Medium Extracted Solvatés), les huiles TDAE (Treated Distillate Aromatic Extracts), les huiles RAE (Residual Aromatic Extract oils), les huiles TRAE (Treated Residual Aromatic Extract) et les huiles SRAE (Safety Residual Aromatic Extract oils), les huiles minérales, les huiles végétales, les plastifiants éthers, les plastifiants esters, les plastifiants phosphates, les plastifiants sulfonates et les mélanges de ces composés.  In particular, the plasticizing oils are chosen from the group consisting of naphthenic oils, paraffinic oils, MES oils (Medium Extracted Solvated), TDAE oils (Treated Distillate Aromatic Extracts), RAE oils (Residual Aromatic Extract oils), TRAE oils (Treated Residual Aromatic Extract) and SRAE oils (Safety Residual Aromatic Extract oils), mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulfonate plasticizers and mixtures of these compounds .
Avantageusement, le taux d’agent plastifiant de la composition est supérieur ou égale à 5 parties pour cent parties d’élastomères, pce, de préférence il va de 5 à 50 pce, plus préférentiellement de 10 à 40 pce et encore plus préférentiellement de 25 à 40 pce. Selon un mode de réalisation préférentiel de l’invention, le taux d’élastomère isoprénique de la composition va de 60 à 100 pce, de préférence de 70 à 100 pce, plus préférentiellement de 80 à 100 pce. De préférence, le taux de charge inorganique renforçante de la composition va de 10 à 60 pce, de préférence de 30 à 55 pce ; la charge inorganique renforçante étant préférentiellement de la silice. Advantageously, the level of plasticizer in the composition is greater than or equal to 5 parts per hundred parts of elastomers, phr, preferably it ranges from 5 to 50 phr, more preferably from 10 to 40 phr and even more preferably from 25 at 40 pce. According to a preferred embodiment of the invention, the level of isoprene elastomer of the composition ranges from 60 to 100 phr, preferably from 70 to 100 phr, more preferably from 80 to 100 phr. Preferably, the level of reinforcing inorganic filler of the composition ranges from 10 to 60 phr, preferably from 30 to 55 phr; the reinforcing inorganic filler preferably being silica.
L’invention concerne également une raquette à neige comprenant une semelle telle que décrite précédemment. The invention also relates to a snowshoe comprising a sole as described above.
L’invention concerne encore une raquette à neige comportant une structure de base en matériau non caoutchoutique formant une zone de chaussure et une zone de portance et dans laquelle la zone de portance comprend un débord latéral de chaque côté de la zone de chaussure, ladite zone de portance se prolonge vers l’arrière de la zone de chaussure pour former une spatule arrière et forme une portion frontale de la raquette à l’opposé de la spatule arrière, la face de contact de la structure de base comportant une semelle telle que décrite précédement. The invention also relates to a snowshoe comprising a basic structure of non-rubber material forming a shoe zone and a lift zone and in which the lift zone comprises a lateral overhang on each side of the shoe zone, said zone of bearing extends towards the rear of the shoe zone to form a rear spatula and forms a front portion of the racket opposite the rear spatula, the contact face of the basic structure comprising a sole as described previously.
DESCRIPTION DETAILLEE DE L’INVENTION DETAILED DESCRIPTION OF THE INVENTION
La présente invention concerne une semelle de raquette à neige comprenant une composition de caoutchouc à base d’au moins un élastomère isoprénique majoritaire, une charge inorganique renforçante, un plastifiant et un système de réticulation. The present invention relates to a snowshoe sole comprising a rubber composition based on at least one majority isoprene elastomer, a reinforcing inorganic filler, a plasticizer and a crosslinking system.
Par l'expression "composition à base de", il faut entendre une composition comportant le mélange et/ou le produit de réaction in situ des différents constituants utilisés, certains de ces constituants pouvant réagir et/ou étant destinés à réagir entre eux, au moins partiellement, lors des différentes phases de fabrication de la composition ; la composition pouvant ainsi être à l’état totalement ou partiellement réticulé ou à l’état non-réticulé. By the expression "composition based on" is meant a composition comprising the mixture and / or the in situ reaction product of the various constituents used, some of these constituents being able to react and / or being intended to react with each other, less partially, during the different manufacturing phases of the composition; the composition thus being able to be in the fully or partially crosslinked state or in the non-crosslinked state.
Dans la présente description, sauf indication expresse différente, tous les pourcentages (%) indiqués sont des pourcentages (%) en masse. D’autre part, tout intervalle de valeurs désigné par l’expression "entre a et b" représente le domaine de valeurs allant de plus de a à moins de b (c’est-à-dire bornes a et b exclues) tandis que tout intervalle de valeurs désigné par l'expression "de a à b" signifie le domaine de valeurs allant de a jusqu'à b (c’est-à-dire incluant les bornes strictes a et b). Par l’expression "partie en poids pour cent parties en poids d’élastomère" (ou pce), il faut entendre au sens de la présente invention, la partie, en masse pour cent parties en masse d’élastomère. In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are percentages (%) by mass. On the other hand, any range of values designated by the expression "between a and b" represents the range of values going from more than a to less than b (ie limits a and b excluded) while any range of values designated by the expression "from a to b" signifies the range of values ranging from a to b (that is to say including the strict limits a and b). By the expression "part by weight per hundred parts by weight of elastomer" (or phr), it is to be understood in the sense of the present invention, the part, by mass per hundred parts by mass of elastomer.
Lorsqu’on fait référence à un composé "majoritaire", on entend au sens de la présente invention, que ce composé est majoritaire parmi les composés du même type dans la composition, c’est-à-dire que c’est celui qui représente la plus grande quantité en masse parmi les composés du même type. Ainsi, par exemple, un élastomère majoritaire est l’élastomère représentant la plus grande masse par rapport à la masse totale des élastomères dans la composition. De la même manière, une charge dite majoritaire est celle représentant la plus grande masse parmi les charges de la composition. A titre d’exemple, dans un système comprenant un seul élastomère, celui-ci est majoritaire au sens de la présente invention ; et dans un système comprenant deux élastomères, G élastomère majoritaire représente plus de la moitié de la masse des élastomères. When reference is made to a “majority” compound, it is understood within the meaning of the present invention, that this compound is predominant among the compounds of the same type in the composition, that is to say that it is that which represents the greatest amount by mass among compounds of the same type. Thus, for example, a majority elastomer is the elastomer representing the largest mass relative to the total mass of the elastomers in the composition. In the same way, a so-called majority charge is that representing the largest mass among the charges of the composition. For example, in a system comprising a single elastomer, the latter is predominant within the meaning of the present invention; and in a system comprising two elastomers, the majority elastomer represents more than half of the mass of the elastomers.
Les composés comprenant du carbone mentionnés dans la description peuvent être d'origine fossile ou biosourcés. Dans ce dernier cas, ils peuvent être, partiellement ou totalement, issus de la biomasse ou obtenus à partir de matières premières renouvelables issues de la biomasse. Sont concernés notamment les polymères, les plastifiants, les charges, etc. The compounds comprising carbon mentioned in the description can be of fossil origin or bio-based. In the latter case, they can be, partially or totally, from biomass or obtained from renewable raw materials from biomass. Are concerned in particular polymers, plasticizers, fillers, etc.
Elastomère diénique Diene elastomer
Par élastomère (ou indistinctement caoutchouc) "diénique", qu’il soit naturel ou synthétique, doit être compris de manière connue un élastomère constitué au moins en partie (i.e., un homopolymère ou un copolymère) d’unités monomères diènes (monomères porteurs de deux doubles liaisons carbone-carbone, conjuguées ou non). By "diene" elastomer (or indistinctly rubber), whether natural or synthetic, must be understood in known manner an elastomer consisting at least in part (ie, a homopolymer or a copolymer) of diene monomer units (monomers carrying two carbon-carbon double bonds, conjugated or not).
Ces élastomères diéniques peuvent être classés dans deux catégories : "essentiellement insaturés" ou "essentiellement saturés". On entend en général par "essentiellement insaturé", un élastomère diénique issu au moins en partie de monomères diènes conjugués, ayant un taux de motifs ou unités d'origine diénique (diènes conjugués) qui est supérieur à 15% (% en moles) ; c'est ainsi que des élastomères diéniques tels que les caoutchoucs butyle ou les copolymères de diènes et d'alpha-oléfïnes type EPDM n’entrent pas dans la définition précédente et peuvent être notamment qualifiés d'élastomères diéniques "essentiellement saturés" (taux de motifs d'origine diénique faible ou très faible, toujours inférieur à 15%). These diene elastomers can be classified into two categories: "essentially unsaturated" or "essentially saturated". In general, the term "essentially unsaturated" means a diene elastomer derived at least in part from conjugated diene monomers, having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (% by moles); This is how diene elastomers such as butyl rubbers or copolymers of dienes and of alpha-olefins of the EPDM type do not enter into the preceding definition and can be qualified in particular as “essentially saturated” diene elastomers (content of motifs of diene origin weak or very weak, always less than 15%).
On entend particulièrement par élastomère diénique susceptible d'être utilisé dans les compositions conformes à l’invention : (a) - tout homopolymère d’un monomère diène, conjugué ou non, ayant de 4 à 18 atomes de carbone ; The expression “diene elastomer capable of being used in the compositions in accordance with the invention” is particularly understood to mean: (a) - any homopolymer of a diene monomer, conjugated or not, having from 4 to 18 carbon atoms;
(b) - tout copolymère d'un diène, conjugué ou non, ayant de 4 à 18 atomes de carbone et d’au moins un autre monomère.  (b) - any copolymer of a diene, conjugated or not, having 4 to 18 carbon atoms and at least one other monomer.
L’autre monomère peut être l’éthylène, une oléfine ou un diène, conjugué ou non. The other monomer can be ethylene, an olefin or a diene, conjugated or not.
A titre de diènes conjugués conviennent les diènes conjugués ayant de 4 à 12 atomes de carbone, en particulier les l,3-diènes, tels que notamment le l,3-butadiène et l’isoprène. As conjugated dienes, conjugated dienes having from 4 to 12 carbon atoms are suitable, in particular 1,3-dienes, such as in particular 1,3-butadiene and isoprene.
A titre d’oléfïnes conviennent les composés vinylaromatiques ayant de 8 à 20 atomes de carbone et les a-monooléfïnes aliphatiques ayant de 3 à 12 atomes de carbone. As olefins suitable are vinyl aromatic compounds having 8 to 20 carbon atoms and aliphatic α-monoolefins having 3 to 12 carbon atoms.
A titre de composés vinylaromatiques conviennent par exemple le styrène, l’ortho-, méta- , para-méthylstyrène, le mélange commercial "vinyle-toluène", le para-tertiobutylstyrène. Examples of vinyl aromatic compounds are styrene, ortho-, meta-, para-methylstyrene, the commercial "vinyl-toluene" mixture, para-tert-butylstyrene.
A titre d’a-monooléfïnes aliphatiques conviennent notamment les a-monooléfïnes aliphatiques acycliques ayant de 3 à 18 atomes de carbone. As aliphatic α-monoolefins suitable in particular are acyclic aliphatic α-monoolefins having 3 to 18 carbon atoms.
Préférentiellement, l'élastomère diénique est choisi dans le groupe constitué par les polybutadiènes (BR), le caoutchouc naturel (NR), les polyisoprènes de synthèse (IR), les copolymères de butadiène, les copolymères d'isoprène, et les mélanges de ces élastomères. Les copolymères de butadiène sont particulièrement choisis dans le groupe constitué par les copolymères de butadiène-styrène (SBR). Preferably, the diene elastomer is chosen from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene copolymers, isoprene copolymers, and mixtures of these. elastomers. The butadiene copolymers are particularly chosen from the group consisting of butadiene-styrene copolymers (SBR).
Par "élastomère isoprénique", on entend de manière connue un homopolymère ou un copolymère d'isoprène, en d'autres termes un élastomère diénique choisi dans le groupe constitué par le caoutchouc naturel (NR), les polyisoprènes de synthèse (IR), les différents copolymères d'isoprène et les mélanges de ces élastomères. Parmi les copolymères d'isoprène, on citera en particulier les copolymères d'isobutène-isoprène (caoutchouc butyle - IIR), d'isoprène-styrène (SIR), d'isoprène-butadiène (BIR) ou d'isoprène-butadiène-styrène (SBIR). Cet élastomère isoprénique est de préférence du caoutchouc naturel ou un polyisoprène cis-l,4 de synthèse; parmi ces polyisoprènes de synthèse, sont utilisés de préférence des polyisoprènes ayant un taux (% molaire) de liaisons cis-l,4 supérieur à 90%, plus préférentiellement encore supérieur à 98%. By "isoprene elastomer" is understood in known manner an isoprene homopolymer or copolymer, in other words a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), different isoprene copolymers and mixtures of these elastomers. Among the isoprene copolymers, mention will be made in particular of isobutene-isoprene (butyl rubber - IIR), isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene copolymers (SBIR). This isoprene elastomer is preferably natural rubber or a synthetic cis-1,4 polyisoprene; among these synthetic polyisoprenes, polyisoprenes are preferably used having a rate (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%.
Bien qu'elle s'applique à tout type d'élastomère diénique, l'homme du métier du pneumatique comprendra que la présente invention est de préférence mise en œuvre avec des élastomères diéniques essentiellement insaturés, en particulier du type (a) ou (b) ci- dessus. L’élastomère diénique peut être modifié, c’est à dire soit couplé et/ou étoilé, soit fonctionnalisé, soit couplé et/ou étoilé et simultanément fonctionnalisé. Although it applies to any type of diene elastomer, a person skilled in the art of tires will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b ) above. The diene elastomer can be modified, that is to say either coupled and / or star-shaped, or functionalized, or coupled and / or star-shaped and simultaneously functionalized.
Ainsi, l’élastomère diénique peut être couplé et/ou étoilé, par exemple au moyen d’un atome silicium ou d’étain qui lie entre elles les chaînes élastomères.  Thus, the diene elastomer can be coupled and / or star-shaped, for example by means of a silicon or tin atom which links the elastomer chains together.
L’élastomère diénique peut être simultanément ou alternativement fonctionnalisé et comprendre au moins groupe fonctionnel. Par groupe fonctionnel, on entend un groupe comprenant au moins un hétéroatome choisi parmi Si, N, S, O, P. Conviennent particulièrement à titre de groupes fonctionnels ceux comprenant au moins une fonction telle que: le silanol, un alcoxysilane, une amine primaire, secondaire ou tertiaire, cyclique ou non, un thiol, un époxyde.  The diene elastomer can be simultaneously or alternately functionalized and comprise at least one functional group. By functional group is meant a group comprising at least one heteroatom chosen from Si, N, S, O, P. Particularly suitable as functional groups are those comprising at least one function such as: silanol, an alkoxysilane, a primary amine , secondary or tertiary, cyclic or not, a thiol, an epoxide.
La composition de caoutchouc de l'invention peut contenir un seul élastomère diénique ou un mélange de plusieurs élastomères diéniques. The rubber composition of the invention may contain a single diene elastomer or a mixture of several diene elastomers.
Préférentiellement le taux d’élastomère isoprénique va de 60 à 100 pce, de préférence de 70 à 100 pce, plus préférentiellement de 80 à 100 pce. Preferably, the level of isoprene elastomer ranges from 60 to 100 phr, preferably from 70 to 100 phr, more preferably from 80 to 100 phr.
Selon une variante de réalisation de l’invention, la composition comprend également un ou plusieurs élastomères choisis dans le groupe constitué par les polybutadiènes (BR), les copolymères de butadiène et les mélanges de ces élastomères. Ainsi avantageusement la composition comprend un taux de 0 à 40 pce de ces élastomères, de préférence de 0 à 30 pce plus préférentiellement de 0 à 20 pce. According to an alternative embodiment of the invention, the composition also comprises one or more elastomers chosen from the group consisting of polybutadienes (BR), butadiene copolymers and mixtures of these elastomers. Thus, advantageously, the composition comprises a level of 0 to 40 phr of these elastomers, preferably of 0 to 30 phr more preferably of 0 to 20 phr.
Charges et agents de couplage Loads and coupling agents
Par charge, on entend ici tout type de charge, qu'elle soit renforçante ou qu'elle soit non- renforçante ou inerte. By filler is meant here any type of filler, whether it is reinforcing or whether it is non-reinforcing or inert.
La composition de caoutchouc de l’invention comprend au moins une charge renforçante. On peut utiliser tout type de charge dite renforçante, connue pour ses capacités à renforcer une composition de caoutchouc utilisable notamment pour la fabrication de pneumatiques, par exemple une charge organique telle que du noir de carbone, une charge inorganique telle que de la silice ou encore un mélange de ces deux types de charges. The rubber composition of the invention comprises at least one reinforcing filler. Any type of reinforcing filler can be used, known for its capacity to reinforce a rubber composition which can be used in particular for the manufacture of tires, for example an organic filler such as carbon black, an inorganic filler such as silica or else a mixture of these two types of charges.
Comme noirs de carbone conviennent tous les noirs de carbone, notamment les noirs conventionnellement utilisés dans les pneumatiques ou leurs bandes de roulement. Parmi ces derniers, on citera plus particulièrement les noirs de carbone renforçants des séries 100, 200, 300, ou les noirs de série 500, 600 ou 700 (grades ASTM D- 1765-2017), comme par exemple les noirs N115, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772). Ces noirs de carbone peuvent être utilisés à l'état isolé, tels que disponibles commercialement, ou sous tout autre forme, par exemple comme support de certains des additifs de caoutchouterie utilisés. Les noirs de carbone pourraient être par exemple déjà incorporés à l’élastomère diénique, notamment isoprénique sous la forme d'un masterbatch (voir par exemple demandes W097/36724-A2 ou W099/16600-A1). As carbon blacks, all carbon blacks are suitable, in particular the blacks conventionally used in tires or their treads. Among the latter, there may be mentioned more particularly the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series (grades ASTM D-1765-2017), such as, for example, the blacks N115, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772). These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a support for some of the rubber additives used. The carbon blacks could for example already be incorporated into the diene elastomer, in particular isoprene, in the form of a masterbatch (see for example applications WO97 / 36724-A2 or WO99 / 16600-A1).
Par « charge inorganique renforçante », doit être entendu ici toute charge inorganique ou minérale, quelles que soient sa couleur et son origine (naturelle ou de synthèse), encore appelée charge « blanche », charge « claire » ou même charge « non-noire » par opposition au noir de carbone, capable de renforcer à elle seule, sans autre moyen qu’un agent de couplage intermédiaire, une composition de caoutchouc destinée à la fabrication de pneumatiques. De manière connue, certaines charges inorganiques renforçantes peuvent se caractériser notamment par la présence de groupes hydroxyle (-OH) à leur surface. By "reinforcing inorganic filler" should be understood here any inorganic or mineral filler, whatever its color and its origin (natural or synthetic), also called "white" filler, "clear" filler or even "non-black" filler As opposed to carbon black, capable of reinforcing on its own, without other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires. In known manner, certain reinforcing inorganic fillers can be characterized in particular by the presence of hydroxyl groups (-OH) on their surface.
Comme charges inorganiques renforçantes conviennent notamment des charges minérales du type siliceux, préférentiellement la silice (Si02) ou du type alumineux, en particulier l’alumine (A1203). La silice utilisée peut être toute silice renforçante connue de l’homme du métier, notamment toute silice précipitée ou pyrogénée présentant une surface spécifique BET ainsi qu'une surface spécifique CTAB toutes deux inférieures à 450 m2/g, de préférence comprises dans un domaine allant de 30 à 400 m2/g, notamment de 60 à 300 m2/g. As reinforcing inorganic fillers, in particular mineral fillers of the siliceous type, preferably silica (Si02) or of the aluminous type, in particular alumina (A1203), are suitable. The silica used can be any reinforcing silica known to those skilled in the art, in particular any precipitated or pyrogenic silica having a BET specific surface as well as a CTAB specific surface both of which are less than 450 m 2 / g, preferably included in a range ranging from 30 to 400 m2 / g, in particular from 60 to 300 m2 / g.
On peut utiliser tout type de silice précipitée, notamment des silices précipitées hautement dispersibles (dites « HDS » pour « highly dispersible » ou « highly dispersible silica »). Ces silices précipitées, hautement dispersibles ou non, sont bien connues de l’homme du métier. On peut citer, par exemple, les silices décrites dans les demandes W003/016215-A1 et W003/016387-A1. Parmi les silices HDS commerciales, on peut notamment utiliser les silices « Ultrasil ® 5000GR », « Ultrasil ® 7000GR » de la société Evonik, les silices « Zeosil ® 1085GR», « Zeosil® 1115 MP », « Zeosil® 1165MP », « Zeosil® Premium 200MP », « Zeosil® HRS 1200 MP » de la Société Solvay. À titre de silice non HDS, les silices commerciales suivantes peuvent être utilisées : les silices « Ultrasil ® VN2GR », « Ultrasil ® VN3GR » de la société Evonik, la silice, les silices « Hi-Sil EZl20G(-D) », « Hi-Sil EZl60G(-D) », « Hi-Sil EZ200G(- D) », « Hi-Sil 243LD », « Hi-Sil 210 », « Hi-Sil HDP 320G » de la société PPG. Any type of precipitated silica can be used, in particular highly dispersible precipitated silicas (called "HDS" for "highly dispersible" or "highly dispersible silica"). These precipitated silicas, highly dispersible or not, are well known to those skilled in the art. Mention may be made, for example, of the silicas described in applications W003 / 016215-A1 and W003 / 016387-A1. Among the commercial HDS silicas, it is possible in particular to use the “Ultrasil® 5000GR”, “Ultrasil® 7000GR” silicas from the company Evonik, the “Zeosil® 1085GR”, “Zeosil® 1115 MP”, “Zeosil® 1165MP”, “ Zeosil® Premium 200MP ”,“ Zeosil® HRS 1200 MP ”from the company Solvay. As non-HDS silica, the following commercial silicas can be used: "Ultrasil ® VN2GR", "Ultrasil ® VN3GR" from Evonik, silica, "Hi-Sil EZl20G (-D)", " Hi-Sil EZl60G (-D) "," Hi-Sil EZ200G (- D) "," Hi-Sil 243LD "," Hi-Sil 210 "," Hi-Sil HDP 320G "from PPG.
L'état physique sous lequel se présente la charge inorganique renforçante est indifférent, que ce soit sous forme de poudre, de microperles, de granulés, ou encore de billes ou toute autre forme densifiée appropriée. Bien entendu on entend également par charge inorganique renforçante des mélanges de différentes charges inorganiques renforçantes, en particulier de silices telles que décrites ci-dessus. L'homme du métier comprendra qu’en remplacement de la charge inorganique renforçante décrite ci-dessus, pourrait être utilisée une charge renforçante d'une autre nature, dès lors que cette charge renforçante d’une autre nature serait recouverte d'une couche inorganique telle que de la silice, ou bien comporterait à sa surface des sites fonctionnels, notamment hydroxyles, nécessitant l'utilisation d'un agent de couplage pour établir la liaison entre cette charge renforçante et l’élastomère diénique. A titre d’exemple, on peut citer des noirs de carbone partiellement ou intégralement recouverts de silice, ou des noirs de carbone modifiés par de la silice, tels que, à titre non limitatif, les charges de type « Ecoblack® » de la série CRX2000 » ou de la série « CRX4000 » de la société Cabot Corporation. The physical state in which the reinforcing inorganic filler is present is immaterial, whether in the form of powder, microbeads, granules, or even balls or any other suitable densified form. Of course, the term reinforcing inorganic filler is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of silicas as described above. Those skilled in the art will understand that, as a replacement for the reinforcing inorganic filler described above, a reinforcing filler of another nature could be used, since this reinforcing filler of another nature would be covered with an inorganic layer. such as silica, or else would have on its surface functional sites, in particular hydroxyls, requiring the use of a coupling agent to establish the connection between this reinforcing filler and the diene elastomer. By way of example, there may be mentioned carbon blacks partially or entirely covered with silica, or carbon blacks modified with silica, such as, without limitation, fillers of the “Ecoblack®” type from the series CRX2000 ”or from the“ CRX4000 ”series from Cabot Corporation.
Avantageusement le taux de charge renforçante total est compris dans un domaine allant de 10 à 100 pce, plus préférentiellement de 10 à 60 pce, plus préférentiellement de 20 à 60 pce ; et encore plus préférentiellement de 30 à 55 pce.  Advantageously, the rate of total reinforcing filler is included in a range from 10 to 100 phr, more preferably from 10 to 60 phr, more preferably from 20 to 60 phr; and even more preferably from 30 to 55 pce.
Selon une variante préférée de l’invention, la charge renforçante est majoritairement une charge renforçante inorganique (de préférence de la silice), c’est-à-dire qu’elle comprend plus de 50 % (>50%) en poids d’une charge renforçante inorganique telle que de la silice par rapport au poids total de la charge renforçante. Optionnellement selon cette variante, la charge renforçante comprend également du noir de carbone. Selon cette option, le noir de carbone est utilisé à un taux inférieur ou égal à 20 pce, plus préférentiellement inférieur ou égal à 10 pce et encore plus préférentiellement la composition ne contient pas de noir de carbone. According to a preferred variant of the invention, the reinforcing filler is mainly an inorganic reinforcing filler (preferably silica), that is to say that it comprises more than 50% (> 50%) by weight of an inorganic reinforcing filler such as silica relative to the total weight of the reinforcing filler. Optionally according to this variant, the reinforcing filler also comprises carbon black. According to this option, the carbon black is used at a rate less than or equal to 20 phr, more preferably less than or equal to 10 phr and even more preferably the composition does not contain carbon black.
Dans le présent exposé, la surface spécifique BET est déterminée par adsorption de gaz à l’aide de la méthode de Brunauer-Emmett-Teller décrite dans « The Journal of the American Chemical Society » (Vol. 60, page 309, février 1938), et plus précisément selon une méthode adaptée de la norme NF ISO 5794-1, annexe E de juin 2010 [méthode volumétrique multipoints (5 points) - gaz: azote - dégazage sous vide: une heure à l60°C - domaine de pression relative p/po : 0,05 à 0,2] In this paper, the BET surface area is determined by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society" (Vol. 60, page 309, February 1938) , and more precisely according to a method adapted from standard NF ISO 5794-1, appendix E of June 2010 [multi-point volumetric method (5 points) - gas: nitrogen - degassing under vacuum: one hour at 160 ° C - relative pressure range w / in: 0.05 to 0.2]
Pour les charges inorganiques telles que la silice par exemple, les valeurs de surface spécifique CT AB ont été déterminées selon la norme NF ISO 5794-1, annexe G de juin 2010. Le procédé est basé sur l'adsorption du CTAB (bromure de N-hexadécyl-N,N,N- triméthylammonium) sur la surface « externe » de la charge renforçante.  For inorganic fillers such as silica for example, the values of specific surface CT AB were determined according to standard NF ISO 5794-1, appendix G of June 2010. The process is based on the adsorption of CTAB (bromide of N -hexadecyl-N, N, N-trimethylammonium) on the "external" surface of the reinforcing filler.
Pour les noirs de carbone, la surface spécifique STSA est déterminée selon la norme ASTM D6556-2016.  For carbon blacks, the specific surface area STSA is determined according to standard ASTM D6556-2016.
Pour coupler la charge inorganique renforçante à l’élastomère diénique, on peut utiliser de manière bien connue un agent de couplage (ou agent de liaison) au moins bifonctionnel destiné à assurer une connexion suffisante, de nature chimique et/ou physique, entre la charge inorganique (surface de ses particules) et l'élastomère diénique. On utilise en particulier des organosilanes ou des polyorganosiloxanes au moins bifonctionnels. Par « bifonctionnel », on entend un composé possédant un premier groupe fonctionnel capable d’interagir avec la charge inorganique et un second groupe fonctionnel capable d’interagir avec l’élastomère diénique. Par exemple, un tel composé bifonctionnel peut comprend un premier groupe fonctionnel comprenant un atome de silicium, le dit premier groupe fonctionnel étant apte à interagir avec les groupes hydroxyles d’une charge inorganique et un second groupe fonctionnel comprenant un atome de soufre, le dit second groupe fonctionnel apte à interagir avec l’élastomère diénique. To couple the reinforcing inorganic filler to the diene elastomer, it is possible to use, in a well-known manner, an at least bifunctional coupling agent (or bonding agent) intended to ensure a sufficient connection, of chemical nature and / or physical, between the inorganic charge (surface of its particles) and the diene elastomer. In particular organosilanes or polyorganosiloxanes which are at least bifunctional are used. By “bifunctional” is meant a compound having a first functional group capable of interacting with the inorganic charge and a second functional group capable of interacting with the diene elastomer. For example, such a bifunctional compound can comprise a first functional group comprising a silicon atom, the said first functional group being capable of interacting with the hydroxyl groups of an inorganic charge and a second functional group comprising a sulfur atom, the so-called second functional group capable of interacting with the diene elastomer.
Préférentiellement, les organosilanes sont choisis dans le groupe constitué par les organosilanes polysulfurés (symétriques ou asymétriques) tels que le tétrasulfure de bis(3-triéthoxysilylpropyl), en abrégé TESPT commercialisé sous la dénomination « Si69 » par la société Evonik ou le disulfure de bis-(triéthoxysilylpropyle), en abrégé TESPD commercialisé sous la dénomination « Si75 » par la société Evonik, les polyorganosiloxanes, les mercaptosilanes, les mercaptosilanes bloqués, tels que le « NXT-Silane » commercialisé par la société Momentive. Plus préférentiellement, l’organosilane est un organosilane polysulfuré. Preferably, the organosilanes are chosen from the group consisting of polysulfurized organosilanes (symmetrical or asymmetrical) such as bis tetrasulfide (3-triethoxysilylpropyl), in short TESPT marketed under the name "Si69" by the company Evonik or bis disulfide - (triethoxysilylpropyle), abbreviated as TESPD marketed under the name “Si75” by the company Evonik, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, such as “NXT-Silane” sold by the company Momentive. More preferably, the organosilane is a polysulfurized organosilane.
Bien entendu pourraient être également utilisés des mélanges des agents de couplage précédemment décrits. Of course, mixtures of the coupling agents described above could also be used.
La teneur en agent de couplage dans la composition de l’invention est avantageusement inférieure ou égale à 20 pce, étant entendu qu’il est en général souhaitable d’en utiliser le moins possible. Typiquement le taux d’agent de couplage représente de 0,5% à 15% en poids par rapport à la quantité de charge inorganique renforçante. Son taux est préférentiellement compris dans un domaine allant de 0,5 à 12 pce, plus préférentiellement compris dans un domaine allant de 3 à 10 pce. Ce taux est aisément ajusté par l’homme du métier selon le taux de charge inorganique renforçante utilisé dans la composition.  The content of coupling agent in the composition of the invention is advantageously less than or equal to 20 phr, it being understood that it is generally desirable to use as little as possible. Typically, the level of coupling agent represents from 0.5% to 15% by weight relative to the amount of reinforcing inorganic filler. Its rate is preferably included in a range from 0.5 to 12 phr, more preferably included in a range ranging from 3 to 10 phr. This rate is easily adjusted by a person skilled in the art according to the rate of reinforcing inorganic filler used in the composition.
La composition de l’invention peut comprendre en outre une charge additionnelle telle qu’une charge inerte, par exemple, une charge semi-renforçante tel que le graphite ou un mélange de ces deux types de charges. The composition of the invention may also comprise an additional filler such as an inert filler, for example, a semi-reinforcing filler such as graphite or a mixture of these two types of filler.
Préférentiellement la composition ne comprend pas de charge additionnelle.  Preferably, the composition does not include any additional filler.
Le plastifiant The plasticizer
La composition selon l’invention comporte au moins un plastifiant. De manière connue de l’homme de l’art des compositions de caoutchouc, ce plastifiant peut être choisi de préférence parmi les résines hydrocarbonées de haute température de transition vitreuse (Tg), les huiles plastifiantes, et leurs mélanges. De préférence, le plastifiant est choisi parmi les huiles plastifiantes, et leurs mélanges. The composition according to the invention comprises at least one plasticizer. In a manner known to those skilled in the art of rubber compositions, this plasticizer can be preferably chosen from hydrocarbon resins of high glass transition temperature (Tg), plasticizing oils, and their mixtures. Preferably, the plasticizer is chosen from plasticizing oils and their mixtures.
Par définition, une résine hydrocarbonée de haute Tg est par définition un solide à température et pression ambiante (20°C, 1 atm), tandis qu’une huile plastifiante est liquide à température ambiante et qu’une résine hydrocarbonée de faible Tg est visqueuse à température ambiante. By definition, a high Tg hydrocarbon resin is by definition a solid at room temperature and pressure (20 ° C, 1 atm), while a plasticizer oil is liquid at room temperature and a low Tg hydrocarbon resin is viscous at room temperature.
La Tg est mesurée selon la norme ASTM D3418 (1999).  The Tg is measured according to standard ASTM D3418 (1999).
Le taux total de plastifiants dans la composition est supérieur ou égal à 5 pce, de préférence il va de 5 à 50 pce, préférentiellement de 10 à 40 pce, et encore plus préférentiellement de 25 à 40 pce. En dessous de 5 pce, l’effet technique visé peut s'avérer insuffisant, alors qu’au-delà de la limite supérieure, le compromis de propriétés visé pour la composition de caoutchouc considérée n’est plus atteint. The total level of plasticizers in the composition is greater than or equal to 5 phr, preferably it ranges from 5 to 50 phr, preferably from 10 to 40 phr, and even more preferably from 25 to 40 phr. Below 5 phr, the targeted technical effect may prove to be insufficient, while beyond the upper limit, the desired compromise in properties for the rubber composition considered is no longer achieved.
Selon un mode de réalisation de l’invention, le plastifiant comporte majoritairement des huiles plastifiantes ou leurs mélanges. According to one embodiment of the invention, the plasticizer mainly comprises plasticizing oils or their mixtures.
Selon un autre mode de réalisation préféré de l’invention, le plastifiant est constitué par une ou des huiles plastifiantes ou leur mélange. Ainsi le taux d’huiles plastifiantes est supérieur ou égal à 5 pce, de préférence supérieur il va de 5 à 50 pce, préférentiellement de 10 à 40 pce, et encore plus préférentiellement de 25 à 40 pce. According to another preferred embodiment of the invention, the plasticizer consists of one or more plasticizing oils or their mixture. Thus the level of plasticizing oils is greater than or equal to 5 phr, preferably greater it ranges from 5 to 50 phr, preferably from 10 to 40 phr, and even more preferably from 25 to 40 phr.
Le plastifiant peut également contenir une huile d’extension (ou huile plastifiante) liquide à 20 °C, dit à « basse Tg », c'est-à-dire qui par définition présente une Tg inférieure à 20 °C, de préférence inférieure à 40 °C. The plasticizer can also contain an extension oil (or plasticizing oil) liquid at 20 ° C, called "low Tg", that is to say which by definition has a Tg below 20 ° C, preferably lower at 40 ° C.
Toute huile d’extension, qu’elle soit de nature aromatique ou non-aromatique connue pour ses propriétés plastifiantes vis-à-vis d'élastomères, est utilisable. A température ambiante (20°C), ces huiles, plus ou moins visqueuses, sont des liquides (c’est-à-dire, pour rappel, des substances ayant la capacité de prendre à terme la forme de leur contenant), par différence notamment avec les résines hydrocarbonées de haute Tg qui sont par nature solides à température ambiante.  Any extension oil, whether of an aromatic or non-aromatic nature known for its plasticizing properties with regard to elastomers, can be used. At room temperature (20 ° C), these oils, more or less viscous, are liquids (that is to say, substances having the capacity to eventually take the form of their container), by difference especially with high Tg hydrocarbon resins which are by nature solid at room temperature.
Conviennent particulièrement les huiles plastifiantes choisies dans le groupe constitué par les huiles naphténiques (à basse ou haute viscosité, notamment hydrogénées ou non), les huiles paraffiniques, les huiles MES (Medium Extracted Solvatés), les huiles TDAE (Treated Distillate Aromatic Extracts), les huiles RAE (Residual Aromatic Extract oils), les huiles TRAE (Treated Residual Aromatic Extract) et les huiles SRAE (Safety Residual Aromatic Extract oils), les huiles minérales, les huiles végétales, les plastifiants éthers, les plastifiants esters, les plastifiants phosphates, les plastifiants sulfonates et les mélanges de ces composés. Particularly suitable are the plasticizing oils chosen from the group consisting of naphthenic oils (low or high viscosity, in particular hydrogenated or not), paraffinic oils, MES oils (Medium Extracted Solvated), TDAE oils (Treated Distillate Aromatic Extracts), RAE (Residual Aromatic Extract oils), TRAE (Treated Residual Aromatic Extract) oils and SRAE (Safety) oils Residual Aromatic Extract oils), mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulfonate plasticizers and mixtures of these compounds.
Selon un mode de réalisation particulier de l’invention, le plastifiant liquide est une huile de pétrole, de préférence non aromatique. Un plastifiant liquide est qualifié de non aromatique dès lors qu’il présente une teneur en composés aromatiques polycycliques, déterminé avec l'extrait dans du DMSO selon la méthode IP 346, de moins de 3 % en poids, par rapport au poids total du plastifiant. A ce titre peut être utilisé un agent plastifiant liquide choisi dans le groupe constitué par les huiles MES, les huiles TDAE, les huiles naphténiques (à basse ou haute viscosité, notamment hydrogénées ou non), les huiles paraffiniques et les mélanges de ces huiles. Conviennent également comme huile de pétrole les huiles RAE, les huiles TRAE et les huiles SRAE ou les mélanges de ces huiles, qui contiennent de faibles teneurs en composés polycycliques. According to a particular embodiment of the invention, the liquid plasticizer is a petroleum oil, preferably non-aromatic. A liquid plasticizer is qualified as non-aromatic when it has a content of polycyclic aromatic compounds, determined with the extract in DMSO according to the IP 346 method, of less than 3% by weight, relative to the total weight of the plasticizer. . As such, a liquid plasticizing agent may be used chosen from the group consisting of MES oils, TDAE oils, naphthenic oils (low or high viscosity, in particular hydrogenated or not), paraffinic oils and mixtures of these oils. RAE oils, TRAE oils and SRAE oils or mixtures of these oils, which contain low contents of polycyclic compounds, are also suitable as petroleum oil.
Conviennent également comme huile plastifiante les polymères liquides issus de la polymérisation d’oléfïnes ou de diènes, comme les polybutènes, les polydiènes, en particulier les polybutadiènes, les polyisoprènes (connus également sous l’appellation « LIR ») ou les copolymères de butadiène et d’isoprène, ou encore les copolymères de butadiène ou d’isoprène et de styrène ou les mélanges de ces polymères liquides. La masse molaire moyenne en nombre de tels polymères liquides est comprise préférentiellement dans un domaine allant de 500 g/mol à 50000 g/mol, préférentiellement de 1000 g/mol à 10000 g/mol. A titre d’exemple peuvent être cités les produits « RICON » de SARTOMER. Liquid polymers resulting from the polymerization of olefins or dienes, such as polybutenes, polydienes, in particular polybutadienes, polyisoprenes (also known under the name "LIR") or copolymers of butadiene, are also suitable as plasticizing oil. isoprene, or the copolymers of butadiene or isoprene and styrene or mixtures of these liquid polymers. The number-average molar mass of such liquid polymers is preferably within a range from 500 g / mol to 50,000 g / mol, preferably from 1,000 g / mol to 10,000 g / mol. By way of example, mention may be made of the "RICON" products from SARTOMER.
Système de réticulation Crosslinking system
Le système de réticulation peut être tout type de système connu de l’homme de l’art dans le domaine des compositions de caoutchouc. Il peut notamment être à base de soufre, et/ou de peroxyde et/ou de bismaléimides. The crosslinking system can be any type of system known to those skilled in the art in the field of rubber compositions. It can in particular be based on sulfur, and / or peroxide and / or bismaleimides.
De manière préférentielle, le système de réticulation est à base de soufre, on parle alors d’un système de vulcanisation. Le soufre peut être apporté sous toute forme, notamment sous forme de soufre moléculaire, ou d’un agent donneur de soufre. Au moins un accélérateur de vulcanisation est également préférentiellement présent, et, de manière optionnelle, préférentielle également, on peut utiliser divers activateurs de vulcanisation connus tels qu’oxyde de zinc, acide stéarique ou composé équivalent tels que les sels d’acide stéarique et sels de métaux de transition, dérivés guanidiques (en particulier diphénylguanidine), ou encore des retardateurs de vulcanisation connus. Le soufre est utilisé à un taux préférentiel compris entre 0,5 et 12 pce, en particulier entre 1 et 10 pce. L’accélérateur de vulcanisation est utilisé à un taux préférentiel compris entre 0,5 et 10 pce, plus préférentiellement compris entre 0,5 et 5,0 pce. On peut utiliser comme accélérateur tout composé susceptible d’agir comme accélérateur de vulcanisation des élastomères diéniques en présence de soufre, notamment des accélérateurs du type thiazoles ainsi que leurs dérivés, des accélérateurs de types sulfénamides, thiurames, dithiocarbamates, dithiophosphates, thiourées et xanthates. A titre d'exemples de tels accélérateurs, on peut citer notamment les composés suivants : disulfure de 2-mercaptobenzothiazyle (en abrégé "MBTS"), N-cyclohexyl-2- benzothiazyle sulfénamide ("CBS"), N,N-dicyclohexyl-2-benzothiazyle sulfénamide ("DCBS"), N-ter-butyl-2-benzothiazyle sulfénamide ("TBBS"), N-ter-butyl-2- benzothiazyle sulfénimide ("TBSI"), disulfure de tetrabenzylthiurame ("TBZTD"), dibenzyldithiocarbamate de zinc ("ZBEC") et les mélanges de ces composés. Additifs divers. Preferably, the crosslinking system is based on sulfur, this is called a vulcanization system. The sulfur can be provided in any form, in particular in the form of molecular sulfur, or of a sulfur donor. At least one vulcanization accelerator is also preferably present, and, optionally, also preferentially, various known vulcanization activators can be used such as zinc oxide, stearic acid or equivalent compound such as stearic acid salts and salts. of transition metals, guanidine derivatives (in particular diphenylguanidine), or also known vulcanization retardants. Sulfur is used at a preferential rate of between 0.5 and 12 phr, in particular between 1 and 10 phr. The vulcanization accelerator is used at a preferential rate of between 0.5 and 10 phr, more preferably of between 0.5 and 5.0 phr. Any compound capable of acting as an accelerator for vulcanization of diene elastomers in the presence of sulfur, in particular accelerators of the thiazole type and their derivatives, accelerators of the sulfenamide, thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthate type can be used as accelerator. Examples of such accelerators include the following compounds: 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide ("CBS"), N, N-dicyclohexyl- 2-benzothiazyle sulfenamide ("DCBS"), N-ter-butyl-2-benzothiazyle sulfenamide ("TBBS"), N-ter-butyl-2-benzothiazyle sulfenimide ("TBSI"), tetrabenzylthiuram disulfide ("TBZTD") , zinc dibenzyldithiocarbamate ("ZBEC") and mixtures of these compounds. Miscellaneous additives.
Additifs divers: Miscellaneous additives:
Les compositions de caoutchouc conformes à l'invention peuvent comporter également tout ou partie des additifs et agents de mise en œuvre usuels, connus de l’homme de l’art et habituellement utilisés dans les compositions de caoutchouc, comme par exemple des pigments, des agents de protection tels que cires anti-ozone, anti-ozonants chimiques, anti-oxydants. Fabrication de compositions de caoutchouc : The rubber compositions in accordance with the invention may also comprise all or part of the usual additives and processing agents known to those skilled in the art and usually used in rubber compositions, such as for example pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants. Manufacture of rubber compositions:
Les compositions de caoutchouc de l’invention sont fabriquées dans des mélangeurs appropriés, en utilisant deux phases de préparation successives selon une procédure générale bien connue de l'homme du métier : une première phase de travail ou malaxage thermo-mécanique (parfois qualifiée de phase "non-productive") sur un mélangeur approprié (par exemple mélangeur de type « Banbury ») à haute température, jusqu'à une température maximale comprise entre l l0°C et 200°C, de préférence entre l35°C et l85°C, suivie d'une seconde phase de travail mécanique (parfois qualifiée de phase "productive") à plus basse température, typiquement inférieure à l20°C, par exemple entre 40°C et l00°C, phase de finition au cours de laquelle est incorporé le système de réticulation ou vulcanisation. The rubber compositions of the invention are produced in suitable mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first working phase or thermo-mechanical kneading (sometimes called a phase "non-productive") on a suitable mixer (for example "Banbury" type mixer) at high temperature, up to a maximum temperature of between 10 ° C and 200 ° C, preferably between 135 ° C and 185 ° C, followed by a second mechanical working phase (sometimes called a "productive" phase) at a lower temperature, typically below 120 ° C, for example between 40 ° C and 100 ° C, the finishing phase during which is incorporated the crosslinking or vulcanization system.
La composition finale ainsi obtenue est ensuite calandrée par exemple sous la forme d’une feuille ou d’une plaque, notamment pour une caractérisation au laboratoire, ou encore extrudée sous la forme d'un semi-fini (ou profilé) de caoutchouc utilisable comme semelle de raquette à neige. The final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for characterization in the laboratory, or still extruded in the form of a semi-finished (or profiled) rubber usable as a snowshoe sole.
La réticulation de la composition peut être conduite de manière connue de l’homme du métier, par exemple à une température comprise entre l30°C et 200°C, sous pression. The crosslinking of the composition can be carried out in a manner known to a person skilled in the art, for example at a temperature between 130 ° C. and 200 ° C., under pressure.
Une semelle pour raquette à neige conforme à l’invention telle que décrite ci-dessus, peut être collée ou adhérisée sur la structure de base d’une raquette à neige, qui est destinée à entrer en contact avec le sol. A sole for snowshoe according to the invention as described above, can be glued or adhered to the basic structure of a snowshoe, which is intended to come into contact with the ground.
Avantageusement la forme de la semelle peut être adaptée à la structure de base de la raquete à neige et peut former une pluralité d’éléments disjoints. Advantageously, the shape of the sole can be adapted to the basic structure of the snowshoe and can form a plurality of disjoint elements.
En particulier une telle semelle peut s’adapter à une raquette à neige telles que décrites dans les demandes de brevet FR 17/71369 ou FR 17/71370, telles qu’illustrée dans la figure unique qui est une représentation schématique en perspective de la raquette à neige. In particular, such a sole can be adapted to a snowshoe as described in patent applications FR 17/71369 or FR 17/71370, as illustrated in the single figure which is a schematic perspective representation of the snowshoe. snow.
Une telle raquette à neige 1 comporte une structure de base comporte une structure de base en matériau non caoutchoutique formant une zone de chaussure 2 et une zone de portance et dans laquelle la zone de portance comprend un débord latéral de chaque côté de la zone de chaussure 2, ladite zone de portance se prolonge vers l’arrière de la zone de chaussure 2 pour former une spatule 3 arrière et forme une portion frontale 4 de la raquette à l’opposé de la spatule arrière 3, la face de contact de la structure de base comportant une semelle 5 selon l’invention agencée sur tout ou partie de ladite face de contact.  Such a snowshoe 1 comprises a basic structure comprises a basic structure of non-rubber material forming a shoe zone 2 and a lift zone and in which the lift zone comprises a lateral overhang on each side of the shoe zone 2, said lift zone extends towards the rear of the shoe zone 2 to form a rear spatula 3 and forms a front portion 4 of the racket opposite the rear spatula 3, the contact face of the structure base comprising a sole 5 according to the invention arranged on all or part of said contact face.
Cette semelle 5 comprend une pluralité d’éléments de sculpture 51 en matériau caoutchoutique sont agencés sur tout ou partie de ladite zone de pied.  This sole 5 comprises a plurality of tread elements 51 of rubber material are arranged over all or part of said foot area.
Cette semelle peut être collée, comme indiqué précédemment, à la structure de base ou réalisée par moulage ou surmoulage. This sole can be glued, as indicated above, to the basic structure or produced by molding or overmolding.
EXEMPLES DE REALISATION DE L’INVENTION De nombreux essais réalisés sur le terrain sur divers types de neige ont montré un avantage net et sensible apporté par l’adhérence élevé de la semelle conforme à l’invention et en particulier une semelle dont la composition inclut 100 pce de caoutchouc naturel, 50 pce de silice, 5 pce de silane et 35 pce d’huile plastifiante et un système de vulcanisation avec ultra-accélérateur. Cela permet un usage sans crainte de glisser, que ce soit en montée, descente ou dévers transverse. EXAMPLES OF EMBODIMENT OF THE INVENTION Numerous tests carried out in the field on various types of snow have shown a clear and appreciable advantage brought by the high grip of the sole in accordance with the invention and in particular a sole whose composition includes 100 pce of natural rubber, 50 pce of silica, 5 pce of silane and 35 pce of plasticizer oil and a vulcanization system with ultra-accelerator. This allows use without fear of slipping, whether uphill, downhill or transverse.
De plus, la combinaison de sculpture avec un matériau caoutchoutique conforme à l’invention, donne des performances signifîcativement meilleures en adhérence sur neige par rapport aux nombreuses autres raquettes testées.  In addition, the combination of tread with a rubber material according to the invention gives significantly better performance in grip on snow compared to the many other snowshoes tested.

Claims

REVENDICATIONS
1) Semelle de raquette à neige comprenant une composition de caoutchouc à base d’au moins un élastomère isoprénique majoritaire, une charge inorganique renforçante, un plastifiant et un système de réticulation. 1) Snowshoe sole comprising a rubber composition based on at least one majority isoprene elastomer, a reinforcing inorganic filler, a plasticizer and a crosslinking system.
2) Semelle selon la revendication 1, dans laquelle le plastifiant possède un Tg inférieure ou égale à 20°C. 3) Semelle selon l’une quelconque des revendications 1 ou 2, dans laquelle le plastifiant est choisi parmi les huiles plastifiantes et leurs mélanges. 2) Sole according to claim 1, wherein the plasticizer has a Tg less than or equal to 20 ° C. 3) Sole according to any one of claims 1 or 2, wherein the plasticizer is chosen from plasticizing oils and their mixtures.
4) Semelle selon la revendication 3, dans laquelle les huiles plastifiantes sont choisies dans le groupe constitué par les huiles naphténiques, les huiles paraffiniques, les huiles MES (Medium Extracted Solvatés), les huiles TDAE (Treated Distillate Aromatic Extracts), les huiles RAE (Residual Aromatic Extract oils), les huiles TRAE (Treated Residual Aromatic Extract) et les huiles SRAE (Safety Residual Aromatic Extract oils), les huiles minérales, les huiles végétales, les plastifiants éthers, les plastifiants esters, les plastifiants phosphates, les plastifiants sulfonates et les mélanges de ces composés. 4) Sole according to claim 3, in which the plasticizing oils are chosen from the group consisting of naphthenic oils, paraffinic oils, MES oils (Medium Extracted Solvated), TDAE oils (Treated Distillate Aromatic Extracts), RAE oils (Residual Aromatic Extract oils), TRAE oils (Treated Residual Aromatic Extract) and SRAE oils (Safety Residual Aromatic Extract oils), mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, plasticizers sulfonates and mixtures of these compounds.
5) Semelle selon l’une quelconque des revendications précédentes, dans laquelle le taux d’agent plastifiant est supérieur ou égale à 5 parties pour cent parties d’élastomères, pce. 6) Semelle selon la revendication 5, dans laquelle le taux d’agent plastifiant va de 5 à 50 pce, de préférence de 10 à 40 pce. 5) Sole according to any one of the preceding claims, in which the level of plasticizing agent is greater than or equal to 5 parts per hundred parts of elastomers, pce. 6) Sole according to claim 5, wherein the level of plasticizing agent ranges from 5 to 50 phr, preferably from 10 to 40 phr.
7) Semelle selon les revendications 5 ou 6, dans laquelle le taux d’agent plastifiant va de 25 à 40 pce. 7) Sole according to claims 5 or 6, wherein the level of plasticizer ranges from 25 to 40 phr.
8) Semelle selon l’une quelconque des revendications précédentes, dans laquelle le taux d’élastomère isoprénique va de 60 à 100 pce, de préférence de 70 à 100 pce, plus préférentiellement de 80 à 100 pce. 9) Semelle selon l’une quelconque des revendications précédentes, dans laquelle le taux de charge inorganique renforçante va de 10 à 60 pce, de préférence de 30 à 55 pce. 8) Sole according to any one of the preceding claims, in which the isoprene elastomer content ranges from 60 to 100 phr, preferably from 70 to 100 phr, more preferably from 80 to 100 phr. 9) Sole according to any one of the preceding claims, in which the rate of reinforcing inorganic filler ranges from 10 to 60 phr, preferably from 30 to 55 phr.
10) Semelle selon l’une quelconque des revendications précédentes, dans laquelle la charge inorganique renforçante est de la silice. 11) Raquette à neige comprenant une semelle selon l’une quelconque des revendications 1 à 10. 10) Sole according to any one of the preceding claims, wherein the reinforcing inorganic filler is silica. 11) Snowshoe comprising a sole according to any one of claims 1 to 10.
12) Raquette à neige (1) comportant une structure de base en matériau non caoutchoutique formant une zone de chaussure (2) et une zone de portance et dans laquelle la zone de portance comprend un débord latéral de chaque côté de la zone de chaussure (2), ladite zone de portance se prolonge vers l’arrière de la zone de chaussure (2) pour former une spatule (3) arrière et forme une portion frontale (4) de la raquette à l’opposé de la spatule arrière (3), la face de contact de la structure de base (2) comportant une semelle (5) selon l’une quelconque des revendication 1 à 10 agencés sur tout ou partie de ladite face de contact. 12) Snowshoe (1) comprising a basic structure of non-rubber material forming a shoe zone (2) and a lift zone and in which the lift zone comprises a lateral overhang on each side of the shoe zone ( 2), said lift zone extends towards the rear of the shoe zone (2) to form a rear spatula (3) and forms a front portion (4) of the racket opposite the rear spatula (3) ), the contact face of the base structure (2) comprising a sole (5) according to any one of claims 1 to 10 arranged on all or part of said contact face.
PCT/EP2019/070106 2018-07-25 2019-07-25 Snowshoe sole WO2020021038A1 (en)

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FR2548545A1 (en) * 1983-07-05 1985-01-11 Michellet Alain Non-slip walking ski
WO1995006502A1 (en) 1993-09-01 1995-03-09 Peter Smith Snow shoe
FR2743501A1 (en) 1996-01-11 1997-07-18 Gouillardon Gaudry Snow shoe
WO1997036724A2 (en) 1996-04-01 1997-10-09 Cabot Corporation Novel elastomer composites, method and apparatus
US5740621A (en) * 1995-09-29 1998-04-21 Wing Enterprises, Inc. Compactible snowshoes and bindings and method of assembly
WO1999016600A1 (en) 1997-09-30 1999-04-08 Cabot Corporation Elastomer composite blends and methods for producing them
WO2003016215A1 (en) 2001-08-13 2003-02-27 Rhodia Chimie Method of preparing silicas, silicas with specific pore-size and/or particle-size distribution and the use thereof, in particular for reinforcing polymers
WO2003016387A1 (en) 2001-08-13 2003-02-27 Societe De Technologie Michelin Diene rubber composition for tyres comprising a specific silicon as a reinforcing filler
US20100132225A1 (en) * 2008-12-02 2010-06-03 Rudy Lucas Samuels Molded snowshoe with pliable heel contact area
FR3022549A1 (en) * 2014-06-18 2015-12-25 Michelin & Cie RUBBER COMPOSITION COMPRISING AN EPOXY ELASTOMER RETICULATED BY A CARBOXYLIC ACIDIC ACID

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FR2548545A1 (en) * 1983-07-05 1985-01-11 Michellet Alain Non-slip walking ski
WO1995006502A1 (en) 1993-09-01 1995-03-09 Peter Smith Snow shoe
US5740621A (en) * 1995-09-29 1998-04-21 Wing Enterprises, Inc. Compactible snowshoes and bindings and method of assembly
FR2743501A1 (en) 1996-01-11 1997-07-18 Gouillardon Gaudry Snow shoe
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WO2003016387A1 (en) 2001-08-13 2003-02-27 Societe De Technologie Michelin Diene rubber composition for tyres comprising a specific silicon as a reinforcing filler
US20100132225A1 (en) * 2008-12-02 2010-06-03 Rudy Lucas Samuels Molded snowshoe with pliable heel contact area
FR3022549A1 (en) * 2014-06-18 2015-12-25 Michelin & Cie RUBBER COMPOSITION COMPRISING AN EPOXY ELASTOMER RETICULATED BY A CARBOXYLIC ACIDIC ACID

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