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    • 专利摘要:
    The present invention relates to a tire comprising a tread which comprises a rubber composition based on at least one elastomer matrix, a reinforcing filler, and carbon fiber fibers, z being the direction normal to the surface of the tread. rolling intended to be in contact with a rolling ground, x and y being two directions orthogonal to z, x the circumferential direction of the tire, y the axial direction relative to the axis of rotation of the tire, Cx, Cy and Cz being the thermal diffusivities measured at 25 ° C of the tread in the baked state in the x, y and z directions respectively, which tire has thermal diffusivity ratios Cz / Cx and Cz / Cy greater than 2. Such a tire presents an improved compromise between the productivity of the baking step in the manufacture of the tire and the wear performance of the tire.
    公开号:FR3014442A1
    申请号:FR1362331
    申请日:2013-12-10
    公开日:2015-06-12
    发明作者:Vincent Abad；Guillaume Hennebert
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:

    [0001] The field of the present invention is that of tires, in particular treads for tires. A particularly sought after performance of tires is wear. The tread which is in contact with the running ground is the part of the tire which is primarily subject to the phenomenon of wear. To improve the wear resistance of the treads, rubber-based materials reinforced with relatively thin fillers are typically used. These relatively thin reinforcing fillers are most often objects of small size, that is to say submicron. Conversely, the use of coarser objects of the order of one micron generally has the effect of reducing the wear resistance of the tread. The manufacture of a tire requires a step of baking the tire which makes it possible to crosslink, in particular to vulcanize, the rubbery components of the tire. This baking step is decisive for the performance of the tire. Indeed, the degree of crosslinking will determine the properties of the rubbery components. To seek productivity gains in the manufacture of tires, it is of interest to be able to reduce the time of this baking step without affecting the desired degree of crosslinking of the rubber components of the tire. One solution to this problem is to make certain rubbery components of the tire conductive thermally, for example by introducing into the compositions of the rubbery components of the tire thermally conductive objects. Among the thermally conductive objects, for example, carbon nanotubes, silicon carbide fibers and carbon fibers may be mentioned. Carbon fibers, however, have the disadvantage of being coarse objects, especially of the order of a micron. Therefore, their use in a tread rubber composition most often has the effect of greatly reducing the wear resistance of the tread. The Applicants have discovered that the use of specific carbon fibers oriented specifically in a tread of a tire makes it possible to offer an improved compromise between the thermal conductivity and the wear resistance of the tread, without substantially penalizing otherwise other performance such as the adhesion of the tire. Thus, a first object of the invention is a tire comprising a tread which comprises a rubber composition based on at least: an elastomer matrix, a reinforcing filler, and carbon fibers. ex-preferably a plasticizer, z being the direction normal to the surface of the tread intended to be in contact with a rolling ground, x and y being two directions orthogonal to z, x the circumferential direction of the tire, y the axial direction relative to the axis of rotation of the tire, Cx, Cy and Cz being the thermal diffusivities measured at 25 ° C of the tread in the baked state in the x, y and z directions respectively, which tire has thermal diffusivity ratios Cz / Cx and Cz / Cy greater than 2.
    [0002] Another object of the invention is a method of manufacturing the tire according to the invention. The subject of the invention is also a layer consisting of the same rubber composition as the tread of the tire according to the invention, which layer has thermal diffusivity ratios C'z '/ C'x' and C'z '/ Cy' greater than 2, - C'x, C'y 'and C'z' being the thermal diffusivities measured at 25 ° C of the layer in the cooked state in the directions x ', y' and z, respectively ', - x', y 'and z' being directions orthogonal to each other, z 'being the preferred direction of the carbon fibers. The invention also relates to a method for manufacturing the layer according to the invention. The subject of the invention is also a tread or a tread portion of a tire, which tread or tread portion consists of the juxtaposition of layers according to the invention assembled along their faces perpendicular to the tread. the direction x ', x' being the direction orthogonal to the mean plane of each layer (y'z ') defined by the directions y' and z ', the direction z' coinciding with the radial direction of the tire.
    [0003] DETAILED DESCRIPTION OF THE INVENTION In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight. The abbreviation "pce" means parts by weight percent of the elastomeric matrix of the rubber composition, the elastomeric matrix consisting of all of the elastomers present in the rubber composition. On the other hand, any range of values designated by the expression "between a and h" represents the range of values greater than "a" and less than "h" (i.e., terminals a and b excluded). while any range of values designated by the expression "from a to h" means the range of values from "a" to "h" (i.e. including the strict limits a and b). By the term "composition-based" is meant in the present description a composition comprising the mixture and / or the reaction product in situ of the various constituents used, some of these basic constituents (for example the elastomer, the filler or other additive conventionally used in a rubber composition intended for the manufacture of tire) being capable of, or intended to react with one another, at least in part, during the different phases of manufacture of the composition intended for the manufacture of a tire . Z is defined as being the normal direction on the surface of the tread intended to be in contact with a rolling ground, x and y being two directions orthogonal to z, x the circumferential direction of the tire, y the axial direction by relative to the axis of rotation of the tire. Cx, Cy and Cz are the thermal diffusivities of the tread in the baked state in the x, y and z directions, respectively. They are measured at 25 ° C. according to the ASTM E 1641 standard. The ratios of the thermal diffusivities measured at 25 ° C., Cz / Cx and Cz / Cy are greater than 2, preferably greater than 3, more preferably greater than or equal to 4. These ratio values characterize a certain thermal anisotropy of the tread caused by a preferential orientation of the carbon fibers in the direction normal to the surface of the tread.
    [0004] The elastomeric matrix may consist of one or more elastomers which differ from each other by their macrostructure or their microstructure. The elastomeric matrix preferably comprises a diene elastomer. By "diene" elastomer (or indistinctly rubber), one or more elastomers consisting at least in part (ie, a homopolymer or a copolymer) of monomeric diene units (monomers carrying two carbon double bonds) must be understood in known manner. -carbon, conjugated or not). These diene elastomers can be classified into two categories: "essentially unsaturated" or "essentially saturated". In general, the term "essentially P10-3214-4-unsaturated" means a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15%. (% by moles); Thus, diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated" diene elastomers ( low or very low diene origin, always less than 15%). In the category of "essentially unsaturated" diene elastomers, the term "highly unsaturated" diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%. These definitions being given, the term "diene elastomer" may be understood more particularly to be used in the compositions according to the invention: (a) - any homopolymer of a conjugated diene monomer, especially any homopolymer obtained by polymerization of a diene monomer conjugate having from 4 to 12 carbon atoms; (b) - any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms; (c) - a ternary copolymer obtained by copolymerization of ethylene, an α-olefin having from 3 to 6 carbon atoms with a non-conjugated diene monomer containing from 6 to 12 carbon atoms, for example elastomers obtained at from ethylene, propylene with a non-conjugated diene monomer of the aforementioned type, such as in particular 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene; (d) - a copolymer of isobutene and isoprene (butyl rubber), as well as the halogenated versions, in particular chlorinated or brominated, of this type of copolymer. Although it is applicable to any type of diene elastomer, one skilled in the art of pneumatics will understand that the present invention is preferably carried out with essentially unsaturated diene elastomers, in particular of the type (a) or ( b) above. In the case of copolymers of type (b), these contain from 20 to 99% by weight of diene units and from 1 to 80% by weight of vinylaromatic units. By way of conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5 alkyl) -1,3-butadienes, such as, for example, 2 , 3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-P10-3214-methyl-3-methyl isopropyl-1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene. Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, alpha-methylstyrene, the "vinyl-toluene" commercial mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene. Preferably, the diene elastomer is a substantially unsaturated elastomer selected from the group consisting of polybutadienes, polyisoprenes, butadiene copolymers, isoprene copolymers, and mixtures of these elastomers. As diene elastomer is particularly suitable polybutadiene (BR), a copolymer of butadiene and styrene (SBR), a natural rubber (NR) or a synthetic polyisoprene (IR) preferably having a molar ratio of cis-1 , 4 greater than 90% or mixtures thereof. As reinforcing filler may be used any type of so-called reinforcing filler known for its ability to reinforce a rubber composition that can be used for the manufacture of tires, for example an organic filler such as carbon black, a reinforcing inorganic filler such as silica to which is associated in a known manner a coupling agent, or a mixture of these two types of filler. Such a reinforcing filler typically consists of nanoparticles whose average size (in mass) is less than one micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm. Suitable carbon blacks are all carbon blacks, especially blacks conventionally used in tires or their treads (so-called pneumatic grade blacks). Among the latter, there will be mentioned more particularly the reinforcing carbon blacks of the series 100, 200, 300, or the series blacks 500, 600 or 700 (ASTM grades), 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 carrier for some of the rubber additives used. "Reinforcing inorganic filler" means any inorganic or mineral filler, irrespective of its color and 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, with no other means than an intermediate coupling agent, a rubber composition intended for the manufacture of pneumatic tires, in other words capable of to replace, in its reinforcing function, a conventional carbon black of pneumatic grade; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface. Suitable reinforcing inorganic fillers are in particular mineral fillers of the siliceous type, preferentially silica (SiO 2). The silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g, especially between 60 and 300 m2 / g. As highly dispersible precipitated silicas (called "HDS"), mention may be made, for example, of the "Ultrasil" 7000 and "Ultrasil" 7005 silicas of the Degussa company, the "Zeosil" 1165MP, 1135MP and 1115MP silicas of the Rhodia company. "Hi-Sil" silica EZ150G from the company PPG, the "Zeopol" silicas 8715, 8745 and 8755 from the Huber Company, the high surface area silicas as described in the application WO 03/016387. In the present disclosure, the BET surface area is determined in a known manner by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society" Vol. 60, page 309, February 1938, more precisely according to the French standard NF ISO 9277 of December 1996 (multipoint volumetric method (5 points) - gas: nitrogen - degassing: 1 hour at 160 ° C - relative pressure range p / po: 0.05 at 0.17). The CTAB specific surface is the external surface determined according to the French standard NF T 45-007 of November 1987 (method B).
    [0005] The physical state under which the reinforcing inorganic filler is present is indifferent, whether in the form of powder, microbeads, granules or beads. Of course, reinforcing inorganic filler is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of highly dispersible silicas as described above. Those skilled in the art will understand that, as an equivalent load of the reinforcing inorganic filler described in this paragraph, it would be possible to use a reinforcing filler of another nature, in particular an organic filler such as carbon black, provided that this filler reinforcing would be covered with an inorganic layer such as silica, or would comprise on its surface functional sites, including hydroxyl, requiring the use of a coupling agent to establish the connection between the filler and the elastomer. By way of example, mention may be made, for example, of carbon blacks for tires as described for example in documents WO 96/37547 and WO 99/28380. The reinforcing filler may comprise a carbon black, an inorganic filler or a mixture thereof, the inorganic filler preferably being a silica.
    [0006] According to a particular embodiment of the invention, the inorganic filler, preferably a silica, represents more than 50% by weight of the reinforcing filler of the rubber composition. It is said that the reinforcing inorganic filler is the majority.
    [0007] When combined with a predominant reinforcing inorganic filler such as silica, the carbon black is preferably used at a level of less than 20 phr, more preferably less than 10 phr (for example between 0.5 and 20 phr, in particular between 2 and 20 phr). and 10 phr). In the ranges indicated, it benefits from the coloring properties (black pigmentation agent) and anti-UV carbon blacks, without otherwise penalizing the typical performance provided by the reinforcing inorganic filler. The person skilled in the art knows how to adjust the total reinforcing filler content in the rubber composition according to the intended application of the rubber composition and according to the amount of plasticizer in the rubber composition in order to be able to carry out the implementation. of the rubber composition (in English "processability"). Therefore for a range of plasticizer levels, the skilled person adapts the rate of reinforcing filler. The total reinforcing filler content is preferably between 30 and 180 phr, more preferably between 40 phr and 160 phr. Within 30 phr, the reinforcement of the rubber composition may be insufficient to provide an adequate level of cohesion or wear resistance of the rubber component of the tire comprising this composition. Beyond 180 phr, there is a risk of increasing the hysteresis and therefore the rolling resistance of the tires. Even more preferably, the total reinforcing filler content is at least 50 phr and at most 160 phr. Advantageously, the total reinforcing filler content varies in a range from 80 phr to 140 phr, especially in a composition intended for a tire tread for tourism. Any of these total reinforcing charge ratio ranges apply to any of the embodiments of the invention.
    [0008] In order to couple the reinforcing inorganic filler to the diene elastomer, an at least bifunctional coupling agent (or bonding agent) is used in a well-known manner to ensure a sufficient chemical and / or physical connection between the inorganic filler (surface of its particles) and the diene elastomer. In particular, organosilanes or at least bifunctional polyorganosiloxanes are used. P10-3214 - 8 - In particular, polysulfide silanes, called "symmetrical" or "asymmetrical" silanes according to their particular structure, are used, as described for example in the applications W003 / 002648 (or US 2005/016651) and W003 / 002649 (or US 2005/016650).
    [0009] In particular, polysulphide silanes having the general formula (V) Z - A - Sx - A - Z (V) in which: - x is an integer of 2 to 8 ( preferably from 2 to 5); the symbols A, which may be identical or different, represent a divalent hydrocarbon radical (preferably a C1-C18 alkylene group or a C6-C12 arylene group, more particularly a C1-C18 alkylene, in particular a C1-C4 alkylene, in particular propylene); the symbols Z, which are identical or different, correspond to one of the following three formulas: ## STR2 ## in which: the R 1 radicals , substituted or unsubstituted, which are identical to or different from one another, represent a C1-C18 alkyl, C5-C18 cycloalkyl or C6-C18 aryl group (preferably C1-C6 alkyl, cyclohexyl or phenyl groups, in particular groups containing C1-C4 alkyl, more particularly methyl and / or ethyl). the radicals R2, substituted or unsubstituted, which are identical to or different from one another, represent a C1-C18 alkoxyl or a C5-C18 cycloalkoxyl group (preferably a group chosen from C1-C8 alkoxyls and C5-C8 cycloalkoxyls, plus still more preferably a group chosen from C1-C4 alkoxyls, in particular methoxyl and ethoxyl).
    [0010] In the case of a mixture of polysulfurized alkoxysilanes corresponding to formula (I) above, in particular common commercially available mixtures, the average value of "x" is a fractional number preferably of between 2 and 5, more preferably close to 4. But the invention can also be advantageously used for example with disulfide alkoxysilanes (x = 2). By way of examples of polysulfide silanes, mention may be made more particularly of polysulfides (in particular disulphides, trisulphides or tetrasulfides) of bis- (C 1 -C 4 alkoxyl) -alkyl (C 1 -C 4) silylalkyl (C 1 -C 4). C4)), such as, for example, bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl) polysulfides. Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated to TESPT, of formula [(C2H50) 3Si (CH2) 352) 2 or bis (triethoxysilylpropyl) disulfide, abbreviated to TESPD, is preferably used. formula [(C2H50) 3Si (CH2) 35] 2. As coupling agent other than polysulfide alkoxysilane, there may be mentioned in particular bifunctional POSS (polyorganosiloxanes) or hydroxysilane polysulfides as described in patent applications WO 02/30939 (or US Pat. No. 6,774,255), WO 02 / 31041 (or US 2004/051210) or silanes or POSS carrying azo-dicarbonyl functional groups, as described for example in patent applications WO 2006/125532, WO 2006/125533, WO 2006/125534.
    [0011] The content of coupling agent is advantageously less than 20 phr, it being understood that it is generally desirable to use as little as possible. Typically the level of coupling agent is from 0.5% to 15% by weight relative to the amount of inorganic filler. Its content is preferably between 0.5 and 15 phr, more preferably in a range from 3 to 13 phr. This level is easily adjusted by those skilled in the art according to the level of inorganic filler used in the composition. According to one embodiment of the invention, the rubber composition comprises a plasticizer. By a plasticizer is meant one or more plasticizers. The plasticizer may be a liquid plasticizer, a resin or a mixture thereof. The term "resin" is hereby reserved, by definition known to those skilled in the art, to a compound that is solid at room temperature (23 ° C), as opposed to a liquid plasticizer such as an oil.
    [0012] Hydrocarbon resins are polymers well known to those skilled in the art, essentially based on carbon and hydrogen but may include other types of atoms, used in particular as plasticizers or tackifying agents in polymeric matrices. They are inherently miscible (i.e., compatible) with the levels used with the polymer compositions for which they are intended, so as to act as true diluents. They have been described, for example, in the book "Hydrocarbon Resins" by R. Mildenberg, M. Zander and G. Collin (New York, VCH, 1997, ISBN 3-527-28617-9), chapter 5 of which is devoted their applications, in particular pneumatic rubber (5.5 "Rubber Tires and Mechanical Goods"). They may be aliphatic, cycloaliphatic, aromatic, hydrogenated aromatic, of the P10-3214-aliphatic / aromatic type, that is to say based on aliphatic and / or aromatic monomers. They may be natural or synthetic, whether or not based on petroleum (if so, also known as petroleum resins). Their Tg is preferably greater than 0 ° C., especially greater than 20 ° C. (most often between 30 ° C. and 95 ° C.).
    [0013] In a known manner, these hydrocarbon resins can also be described as thermoplastic resins in that they soften by heating and can thus be molded. They can also be defined by a point or softening point (in English, "softening point"). The softening temperature of a hydrocarbon resin is generally about 40 to 60 ° C. higher than its Tg value. The softening point is measured according to ISO 4625 ("Ring and Ball" method). The macrostructure (Mw, Mn and Ip) is determined by size exclusion chromatography (SEC) as indicated below.
    [0014] As a reminder, the SEC analysis, for example, consists in separating the macromolecules in solution according to their size through columns filled with a porous gel; the molecules are separated according to their hydrodynamic volume, the larger ones being eluted first. The sample to be analyzed is simply solubilized beforehand in a suitable solvent, tetrahydrofuran at a concentration of 1 g / liter. The solution is then filtered through a 0.45 μm porosity filter before injection into the apparatus. The equipment used is for example a "Waters alliance" chromatographic chain according to the following conditions: elution solvent: tetrahydrofuran, temperature 35 ° C .; - concentration 1 g / liter; flow rate: 1 ml / min; volume injected: 100 μl; - Moore calibration with polystyrene standards; - set of 3 columns "Waters" in series ("Styragel HR4E", "Styragel HR1" and "Styragel HR 0.5"); - Differential refractometer detection (for example "WATERS 2410") that can be equipped with operating software (for example "Waters Millenium"). A Moore calibration is conducted with a series of low lp (less than 1.2) polystyrene commercial standards of known molar masses covering the field of masses to be analyzed. The mass-averaged molecular mass (Mw), the number average molecular weight (Mn) and the polymolecularity index (lp = Mw / Mn) are deduced from the recorded data (mass distribution curve of the molar masses). P10-3214 All the molar mass values given in the present application are therefore relative to calibration curves made with polystyrene standards. According to a preferred embodiment of the invention, the hydrocarbon resin has at least one, more preferably all of the following characteristics: a Tg greater than 25 ° C (in particular between 30 ° C and 100 ° C), more preferably greater than 30 ° C (especially between 30 ° C and 95 ° C); a softening point greater than 50 ° C (in particular between 50 ° C and 150 ° C); a number-average molar mass (Mn) of between 400 and 2000 g / mol, preferably between 500 and 1500 g / mol; a polymolecularity index (Ip) of less than 3, preferably of 2 (booster: I p = Mw / Mn with Mw weight average molar mass).
    [0015] As examples of such hydrocarbon resins, mention may be made of those selected from the group consisting of cyclopentadiene homopolymer or copolymer resins (abbreviated to CPD), dicyclopentadiene homopolymer or copolymer resins (abbreviated to DCPD), terpene homopolymer or copolymer resins, C5 homopolymer or copolymer resins, C9 homopolymer or copolymer resins, alpha-methyl-styrene homopolymer or copolymer resins, and these resins. Among the above copolymer resins, mention may be made more particularly of those selected from the group consisting of (D) CPD / vinylaromatic copolymer resins, (D) CPD / terpene copolymer resins, terpene phenol copolymer resins, (D) CPD / C5 cut copolymer resins, (D) CPD / C9 cut copolymer resins, terpene / vinylaromatic copolymer resins, terpene / phenol copolymer resins, C5 / vinylaromatic cut copolymer resins, and mixtures of these resins.
    [0016] The term "terpene" includes, in a known manner, the alpha-pinene, beta- pinene and limonene monomers; preferably, a limonene monomer is used which is present in a known manner in the form of three possible isomers: L-limonene (laevorotatory enantiomer), D-limonene (dextrorotatory enantiomer), or the dipentene, racemic of the dextrorotatory and levorotatory enantiomers. . Suitable vinylaromatic monomers are, for example, styrene, alpha-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyl-toluene, paratertiobutylstyrene, methoxystyrenes, chlorostyrenes and hydroxystyrenes. vinylmesitylene, divinylbenzene, vinylnaphthalene, any vinylaromatic monomer from a C9 cut (or more generally from a C8 to C10 cut).
    [0017] More particularly, the resins selected from the group consisting of homopolymer resins (D) CPD, copolymer resins (D) CPD / styrene, polylimonene resins, copolymer resins limonene / styrene, limonene / D (CPD) copolymer resins, C5 / styrene cut copolymer resins, C5 / C9 cut copolymer resins, and mixtures of these resins. All the above resins are well known to those skilled in the art and commercially available, for example sold by the company DRT under the name "Dercolyte" for polylimonene resins, by the company Neville Chemica I Company under the name " Super Nevtac ", by Kolon under the name" Hikorez "or by the company Exxon Mobil under the name" Escorez "with regard to the C5 / styrene resins or C5 / Cg cut resins, or by the Struktol company under the name" 40 MS "or" 40 NS "(mixtures of aromatic and / or aliphatic resins).
    [0018] Any liquid plasticizer, particularly an oil, known for its plasticizing properties vis-à-vis diene elastomers, is usable. At room temperature (23 ° C.), these plasticizers or these oils, more or less viscous, are liquids (that is to say, as a reminder, substances having the capacity to eventually take on the shape of their container) , in contrast in particular to hydrocarbon plasticizing resins which are inherently solid at room temperature. Liquid plasticizers selected from the group consisting of liquid diene polymers, polyolefin oils, naphthenic oils, paraffinic oils, DAE oils, MES (Medium Extracted Solvates) oils, TDAE (Treated Distillate Aromatic Extracts) oils are particularly suitable. ), Residual Aromatic Extract oils (RAE), Treated Residual Aromatic Extract (TREE) oils and Safety Residual Aromatic Extract oils (SRAE), mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulphonate plasticizers and mixtures of these compounds. According to a more preferred embodiment, the liquid plasticizer is selected from the group consisting of MES oils, TDAE oils, naphthenic oils, vegetable oils and mixtures of these oils. The level of plasticizer, ie liquid plasticizer or resin or their mixture, in the rubber composition can vary widely depending on the amount of reinforcing filler and carbon fibers ex-bile introduced into the rubber composition, but also for example depending on the viscosity of the elastomeric matrix and the desired raw and baked stiffness levels of the rubber composition. The amount of plasticizer is determined according to a chosen dilution ratio. P10-3214 - 13 - dilution means the ratio of the mass of the plasticizer to the sum of the masses of the plasticizer and the elastomeric matrix. According to one embodiment of the invention, the amount of plasticizer in the rubber composition is adjusted so as to achieve a dilution ratio greater than 0.35. The dilution ratio is preferably between 0.35 and 0.60, more preferably between 0.35 and 0.55. Due to the anisotropy of the tread of the tire caused by a preferential orientation of the carbon fibers in the direction normal to the surface of the tread, the tread of the tire according to the invention has different rigidities in the x, y, z directions. The dilution ratio makes it possible to adjust these rigidities in order to reach a compromise between these rigidities. The optimization of this compromise optimizes in turn the operation of the tire.
    [0019] The ex-pitch carbon fibers are derived from pitches (pitch, for example coal pitches or petroleum pitches) and can be prepared according to the following process: the pitches are in a first step converted into fibrillar precursors by first melt spinning step, these fibrillary precursors are then generally thermally stabilized by a first heat treatment under an oxidizing atmosphere (100 ° C-400 ° C) before undergoing treatment at higher temperatures under an inert atmosphere carbonization (1000-1600 ° C) and graphitization (2500 ° C-3000 ° C). The process for producing carbon fibers ex is described extensively, for example in the journal "Nippon Steel Technical Report, No. 59, October 1993, page 65" or in the reference work "Carbon Fibers"; 1998; 3rd edition; Donnet, J.-B., Wang, T.K., Rebouillat, S., Peng, J.C.M. Exbri carbon fibers are objects generally characterized by a fiber diameter of at least one micron. Their diameter may vary from 1 μm to 50 μm, preferably from 3 μm to 20 μm, more preferably from 5 μm to 15 μm. These preferred ranges of diameter of the carbon fibers ex brai apply to any of the embodiments of the invention. The carbon fibers may have a length that varies widely. The choice of length lengths of carbon fiber ex-fib is generally limited to the products offered by the suppliers. Those skilled in the art also understand that the length of the carbon fibers ex-fib is limited by the dimensions of the mixing equipment used to mix the various ingredients of the rubber composition, since it must be able to introduce them into the mixing tools. For example, irrespective of the embodiment of the invention, ex-beryllium carbon fibers having a number average length ranging from about 100 microns to a few millimeters are suitable, for example from 50 μm to 50 μm. 30 mm or 50 μm to 3 mm. Carbon fibers of length preferably ranging from 50 μm to 500 μm, more preferably 50 μm to 250 μm, are used. These preferred length ranges of carbon fibers ex-pitch apply to any of the embodiments of the invention. Chopped fibers are typically used, or milled fibers. The average length of the carbon fibers ex-fib is determined according to the method described in paragraph 11.1.3, more precisely from the second operation described in subparagraph ii). During the mixing of the ex-fibril carbon fibers with the other ingredients of the rubber composition, the mechanical action can cut the carbon fibers ex-fib into a length shorter than their original length, i.e. say the length they had before mixing. The number average length of the carbon fibers in the rubber composition can range from 50 μm to 250 μm. According to one embodiment of the invention applicable to the described embodiments, the volume fraction of the carbon fibers ex-fib in the rubber composition varies in a range from 1 to 15%. Preferably this volume fraction varies in a range from 3 to 12%. The volume fraction of the carbon fibers ex-fib is defined as the ratio of the volume of the carbon fibers ex-fib on the volume of all the constituents of the rubber composition, it being understood that the volume of all the constituents is calculated by adding the volume of each of the constituents of the rubber composition. Below 1%, it is found that the rubber composition is insufficiently conductive to substantially reduce the cooking time of the tire. Beyond 15%, the wear performance of the tire can be penalized as well as the adhesion performance of the tire due to too high rigidity of the rubber composition that makes up the tread. The preferential range of 3 to 12% makes it possible to further optimize the compromise thermal conductivity of the tread. The amount of carbon fibers ex-fibered in the rubber composition is determined by its volume fraction and thus depends on the amount of the other components of the rubber composition, including the amount of plasticizer in the rubber composition. The amount of plasticizer for adjusting the rigidity of the rubber composition and its processability, the amount of carbon fiber ex-fib is adjusted according to the volume fraction of carbon fibers ex pitch in the rubber composition and according to the target stiffness and viscosity of the rubber composition. For a dilution ratio ranging from 0.35 to 0.60, the amount of carbon fiber may vary from 4 to 160 phr, depending on the volume fraction of carbon fibers ex-fibi in the rubber composition, especially for volume fractions ranging from 1 to 15%. For example, for a dilution ratio of 0.35, the amount of carbon fibers ex-fib in the rubber composition can vary from 4 to 100 phr. For example, for a dilution ratio of 0.60, the amount of carbon fibers ex-fib in the rubber composition can vary from 7 to 160 phr. The rubber composition in accordance with the invention may also comprise all or part of the usual additives normally used in elastomer compositions intended to constitute external mixtures of finished articles of rubber such as tires, in particular treads, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents, a crosslinking system, vulcanization accelerators or retarders, vulcanization activators. Whatever the embodiment of the invention described, the crosslinking system is preferably based on sulfur, but it may also be based on sulfur donors, peroxide, bismaleimides or their mixtures. The mixing of the constituents of the rubber composition can be carried out as traditionally in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (so-called "non-productive phase" At high temperature, up to a maximum temperature of between 130 ° C. and 200 ° C., followed by a second mechanical working phase ("productive" phase) to a lower temperature, typically less than 110 ° C. ° C, for example between 40 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system. The tread of the tire according to the invention may be prepared according to a process which comprises the following steps: - mixing the elastomer matrix, the reinforcing filler, the carbon fibers ex brn, where appropriate the plasticizer to form a mixture, - Calender the mixture to form a layer having a mean plane (y'z ') defined by two directions y' and z 'orthogonal to each other, z' being the direction of the calendering, so as to orient the carbon fiber ex-fibi in the direction of the calendering, - then cut the layer in identical portions along a section plane perpendicular to the direction z ', - assemble the portions by juxtaposing them in pairs according to their respective faces perpendicular to the direction x' orthogonal to the mean plane ( y'z '). By layer is meant a more or less uniform extent of the composition, the thickness of which is small relative to the superficial extent. In general, a layer P10-3214 - 16 - has a mean plane (y'z ') defined by two directions y' and z 'orthogonal. We define x 'as the direction orthogonal to the mean plane (y'z'). During the assembly of a tire usually comprising, radially from the outside towards the inside, a tread, a crown reinforcement and a carcass reinforcement, the tread may be laid radially on the outside. of the crown reinforcement of the tire so that the carbon fibers ex preferably are oriented radially relative to the axis of rotation of the tire.
    [0020] Depending on the particular embodiment of the invention, the thickness of the layer is adjusted during the calendering step so as to obtain the orientation of the carbon fibers ex-bra in the direction of the calendering. The orientation of the carbon fibers ex-fibi in the layer may be carried out typically after homogenization of the vulcanization system by passing several times the mixture in a calender still in the same direction. Alternatively, the tread of the tire according to the invention may be prepared according to the method described above by replacing the cutting and assembly step by zigzag folding of the layer, as described, for example, in the US Pat. 6666247. According to a preferred embodiment of the invention, the tread of the tire according to the invention consists solely of the rubber composition described according to any one of the embodiments of the invention. The layer, another object of the invention, has the essential feature of being made of the same rubber composition as the tread of the tire according to the invention. The layer according to the invention also has the essential characteristic of having thermal diffusivity ratios C'z '/ C'x' and C'z '/ C'y' greater than 2, - C'x, C'y and C'z 'being the thermal diffusivities measured at 25 ° C of the layer in the baked state in the directions x', y 'and z' respectively, where x ', y' and z 'are orthogonal directions between they, z 'being the preferred direction of the carbon fibers. Whatever the embodiment of the layer according to the invention, the thermal diffusivity ratios C'z '/ C'x' and C'z '/ C'y', also measured at 25 ° C, are preferentially greater than 3, more preferably greater than or equal to 4. These preferential ratios P10-3214 apply to the layer consisting of a composition defined according to any one of the embodiments of the invention. According to a particular embodiment of the invention, y 'and z' define the mean plane of the layer, x 'is the direction orthogonal to the mean plane (y'z'). This embodiment is illustrated in FIG. 1. According to this particular embodiment, the layer according to the invention is used as element of a tread of a tire. In this case, the tread or a tread portion is constituted by the juxtaposition of layers according to the invention assembled along their faces perpendicular to the direction x ', x' being the direction orthogonal to the mean plane of each layer (y'z ') defined by the directions y' and z ', the direction z' coinciding with the radial direction of the tire '. According to this particular embodiment of the invention, x 'preferably coincides with the circumferential direction of the tire. The layer may be prepared by a process which comprises the following steps: - mixing the elastomer matrix, the reinforcing filler, the carbon fiber ex-fib, if necessary the plasticizer to form a mixture, - calender the mixture to form a layer of so as to orient the carbon fiber ex-fibri in the direction of the calendering, z 'coinciding with the direction of the calendering.
    [0021] The aforementioned features of the present invention, as well as others, will be better understood on reading the following description of several embodiments of the invention, given by way of illustration and not limitation.
    [0022] II. EXAMPLES OF EMBODIMENT OF THE INVENTION II.1-Measurements and Tests Used: 11.1.1 Wear Test: The wear resistance of each tire was determined by means of a relative wear index which is a function of the height of remaining rubber, after rolling on a severe circuit for wear that is very virile and whose coating is characterized by micro-roughness, at an average speed of 77 km / h and until the wear reaches the wear indicators arranged in the grooves of the treads. For each of the examples, this relative wear index was obtained by comparing the remaining gum height of the tread studied with the remaining gum height of the control tread, which by definition has a wear index of 100. 11.1.2 Thermal diffusivity: Thermal diffusivity is determined according to ASTM E 1641 at 25 ° C. The thermal diffusivity of the CA or CB layer is expressed in base 100 with respect to the CT layer taken as a control. The higher the value is greater than 100, the more the plate is conductive in the direction considered.
    [0023] The thermal anisotropy of the layer is expressed by the ratio C'z '/ C'x' and C'z '/ C'y', knowing that the direction z 'is the direction normal to a surface of the layer and corresponds in the sense of calendering. 11.1.3 Microscopy analysis: The number average length of the carbon fibers in the rubber composition is determined according to the method described below. The dimensions are measured according to the procedure described hereinafter in several steps. The object consisting of the rubber composition after compounding the constituents of the rubber composition and after vulcanization is called the mixture. II.1.3.i) The first step consists of extracting the carbon fibers from the mixture by operating as follows: the mixture is cut into small pieces and then extraction with acetone is carried out so as to eliminate as much as possible the additives such as oils, resins, waxes, anti-oxidants ... - the mixture is then pyrolyzed under an inert atmosphere (N2) at 550 ° C., so as to eliminate the organic materials by cracking: polymers, sulfur network, accelerators, residual plasticizers the residue obtained then contains the carbon fibers, the carbon black and inorganic products initially present in the mixture (such as silica) or possibly formed during the pyrolysis. II.1.3.ii) The second step consists in preparing the sample to be placed in the scanning electron microscope (SEM) by operating as follows: - At the end of the first step, the combustion residues containing the carbon fibers. These are very slightly compressed with a mortar and pestle to separate the fibers from each other. The carbon fibers are thus recovered on a sample holder comprising a carbon adhesive. It is also possible to directly stamp the P10-3214 -19- aluminum sample holder supported carbon adhesive on the extracted fibers. - The samples are then blown with dry air to remove loose fibers that could damage the microscope column.
    [0024] II.1.3.iii) The third step is to determine the dimensions of the carbon fibers: - The samples are observed by Scanning Electron Microscopy (SEM-FEG) on a FEI Quanta 400 microscope in degraded void. The observations are made in contrast of topography. We mainly work with field widths of 1mm or 2mm, 500um and 250um in order to scan the entire size range. - Once the observations are made, length measurements are carried out via an AnalySlS image processing software. A matrix observation of the samples is carried out: adjacent fields have been made to cover about 5mm2 on the sample holder, with fields of observations of 500um. The raster image was reconstructed using the AnalySlS image processing software. The set of results is compiled to obtain the characteristic data of the extracted fiber mixture (average length, minimum length, maximum length, standard deviation, number distribution). For each sample, at least 50 objects are measured. II.2-Preparation of rubber compositions: The formulations (in phr) of compositions T, A and B are described in Table I.
    [0025] Compositions A and B both contain carbon fibers at a volume fraction of 10%. They differ in that the composition A contains carbon fibers ex PAN (polyacrylonitrile), the composition B contains ex-bile carbon fibers. Composition T differs from compositions A and B in that it does not contain carbon fibers. The dilution ratio of compositions A, B and T is identical (0.4). The compositions are prepared by thermomaxing the constituents of the composition according to the following procedure: The compositions are prepared in the following manner: an internal mixer is introduced (final filling ratio: approximately 70% by volume), whose initial tank temperature is about 80 ° C., the elastomer, the reinforcing filler, the coupling agent, the plasticizers, the carbon fibers and the various other ingredients with the exception of the vulcanization system . Thermomechanical (non-productive phase) work is then carried out in one step, which lasts about 5 minutes to 6 minutes, until a maximum "falling" temperature of about 160 ° C. is reached. The mixture thus obtained is recovered, cooled and the sulfur and the sulfenamide accelerator are incorporated on a mixer (homo-finisher) at 23 ° C., mixing the whole (productive phase) for a suitable time (for example between 5 ° C.). and 12 min). This operation of homogenization of the vulcanization system (sulfur and sulfenamide) consists of passing the mixture twelve times between the rolls, changing each time the direction of introduction (the mixture is recovered under the rolls, folded and reintroduced between the cylinders by changing the direction of the passage) In the case of compositions A and B, after homogenization of the vulcanization system, twelve additional passages are carried out without changing the direction of introduction of the mixture, in order to orient the fibers of carbon (within the mixing sheet) in the direction of the calendering.
    [0026] Next, the CT, CA and CB layers constituted respectively of the compositions T, A and B are cut in the form of a test-tube and then vulcanized. In the case of making the test specimens from the CA and CB layers, the dimensioning of a layer to the size of a specimen of 2.5 mm thickness is achieved by gradually reducing the thickness of the layer. passing the mixture in a calender keeping the direction imposed during the orientation of the carbon fibers on the homo-finisher. The vulcanized layers are characterized to determine: their thermal diffusivities respectively in the direction normal to the surface of the layer z ', along x' and y 'directions orthogonal to each other and to z' - and their thermal anisotropy The compositions A, B and T are used respectively as CA, CB and CT layers to form treads of a tire. The layers are laid radially outside the crown reinforcement of the tire so that the carbon fibers are preferably oriented in the radial direction with respect to the axis of rotation of the tire. The treads are produced according to the method described above which implements cutting and assembly steps. 11.3- Results The results are shown in Table II and Table III. The number average length of the carbon fibers in the rubber composition is 172 μm and 100 μm respectively for the CA and CB layers.
    [0027] P10-3214 - 21 - Thermal diffusivity and anisotropy: The C'z '/ C'x' and C'z '/ C'y' ratios of the CA and CB layers demonstrate their thermal anisotropy as well as the preferential orientation of the carbon in the direction of the calendering. The value C'z '/ C'x' and C'z '/ C'y' being equal to 1 for the CT layer, it is verified that the CT layer is isotropic. The CB layer is the material that has both the best thermal diffusivity and the strongest thermal anisotropy compared to the CA layer.
    [0028] Wear: By using the CA layer, very large material stripping in the form of a block was very quickly observed, the wear test becoming unquantifiable. This very rapid and very significant deterioration shows that the CA layer used as tread of a tire is practically not resistant to wear.
    [0029] On the other hand, the tread comprising the CB layer according to the invention has a certain wear resistance (index at 80), albeit a little behind the tread comprising the CT layer. It is found that the tire according to the invention offers a better compromise thermal conductivity wear than the tire not according to the invention comprising carbon fibers ex PAN. Furthermore, the tire according to the invention has a compromise between improved thermal conductivity and wear relative to the control tire which does not comprise carbon fibers. The improvement of this compromise also makes it possible to improve the compromise between the productivity of the baking step in the manufacture of the tire and the wear performance of the tire. P10-3214 - 22 - Table I Composition TAB SBR (1) 100 100 100 Carbon black (2) 4 4 4 Silica (3) 109 109 109 Ex-PAN carbon fibers (4) 49 Ex-pitch carbon fibers ( 5) 61 Coupling agent (6) 8 8 8 DPG (7) 1.7 1.7 1.7 Oil (8) 14 14 14 Resin (9) 54 54 54 6PPD (10) 2.3 2.3 2.3 Stearic acid (11) 2 2 2 ZnO ( 12) 2.5 2.5 2.5 CBS (13) 1.8 1.8 1.8 Sulfur 1.4 1.4 1.4 Carbon fiber fraction by volume (%) 0 10% 10% (1) SBR 26% styrene and 24% 1,2-butadiene butadiene part having a -SiOH function at the chain end; (2) N234 carbon black; (3) "Zeosil 1165 MP" silica (4) Ex-PAN carbon fibers, "SIGRAFIL C 30 APS" from SGL Group; (5) Ex-pitch carbon fiber, "XN-100" from Nippon Graphite Fiber Corporation; (6) Bis (triethoxysilylpropyl) tetrasulfide, "Si69" from Evonik; (7) Diphenylguanidine, "Perkacit DPG" from Flexsys; (8) Oleic sunflower oil (Lubrirob TOD 1880 from Novance); (9) Resin C5 / C9 "Wingtack STS" from Cray Valley Corporation; (10) N-1,3-dimethylbutyl-N-phenylparaphenylenediamine, "Santoflex 6PPD" from Eastman; (11) stearic acid; (12) Zinc oxide (industrial grade - Umicore company); (13) N-cyclohexyl-2-benzothiazyl sulfenamide ("Santocure CBS" from Flexsys); P10-3214 - 23 - Table II CT layer CA CB C'z '/ C'x' 1 2.7 5.2 C'z '/ C'y' 1 2.7 5.2 C'z '100 342 770 Table III LC layer CB CB Wear 100 no 80 quantifiable P10-3214
    权利要求:
    Claims (24)
    [0001]
    REVENDICATIONS1. A tire comprising a tread which comprises a rubber composition based on at least: - an elastomer matrix, - a reinforcing filler, - carbon fiber ex-fibers, - optionally a plasticizer, z being the direction normal to the surface of the tread intended to be in contact with a rolling ground, x and y being two directions orthogonal to z, x the circumferential direction of the tire, y the axial direction with respect to the axis of rotation of the tire, Cx, Cy and Cz being the thermal diffusivities measured at 25 ° C of the tread in the baked state in the x, y and z directions respectively, which tire has thermal diffusivity ratios Cz / Cx and Cz / Cy greater than
    [0002]
    2. The tire of claim 1 wherein the elastomeric matrix comprises a diene elastomer.
    [0003]
    A tire according to any one of claims 1 to 2 wherein the rubber composition comprises a plasticizer.
    [0004]
    4. A tire according to claim 3 wherein the ratio of the mass of the plasticizer to the sum of the masses of the plasticizer and the elastomeric matrix is greater than 0.35.
    [0005]
    5. A tire according to claim 4 wherein the ratio of the mass of the plasticizer to the sum of the masses of the plasticizer and the elastomeric matrix is between 0.35 and 0.60, preferably between 0.35 and 0.55.
    [0006]
    A tire according to any one of claims 1 to 5 wherein the volume fraction of the carbon fibers ex-fib in the rubber composition varies in a range from 1 to 15%.
    [0007]
    A tire according to claim 6 wherein the volume fraction of the carbon fibers ex-fib in the rubber composition varies in a range from 3 to 12%. P10-3214 40- 25 -
    [0008]
    8. A tire according to any one of claims 1 to 7 wherein the reinforcing filler comprises a carbon black.
    [0009]
    9. A tire according to any one of claims 1 to 8 wherein the reinforcing filler comprises an inorganic filler.
    [0010]
    The tire of claim 9 wherein the inorganic filler is a silica.
    [0011]
    11. A tire according to any one of claims 9 to 10 wherein the inorganic filler represents more than 50% by weight of the reinforcing filler.
    [0012]
    12. A tire according to any one of claims 9 to 11 wherein the composition comprises a coupling agent.
    [0013]
    13. A tire according to any one of claims 11 to 12 wherein the carbon black content is less than 20 phr, preferably less than 10 phr, more preferably between 2 and 10 phr.
    [0014]
    A tire according to any of claims 2 to 13 wherein the diene elastomer is substantially unsaturated selected from the group consisting of polybutadienes, polyisoprenes, butadiene copolymers, isoprene copolymers and mixtures thereof.
    [0015]
    15. A tire according to claim 14 wherein the diene elastomer is an SBR, a polybutadiene, a synthetic polyisoprene, a natural rubber or mixtures thereof.
    [0016]
    16. A tire according to any one of claims 1 to 15 wherein the thermal diffusivity ratios Cz / Cx and Cz / Cy are greater than 3.
    [0017]
    17. A tire according to claim 16 wherein the thermal diffusivity ratios Cz / Cx and Cz / Cy are greater than or equal to 4.
    [0018]
    18. A method for preparing a tire according to any one of claims 1 to 17 which comprises the following steps: - mixing the elastomer matrix, the reinforcing filler, the carbon fibers ex bri, where appropriate the plasticizer to form a mixture, - Calender the mixture to form a layer having a mean plane (y'z ') defined by two directions y' and z 'orthogonal to each other, z' being the direction of P10-3214- calendering, so as to guide the carbon fibers ex brai in the direction of the calendering, - then cut the layer in identical portions along a sectional plane perpendicular to the direction z ', - assemble the portions by juxtaposing them in pairs according to their respective faces perpendicular to the direction x orthogonal to the middle plane (y'z ').
    [0019]
    19. A method for preparing a tire according to any one of claims 1 to 17 which comprises the following steps: - mixing the elastomer matrix, the reinforcing filler, the carbon fibers ex brn, if necessary the plasticizer to form a mixture, - Calender the mixture to form a layer having a mean plane (y'z ') defined by two directions y' and z 'orthogonal to each other, z' being the direction of the calendering, so as to orient the carbon fiber ex-fibi in the direction of the calendering, - zigzag fold the layer.
    [0020]
    20. A layer consisting of a rubber composition as defined in any one of claims 1 to 17, which layer has thermal diffusivity ratios C'z '/ C'x' and C'z '/ Cy' greater than 2, - C'x, C'y 'and C'z' being the thermal diffusivities measured at 25 ° C of the layer in the baked state in the directions x ', y' and z ', - x', respectively; y 'and z' being directions orthogonal to each other, z 'being the preferred direction of the carbon fibers. 25
    [0021]
    21. The layer of claim 20 wherein y 'and z' define the average plane of the layer, x 'is the direction orthogonal to the mean plane (y'z').
    [0022]
    22. Tread or tread portion of a tire constituted by the juxtaposition of layers, which layers are defined according to claim 21, and are assembled along their faces perpendicular to the direction x ', the z direction coinciding with the radial direction of the tire.
    [0023]
    23. A tread or tread portion of a tire according to claim 22 wherein x 'coincides with the circumferential direction of the tire.
    [0024]
    24. A process for preparing a layer according to claim 21 which comprises the following steps: - mixing the elastomer matrix, the reinforcing filler, the carbon fiber ex-fib, if necessary the plasticizer to form a mixture, - Calender the mixture to form a layer so as to orient the carbon fibers ex brai in the direction of calendering, z 'coinciding with the direction of calendering. P10-3214
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    同族专利:
    公开号 | 公开日
    FR3014442B1|2016-01-01|
    EP3094505A1|2016-11-23|
    JP2017500403A|2017-01-05|
    CN105813858B|2018-08-10|
    WO2015086449A1|2015-06-18|
    CN105813858A|2016-07-27|
    EP3094505B1|2018-02-07|
    US20160311258A1|2016-10-27|
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    法律状态:
    2015-12-21| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-22| PLFP| Fee payment|Year of fee payment: 4 |
    2017-12-21| PLFP| Fee payment|Year of fee payment: 5 |
    2019-09-27| ST| Notification of lapse|Effective date: 20190906 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362331A|FR3014442B1|2013-12-10|2013-12-10|TIRE COMPRISING A ROLLER BAND BASED ON A RUBBER COMPOSITION COMPRISING EX BRAI CARBON FIBERS|FR1362331A| FR3014442B1|2013-12-10|2013-12-10|TIRE COMPRISING A ROLLER BAND BASED ON A RUBBER COMPOSITION COMPRISING EX BRAI CARBON FIBERS|
    EP14808612.7A| EP3094505B1|2013-12-10|2014-12-05|Tyre comprising a tread based on a rubber composition comprising ex-pitch carbon fibres|
    CN201480067295.2A| CN105813858B|2013-12-10|2014-12-05|It include the tire of the tyre surface based on the rubber composition comprising preceding asphalt-based carbon fiber|
    US15/103,766| US20160311258A1|2013-12-10|2014-12-05|Tire including a tread based on a rubber composition comprising ex-pitch carbon fibers|
    PCT/EP2014/076696| WO2015086449A1|2013-12-10|2014-12-05|Tyre comprising a tread based on a rubber composition comprising ex-pitch carbon fibres|
    JP2016538804A| JP2017500403A|2013-12-10|2014-12-05|Tire comprising tread based on rubber composition containing pitch-based carbon fiber|
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