• 专利附录
  • 专利说明
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    • 专利摘要:
    The present invention relates to a rubber composition based on at least one vinylaromatic diene elastomer, a reinforcing filler, a crosslinking system, a thermoplastic resin comprising optionally substituted polyphenylene ether units, said resin having a number-average molecular weight ( Mn) less than 6000 g / mol. The invention also relates to semi-finished tires and tires comprising this composition.
    公开号:FR3015505A1
    申请号:FR1363154
    申请日:2013-12-20
    公开日:2015-06-26
    发明作者:Vincent Abad
    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] [1] The present invention relates to rubber compositions especially for the manufacture of tires or semi-finished products for tires, in particular tire tread rubber compositions having a high ease of manufacture of the mixtures and a good resistance to wear in the tire.  [2] Tires are subject to numerous demands during their use.  Tire treads in particular must comply with a large number of technical requirements, which are often antithetical, including high wear resistance and good adhesion, on both dry and wet roads.  Mixtures for these tires must also have good processability, that is they must be easy to manufacture.  [3] It is known to use in elastomer tire compositions, combined with reinforcing fillers, and plasticizing agents.  Conventionally, these plasticizers may be plasticizing oils or plasticizing resins, as described in numerous documents, for example in patent applications FR 2866028, FR 2877348 or FR 2889538, describing in particular the use of thermoplastic resins as plasticizing resins .  [4] Furthermore, Japanese JP 2004-238547 discloses a composition comprising particles of micrometric size (approximately 10 μm or 45 μm) of a polyphenylene ether resin, which make it possible to increase the rigidity of the compositions, with a an acceptable increase in the hysteresis of the compositions.  In this document, the polyphenylene ether resin is used in the form of micrometric particles (approximately 10 μm or 45 μm), and not in the form of a compatible plasticizer, dispersed and intimately mixed with the elastomeric matrix of the composition.  [005] At present, the Applicants have discovered during their research that a thermoplastic resin based on optionally substituted polyphenylene ether units can advantageously be used as a plasticizing resin in a composition in which the majority elastomer is a vinylaromatic diene elastomer.  The use of a plasticizing resin surprisingly makes it possible to improve the compromise of performance between the ease of manufacture of the mixtures and the adhesion of the tires.  In addition, the use of these thermoplastic resins based on optionally substituted polyphenylene ether units makes it possible to reduce the amount of resin compared to conventional plasticizing thermoplastic resins, which makes it possible to have a decrease in the raw tackiness of the compositions bonded to the use of these resins and thus facilitate the manufacture of tires comprising these compositions.  [6] Accordingly, a first subject of the invention relates to a rubber composition based on at least one major vinylaromatic diene elastomer, a reinforcing filler, a crosslinking system, a thermoplastic resin comprising polyphenylene ether units. optionally substituted, said resin having a number average molecular weight (Mn) of less than 6000 g / mol.  [7] Preferably, the invention relates to a composition as defined above, wherein said resin has a number-average molecular weight (Mn) of less than 3500 g / mol, more preferably in a range from 700 to 2500 g / mol.  [008] Preferably, the invention relates to a composition as defined above, wherein the vinylaromatic diene elastomer has a vinylaromatic content greater than 10%, preferably between 15% and 60%, more preferably between 20% and 50%, very preferably between 30 and 50% and still more preferably between 35 and 50%.  Preferably, the vinylaromatic diene elastomer is chosen from the group consisting of butadiene and styrene copolymers, isoprene and styrene copolymers, butadiene, isoprene and styrene copolymers and mixtures of these elastomers, and preferably in the group consisting of copolymers of butadiene and styrene and the mixture thereof.  Also preferably, the vinylaromatic diene elastomer content is in a range from 70 to 100 phr (parts by weight per hundred parts of elastomer), and more preferably from 85 to 100 phr.  [009] Preferably, the invention relates to a composition as defined above, in which the thermoplastic resin based on optionally substituted polyphenylene ether units has a glass transition temperature (Tg), measured by DSC according to the ASTM D3418 standard. of 1999, in a range from 0 to 215 ° C, preferably from 5 to 200 ° C and more preferably from 5 to 185 ° C.  Preferably, the invention relates to a composition as defined above, in which the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I): -3 in which: (I) - R 1, R 2, R 3 and R 4 represent, independently of one another, identical or different groups chosen from hydrogen, hydroxy, alkoxy, halogen, amino, alkylamino, dialkylamino groups or hydrocarbon groups containing at least 2 carbon atoms, optionally interrupted by heteroatoms and optionally substituted; R1 and R3 on the one hand and R2 and R4 on the other hand can form together with the carbon atoms to which they are attached one or more rings contiguous to the benzene ring of the compound of formula (I) - n is an integer included in a domain ranging from 3 to 300.  Preferably, the invention relates to a composition as defined above, in which the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I) in which R 1, R2, R3 and R4 independently of one another represent identical or different groups chosen from: - hydrogen, - hydroxy, alkoxy, halogen, amino, alkylamino, dialkylamino groups, - linear, branched or cyclic alkyl groups, comprising: from 1 to 25 carbon atoms (preferably from 2 to 18), optionally interrupted by heteroatoms chosen from nitrogen, oxygen and sulfur, and optionally substituted with hydroxyl, alkoxy, amino, alkylamino or dialkylamino groups, or halogen.  aryl groups comprising from 6 to 18 carbon atoms (preferably from 6 to 12), optionally substituted with hydroxyl, alkoxy, amino, alkylamino, dialkylamino, alkyl or halogen groups, [0012] Preferably, the invention relates to a composition as defined above, in which the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I) in which R1, R2, R3 and R4 represent independently from each other identical or different groups chosen from: - hydrogen, - hydroxy, alkoxy groups containing from 1 to 6 carbon atoms, halogen, amino, alkylamino containing from 1 to 6 carbon atoms, dialkylamino containing from 2 to at 12 carbon atoms, linear, branched or cyclic alkyl groups comprising from 1 to 12 carbon atoms (preferably from 2 to 6 carbon atoms). ) optionally interrupted by heteroatoms and optionally substituted by hydroxy, alkoxy groups having from 1 to 6 carbon atoms, amino, alkylamino comprising from 1 to 6 carbon atoms, dialkylamino containing from 2 to 12 carbon atoms, or halogen.  aryl groups comprising from 6 to 18 carbon atoms (preferably from 6 to 12), optionally substituted with hydroxyl groups, alkoxy groups having from 1 to 6 atoms, amino, alkylamino groups having from 1 to 6 atoms, dialkylamino group having from 2 to to 12 carbon atoms, alkyl having 1 to 12 carbon atoms, or halogen.  Preferably, the invention relates to a composition as defined above, wherein R1 and R2 represent an alkyl group and in particular a methyl group; and R3 and R4 represent hydrogen atoms.  More preferably, the invention relates to a composition as defined above, in which the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I) in which n is an integer in a range from 3 to 50, preferably from 5 to 30 and more preferably from 6 to 20.  Preferably, the invention relates to a composition as defined above, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising more than 80% by weight, polyphenylene units of general formula ( I), preferably greater than 95% by weight.  Preferably, the invention relates to a composition as defined above, in which the level of said thermoplastic resin based on optionally substituted polyphenylene ether units is in a range from 1 to 90 phr, preferably from 2 to 80 phr, more preferably 3 to 60 phr, more preferably 5 to 60 phr.  [0017] Preferably, the invention relates to a composition as defined above, wherein the reinforcing filler comprises carbon black and / or silica.  Also preferably, the invention relates to a composition as defined above, in which the reinforcing filler represents between 20 and 250 phr, more preferably between 30 and 180 phr.  Preferably, the invention relates to a composition as defined above, wherein the reinforcing filler comprises predominantly carbon black.  Preferably, the carbon black represents from 40 to 150 phr, preferably from 50 to 120 phr.  Alternatively and preferably also, the invention relates to a composition as defined above, wherein the reinforcing filler comprises predominantly silica.  Preferably, the silica represents from 40 to 150 phr, preferably from 50 to 120 phr.  The invention also relates to finished or semi-finished rubber articles comprising a rubber composition according to the invention.  The invention also relates to tires comprising a rubber composition according to the invention, and in particular the tires in which the tread comprises a rubber composition according to the invention.  The tires according to the invention are particularly intended for passenger vehicles such as two-wheeled vehicles (motorcycle, bicycle), industrial vehicles chosen from vans, "heavy-weight" - i. e. , metro, bus, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles, agricultural or engineering machinery, airplanes, other transport or handling vehicles.  The invention as well as its advantages will be readily understood in light of the description and the following exemplary embodiments.  I.  Tests [0025] The rubber compositions are characterized, before and after firing, as indicated below. 30 -6- 1. 1.  Dynamic properties after firing The dynamic properties G * are measured on a viscoanalyzer (Metravib VA4000), according to the ASTM D 5992-96 standard.  The response of a sample of vulcanized composition (ie cooked to a conversion of at least 90%) is recorded (cylindrical specimen 2 mm thick and 78.5 mm 2 in section). subjected to sinusoidal stress in single shear alternates at a frequency of 10 Hz.  A temperature sweep is carried out at a constant temperature rise rate of +1. 5 ° C / min at peak-peak shear stress imposed 0.7MPa.  The specimen is stressed in sinusoidal shear at 10 Hz, symmetrically around its equilibrium position.  The results used are the complex dynamic shear modulus (G *), the viscous shear modulus (G "), denoted G" (T).  The glass transition temperature (denoted by Tg) according to the invention corresponds to the temperature at which the observed maximum of G "is observed during the temperature sweep.  Thus, in the present description, unless otherwise expressly indicated, the Tg is defined as the temperature at which the maximum of G "is observed (G" representing in a known manner the viscous part of the shear modulus), during the temperature sweep. a cross-linked sample subjected to a sinusoidal stress at imposed stress of 0.7 MPa and at a frequency of 10 Hz.  As indicated previously, this Tg is measured during the measurement of the dynamic properties, on a viscoanalyzer (Metravib VA4000), according to the ASTM D 5992-96 standard.  The sample for this measurement of Tg is cross-linked with sulfur at a level of about 1.5 phr and N-cyclohexyl benzothiazyl sulphenamide (CBS) at a rate of about 2 phr.  1. 2.  Rheometry Measurements are carried out at 150 ° C. with an oscillating chamber rheometer according to DIN 53529 - Part 3 (June 1983).  The evolution of the rheometric torque, ACouple, as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization reaction.  The measurements are processed according to DIN 53529 - Part 2 (March 1983): To is the induction time, ie the time required for the beginning of the vulcanization reaction; Ta, (for example T99) is the time necessary to reach a conversion of a%, that is to say a% (for example 99%) of the difference between the minimum and maximum couples.  The conversion rate constant denoted by K (expressed in min-1), of order 1, calculated between 30% and 80% conversion, which makes it possible to evaluate the kinetics of vulcanization, is also measured.  -7- 1. 3.  Measurement of the Particle Content [0030] The measurements are carried out under a transmission optical microscope (MOT) on a device from Olympus, reference BX-51.  The observations are made in bright field mode ("Bright Field") at a magnification of "times 40" (Objective x40 - additional magnification x1 - magnification camera ring x1).  The images are obtained in black and white by an Olympus DP-50 acquisition camera.  For this magnification, the field of view corresponding to an image is 160 μm x 120 μm.  In order to cover a significant area, particle surface rate measurements are performed on a minimum of 10 images.  The samples observed are obtained by cryomicrotomy at -60 ° C. and with a cutting instruction at 2 μm.  For the purposes of the present application, when speaking of compatibility of the PPE resin and the majority vinylaromatic diene elastomer, it is understood by compatible that this PPE resin does not form a particle in the composition, that is, that is, in a mixture of the PPE resin with the vinylaromatic diene elastomer, a composition having less than 10% of its volume in the form of particles larger than 2 microns (μm) in size will be observed.  More preferably, in a mixture of the PPE resin with the vinylaromatic diene elastomer, a composition having less than 5% of its volume in the form of particles having a size greater than 2 microns and preferably less than 2% will be observed. .  This observation of the particle rate and their sizes can be done at the MOT as described above.  A composition in which less than 10% of said resin is in the form of particles having a size greater than 2 microns corresponds to a composition in which, if 10 contiguous images are observed on sections of 2 μm at the MOT. as described above, less than 10% of the observed surface area corresponding to particles larger than 2 μm will be found on average.  He.  Conditions for Carrying Out the Invention The rubber composition according to the invention is based on at least one major vinylaromatic diene elastomer, a reinforcing filler, a crosslinking system, a thermoplastic resin comprising optionally substituted polyphenylene ether units. said resin having a number average molecular weight (Mn) of less than 6000 g / mol.  By the term "composition based on" is meant a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended for to react with each other, at least in part, during the various phases of manufacture of the composition, in particular during its crosslinking or vulcanization.  In the present description, unless otherwise expressly indicated, all the percentages (%) indicated are percentages (%) by weight.  On the other hand, any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term "from a to b" means the range from a to b (i.e., including the strict limits a and b).  When reference is made to a "majority" compound, the meaning of the present invention is understood to mean that this compound is predominant among the compounds of the same type in the composition, that is to say that it is the one which represents the largest quantity in mass among the 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, it is the majority 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.  11. 1.  Elastomers [0037] The rubber composition according to the invention comprises a majority vinylaromatic diene elastomer.  By elastomer or "diene" rubber, must be understood in a known manner (one or more) elastomer derived at least in part (i. e. , a homopolymer or a copolymer) of diene monomers (monomers bearing two carbon-carbon double bonds, conjugated or otherwise).  These definitions being given, more particularly refers to vinylaromatic diene elastomer 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; As 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- -9-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-yl; isopropyl-1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.  As vinylaromatic compounds are suitable for example styrene, alphamethylstyrene, ortho-, meta-, para-methylstyrene, the commercial mixture "vinyl-5 toluene", para-tert-butylstyrene, methoxystyrenes, chlorostyrenes vinylmesitylene, divinylbenzene, vinylnaphthalene.  The copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units.  The elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used.  The elastomers can be for example block, statistical, sequence, microsequential, and be prepared in dispersion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.  For coupling to carbon black, there may be mentioned, for example, functional groups comprising a C-Sn bond or amino functional groups such as benzophenone, for example; for coupling to a reinforcing inorganic filler such as silica, mention may be made, for example, of silanol or polysiloxane functional groups having a silanol end (as described, for example, in FR 2,740,778 or US Pat. No. 6,013,718), alkoxysilane groups (such as as described for example in FR 2 765 882 or US Pat. No. 5,977,238), carboxyl groups (as described for example in WO 01/92402 or US Pat. No. 6,815,473, WO 2004/096865 or US 2006/0089445) or else polyether groups (as described for example in EP 1 127 909 or US Pat. No. 6,503,973).  As other examples of functionalized elastomers, mention may also be made of vinylaromatic diene elastomers (such as SBR) of the epoxidized type.  [0043] Preferably, the vinylaromatic diene elastomer of the composition in accordance with the invention has a vinylaromatic content of greater than 10%, preferably between 15% and 60%, more preferably between 20% and 50%, of very preferably between 30 and 50% and even more preferably between 35 and 50%.  More preferably, the vinylaromatic diene elastomer of the composition according to the invention is a styrenic diene elastomer (that is to say that the vinylaromatic part is a styrene part), with a styrene content greater than 10%, of preferably between 15% and 50%, more preferably between 20% and 50%, very preferably between 30 and 50% and even more preferably between 35 and 50%.  Preferably, the vinylaromatic diene elastomer of the composition according to the invention is preferably chosen from the group of highly unsaturated styrenic diene elastomers consisting of styrene butadiene copolymers, styrene copolymers of isoprene and mixtures of these elastomers.  Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-styrene copolymers (SIR) and isoprene-butadiene-styrene copolymers (SBIR).  In particular, butadiene-styrene copolymers (SBR) and in particular those having a Tg (glass transition temperature) measured by DSC according to the ASTM D3418 standard of 1999 between 20 ° C. and -70 ° C. and more are suitable. particularly between 0 ° C. and -50 ° C., a styrene content of between 10% and 60% by weight and more particularly between 20% and 50%, a content (mol%) in -1,2-bonds of the butadiene part. between 4% and 75%, a content (mol%) in trans-1,4 bonds of between 10% and 80%.  Isoprene-styrene copolymers (SIR) and in particular those having a styrene content of between 15% and 60% by weight and more particularly between 20% and 50% and a Tg, measured by DSC according to the standard, are also suitable. ASTM D3418 from 1999, between 25 ° C and -50 ° C.  In the case of butadiene-styrene-isoprene copolymers (SBIR) are particularly suitable those having a styrene content of between 15% and 60% by weight, more particularly between 20% and 50%, an isoprene content of between 15% and 60% by weight and more particularly between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly between 20% and 40%, a content (mol%) in units. -1.2 of the butadiene part of between 4% and 85%, a content (mol%) in trans units -1.4 of the butadiene part of between 6% and 80%, a content (mol%) in units - 1.2 plus -3.4 of the isoprenic portion of between 5% and 70% and a content (mol%) in trans units -1.4 of the isoprenic portion of between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg, measured by DSC according to ASTM D3418 of 1999, of between 20 ° C and -60 ° C.  Very preferably, the vinylaromatic diene elastomer of the composition according to the invention is an SBR.  In known manner, the SBR can be prepared in emulsion ("ESBR") or prepared in solution ("SSBR").  In the case of an SBR elastomer (ESBR or SSBR), an SBR having an average styrene content, for example between 25 and 50% by weight, preferably between 35% and 50% by weight, is used.  The compositions of the invention may contain a single vinylaromatic diene elastomer or a mixture of several vinylaromatic diene elastomers, the vinylaromatic diene elastomer (s), still predominant, which may be used in combination with other elastomers known from the art. skilled in the art such as for example a natural rubber (NR) or a polybutadiene (BR).  The vinylaromatic diene elastomer content is in a range from 70 to 100 phr, more preferably from 85 to 100 phr, and very preferably this rate is 100 phr, that is to say that it does not exceed 100 phr. Only vinylaromatic diene elastomers are present in the composition.  11. 2.  Reinforcing filler Any type of 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, or a blend of these two types of filler, including a cut of carbon black and silica.  As carbon blacks are suitable for all carbon blacks, including black type HAF, ISAF, SAF conventionally used in tires (so-called pneumatic grade black).  Among these, mention will be made more particularly of reinforcing carbon blacks of the series 100, 200 or 300 (ASTM grades), for example blacks N115, N134, N234, N326, N330, N339, N347, N375, or again, depending on the targeted applications, the blacks of higher series (for example N660, N683, N772).  The carbon blacks could for example already be incorporated into an isoprene elastomer in the form of a masterbatch (see for example WO 97/36724 or WO 99/16600).  As examples of organic fillers other than carbon blacks, mention may be made of the functionalized polyvinyl organic fillers as described in applications WO-A-2006/069792, WO-A-2006/069793, WO-A-1, 2008/003434 and WO-A2008 / 003435.  By "reinforcing inorganic filler" must be understood in the present application, by definition, any inorganic or mineral filler (regardless of its color and its natural or synthetic origin), also called "white" charge, charge " clear "or" non-black filler "charge as opposed to carbon black, capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition for the manufacture of pneumatic, in other words able to replace, in its reinforcing function, a conventional pneumatic grade carbon black; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.  The physical state in which the reinforcing inorganic filler is present is indifferent, whether in the form of powder, microbeads, granules, beads or any other suitable densified form.  Of course, the term "reinforcing inorganic filler" also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.  As reinforcing inorganic fillers are especially suitable mineral fillers of the siliceous type, in particular of silica (SiO 2), or of the aluminous type, in particular of alumina (Al 2 O 3).  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 / boy Wut.  As highly dispersible precipitated silicas (known as "HDS"), mention may be made of, for example, the Ultrasil 7000 and Ultrasil 7005 silicas from Degussa, the Zeosil 1165MP, 1135MP and 1115MP silicas from Rhodia, the Hi-Sil EZ150G silica from the PPG company, the Zeopol 8715, 8745 and 8755 silicas of the Huber Company, the high surface area silicas as described in the application WO 03/16837.  The reinforcing inorganic filler used, in particular if it is silica, preferably has a BET surface area of between 45 and 400 m 2 / g, more preferably between 60 and 300 m 2 / g.  Preferably, the total reinforcing filler content (carbon black and / or reinforcing inorganic filler such as silica) is between 20 and 200 phr, more preferably between 30 and 160 phr, the optimum being in a known manner. different depending on the particular applications targeted: the level of reinforcement expected on a bicycle tire, for example, is of course less than that required on a tire capable of driving at high speed in a sustained manner, for example a motorcycle tire, a tire for a vehicle for tourism or for commercial vehicles such as Trucks.  According to a first preferred embodiment of the invention, carbon black is used as the predominant reinforcing filler between 60 and 160 phr, more preferably between 70 and 150 phr.  According to another preferred embodiment of the invention, silica is used as reinforcing filler majority between 60 and 160 phr, more preferably between 70 and 150 phr, and optionally carbon black; the carbon black, when present, is preferably used at a level of less than 20 phr, more preferably less than 10 phr (for example between 0.1 and 5 phr).  To couple the reinforcing inorganic filler to the diene elastomer, it is known to use a coupling agent (or bonding agent) at least bifunctional intended to ensure a sufficient connection, chemical and / or physical, between the inorganic filler (surface of its particles) and the diene elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.  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).  In particular, the following definition is not limiting, so-called "symmetrical" polysulfide silanes having the following general formula: Z - A - Sx - A - Z, in which: - x is an integer of 2 to 8 (preferably 2 to 5); A - is a divalent hydrocarbon radical (preferably C 1 -C 18 alkylene groups or C 6 -C 12 arylene groups, more particularly C 1 -C 10 alkylenes, especially C 1 -C 4 alkylenes, in particular propylene); Z corresponds to one of the following formulas: ## STR2 ## in which: the radicals R 1, substituted or unsubstituted, identical or different between they represent a C 1 -C 18 alkyl, C 5 -C 18 cycloalkyl or C 6 -C 18 aryl group (preferably C 1 -C 6 alkyl, cyclohexyl or phenyl groups, especially C 1 -C 4 alkyl groups, 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 selected from C 1 -C 4 alkoxyls, in particular methoxyl and ethoxyl).  In the case of a mixture of polysulfurized alkoxysilanes corresponding to the above formula, in particular common commercially available mixtures, the average value of the "x" is a fractional number preferably 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 polysulphurized 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) alkyl-silyl (C 1 -C 4) )), such as, for example, bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl) polysulfides.  Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT, of formula [(C2H50) 3Si (CH2) 3S2] 2 or bis (triethoxysilylpropyl) disulfide, abbreviated as TESPD, is especially used. formula [(C2H50) 3Si (CH2) 3S] 2.  Mention may also be made, by way of preferred examples, of polysulphides (in particular disulphides, trisulphides or tetrasulfides) of bis- (monoalkoxyl (C1-C4) -dialkyl (C1-C4) silylpropyl), more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide, as described above. in the patent application WO 02/083782 (or US 2004/132880).  As coupling agent other than polysulfide alkoxysilane, mention may be made of bifunctional POS (polyorganosiloxanes) or hydroxysilane polysulfides (R 2 = OH in the formula above) as described in the US Pat. WO 02/30939 (or US Pat. No. 6,774,255) and WO 02/31041 (or US 2004/051210), or else silanes or POS bearing azo-dicarbonyl functional groups, as described for example in the patent applications WO 2006 / 125532, WO 2006/125533, WO 2006/125534.  In the rubber compositions according to the invention, the content of coupling agent is preferably between 4 and 16 phr, more preferably between 5 and 15 phr.  Those skilled in the art will understand that as an equivalent load of the reinforcing inorganic filler described in this paragraph, could be used a reinforcing filler of another nature, especially organic, since this reinforcing filler would be covered an inorganic layer such as silica, or would comprise on its surface functional sites, especially hydroxyl, requiring the use of a coupling agent to establish the bond between the filler and the elastomer.  11. 3.  PPE resin -15- The composition according to the invention comprises a thermoplastic resin based on optionally substituted polyphenylene ether units (abbreviated as "PPE resin").  This type of compound is described for example in the encyclopedia "Ullmann's Encyclopedia of Industrial Chemistry" published by VCH, vol A 21, pages 605-614, 5th edition, 1992.  In known manner, the EPP resins usually have variable number average molecular weights (Mn), usually from 15,000 to 30,000 g / mol, in the case of high masses such as these, the Mn is measured from a manner known to those skilled in the art by SEC (also named GPC, as in reference US4588806, column 8).  For the purposes of the invention, the composition of the invention uses a PPE resin having a mass Mn less than the masses regularly encountered and in particular less than 6000 g / mol, preferably less than 3500 g / mol and in particular Mn within a range of 700 to 2500 g / mol.  The number-average molecular weight (Mn) of PPE with a mass of less than 6000 g / mol is measured by NMR, the conventional measurement by SEC not being sufficiently precise.  This measurement by NMR is carried out in a manner known to those skilled in the art, either by assaying end-chain functions or by assaying the polymerization initiators, as explained, for example, in "Application of NMR spectroscopy in molecular weight determination of polymers "by Subhash C.  Shit and Sukumar Maiti in "European Polymer Journal" vol. 22, No. 12, pages 1001-1008 (1986).  Preferably, the value of the polydispersity index Ip (booster: Ip = Mw / Mn with Mw weight average molecular weight and Mn number-average molecular mass) of the PPE resin is less than or equal to 5, more preferably less than or equal to 3 and more preferably still less than or equal to 2.  The PPE resin useful for the purposes of the invention preferably has a glass transition temperature (Tg), measured by DSC according to the ASTM D3418 standard of 1999, in a range from 0 to 215 ° C., preferably from at 200 ° C and more preferably from 5 to 185 ° C.  Below 0 ° C, the EPP resin does not allow a shift of sufficient Tg in the composition comprising it and above 215 ° C, one can meet manufacturing problems including to obtain a homogeneous mixture.  Preferably, the PPE resin is a compound comprising predominantly polyphenylene units of general formula (I): in which: (I) - R 1, R 2, R 3 and R 4 represent, independently of one another, identical groups or different ones selected from hydrogen; hydroxy, alkoxy, halogen, amino, alkylamino, dialkylamino groups; hydrocarbon groups containing at least 2 carbon atoms, optionally interrupted by hetero atoms and optionally substituted; R1 and R3 on the one hand and R2 and R4 on the other hand can form together with the carbon atoms to which they are attached one or more rings contiguous to the benzene ring of the compound of formula (I) - n is an integer included in a domain ranging from 3 to 300.  Preferably, R1, R2, R3 and R4 represent, independently of one another, identical or different groups chosen from: - hydrogen - hydroxy, alkoxy, halogen, amino, alkylamino, dialkylamino groups, - linear alkyl groups , branched or cyclic, comprising from 1 to 25 carbon atoms (preferably from 2 to 18), optionally interrupted by heteroatoms selected from nitrogen, oxygen and sulfur, and optionally substituted by hydroxy, alkoxy groups, amino, alkylamino, dialkylamino, or halogen.  aryl groups comprising from 6 to 18 carbon atoms (preferably from 6 to 12), optionally substituted with hydroxyl, alkoxy, amino, alkylamino, dialkylamino, alkyl or halogen groups, More preferably, R1, R2 R3 and R4 represent, independently of one another, identical or different groups chosen from: hydrogen, alkoxy groups containing from 1 to 6 carbon atoms, halogen, amino, alkylamino containing from 1 to 6; carbon atoms, dialkylamino having 2 to 12 carbon atoms, - linear, branched or cyclic alkyl groups comprising from 1 to 12 carbon atoms (preferably from 2 to 6), optionally interrupted by hetero atoms and optionally substituted with hydroxy, alkoxy having 1 to 6 carbon atoms, amino, alkylamino having 1 to 6 carbon atoms, dialkylamino having 2 to 12 carbon atoms, or halogens no.  aryl groups comprising from 6 to 18 carbon atoms (preferably from 6 to 12), optionally substituted with hydroxyl groups, alkoxy groups having from 1 to 6 atoms, amino, alkylamino groups having from 1 to 6 atoms, dialkylamino group having from 2 to to 12 carbon atoms, alkyl having 1 to 12 carbon atoms, or halogen.  Even more preferably, R1 and R2 represent an alkyl group and in particular a methyl group; and R3 and R4 represent hydrogen atoms.  In this case, the PPE resin is a poly (2,6-dimethyl-1,4-phenylene ether).  Also preferably, n is an integer comprised in a range from 3 to 50, more preferably from 5 to 30, preferably from 6 to 20.  Preferably, the EPP resin is a compound comprising more than 80% by weight, and more preferably more than 95% by weight, polyphenylene units of general formula (I).  By way of examples, mention may be made of poly (2,6-dimethyl-1,4-phenylene ether) and in particular "Noryl SA 120" from Sabic or "Xyron S201" from Asahi. Kasei.  The PPE resin useful for the purposes of the invention is preferably "compatible" with the vinylaromatic diene elastomer of the composition.  As defined above, the term "compatible" means that this PPE resin does not form particles in the composition, that is to say that a resin which, in mixture with the vinylaromatic diene elastomer will give a composition having less 10% of its volume in the form of particles of a size greater than 2 microns, preferably less than 5% and more preferably less than 2%.  The measurement method, in the MOT, is described previously.  Alternatively and preferably also, this PPE resin is compatible with the vinylaromatic diene elastomer in such a way that it is capable of increasing the Tg of the elastomer, that is to say that it will allow the glass transition temperature. , Tg, of a mixture of said vinylaromatic diene elastomer and said resin to increase by more than 10 ° C, preferably by more than 12 ° C for 25 parts by weight per hundred parts by weight of elastomer ( pce) of said resin, based on the Tg of said vinylaromatic diene elastomer alone.  The level of PPE resin in the composition is preferably in a range from 1 to 90 phr, more preferably from 2 to 80 phr, more preferably from 3 to 60 phr and very preferably from 5 to 60 phr.  11. 4.  Crosslinking system [0084] The crosslinking system may be a vulcanization system, it is preferably based on sulfur or sulfur donors and primary vulcanization accelerator (preferably 0.5 to 10.0 phr of primary accelerator ).  To this vulcanization system are optionally added, various known secondary accelerators and / or vulcanization activators such as zinc oxide (preferentially for 0.5 to 10.0 phr), stearic acid or others.  Sulfur is used at a preferred level of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr, for example between 0.5 and 3.0 phr, when the invention is applied to tire tread.  It is possible to use as accelerator (primary or secondary) any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur, especially thiazole type accelerators and their derivatives, thiuram type accelerators, dithiocarbamates. of zinc.  These accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "M BTS"), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated "CBS"), N, N-dicyclohexyl benzothiazyl sulfenamide (abbreviated "DCBS"), N-tert-butyl-2-benzothiazylsulfenamide (abbreviated "TBBS"), N-tert-butyl-2-benzothiazylsulfenimide (abbreviated "TBSI"), zinc dibenzyldithiocarbamate (in abbreviated "ZBEC") and mixtures of these compounds.  Preferably, a primary accelerator of the sulfenamide type is used.  11. 5.  Various additives The rubber compositions of the treads according to the invention also comprise all or part of the usual additives normally used in elastomer compositions intended for the production of treads, such as, for example, pigments. protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents, reinforcing resins or plasticizing agents.  Preferably this plasticizer is a solid hydrocarbon resin other than the previously described resin (or plasticizing resin), an extender oil (or plasticizing oil), or a mixture of both.  These compositions may also contain, in addition to the coupling agents, coupling activators, inorganic charge-covering agents or, more generally, processing aid agents that are capable in a known manner, by means of an improvement. of the dispersion of the filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to use in the green state, these agents being, for example, hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxyl or hydrolyzable polyorganosiloxanes.  11. 6.  Preparation of the rubber compositions The compositions used in the treads of the invention may be manufactured 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 110 ° C. and 190 ° C., preferably between 130 ° C. and 180 ° C., followed by a second phase of mechanical work (so-called "productive" phase) up to a lower temperature, typically below 110 ° C, for example between 40 ° C and 100 ° C, finishing phase during which the crosslinking system is incorporated.  The process for preparing such compositions comprises, for example, the following steps: incorporating, to the elastomers, in particular the vinylaromatic diene elastomer, during a first step (called "non-productive"), the reinforcing filler the PPE resin and any other ingredients of the composition with the exception of the crosslinking system, by thermomechanically kneading the whole (for example in one or more times), until a maximum temperature of between 110 ° C. and 190 is reached. ° C; - cool all at a temperature below 100 ° C; - Then incorporate, in a second step (called "productive"), a crosslinking system; - mix everything up to a maximum temperature of less than 110 ° C.  By way of example, the non-productive phase is carried out in a single thermomechanical step in the course of which, in a suitable mixer, such as a conventional internal mixer, all the constituents are initially introduced. necessary base (elastomers, reinforcing filler, EPP resin and others), then in a second step, for example after one to two minutes of mixing, the other additives, any agents for recovery of the charge or implementation with the exception of the crosslinking system.  The total mixing time in this non-productive phase is preferably between 1 and 15 minutes.  After cooling the mixture thus obtained, it is then incorporated in an external mixer such as a roll mill, maintained at low temperature (for example between 40 ° C and 100 ° C), the crosslinking system.  The whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.  The final composition thus obtained can then be calendered, for example in the form of a sheet, a plate especially for a characterization in the laboratory, or else extruded, for example to form a rubber profile used for manufacture of a tire.  The invention relates to tires and semi-finished products for tires previously described, the rubber articles both in the raw state (that is to say, before cooking) and in the cooked state (c '). that is, after crosslinking or vulcanization).  11. 7.  Pneumatic of the invention The rubber composition according to the invention can be used in different parts of the tire, in particular in the crown, the carcass, the bead zone, the sidewall zone and the tread (including in particular the underlayer of the tread).  According to a preferred embodiment of the invention, the rubber composition described above can be used in the tire as a rigid elastomeric layer in at least a portion of the tire.  By elastomeric "layer" is meant any three-dimensional element, made of rubber composition (or "elastomer", both of which are considered synonymous), of any shape and thickness, in particular sheet, strip, or other element. of any cross section, for example rectangular or triangular.  First of all, the elastomer layer may be used as a tread sub-layer disposed in the crown of the tire, between, on the one hand, the tread, i. e. , the portion intended to come into contact with the road during taxiing, and secondly the belt reinforcing said vertex.  The thickness of this elastomeric layer is preferably in a range from 0.5 to 10 mm, especially in a range of 1 to 5 mm.  According to another preferred embodiment of the invention, the rubber composition according to the invention can be used to form an elastomeric layer, disposed in the region of the region of the bead of the tire, radially between the carcass ply, the bead and the overturning of the carcass ply.  Another preferred embodiment of the invention may be the use of the composition according to the invention to form an elastomeric layer disposed in the area of the sidewall of the tire.  Alternatively, the composition of the invention may advantageously be used in the tread of the tire.
    [0002] III. EXAMPLES OF CARRYING OUT THE INVENTION 111.1. Preparation of the Compositions The following tests are carried out as follows: one introduces into an internal mixer (final filling ratio: approximately 70% by volume), the initial tank temperature of which is approximately 60 ° C. , successively the vinylaromatic diene elastomer, the reinforcing filler and the PPE resin, as well as the various other ingredients with the exception of the vulcanization system. Thermomechanical work (non-productive phase) is then carried out in one step, which lasts in total about 3 to 4 min, until a maximum temperature of "fall" of 180 ° C is reached. The mixture thus obtained is recovered, cooled and then sulfur is incorporated, a sulfenamide type accelerator on a mixer (homo-finisher) at 30 ° C, mixing the whole (productive phase) for a suitable time (by example between 5 and 12 min). The compositions thus obtained are then calendered either in the form of plates (thickness of 2 to 3 mm) or thin sheets of rubber for the measurement of their physical or mechanical properties, or extruded in the form of a profile. 111.2. Tests of Rubber Compositions [00103] This test illustrates rubber compositions used in tire treads. These compositions make it possible to increase the Tg of the mixture with respect to a conventional rubber composition (comprising a conventional plasticizing resin). For this, rubber compositions have been prepared as indicated above. Control compositions C1, C2 and C3 are conventional compositions for those skilled in the art, used to manufacture tire tread mixtures. The compositions of the invention C4 to C6 contain a thermoplastic resin based on optionally substituted polyphenylene ether units (abbreviated as "PPE resin"), as previously described in replacement of the usual plasticizing C5 / C9 cutting resin for those skilled in the art and used in the C2 and C3 controls. The formulations (in phr or parts by weight per hundred parts of elastomer) and their mechanical properties have been summarized in Tables 1 and 2 below.
    [0003] Table 1 Composition Cl C2 C3 C4 C5 C6 SBR (1) 100 100 100 100 100 100 Carbon black (2) 60 75 85 75 85 85 Plasticizing resin (3) - 25 50 - - - Resin EPP 1 (4) - - - 25 50 - Resin EPP 2 (5) - - - - - 50 ZnO (6) 3 3 3 3 3 3 Stearic acid (7) 2 2 2 2 2 2 6PPD (8) 2 2 2 2 2 2 Sulfur 1, 4 1.4 1.4 1.4 1.4 1.4 CBS (9) 2.1 2.1 2.1 2.1 2.1 2.1 (1) SBR with 41% styrene pattern and 24 % 1.2 of the butadiene moiety (Tg measured by DSC according to ASTM D3418 of 1999 of -25 ° C); (2) ASTM grade N234 (Cabot company); (3) Resin C5 / C9 "Escorez 2173" from Exxon; (4) EPP resin 1: Poly (2,6-dimethyl-1,4-phenylene ether) "Noryl SA120" from Sabic, Mn = 2350 g / mol; (5) PPE 2 resin: Poly (2,6-dimethyl-1,4-phenylene ether) "Xyron S201 A" from Sabic, Mn = 19000g / mol; (6) Zinc oxide (industrial grade - Umicore company); (7) Stearin ("Pristerene 4931" from Uniqema); (8) N-1,3-dimethylbutyl-N-phenylparaphenylenediamine Santoflex 6-PPD from Flexsys; (9) N-cyclohexyl benzothiazyl sulphenamide (Santocure CBS from Flexsys). Table 2 Composition Cl C2 C3 C4 C5 C6 Tg -17 ° C -10.5 ° C -6.5 ° C -1 ° C + 8.5 ° C -12 ° C% vol particles <2% <2% <2% <2% < 2%> 10%> 2pm [00106] It is noted that the replacement of the usual resin with a PPE resin in the compositions of the invention C4 and C5 makes it possible to obtain an increase in the temperature corresponding to the maximum of G "(T ), therefore an increase in the Tg of the mixture, relative to the respective control compositions C2 and C3, representative of the plasticizing effect of the PPE resin greater than that of the conventional plasticizing resins It is also noted that the resin used in the composition C6 Having a mass Mn greater than 6000 g / mol does not make it possible to obtain this plasticizing effect. [00107] For the compositions of the invention, thanks to this plasticizing effect superior to conventional plasticizing resins, it is possible to reduce the of resin used and thereby to reduce the raw tackiness induced by the resins plasticizers and thus to facilitate the manufacture of mixtures.
    权利要求:
    Claims (31)
    [0001]
    REVENDICATIONS1. A rubber composition based on at least one major vinylaromatic diene elastomer, a reinforcing filler, a crosslinking system, a thermoplastic resin comprising optionally substituted polyphenylene ether units, said resin having a number average molecular weight (Mn) of less than 6000 g / mol.
    [0002]
    The composition of claim 1, wherein said resin has a number average molecular weight (Mn) of less than 3500 g / mol.
    [0003]
    3. Composition according to claim 2, wherein said resin has a number average molecular weight (Mn) in a range from 700 to 2500 g / mol.
    [0004]
    4. Composition according to any one of claims 1 to 3 wherein the vinylaromatic diene elastomer has a vinylaromatic content greater than 10%.
    [0005]
    5. Composition according to claim 4, wherein the vinylaromatic diene elastomer has a vinylaromatic content of between 15% and 60%, preferably between 20% and 50%.
    [0006]
    6. The rubber composition of claim 5, wherein the vinylaromatic diene elastomer has a vinylaromatic content between 30 and 50%, preferably between 35 and 50%.
    [0007]
    A rubber composition according to any one of the preceding claims, wherein the vinylaromatic diene elastomer is selected from the group consisting of butadiene and styrene copolymers, isoprene and styrene copolymers, butadiene copolymers, isoprene and styrene and mixtures of these elastomers, and preferably in the group consisting of butadiene copolymers and styrene and mixtures thereof.
    [0008]
    8. A rubber composition according to any one of the preceding claims, wherein the vinylaromatic diene elastomer level is in a range of 70 to 100 phr (parts by weight per hundred parts of elastomer).
    [0009]
    9. A rubber composition according to claim 8, wherein the vinylaromatic diene elastomer level is in a range of 85 to 100 phr.
    [0010]
    A rubber composition according to any one of the preceding claims, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units has a glass transition temperature (Tg) as measured by DSC according to ASTM D3418 of 1999. , in a range from 0 to 215 ° C.
    [0011]
    The rubber composition according to claim 10, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units has a glass transition temperature (Tg), measured by DSC according to ASTM D3418 of 1999, in a range from 5 at 200 ° C.
    [0012]
    The rubber composition according to claim 11, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units has a glass transition temperature (Tg), measured by DSC according to ASTM D3418 of 1999, in a range from 5 at 185 ° C.
    [0013]
    13. A rubber composition according to any one of the preceding claims, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I): wherein: (I) - R1 R 2, R 3 and R 4 represent independently of each other identical or different groups chosen from hydrogen, hydroxy, alkoxy, halogen, amino, alkylamino, dialkylamino groups or hydrocarbon groups containing at least 2 carbon atoms, optionally interrupted by heteroatoms and optionally substituted; R1 and R3 on the one hand and R2 and R4 on the other hand can form together with the carbon atoms to which they are attached one or more rings contiguous to the benzene ring of the compound of formula (I) - n is an integer included in a domain ranging from 3 to 300.
    [0014]
    14. A rubber composition according to claim 13, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I) in which R1, R2, R3 and R4 represent independently of each other identical or different groups selected from: - hydrogen, - hydroxy, alkoxy, halogen, amino, alkylamino, dialkylamino groups, - linear, branched or cyclic alkyl groups, comprising from 1 to 25 carbon atoms. carbon (preferably from 2 to 18), optionally interrupted by heteroatoms selected from nitrogen, oxygen and sulfur, and optionally substituted by hydroxy, alkoxy, amino, alkylamino, dialkylamino or halogen groups. aryl groups comprising from 6 to 18 carbon atoms (preferably from 6 to 12), optionally substituted with hydroxyl, alkoxy, amino, alkylamino, dialkylamino, alkyl or halogen groups,
    [0015]
    15. A rubber composition according to claim 14, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I) in which R1, R2, R3 and R4 independently represent one another. others identical or different groups chosen from: - hydrogen, - hydroxy groups, alkoxy having 1 to 6 carbon atoms, halogen, amino, alkylamino having 1 to 6 carbon atoms, dialkylamino comprising from 2 to 12 carbon atoms, linear, branched or cyclic alkyl groups comprising from 1 to 12 carbon atoms (preferably from 2 to 6), optionally interrupted by hetero atoms and optionally substituted with hydroxyl groups, alkoxy groups comprising from 1 to 6 carbon atoms, amino, alkylamino having 1 to 6 carbon atoms, dialkylamino having 2 to 12 atoms s of carbon, or halogen. aryl groups comprising from 6 to 18 carbon atoms (preferably from 6 to 12), optionally substituted with hydroxyl groups, alkoxy groups having from 1 to 6 atoms, amino, alkylamino groups having from 1 to 6 atoms, dialkylamino group having from 2 to to 12 carbon atoms, alkyl having 1 to 12 carbon atoms, or halogen.
    [0016]
    16. A rubber composition according to any one of claims 13 to 15, wherein R1 and R2 represent an alkyl group and in particular a methyl group; and R3 and R4 represent hydrogen atoms.
    [0017]
    17. A rubber composition according to any one of claims 13 to 16, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I) in which n is an integer inclusive. in a range from 3 to 50, preferably from 5 to 30.
    [0018]
    18. A rubber composition according to claim 17, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I) in which n is an integer within a range from at 20.
    [0019]
    19. A rubber composition according to any one of claims 13 to 18, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising more than 80% by weight, polyphenylene units of general formula (I) .
    [0020]
    20. A rubber composition according to any one of claims 13 to 19, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising more than 95% by weight, polyphenylene units of general formula (I) .
    [0021]
    21. A rubber composition according to any one of the preceding claims wherein the level of said thermoplastic resin based on optionally substituted polyphenylene ether units is in a range from 1 to 90 phr, preferably from 2 to 80 phr.
    [0022]
    22. A rubber composition according to claim 21 wherein the level of said thermoplastic resin based on optionally substituted polyphenylene ether units is in a range from 3 to 60 phr, preferably from 5 to 60 phr.
    [0023]
    23. A rubber composition according to any one of claims 1 to 22, wherein the reinforcing filler comprises carbon black and / or silica.
    [0024]
    24. A rubber composition according to any one of claims 1 to 23, wherein the reinforcing filler is between 20 and 200 phr, more preferably between 30 and 160 phr.
    [0025]
    25. A rubber composition according to any one of claims 1 to 24, wherein the reinforcing filler comprises predominantly carbon black.
    [0026]
    26. A rubber composition according to claim 25, wherein the carbon black is 60 to 160 phr, preferably 70 to 150 phr.
    [0027]
    27. A rubber composition according to any one of claims 1 to 24, wherein the reinforcing filler comprises predominantly silica.
    [0028]
    28. A rubber composition according to claim 27, wherein the silica is from 60 to 160 phr, preferably from 70 to 150 phr.
    [0029]
    29. A finished or semi-finished rubber article comprising a rubber composition according to any one of claims 1 to 28.
    [0030]
    30. A tire comprising a rubber composition according to any one of claims 1 to 28.
    [0031]
    31. A tire according to claim 30, the tread of which comprises a rubber composition according to any one of claims 1 to 28.
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    同族专利:
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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
    FR1363154A|FR3015505B1|2013-12-20|2013-12-20|RUBBER COMPOSITION COMPRISING A POLYPHENYLENE ETHER RESIN AS A PLASTICIZER|FR1363154A| FR3015505B1|2013-12-20|2013-12-20|RUBBER COMPOSITION COMPRISING A POLYPHENYLENE ETHER RESIN AS A PLASTICIZER|
    US15/105,966| US10435544B2|2013-12-20|2014-12-19|Rubber composition comprising a polyphenylene ether resin as plasticizer|
    EP14827207.3A| EP3083813B1|2013-12-20|2014-12-19|Latex composition comprising a polyphenylene ether resin as plastisizer|
    CN201480068580.6A| CN105829434A|2013-12-20|2014-12-19|Rubber composition comprising a polyphenylene ether resin as plasticizer|
    PCT/EP2014/078680| WO2015091921A1|2013-12-20|2014-12-19|Rubber composition comprising a polyphenylene ether resin as plasticizer|
    JP2016541661A| JP6515103B2|2013-12-20|2014-12-19|Rubber composition containing polyphenylene ether resin as plasticizer|
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