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    • 专利摘要:
    The present invention relates to a tire comprising a tread, a crown with a crown reinforcement, two sidewalls, two beads, a carcass reinforcement anchored to the two beads and extending from one side to the other, in which the tread comprises at least one thermoplastic elastomer, said thermoplastic elastomer being a block copolymer comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic type thermoplastic block, and the total amount of thermoplastic elastomer being within a range of 65 to 100 phr (parts by weight per hundred parts of elastomer).
    公开号:FR3016886A1
    申请号:FR1450667
    申请日:2014-01-28
    公开日:2015-07-31
    发明作者:Vincent Abad；Emmanuel Custodero；Christophe Chouvel；Marc Greiveldinger
    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 present invention relates to tires provided with a tread.  In a conventional tire, the tread comprises mainly diene elastomers.  [0003] A constant objective of tire manufacturers is to reduce the rolling resistance of tires.  As part of the compromise between improving the rolling resistance and improving the adhesion of wet tires, the applicants have previously described in WO 2012/152686 a tire equipped with a tire. tread comprising at least one thermoplastic elastomer, said thermoplastic elastomer being a block copolymer comprising at least one elastomer block and at least one thermoplastic block, and the total content of thermoplastic elastomer being within a range of 65 to 100 phr ( parts by weight per hundred parts of elastomer).  In particular, the applicants have described a tread comprising, as thermoplastic elastomer, the styrene-isoprene-styrene triblock copolymer (SIS) as permitting a reduction in rolling resistance compared with treads of conventional composition.  [0005] At present, the applicants have surprisingly found that a tire provided with a tread comprising a specific thermoplastic elastomer 20 makes it possible to obtain a very large decrease in rolling resistance, also compared with the belts. of thermoplastic elastomer bearing already described.  The invention therefore relates to a tire comprising a tread, a vertex with a crown reinforcement, two flanks, two beads, a carcass reinforcement anchored to the two beads and extending from a sidewall to the rear. another, wherein the tread comprises at least one thermoplastic elastomer, said thermoplastic elastomer being a block copolymer comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic thermoplastic block, and the total content of thermoplastic elastomer being within a range of from 65 to 100 phr (parts by weight per hundred parts of elastomer).  [0007] Preferably, the invention relates to a tire as defined above, in which the number-average molecular weight of the thermoplastic elastomer is between 30,000 and 500,000 g / mol.  Also preferably, the invention relates to a tire as defined above, wherein the one or more elastomeric blocks of the block copolymer are chosen from elastomers having a glass transition temperature of less than 25 ° C.  [0009] Preferably, the invention also relates to a tire as defined above, in which the SBR elastomer block or blocks have a styrene content ranging from 10 to 60%. Preferably, the elastomer block or blocks SBR have a content of -1,2 bonds for the butadiene part in a range from 4% to 75% molar, and a -1,4-linkage content in a range from 20% and 96% molar.  Also preferably, the SBR elastomer block or blocks are hydrogenated in such a way that 25 to 100 mol% of the double bonds in the butadiene portion are hydrogenated, more preferably 50 to 100 mol%, and preferably from 80 to 100 mol% of the double bonds in the butadiene portion are hydrogenated.  [0010] Preferably, the invention relates to a tire as defined above, in which the styrene thermoplastic block or blocks of the block copolymer are chosen from polymers having a glass transition temperature greater than 80 ° C., and in the case of a semi-crystalline thermoplastic block, a melting point of greater than 80 ° C.  Preferably, the styrenic thermoplastic block fraction in the block copolymer is within a range of 5 to 70%. Preferably, the thermoplastic block or blocks of the block copolymer are chosen from polystyrenes, preferably from polystyrenes obtained from styrene monomers chosen from the group consisting of unsubstituted styrene, substituted styrenes and their mixtures; and more preferably, among the polystyrenes obtained from styrene monomers selected from the group consisting of unsubstituted styrene, -3 methylstyrenes, para-tert-butylstyrene, chlorostyrenes, bromo styrenes, fluorostyrenes, para-tert-butylstyrene, hydroxy-styrene, and mixtures thereof.  Very preferably, the thermoplastic block (s) of the block copolymer are chosen from polystyrenes obtained from styrene monomers chosen from the group consisting of unsubstituted styrene, o-methylstyrene, m-methylstyrene and p-methylstyrene. alpha-methyl styrene, alpha-2-dimethyl styrene, alpha-4-dimethylstyrene, diphenylethylene, para-tert-butylstyrene, o-chlorostyrene, mchlorostyrene, p-chlorostyrene, , 4-dichlorostyrene, 2,6-dichlorostyrene, 2,4,6-trichlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene , 2,4,6-tribromostyrene, o-fluorostyrene, mfluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6-difluorostyrene, 2,4,6-trifluorostyrene, para- hydroxy-styrene, and mixtures thereof.  More preferably, the thermoplastic block (s) of the block copolymer are obtained from unsubstituted polystyrene.  Preferably, the invention relates to a tire as defined above, wherein the thermoplastic elastomer or elastomers are the only elastomers of the tread.  Also preferably, the invention relates to a tire as defined above, wherein the tread further comprises a thermoplastic resin comprising optionally substituted polyphenylene ether units.  Preferably, 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.  Also preferably, the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I): -4 (I) in which: - R1, R2, R3 and R4 represent independently others identical or different groups selected from hydrogen, hydroxy, alkoxy, halogen, amino, alkylamino, dialkylamino or 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), 1 () - n is a integer in a range from 3 to 300.  Preferably, the invention relates to a tire as defined above, wherein R1 and R2 represent an alkyl group and in particular a methyl group; and R3 and R4 represent hydrogen atoms.  Also preferably, 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 from 3 to 60 phr, more preferably 5 to 60 phr.  The invention relates more particularly to tires intended to equip non-motorized vehicles such as bicycles, or tourism-type motor vehicles, SUV ("Sport Utility Vehicles"), two wheels (including motorcycles), airplanes, as industrial vehicles selected from light trucks, "heavy goods vehicles" - that is, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural vehicles or civil engineering - other transport or handling vehicles.  DETAILED DESCRIPTION OF THE INVENTION In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are percentages by weight.  Furthermore, the term "phr" means, within the meaning of the present patent application, part by weight per hundred parts of elastomer, thermoplastic and non-thermoplastic combined.  For the purposes of the present invention, thermoplastic elastomers (TPE) are part of the elastomers.  On the other hand, any range of values designated by the expression "between a and b" represents the range 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 strict bounds a and b).  1.  Composition of the Tread [0018] The tire according to the invention has the essential characteristic of comprising a tread, a crown with a crown reinforcement, two sidewalls, two beads, a carcass reinforcement anchored to the two beads and extending from one side to the other, in which the tread comprises at least one thermoplastic elastomer, said thermoplastic elastomer being a block copolymer comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one a thermoplastic block of styrenic type, and the total content of thermoplastic elastomer being in a range of 65 to 100 phr (parts by weight per hundred parts of elastomer).  1. 1 Thermoplastic elastomer (TPE) specific to SBR and PS blocks [0019] In general, thermoplastic elastomers (abbreviated as "TPE") have an intermediate structure between thermoplastic polymers and elastomers.  They are block copolymers made up of rigid, thermoplastic blocks connected by flexible, elastomeric blocks.  For the purposes of the invention, said specific thermoplastic elastomer is a block copolymer comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block (SBR) and at least one styrenic copolymer-type thermoplastic block ( PS).  In what follows, when reference is made to an SBR block, it is therefore a predominantly elastomeric block (that is to say more than 50% by weight, preferably greater than 80% by weight). % by weight) composed of a random copolymer of butadiene and styrene, this copolymer may or may not be hydrogenated, and, when it is referred to a styrenic block, it is a predominantly composed block (c ') that is, more than 50% by weight, preferably greater than 80% by weight) of a styrenic polymer such as polystyrene.  1. 1. 1.  Structure of SBR and PS Block TPE [0021] The number-average molecular weight (denoted Mn) of the SBR and PS block TPE is preferably between 30,000 and 500,000 g / mol, more preferably between 40,000 and 400,000. g / mol.  Below the minima indicated, the cohesion between the SBR elastomer chains of SBR and PS block TPE, in particular because of its possible dilution (in the presence of an extension oil), may be affected; on the other hand, an increase in the temperature of use may affect the mechanical properties, including the properties at break, resulting in reduced performance "hot".  Moreover, a mass Mn that is too high can be penalizing for the implementation.  Thus, it has been found that a value within a range from 50,000 to 300,000 g / mol and better still from 60,000 to 150,000 was particularly well suited, in particular to a use of SBR and PS block TPE in a composition. for tire tread.  The number-average molecular weight (Mn) of SBR 25 and PS block TPE elastomer is determined in known manner by steric exclusion chromatography (SEC).  For example, in the case of styrenic thermoplastic elastomers, the sample is solubilized beforehand in tetrahydrofuran at a concentration of approximately 1 g / l; then the solution is filtered on a filter of porosity 0.45 i. tm before injection.  The apparatus used is a "WATERS alliance" chromatographic chain.  The eluting solvent is tetrahydrofuran, the flow rate 0.7 ml / min, the system temperature 35 ° C and the analysis time 90 min.  A set of four WATERS columns in series, of trade names "STYRAGEL" ("HIMW7", "HIMW6E" and two "HT6E") is used.  The injected volume of the solution of the polymer sample is 100. he.  The detector is a "WATERS 2410" differential refractometer and its associated software for the exploitation of chromatographic data is the "WATERS MILLENIUM" system.  The calculated average molar masses relate to a calibration curve made with polystyrene standards.  The conditions are adaptable by those skilled in the art.  The value of the polydispersity index Ip (booster: Ip = Mw / Mn with Mw weight average molecular weight and Mn number-average molecular weight) of the SBR and PS block TPE is preferably less than 3; more preferably less than 2 and even more preferably less than 1.5.  As is known, the block TPEs SBR and PS have two glass transition temperature peaks (Tg, measured according to ASTM D3418), the lowest temperature being relative to the SBR elastomer part of SBR block TPE and PS, and the highest temperature being relative to the thermoplastic part PS of SBR and PS block TPE.  Thus, the SBR soft blocks of the SBR and PS block TPEs are defined by a Tg lower than the ambient temperature (25 ° C), whereas the rigid blocks PS have a Tg greater than 80 ° C.  In the present application, when reference is made to the glass transition temperature of the SBR and PS block TPE, this is the Tg relative to the SBR elastomer block.  The SBR and PS block TPE preferably has a glass transition temperature ("Tg") which is preferably less than or equal to 25 ° C, more preferably less than or equal to 10 ° C.  A value of Tg higher than these minima can reduce the performance of the tread when used at very low temperatures; for such use, the Tg of SBR and PS block TPE is more preferably less than or equal to -10 ° C.  Also preferentially, the Tg of SBR and PS block TPE is greater than -100 ° C.  The SBR and PS block TPEs may be copolymers with a small number of blocks (less than 5, typically 2 or 3), in which case these blocks preferably have high masses -8, greater than 15000 g / mol .  These SBR and PS block TPEs may be, for example, diblock copolymers comprising a thermoplastic block and an elastomer block.  They are often also triblock elastomers with two rigid segments connected by a flexible segment.  The rigid and flexible segments can be arranged linearly, star or connected.  Typically, each of these segments or blocks often contains at least more than 5, usually more than 10 base units (e.g., styrene units and butadiene / styrene units for a styrene / SBR / styrene block copolymer).  The block TPEs SBR and PS may also comprise a large number of blocks (more than 30, typically from 50 to 500) smaller, in which case these blocks preferably have 1 () low masses, for example 500 to 5000 g / mol, these SBR and PS block TPEs will be called block SBR and PS multiblock TPEs thereafter, and are a series of elastomeric blocks - thermoplastic blocks.  According to a first variant, the block TPE SBR and PS is in a linear form.  For example, SBR and PS block TPE is a diblock copolymer: PS block / SBR block.  The SBR and PS block TPE can also be a triblock copolymer: PS block / SBR block / PS block, that is to say a central elastomer block and two terminal thermoplastic blocks, at each of the two ends of the elastomer block.  Also, the SBR and PS multiblock block TPE can be a linear sequence of SBR elastomeric blocks - PS thermoplastic blocks.  According to another variant of the invention, the SBR and PS block TPE useful for the purposes of the invention is in a star shape with at least three branches.  For example, the block TPE SBR and PS may then consist of a star-branched SBR elastomer block having at least three branches and a thermoplastic block PS, located at the end of each of the branches of the SBR elastomer block.  The number of branches of the central elastomer may vary, for example from 3 to 12, and preferably from 3 to 6.  According to another variant of the invention, the block TPE SBR and PS is in a branched form or dendrimer.  The SBR and PS block TPE may then consist of a branched SBR elastomer or dendrimer block and a PS thermoplastic block, located at the end of the branches of the elastomer dendrimer block.  -9 1. 1. 2.  Nature of Elastomeric Blocks The elastomer blocks of the SBR and PS block TPE for the purposes of the invention may be all butadiene and styrene random copolymer (SBR) type elastomers known to those skilled in the art. art.  The SBR elastomer block fraction in SBR and PS block TPE is in a range from 30 to 95%, preferably from 40 to 92%, more preferably from 50 to 90%.  These SBR blocks preferably have a Tg (glass transition temperature) measured by DSC according to the ASTM D3418 standard of 1999, less than 25 ° C, preferably less than 10 ° C, more preferably less than 0 ° C and very preferably below -10 ° C.  Also preferably, the Tg of the SBR blocks is greater than -100 ° C.  Particularly suitable are SBR blocks having a Tg of between 20 ° C and -70 ° C and more particularly between 0 ° C and -50 ° C.  As is well known, the SBR block comprises a styrene content, a 1,2-butadiene content of the butadiene part, and a 1,4-butadiene content of the butadiene part, the latter consisting of a trans-1,4-linkage content and a cis-1,4 bond content when the butadiene moiety is not hydrogenated.  Preferably, an SBR block having a styrene content of, for example, a range of from 10 to 60% by weight, preferably from 20 to 50% by weight, is used, and for the part butadiene, a 1,2-linkage content in a range from 4% to 75% (mol%), and a -1,4-linkage content in a range from 20% to 96% (mol%) .  According to the degree of hydrogenation of the SBR block, the double bond content of the butadiene part of the SBR block may decrease to a content of 0 mol% for a completely hydrogenated SBR block.  Preferably, in the SBR and PS block TPEs useful for the purposes of the invention, the SBR elastomer block is hydrogenated in such a way that a proportion ranging from 25 to 100 mol% of the double bonds in the butadiene portion are hydrogenated.  More preferably 50 to 100 mol% and very preferably 80 to 100 mol% of the double bonds in the butadiene portion are hydrogenated.  For the purposes of the present invention, the styrenic part of the SBR blocks may be composed of monomers chosen from styrene monomers, and in particular chosen from the group consisting of unsubstituted styrene, substituted styrenes and mixtures thereof.  Among the substituted styrenes, those selected from the group consisting of methylstyrenes (preferentially o-methylstyrene, dimethylstyrene and p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha 4-dimethylstyrene and diphenylethylene), para-tert-butylstyrene, chlorostyrenes (preferentially o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene and 2-dichlorostyrene). , 4,6-trichlorostyrene), bromostyrenes (preferentially o-bromostyrene, m-bromostyrene, pbromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene and 2,4,6-tribromostyrene), fluorostyrenes (preferentially o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6-difluorostyrene and 2,4,6-trifluorostyrene), para-hydroxy-styrene , and mixtures thereof.  According to a preferred embodiment of the invention, the SBR and PS block TPE elastomer blocks have in total a number-average molecular weight ("Mn") ranging from 25,000 g / mol to 350,000 g / m 2. mol, preferably from 35,000 g / mol to 250,000 g / mol so as to give the SBR and PS block TPE good elastomeric properties and sufficient mechanical strength and compatible with the use in tire tread.  The elastomeric block may also consist of several elastomeric blocks as defined above.  1. 1. 3.  Nature of the Thermoplastic Blocks The definition of the thermoplastic blocks will use the glass transition temperature characteristic (Tg) of the thermoplastic rigid block.  This characteristic is well known to those skilled in the art.  It allows in particular to choose the temperature of industrial implementation (transformation).  In the case of an amorphous polymer (or polymer block), the operating temperature is chosen to be substantially greater than the Tg.  In the specific case of a semicrystalline polymer (or polymer block), a melting temperature can be observed, then greater than the glass transition temperature.  In this case, it is rather the melting temperature (Tf) which makes it possible to choose the temperature of implementation of the polymer (or polymer block) considered.  Thus, later, when we speak of "Tg (or Tf, if any)", we must consider that this is the temperature used to choose the temperature of implementation.  For the purposes of the invention, the SBR and PS block TPE elastomers comprise one or more thermoplastic block (s) preferably having a Tg (or Tf, where appropriate) greater than or equal to 80 ° C. C and constituted (s) from polymerized styrenic monomers (PS).  Preferably, this thermoplastic block has a Tg (or Tf, if applicable) in a range of 80 ° C to 250 ° C.  Preferably, the Tg (or Tf, if appropriate) of this thermoplastic block is preferably from 80 ° C to 200 ° C, more preferably from 80 ° C to 180 ° C.  The fraction of PS thermoplastic block in the block TPE SBR and PS is in a range from 5 to 70%, preferably from 8 to 60%, more preferably from 10 to 50%.  The thermoplastic blocks of SBR block TPE are polystyrene blocks.  Preferred polystyrenes are obtained from styrenic monomers selected from the group consisting of unsubstituted styrene, substituted styrenes, and mixtures thereof.  Among the substituted styrenes, those selected from the group consisting of methylstyrenes (preferentially o-methylstyrene, m-methylstyrene and p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha-4-dimethylstyrene and diphenylethylene), para-tert-butylstyrene, chlorostyrenes (preferentially o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, dichlorostyrene and 2,4,6-trichlorostyrene), bromostyrenes (preferentially o-bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene and 2,4-dibromostyrene). , 6-tribromostyrene), fluorostyrenes (preferably o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6-difluorostyrene and 2,4,6-difluorostyrene). trifluorostyrene), para-hydroxystyrene, and mixtures thereof.  Very preferably, the thermoplastic blocks of SBR block TPE are blocks obtained from unsubstituted polystyrene.  According to a variant of the invention, the polystyrene block as defined above may be copolymerized with at least one other monomer so as to form a thermoplastic block having a Tg (or Tf, where appropriate) as defined above.  By way of illustration, this other monomer capable of copolymerizing with the polymerized monomer may be chosen from diene monomers, more particularly conjugated diene monomers having 4 to 14 carbon atoms, and vinylaromatic-type monomers. having from 8 to 20 carbon atoms.  According to the invention, the thermoplastic blocks of SBR and PS block TPE have in total a number-average molecular weight ("Mn") ranging from 5,000 g / mol to 150,000 g / mol, so as to confer SBR and PS blocks of good elastomeric properties and sufficient mechanical strength and compatible with the use of tread tire.  The thermoplastic block may also consist of several thermoplastic blocks as defined above.  1. 1. 4.  Examples of SBR and PS block TPEs [0049] As examples of commercially available SBR and PS block TPE elastomers, mention may be made of SOE type elastomers marketed by Asahi Kasei under the name "SOE 51611". "," SOE L605 "or" SOE L606 ".  1. 1. 5.  Quantity of SBR and PS Block TPE [0050] If any other (non-thermoplastic) elastomers are used in the composition, the SBR and PS block TPE elastomer (s) constitute the majority by weight; they then represent at least 65%, preferably at least 70% by weight, more preferably at least 75% by weight of all the elastomers present in the elastomer composition.  Also preferably, the SBR and PS block TPE elastomers represent at least 95% (in particular 100%) by weight of all the elastomers present in the elastomer composition.  Thus, the amount of block TPE elastomer SBR and PS is in a range from 65 to 100 phr, preferably from 70 to 100 phr and especially from 75 to 100 phr.  Also preferably, the composition contains from 95 to 100 phr of SBR and PS block TPE elastomer.  The SBR and PS block TPE elastomer (s) are preferably the sole elastomer (s) of the tread.  1. Non-Thermoplastic Elastomer [0052] The thermoplastic elastomer (s) described above are sufficient on their own for the tread according to the invention to be usable.  The composition of the tread according to the invention may comprise at least one (that is to say one or more) diene rubber as non-thermoplastic elastomer, this diene rubber may be used alone, or in cutting with at least one (i.e. one or more) other non-thermoplastic rubber or elastomer.  The optional total non-thermoplastic elastomer content is in a range from 0 to 35 phr, preferably from 0 to 30 phr, more preferably from 0 to 25 phr, and even more preferably from 0 to 5 phr. .  Thus, when the tread contains, the non-thermoplastic elastomers represent at most 35 phr, preferably at most 30 phr, more preferably at most 25 phr and very preferably at most 5 phr.  Also very preferentially, the tread of the tire according to the invention does not contain a non-thermoplastic elastomer.  By elastomer or "diene" rubber, must be understood in a known manner (one or more) elastomer at least in part (i.e. e.  ; a homopolymer or a copolymer) of diene monomers (monomers carrying two carbon-carbon double bonds, conjugated or otherwise).  These diene elastomers can be classified into two categories "essentially unsaturated" or "essentially saturated".  The term "essentially unsaturated" is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (% by weight). mole).  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%.  Thus diene elastomers such as certain butyl rubbers or copolymers of dienes and alpha olefins EPDM type can be qualified as "essentially saturated" diene elastomers (low or very low diene origin ratio). low, always less than 15%).  These definitions being given, the term "diene elastomer" is understood to mean, whatever the category above, which may be used in the compositions according to the invention: (a) - any homopolymer obtained by polymerization of a conjugated diene monomer having 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, of an α-olefin having 3 to 6 carbon atoms with a non-conjugated diene monomer having from 6 to 12 carbon atoms, for example elastomers obtained from 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 diene rubber), as well as the halogenated, in particular chlorinated or brominated, versions of this type of copolymer.  Any type of diene elastomer can be used in the invention.  When the composition contains a vulcanization system, essentially unsaturated elastomers, especially types (a) and (b) above, are preferably used for the manufacture of the tread of the tire according to the present invention.  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-methyl-3 isopropyl-1,3-butadiene, 1,3-aryl-butadiene, 1,3-p-1,3-pentadiene, 2,4-hexadiene.  Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, paratertiobutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene and 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 may for example 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 with 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, there may be mentioned, for example, 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 ( as described for example in FR 2,765,882 or US 5,977,238), carboxylic groups (as described for example in WO 01/92402 or US 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 6,503,973).  As other examples of functionalized elastomers, mention may also be made of elastomers (such as SBR, BR, NR or IR) of the epoxidized type.  1. 3.  PPE resin The thermoplastic elastomer (s) described above are sufficient on their own to make the tread according to the invention usable.  Preferably, the composition according to the invention may further comprise a thermoplastic resin based on optionally substituted polyphenylene ether units (abbreviated as "EPP resin").  This type of compound is described, for example, in the encyclopaedia "Ullmann's encyclopedia of industrial chemistry" published by VCH, vol. A 10 21, pages 605-614, 5th edition, 1992.  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 PPE resin does not allow a sufficient shift of Tg in the composition comprising it and above 215 ° C., manufacturing problems can be encountered in particular to obtain a homogeneous mixture.  Preferably, the PPE resin is a compound comprising predominantly polyphenylene units of general formula (I): embedded image in which: R 1, R 2, R 3 and R 4 represent, independently of one another, groups identical or different 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, R 1, R 2, R 3 and R 4 represent, independently of one another, identical or different groups chosen from: - hydrogen - the hydroxyl, alkoxy, halogen, amino, alkylamino and dialkylamino groups, - the alkyl groups linear, branched or cyclic, 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 groups, alkoxy, 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 R 1, R2, R3 and R4 independently of one another represent 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; carbon, dialkylamino having 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 heteroatoms and optionally substituted with hydroxy, alkoxy groups having 1 to 6 carbon atoms, amino, alkylamino having 1 to 6 carbon atoms, dialkylamino having 2 to 12 carbon atoms, o 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.  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 within a range of 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 5202A" from Company 20 Asahi Kasei.  In a known manner, the PPE resins have for example and preferably variable number average molecular weights (Mn), most often from 15,000 to 30,000 g / mol, in the case of high masses such as these, the Mn is measured in a manner known to those skilled in the art by SEC (also named GPC, as in US4588806, column 8).  For the purposes of the invention, it may also and preferably also be used for the composition of the invention 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 - 19 - ranging from 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 10 with Mw weight average molecular weight and Mn number-average molecular mass) of the EPP resin is less than or equal to 5, plus preferably less than or equal to 3 and more preferably still less than or equal to 2.  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 still from 3 to 60 phr, and most preferably from 5 to 60 phr.  1. 4.  Nanometric charge, g i. The thermoplastic elastomer (s) described above are sufficient on their own for the tread according to the invention to be usable.  Preferably, the composition according to the invention may further comprise a reinforcing filler.  When a reinforcing filler is used, it is possible to use any type of filler usually used for the manufacture of tires, for example an organic filler such as carbon black, an inorganic filler such as silica, or a filler. cutting of these two types of filler, especially a blend of carbon black and silica.  As carbon blacks are suitable all carbon blacks conventionally used in tires (so-called pneumatic grade black).  For example, mention will be made more particularly of reinforcing carbon blacks of the series 100, 200 or 300 (ASTM grades), for example the N115, N134, N234, N326, N330, N339, N347 or N375 blacks, or else , depending on the targeted applications, black higher series (eg N660, N683, N772), or even N990.  By "reinforcing inorganic filler" is meant in this application, by definition, any inorganic or mineral filler (whatever its color and origin (natural or synthetic), also called "white" filler, charge "clear" or "charge non-black" ("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 tires, in other words, able 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.  The physical state in which the reinforcing inorganic filler is present is immaterial, 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.  Suitable reinforcing inorganic fillers are in particular mineral fillers of the siliceous type, in particular silica (SiO 2), or of the aluminous type, in particular 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 (called "HDS"), mention may be made, for example, of the "Ultrasil" 7000 and "Ultrasil" 7005 silicas of Degussa, the "Zeosil" 1165MP, 1135MP and 1115MP silicas of Rhodia, the "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 03/16837.  In order to couple the reinforcing inorganic filler to the elastomer, it is possible, for example, to use, in known manner, at least a bifunctional coupling agent (or bonding agent) intended to provide a sufficient connection of a chemical nature and / or or physically, between the inorganic filler (surface of its particles) and the elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.  The reinforcing charge volume ratio, optional, in the composition (carbon black and / or reinforcing inorganic filler such as silica) is in a range of 0 to 20%, which corresponds to a rate of 0 to 50 pce for a composition without plasticizer.  Preferably the composition comprises less than 30 phr of reinforcing filler and more preferably less than 10 phr.  According to a preferred variant of the invention, the composition of the tread does not contain a reinforcing filler.  1. 5.  Various Additives The thermoplastic elastomer (s) described above are sufficient on their own for the tread according to the invention to be usable.  However, according to a preferred embodiment of the invention, the elastomer composition described above may also comprise a plasticizing agent, such as an oil (or plasticizing oil or extender oil) or a plasticizing resin whose function is to facilitate the implementation of the tread, particularly its integration with the tire by a lowering of the module and an increase in tackiness.  Any oil, preferably of a slightly polar nature, capable of extending and plasticizing elastomers, in particular thermoplastics, may be used.  At room temperature (23 ° C), these oils, more or less viscous, are liquids (that is to say, as a reminder, substances having the ability to eventually take the shape of their container), as opposed in particular to resins or rubbers which are inherently solid.  Any type of plasticising resin known to those skilled in the art can also be used.  Those skilled in the art will know, in the light of the description and examples of embodiment which follow, adjust the amount of plasticizer according to the TPE elastomer SBR and PS blocks used (as indicated above) ; particular conditions of use of the tire provided with the tread, and in particular according to the pneumatic object in which it is intended to be used.  When it is used, it is preferred that the level of extender oil is in a range from 0 to 80 phr, preferably from 0 to 50 phr, more preferably from 5 to 50 phr, according to the Tg. and the intended module for the tread.  The tread described above may also include the various additives usually present in the treads known to those skilled in the art.  For example, one or more additives chosen from protective agents such as antioxidants or antiozonants, anti-UV agents, the various processing agents or other stabilizers, or promoters capable of promoting adhesion to the rest of the structure of the pneumatic object.  Preferably, the tread does not contain all these additives at the same time and even more preferably, tread contains none of these agents.  [0090] Also and optionally, the tread composition of the invention may contain a crosslinking system known to those skilled in the art.  Preferably, the composition does not contain a crosslinking system.  In the same way, the tread composition of the invention may contain one or more inert micrometric fillers such as lamellar fillers known to those skilled in the art.  Preferably, the composition contains no micron charge.  2.  Preparation The SBR and PS block TPE elastomers can be used in a conventional manner for TPE, by extrusion or molding, for example from a raw material available in the form of beads or granules.  The tread for the tire according to the invention is prepared in a conventional manner, for example by incorporating the various components into a twin-screw extruder, so as to effect the melting of the matrix and incorporation of all the components. the ingredients, then use a die to make the profile.  The tread is then carved in the tire baking mold.  If the elastomer block of SBR and PS block TPE is a totally hydrogenated SBR block, it may be necessary to include in the tire an underlayer or adhesion layer under the carved portion of the tread which will contain a SBR and PS block-block TPE with unsaturated elastomer block to promote adhesion between said tread and the adjacent layer (eg crown reinforcement or belt) within the finished tire.  This tread may be mounted on a pneumatic manner 1 () conventional, said tire comprising in addition to the tread according to the invention, a top, two sides and two beads, a carcass reinforcement anchored to the two beads, and a crown reinforcement.  Optionally and as indicated above, the tire according to the invention may further comprise an underlayer or an adhesion layer between the carved portion of the tread and the crown reinforcement.  EXAMPLES OF CARRYING OUT THE INVENTION Tire tread compositions according to the invention have been prepared as indicated above.  Tires according to the invention were then prepared according to the usual methods, with the conventional constituents known to those skilled in the art: a top, two flanks and two beads, a carcass reinforcement anchored to the two beads, a crown reinforcement and a tread, the tread being that described for the purposes of the present invention.  [0097] The properties of the tires according to the invention can be evaluated by tire tests or from tests on tread composition samples as set forth below.  Dynamic properties (after curing) The dynamic properties G * and tan (8) max are measured on a viscoanalyzer (Metravib V A4000), according to the ASTM D 5992 - 96 standard.  The response of a sample of desired composition (cylindrical specimen 2 mm thick and 78 mm 2 in section), subjected to a sinusoidal stress in alternating simple shear, at the frequency of 10 Hz, at a temperature of 40 °, is recorded. C and according to ASTM D 1349 - 99.  A peak to peak deformation amplitude sweep of 0.1 to 50% (forward cycle) and then 50% to 0.1% (return cycle) are performed.  The results exploited are the complex dynamic shear modulus (G *) and the loss factor (tan Ô).  For the return cycle, we indicate the maximum value of tan b observed (tan (8). ), as well as the complex modulus difference (4G *) between the 0.1% and 50% deformation values (Payne effect).  For more readability the results will be indicated in performance in base 100, the value 100 being attributed to the witness.  Thus, for the measurement of (tan Ô), a result greater than 100, will indicate a better performance and therefore a decrease in the value concerned, and conversely, a result lower than 100 indicates a lower performance and therefore an increase in the value concerned. .  Measurements of E "[0099] The measurement method of E" is done by means of a machine DMA METRAVIB 450+ equipped with compression trays PET10003000B.  The test carried out is a dynamic compression test on a cylindrical sample of diameter 10 mm and height 15 mm.  The TPE formulation or the raw elastomer mixture chosen is first put into the form of a sheet (eg in press for the TPE, to the roller mixer for the elastomer mixture).  We then cut small discs lOmm diameter 25 by means of a punch.  These discs are stacked up to a height of at least 15mm.  These stacked disks are then placed in a mold whose internal dimensions are lOmm in diameter and 15mm high.  The whole is pressed to melt the non-crosslinkable mixture or cook the crosslinkable mixture and form a cylindrical sample 10 mm in diameter and 15 mm high.  Typically this baking heat treatment (for the crosslinkable mixture) or shaping (for the non-crosslinkable mixture) is 17 min at 170 ° C. under 16 bar.  After forming, and if necessary, cooking, the cylindrical sample obtained is secured to the compression plates by means of a Loctite 406 adhesive.  A drop of this glue is first deposited in the center of the lower plate.  The cylindrical sample is placed on this drop and a second drop is deposited on top of it.  We then come down the cross of the Metravib to stick the top plate 10 on the top of the sample, being careful not to crush (force virtually zero).  After a few minutes of drying of the adhesive, this cylindrical sample is applied to a sinusoidal stress at a static deformation rate of 10% and a dynamic deformation rate of 0.1% at 1 Hz.  The variation of the modulus E "is studied as a function of the temperature for a range varying from 40 ° C. to 200 ° C. with a rate of variation of 1 ° C./min.  Typically, we then obtain a plot of the evolution of the module E "as a function of temperature.  From this curve, the temperature corresponding to the maximum of E "can be extracted from the values. This maximum temperature is representative, for the compositions based on thermoplastic, of the glass transition of the composition which reflects its thermal behavior.  For more readability the results will be indicated in performance in base 100, the value 100 being attributed to the witness.  A result lower than 100 indicating a decrease in the performance concerned, and conversely a result greater than 100, will indicate an increase in the performance concerned.
    [0002] EXAMPLE [00105] Three tire tread compositions according to the invention (A3, A4 and A5) were prepared as previously described and compared to two controls: a tire type tread composition of a tire type. green "low rolling resistance (A1), and a composition for rolling tape as described in WO 2012/152686 (A2). The compositions of these treads are presented in Table 1 below. Table 1 Composition A-1 A-2 A-3 A-4 A-5 SBR (1) 40 0 0 0 0 SBR (2) 60 0 0 0 0 Elastomer TPE (3) 0 100 0 0 0 TPE Elastomer (4) ) 0 0 100 100 100 Charge (5) 90 0 0 0 0 Coupling agent (6) 7.5 0 0 0 0 Carbon black (7) 4 0 0 0 0 Liquid plasticizer 1 (8) 20 0 0 0 0 Liquid plasticizer 2 (9) 0 20 0 0 0 Resin (10) 20 0 0 0 0 Resin EPP 1 (11) 0 18 0 Resin EPP 2 (12) 0 0 18 Anti-ozone wax 1.5 0 0 0 0 Agent anti-oxidant (13) DPG (14) 1.5 0 0 0 0 ZnO (15) 2.75 0 0 0 0 stearic acid (16) 2 0 0 0 0 CBS (17) 2.1 0 0 0 0 Sulfur 1.4 0 0 0 0 (1) SSBR solution (expressed as dry SBR: 41% styrene, 24% polybutadiene units 1-2 and 51% polybutadiene units 1-4 trans ( Tg = -25 ° C) (2) SSBR solution (dry SBR content: 29% styrene, 5% polybutadiene units 1-2 and 80% polybutadiene units 1-4 trans (Tg = -56) ° C); (3) thermoplastic elastomer SIS "Hybrar 5125" from Kuraray; (4) Thermoplastic elastomer SOE "SOE L606" from the company Asahi Kasei; (5) Silica ("Zeosil 1165MP" from Rhodia); (6) coupling agent TESTP ("Si69" from Degussa); (7) Carbon black N234; (8) TDAE oil "Vivatec 500" from Hansen & Rosenthal (9) Paraffinic oil "Extensoil 51 24T" from Repsol, or "Tudalen 1968" from Klaus Dahleke; (10) C5 / C9 Resin "CrayValley Wingtack" from STS; (11) PPE resin 1 Poly (2,6-dimethyl-1,4-phenylene ether) "Noryl SA120" from Sabic, Mn = 2350 g / mol; (12) Resin PPE 2 Poly (2,6-dimethyl-1,4-phenylene ether) "Xyron S202 A" from Sabic, Mn = 19000g / mol; (13) N-1,3-dimethylbutyl-N-phenylparaphenylenediamine ("Santoflex 6-PPD" from Flexsys); (14) DPG = Diphenylguanidine ("Perkacit DPG" from Flexsys); - (15) zinc oxide (industrial grade - Umicore company); (16) stearin ("Pristerene" from Uniquema); (17) N-cyclohexyl-2-benzothiazyl sulfenamide ("Santocure CBS" from Flexsys). [00106] It is possible to note in these compositions the great economy of means, related to the use of TPE elastomers with SBR and PS blocks in the composition of the tread. The performances of the compositions of the invention were then evaluated as to their hysteresis and their thermal resistance. The results are shown in Table 2. Table 2 Composition A-1 A-2 A-3 A-4 A-5 tan (8) max at 40 ° C (base 100) 100 123 386 300 300 Temperature of E ' [00108] The results presented in Table 2 show that the treads of composition A3, A4 and A5 according to the invention allow a significant improvement in hysteresis performance, representative of the resistance performance. rolling. Moreover, it is very surprising in view of the state of the art, that the SBR and PS block TPE and a PPE resin, are sufficient to obtain a tread whose hysteresis performance is so improved, vis-à-vis a conventional diene tread but also vis-à-vis a TPE tread, as described in WO 2012/152686. Moreover, the results also show for the compositions A4 and A5 in particular a significant improvement in the thermal resistance with respect to the composition A3.
    权利要求:
    Claims (21)
    [0001]
    REVENDICATIONS1. A tire comprising a tread, a crown with a crown reinforcement, two sidewalls, two beads, a carcass reinforcement anchored to the two beads and extending from one side to the other, characterized in that the bearing comprises at least one thermoplastic elastomer, said thermoplastic elastomer being a block copolymer comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic type thermoplastic block, and the total content of thermoplastic elastomer being in a range of 65 to 100 phr (parts by weight per hundred parts of elastomer).
    [0002]
    The tire of claim 1, wherein the number average molecular weight of the thermoplastic elastomer is between 30,000 and 500,000 g / mol. 15
    [0003]
    3. A tire according to one of claims 1 or 2 wherein the one or more elastomeric blocks of the block copolymer are chosen from elastomers having a glass transition temperature of less than 25 ° C. 20
    [0004]
    4. A tire according to any one of the preceding claims wherein the SBR elastomeric block or blocks have a styrene content ranging from 10 to 60%.
    [0005]
    A tire according to any one of the preceding claims wherein the SBR elastomeric block (s) have a 1,2-bond content for the butadiene part in a range from 4% to 75% molar, and a -1,4 bonds in a range of 20% and 96 mol%.
    [0006]
    Tire according to any one of the preceding claims wherein the SBR elastomeric block (s) are hydrogenated in such a way that 25 to 100 mol% of the double bonds in the butadiene portion are hydrogenated.
    [0007]
    7. A tire according to claim 6 wherein the SBR elastomer block or blocks are hydrogenated in such a way that a proportion ranging from 50 to 100 mol%, and preferably from 80 to 100 mol% of the double bonds in the butadiene portion are hydrogenated. .
    [0008]
    8. A tire according to any one of the preceding claims wherein the styrenic thermoplastic block (s) of the block copolymer are chosen from polymers having a glass transition temperature greater than 80 ° C., and in the case of a semi-thermoplastic block crystalline, a melting point above 80 ° C.
    [0009]
    A tire according to any one of the preceding claims wherein the styrenic thermoplastic block fraction in the block copolymer is within a range of from 5 to 70%. 15
    [0010]
    10. A tire according to any one of the preceding claims wherein the thermoplastic block (s) of the block copolymer are chosen from polystyrenes.
    [0011]
    Tire according to the preceding claim, in which the thermoplastic block or blocks of the block copolymer are chosen from polystyrenes obtained from styrene monomers chosen from the group consisting of unsubstituted styrene, substituted styrenes and their mixtures.
    [0012]
    Tire according to the preceding claim, in which the thermoplastic block or blocks of the block copolymer are chosen from polystyrenes obtained from styrene monomers chosen from the group consisting of unsubstituted styrene, methylstyrenes and para-tert-butylstyrene. chlorostyrenes, bromostyrenes, fluorostyrenes, para-hydroxy-styrene, and mixtures thereof.
    [0013]
    Tire according to the preceding claim, in which the thermoplastic block or blocks of the block copolymer are chosen from polystyrenes obtained from styrene monomers chosen from the group consisting of unsubstituted styrene, o-methylstyrene and m-methylstyrene. p-methylstyrene, alpha-methylstyrene, alpha-10-30-2-dimethylstyrene, alpha-4-dimethylstyrene, diphenylethylene, para-tert-butylstyrene, o-chlorostyrene, m-chlorostyrene , p-chlorostyrene, 2,4dichlorostyrene, 2,6-dichlorostyrene, 2,4,6-trichlorostyrene, o-bromostyrene, mbromostyrene, p-bromostyrene, 2,4-dibromostyrene, , 6-dibromostyrene, 2,4,6-tribromostyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6-difluorostyrene, 2,4,6-dibromostyrene, trifluorostyrene, para-hydroxy-styrene, and mixtures thereof.
    [0014]
    Tire according to the preceding claim wherein the thermoplastic block (s) of the block copolymer are obtained from unsubstituted polystyrene.
    [0015]
    15. A tire according to any one of the preceding claims, wherein the thermoplastic elastomer or elastomers are the only elastomers in the tread. 15
    [0016]
    The tire of any one of claims 1 to 15, wherein the tread further comprises a thermoplastic resin comprising optionally substituted polyphenylene ether units.
    [0017]
    Tire according to claim 16, 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.degree. at 215 ° C.
    [0018]
    18. The tire according to claim 16, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I): embedded image 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 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 being able to 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 an area ranging from 3 to 300.
    [0019]
    19. The tire according to claim 18, wherein R1 and R2 represent an alkyl group and in particular a methyl group; and R3 and R4 represent hydrogen atoms.
    [0020]
    20. A tire according to one of claims 16 to 19, 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.
    [0021]
    21. A tire according to one of claims 16 to 20, 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.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3099742B1|2020-04-15|Tyre provided with a tread comprising a thermoplastic elastomer
    EP3160759B1|2018-05-23|Tyre provided with a tread comprising a thermoplastic elastomer and a diene elastomer
    EP2895335B1|2018-02-21|Tire provided with a tread including a thermoplastic elastomer and carbon black
    EP2707232B1|2015-10-21|Tyre provided with a tread comprising a thermoplastic elastomer
    EP3310585B1|2019-04-17|Tyre provided with a tread comprising a diene elastomer and thermoplastic elastomer system
    EP3310584B1|2020-03-11|Tyre provided with a tread comprising a diene elastomer, a thermoplastic elastomer and a thermoplastic resin having polyphenylene ether patterns
    EP3541633B1|2020-12-30|Tire comprising a tread comprising a thermoplastic elastomer and a crosslinking system based on one or more peroxides
    EP3390073B1|2020-04-15|Tyre provided with a tread comprising a diene elastomer, a thermoplastic elastomer and a peroxide
    EP3099486B1|2018-01-03|Multilayer laminate for a tyre
    EP3541634B1|2020-12-30|Tire comprising a tread comprising a thermoplastic elastomer and a crosslinking system based on sulfur
    EP3380341B1|2020-08-26|Tyre provided with a tread comprising a thermoplastic elastomer and a diene elastomer
    FR3081874A1|2019-12-06|TIRE PROVIDED WITH AN EXTERNAL SIDING COMPRISING ONE OR MORE THERMOPLASTIC ELASTOMERS AND ONE OR MORE SYNTHETIC DIENE ELASTOMERS
    FR3081875A1|2019-12-06|TIRE PROVIDED WITH AN EXTERNAL SIDING COMPRISING ONE OR MORE THERMOPLASTIC ELASTOMERS AND ONE OR MORE SYNTHETIC DIENE ELASTOMERS
    FR3081877A1|2019-12-06|TIRE PROVIDED WITH AN EXTERNAL SIDING COMPRISING ONE OR MORE THERMOPLASTIC ELASTOMERS AND ONE OR MORE SYNTHETIC DIENE ELASTOMERS
    WO2019229327A2|2019-12-05|Tire having an outer sidewall comprising one or more thermoplastic elastomers and one or more synthetic diene elastomers
    WO2019229326A2|2019-12-05|Tyre provided with an outer sidewall comprising one or more thermoplastic elastomers and one or more synthetic diene elastomers
    WO2019097175A1|2019-05-23|Tyre provided with an outer sidewall comprising a liquid plasticiser having a low glass transition temperature
    FR3056595A1|2018-03-30|TIRE TREAD COMPRISING A THERMOPLASTIC ELASTOMER
    同族专利:
    公开号 | 公开日
    US20160339743A1|2016-11-24|
    EP3099742A1|2016-12-07|
    US10369842B2|2019-08-06|
    CN106414603A|2017-02-15|
    WO2015113966A1|2015-08-06|
    EP3099742B1|2020-04-15|
    FR3016886B1|2016-01-29|
    JP2017507207A|2017-03-16|
    JP6553060B2|2019-07-31|
    CN106414603B|2019-10-01|
    引用文献:
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    WO2012152686A1|2011-05-12|2012-11-15|Compagnie Generale Des Etablissements Michelin|Tyre provided with a tread comprising a thermoplastic elastomer|
    IT1275534B|1995-07-14|1997-08-07|Pirelli|VULCANIZABLE RUBBER MIXTURE FOR TIRES OF VEHICLE TIRES|
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    AT290565T|2000-02-24|2005-03-15|Michelin Soc Tech|VULCANIZABLE RUBBER MIXTURE FOR MANUFACTURING AN AIR RIFE AND AIR TIRE CONTAINING SUCH A COMPOSITION|
    CN1140570C|2000-05-26|2004-03-03|米其林技术公司|Rubber composition for use as tyre running tread|
    JP2002212339A|2001-01-18|2002-07-31|Sumitomo Rubber Ind Ltd|Rubber composition for tire tread and tire using the same|
    US7279532B2|2002-03-01|2007-10-09|Asahi Kasei Chemicals Corporation|Modified hydrogenated copolymer|
    JP4060105B2|2002-03-25|2008-03-12|旭化成ケミカルズ株式会社|Hydrogenated copolymer composition|
    FR2854404B1|2003-04-29|2005-07-01|Michelin Soc Tech|METHOD OF OBTAINING GRAFT ELASTOMER WITH FUNCTIONAL GROUPS ALONG THE CHAIN AND RUBBER COMPOSITIONS|
    JP2010270314A|2009-04-22|2010-12-02|Bridgestone Corp|Rubber composition and tire using the same|
    JP5443820B2|2009-04-30|2014-03-19|株式会社ブリヂストン|Rubber composition and tire using the same|
    JP2010280853A|2009-06-05|2010-12-16|Bridgestone Corp|Rubber composition and pneumatic tire using the same|
    FR2952644B1|2009-11-17|2011-12-30|Michelin Soc Tech|TIRE HAVING TREAD BAND HAVING A THERMOPLASTIC ELASTOMER|
    FR2954333B1|2009-12-23|2012-03-02|Michelin Soc Tech|PNEUMATIC HAVING THE TOP ZONE PROVIDED WITH A SUB-LAYER COMPRISING A THERMOPLASTIC ELASTOMER|
    US8536266B2|2011-12-21|2013-09-17|The Goodyear Tire & Rubber Company|Pneumatic tire|
    FR2995559B1|2012-09-17|2014-09-05|Michelin & Cie|TIRE WITH TREAD COMPRISING A THERMOPLASTIC ELASTOMER AND CARBON BLACK|
    FR3016829B1|2014-01-28|2016-01-29|Michelin & Cie|MULTILAYER LAMINATE FOR PNEUMATIC|
    FR3022912B1|2014-06-30|2016-06-24|Michelin & Cie|TIRE WITH TREAD COMPRISING A THERMOPLASTIC ELASTOMER AND DIENE ELASTOMER|
    FR3037592B1|2015-06-18|2017-06-09|Michelin & Cie|TIRE COMPRISING A TREAD COMPRISING A DIENE ELASTOMER AND A THERMOPLASTIC ELASTOMER SYSTEM|
    FR3037591A1|2015-06-18|2016-12-23|Michelin & Cie|TIRE WITH A TREAD COMPRISING A DIENE ELASTOMER, A THERMOPLASTIC ELASTOMER AND A THERMOPLASTIC RESIN COMPRISING POLYPHENYLENE ETHER PATTERNS|FR3022912B1|2014-06-30|2016-06-24|Michelin & Cie|TIRE WITH TREAD COMPRISING A THERMOPLASTIC ELASTOMER AND DIENE ELASTOMER|
    US10428203B2|2014-09-08|2019-10-01|Sumitomo Rubber Industries, Ltd.|Pneumatic tire|
    FR3037592B1|2015-06-18|2017-06-09|Michelin & Cie|TIRE COMPRISING A TREAD COMPRISING A DIENE ELASTOMER AND A THERMOPLASTIC ELASTOMER SYSTEM|
    FR3037591A1|2015-06-18|2016-12-23|Michelin & Cie|TIRE WITH A TREAD COMPRISING A DIENE ELASTOMER, A THERMOPLASTIC ELASTOMER AND A THERMOPLASTIC RESIN COMPRISING POLYPHENYLENE ETHER PATTERNS|
    FR3045632A1|2015-12-18|2017-06-23|Michelin & Cie|TIRE WITH TREAD COMPRISING DIENE ELASTOMER, THERMOPLASTIC ELASTOMER AND PEROXIDE|
    JP6716942B2|2016-02-18|2020-07-01|住友ゴム工業株式会社|Pneumatic tire and method for manufacturing pneumatic tire|
    JP6972534B2|2016-10-31|2021-11-24|住友ゴム工業株式会社|Polymer for kneading machine input|
    JP6862787B2|2016-11-22|2021-04-21|住友ゴム工業株式会社|Pneumatic tires|
    US10851270B2|2016-12-19|2020-12-01|Eastman Chemical Company|Adhesives comprising polyindane resins|
    US11008444B2|2016-12-19|2021-05-18|Eastman Chemical Company|Tires comprising polyindane resins and uses thereof|
    WO2019139623A1|2018-01-12|2019-07-18|Compagnie Generale Des Etablissements Michelin|Rubber compositions with dissaggregated carbon nanotubes|
    WO2020128332A1|2018-12-21|2020-06-25|Compagnie Generale Des Etablissements Michelin|Tyre provided with an outer sidewall, the composition of which contains a thermoplastic elastomer and a hydrocarbon resin|
    FR3090673A3|2018-12-21|2020-06-26|Michelin & Cie|Tire provided with an external sidewall, the composition of which comprises a thermoplastic elastomer and a hydrocarbon resin|
    法律状态:
    2015-01-22| PLFP| Fee payment|Year of fee payment: 2 |
    2016-01-21| PLFP| Fee payment|Year of fee payment: 3 |
    2017-01-20| PLFP| Fee payment|Year of fee payment: 4 |
    2018-01-19| 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
    FR1450667A|FR3016886B1|2014-01-28|2014-01-28|TIRE COMPRISING A TREAD COMPRISING A THERMOPLASTIC ELASTOMER|FR1450667A| FR3016886B1|2014-01-28|2014-01-28|TIRE COMPRISING A TREAD COMPRISING A THERMOPLASTIC ELASTOMER|
    PCT/EP2015/051588| WO2015113966A1|2014-01-28|2015-01-27|Tyre provided with a tread comprising a thermoplastic elastomer|
    EP15701043.0A| EP3099742B1|2014-01-28|2015-01-27|Tyre provided with a tread comprising a thermoplastic elastomer|
    CN201580005435.8A| CN106414603B|2014-01-28|2015-01-27|It is provided with the tire of the tyre surface comprising thermoplastic elastomer |
    JP2016548640A| JP6553060B2|2014-01-28|2015-01-27|Tire with tread comprising thermoplastic elastomer|
    US15/114,499| US10369842B2|2014-01-28|2015-01-27|Tire provided with a tread comprising a thermoplastic elastomer|
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