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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, characterized in that that the tread comprises a composition based on at least one diene elastomer, at a level of between 35 and 99 phr (parts by weight per hundred parts of elastomer), a thermoplastic elastomer system, at a total between 1 and 65 phr, said thermoplastic elastomer system comprising at least two block copolymers, called polystyrene and poly (butadiene-styrene) block copolymers, each comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic thermoplastic block, one of the two polystyrene and poly (butadiene-styrene) block copolymers being hydrogenated in such a way that that a proportion ranging from 95 to 100 mol% of the double bonds in the butadiene portion are hydrogenated, the latter being said block copolymer polystyrene and poly (butadiene-styrene) substantially hydrogenated.
    公开号:FR3037592A1
    申请号:FR1555571
    申请日:2015-06-18
    公开日:2016-12-23
    发明作者:Christophe Chouvel
    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, as elastomer, diene elastomers.  This type of tread is well known and described in many documents.  In a few documents, it has been described treads comprising a mixture of diene elastomer and thermoplastic elastomer.  For example, the document WO 2012/105984 describes tread compositions comprising a styrene-butadiene copolymer (SBR), a polybutadiene (BR) and an unsaturated thermoplastic styrene elastomer (TPS) and a reinforcing filler to improve the resistance tire wear.  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] A constant objective of tire manufacturers remains to improve a balance of performance that is difficult to reconcile, namely the rolling resistance of tires and their grip on wet surfaces.  [0006] At present, the applicants have found, surprisingly, that a tire provided with a tread comprising a system of specific thermoplastic elastomers 3037592 -2 and a diene elastomer makes it possible to obtain an excellent balance between the resistance to rolling and grip on wet ground.  The invention therefore 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. the other, characterized in that the tread comprises a composition based on at least one diene elastomer, at a level of between 35 and 99 phr (parts by weight per hundred parts of elastomer), and a system of thermoplastic elastomer, at a total content of between 1 and 65 phr, said thermoplastic elastomer system comprising at least two block copolymers, called polystyrene and poly (butadiene-styrene) block copolymers, each comprising at least one elastomer block; an optionally hydrogenated butadiene-styrene random copolymer type and at least one styrenic type thermoplastic block, one of the two polystyrene and poly (butadiene-styrene) block copolymers being hydrogenated such that from 95 to 100 mol% of the double bonds in the butadiene portion are hydrogenated, the latter being said block copolymer polystyrene and poly (butadienethyrene) substantially hydrogenated.  [0008] Preferably, the invention relates to a tire as defined above, in which the diene elastomer content is in a range from 40 to 90 phr and the level of thermoplastic elastomer is included in an area ranging from 10 to 60 phr.  Preferably, the content of diene elastomer is in a range from 50 to 80 phr and the level of thermoplastic elastomer is in a range from 20 to 50 phr.  More preferably, the content of diene elastomer is in a range from 55 to 70 phr and the level of thermoplastic elastomer is in a range from 30 to 45 phr.  Preferably, the invention relates to a tire as defined above, wherein the number-average molecular weight of the polystyrene and poly (butadiene-styrene) block copolymers of between 30,000 and 500,000 g / mol.  Also preferably, the invention relates to a tire as defined above, in which the poly (butadiene-styrene) blocks of the polystyrene and poly (butadiene-styrene) block copolymers are chosen from poly ( butadiene-styrene) having a glass transition temperature of less than 25 ° C.  [0011] Preferably, the invention also relates to a tire as defined above, in which the poly (butadiene-styrene) blocks have a styrene content ranging from 10 to 60%.  Preferably, the poly (butadiene-butyrene) blocks have a 1,2-bond content for the butadiene moiety within a range of from 4% to 75% by mole, and a 1,4-linkage content within a range from 20% and 96% molar.  Preferably, the invention relates to a tire as defined above, wherein the substantially hydrogenated block copolymer is hydrogenated such that a proportion ranging from 96 to 100 mol%, and preferably from 98 to 100 molar. mol% of the double bonds in the butadiene portion are hydrogenated.  [0013] Preferably also, the invention relates to a tire as defined above, wherein the thermoplastic elastomer system further comprises the essentially hydrogenated polystyrene and poly (butadiene-styrene) block copolymer, a block copolymer polystyrene and poly (butadiene-styrene) said partially hydrogenated, hydrogenated such that a proportion ranging from 25 to 95 mol% of the double bonds in the butadiene portion are hydrogenated.  Preferably, the partially hydrogenated polystyrene and poly (butadiene-styrene) block copolymer is hydrogenated in such a way that a proportion ranging from 25 to 80 mol%, and preferably from 40 to 70 mol%, of the double bonds in the butadiene portion are hydrogenated.  [0014] Preferably, the invention also relates to a tire as defined above, in which the thermoplastic elastomer system comprises from 20 to 50 phr, preferably from 25 to 35 phr, of polystyrene and poly block copolymer. (Butadiene-styrene) essentially hydrogenated and from 1 to 15 phr, preferably 3 3037592 -4 to 10 phr, of partially hydrogenated polystyrene and poly (butadiene-styrene) block copolymer.  Preferably, the invention relates to a tire as defined above, in which the styrene thermoplastic block (s) of the polystyrene and poly (butadiene-styrene) block copolymer 5 are chosen from polymers having a temperature of glass transition above 80 ° C, and, in the case of a semi-crystalline thermoplastic block, a melting temperature above 80 ° C.  Preferably, the styrenic thermoplastic block fraction in the polystyrene and poly (butadiene-styrene) block copolymer is within a range of 5 to 70%.  Preferably, the thermoplastic block or blocks of the polystyrene and poly (butadiene-styrene) block copolymer are chosen from polystyrenes, preferably from polystyrenes obtained from styrene monomers chosen from the group consisting of unsubstituted styrene and substituted styrenes. and their mixtures; and more preferably, among the polystyrenes obtained from styrenic monomers selected from the group consisting of unsubstituted styrene, methylstyrenes, para-tert-butylstyrene, chlorostyrenes, bromostyrenes, fluorostyrenes, parahydroxystyrene, and mixtures of these.  Most preferably, the thermoplastic block or blocks of the polystyrene and poly (butadiene-styrene) block copolymer are selected from polystyrenes obtained from styrenic monomers selected from the group consisting of unsubstituted styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha-4-dimethylstyrene, diphenylethylene, para-tert-butylstyrene, o-chlorostyrene, n-methylstyrene, chlorostyrene, p-chlorostyrene, 2,4-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, m-fluorostyrene, 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 polystyrene and poly (butadiene-styrene) block copolymer are obtained from unsubstituted polystyrene.  Preferably, the invention relates to a tire as defined above, wherein the diene elastomer (that is to say the diene elastomer or elastomers) 3037592 -5 is chosen from the group consisting of elastomers. essentially unsaturated dienes, and mixtures thereof.  Preferably, the diene elastomer is chosen from the group consisting of the homopolymers obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms, the copolymers obtained by copolymerization of one or more conjugated dienes with each other or with one or more aromatic vinyl compounds having 8 to 20 carbon atoms, and mixtures thereof.  More preferably, the diene elastomer is selected from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.  Most preferably, the diene elastomer is selected from the group consisting of butadiene and styrene copolymers.  Also preferably, the invention relates to a tire as defined above, wherein the composition of the tread further comprises reinforcing filler at a rate of less than 80 phr, preferably less than 80 phr. 15 60 pce.  Preferably, the level of reinforcing filler is from 3 to 50 phr, preferably from 5 to 40 phr.  Preferably, the reinforcing filler is carbon black and / or silica.  According to a preferred embodiment, the majority reinforcing filler is silica.  Alternatively and preferentially also, the majority reinforcing filler is carbon black.  [0018] According to a preferred embodiment, the invention relates to a tire as defined above, wherein the composition of the tread further comprises a thermoplastic resin based on polyphenylene ether units which are optionally substituted, rate in a range from 1 to 50 phr, preferably from 2 to 40 phr.  Preferentially, the level of said thermoplastic resin based on optionally substituted polyphenylene ether units is in a range from 2 to 30 phr, preferably from 2 to 20 phr.  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 280 ° C., preferably from 5 to 250 ° C.  Also preferably, 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, R 2, R 3 and R 4 represent, independently, each other identical or different groups selected from hydrogen, hydroxy, alkoxy, halogen, amino, alkylamino, dialkylamino groups 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, 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); in a range from 3 to 300.  According to this same preferred embodiment, the invention relates to a tire as defined above, in which R 1 and R 2 represent an alkyl group and in particular a methyl group; and R3 and R4 represent hydrogen atoms.  Also preferably, 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, better from 6 to 20.  Also preferably according to this embodiment, the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising more than 80% by weight, preferably greater than 95% by weight, polyphenylene units of general formula (I) .  Preferably, the invention relates to a tire as defined above, in which the composition of the tread does not comprise or comprises a plasticizer system with a total plasticizer content of less than 20 phr. preferably less than 15 phr.  More preferably, the composition of the tread band does not comprise any plasticizer system other than the optional thermoplastic resin based on polyphenylene ether units, or comprises thereof with a total plasticizer content of less than 10 phr, preferably less than 5 pc.  [0021] Preferably, the invention relates to a tire as defined above, wherein the composition of the tread further comprises a crosslinking system.  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, ie "heavy goods vehicles" - that is to say metro, 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 [0023] In the present description, unless expressly indicated otherwise, all percentages (%) indicated are percentages by weight.  Furthermore, the term "phr" (in English "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 referred to as "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 "3037592 -8 a to b" means the range from a to b (i.e., including strict bounds a and b) .  Finally, when reference is made to a "majority" compound, in the sense of the present invention, it is understood 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 reinforcing filler is the reinforcing filler representing the largest mass relative to the total weight of the reinforcing fillers in the composition.  In contrast, a "minor" compound is a compound that does not represent the largest mass fraction among compounds of the same type.  1.  Tread Composition [0027] 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 15 extending from one side to the other, wherein the tread comprises a composition based on at least one diene elastomer, at a level of between 35 and 99 phr (parts by weight per hundred parts of elastomer ), and a thermoplastic elastomer system, at a total content of between 1 and 65 phr, said thermoplastic elastomer system comprising at least two block copolymers, called polystyrene and poly (butadiene-styrene) block copolymers, each comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic thermoplastic block, one of the two polysty block copolymers and poly (butadiene-styrene) being hydrogenated such that 95 to 100 mol% of the double bonds in the butadiene portion are hydrogenated, the latter being said block copolymer polystyrene and poly (butadiene-styrene) essentially hydrogenated.  1. 1 Thermoplastic elastomer (TPE) specific to SBR and PS blocks [0028] In general, thermoplastic elastomers (abbreviated as "TPE") have an intermediate structure between thermoplastic polymers and elastomers.  This 3037592 -9 are block copolymers, consisting of rigid blocks, thermoplastic, connected by flexible blocks, elastomers.  For the purposes of the invention, said thermoplastic elastomer system comprises at least two block copolymers, called polystyrene block copolymers (denoted "PS") and poly (butadiene-styrene) (denoted "SBR"), each comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic type thermoplastic block, one of the two polystyrene and poly (butadiene-styrene) block copolymers being hydrogenated in such a way that from 95 to 100 mol% of the double bonds in the butadiene portion are hydrogenated, the latter being said essentially hydrogenated polystyrene and poly (butadiene-styrene) block copolymer.  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 more than 80% 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 to say more than 50% by weight, preferably more than 80% by weight) of a styrenic polymer such as polystyrene.  [0030] Unless specifically mentioned in the following, the information given for block TPEs SBR and PS, also known as polystyrene block copolymers (PS) and polybutadiene-styrene copolymers (SBR), are valid for all copolymers with polystyrene and poly (butadiene-styrene) blocks of the thermoplastic elastomer system, that is to say, whatever their level of hydrogenation, they are essentially hydrogenated or partially hydrogenated or even non-hydrogenated.  1. 1. 1.  Structure of the SBR and PS block TPEs [0031] The number-average molecular weight (denoted Mn) of the SBR and PS block TPEs 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 3037592 - 10 - 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 too high mass Mn can be penalizing for the implementation.  Thus, it has been found that a value in the range of 50,000 to 300,000 g / mol and more preferably 60,000 to 150,000 is particularly well suited, especially to the use of SBR and PS block TPE in a tire tread composition.  The number-average molecular weight (Mn) of SBR and PS block TPE elastomers 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 through a 0.45 μm porosity filter 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" ("HMW7", "HIMW6E" and two "HT6E") is used.  The injected volume of the solution of the polymer sample is 100 μl.  The detector is a WATERS 2410 differential refractometer and its associated chromatographic data exploitation software 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.  [0033] The value of the polydispersity index Ip (booster: Ip = Mw / Mn with Mw weight average molecular weight and Mn number-average molecular weight) of SBR and PS block TPEs is preferably less than 3; more preferably less than 2 and even more preferably less than 1.5.  In known manner, 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 portion of SBR and PS block TPEs. , and the highest temperature being relative to the thermoplastic part PS of the block TPE 3037592 SBR and PS.  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 TPEs, it is the Tg relative to the SBR elastomer block.  The SBR and PS block TPEs preferably have 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 higher Tg value than these minima can decrease tread performance when used at very low temperatures; for such use, the Tg of the SBR and PS block TPEs is more preferably less than or equal to -10 ° C.  Also preferentially, the Tg of SBR and PS block TPEs 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, greater than 15,000 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 SBR and PS block TPEs may also comprise a large number of blocks (more than 30, typically from 50 to 500) smaller, in which case these blocks preferably have low masses, for example from 500 to 500. 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.  In a first variant, the block TPE SBR and PS is in a linear form.  For example, the SBR and PS block TPE is a diblock copolymer: block PS / block SBR.  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 block TPE SBR and PS multiblock can be a linear sequence of 5 SBR elastomer blocks - PS thermoplastic blocks.  According to another variant of the invention, the block SBR and PS TPE useful for the purposes of the invention is in a star shape 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 elastomer block SBR.  The number of branches of the central elastomer can 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 or dendrimer SBR elastomer block and a PS thermoplastic block, located at the end of the branches of the dendrimer elastomeric block.  1. 1. 2.  Nature of the Elastomeric Blocks The SBR and PS block TPE elastomer blocks for the purposes of the invention may be all random copolymer elastomers of butadiene and styrene (SBR) known to the man of the invention. art.  The SBR elastomer block fraction in the SBR and PS block TPE is in a range from 30 to 95%, preferably 40 to 92%, more preferably 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 lower than -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-linkage 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. 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 can decrease to a content of 0 mol% for a completely hydrogenated SBR block.  According to the invention, the thermoplastic elastomer system comprises at least one essentially hydrogenated polystyrene and poly (butadiene-styrene) block copolymer, that is to say hydrogenated in such a way that a proportion ranging from 95 to 100 mol% of the double bonds in the butadiene portion are hydrogenated.  The determination of the degree of hydrogenation is carried out by NMR analysis.  The spectra are acquired on a BRUKER 500 MHz Avance spectrometer equipped with a 1H-X 5 mm Cryoprobe.  The quantitative 1E1 NMR experiment uses a 30 ° single pulse sequence and a 5 second repetition time between each acquisition.  64 accumulations are made.  The samples (about 25mg) are solubilized in CS2 about 1mL, 1041 of deuterated cyclohexane are added to make the lock during acquisition.  The chemical shifts are calibrated with respect to the protonated impurity of CS2 ppm 1E1 to 7. 18 ppm referenced on the TMS Oppm 1E1 to 25 Oppm).  The 1 H NMR spectrum makes it possible to quantify the microstructure by integrating the signal mass characteristic of the various units: styrene originating from SBR and polystyrene blocks.  It is quantifiable in the aromatics zone between 6, Oppm and 7.3ppm for 5 protons (by removing the integral of the CS2 impurity signal at 7.18ppm).  3037592 - 14 - - The PB1-2 from the SBR.  It is quantifiable in the ethylenic zone between 4.6ppm and 5.1ppm for 2 protons.  - PB1-4 from the SBR.  It is quantifiable in the ethylenic zone between 5.1 ppm and 6.1 ppm for 2 protons and removing 1 proton from the PB1-2 motif.  5 - The hydrogenated PB1-2 from the hydrogenation and having only aliphatic protons.  The CH3 during hydrogenated PB1-2 have been identified and are quantifiable in the aliphatic zone between 0.4 and 0.8 ppm for 3 protons.  - The hydrogenated PB1-4 from the hydrogenation and having only aliphatic protons.  It will be deduced by subtracting the aliphatic protons from the different 1 () patterns by considering it for 8 protons.  The quantification of the microstructure can be carried out in molar% as follows:% molar of a unit = Integral 1H of a pattern // (integrals 1H of each pattern).  For example, for a styrene unit: styrene% molar = (Integral 1H of styrene) / (Integral 1H of styrene + Integral 1H of PB1-2 + Integral 1H of PB1-4 + Integral 1H of hydrogenated PB1-2 + Integral 1H hydrogenated PB1-4).  Preferably, the substantially hydrogenated block copolymer is hydrogenated in such a way that a proportion ranging from 96 to 100 mol%, and preferably from 98 to 100 mol% of the double bonds in the butadiene portion are hydrogenated.  According to a preferred embodiment, the thermoplastic elastomer system 20 comprises, in addition to the essentially hydrogenated polystyrene and poly (butadiene-styrene) block copolymer, a polystyrene and poly (butadiene-styrene) block copolymer said to be partially hydrogenated, hydrogenated to such a degree. in that a proportion ranging from 25 to 95 mol% of the double bonds in the butadiene portion are hydrogenated.  Preferably, the partially hydrogenated polystyrene and poly (butadiene-styrene) block copolymer is hydrogenated such that a proportion ranging from 25 to 80 mol%, and preferably from 40 to 70 mol%, of the double bonds in the butadiene portion. are hydrogenated.  Within the meaning of the present invention, the styrenic part of the SBR blocks can be composed of monomers chosen from styrene monomers, and especially chosen from the group consisting of unsubstituted styrene, substituted styrenes and their derivatives. mixtures.  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) are preferably chosen. , alpha-4-dimethyl styrene and diphenylethylene), para-tert-butylstyrene, chlorostyrenes (preferentially ochlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6 Dichlorostyrene and 2,4,6-trichlorostyrene), bromostyrenes (preferentially o-bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene and the like). , 4,6-tribromostyrene), fluorostyrenes (preferably ofluorostyrene, 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.sup.2. mol, preferably 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 tread tire.  The elastomeric block may also consist of several elastomeric blocks as defined above.  1. 1. 3.  Nature of Thermoplastic Blocks The thermoplastic block definition will be used to describe the glass transition temperature (Tg) characteristic 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 higher than the Tg.  In the specific case of a semi-crystalline polymer (or a polymer block), a melting point can be observed, then greater than the glass transition temperature.  In this case, it is rather the melting temperature (Tf) that makes it possible to choose the temperature of use 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 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 PS thermoplastic block fraction in SBR and PS block TPE is in a range from 5 to 70%, preferably 8 to 60%, more preferably 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 and 2,4,6-trichlorostyrene), bromostyrenes (preferentially obromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene and 2,4 6-tribromostyrene), the fluorostyrenes (preferentially o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6-difluorostyrene and 2,4,6-difluorostyrene). trifluorostyrene), para-hydroxy-styrene, 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) such that 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 the SBR and PS block TPE have good elastomeric properties and sufficient mechanical strength and compatibility with the use of tire treads.  The thermoplastic block may also consist of several thermoplastic blocks as defined above.  1. 1. 4.  Examples of SBR and PS block TPEs [0064] 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 S1611". "," SOE L605 "or" SOE L606 ".  Among them, for example, the SOE "SOE L606" from Asahi Kasei is classified as essentially hydrogenated with 0.6% of polybutadiene, 49.7% of hydrogenated polybutadiene (that is to say 98%), 8% hydrogenation), and 49.7% styrene.  For example, the SOE "SOE 51611" from Asahi Kasei is classified as partially hydrogenated with 19.7% of polybutadiene and 18.6% of hydrogenated polybutadiene (ie 48.5% of hydrogenation). ), and 61.7% styrene.  1. 1. 5.  Quantity of SBR and PS Block TPE [0067] In the tread composition of the tire of the invention, the TPE elastomer (ie the TPE elastomer or elastomers) with SBR and PS blocks represents between 1 and 65%, preferably from 10 to 60% by weight, more preferably from 20 to 50% and most preferably from 30 to 45% by weight of all the elastomers present in the elastomer composition.  1 () [0068] Thus, the amount of block TPE elastomer SBR and PS is in a range that varies between 1 and 65 phr, preferably from 10 to 60 phr, better still from 20 to 50 phr, and in particular from 30 to 50 phr. 45 pce.  Indeed, with an amount of TPE elastomer with SBR and PS blocks of less than 1 phr, the effect on the reduction in rolling resistance is noticeable, whereas beyond 65 phr of TPE elastomer with SBR blocks and PS, the composition takes a thermoplastic nature resulting in a very strong evolution of properties with temperature.  Preferably, the thermoplastic elastomer system comprises from 20 to 50 phr, preferably from 25 to 35, of essentially hydrogenated polystyrene and poly (butadiene-styrene) block copolymer and from 1 to 15 phr, preferably from 3 to 25 phr. 20 to 10 phr of partially hydrogenated polystyrene and poly (butadiene-styrene) block copolymer.  1. Diene Elastomer [0070] The composition of the tread according to the invention comprises at least one (that is to say one or more) diene rubber.  The total diene elastomer content is between 35 and 99 phr, preferably in a range of from 40 to 90 phr, preferably from 50 to 80 phr, more preferably from 55 to 70 phr.  By elastomer or "diene" rubber, must be understood in a known manner (one means one or more) elastomer derived at least in part (i. e.  ; a homopolymer or a copolymer) of monomers dienes (monomers carrying two double carbon carbon bonds, conjugated or not).  These diene elastomers can be classified in two categories: "essentially unsaturated" or "essentially saturated".  In general, the term "essentially unsaturated" means a diene elastomer derived at least in part from conjugated diene monomers, having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (%). in 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 diene origin ratio (conjugated dienes) of greater than 50%.  Thus diene elastomers such as certain butyl rubbers or copolymers of dienes and alpha olefins EPDM type can be qualified as "substantially saturated" diene elastomers (low or very low diene origin ratio). low, always less than 15%).  As these definitions are given, the term "diene elastomer", in any of the above categories, may be used more particularly and may be used in the compositions according to the invention: (a) - any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms; (B) - any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinyl aromatic compounds having 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.  As conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5 alkyl) -1,3-butadienes, such as 2,3-Dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3 are used. isopropyl-1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.  Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, 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 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 polyether groups (as described for example in EP 1 127 909 or US 6 3037592 - 21 - 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 [0079] The elastomers 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 thermoplastic resin based on optionally substituted polyphenylene ether units (abbreviated as "EPP 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.  The PPE resin that can be used according to 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 280 ° C., preferably from 5 to 250. ° C and more preferably from 5 to 220 ° C.  Below 0 ° C, the PPE resin does not allow a sufficient shift of Tg in the composition comprising it and above 280 ° C, one can meet manufacturing problems including to obtain a homogeneous mixture.  [0081] Preferably, the PPE resin is a compound comprising predominantly polyphenylene units of general formula (I): (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; 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 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.  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, alkyl groups; linear, 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 with hydroxy, alkoxy groups; amino, alkylamino, dialkylamino, or halogen.  Aryl groups comprising from 6 to 18 carbon atoms (preferably from 6 to 12), optionally substituted by hydroxy, alkoxy, amino, alkylamino, dialkylamino, alkyl or halogen groups.  More preferably, R 1, R 2, R 3 and R 4 represent independently of each other identical or different groups chosen from: - hydrogen - hydroxy, alkoxy groups containing from 1 to 6 carbon atoms, halogen, amino , alkylamino having from 1 to 6 carbon atoms, dialkylamino containing 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 hydroxy, alkoxy groups having 1 to 6 carbon atoms, amino, alkylamino having 1 to 6 carbon atoms, dialkylamino having 2 to 12 carbon atoms, or halogen aryl groups comprising from 6 to 18 carbon atoms (preferably from 6 to 12), optionally substituted by hydroxy, alkoxy groups containing from 1 to 6 atoms, amin; o, alkylamino having 1 to 6 atoms, dialkylamino having 2 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 3 to 50, more preferably 5 to 30, preferably 6 to 20.  Preferably, the EPP resin is a compound comprising more than 80% by weight, and more preferably still greater than 95% by weight, polyphenylene units of general formula (I).  [0087] 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 S202" from the company Asahi Kasei.  In a known manner, the PPE resins have variable number average molecular weights (Mn) in particular of approximately 1000 to 45000 g / mol, most often from 15000 to 45000 g / mol, the Mn being measured in a controlled 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, for the composition of the invention, preference is given to a PPE resin having a mass Mn within a range of from 10,000 to 45,000 g / mol, preferably from 15,000 to 40,000 g / mol, and more preferably from 25,000. at 40000 g / mol.  Preferably, the value of the polydispersity index Ip (recall: Ip = Mw / Mn with Mw weight average molecular weight and Mn average molecular weight) of the EPP resin is less than or equal to 5, plus 3037592 Preferably less than or equal to 3 and more preferably still less than or equal to 2.  When present in the composition, the level of PPE resin in the composition is preferably in a range from 1 to 50 phr, more preferably from 2 to 40 phr, more preferably from 2 to 30 phr. and very preferably from 2 to 20 phr.  1. 4.  Nanometric or reinforcing charge [0091] The elastomers 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 cutting of these two types of filler, especially a blend of carbon black and silica.  Preferentially for the purposes of the invention, the majority reinforcing filler may be silica, or alternatively carbon black.  As carbon blacks are suitable all carbon blacks conventionally used in tires (so-called pneumatic grade black).  For example, the reinforcing carbon blacks of the series 100, 200 or 300 (ASTM grades), for example blacks N115, N134, N234, N326, N330, N339, N347 or N375, or even targeted applications, blacks of higher series (for example N660, N683, N772), or even N990.  By "reinforcing inorganic filler" is meant in the present 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 pneumatic manufacture, in other words able to replace, in its reinforcing function, a conventional carbon black of pneumatic grade, such a charge 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 found 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 hereinafter.  As reinforcing inorganic fillers are particularly 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 pyrogenic silica having a BET surface and a CTAB specific surface area 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 the Degussa company, the "Zeosil" 1165MP, 1135MP and 1115MP silicas of the Rhodia company. "Hi-Sil" silica EZ150G from PPG, "Zeopol" 8715, 8745 and 8755 silicas from Huber, high surface area silicas as described in WO 03/16837.  To couple the reinforcing inorganic filler to the elastomer, it is possible, for example, to use, in a known manner, at least one bifunctional coupling agent (or bonding agent) intended to ensure a sufficient connection, of a chemical and / or physical nature. 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 within a range of 0 to 20%, which corresponds to a level of 0 to 50%. pce for a plasticizer-free composition.  Preferably the composition comprises less than 80 phr of reinforcing filler (in particular between 1 and 80 phr), preferably less than 60 phr (in particular between 1 and 60 phr), more preferably a content ranging from 3 to 50 phr, better from 5 to 40 pce.  5 1. 5.  Plasticizers [0099] The elastomers described above are sufficient on their own for the tread according to the invention to be usable.  [0099] Thus, according to a preferred embodiment of the invention, the elastomer composition described above does not comprise any plasticizer of the oil or thermoplastic resin type other than a possible PPE resin, or, if it comprises any, it comprises less than 20 phr (in particular between 0.5 and 20 phr), preferably less than 15 phr (especially between 0.5 and 15 phr), more preferably less than 10 phr (especially between 0.5 and 10 phr). ), better, less than 5 phr (especially between 0.5 and 5 phr).  Also preferentially, the composition does not comprise any plasticizer other than a possible PPE resin.  In a manner known to those skilled in the art, the term plasticizing agent is 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 into the tread. pneumatic by a lowering of the module and an increase in the tackifying power.  [00101] Any oil, preferably of weakly polar nature, capable of extending, plasticizing elastomers, especially 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 especially 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 the following exemplary embodiments, adjust the amount of plasticizer according to the SBR and PS block TPE elastomer 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.  1. 6.  Various additives [00103] The thermoplastic elastomers 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 elastomeric composition described above may also include the various additives usually present in the bearing strips 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.  [00105] Also and optionally, the composition of the tread of the invention may contain a crosslinking system known to those skilled in the art, such as a vulcanization system comprising sulfur or a donor agent. sulfur, and optionally, one or more accelerators and / or vulcanization activators.  2.  Preparation [00106] The tread compositions for the tire according to the invention are manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomixing. mechanical (sometimes referred to as "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 (sometimes referred to as a "productive" phase) at a lower temperature, typically less than 110 ° C, for example between 60 ° C and 100 ° C, finishing phase during which the crosslinking or vulcanization system is incorporated ; such phases have been described for example in the applications EP-A-0501227, EP-A-0735088, EP-A0810258, W000 / 05300 or W000 / 05301.  The SBR and PS block TPE elastomers are introduced in the first step, directly in their commercial form, for example in the form of beads or granules.  The tread for the tire according to the invention is then extruded in a conventional manner, in order to produce the profile.  The tread is then carved into the tire baking mold.  [00108] This tread may be mounted on a tire in a conventional manner, said tire comprising in addition to the tread according to the invention, a top, two flanks and two beads, a carcass reinforcement anchored to the two beads. , and a crown frame.
    [0002] EXAMPLES OF CARRYING OUT THE INVENTION [00109] Tire tread compositions according to the invention have been prepared as indicated above. Tests performed in the laboratory on the compositions - Dynamic properties [00110] The dynamic properties G * and tan (8) max are measured on a viscoanalyzer (Metravib V A4000), according to the ASTM D 5992 - 96 standard. a sample of vulcanized composition (cylindrical test specimen 4 mm thick and 400 mm 2 in section) subjected to a sinusoidal stress in alternating single shear, at the frequency of 10 Hz, according to ASTM D 1349-99, 20 to a temperature of 40 ° C. A peak to peak deformation amplitude sweep of 0.1 to 50% (forward cycle) is performed, followed by 50% to 1% (return cycle). The results exploited are the complex dynamic shear modulus (G *) and the loss factor (tan Ô). For the return cycle, the maximum value of tan b observed (tan (8) max), as well as the complex modulus difference (DG *) between the values at 0.1% and at 50% deformation are indicated ( Payne effect). For the value of tan (8) max at 40 ° C, the lower the value, the lower the composition will have a low hysteresis and therefore a low rolling resistance. For more readability the results will be indicated according to the performance, in base 100, the value 100 being attributed to the witness. A result lower than 100 indicating a decrease in the rolling resistance performance (increase in the value of tan (5) max at 40 ° C), and conversely, a result greater than 100, will indicate an increase of the performance (decrease the value of tan (8) max at 40 ° C). Dynamic Coefficient of Friction Dynamic friction coefficient measurements were carried out according to a method identical to that described by L. Busse, A. Le Gal, and M. Küppel (Modeling of Dry and Wet Friction Silica Filled Elastomers). on Self-Affine Road Surfaces, 10 Elastomer Friction, 2010, 51, 8). The test pieces are made by molding followed by vulcanization of a square test specimen (50mm × 50mm) 6 mm thick. After closing the mold, it is placed in a hot plate press at 150 ° C for 50 minutes at a pressure of 16 bar. The soil used to carry out these measurements is a core sampled on a road pavement made of bituminous concrete type BBTM (standard NF P 98-137). To avoid dewetting phenomena and the appearance of parasitic adhesion forces between the soil and the material, the soil + specimen system is immersed in a 5% aqueous solution of a surfactant (Sinnozon - CAS number: 25155-30-0). The temperature of the aqueous solution is regulated using a thermostatic bath. The specimen is slidably translated in parallel with the plane of the ground. The sliding speed Vg is set at 0.03 m / sec. The normal applied stress sn is 100 kPa. These conditions are described below as "wet soil conditions". The tangential stress opposite to the motion of the test piece on the floor is continuously measured. The ratio between the tangential stress st and the normal stress sn gives the coefficient of dynamic friction p. The values indicated in the table below are the values of dynamic coefficient of friction, obtained in steady state after stabilization of the value of tangential stress st. For more readability the results will be indicated according to the performance, in base 100, the value 100 being attributed to the witness. A score below 100 indicating a decrease in wet grip performance, and conversely a result greater than 100, will indicate an increase in wet grip performance. EXAMPLES [00114] Tire tread compositions according to the invention (A2, A3 and A4) were prepared as indicated above and compared to two control compositions: a common tire tread composition (A0) and a non-blended thermoplastic elastomer composition with SBR and PS (A1) blocks. The compositions of these treads are presented in Table 1 below.
    [0003] Table 1 Composition A-0 A-1 A-2 A-3 A-4 BR (1) 15 0 0 0 0 SBR (2) 85 60 60 60 60 TPE Elastomer (3) 0 40 35 30 35 TPE elastomer ( 4) 0 0 5 10 5 PPE resin (5) 0 0 0 0 5 Carbon black (6) 5 5 5 5 Silica (7) 70 26 26 26 26 Coupling agent (8) 6 2 2 2 2 Oil ( 9) 2 0 0 0 0 Resin (10) 15 0 0 0 0 Anti-ozone wax 1,5 1,5 1,5 1,5 1,5 Antioxidant (11) 2 2 2 2 2 DPG (12) ) 1.3 0.5 0.5 0.5 0.5 ZnO (13) 0.5 0.5 0.5 0.5 0.5 Stearic acid (14) 2 2 2 2 2 CBS (15) 1 , 7 1.7 1.7 1.7 1.7 Sulfur 1 1 1 1 1 (1) BR with 4% 1,2- and 93% 1,4-cis unit (Tg = -106 ° C) ; (2) SSBR solution (expressed as dry SBR: 41% styrene, 24% polybutadiene units 1-2 and 50% polybutadiene units 1-4 trans (Tg = -25 ° C); (3) SOE L606 essentially hydrogenated SOE thermoplastic elastomer from Asahi Kasei with 0.6% polybutadiene, 49.7% hydrogenated polybutadiene (98.8% hydrogenation), 49.7% styrene, (4) thermoplastic elastomer SOE SOE S1611 "from Asahi Kasei Company with 19.7% polybutadiene, 18.6% hydrogenated polybutadiene (48.5% hydrogenation), 61.7% styrene, 3037592 -31- (5) EPP resin: Poly ( 2,6-dimethyl-1,4-phenylene ether) "Xyron S202 A" from Asahi Kasei, Mn = 37000g / mol, Tg = 215 ° C (6) Carbon black N234, (7) Silica (" Zeosil 1165MP "from Rhodia); 5 (8) coupling agent TESTP (" Si69 "from Degussa); (9) MES oil" Catenex SNR "from Shell; (10) C5 / C9 resin" CrayValley Wingtack "of the company STS; (11) N-1 3-dimethylbutyl-N-phenylparaphenylenediamine ("Santoflex 6-PPD" from Flexsys); (12) DPG = Diphenylguanidine ("Perkacit DPG" from Flexsys); (13) zinc oxide (industrial grade - Umicore company); (14) stearin ("Pristerene" from Uniquema); (15) N-cyclohexyl-2-benzothiazyl sulfenamide ("Santocure CBS" from Flexsys). [00115] It may be noted in these compositions the possibility of lowering the level of reinforcing filler and plasticizer vis-à-vis the control composition, through the use of SBR and PS block TPE elastomers in blending with the diene elastomer in the composition of the tread. The performance of the invention was evaluated in the laboratory, and the results are shown in Table 2 below. Table 2 Composition A-0 A-1 A-2 A-3 A-4 Hysteresis performance (base 100) 52 100 96 90 93 Adhesion performance on dry ground (base 100) 112 100 116 119 119 Average performance hysteresis and adhesion 82 The results presented in Table 2 show that the compositions according to the invention make it possible to replace a portion of the diene elastomer with a SBR and PS block TPE, and that by a blending of two SBR and PS block TPEs, one of which is essentially hydrogenated, can achieve a noticeable improvement in the balance of performance (A2 to A4) that can be expected in rolling resistance and wet braking. Moreover, it is very surprising in view of the state of the art, that SBR and PS block TPE in blending with a diene elastomer, make it possible to significantly reduce the amount of filler and plasticizer in the composition of the strip. of rotation, thus allowing economy of means and ease of implementation.
    权利要求:
    Claims (37)
    [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 a composition based on at least: - a diene elastomer, at a level of between 35 and 99 phr (parts by weight per hundred parts of elastomer), 10 - a thermoplastic elastomer system, at a total rate between 1 and 65 phr, said thermoplastic elastomer system comprising at least two block copolymers, called polystyrene and poly (butadiene-styrene) block copolymers, each comprising: at least one elastomeric block of random butadiene-styrene chemical copolymer type, optionally hydrogenated, and At least one thermoplastic block of styrenic type, one of the two polystyrene and poly (butadiene-styrene) block copolymers being hydrogenated in such a way that a pro portion ranging from 95 to 100 mol% of the double bonds in the butadiene portion are hydrogenated, the latter being said block copolymer polystyrene and poly (butadiene-styrene) substantially hydrogenated. 20
    [0002]
    2. A tire according to claim 1, wherein the content of diene elastomer is in a range from 40 to 90 phr and the level of thermoplastic elastomer is in a range from 10 to 60 phr. 25
    [0003]
    3. A tire according to claim 2, wherein the content of diene elastomer is in a range from 50 to 80 phr and the level of thermoplastic elastomer is in a range from 20 to 50 phr.
    [0004]
    4. The tire according to claim 3, wherein the content of diene elastomer is in a range from 55 to 70 phr and the total content of thermoplastic elastomer is in a range from 30 to 45 phr. 3037592 - 33 -
    [0005]
    A tire according to any one of the preceding claims, wherein the number average molecular weight of the polystyrene and poly (butadiene-styrene) block copolymers is between 30,000 and 500,000 g / mol.
    [0006]
    A tire according to any preceding claim, wherein the poly (butadiene-styrene) blocks of the polystyrene and poly (butadiene-styrene) block copolymers are selected from poly (butadiene-styrene) having a glass transition temperature of less than 25 ° C.
    [0007]
    A tire according to any one of the preceding claims wherein the polybutadiene-styrene blocks have a styrene content within a range of from 10 to 60%.
    [0008]
    A tire according to any one of the preceding claims wherein the poly (butadiene-styrene) blocks have a 1,2-bond content for the butadiene part in a range of from 4% to 75% by mole, and a -1,4-linkage content in a range from 20% to 96% molar.
    [0009]
    A tire according to any one of the preceding claims, wherein the substantially hydrogenated block copolymer is hydrogenated such that a proportion of from 96 to 100 mol%, and preferably from 98 to 100 mol% of the double bonds in the butadiene portion is hydrogenated.
    [0010]
    A tire according to any one of the preceding claims wherein the thermoplastic elastomer system further comprises a substantially hydrogenated polystyrene and poly (butadiene-styrene) block copolymer, a polystyrene and poly (butadiene-styrene) block copolymer. said partially hydrogenated, hydrogenated such that a proportion ranging from 25 to 95 mol% of the double bonds in the butadiene portion are hydrogenated. 30
    [0011]
    The tire of claim 10 wherein the partially hydrogenated polystyrene and poly (butadiene-styrene) block copolymer is hydrogenated such that a proportion of 25 to 80 mol%, and preferably 40 to 70 mol% of the double bonds in the butadiene portion are hydrogenated.
    [0012]
    A tire according to any one of claims 10 or 11 wherein the thermoplastic elastomer system comprises from 20 to 50 phr, preferably from 25 to 35 phr, of polystyrene and poly (butadiene-styrene) block copolymer essentially hydrogenated and 1 to 15 phr, preferably 3 to 10 phr, of partially hydrogenated polystyrene and poly (butadiene-styrene) block copolymer. 10
    [0013]
    Tire according to any one of the preceding claims, in which the styrene thermoplastic block or blocks of the polystyrene and poly (butadiene-styrene) 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 temperature of greater than 80 ° C.
    [0014]
    A tire according to any one of the preceding claims wherein the styrenic thermoplastic block fraction in the polystyrene and poly (butadiene-styrene) block copolymer is within a range of 5 to 70%.
    [0015]
    15. A tire according to any one of the preceding claims wherein the thermoplastic block (s) of the polystyrene and poly (butadiene-styrene) block copolymer are chosen from polystyrenes.
    [0016]
    Tire according to the preceding claim wherein the thermoplastic block (s) of the polystyrene and poly (butadiene-styrene) block copolymer are selected from polystyrenes obtained from styrenic monomers selected from the group consisting of unsubstituted styrene, substituted styrenes and mixtures thereof
    [0017]
    Tire according to the preceding claim, in which the thermoplastic block (s) of the polystyrene and poly (butadiene-styrene) block copolymer are chosen from polystyrenes obtained from styrene monomers chosen from the group consisting of unsubstituted styrene, methylstyrenes, para-tert-butylstyrene, chlorostyrenes, bromostyrenes, fluorostyrenes, para-hydroxystyrene, and mixtures thereof.
    [0018]
    Tire according to the preceding claim wherein the thermoplastic block (s) of the polystyrene and poly (butadiene-styrene) block copolymer are chosen from polystyrenes obtained from styrene monomers chosen from the group consisting of unsubstituted styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha-4-dimethylstyrene, diphenylethylene, para-tert-butylstyrene, o chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 2,4,6-trichlorostyrene, o-bromostyrene, m-bromostyrene, p-chlorostyrene, 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. 15
    [0019]
    Tire according to the preceding claim wherein the thermoplastic block or blocks of the polystyrene and poly (butadiene-styrene) block copolymer are obtained from unsubstituted polystyrene. 20
    [0020]
    20. A tire according to any one of the preceding claims, wherein the diene elastomer is selected from the group consisting of essentially unsaturated diene elastomers, and mixtures of these elastomers.
    [0021]
    21. Tire according to the preceding claim, wherein the diene elastomer is selected from the group consisting of homopolymers obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms, the copolymers obtained by copolymerization of one or several dienes conjugated with one another or with one or more vinyl aromatic compounds having 8 to 20 carbon atoms, and mixtures thereof.
    [0022]
    Tire according to the preceding claim, wherein the diene elastomer is selected from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and blends. of these elastomers.
    [0023]
    23. A tire according to any one of the preceding claims, wherein the composition of the tread further comprises reinforcing filler, at a rate of less than 80 phr, preferably less than 60 phr.
    [0024]
    24. A tire according to the preceding claim, wherein the reinforcing filler content is 3 to 50 phr, preferably 5 to 40 phr. 10
    [0025]
    25. A tire according to any one of claims 23 or 24, wherein the reinforcing filler is carbon black and / or silica.
    [0026]
    Tire according to any one of claims 23 to 25, wherein the majority reinforcing filler is silica.
    [0027]
    27. The tire according to any one of claims 23 to 25, wherein the majority reinforcing filler is carbon black. 20
    [0028]
    28. A tire according to any one of the preceding claims, in which the composition of the tread further comprises a thermoplastic resin based on polyphenylene ether units which are optionally substituted, at a level ranging from 1 to 50 phr, preferably from 2 to 40 phr. 25
    [0029]
    29. A tire according to claim 28, wherein the level of said thermoplastic resin based on optionally substituted polyphenylene ether units is in a range from 2 to 30 phr, preferably from 2 to 20 phr.
    [0030]
    A tire according to any of claims 28 or 29, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units has a glass transition temperature (Tg) as measured by DSC according to ASTM standard 3037592 -37-D3418. from 1999, in a range from 0 to 280 ° C, preferably from 5 to 250 ° C.
    [0031]
    31. A tire according to any one of claims 28 to 30, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I): R4 (I) in which: R1, R2, R3 and R4 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 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 inclusive in a range from 3 to 300.
    [0032]
    32. The tire according to claim 31, wherein R1 and R2 represent an alkyl group and in particular a methyl group; and R3 and R4 represent hydrogen atoms.
    [0033]
    Tire according to any one of claims 31 or 32, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I) wherein n is an integer included in a range from 3 to 50, preferably from 5 to 30, more preferably from 6 to 20. 3037592 -38-
    [0034]
    Tire according to any one of claims 31 to 33, wherein the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising more than 80% by weight, preferably greater than 95% by weight, 5 polyphenylene units of general formula (I).
    [0035]
    A tire according to any one of the preceding claims, wherein the tread composition does not comprise a plasticizer system other than the optional thermoplastic resin based on polyphenylene ether units, or comprises thereof with a total plasticizer less than 20 phr, preferably less than 15 phr.
    [0036]
    36. A tire according to the preceding claim, wherein the composition of the tread does not comprise or comprises a plasticizer system with a total plasticizer content of less than 10 phr, preferably less than 5 phr. 15
    [0037]
    37. Tire according to the preceding claim, wherein the composition of the tread further comprises a crosslinking system.
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    FR3081875A1|2019-12-06|TIRE PROVIDED WITH AN EXTERNAL SIDING COMPRISING ONE OR MORE THERMOPLASTIC ELASTOMERS AND ONE OR MORE SYNTHETIC DIENE ELASTOMERS
    FR3081873A1|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
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    同族专利:
    公开号 | 公开日
    FR3037592B1|2017-06-09|
    CN107709039B|2019-10-25|
    WO2016202646A1|2016-12-22|
    US20180178584A1|2018-06-28|
    EP3310585B1|2019-04-17|
    EP3310585A1|2018-04-25|
    US10780740B2|2020-09-22|
    JP2018519384A|2018-07-19|
    CN107709039A|2018-02-16|
    JP6866312B2|2021-04-28|
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    法律状态:
    2016-06-27| PLFP| Fee payment|Year of fee payment: 2 |
    2016-12-23| PLSC| Publication of the preliminary search report|Effective date: 20161223 |
    2017-06-21| PLFP| Fee payment|Year of fee payment: 3 |
    2018-06-26| PLFP| Fee payment|Year of fee payment: 4 |
    2020-03-13| ST| Notification of lapse|Effective date: 20200206 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1555571A|FR3037592B1|2015-06-18|2015-06-18|TIRE COMPRISING A TREAD COMPRISING A DIENE ELASTOMER AND A THERMOPLASTIC ELASTOMER SYSTEM|FR1555571A| FR3037592B1|2015-06-18|2015-06-18|TIRE COMPRISING A TREAD COMPRISING A DIENE ELASTOMER AND A THERMOPLASTIC ELASTOMER SYSTEM|
    CN201680035711.XA| CN107709039B|2015-06-18|2016-06-07|It is provided with the tire of the tyre surface comprising diene elastomer and thermoplastic elastomer system|
    JP2017565735A| JP6866312B2|2015-06-18|2016-06-07|Tires with treads containing diene elastomers and thermoplastic elastomers|
    US15/737,537| US10780740B2|2015-06-18|2016-06-07|Tire provided with a tread comprising a diene elastomer and thermoplastic elastomer system|
    EP16730297.5A| EP3310585B1|2015-06-18|2016-06-07|Tyre provided with a tread comprising a diene elastomer and thermoplastic elastomer system|
    PCT/EP2016/062911| WO2016202646A1|2015-06-18|2016-06-07|Tyre provided with a tread comprising a diene elastomer and thermoplastic elastomer system|
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