Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C1/0016—Compositions of the tread
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/06—Copolymers with styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

• a tire having a tread comprising a diene elastomer, a thermoplastic elastomer and a thermoplastic resin comprising polyphenylene ether units
• the present invention relates to tires provided with a tread.
• the tread comprises, as elastomer, diene elastomers. This type of tread is well known and described in many documents.
• treads comprising a mixture of diene elastomer and thermoplastic elastomer.
• WO 2010/105984 discloses 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 strength tire wear.
• SBR styrene-butadiene copolymer
• BR polybutadiene
• TPS unsaturated thermoplastic styrene elastomer
• 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).
• SIS styrene-isoprene-styrene triblock copolymer
• a tire provided with a tread comprising a specific thermoplastic elastomer, a diene elastomer and a specific thermoplastic resin makes it possible to obtain an excellent balance between rolling resistance. and wet grip.
• the invention therefore relates to a tire comprising a tread, a crown with a crown reinforcement, two flanks, two beads, a carcass reinforcement anchored to the two beads and extending from a flank to the rear.
• 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, a content of between 1 and 65 phr, and a thermoplastic resin comprising optionally substituted polyphenylene ether units, said thermoplastic elastomer being a block copolymer comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one thermoplastic block of styrenic type.
• the invention relates to a tire as defined above, wherein the number-average molecular weight of the thermoplastic elastomer is between 30,000 and 500,000 g / mol.
• 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 below 25 ° C.
• the invention relates to a tire as defined above, wherein the SBR elastomer block or blocks have a styrene content in a range from 10 to 60%.
• 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% to 96% o molar.
• the SBR elastomer block or blocks are 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 a proportion of 50 at 100 mol%, and preferably from 80 to 100 mol% of the double bonds in the butadiene portion are hydrogenated.
• 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 temperature of greater than 80 ° C.
• the styrenic thermoplastic block fraction in the block copolymer is within a range of 5 to 70%.
• 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, methylhyrenes, para-tert-butylstyrene, chlorostyrenes, bromostyrenes, fluorostyrenes, para-hydroxystyrene, and mixtures thereof.
• polystyrenes preferably from polystyrenes obtained from styrene monomers chosen from the group consisting of unsubstituted styrene, methylhyrenes, para-tert-butylstyrene, chlorostyrenes, bromostyrenes, fluor
• thermoplastic block or blocks of the block copolymer are chosen from polystyrenes obtained from styrene monomers chosen from the group consisting of unsubstituted styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, alpha methylstyrene, alpha-2-dimethylstyrene, alpha-4-dimethylstyrene, diphenylethylene, para-tert-butylstyrene, ⁇ -chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 2,4,6-trichlorostyrene, 1,3-bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene, 2,6-d
• the invention relates to a tire as defined above, in which the diene elastomer (that is to say the diene elastomer or elastomers) is chosen from the group consisting of essentially unsaturated diene elastomers. , and mixtures thereof.
• the diene elastomer is chosen from the group consisting of homopolymers obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms, copolymers obtained by copolymerization of one or more conjugated dienes with one another or with one or more vinyl aromatic compounds having from 8 to 20 atoms of carbon, and mixtures thereof.
• the diene elastomer is selected from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• the diene elastomer is selected from the group consisting of butadiene and styrene copolymers.
• the invention relates to a tire as defined above, in which the content of diene elastomer is in a range from 40 to 90 phr and the level of thermoplastic elastomer is included in a range of range from 10 to 60 phr.
• 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 level 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.
• the invention relates to a tire as defined above, in which the thermoplastic resin based on optionally substituted polyphenylene ether units has a glass transition temperature (Tg), measured by DSC according to ASTM standard D3418. 1999, in a range from 0 to 280 ° C, preferably from 5 to 250 ° C.
• Tg glass transition temperature
• the invention relates to a tire as defined above, in which the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I):
• R 1, R 2, R 3 and R 4 represent, independently of one another, identical or different groups chosen from hydrogen, hydroxy, alkoxy, halogen, amino, alkylamino, dialkylamino groups or hydrocarbon groups containing at least 2 carbon atoms, which are 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 in a range from 3 to 300.
• thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I).
• R1, R2, R3 and R4 represent, independently of one another, identical or different groups chosen from:
• linear, branched or cyclic alkyl groups comprising from 1 to 25 carbon atoms (preferably from 2 to 18), optionally interrupted by heteroatoms chosen from nitrogen, oxygen and sulfur, and optionally substituted with hydroxy, alkoxy, amino, alkylamino, dialkylamino or halogen groups,
• thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I) in which RI, R2, R3 and R4 represent, independently of one another, identical or different groups chosen from:
• 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 by hydroxyl or alkoxy groups containing from 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 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.
• 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.
• the invention relates to a tire as defined above, in which the thermoplastic resin based on optionally substituted polyphenylene ether units is a compound comprising predominantly polyphenylene units of general formula (I) in which n is a integer in a range of 3 to 50, preferably 5 to 30, more preferably 6 to 20.
• 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 a integer in a range of 3 to 50, preferably 5 to 30, more preferably 6 to 20.
• the invention relates to a tire as defined above, in which the thermoplastic resin based on polyphenylene ether units optionally substituted is a compound comprising more than 80% by weight, preferably greater than 95% by weight, polyphenylene units of general formula (I).
• the invention relates to a tire as defined above, in which the level of said thermoplastic resin based on optionally substituted polyphenylene ether units is in a range from 1 to 50 phr, preferably from 2 to 40 pce. More preferably, 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.
• 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. 60 pce.
• the level of reinforcing filler is from 3 to 50 phr, preferably from 5 to 40 phr.
• the reinforcing filler is carbon black and / or silica.
• the majority reinforcing filler is silica.
• the majority reinforcing filler is carbon black.
• the invention relates to a tire as defined above, in which the composition of the tread does not comprise a plasticizer system other than the PPE resin, or comprises thereof with a lower total plasticizer content. at 20 phr, preferably less than 15 phr.
• 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 motor vehicles of tourism type, SUV ("Sport Utility Vehicles"), two wheels (including motorcycles), aircraft, as industrial vehicles chosen from vans, "heavy goods vehicles” - that is, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering -, other transport or handling vehicles.
• non-motorized vehicles such as bicycles, or motor vehicles of tourism type, SUV ("Sport Utility Vehicles")
• two wheels including motorcycles
• aircraft as industrial vehicles chosen from vans, "heavy goods vehicles” - that is, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering -, other transport or handling vehicles.
• thermoplastic elastomers in English “phr" means within the meaning of the present patent application, part by weight per hundred parts of elastomer, thermoplastic and non-thermoplastics combined.
• thermoplastic elastomers TPE are part of the elastomers.
• any range of values designated by the expression “between a and b” represents the range of values from more than a to less than b (that is, terminals a and b excluded). ) while any range of values designated by the expression “from a to b” signifies the range of values from a to b (that is to say, including the strict limits a and b).
• a majority reinforcing filler is the reinforcing filler representing the largest mass relative to the total weight of the reinforcing fillers in the composition.
• a “minor” compound is a compound that does not represent the largest mass fraction among compounds of the same type.
• 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 a sidewall.
• 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, with a content of between 1 and 65 phr, and a thermoplastic resin comprising optionally substituted polyphenylene ether units, said thermoplastic elastomer being a block copolymer comprising at least at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic type thermoplastic block.
• 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 blocks, elastomers.
• 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 thermoplastic block of styrene copolymer (PS) type. .
• SBR butadiene-styrene random copolymer elastomer block
• PS thermoplastic block of styrene copolymer
• an SBR block 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 (this is that is to say more than 50% by weight, preferably more than 80% by weight) of a styrenic polymer such as polystyrene.
• the number-average molecular weight (denoted Mn) of 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.
• Mn number-average molecular weight
• the number-average molecular weight (Mn) of the SBR and PS block TPE elastomer is determined in known manner by steric exclusion chromatography (SEC).
• SEC steric exclusion chromatography
• the sample is solubilized beforehand in tetrahydrofuran at a concentration of approximately 1 g / l; then the solution is filtered on 0.45 ⁇ porosity filter before injection.
• the apparatus used is a "WATERS alliance" chromatographic chain.
• the elution 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", “HMW6E” and two “HT6E”) is used.
• the injected volume of the solution of the polymer sample is 100 ⁇ .
• 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 SBR and PS block TPEs 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 portion PS of SBR and PS block TPE.
• Tg glass transition temperature
• the Tg of SBR and PS block TPE when reference is made to the glass transition temperature of SBR and PS block TPE, it is the Tg relative to the SBR elastomer block.
• the Block TPE SBR and PS 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.
• Tg glass transition temperature
• 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.
• 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, 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.
• 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).
• 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 5000 g / mol, these SBR and PS block TPEs will be called block SBR and PS multiblock TPEs thereafter, and are a sequence of elastomeric blocks - thermoplastic blocks.
• the block TPE SBR and PS is in a linear form.
• 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.
• the SBR and PS multiblock block TPE can be a linear sequence of SBR elastomeric blocks - PS thermoplastic blocks.
• the block SBR and PS TPE useful for the purposes of the invention is in a star shape with at least three branches.
• 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.
• the block TPE SBR and PS is in a branched or dendrimer form.
• 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.
• the elastomer blocks of 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.
• 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.
• 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 content of trans-1,4 bonds and a content of cis-1,4 bonds when the butadiene part is not 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 1H NMR experiment uses a 30 ° single pulse sequence and a 5 second repetition time between each acquisition. 64 accumulations are made.
• the samples (approximately 25 mg) are solubilized in the CS 2 approximately 1 ml, ⁇ of deuterated cyclohexane are added to make the lock during the acquisition.
• the chemical shifts are calibrated against the impurity protonated CS 2? Ppm to 7.18 ppm 1H referenced on TMS (? Ppm in 1H OPPM).
• the 1H NMR spectrum makes it possible to quantify the microstructure by integrating the signal mass characteristic of the different patterns:
• Styrene from SBR and polystyrene blocks It is quantifiable in the aromatics zone between 6.0ppm and 7.3ppm for 5 protons (by removing the signal integral of the CS2 impurity at 7.18ppm).
• PB 1-4 from SBR. It is quantifiable in the ethylenic zone between 5, lppm and 6, lppm for 2 protons and by removing 1 proton of the pattern PB 1-2.
• the hydrogenated PB 1-2 from the hydrogenation and having only aliphatic protons.
• the CH3 during hydrogenated PB 1-2 have been identified and are quantifiable in the aliphatic zone between 0.4 and 0.8 ppm for 3 protons.
• styrene unit:% styrene (Integral 1H styrene) / (Integral 1H styrene + Integral 1H PB 1-2 + Integral 1H PB 1-4 + Integral 1H hydrogenated PB 1-2 + Integral 1H of hydrogenated PB 1-4).
• 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.
• 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 from 50 to 100 mol% and very preferably from 80 to 100 mol% of the double bonds in the butadiene portion are hydrogenated.
• 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.
• substituted styrenes those selected from the group consisting of methylstyrenes (preferentially ⁇ -methylstyrene, m-methylstyrene and p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha 4-dimethylstyrene and diphenylethylene), para-tert-butylstyrene, chlorostyrenes (preferentially ⁇ -chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene and 2-chlorostyrene).
• methylstyrenes preferentially ⁇ -methylstyrene, m-methylstyrene and p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha 4-di
• bromostyrenes preferentially o-bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene and 2,4,6-tribromostyrene
• fluoro styrenes preferentially ⁇ -fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6-difluorostyrene and 2,4,6-trifluorostyrene
• para-hydroxy- styrene and mixtures thereof.
• 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 a sufficient mechanical strength and compatible with the use in tire tread.
• Mn number-average molecular weight
• the elastomeric block may also consist of several elastomeric blocks as defined above.
• the glass transition temperature characteristic (Tg) of the thermoplastic rigid block will be used. 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 a polymer block), the implementation temperature is chosen to be substantially greater than the Tg. In the specific case of a polymer (or a polymer block) semi - Crystalline, we can observe a melting temperature then higher than the glass transition temperature. In this case, it is rather the melting temperature (Tf) which makes it possible to choose the implementation temperature 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.
• 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).
• this thermoplastic block has a Tg (or Tf, if applicable) in a range of 80 ° C to 250 ° C.
• 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.
• substituted styrenes those selected from the group consisting of methylstyrenes (preferentially ⁇ -methylstyrene, m-methylstyrene and p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha 4-dimethylstyrene and diphenylethylene), para-tert-butylstyrene, chlorostyrenes (preferentially ⁇ -chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene and 2-chlorostyrene).
• methylstyrenes preferentially ⁇ -methylstyrene, m-methylstyrene and p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha 4-
• thermoplastic blocks of SBR block TPE are blocks obtained from unsubstituted polystyrene.
• 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.
• 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.
• 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 with SBR and PS blocks of good elastomeric properties and sufficient mechanical strength and compatible with the use of tire tread.
• Mn number-average molecular weight
• the thermoplastic block may also consist of several thermoplastic blocks as defined above.
• SOE-type elastomers marketed by the company Asahi Kasei under the name "SOE SI 611", “SOE L605" or else "SOE L606”.
• 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 very preferably from 30 to 45% by weight of all the elastomers present in the elastomer composition.
• the amount of SBR and PS block TPE elastomer is in a range from 1 to 65 phr, preferably from 10 to 60 phr, more preferably from 20 to 50 phr and especially from 30 to 45 phr.
• the 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 change in properties with temperature.
• 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 ranging from 40 to 90 phr, preferably from 50 to 80 phr, more preferably from 55 to 70 phr.
• elastomer or "diene” rubber must be understood in a known way (one or more) elastomer is at least partly derived (ie a homopolymer or a copolymer) of diene monomers (monomers carrying two carbon-carbon double bonds, conjugated or otherwise).
• diene elastomers can be classified in 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).
• 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%.
• diene elastomers such as certain butyl rubbers or copolymers of dienes and alpha olefins EPDM type can be described as "essentially saturated" diene elastomers (low or very low diene origin ratio). low, always less than 15>).
• diene elastomers low or very low diene origin ratio. low, always less than 15>.
• diene elastomer Any type of diene elastomer can be used in the invention.
• the composition contains a vulcanization system, essentially unsaturated elastomers, in particular types (a) and (b) above, are preferably used for the manufacture of the tread of the tire according to the present invention.
• 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, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
• 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, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-he
• Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tertiarybutylstyrene, 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.
• a coupling agent for example, there may be mentioned for example functional groups comprising a C-Sn bond or amino functional groups such as benzophenone for example;
• a reinforcing inorganic filler such as silica, mention may be made, for example, of silanol or polysiloxane functional groups having a silanol end (as described, for example, in FR 2,740,778 or US Pat. No.
• alkoxysilane groups such as 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 groups polyethers (as described for example in EP 1 127 909 or US Pat. No. 6,503,973).
• elastomers functionalized one can also mention elastomers (such as SBR, BR, NR or IR) of the epoxidized type.
• composition according to the invention comprises a thermoplastic resin based on optionally substituted polyphenylene ether units (abbreviated as "EPP resin”).
• EPP resin optionally substituted polyphenylene ether units
• the PPE resin that is 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 280.degree. C., preferably from 0.degree. at 250 ° C and more preferably from 5 to 220 ° C. Below 0 ° C, the EPP resin does not allow a shift of sufficient Tg in the composition comprising it and above 280 ° C, one can meet manufacturing problems including to obtain a homogeneous mixture.
• Tg glass transition temperature
• the PPE resin is a compound comprising predominantly polyphenylene units of general formula (I):
• 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; RI 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 in a range from 3 to 300.
• R1, R2, R3 and R4 represent, independently of each other, identical or different groups chosen from:
• linear, branched or cyclic alkyl groups comprising from 1 to 25 carbon atoms (preferably from 2 to 18), optionally interrupted by heteroatoms chosen from nitrogen, oxygen and sulfur, and optionally substituted with hydroxy, alkoxy, amino, alkylamino, dialkylamino, or halogen groups.
• R 1, R 2, R 3 and R 4 represent independently of each other identical or different groups chosen from:
• 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 by hydroxyl or alkoxy groups containing from 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 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.
• R 1 and R 2 represent an alkyl group and in particular a methyl group; and R3 and R4 represent hydrogen atoms.
• the PPE resin is a poly (2,6-dimethyl-1,4-phenylene ether).
• n is an integer within a range of from 3 to 50, more preferably from 5 to 30, preferably from 6 to 20.
• the EPP resin is a compound comprising from more than 80% by weight, and more preferably more than 95% by weight, polyphenylene units of general formula (I).
• PPE resins have variable number average molecular weights (Mn) in particular from about 1000 to 45,000 g / mol, most often from 15,000 to 45,000 g / mol, the Mn being measured in a known manner.
• Mn number average molecular weights
• SEC also named GPC, as in US4588806, column 8
• 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.
• composition according to the invention may further comprise a reinforcing filler.
• 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, including a cut of carbon black and silica.
• the majority reinforcing filler may be silica, or alternatively carbon black.
• carbon blacks are suitable all carbon blacks conventionally used in tires (so-called pneumatic grade black).
• reinforcing carbon blacks of the series 100, 200 or 300 such as for example the blacks NI 15, N134, N234, N326, N330, N339, N347, N375, or else according to targeted applications, blacks of higher series (for example N660, N683, N772), or even N990.
• any inorganic or mineral filler (regardless of its color and origin (natural or synthetic), also called “white” charge, charge “clear” or “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 for manufacturing tire, in other words able to replace, in its reinforcing function, a conventional carbon black pneumatic grade, such a charge is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) at its area.
• -OH hydroxyl groups
• reinforcing inorganic filler is present indifferent, whether in the form of powder, microbeads, granules, beads or any other suitable densifed form.
• reinforcing inorganic filler also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.
• 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 fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
• HDS highly dispersible precipitated silicas
• a coupling agent or bonding agent
• a coupling agent at least bifunctional for ensuring 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 is in a range of 0 to 20%, which corresponds to a rate of 0 to 50 pce for a composition without plasticizer.
• 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. 1.5. plasticizers
• the elastomer (s) and the EPP resin described above are sufficient on their own for the tread according to the invention to be usable.
• the elastomer composition described above does not comprise a plasticizer of the oil or thermoplastic resin type other than the PPE resin, or, if it comprises, it comprises less than 20 phr (in particular between 0.5 and 20 phr), preferably less than 15 phr (in particular between 0.5 and 15 phr), more preferably less than 10 phr (in particular between 0.5 and 10 phr), better , less than 5 phr (in particular between 0.5 and 5 phr). Also preferentially, the composition does not comprise any plasticizer other than the PPE resin.
• plasticizing agent is called an oil (or plasticizing oil or extension 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 tackifiant power.
• 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.
• thermoplastic elastomer (s) and the PPE resin described above are sufficient on their own for the tread according to the invention to be usable.
• the elastomer composition described above may also include the various additives usually present in the bearing strips known to those skilled in the art.
• one or more additives chosen from protective agents such as antioxidants or antiozonants, anti-UV agents, the various agents of implementation or other stabilizers, or the promoters able to promote the adhesion to the rest of the structure will be chosen. of the pneumatic object.
• the tread composition of the invention may contain a crosslinking system known to those skilled in the art, such as a vulcanization system comprising sulfur or a sulfur donor agent and, optionally, one or more vulcanization accelerators and / or activators.
• a crosslinking system known to those skilled in the art, such as a vulcanization system comprising sulfur or a sulfur donor agent and, optionally, one or more vulcanization accelerators and / or activators.
• the tread compositions for the tire according to the invention are manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes referred to as a "non-productive" phase) at a 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 mechanical working phase (sometimes referred to as a "productive" phase) at a lower temperature, typically below 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 EP-A-0501227, EP-A-0735088, EP-A-0810258, WO00 / 05300 or WO00 / 05301.
• a first phase of work or thermomechanical mixing sometimes referred to as a "non-productive" phase
• a second mechanical working phase sometimes referred to as
• the SBR and PS block TPE elastomers and the PPE resin are introduced during the first stage, directly in their commercial form, for example in the form of beads or granules.
• a preferred alternative may be to prepare a masterbatch comprising the SBR and PS block TPE elastomers and the PPE resin only, which masterbatch is then used for the preparation of the complete blend.
• this masterbatch can be prepared in a twin-screw extruder at a temperature between 180 ° C and 280 ° C, for example at 230 ° C.
• 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 in the tire baking mold.
• 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.
• Tire tread compositions according to the invention were prepared as indicated above.
• the dynamic properties G * and tan ( ⁇ ) max are measured on a viscoanalyzer (Metravib V A4000), according to the ASTM D 5992 - 96 standard.
• the response of a sample of vulcanized composition (cylindrical specimen of 4) is recorded. mm thick and 400 mm2 in section), subjected to a sinusoidal stress in alternating single shear, at a frequency of 10 Hz, according to ASTM D 1349-99, at 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 ⁇ ).
• the maximum value of tan ⁇ observed (tan ( ⁇ ) max) and the complex modulus difference (DG *) between the values at 0.1% and at 50%> deformation are indicated ( Payne effect).
• tan ( ⁇ ) max at 40 ° C For the value of tan ( ⁇ ) 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 less than 100 indicating a decrease in rolling resistance performance (increasing the value of tan (ô) max to 40 ° C), and conversely, a result greater than 100, will indicate an increase in performance (decrease in the value of tan (ô) max to 40 ° C).
• Dynamic coefficient of friction [00108] The dynamic coefficient of friction measurements were carried out according to a method identical to that described by L. Busse, A. Le Gai, and M. Kippel (Modeling of Dry and Wet Friction Silica Filled Elastomers on Self-Affine Road Surfaces, Elastomere 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 surface of asphalt concrete type BBTM (standard NF P 98-137).
• the soil + specimen system is immersed in a 5% aqueous solution of a surfactant (Sinnozon - CAS number: 25155-30-0).
• a surfactant Tinozon - CAS number: 25155-30-0.
• the temperature of the aqueous solution is regulated using a thermostatic bath.
• the test piece is subjected to a sliding movement in translation parallel to 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 ⁇ .
• the values given 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
• a tire tread composition according to the invention (A2) was prepared as indicated above and compared to two control compositions: a common tire tread composition (A0) and a composition without EPP resin (Al).
• the compositions of these treads are presented in Table 1 below.
• DPG Diphenylguanidine ("Perkacit DPG" from Flexsys);

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