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    • 专利摘要:
    The invention relates to a tire intended to equip a vehicle carrying heavy loads, this tire comprising a tread having at least one rubber composition based on at least: an elastomer matrix comprising, for the most part, a copolymer based on styrene and butadiene having a glass transition temperature Tg strictly greater than -65 ° C and less than or equal to -30 ° C, - a reinforcing filler comprising predominantly silica, - a chemical crosslinking system, an agent for coupling, and a plasticizer system comprising from 0 to 15 phr, preferably from 0 to 9 phr, of at least one plasticizing resin having a glass transition temperature Tg greater than or equal to 20 ° C., and whose total plasticizer system in the composition ranges from 0 to 17 phr.
    公开号:FR3045636A1
    申请号:FR1563039
    申请日:2015-12-22
    公开日:2017-06-23
    发明作者:Etienne Fleury；Perrine Vallat；Garance Lopitaux
    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:

    The field of the present invention is that of tires for vehicles carrying heavy loads, in particular heavy goods vehicles, buses, civil engineering vehicles, etc.
    More particularly, the invention relates to a tire intended to equip vehicles carrying heavy loads comprising a tread having at least one new rubber composition.
    Tires intended for vehicles carrying heavy loads have specific characteristics of dimensions, robustness, architecture that distinguish them from other tires, including tires for passenger vehicles. Their treads must obey a large number of technical performances such as a high resistance to wear, a low rolling resistance and a good resistance to attacks of foreign bodies that are present on the surface on which the tire rolls.
    Indeed, the use of these tires on terrain with many pebbles and other bodies or potholes, generates attacks of the tread. For machines carrying heavy loads, including trucks, it is known that the treads of tires fitted to these vehicles are subject to repetitive shocks that can cause tearing of the tread material. It is therefore necessary that the tire treads of these vehicles have good resistance to aggression. On the other hand, some heavy-duty vehicles are also intended to travel on longer journeys, due to the improvement of the road network and the growth of the motorway network in the world. The wear of the tread of these tires must therefore be as small as possible for a given travel distance and the energy losses associated with the rolling of the tires must also be reduced as much as possible. It is therefore necessary, in addition to good wear resistance and good resistance to attack, to also seek good rolling resistance.
    Tire manufacturers are therefore constantly seeking a good compromise between these three properties. However, it is well known to those skilled in the art that the improvement of a performance for tires is often obtained at the expense of other performance. By way of example, it is known, for improving the wear resistance of tires fitted to vehicles carrying heavy loads, to increase the bending stiffness of their tread by increasing the level of reinforcing filler, particularly the carbon black, and / or using a high level of synthetic elastomers in the constituent rubber compositions of these treads. The resulting compositions give the corresponding treads satisfactory results in terms of stiffness, and therefore wear resistance. However, these compositions then generally have high hysteresis losses and therefore a high rolling resistance.
    There is therefore still an unmet need to provide a tire for vehicles carrying heavy loads having a good compromise in performance - rolling resistance, wear resistance and resistance to attack.
    The present invention therefore aims to provide a tire for heavy load carrying vehicle overcomes the aforementioned drawbacks.
    This object is achieved by the invention which relates to a tire intended to equip a vehicle carrying heavy loads, this tire comprising a tread having at least one rubber composition based on at least: an elastomer matrix comprising predominantly a copolymer based on styrene and butadiene having a glass transition temperature Tg strictly greater than -65 ° C and less than or equal to -30 ° C, - a reinforcing filler comprising predominantly silica, - a chemical crosslinking system, - a coupling agent, and - a plasticizer system comprising from 0 to 15 phr, preferably from 0 to 9 phr, of at least one plasticizing resin having a glass transition temperature Tg greater than or equal to 20 ° C, and whose total content of the plasticizer system in the composition ranges from 0 to 17 phr, preferably from 0 to 11 phr. The advantage of this composition is that it has a good compromise of properties (hysteresis, rigidity and especially limiting properties), including an improved compromise compared to the rubber compositions conventionally used in the manufacture of tire bearing strips intended to equip a vehicle carrying heavy loads.
    Surprisingly, the Applicant has found that the combination of a copolymer based on styrene and butadiene having a glass transition temperature
    Tg strictly greater than -65 ° C and less than or equal to -30 ° C and present predominantly in a rubber composition with a reinforcing filler comprising a majority of silica allowed to obtain a tread having a good resistance to abrasion. wear and good rolling resistance without the performance of resistance to attack is penalized. In some embodiments, this performance is even improved. This compromise is unexpected.
    Indeed, the use, in the field of tires intended to equip vehicles carrying heavy loads, compositions based in particular on butadiene-styrene copolymer (SBR), carbon black and a plasticizing resin is known in particular from the application. FR2995609. It is also known that the replacement of carbon black with silica in a rubber composition improves the hysteresis of this composition but at the expense of limiting properties and rigidity properties. Achieving, and in particular improving, the compromise in performance - rolling resistance, wear resistance and resistance to attack - is an important difficulty for the skilled person because of the antinomic choices that he is led to consider. Surprisingly, the Applicant has found that the specific combination of two compounds, namely a styrene-butadiene-based copolymer having a glass transition temperature strictly greater than 65 ° C and less than or equal to -30 ° C and a silica as reinforcing filler allowed to obtain a good compromise of performances.
    According to one embodiment, the plasticizer system may comprise from 2 to 15 phr, preferably from 2 to 9 phr of the plasticizing resin, the total content of the plasticizer system in the composition ranges from 2 to 17 phr, preferably from 2 to 17 phr. 11 pce.
    Preferably, the copolymer based on styrene and butadiene can be obtained by solution polymerization.
    Preferably, the styrene-butadiene copolymer has a glass transition temperature Tg of -60 ° C to -40 ° C.
    Preferably, the styrene-based butadiene copolymer may be a styrene-butadiene copolymer.
    In one embodiment of the invention, the elastomer matrix may further comprise at least one second diene elastomer different from the styrene-butadiene-based copolymer; in particular, said second diene elastomer being chosen from the group formed by polybutadienes, natural rubber, synthetic isoprenes, butadiene copolymers other than butadiene-styrene copolymers, isoprene copolymers and mixtures of these polymers and copolymers ; preferably said second diene elastomer may be a polybutadiene.
    Preferably, the level of the second diene elastomer may range from 5 to 49 phr, preferably from 15 to 35 phr.
    In one embodiment of the invention, the elastomer matrix may also comprise at least a third diene elastomer different from the styrene-butadiene-based copolymer and the second diene elastomer, in particular the third diene elastomer may be chosen from natural rubber and an isoprene elastomer, preferably it may be made of natural rubber.
    Preferably, the level of the second diene elastomer may range from 0.5 to 35 phr and a level of the third diene elastomer may range from 0.5 to 35 phr, preferably the level of the second diene elastomer may range from 9 to 31 phr. and a rate of the third diene elastomer may range from 4 to 24 phr.
    Preferably, the composition may further comprise carbon black; in particular the carbon black content may be less than or equal to 10 phr, less than or equal to 5 phr, preferably the carbon black content may range from 0.5 to 4 phr.
    Preferably, the level of the reinforcing filler can range from 55 to 200 phr, preferably from 55 to 150 phr, more preferably from 55 to 80 phr.
    Preferably, the plasticizing resin may have a glass transition temperature Tg greater than or equal to 30 ° C, preferably ranging from 30 to 100 ° C; and in particular, the plasticizing resin may be selected from the group consisting of cyclopentadiene homopolymer or copolymer resins, dicyclopentadiene homopolymer or copolymer resins, terpene homopolymer or copolymer resins, homopolymer resins or C5 cutting copolymer, homopolymer or C9 cut copolymer resins, homopolymer resins, including C5 cut homopolymer or copolymer resin blends and C9 cut homopolymer or copolymer resins, and alpha-methyl-styrene copolymer resins and mixtures of these resins.
    Preferably, the plasticizer system may comprise from 0 to 2 phr of at least one plasticizer that is liquid at room temperature (23 ° C.).
    In one embodiment, the composition may be free of a plasticizer system.
    Preferably, the tire of the invention may be intended to equip a heavy vehicle.
    I - DETAILED DESCRIPTION OF THE INVENTION
    In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are percentages by mass. On the other hand, any range of values designated by the expression "between a and b" represents the range of values from more than "a" to less than "b" (i.e. terminals a and b excluded) while any range of values referred to as "a to b" means the range of values from "a" to "b" (ie including strict bounds a and b ). The abbreviation "pce" (usually "phr" in English for "per hundred part of rubber") means parts by weight per hundred parts of elastomers (of the total elastomers if several elastomers are present) or rubber present in the composition of rubber.
    By "tire intended to equip a vehicle carrying heavy loads" is meant generically any tire intended to equip trucks, buses, civil engineering vehicles, agricultural vehicles or aircraft. The invention is particularly well suited to tires intended to equip trucks.
    "Rubber composition based on" means a rubber composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended to react with each other, less in part, during the various phases of manufacture of the composition, in particular during its crosslinking or vulcanization.
    By "elastomeric matrix" or "elastomeric matrix" is meant all of the elastomer (s) present in the rubber composition.
    By "diene" elastomer (or indistinctly rubber), whether natural or synthetic, must be understood an elastomer consisting at least in part (ie a homopolymer or a copolymer) of monomer (s) diene (s) ) (ie, carrier (s) of two carbon-carbon double bonds, conjugated or not).
    These diene elastomers can be classified into two categories: "essentially unsaturated" or "essentially saturated". The term "essentially unsaturated" is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%); Thus, diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated" diene elastomers ( low or very low diene origin, always less than 15%). In the category of "essentially unsaturated" diene elastomers, the term "highly unsaturated" diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
    These definitions being given, the term "diene elastomer" may be understood more particularly to be used in the compositions according to the invention: (a) - any homopolymer of a conjugated diene monomer, especially any homopolymer obtained by polymerization of a diene monomer conjugate having from 4 to 12 carbon atoms; (b) - any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with an ethylene monomer or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms; (c) - a ternary copolymer obtained by copolymerization of ethylene, an α-olefin having 3 to 6 carbon atoms with a non-conjugated diene monomer having from 6 to 12 carbon atoms, for example elastomers obtained from ethylene, propylene with a non-conjugated diene monomer of the aforementioned type such as in particular 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene; (d) - a copolymer of isobutene and isoprene (butyl rubber), as well as the halogenated versions, in particular chlorinated or brominated, of this type of copolymer.
    Although it applies to any type of diene elastomer, the person skilled in the tire art will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b). ) above.
    The diene 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 diene elastomers may be for example block, random, block, microsequential, and be prepared in dispersion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization. For coupling with a reinforcing inorganic filler such as silica, mention may be made, for example, of silanol or polysiloxane functional groups having a silanol end (as described, for example, in FR 2 740 778 or US Pat. No. 6,013,718, and WO 2008/141702). , 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 6,503,973, WO 2009/000750 and WO 2009/000752).
    Functional diene elastomers that may be mentioned include those prepared by the use of a functional initiator, especially those carrying an amine or tin function (see, for example, WO 2010072761).
    As other examples of functionalized diene elastomers, mention may also be made of elastomers (such as BR, NR or IR) of the epoxidized type.
    By "majority" or "majority" is meant in the sense of the present invention, the compound is the majority of the compounds of the same type in the composition, that is to say that it is the one that represents the greater amount by mass among the compounds of the same type. In other words, the mass of this compound represents at least 51% of the total mass of the compounds of the same type in the composition. For example, in a system comprising a single elastomer, it is the majority within the meaning of the present invention; and in a system comprising two elastomers, the majority elastomer represents more than half of the total mass of the elastomers, ie the mass of this elastomer represents at least 51% of the total mass of the elastomers. In the same way, a so-called majority charge is that representing the largest mass among the charges of the composition. In other words, the mass of this charge represents at least 51% of the total mass of the charges in the composition.
    "Minority" means a compound that does not represent the largest mass fraction among compounds of the same type.
    All values of glass transition temperature "Tg" are measured in a known manner by DSC (Differential Scanning Calorimetry) according to ASTM D3418 (1999).
    By "compound X-free" it is meant that compound X is not detectable by measurements known to those skilled in the art or that compound X is present in small amounts which represent impurities (i.e. -to say in the order of ppm (parts by weight per million)).
    In the context of the invention, the carbonaceous products mentioned in the description may be of fossil origin or biobased. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. These include compounds (such as monomers, polymers), reagents and other components mentioned in the description, such as plasticizers, fillers, etc.
    Copolymer based on styrene and butadiene
    The elastomeric matrix of the rubber composition of the tire according to the invention mainly comprises a styrene-based copolymer based on butadiene having a glass transition temperature Tg strictly greater than -65 ° C. and less than or equal to 30 ° C. In other words, the weight of the styrene-butadiene-based copolymer having a glassy Tg transition temperature strictly greater than -65 ° C. and less than or equal to -30 ° C. represents at least 51% of the mass. total of the elastomeric matrix.
    By copolymer based on styrene and butadiene is meant here a copolymer of at least one styrene monomer and at least one butadiene monomer (and of course also any mixture of such copolymers) having a glass transition temperature Tg strictly greater at -65 ° C and less than or equal to -30 ° C; in other words, said copolymer based on styrene and butadiene comprises by definition at least styrene units (derived from the styrene monomer) and butadiene units (derived from the butadiene monomer) and has a glass transition temperature Tg strictly greater than -65 ° C and less than or equal to -30 ° C. As butadiene monomers, 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-1-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl- 1,3-butadiene, an aryl-1,3-butadiene. As styrene monomers are especially suitable styrene, methylstyrenes, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes.
    The copolymer based on styrene and butadiene 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.
    Preferably, the copolymer based on styrene and butadiene can be obtained by solution polymerization. More preferably, it may be a styrene-butadiene copolymer (abbreviated to SBR), in particular an SBR prepared by solution polymerization (abbreviated S-SBR). It will be noted advantageously that the rubber composition of the tire according to the invention may not comprise or may comprise in a very small amount a copolymer based on styrene and extended butadiene; in other words, the level of copolymer based on styrene and extended butadiene, if this type of copolymer is present, may be less than or equal to 2 phr, preferably at this level may correspond to an impurity. More particularly, the rubber composition of the tire according to the invention may be free of styrene-based copolymer and extended butadiene. By extended copolymer is meant an extended and stabilized copolymer with an oil, especially of paraffinic, naphthenic or aromatic type.
    Among the copolymers based on styrene and butadiene, in particular SBR, in particular S-SBR, mention may be made especially of those having a styrene content of between 5% and 60% by weight, and more particularly between 20% and 50% by weight. weight relative to the weight of the copolymer, a molar content (mol%) in -1,2 bonds of the butadiene part of between 4% and 75%, a molar content (mol%) in trans-1,4 bonds of the part butadiene between 10% and 80%. The styrene content by weight, the molar content of the -1,2 bonds of the butadiene part and the molar content in trans-1,4 bond are measured by techniques well known to those skilled in the art.
    Preferably, the glass transition temperature Tg of the copolymer based on styrene and butadiene, in particular SBR (in particular an S-SBR), can range from -60 ° C. to -40 ° C. Those skilled in the art know how to modify the microstructure of a copolymer based on styrene and butadiene, in particular on an SBR (in particular an S-SBR), in order to adjust its Tg, in particular by controlling the contents of styrene, in -1,2 bonds of the butadiene part or in trans-1,4 bonds of the butadiene part.
    Preferably, the content of the copolymer based on styrene and butadiene, in particular SBR (in particular S-SBR) in the rubber composition of the tire according to the invention, may range from 51 to 100 phr, preferably from 60 to 60 phr. 100 phr, even more preferably 60 to 85 phr.
    The copolymer based on styrene and butadiene, in particular SBR and in particular S-SBR, may advantageously be used in blending (mixing) with one or more other diene elastomer (s) different (s) said copolymer based on styrene and butadiene. In the case of a cutting, it is understood that the sum of the different elastomers used is equal to 100 phr.
    Thus, in one embodiment of the tire according to the invention, the copolymer based on styrene and butadiene above, in particular SBR and in particular S-SBR, may be optionally combined with at least one second diene elastomer, different from said copolymer based on styrene and butadiene; that is to say that the second diene elastomer does not contain units derived from styrene and butadiene. When it is present, the second diene elastomer may be chosen from the group formed by polybutadienes (BR), natural rubber (NR), synthetic isoprenes (IR), butadiene copolymers other than butadiene-styrene copolymers copolymers of isoprenes and mixtures of these polymers and copolymers. Preferably, said second diene elastomer may be a polybutadiene (BR). When it is present, the level of the second diene elastomer may be at most equal to 49 phr, preferably at most equal to 35 phr. Preferably, the content of the second diene elastomer can range from 5 to 49 phr (as a reminder, ie, parts by weight per hundred parts of elastomer, ie of the total of the elastomers present in the tread). preferably from 15 to 35 phr.
    In another embodiment of the tire according to the invention, the copolymer based on styrene and butadiene, in particular SBR and in particular S-SBR, may optionally be combined with at least one second diene elastomer, different from said copolymer with styrene and butadiene base (that is to say not having units derived from styrene and butadiene) and a third elastomer different from said copolymer based on styrene and butadiene and the second diene elastomer. Preferably, the third diene elastomer may be an isoprene elastomer. Preferably, the second diene elastomer may be chosen from the group formed by polybutadienes (BR) and butadiene copolymers other than butadiene-styrene copolymers; and the third diene elastomer may be selected from the group consisting of natural rubber (NR), synthetic isoprenes (IR), copolymers of isoprenes and mixtures of these polymers and copolymers. Preferably, the second diene elastomer may be butadiene and the third diene elastomer may be natural rubber or synthetic isoprene. Preferably, the level of the second elastomer may range from 0.5 to 35 phr, and the level of the third elastomer may range from 0.5 to 35 phr; more preferably, the rate of the second elastomer may range from 9 to 31 phr and the level of the third elastomer may range from 4 to 24 phr.
    Of the polybutadienes or copolymers of butadiene used in the above blends, polybutadienes having a content (mol%) in units -1.2 of between 4% and 80% or those having a content (mol%) of cis-1,4 greater than 80%, more particularly greater than 90%, butadiene-isoprene copolymers and especially those having an isoprene content of between 5% and 90% by weight and a Tg of -40 ° C to -80 ° C., isoprene-styrene copolymers and in particular those having a styrene content of between 5% and 50% by weight and a Tg of between -25 ° C. and -50 ° C. In the case of butadiene-styrene-isoprene copolymers are especially suitable those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60%. by weight and more particularly between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly between 20% and 40%, a content (mol%) in -1,2 units of the butadiene part of between 4% and 85%, a content (mol%) in trans units -1,4 of the butadiene part of between 6% and 80%, a content (mol%) in units -1,2 plus -3 , 4 of the isoprenic part of between 5% and 70% and a content (mol%) in trans-1,4 units of the isoprene part of between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg between -20 ° C and -70 ° C.
    Among the isoprenic elastomers (ie, homopolymers or copolymers of isoprene) used in the above blends, mention will in particular be made of NR, IR, isoprene copolymers such as isobutene-isoprene copolymers (butyl rubber or IIR), isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene (SBIR). Among these synthetic polyisoprenes, polyisoprenes having a level (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, can be used.
    The diene elastomers previously described may also be associated, in a minor amount, with synthetic elastomers other than dienes, or even polymers other than elastomers, for example thermoplastic polymers.
    Reinforcing charge
    The rubber composition used in the tires of the invention comprises at least one reinforcing filler comprising mainly silica, that is to say that the mass of the silica represents at least 51% of the total mass of the constituents reinforcing filler. Preferably, the silica mass represents more than 60%, preferably more than 70% of the total mass of the reinforcing filler.
    In the present disclosure, the BET surface area is determined in a known manner by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society" Vol. 60, page 309, February 1938, more precisely according to the French standard NF ISO 9277 of December 1996 (volumetric method (5 gas point: nitrogen - degassing: 1 hour at 160 ° C. - relative pressure range p / po: 0.05 to 0.17 The CTAB specific surface is the external surface determined according to the French standard NF T45-007 of November 1987 (method B).
    "Reinforcing inorganic filler" means any inorganic or mineral filler, irrespective of its color and origin (natural or synthetic), also called "white" filler, "clear" filler or even "non-black" filler. ("Non-black filler") as opposed to carbon black; this inorganic filler being able to reinforce on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of pneumatic tires, 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, requiring to be used as a reinforcing filler the use of an agent or coupling system intended to provide a link stable chemical charge and elastomeric matrix.
    As inorganic reinforcing fillers are particularly suitable mineral fillers of the siliceous type, preferably silica (SiO 2). The silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g, especially between 60 and 300 m2 / g. Highly dispersible precipitated silicas ("HDS") include, for example, "Ultrasil 7000" and "Ultrasil 7005" silicas from Evonik, "Zeosil 1165MP, 1135MP and 1115MP" silicas and "Zeosil" silica. Premium 200 "from Solvay, the" Hi-Sil EZ150G "silica from PPG, the" Zeopol 8715, 8745 and 8755 "silicas from Huber, the high surface area silicas as described in application WO 03 / 016387.
    Of course, inorganic reinforcing filler is also understood to mean mixtures of different reinforcing inorganic fillers, in particular highly dispersible silicas as described above or a mixture of siliceous type inorganic fillers and inorganic non-siliceous fillers. Non-siliceous inorganic fillers include mineral fillers of the aluminous type, in particular alumina (Al 2 O 3) or (oxides) hydroxides of aluminum, or reinforcing titanium oxides, for example described in US Pat. 6,610,261 and US 6,747,087. Non-siliceous inorganic fillers, when present, are minor in the reinforcing filler. The physical state in which the inorganic reinforcing filler is presented is indifferent, whether in the form of powder, microbeads, granules or beads.
    According to one embodiment, the level of the reinforcing filler in the rubber composition of the tire according to the invention may range from 55 phr to 200 phr, preferably from 55 to 150 phr, more preferably from 55 to 150 phr. 80 pce. These preferred ranges apply to any of the embodiments of the invention. Those skilled in the art will understand that as an equivalent load of the reinforcing inorganic filler described in this paragraph, it would be possible to use a reinforcing filler of another nature, in particular an organic filler such as carbon black, since this filler reinforcing would be covered with an inorganic layer such as silica, or would comprise on its surface functional sites, including hydroxyl, requiring the use of a coupling agent to establish the connection between the filler and the elastomer. By way of example, mention may be made, for example, of carbon blacks for tires as described for example in documents WO 96/37547 and WO 99/28380.
    Carbon black:
    According to one embodiment of the tire according to the invention, the rubber composition may further comprise carbon black.
    The carbon black, when present, may be used preferably at a level of less than or equal to 10 phr, preferably less than or equal to 5 phr. Preferably, the carbon black content may range from 0.5 to 4 phr. These preferred ranges apply to any of the embodiments of the invention.
    Suitable carbon blacks are all carbon blacks, especially blacks conventionally used in tires or their treads (so-called pneumatic grade blacks). Among these, the reinforcing carbon blacks of the 100, 200, 300 series, or the 500, 600 or 700 series blacks (ASTM grades), for example the blacks NI 15, N134, N234, N326, are especially suitable. N330, N339, N347, N375, N550, N683, N772). These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used.
    The coupling agents
    To couple the reinforcing inorganic filler to the elastomeric matrix (ie to the copolymer based on styrene and butadiene, in particular to SBR and S-SBR, and to diene elastomers when they are present), it is possible to use in a well known manner an at least bifunctional coupling agent (or bonding agent) intended to ensure a sufficient chemical and / or physical connection between the inorganic filler (surface of its particles) and the elastomeric matrix. In particular, organosilanes or at least bifunctional polyorganosiloxanes may be used.
    In particular, polysulfide silanes, known as "symmetrical" or "asymmetrical" silanes, may be used, depending on their particular structure, as described, for example, in claims WO00 / 002648 (or US 2005/016651) and WO00 / 002649 (or US 2005/016650). .
    Particularly suitable, but not limited to, polysulfide silanes having the following general formula (I): (I) Z - A - Sx - A - Z, wherein: - x is an integer of 2 at 8 (preferably from 2 to 5); the symbols A, which are identical or different, represent a divalent hydrocarbon radical (preferably a C 1 -C 10 alkylene group or a C 6 -C 12 arylene group, more particularly a C 1 -C 10, especially C 1 -C 4, alkylene, in particular propylene); the symbols Z, identical or different, correspond to one of the three formulas below:
    in which: the radicals R1, substituted or unsubstituted, which are identical to or different from one another, represent a C1-C16 alkyl, C5-C18 cycloalkyl or C6-C18 aryl group (preferably C1-C6 alkyl or cyclohexyl groups); or phenyl, especially C1-C4 alkyl groups, more particularly methyl and / or ethyl). the radicals R2, substituted or unsubstituted, identical or different from each other, represent a C 1 -C 18 alkoxyl or C 5 -C 18 cycloalkoxyl group (preferably a group chosen from C 1 -C 8 alkoxyls and C 5 -C 8 cycloalkoxyls, more preferentially still another group chosen from C1-C4 alkoxyls, in particular methoxyl and ethoxyl).
    In the case of a mixture of polysulfurized alkoxysilanes corresponding to formula (I) above, in particular common commercially available mixtures, the average value of "x" is a fractional number preferably of between 2 and 5, more preferably close to 4. But the invention can also be advantageously implemented for example with disulfide alkoxysilanes (x = 2). By way of examples of polysulphurized silanes, mention may be made more particularly of bis (C 1 -C 4 alkoxy-C 1 -C 4 alkylsilyl-C 1 -C 4 alkyl) polysulfides (especially disulfides, trisulphides or tetrasulfides), as for example polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl). Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT, of formula [(C2H50) 3Si (CH2) 3S2] 2 or bis (triethoxysilylpropyl) disulfide, abbreviated as TESPD, is especially used. formula [(C2H50) 3Si (CH2) 3S] 2. Mention may also be made, by way of preferred examples, of polysulfides (in particular disulphides, trisulphides or tetrasulfides) of bis- (C 1 -C 4 monoalkoxyl) -dialkyl (C 1 -C 4) silylpropyl), more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide, as described above. in the aforementioned patent application WO 02/083782 (or US 7,217,751). By way of example of coupling agents other than a polysulphurized alkoxysilane, particular mention may be made of bifunctional POS (polyorganosiloxanes) or polysulfides of hydroxysilane (R 2 = OH in formula I above) as described, for example in patent applications WO 02/30939 (or US Pat. No. 6,774,255), WO 02/31041 (or US 2004/051210), and WO2007 / 061550, or else silanes or POS bearing functional azo-dicarbonyl groups, such as described for example in patent applications WO 2006/125532, WO 2006/125533, WO 2006/125534. As examples of other sulphurized silanes, mention may be made, for example, of silanes carrying at least one thiol function (-SH) (called mercaptosilanes) and / or of at least one blocked thiol function, as described for example in patents or patent applications US 6,849,754, WO 99/09036, WO 2006/023815, WO 2007/098080, WO 2010/072685 and WO 2008/055986.
    Of course, it would also be possible to use mixtures of the coupling agents described above, as described in particular in the aforementioned application WO 2006/125534.
    The content of coupling agent is advantageously less than 20 phr, it being understood that it is generally desirable to use as little as possible. Typically the level of coupling agent is from 0.5% to 15% by weight relative to the amount of inorganic filler. Its level is preferably between 0.5 and 12 phr, more preferably in a range from 3 to 10 phr. This level is easily adjusted by those skilled in the art according to the level of inorganic filler used in the composition. These preferred ranges apply to any of the embodiments of the invention.
    Collection agents:
    These compositions may also contain, in addition to the coupling agents, coupling activators, inorganic charge-covering agents or, more generally, processing aids that can be used in a known manner, thanks to an improvement in the dispersion. of the charge in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to use in the green state, these agents being for example hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes.
    Plasticizing system
    The rubber composition of the tires according to the invention may comprise from 0 to 17 phr of a plasticizer system, this system comprising from 0 to 15 phr of at least one plasticizing resin having a glass transition temperature Tg greater than or equal to 20 ° C, and preferably from 0 to 2 phr of a liquid plasticizer at room temperature.
    In a manner known to those skilled in the art, the term "resin" is reserved in this application, by definition, to a compound which is solid at room temperature (23 ° C.), as opposed to a liquid plasticizer at room temperature such as than an oil.
    Plasticizing resins are polymers well known to those skilled in the art. These are hydrocarbon resins essentially based on carbon and hydrogen but may comprise other types of atoms, used in particular as plasticizers or tackifying agents in polymeric matrices. They are inherently miscible (i.e., compatible) with the levels used with the diene elastomer compositions to which they are intended, so as to act as true diluents. They have been described, for example, in the book "Hydrocarbon Resins" by R. Mildenberg, M. Zander and G. Collin (New York, VCH, 1997, ISBN 3-527-28617-9), chapter 5 of which is devoted their applications, in particular pneumatic rubber (5.5 Rubber Tires and Mechanical Goods, r), which may be aliphatic, cycloaliphatic, aromatic, hydrogenated aromatic, aliphatic / aromatic type, that is to say based on aliphatic monomers, and / or aromatic They can be natural or synthetic, whether or not based on petroleum (if this is the case, also known as petroleum resins) Their Tg is preferably greater than 0 ° C., especially greater than 20 ° C. ° C (most often between 30 ° C and 95 ° C).
    In a known manner, these plasticizing resins can also be called thermoplastic resins in that they soften by heating and can thus be molded. They can also be defined by a point or softening point (in English, "softening point"). The softening temperature of a plasticizing resin is generally about 50 to 60 ° C. higher than its Tg value. The softening point is measured according to ISO 4625 ("Ring and Bail" method). The macrostructure (Mw, Mn and Ip) is determined by size exclusion chromatography (SEC) as indicated below.
    As a reminder, the SEC analysis, for example, consists in separating the macromolecules in solution according to their size through columns filled with a porous gel; the molecules are separated according to their hydrodynamic volume, the larger ones being eluted first. The sample to be analyzed is simply solubilized beforehand in a suitable solvent, tetrahydrofuran at a concentration of 1 g / liter. The solution is then filtered through a 0.45 μm porosity filter before injection into the apparatus. The apparatus used is for example a "Waters alliance" chromatographic chain according to the following conditions: elution solvent: tetrahydrofuran; temperature 35 ° C; concentration 1 g / liter; flow rate: 1 ml / min; injected volume: 100 μΐ; Moore calibration with polystyrene standards; set of 3 columns "Waters" in series ("Styragel HR4E", "Styragel HR1" and "Styragel HR 0.5"); detection by differential refractometer (for example "WATERS 2410") that can be equipped with operating software (for example "Waters Millenium").
    A Moore calibration is conducted with a series of low Ip (less than 1.2) polystyrene commercial standards of known molar masses covering the field of masses to be analyzed. The mass-averaged molecular weight (Mw), the number-average molecular weight (Mn) and the polymolecularity index (Ip = Mw / Mn) are deduced from the recorded data (mass distribution curve of the molar masses). All the molar mass values indicated in the present application are therefore relative to calibration curves made with polystyrene standards.
    According to a preferred embodiment of the invention, the plasticizing resin may have at least one of the following characteristics: a Tg greater than or equal to 20 ° C (in particular between 30 ° C and 100 ° C), more preferably higher or equal to 30 ° C (in particular between 30 ° C and 95 ° C); a softening point greater than or equal to 40 ° C (in particular between 40 ° C and 150 ° C); a number-average molar mass (Mn) of between 400 and 2000 g / mol, preferably between 500 and 1500 g / mol; a polymolecularity index (Ip) of less than 3, preferably of 2 (booster: Ip = Mw / Mn with Mw weight average molar mass).
    More preferably, the plasticizing resin may have all of the above preferred characteristics. By way of examples of such plasticizing resins, mention may be made of those selected from the group consisting of cyclopentadiene homopolymer or copolymer resins (abbreviated as CPD), dicyclopentadiene homopolymer or copolymer resins (abbreviated to DCPD), terpene homopolymer or copolymer resins, homopolymer or C5 cut copolymer resins, C9 homopolymer or cut copolymer resins, C5 homopolymer or copolymer resin blends, and homopolymer resins or C9 cutting copolymer, alpha-methyl-styrene homopolymer or copolymer resins and mixtures of these resins.
    Among the above copolymer resins, mention may be made more particularly of those selected from the group consisting of CPD / vinylaromatic copolymer resins, DCPD / vinylaromatic copolymer resins, CPD / terpene copolymer resins, DCPD copolymer resins. terpene, terpene phenol copolymer resins, CPD / C5 cut copolymer resins, DCPD / C5 cut copolymer resins, CPD / C9 cut copolymer resins, DCPD / C9 cut copolymer resins, resin blends C5 and C9 cutters, terpene / vinylaromatic copolymer resins, terpene / phenol copolymer resins, C5 / vinylaromatic cut copolymer resins, and mixtures of these resins.
    The term "terpene" here combines in a known manner the alpha-pinene, beta-pinene and limonene monomers; preferably, a limonene monomer is used which is present in a known manner in the form of three possible isomers: L-limonene (laevorotatory enantiomer), D-limonene (dextrorotatory enantiomer), or the dipentene, racemic of the dextrorotatory and levorotatory enantiomers. . Suitable vinylaromatic monomers are, for example, styrene, alpha-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyl-toluene, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, hydroxystyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene, any vinylaromatic monomer resulting from a C9 cut (or more generally from a C8 to C10 cut).
    More particularly, mention may be made of the resins chosen from the group consisting of homopolymer resins CPD, homopolymer resins DCPD, CPD / styrene copolymer resins, DCPD / styrene copolymer resins, polylimonene resins, limonene / styrene copolymer resins, limonene / CPD copolymer resins, limonene / DCPD copolymer resins, C5 / styrene cut copolymer resins, C5 / C9 cut copolymer resin resins, and mixtures of these resins.
    All the resins above are well known to those skilled in the art and commercially available, for example sold by the company DRT under the name "Dercolyte" for polylimonene resins, by the company Neville Chemical Company under the name "Super Nevtac ", by Kolon under the name" Hikorez "or by the company Exxon Mobil under the name" Escorez "with regard to C5 / styrene resins or C5 / C9 cut resins or by Struktol under the name" 40 MS "or" 40 NS "(mixtures of aromatic and / or aliphatic resins).
    According to one embodiment of the invention, the plasticizer system may further comprise a liquid plasticizer at room temperature (at 23 ° C) present at a rate of less than or equal to 2 phr.
    Any extender oil, whether of aromatic or non-aromatic nature, any liquid plasticizer at ambient temperature known for its plasticizing properties with respect to diene elastomers, can be used in addition to the plasticizing resin. At room temperature (23 ° C.), these plasticizers or these oils, more or less viscous, are liquids (that is to say, as a reminder, substances having the capacity to eventually take on the shape of their container) , in contrast in particular to hydrocarbon plasticizing resins which are inherently solid at room temperature.
    As liquid plasticizers at room temperature, particular mention may be made of liquid diene polymers, polyolefinic oils, naphthenic oils, paraffinic oils, DAE (Distillate Aromatic Extracts) oils, MES (Medium Extracted Solvates) oils, TDAE ( Treated Distillate Aromatic Extracts), Residual Aromatic Extract oils (RAE), Treated Residual Aromatic Extract (TREE) oils, Safety Residual Aromatic Extract oils (SRAE), mineral oils, vegetable oils, ethers, ester plasticizers, phosphate plasticizers, sulphonate plasticizers and mixtures of these compounds. According to a more preferred embodiment, the liquid plasticizer at ambient temperature is chosen from the group consisting of MES oils, TDAE oils, naphthenic oils, vegetable oils and mixtures of these oils.
    In one embodiment, the rubber composition of tires according to the invention comprises from 0 to 17 phr, preferably from 0 to 11 phr, of a plasticizer system comprising from 0 to 15 phr, preferably from 0 to 9 phr. pce, at least one plasticizing resin having a glass transition temperature Tg greater than or equal to 20 ° C, and preferably from 0 to 2 phr of a liquid plasticizer at room temperature. The preferred characteristics of the plasticizing resin as described above and the preferred characteristics of the liquid plasticizer at room temperature, when present, apply to this embodiment.
    In another embodiment, the rubber composition of tires according to the invention may comprise from 2 to 17 phr, preferably from 2 to 11 phr, of a plasticizer system comprising from 2 to 15 phr, preferably from 2 to 15 phr. at 9 phr, at least one plasticizing resin having a glass transition temperature Tg greater than or equal to 20 ° C, and preferably from 0 to 2 phr of a liquid plasticizer at room temperature. The preferred characteristics of the plasticizing resin as described above and the preferred characteristics of the liquid plasticizer at room temperature, when present, apply to this embodiment.
    In another embodiment, the plasticizer system may consist of 0 or 2 to 15 phr, preferably 0 or 2 to 9 phr, of a plasticizing resin having a glass transition temperature Tg greater than or equal to 20 ° C or a mixture of plasticizing resins having a glass transition temperature Tg greater than or equal to 20 ° C. In this embodiment, the tire rubber composition according to the invention is free of liquid plasticizer at room temperature. The preferred characteristics of the plasticizing resin as described above apply to this embodiment.
    In another embodiment, the rubber composition of tires according to the invention may be free of plasticizer system.
    Various additives
    The rubber compositions of the tires in accordance with the invention may also comprise all or part of the usual additives normally used in elastomer compositions intended to constitute external mixtures of finished articles made of rubber such as tires, in particular tire strips. rolling, such as for example protective agents such as anti-ozone waxes such as paraffin, chemical antiozonants, anti-oxidants, anti-fatigue agents, pigments.
    Crosslinking system
    The crosslinking system is preferably a vulcanization system, that is to say a system based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator. To this basic vulcanization system can be added, incorporated during the first non-productive phase and / or during the productive phase as described later, various known secondary accelerators or vulcanization activators such as zinc oxide. , stearic acid or equivalent compounds, guanidine derivatives (in particular diphenylguanidine), or known vulcanization retarders.
    When sulfur is used, it is used at a preferential rate of between 0.5 and 12 phr, in particular between 1 and 10 phr. These preferred ranges apply to any of the embodiments of the invention. The primary vulcanization accelerator is used at a preferred level of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr. These preferred ranges apply to any of the embodiments of the invention.
    The sulfur content used in the rubber composition of the tread according to the invention is most often between 0.5 and 3.0 phr, that of the primary accelerator between 0.5 and 5.0 phr. . These preferred ranges apply to any of the embodiments of the invention.
    It is possible to use as accelerator (primary or secondary) any compound capable of acting as accelerator for vulcanization of diene elastomers in the presence of sulfur, in particular thiazole-type accelerators and their derivatives, accelerators of the thiuram type, zinc dithiocarbamates. These accelerators are for example selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS"), tetrabenzylthiuram disulfide ("TBZTD"), N-cyclohexyl-2-benzothiazyl sulfenamide ("CBS"), N, N dicyclohexyl-2-benzothiazyl sulphenamide ("DCBS"), N-tert-butyl-2-benzothiazyl sulphenamide ("TBBS"), N-tert-butyl-2-benzothiazyl sulphenimide ("TBSI"), zinc dibenzyldithiocarbamate (" ZBEC ") and mixtures of these compounds.
    Preferred embodiment
    Among the preferred embodiments of the invention, mention may be made of: a tire for a vehicle carrying heavy loads comprising a tread having at least one rubber composition based on at least: an elastomer matrix comprising 51 to 85 phr of a copolymer based on styrene and butadiene having a glass transition temperature Tg strictly greater than -65 ° C and less than or equal to -30 ° C, and 15 phr to 49 phr of a polybutadiene ; from 55 to 100 phr of a reinforcing filler comprising predominantly silica; a chemical crosslinking system; a coupling agent; and from 0 to 4 phr of carbon black; the preferred characteristics of each of the constituents as described above apply to this embodiment; A tire for a vehicle carrying heavy loads comprising a tread having at least one rubber composition based on at least: an elastomer matrix comprising from 51 to 85 phr of a copolymer based on styrene and butadiene; having a glass transition temperature Tg strictly greater than -65 ° C and less than or equal to -30 ° C, and 15 phr to 49 phr of a polybutadiene; from 55 to 100 phr of a reinforcing filler comprising predominantly silica; a chemical crosslinking system; a coupling agent; from 0 to 4 phr of carbon black; and a plasticizer system comprising from 2 to 9 phr of at least one plasticizing resin having a glass transition temperature Tg greater than or equal to 20 ° C., and preferably from 0 to 2 phr of a liquid plasticizer at ambient temperature the total content of the plasticizer system in the composition ranges from 2 to 11 phr; the preferred characteristics of each of the constituents as described above apply to this embodiment; A tire for a vehicle carrying heavy loads comprising a tread having at least one rubber composition based on at least: an elastomer matrix comprising from 51 to 75 phr of a copolymer based on styrene and butadiene; having a glass transition temperature Tg strictly greater than -65 ° C and less than or equal to -30 ° C, from 9 phr to 31 phr of polybutadiene and from 4 to 16 phr of natural rubber; from 55 to 100 phr of a reinforcing filler comprising predominantly silica; a chemical crosslinking system; a coupling agent; and from 0 to 4 phr; the preferred characteristics of each of the constituents as described above apply to this embodiment; A heavy-weight vehicle tire having a tread having at least one rubber composition based on at least one elastomeric matrix comprising from 51 to 75 phr of a styrene-butadiene-based copolymer having a glass transition temperature Tg strictly greater than -65 ° C and less than or equal to -30 ° C, from 9 phr to 31 phr of polybutadiene and from 4 to 16 phr of natural rubber; from 55 to 100 phr of a reinforcing filler comprising predominantly silica; a chemical crosslinking system; a coupling agent; from 0 to 4 phr; and a plasticizer system comprising from 2 to 9 phr, of at least one plasticizing resin having a glass transition temperature Tg greater than or equal to 20 ° C., and preferably from 0 to 2 phr of a liquid plasticizer at temperature ambient, the total content of the plasticizer system in the composition ranges from 2 to 11 phr; the preferred features of each of the components as described above apply to this embodiment.
    Composition and tire manufacturing
    The rubber composition can be manufactured in suitable mixers, using two successive preparation phases according to a general procedure 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 high temperature, up to a maximum temperature of between 130 ° C and 200 ° C, preferably between 145 ° C and 185 ° C, followed by a second phase of mechanical work (sometimes referred to as "productive" phase) at lower temperature, typically below 120 ° C, for example between 60 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system or vulcanization.
    After the incorporation of all the ingredients of the rubber composition, the final composition thus obtained can then be calendered, for example in the form of a sheet or a plate, in particular for a characterization in the laboratory, or else extruded, to form for example a rubber profile used as tread of a tire for a vehicle carrying heavy loads, in particular for a heavy-duty vehicle or for a civil engineering vehicle.
    The tire according to the invention is preferably a tire intended to equip a vehicle carrying heavy loads, such as heavy goods vehicles, buses, civil engineering vehicles. Preferably, the tire according to the invention is a tire intended to equip a heavy vehicle.
    The tire may be manufactured by any method well known to those skilled in the art.
    The aforementioned features of the present invention, as well as others, will be better understood on reading the following description of several embodiments of the invention, given by way of illustration and not limitation. II - EXAMPLES OF CARRYING OUT THE INVENTION II-1 Measurements and tests used:
    Traction tests
    These tensile tests make it possible to determine the elastic stress and the properties at break. Unless otherwise indicated, they are based on the French standard NFT 46-002.
    Elongations at break (in%) are measured. All these tensile measurements are carried out at a temperature of 60 ° C ± 2 ° C, and under normal humidity conditions (50 ± 5% relative humidity). tearability
    The indices of tearability are measured at 100 ° C. In particular, the force to be exerted to obtain the fracture (FRD, in Mpa (in N / mm)) is determined and the breaking strain (DRD, in%) is measured on a specimen of dimensions 10 x 105 x 2.5 mm notched. at the center of its length by 3 notches to a depth of 5 mm, to cause the rupture of the test piece. Thus the Energy can be determined to cause the rupture (Rupture Energy) of the specimen which is the product of the FRD and DRD.
    For more visibility, the results will be indicated in base 100; the value 100 being attributed to the witness T0. A result less than 100 for elongation at break (%) and for tearability will indicate a decrease in the value concerned, and conversely, a result greater than 100 will indicate an increase in the value concerned.
    Dynamic Properties
    The dynamic properties including tan (δ) max, representative of the hysteresis, are measured on a viscoanalyzer (Metravib VA4000), according to the ASTM D 5992-96 standard. The response of a sample of the vulcanized composition (cylindrical specimens 4 mm thick and 400 mm 2 in section), subjected to sinusoidal stress in alternating simple shear, at the frequency of 10 Hz, at a temperature of 60 is recorded. ° C. A strain amplitude sweep is carried out from 0.1% to 100% peak-to-peak (forward cycle), then from 100% to 0.1% peak-to-peak (return cycle). The results exploited are the complex dynamic shear modulus (G *) and the loss factor tan (δ). For the forward cycle, we indicate the maximum value of tan (δ) observed, denoted tan (δ) maX; as well as the modulus G * at 50% deformation noted G * 50%
    For more visibility, the results will be indicated in base 100; the value 100 being attributed to the witness T0. A result less than 100 indicating a decrease in the value of tan (δ) max (decrease in rolling resistance), and conversely, a result greater than 100, will indicate an increase in the value of tan (δ) max (increase of rolling resistance).
    The results of G * are also expressed in base 100, the value 100 being attributed to the control T0. A result less than 100 indicating a decrease in the value concerned, and vice versa, a result greater than 100, will indicate an increase in the value concerned. II-2: Preparation of rubber compounds:
    The following tests are carried out for the preparation of the compositions in the following manner: the mixed diene elastomers (SBR) are introduced into an internal mixer, 70% filled and having an initial tank temperature of about 50.degree. BR and NR when present), the reinforcing filler (silica), optionally the carbon black, the coupling agent and, after one to two minutes of mixing, the various other ingredients (including the resin when it is present). is present) with the exception of the vulcanization system. Thermomechanical work (non-productive phase) is then carried out in one step (total mixing time equal to about 5 minutes), until a maximum temperature of "fall" of about 165 ° C. is reached.
    The mixture thus obtained is recovered, cooled and the vulcanization system (sulfur and accelerator) is added to an external mixer (homo-finisher) at 70 ° C., mixing the whole (productive phase) for about 5 to 6 minutes. .
    The compositions thus obtained are then calendered either in the form of plates (thickness of 2 to 3 mm) or of thin sheets of rubber for the measurement of their physical or mechanical properties after firing, or in the form of profiles that can be used directly, after cutting. and / or assembly to the desired dimensions, for example as semi-finished products for tires, in particular as treads of tires.
    The composition TO is a control composition conventionally used and marketed for the manufacture of tire treads intended to equip vehicles carrying heavy loads. It therefore represents an understanding of performance - rolling resistance, wear resistance and resistance to attack - for tires that are marketed.
    It has been sought to achieve or improve this compromise by modifying several parameters in a rubber composition. These modifications are detailed in tests A. Tests B to D illustrate other embodiments of the invention. II-3: Test A:
    The examples presented in Table 1 are intended to compare the different rubber properties of compositions C1 and C2 according to the invention to a series of control compositions (TO to T3). The results of the properties measured after firing are presented in Table 2.
    The levels of the various constituents of the compositions presented in Table 1 are expressed in phr. All the compositions (TO to T3 and C1 to C2) comprise a crosslinking system conventionally used in the manufacture of tire treads; this crosslinking system comprising in particular sulfur, ZnO of stearic acid and an accelerator.
    Table 1
    (1) SBR non-functional, unexpanded solution with 24% 1,2-polybutadiene units; 26.5% styrene units and Tg = -48 ° C; (2) SBR solution functionalized tin, not extended, with 24%> of polybutadiene units 1,2: 15,5% of styrene unit, and a Tg = -65 ° C; (3) Natural rubber; (4) Polybutadiene neodymium with 98% 1,4-cis butadiene units and a Tg = -108 ° C; (5) "Zeosil 1165 MP" silica type "HDS" from Solvay; (6) NI 34 carbon black; (7) Resin C5 / C9 cut sold by the company Cray Valley under the name "Resin THER 8644" (Tg = 44 ° C); (8) coupling agent: TESPT ("Si69" from Evonik - Degussa); (9) Diphenylguanidine ("Perkacit" DPG from Flexsys); (10) N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine marketed by Flexsys under the name "Santoflex 6-PPD".
    The composition T1 differs from the composition TO by the nature of the elastomeric matrix. The amount of styrene butadiene copolymer (SBR) having a glass transition temperature of -65 ° C was increased. This copolymer is the majority copolymer in the composition T1.The majority charge is carbon black.
    The composition T2 differs from the composition T1 by the nature of the SBR copolymer. The SBR used in the T2 composition has a higher glass transition temperature than the SBR copolymer of the composition T1.
    The composition T3 differs from the composition T1 by the nature of the reinforcing filler. The organic black carbon charge of the composition T1 was replaced by an inorganic filler: silica. The charge rate is substantially equivalent.
    The composition C1, according to the invention, differs from the composition T3 by the nature of the SBR copolymer. The SBR used in the composition C1 has a glass transition temperature higher than that of the SBR copolymer of the composition T3.
    The composition C2 according to the invention differs from the composition C1 in that the silica content has been increased.
    The properties of the compositions are shown in Table 2 below.
    Table 2
    Although some of its properties are improved (relative to the composition TO), the composition T1 has hysteresis properties which are not acceptable. The compromise of performance is not obtained with this composition. The same observation is made with the T2 composition. The composition T3 has an improvement of the hysteresis properties but to the detriment of its limiting properties which are degraded too much. The compromise of performances is also not obtained with the composition T3.
    It is found that the compositions C1 and C2 which represent the compositions according to the invention have, surprisingly, a good compromise of performance with respect to the control compositions T2 and T3. This finding is all the more surprising, since it clearly appears from the control compositions T2 and T3 that the use of an SBR having a high glass transition temperature and that the use of silica as a predominant reinforcing filler negatively the properties of these compositions. We would not have combined these two compounds in order to improve the performance compromise. Surprisingly, it is found that the combination of an SBR having a high glass transition temperature with a siliceous filler makes it possible to improve both the hysteresis priorities and the limiting properties. The improvement of the mechanical properties translated by the gain in rigidity is favorable in terms of wear resistance of a tire provided with a tread constituted by such a composition. The improvement of the hysteretic properties is favorable for reducing the rolling resistance of a tire provided with a tread constituted by such a composition. The improvement of the limiting properties (tearability and elongation at break) is favorable with regard to the resistance to attack of a tire provided with a tread constituted by such a composition.
    In conclusion, these results show that the specific combination of an SBR having a glass transition temperature strictly greater than -65 ° C and less than or equal to -30 ° C as being the majority copolymer in the elastomer matrix with a majority charge that is a silica makes it possible, surprisingly, to obtain properties of rigidity, limiting properties and hysteresis properties that are comparable, or even improved, with respect to a control composition conventionally used for the manufacture of tread for tires intended for equip vehicles carrying heavy loads. II-4: Test B:
    The examples presented in Table 3 are intended to show the different rubber properties of the compositions according to the invention (C3 to C5) as a function of the silica content. The results of the properties measured after firing are presented in Table 4 and are compared with the results of the TO composition previously described.
    The levels of the various constituents of the compositions presented in Table 3 are expressed in phr. All the compositions (C3 to C5) comprise a crosslinking system conventionally used in the manufacture of tire treads; this crosslinking system comprising sulfur, ZnO of stearic acid and an accelerator.
    Table 3
    (1) SBR non-functional, unexpanded solution with 24% 1,2-polybutadiene units; 26.5% styrene units and a T g = -48 ° C; (2) SBR solution functionalized tin, not extended, with 24% of 1,2-polybutadiene units: 15,5% of styrene unit, and a Tg = -65 ° C; (3) Natural rubber; (4) Polybutadiene Neodymium with 98% 1,4-cis and Tg = -108 ° C; (5) "Zeosil 1165 MP" silica type "H DS" from Solvay; (6) NI 34 carbon black; (7) coupling agent: TESPT ("Si69" from Evonik - Degussa); (8) Diphenylguanidine ("Perkacit" DPG from Flexsys); (9) N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine marketed by Flexsys under the name "Santoflex 6-PPD"; (10) Resin cut C5 / C9 marketed by Cray Valley under the name "Resin THER 8644" (Tg = 44 ° C).
    Table 4
    The compositions C3 to C5 according to the invention represent another embodiment of the invention in which the elastomeric matrix is a ternary mixture. The silica content was gradually increased in these compositions.
    Table 4 shows the properties of the compositions C3 to C5 according to the invention compared to the composition TO which is conventionally used for the manufacture of tread tires intended to equip vehicles carrying heavy loads.
    It is found that the three compositions according to the invention C3, C4 and C5 surprisingly have a good understanding of performance.
    II-5: Test C
    The examples presented in Table 5 are intended to show the different rubber properties of the compositions according to the invention (C6 to C8) as a function of different levels of plasticizing resin. The results of the properties measured after firing are presented in Table 6.
    The levels of the various constituents of the compositions presented in Table 5 are expressed in phr. All the compositions (C6 to C8) comprise a crosslinking system conventionally used in the manufacture of tire treads; this crosslinking system comprising sulfur, ZnO of stearic acid and an accelerator.
    Table 5
    (1) SBR non-functional, unexpanded solution with 24% 1,2-polybutadiene units; 26.5% styrene units and a T g = -48 ° C; (2) SBR solution functionalized tin, not extended, with 24% of 1,2-polybutadiene units: 15,5% of styrene unit, and a Tg = -65 ° C; (3) Natural rubber; (4) Polybutadiene Neodymium with 98% 1,4-cis and Tg = -108 ° C; (5) "Zeosil 1165 MP" silica type "HDS" from Solvay; (6) NI 34 carbon black; (7) coupling agent: TESPT ("Si69" from Evonik - Degussa); (8) Diphenylguanidine ("Perkacit" DPG from Flexsys); (9) N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine marketed by Flexsys under the name "Santoflex 6-PPD"; (10) Resin cut C5 / C9 marketed by Cray Valley under the name "Resin THER 8644" (Tg = 44 ° C).
    Table 6
    The compositions C6 to C8 according to the invention represent another embodiment of the invention in which the elastomeric matrix is a ternary mixture and in which the silica content is higher than that of the compositions C1 and C2. The resin content was gradually increased in the C6 to C8 compositions.
    Table 6 shows the properties of the compositions C6 to C8 according to the invention with respect to the composition TO which is conventionally used for the manufacture of tread of tires intended to equip vehicles carrying heavy loads.
    It is found that the three compositions according to the invention C6, C7 and C8 surprisingly have a good understanding of performance.
    II-5: Test D The example presented in Table 7 is intended to show the different rubber properties of a composition according to the invention (C9) comprising no resin. The results of the properties measured after firing are presented in Table 8.
    The levels of the various constituents of the composition shown in Table 7 are expressed in phr. The composition C9 comprises a crosslinking system conventionally used in the manufacture of tire treads; this crosslinking system comprising sulfur, ZnO of stearic acid and an accelerator.
    Table 7
    (1) SBR non-functional, unexpanded solution with 24% 1,2-polybutadiene units; 26.5% styrene units and a T g = -48 ° C; (2) SBR solution functionalized tin, not extended, with 24% of 1,2-polybutadiene units: 15,5% of styrene unit, and a Tg = -65 ° C; (3) Natural rubber; (4) Polybutadiene Neodymium with 98% 1,4-cis and Tg = -108 ° C; (5) "Zeosil 1165 MP" silica type "H DS" from Solvay; (6) NI 34 carbon black; (7) coupling agent: TESPT ("Si69" from Evonik - Degussa); (8) Diphenylguanidine ("Perkacit" DPG from Flexsys); (9) N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine marketed by Flexsys under the name "Santoflex 6-PPD"; (10) Resin cut C5 / C9 marketed by Cray Valley under the name "Resin THER 8644" (Tg = 44 ° C).
    Table 8
    The composition C9 according to the invention represents another embodiment of the invention in which the elastomeric matrix is a ternary mixture. This composition does not include resin.
    Table 8 shows the properties of the composition C9 according to the invention with respect to the composition TO which is conventionally used for the manufacture of tread of tires intended to equip vehicles carrying heavy loads.
    It is found that the composition according to the invention C9 surprisingly has a good understanding of performance.
    权利要求:
    Claims (19)
    [1" id="c-fr-0001]
    A pneumatic tire intended to equip a vehicle carrying heavy loads, this tire comprising a tread having at least one rubber composition based on at least: an elastomer matrix comprising in majority a styrene-based copolymer; butadiene having a glass transition temperature Tg strictly greater than -65 ° C and less than or equal to -30 ° C, - a reinforcing filler comprising predominantly silica, - a chemical crosslinking system, - a coupling agent, and a plasticizer system comprising from 0 to 15 phr, preferably from 0 to 9 phr, of at least one plasticizing resin having a glass transition temperature Tg of greater than or equal to 20 ° C., and whose total content of the plasticizer system in the composition ranges from 0 to 17 phr, preferably from 0 to 11 phr.
    [2" id="c-fr-0002]
    2. A tire according to claim 2, in which the plasticizer system comprises from 2 to 15 phr, preferably from 2 to 9 phr of the plasticizing resin, the total content of the plasticizer system in the composition ranges from 2 to 17 phr, preferably from 2 to 11 pce.
    [3" id="c-fr-0003]
    3. A tire according to any one of claims 1 to 2, wherein the copolymer based on styrene and butadiene is obtained by solution polymerization.
    [4" id="c-fr-0004]
    A tire according to any one of claims 1 to 3, wherein the styrene-butadiene copolymer has a glass transition temperature Tg of from -60 ° C to -40 ° C.
    [5" id="c-fr-0005]
    A tire according to any one of claims 1 to 4, wherein the styrene-based butadiene-based copolymer is a styrene-butadiene copolymer.
    [6" id="c-fr-0006]
    A tire according to any one of claims 1 to 5, wherein the elastomeric matrix further comprises at least a second diene elastomer other than the styrene-butadiene copolymer.
    [7" id="c-fr-0007]
    A tire according to claim 6, wherein the second diene elastomer is selected from the group consisting of polybutadienes, natural rubber, synthetic isoprenes, butadiene copolymers other than butadiene-styrene copolymers, copolymers of isoprenes and mixtures of these polymers and copolymers; preferably the second diene elastomer is a polybutadiene.
    [8" id="c-fr-0008]
    8. A tire according to claim 6 or 7, wherein the content of the second diene elastomer ranges from 5 to 49 phr, preferably from 15 to 35 phr.
    [9" id="c-fr-0009]
    9. A tire according to claim 6 or 7, wherein the elastomeric matrix further comprises at least a third diene elastomer different from the copolymer based on styrene and butadiene and the second diene elastomer.
    [10" id="c-fr-0010]
    10. A tire according to claim 9 wherein the third diene elastomer is selected from natural rubber and an isoprene elastomer, preferably it is made of natural rubber.
    [11" id="c-fr-0011]
    11. A tire according to claim 9 or 10, wherein the content of the second diene elastomer ranges from 0.5 to 35 phr and the content of the third diene elastomer ranges from 0.5 to 35 phr, preferably the level of the second diene elastomer. ranges from 9 to 31 phr and the rate of the third diene elastomer ranges from 4 to 24 phr.
    [0012]
    Pneumatic tire according to one of claims 1 to 11, wherein the composition further comprises carbon black.
    [13" id="c-fr-0013]
    13. A tire according to claim 12, wherein the carbon black content is less than or equal to 10 phr, less than or equal to 5 phr, preferably the carbon black content is from 0.5 to 4 phr.
    [14" id="c-fr-0014]
    14. A tire according to any one of claims 1 to 13, wherein the level of the reinforcing filler is 55 to 200 phr, preferably 55 to 150 phr, more preferably 55 to 80 phr.
    [15" id="c-fr-0015]
    15. A tire according to any one of claims 1 to 14, wherein the plasticizing resin has a glass transition temperature Tg greater than or equal to 30 ° C, preferably from 30 to 100 ° C.
    [16" id="c-fr-0016]
    A tire according to any one of claims 1 to 15, wherein the plasticizing resin is selected from the group consisting of cyclopentadiene homopolymer or copolymer resins, dicyclopentadiene homopolymer or copolymer resins, resins of homopolymer or terpene copolymer, C5 homopolymer or copolymer resins, C9 homopolymer or copolymer resins, C5 homopolymer or copolymer resin blends and homopolymer or copolymer resins C9, alpha-methyl-styrene homopolymer or copolymer resins and mixtures of these resins.
    [17" id="c-fr-0017]
    17. A tire according to any one of claims 1 to 16, wherein the plasticizer system comprises from 0 to 2 phr of at least one plasticizer liquid at room temperature.
    [18" id="c-fr-0018]
    18. A tire according to any one of claims 1 to 14, in the composition is free of a plasticizer system.
    [19" id="c-fr-0019]
    19. A tire according to any one of claims 1 to 18, characterized in that it is intended to equip a heavy vehicle.
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    同族专利:
    公开号 | 公开日
    CN108290446A|2018-07-17|
    BR112018012857A2|2018-12-04|
    WO2017109400A1|2017-06-29|
    EP3393823A1|2018-10-31|
    EP3393823B1|2021-12-01|
    FR3045636B1|2017-12-29|
    引用文献:
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    WO2002088238A1|2001-03-12|2002-11-07|Societe De Technologie Michelin|Rubber composition for tyre running tread|
    WO2015091933A1|2013-12-20|2015-06-25|Compagnie Generale Des Etablissements Michelin|Tyre for vehicles intended to bear heavy loads|
    WO2015091929A1|2013-12-20|2015-06-25|Compagnie Generale Des Etablissements Michelin|Tire for vehicle bearing heavy loads|
    WO2015185395A1|2014-06-05|2015-12-10|Compagnie Generale Des Etablissements Michelin|Tyre with low rolling resistance|WO2022008818A1|2020-07-07|2022-01-13|Compagnie Generale Des Etablissements Michelin|Tyre having improved properties of endurance and rolling resistance|JP4890834B2|2005-10-27|2012-03-07|東洋ゴム工業株式会社|Pneumatic tires for passenger cars|
    EP1884376B1|2006-08-03|2010-02-10|The Yokohama Rubber Co., Ltd.|Pneumatic tire|
    US7594528B2|2007-03-08|2009-09-29|The Goodyear Tire & Rubber Company|Tire with sidewall comprised of emulsion styrene/butadiene rubber, cis 1,4-polyisoprene rubber and cis 1,4-polybutadiene rubber|
    KR101114857B1|2008-12-23|2012-03-06|한국타이어 주식회사|Rubber composition for tire tread|
    FR3017871B1|2014-02-21|2016-02-19|Michelin & Cie|RUBBER COMPOSITION COMPRISING A PLASTICIZING SYSTEM BASED ON HYDROCARBONATED RESIN WITH LOW GLASS TRANSITION TEMPERATURE|CN110914067A|2017-06-30|2020-03-24|米其林集团总公司|Aircraft tire|
    WO2020084246A1|2018-10-25|2020-04-30|Compagnie Generale Des Etablissements Michelin|Agricultural vehicle tyre|
    FR3087783A3|2018-10-25|2020-05-01|Compagnie Generale Des Etablissements Michelin|AGRICULTURAL VEHICLE TIRES|
    US10947368B2|2019-03-04|2021-03-16|The Goodyear Tire & Rubber Company|Pneumatic tire|
    CN112143056A|2020-09-02|2020-12-29|中策橡胶集团有限公司|Tread rubber composition and application thereof in production of racing tires for drifting|
    法律状态:
    2016-12-22| PLFP| Fee payment|Year of fee payment: 2 |
    2017-06-23| PLSC| Publication of the preliminary search report|Effective date: 20170623 |
    2017-12-21| PLFP| Fee payment|Year of fee payment: 3 |
    2019-09-27| ST| Notification of lapse|Effective date: 20190906 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1563039A|FR3045636B1|2015-12-22|2015-12-22|TIRE FOR VEHICLE CARRYING HEAVY LOADS COMPRISING A NEW BEARING BAND|FR1563039A| FR3045636B1|2015-12-22|2015-12-22|TIRE FOR VEHICLE CARRYING HEAVY LOADS COMPRISING A NEW BEARING BAND|
    CN201680069720.0A| CN108290446A|2015-12-22|2016-12-21|The tire for including novel tread for carrying maximum type vehicle|
    PCT/FR2016/053594| WO2017109400A1|2015-12-22|2016-12-21|Tyre for vehicle carrying heavy loads comprising a novel tread|
    BR112018012857-0A| BR112018012857B1|2015-12-22|2016-12-21|TIRE FOR A HEAVY DUTY CARRIER VEHICLE INCLUDING AN INNOVATIVE TREADMILL|
    EP16826424.0A| EP3393823B1|2015-12-22|2016-12-21|Tire for vehicles transporting heavy loads comprising a new tread|
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