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    • 专利摘要:
    The invention therefore relates to a rubber composition based on at least one diene elastomer, a reinforcing filler, a vulcanization system and a combination of plasticizers, said combination of plasticizers comprising more than 15 phr (parts by weight per hundred parts by weight). weight of elastomer) of hydrocarbon resin with a glass transition temperature (Tg) of between -40 ° C. and 20 ° C. and a resin of Tg greater than 20 ° C., the total plasticizer content being greater than or equal to 40 phr and the levels of reinforcing filler and plasticizer being such that the ratio of the total charge rate and the total plasticizer content is in a range from 1.3 to 2.
    公开号:FR3017870A1
    申请号:FR1451386
    申请日:2014-02-21
    公开日:2015-08-28
    发明作者:Philippe Labrunie；Jean-Christophe Gallego
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:

    [0001] The invention relates to compositions, in particular for tires and more particularly to compositions comprising a plasticizer system based on low glass transition temperature resin (Tg).  [002] Since fuel savings and the need to protect the environment have become a priority, it has been necessary to produce tires with reduced rolling resistance without penalizing the other properties of the tire.  Manufacturers have developed tire compositions that make it possible to reduce this rolling resistance, in particular by introducing silica as reinforcing filler, or resin with a high glass transition temperature as plasticizer.  [3] For example, the Applicants have already described the use of high Tg resins, as described in WO-2005/087859 or WO-2006/061064.  [4] Some documents describe the use of low Tg resins, as for example in the document JP-2005213486 which proposes the use of low Tg resin at a rate of between 0.5 and 5 phr to improve the adhesive strength. vintage and the industrial feasibility of the compositions.  Document US-2007/0167557 proposes the use of low Tg resin at a rate of 10 phr to improve the resistance to flaking.  JP-2001144262 discloses compositions which have improved abrasion resistance and adhesion and include low Tg resins.  [5] Nevertheless, manufacturers are still looking for solutions to improve at the same time all the performances of the tire compositions and in particular the rolling resistance, the adhesion on dry ground, the adhesion on wet ground, the hardness of the cooked compositions, associated with the road behavior and driving comfort, along with the viscosity of the raw compositions, associated with the ease of industrial implementation of the compositions (processability).  [6] At present, the Applicants have shown that particular compositions based on low Tg resin, allowed to have an improved compromise between many desired performances for the tire compositions, that is to say rolling, the adhesion on dry ground, the adhesion on wet ground, the hardness of the cooked compositions, at the same time as the viscosity of the raw compositions.  [007] The invention therefore relates to a rubber composition based on at least one diene elastomer, a reinforcing filler, a vulcanization system and a combination of plasticizers, said combination of plasticizers comprising more than 15 phr (parts in weight per hundred parts by weight of elastomer) of hydrocarbon resin with a glass transition temperature (Tg) of between -40 ° C. and 20 ° C. and a resin of Tg greater than 20 ° C., the total amount of plasticizer being greater than or equal to 40 phr and the levels of reinforcing filler and plasticizer being such that the ratio of the total charge rate and the total plasticizer content is in a range from 1.3 to 2.  [008] Preferably, the invention relates to a composition as defined above wherein said diene elastomer is selected from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, copolymers of isoprene and mixtures of these elastomers.  Preferably, said diene elastomer is selected from the group consisting of polybutadienes, butadiene and styrene copolymers, and mixtures of these elastomers.  [009] Preferably also, the invention relates to a composition as defined above in which the reinforcing filler is selected from the group consisting of silicas, carbon blacks and mixtures thereof.  Preferably, the level of reinforcing filler is in a range from 30 to 200 phr, preferably from 30 to 150 phr.  According to a first preferred embodiment, the invention relates to a composition as defined above in which the majority reinforcing filler is carbon black.  Preferably, the level of carbon black is in a range from 50 to 140 phr, preferably from 60 to 110 phr.  According to a second preferred embodiment, alternative to the first embodiment above, the invention relates to a composition as defined above in which the majority reinforcing filler is silica.  Preferably, the silica content is in a range from 50 to 140 phr, preferably from 70 to 120 phr.  Preferably, the invention relates to a composition as defined above wherein the total level of plasticizers is greater than or equal to 50 phr, preferably within a range of 50 to 120 phr.  Preferably, the total level of plasticizers is in a range from 50 to 100 phr, preferably from 50 to 80 phr.  Preferably, the invention relates to a composition as defined above in which the hydrocarbon resin content of Tg between -40 ° C and 20 ° C is in a range from 15 to 70 phr, from preferably from 15 to 50 phr, and more preferably from 20 to 40 phr.  Also preferably, the invention relates to a composition as defined above in which the hydrocarbon resin previously mentioned as a hydrocarbon resin with a Tg between -40 ° C and 20 ° C has a Tg between -20 ° C and 0 ° C.  More preferably, the invention relates to a composition as defined above in which the hydrocarbon resin previously mentioned as hydrocarbon resin with a Tg of between -40 ° C. and 20 ° C. has a number-average molecular mass less than 800 g / mol, preferably less than 600 g / mol; and more preferably, less than 400 g / mol.  Preferably, the invention relates to a composition as defined above in which the hydrocarbon resin previously mentioned as hydrocarbon resin of Tg between -40 ° C and 20 ° C has a softening point included in a range from 0 to 40 ° C, preferably 10 to 30 ° C.  Also preferably, the invention relates to a composition as defined above in which the hydrocarbon resin previously mentioned as hydrocarbon resin of Tg between -40 ° C and 20 ° C has a polymolecularity index (Ip) less than 3, preferably less than 2.  Preferably, the invention relates to a composition as defined above in which the hydrocarbon resin content of Tg greater than 20 ° C is in a range from 5 to 50 phr, preferably from 7 to 40 phr, more preferably 10 to 35 phr.  [0019] Also preferably, the invention relates to a composition as defined above in which the hydrocarbon resin previously mentioned as a hydrocarbon resin with a Tg greater than 20 ° C. has a Tg greater than 30 ° C.  [0020] More preferably, the invention relates to a composition as defined above in which the hydrocarbon resin previously mentioned as a hydrocarbon resin with a Tg greater than 20 ° C has a number-average molecular weight of between 400 and and 2000 g / mol, preferably between 500 and 1500 g / mol.  Also preferably, the invention relates to a composition as defined above in which the hydrocarbon resin previously mentioned as a hydrocarbon resin with a Tg greater than 20 ° C. has a polymolecularity index (Ip) of less than 3, preferably less than to 2.  More preferably, the invention relates to a composition as defined above in which the ratio of the total charge rate and the total plasticizer content is in a range from 1.3 to 1.8, preferably from 1.4 to 1.7.  Preferably, the invention relates to a composition as defined above further comprising in the combination of plasticizers, a plasticizing oil.  Preferably, the invention relates to a composition as defined above in which the plasticizing oil is chosen from the group consisting of naphthenic oils, paraffinic oils, MES oils (Medium Extracted Solvates), TDAE oils. (Treated Distillate Aromatic Extracts), mineral oils, vegetable oils, ethers plasticizers, ester plasticizers, phosphate plasticizers, sulphonate plasticizers and mixtures thereof.  Also preferably, the invention relates to a composition as defined above in which the level of plasticizing oil is in a range from 2 to 80 phr, preferably from 5 to 60 phr.  The invention also relates to a tire comprising a composition as defined above.  Preferably, the invention relates to a tire as defined above comprising said composition as defined above in all or part of the tread.  Preferably, the tire according to the invention will be selected from tires intended to equip a two-wheeled vehicle, a passenger vehicle, or a vehicle called "heavyweight" (that is to say, subway, bus , off-the-road vehicles, road transport vehicles such as trucks, tractors, trailers), or aircraft, civil engineering, agrarian, or handling equipment.  I-Constituents of the Composition The rubber compositions according to the invention are based on at least one diene elastomer, a reinforcing filler, a vulcanization system and a combination of plasticizers, said combination of plasticizers comprising more than pf (parts by weight per hundred parts by weight of elastomer) of hydrocarbon resin with a glass transition temperature (Tg) of between -40 ° C and 20 ° C and a resin of Tg greater than 20 ° C, the total plasticizer being greater than or equal to 40 phr and the levels of reinforcing filler and plasticizer being such that the ratio of the total charge rate and the total plasticizer content is in a range from 1.3 to 2.  By the term "composition based on" is meant a composition comprising the mixture and / or the reaction product in situ of the various basic constituents used, some of these constituents being able to react and / or being intended to react. between them, at least partially, during the various phases of manufacture of the composition, or during the subsequent firing, modifying the composition as it was initially prepared.  Thus, the compositions as implemented for the invention may be different in the uncrosslinked state and in the crosslinked state.  In the present description, unless otherwise expressly indicated, all the percentages (%) indicated are percentages by weight.  On the other hand, any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term "from a to b" means the range from a to b (i.e., including the strict limits a and b).  1-1 Diene Elastomer [0032] The compositions may contain a single diene elastomer or a mixture of several diene elastomers.  By elastomer (or "rubber", the two terms being considered synonymous) of the "diene" type, it is recalled here that must be understood in a known way (one or more) elastomer at least in part ( i. e. , a homopolymer or a copolymer) of diene monomers (monomers bearing two carbon-carbon double bonds, conjugated or otherwise).  The 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 level 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 as meaning that may be used in the compositions according to the invention: (a) any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms ; (b) any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinyl aromatic compounds having 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 nonconjugated 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 art of the tire will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b) above.  As conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (1-O-alkyl) -1,3-butadienes are particularly suitable. 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.  Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial "vinyl-toluene" mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.  The copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units.  The elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used.  The elastomers can be for example block, statistical, sequence, microsequential, and be prepared in dispersion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.  For coupling with carbon black, there may be mentioned, for example, functional groups comprising a C-Sn bond or amine functional groups such as aminobenzophenone for example; for coupling to a reinforcing inorganic filler such as silica, mention may be made, for example, of silanol or polysiloxane functional groups having a silanol end (as described, for example, in FR 2,740,778, US 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, US 6,503,973, WO 2009/000750 and WO 2009/000752).  As other examples of functionalized elastomers, mention may also be made of elastomers (such as SBR, BR, NR or IR) of the epoxidized type.  These functionalized elastomers may be used in a blend with each other or with unfunctionalized elastomers.  For example, it is possible to use a silanol or polysiloxane functionalized elastomer having a silanol end, in admixture with a coupled and / or tin-starred elastomer (described in WO 11/042507), the latter representing a rate of from 5 to 50 %, for example from 25 to 50%.  Suitable polybutadienes and in particular those having a content (mol%) in units -1,2 between 4% and 80% or those having a content (% - 8 molar) in cis-1,4 greater than 80%, polyisoprenes, butadiene-styrene copolymers and in particular those having a Tg (glass transition temperature (Tg, measured according to ASTM D3418) between 0 ° C. and -70 ° C. and more particularly between -10 ° C. and -60 ° C, a styrene content of between 5% and 60% by weight and more particularly between 20% and 50%, a content (mol%) in -1,2 bonds of the butadiene part of between 4% and 75%, a content (mol%) of trans-1,4 bonds of between 10% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a Tg from -40 ° C. to -80 ° C., the isoprene-styrene copolymers and in particular those having a styrene content of between 5% and 50% by weight and a Tg c omprise between -5 ° C and -60 ° C.  In the case of butadiene-styrene-isoprene copolymers, those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40% and an isoprene content of between 15% and 60% by weight are particularly suitable. 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. 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 units -1,4 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.  In summary, the diene elastomer of the composition is preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated as "BR"), synthetic polyisoprenes (IR) and natural rubber (NR). , butadiene copolymers, isoprene copolymers and mixtures of these elastomers.  Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene-copolymers of butadiene-styrene (SBIR), butadiene-acrylonitrile copolymers (NBR), butadiene-styrene-acrylonitrile copolymers (NSBR) or a mixture of two or more of these compounds.  According to one particular embodiment, the composition comprises from 50 to 100 phr of an SBR elastomer, whether it be an emulsion prepared SBR ("ESBR") or an SBR prepared in solution. ( "SSBR").  According to another particular embodiment, the diene elastomer is a blend (mixture) SBR / BR.  According to other possible embodiments, the diene elastomer is a SBR / NR (or SBR / IR), BR / NR (or BR / IR) or SBR / BR / NR (or SBR / BR / IR).  In the case of an SBR elastomer (ESBR or SSBR), an SBR having an average styrene content, for example between 20% and 35% by weight, or a high styrene content, for example, is used. from 35 to 45%, a vinyl ring content of the butadiene part of between 15% and 70%, a content (mol%) of trans-1,4 bonds of between 15% and 75% and a Tg of between -10 ° C and -55 ° C; such an SBR can be advantageously used in admixture with a BR preferably having more than 90% (mol%) of cis-1,4 bonds.  According to another particular embodiment, the diene elastomer is a predominantly isoprene elastomer (that is to say whose mass fraction of isoprene elastomer is the largest, compared to the mass fraction of other elastomers) .  By "isoprene elastomer" is meant in known manner a homopolymer or copolymer of isoprene, in other words a diene elastomer selected from the group consisting of natural rubber (NR) which can be plasticized or peptized, the polyisoprenes of synthesis (IR), the various isoprene copolymers and the mixtures of these elastomers.  Among the isoprene copolymers, mention will in particular be made of copolymers of isobutene-isoprene (butyl rubber - IIR), isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene (SBIR).  This isoprene elastomer is preferably natural rubber or synthetic cis-1,4 polyisoprene; of these synthetic polyisoprenes, polyisoprenes having a content (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used.  Preferably, according to another embodiment, the rubber composition comprises predominantly (that is to say, with the highest mass ratio), a non-isoprene diene elastomer.  By "non-isoprene diene elastomer" is meant within the meaning of the present application an elastomer derived at least in part (i. e. homopolymer or copolymer) of diene monomers (monomers carrying two carbon-to-carbon double bonds) other than isoprene.  Thus, non-isoprenic diene elastomers as defined herein also include copolymers comprising isoprene as co-monomer.  Natural rubber and isoprenic homopolymers (ie consisting of isoprene functionalized monomers or not) are excluded from the present definition.  According to this preferred embodiment, all the elastomers mentioned above with the exception of natural rubber and polyisoprenes are suitable as non-isoprene diene elastomer.  In particular, it is possible to use non-isoprenic diene elastomers preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated to "BR"), butadiene copolymers, isoprene copolymers and mixtures of these elastomers.  Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-copolymers. butadiene-styrene (SBIR).  Still according to this preferred embodiment, it will be understood that, in the case of elastomer cutting, the total content of so-called "non-isoprenic" elastomers must be greater than the total content of the elastomers chosen from the group consisting of natural rubber and polyisoprenes. synthesis and mixtures thereof.  Preferably, according to this embodiment, the level of non-isoprene diene elastomer is more than 50 phr, more preferably at least 60 phr, more preferably at least 70 phr, more preferably at least 80 phr. pce and very preferably at least 90 phr.  In particular according to this embodiment, the level of non-isoprene diene elastomer is very preferably 100 phr.  According to another preferred embodiment of the invention, the rubber composition comprises a blend of one (or more) diene elastomers said "high Tg" having a Tg between -70 ° C and 0 ° C and a (one or more) diene elastomers called "low Tg" between -110 ° C and -80 ° C, more preferably between -105 ° C and -90 ° C.  The high Tg elastomer is preferably selected from the group consisting of S-SBR, E-SBR, natural rubber, synthetic polyisoprenes (having a content (mol%) of cis-1,4 preferably greater than 95%), BIRs, SIRs, SBIRs, and mixtures of these elastomers.  The low Tg elastomer preferably comprises butadiene units at a level (mol%) of at least 70%; it consists preferably of a polybutadiene (BR) having a content (mol%) of cis-1,4 chains greater than 90%.  According to another particular embodiment of the invention, the rubber composition comprises for example between 30 and 90 phr, in particular between 40 and 90 phr, of a high Tg elastomer in a blend with a low-grade elastomer. Tg.  According to another particular embodiment of the invention, the diene elastomer of the composition according to the invention comprises a blend of a BR (as low elastomer Tg) having a molar ratio (mol%) of cis-1,4 chains higher than 90%, with one or more S-SBR or E-SBR (as elastomer (s) high Tg).  1-2 Reinforcing Charge [0051] The composition according to the invention comprises a reinforcing filler.  Any type of reinforcing filler known for its ability to reinforce a rubber composition that can be used for the manufacture of tires, for example an organic filler such as carbon black, a reinforcing inorganic filler such as silica or alumina, or a blend of these two types of filler.  As carbon blacks are suitable for all carbon blacks, especially so-called pneumatic grade blacks.  Among these, the reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades), for example the N115, N134, N234, N326, N330, N339, N347 or N375 blacks, or even targeted applications, blacks of higher series (eg N660, N683, N772).  The carbon blacks could for example already be incorporated into an isoprene elastomer in the form of a masterbatch (see for example WO 97/36724 or WO 99/16600).  As examples of organic fillers other than carbon blacks, mention may be made of the functionalized polyvinyl organic fillers as described in applications WO-A-2006/069792, WO-A-2006/069793, WO-A-1, 2008/003434 and WOA-2008/003435.  The composition may contain a type of silica or a blend of several silicas.  The silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / boy Wut.  As highly dispersible precipitated silicas (called "HDS"), there may be mentioned for example the silicas "Ultrasil 7000" and "Ultrasil 7005" of the company -12- Degussa, the silicas "Zeosil" 1165MP, 1135MP and 1115MP of the company Rhodia, the "Hi-Sil EZ150G" silica from the PPG company, the "Zeopol" 8715, 8745 and 8755 silicas from the Huber Company, processed precipitated silicas, such as, for example, the "aluminum doped" silicas described in FIG. Application EP-A-0735088 or silicas with high specific surface area as described in WO 03/16837.  The silica preferably has a BET surface area of between 45 and 400 m 2 / g, more preferably between 60 and 300 m 2 / g.  These compositions may optionally also contain, in addition to the coupling agents, coupling activators, inorganic charge-covering agents or, more generally, processing aid agents that are capable in a known manner, by means of a improving the dispersion of the filler in the rubber matrix and lowering the viscosity of the compositions, improving their ability to use in the green state, these agents being, for example, hydrolysable silanes such as alkylalkoxysilanes, polyols, fatty acids, polyethers, primary, secondary or tertiary amines, hydroxyl or hydrolyzable polyorganosiloxanes.  In particular, polysulfide silanes, known as "symmetrical" or "asymmetrical" silanes, are used according to their particular structure, as described for example in the applications W003 / 002648 (or US 2005/016651) and W003 / 002649 (or US 2005 / 016650).  In particular, the following definition may be limiting, so-called "symmetrical" polysulfide silanes having the following general formula (III): (III) Z-A-Sx-A-Z, in which: x is an integer of 2 to 8 (preferably 2 to 5); A is a divalent hydrocarbon radical (preferably C 1 -C 18 alkylene groups or C 6 -C 12 arylene groups, more particularly C 1 -C 10 alkylenes, especially C 1 -C 4 alkylenes, in particular propylene); Z corresponds to one of the following formulas: ## STR2 ## in which: the radicals R 1, substituted or unsubstituted, identical or different from each other, represent a C 1 -C 18 alkyl, C 5 -C 18 cycloalkyl or C 6 -C 18 aryl (preferably C 1 -C 6 alkyl, cyclohexyl or phenyl groups, especially C 1 -C 4 alkyl groups, more particularly methyl and / or 'ethyl).  the radicals R2, substituted or unsubstituted, which are identical to or different from one another, represent a C1-C18 alkoxyl or a C5-C18 cycloalkoxyl group (preferably a group chosen from C1-C8 alkoxyls and C5-C8 cycloalkoxyls, plus preferably still a group selected from C1-4 alkoxyls, in particular methoxyl and ethoxyl).  In the case of a mixture of polysulfurized alkoxysilanes corresponding to formula (III) above, especially common commercially available mixtures, the average value of "x" is a fractional number preferably between 2 and 5 , more preferably close to 4.  But the invention can also be advantageously used for example with disulfide alkoxysilanes (x = 2).  By way of examples of polysulphurized silanes, mention may be made more particularly of polysulfides (in particular disulphides, trisulphides or tetrasulphides) of bis- (C 1 -C 4) alkoxyl-C 1 -C 4 alkylsilyl-C 1 -C 4 alkylsulphides. )), such as, for example, bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl) polysulfides.  Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT, of formula [(C2H50) 3Si (CH2) 3S2] 2 or bis (triethoxysilylpropyl) disulfide, abbreviated as TESPD, is especially used. formula [(C2H50) 3Si (CH2) 3S] 2.  Mention may also be made, by way of preferred examples, of bis (monoalkoxyl (C1-C4) -dialkyl (C1-C4) silylpropyl) polysulfides (especially disulfides, trisulphides or tetrasulfides), more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide as described in US Pat. the patent application WO 02/083782 (or US 2004/132880).  As coupling agent other than polysulfide alkoxysilane, mention may also be made of bifunctional POS (polyorganosiloxanes) or hydroxysilane polysulfides (R 2 = OH in formula III above) as described in the patent applications. WO 02/30939 (or US Pat. No. 6,774,255) and WO 02/31041 (or US 2004/051210), or alternatively silanes or POS bearing azo-dicarbonyl functional groups, as described, for example, in the patent applications WO 2006 / 125532, WO 2006/125533, WO 2006/125534.  In the rubber compositions according to the invention, the content of coupling agent is preferably between 2 and 15 phr, more preferably between 3 and 13 and even more preferably between 5 and 11 phr.  Those skilled in the art will understand that as an equivalent load of the silica described in this paragraph, could be used a reinforcing filler of another nature, especially organic, since this reinforcing filler would be covered with a silica layer, or would comprise on its surface functional sites, especially hydroxyl, requiring the use of a coupling agent to establish the bond between the filler and the elastomer.  The physical state in which the reinforcing filler is present is indifferent, whether in the form of powder, microbeads, granules, beads or any other suitable densified form.  The volume fraction of reinforcing filler in the rubber composition is defined as being the ratio of the volume of the reinforcing filler to the volume of all the constituents of the composition, it being understood that the volume of all the constituents is calculated by adding the volume of each of the constituents of the composition.  The volume fraction of reinforcing filler in a composition is therefore defined as the ratio of the volume of the reinforcing filler to the sum of the volumes of each of the constituents of the composition, typically this volume fraction is between 10% and 30%, preferably between 15% and 25%.  In a preferentially equivalent manner, the total reinforcing filler content (carbon black and / or reinforcing inorganic filler such as silica) is 30 to 200 phr, more preferably 30 to 150 phr, and very preferably 50 to 100 phr. 135 pce.  Below 30 pce of load, the composition could be less effective in wear resistance while above 200 pce of load, the composition could be less effective in rolling resistance.  By major reinforcing filler is meant that which has the highest rate among the reinforcing fillers present in the composition.  In particular, the term "majority reinforcing filler" means any reinforcing filler which represents at least 50% by weight of the reinforcing fillers present, preferably more than 50% and more preferably more than 60%.  According to one embodiment, the composition comprises carbon black as a majority filler, in optional cutting with silica, as a minority filler.  In this case, the black level is preferably within a range of 50 to 140 phr, preferably 60 to 110 phr.  The level of silica is preferably in a range from 0 to 50 phr, preferably from 0 to 30 phr.  In this embodiment, the silica content is preferably 0 phr or less than 10 phr.  According to one embodiment, the composition comprises silica as a majority filler, possibly in combination with carbon black, as a minority filler.  In this case, the silica content is preferably in a range from 50 to 140 phr, preferably from 70 to 120 phr.  The level of black is preferably in a range from 0 to 50 phr, preferably from 1 to 30 phr.  In this embodiment, the black level is preferably in a range from 1 to 5 phr and preferably less than or equal to 4 phr.  1-3 Vulcanization System The vulcanization system itself is based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.  To this basic vulcanization system are added, incorporated during the first non-productive phase and / or during the production 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).  The sulfur is used at a preferred level of between 0.5 and 10 phr, more preferably between 0.5 and 5 phr, in particular between 0.5 and 3 phr, when the composition of the invention is intended, according to a preferred embodiment of the invention, to constitute a tire tread.  The vulcanization system of the composition according to the invention may also comprise one or more additional accelerators, for example compounds of the thiuram family, zinc dithiocarbamate derivatives, sulfenamides, guanidines or thiophosphates.  In particular, any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur, in particular thiazole type accelerators and their derivatives, thiuram type accelerators, zinc dithiocarbamates, may be used in particular.  These accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "M BTS"), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated "CBS"), N, N-dicyclohexyl -2-benzothiazyl sulphenamide (abbreviated "DCBS"), N-tert-butyl-2-benzothiazyl sulphenamide (abbreviated "TBBS"), N-tert-butyl-2-benzothiazyl sulphenimide (abbreviated "TBSI"), dibenzyldithiocarbamate zinc (abbreviated as "ZBEC") and mixtures of these compounds.  Preferably, a primary accelerator of the sulfenamide type is used.  1-4 Combination of Plasticizers [0072] The composition according to the invention further comprises a combination of plasticizers or plasticizer system.  This combination of plasticizer is composed of at least one hydrocarbon resin of low Tg and a hydrocarbon resin of high Tg.  In addition to these two plasticizers, the composition may optionally include a plasticizing oil.  The total level of plasticizer in the composition is greater than or equal to 40 phr, more preferably greater than or equal to 50 phr, preferably 50 to 120 phr, in particular 50 to 100 phr, for example 50 to 80 phr. pc.  Below 50 phr, and especially below 40 phr of plasticizer, the composition could be less efficient in terms of industrial processability.  1-4-1 Low Tg Resin [0074] The first plasticizer of the plasticizer combination of the composition of the invention is a viscous hydrocarbon resin at 20 ° C, referred to as "low Tg", i.e. which by definition has a Tg in the range of -40 ° C to 20 ° C.  Preferably, the low Tg hydrocarbon plasticizing resin has at least one of the following characteristics: a Tg in a range of -20 ° C and 0 ° C; a number-average molecular mass (Mn) of less than 800 g / mol, preferably less than 600 g / mol and more preferentially less than 400 g / mol; - a softening point in a range from 0 to 40 ° C, preferably from 10 to 30 ° C; A polymolecularity index (Ip) of less than 3, more preferably less than 2 (booster: Ip = Mw / Mn with Mw weight average molecular weight).  More preferably, this low Tg hydrocarbon plasticizing resin has all of the above preferred characteristics.  The softening point is measured according to ISO 4625 ("Ring and Ball" method).  Tg is measured according to ASTM D3418 (1999).  The macrostructure (Mw, Mn and Ip) of the hydrocarbon resin is determined by steric exclusion chromatography (SEC): solvent tetrahydrofuran; temperature 35 ° C; concentration 1 g / I; flow rate 1 ml / min; filtered solution on 0.45 μm porosity filter before injection; Moore calibration with polystyrene standards; set of 3 columns "WATERS" in series ("STYRAGEL" HR4E, HR1 and HR0. 5); differential refractometer detection ("WATERS 2410") and its associated operating software ("WATERS EMPOWER").  The thermoplastic hydrocarbon resins may be aliphatic or aromatic or alternatively of the aliphatic / aromatic type, that is to say based on aliphatic and / or aromatic monomers.  They may be natural or synthetic, whether or not based on petroleum (if so, also known as petroleum resins).  As aromatic monomers are suitable for example styrene, alpha-methylstyrene, ortho-, meta-, para-methylstyrene, vinyl-toluene, paratertiobutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene, any vinylaromatic monomer from a C9 cut (or more generally from a C8 to C10 cut).  Preferably, the vinylaromatic monomer is styrene or a vinylaromatic monomer derived from a C9 cut (or more generally from a C8 to C10 cut).  Preferably, the vinylaromatic monomer is the minor monomer, expressed as a mole fraction, in the copolymer under consideration.  According to a particularly preferred embodiment, the plasticizing hydrocarbon resin is selected from the group consisting of homopolymer resins or copolymers of cyclopentadiene (abbreviated CPD) or dicyclopentadiene (abbreviated DCPD), homopolymer resins or terpene copolymers, terpene phenol homopolymer or copolymer resins, homopolymer resins or C5 cutting copolymers, homopolymer resins or C9 cutting copolymers, and mixtures of these resins, which may be used alone or in combination with a liquid plasticizer, for example a MES or TDAE oil.  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. .  Among the above-mentioned hydrocarbon plasticizing resins, there may be mentioned resins of homo- or copolymers of alphapinene, betapinene, dipentene or polylimonene.  The preferred resins above are well known to those skilled in the art and commercially available, for example sold with respect to: - aliphatic resins: by the company CRAY VALLEY under the name "Wingtack 10" (Mn = 480 g / mol, Mw = 595 g / mol, Ip = 1. 2; SP = 10 ° C; Tg = -28 ° C.), - coumarone indene resins: by Rütgers Chemicals under the name "Novares C30" (Mn = 295 g / mol, Mw = 378 g / mol, Ip = 1. 28; SP = 25 ° C; Tg = -19 ° C); aliphatic and aromatic C9 cutting resins: by Rütgers Chemicals under the name "Novares TT30" (Mn = 329 g / mol, Mw = 434 g / mol, Ip = 1. 32; SP = 25 ° C; Tg = -12 ° C).  The level of hydrocarbon plasticizing resin of low Tg is greater than or equal to 15 phr, preferably in a range from 15 phr to 70 phr, preferably from 15 to 50 phr, more preferably between 20 and 40 phr.  Indeed, below 15 phr of low Tg resin, the composition could have sticky problems and thus industrial processability 1-4-2 High Tg resin [0083] The second plasticizer of the combination of plasticizers of the composition is a thermoplastic hydrocarbon resin whose Tg is greater than 20 ° C.  This resin is a solid at room temperature (23 ° C), as opposed to a liquid plasticizer such as an oil or viscous such as a low Tg resin.  Preferably, the thermoplastic hydrocarbon plasticizing resin has at least one of the following characteristics: a Tg greater than 30 ° C .; a number-average molecular mass (Mn) of between 400 and 2000 g / mol, more preferentially between 500 and 1500 g / mol; a polymolecularity index (Ip) of less than 3, more preferably less than 2 (booster: Ip = Mw / Mn with Mw weight average molecular weight).  More preferably, this thermoplastic hydrocarbon plasticizing resin has all of the above preferred characteristics.  The macrostructure (Mw, Mn and Ip) of the hydrocarbon resin is determined by steric exclusion chromatography (SEC): solvent tetrahydrofuran; temperature 35 ° C; concentration 1 g / I; flow rate 1 ml / min; filtered solution on 0.45 μm porosity filter before injection; Moore calibration with polystyrene standards; set of 3 columns "WATERS" in series ("STYRAGEL" HR4E, HR1 and HR0. 5); differential refractometer detection ("WATERS 2410") and its associated operating software ("WATERS EMPOWER").  The thermoplastic hydrocarbon resins may be aliphatic or aromatic or alternatively of the aliphatic / aromatic type, that is to say based on aliphatic and / or aromatic monomers.  They may be natural or synthetic, whether or not based on petroleum (if so, also known as petroleum resins).  As aromatic monomers are suitable for example styrene, alphamethylstyrene, ortho-, meta-, para-methylstyrene, vinyl-toluene, paratertiobutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinyl naphthalene, any vinylaromatic monomer resulting from a C9 cut (or more generally from a C8 to C10 cut).  Preferably, the vinylaromatic monomer is styrene or a vinylaromatic monomer derived from a C9 cut (or more generally from a C8 to C10 cut).  Preferably, the vinylaromatic monomer is the minor monomer, expressed as a mole fraction, in the copolymer under consideration.  According to a particularly preferred embodiment, the plasticizing hydrocarbon resin is chosen from the group consisting of homopolymer resins or copolymers of cyclopentadiene (abbreviated as CPD) or dicyclopentadiene (abbreviated as DCPD), homopolymer resins or terpene copolymers, terpene phenol homopolymer or copolymer resins, homopolymer resins or C5 cutting copolymers, C9 homopolymer or copolymer resins, alpha-methyl homopolymer and copolymer resins styrene and the mixtures of these resins, which may be used alone or in combination with a liquid plasticizer, for example a MES or TDAE oil.  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. .  Among the above-mentioned hydrocarbon plasticizing resins, there may be mentioned resins of homo- or copolymers of alphapinene, betapinene, dipentene or polylimonene.  The preferred resins above are well known to those skilled in the art and commercially available, for example sold with regard to: - polylimonene resins: by the company DRT under the name "Dercolyte L120" (Mn = 625 g / mol, Mw = 1010 g / mol, Ip = 1.6, Tg = 72 ° C.) or by ARIZONA under the name "Sylvagum TR7125C" (Mn = 630 g / mol, Mw = 950 g / mol; Ip = 1.5, Tg = 70 ° C); C5 / vinylaromatic cut copolymer resins, in particular C5 / styrene cut or C5 / C9 cut cut: by Neville Chemical Company under the names "Super Nevtac 78", "Super Nevtac 85" or "Super Nevtac 99", by Goodyear Chemicals under "Wingtack Extra" denomination, by Kolon under the names "Hikorez T1095" and "Hikorez T1100", by Exxon under the names "Escorez 2101" and "Escorez 1273"; limonene / styrene copolymer resins: by DRT under the name "Dercolyte TS 105" from the company DRT, by ARIZONA Chemical Company under the names "ZT115LT" and "ZT5100".  By way of examples of other preferred resins, mention may also be made of phenol-modified alpha-methyl-styrene resins.  To characterize these phenol-modified resins, it is recalled that a so-called "hydroxyl number" index (measured according to ISO 4326 and expressed in mg KOH / g) is used in a known manner.  The alpha-methyl-styrene resins, in particular those modified phenol, are well known to those skilled in the art and commercially available, for example sold by Arizona Chemical under the names "Sylvares SA 100" (Mn = 660 g / mol; Ip = 1.5, Tg = 53 ° C); "Sylvares SA 120" (Mn = 1030 g / mol, Ip = 1.9, Tg = 64 ° C); "Sylvares 540" (Mn = 620 g / mol, Ip = 1.3, Tg = 36 ° C, hydroxyl number = 56 mg KOH / g); "Silvares 600" (Mn = 850 g / mol, Ip = 1.4, Tg = 50 ° C., hydroxyl number = 31 mg KOH / g).  Preferably, the level of plasticizing hydrocarbon resin is in a range from 5 to 50 phr, preferably from 7 to 40 phr, more preferably from 10 to 35 phr.  Preferably also, the level of plasticizing resin is in a range from 5 to 20 phr, and more preferably from 5 to 15 phr.  1-4-3 Plasticizing Oil Optionally, the combination of plasticizer may also contain an extender oil (or plasticizing resin) which is liquid at 20 ° C., called "low Tg", that is to say which by definition has a Tg lower than -20 ° C, preferably lower than -40 ° C.  Any extender oil, whether of aromatic or non-aromatic nature known for its plasticizing properties vis-à-vis diene elastomers, is usable.  At ambient temperature (20 ° 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 hydrocarbon plasticizing resins which are inherently solid at room temperature.  Especially suitable extension oils selected from the group consisting of naphthenic oils (low or high viscosity, including hydrogenated or not), paraffinic oils, oils MES (Medium Extracted Solvates), TDAE oils (Treated Distillate Aromatic Extracts), mineral oils, vegetable oils, ethers plasticizers, ester plasticizers, phosphate plasticizers, sulphonate plasticizers and mixtures of these compounds.  For example, there may be mentioned those containing between 12 and 30 carbon atoms, for example trioctyl phosphate.  By way of examples of non-aqueous and non-water-soluble ester plasticizers, mention may be made in particular of compounds selected from the group consisting of trimellitates, pyromellitates, phthalates, 1,2-cyclohexane dicarboxylates, adipates, azela- sebacates, glycerol triesters and mixtures of these compounds.  Among the triesters above, mention may be made in particular of glycerol triesters, preferably consisting predominantly (for more than 50%, more preferably for more than 80% by weight) of an unsaturated C 18, C 18 fatty acid. that is, selected from the group consisting of oleic acid, linoleic acid, linolenic acid, and mixtures of these acids.  More preferably, whether of synthetic or natural origin (for example vegetable oils of sunflower or rapeseed), the fatty acid used is more than 50% by weight, more preferably still more than 80% by weight. % by weight of oleic acid.  Such high oleic acid triesters (trioleates) are well known and have been described, for example, in application WO 02/088238, as plasticizers in tire treads.  According to a particular embodiment of the invention, when it is included in the composition, the extension oil content is between 2 and 80 phr, more preferably between 5 and 60 phr, more preferably between 10 and 50 pce.  Below 2 phr of oil or above 80 phr of oil, the composition could be less effective in adhesion on wet ground, with a Tg of the mixture too high or too low.  [0097] According to the invention, the levels of reinforcing filler and of plasticizer are such that the ratio of the total charge rate and the total plasticizer content is within a range from 1.3 to 2.  Below 1.3 the composition may have a lower hardness leading to a lower performance of vehicle behavior while above 2 the composition could have a strong mooney resulting in less industrial processability.  Preferably, the ratio of the total charge rate and the total plasticizer content is in a range from 1.3 to 1.8 and preferably from 1.4 to 1.7.  1-6 Other Possible Additives The rubber compositions in accordance with the invention optionally also include all or part of the usual additives normally used in elastomer compositions intended in particular for the production of treads, such as, for example, pigments. protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, plasticizers other than those previously described, anti-fatigue agents, reinforcing resins, acceptors (for example phenolic resin). novolak) or methylene donors (eg HMT or H3M).  Of course, the compositions according to the invention can be used alone or in a cut (i. e. , in admixture) with any other rubber composition usable for the manufacture of tires.  It goes without saying that the invention relates to the rubber compositions described above both in the said state "raw" or uncrosslinked (i. e. , before cooking) in the so-called "cooked" or crosslinked state, or vulcanized (i. e. after crosslinking or vulcanization).
    [0002] II- Preparation of rubber compositions The compositions are manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes called phase "non-productive") at high temperature, up to a maximum temperature of between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, followed by a second mechanical working phase (sometimes referred to as "productive" phase) at a lower temperature, typically below 110 ° C, for example between 60 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system or vulcanization; such phases have been described, for example, in EP-A-0501227, EP-A-0735088, EP-A-0810258, W000 / 05300 or W000 / 05301. The first (non-productive) phase is preferably carried out in several thermomechanical steps. In a first step, the elastomers, the reinforcing fillers, the combination of plasticizers (and optionally the coupling agents and / or other ingredients at the same time) are introduced into a suitable mixer such as a conventional internal mixer. exception of the vulcanization system), at a temperature of between 20 ° C and 100 ° C and preferably between 25 ° C and 100 ° C. After a few minutes, preferably from 0.5 to 2 min and a rise in temperature to 90 ° C to 100 ° C, the other ingredients (ie, those that remain if all were not put initially) are added at once or in portions, except for the vulcanization system during mixing ranging from 20 seconds to a few minutes. The total mixing time, in this non-productive phase, is preferably between 2 and 10 minutes at a temperature of less than or equal to 180 ° C, and preferably less than or equal to 170 ° C. After cooling the mixture thus obtained, the vulcanization system is then incorporated at low temperature (typically below 100 ° C.), generally in an external mixer such as a roller mixer; the whole is then mixed (productive phase) for a few minutes, for example between 5 and 15 min. The final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for a characterization in the laboratory, or extruded, to form for example a rubber profile used for the manufacture semi-finished to obtain products such as a tread. These products can then be used for the manufacture of tires, according to the techniques known to those skilled in the art. The vulcanization (or baking) is conducted in a known manner at a temperature generally between 130 ° C and 200 ° C, under pressure, for a sufficient time which may vary for example between 5 and 90 min depending in particular on the cooking temperature, the vulcanization system adopted, the kinetics of vulcanization of the composition in question or the size of the tire. The examples which follow illustrate the invention without however limiting it. III-Examples of embodiment of the invention III-1 Preparation of examples [00108] In the examples which follow, the rubber compositions were produced as described previously.
    [0003] III-2 Characterization of the Examples [00109] In the examples, the rubber compositions are characterized before and / or after cooking as indicated below. - Mooney viscosity or Mooney plasticity (before firing): [00110] An oscillating consistometer is used as described in the French standard NF T 43-005 (1991). The Mooney plasticity measurement is carried out according to the following principle: the composition in the green state (i.e., before firing) is molded in a cylindrical chamber heated to 100 ° C. After one minute of preheating, the rotor rotates within the test tube at 2 revolutions / minute and the useful torque is measured to maintain this movement after 4 minutes of rotation. The Mooney plasticity (ML 1 + 4) is expressed in "Mooney unit" (UM, with 1 UM = 0.83 Newton.meter). The lower the Mooney value, the lower the pre-firing viscosity and the better the processability of the composition. Shore A Hardness: The Shore A hardness of the compositions after curing is assessed according to ASTM D 2240-86. Dynamic properties (after firing): The dynamic properties G * and tan (δ) 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 is recorded. (cylindrical specimen with a thickness of 4 mm and a cross sectional thickness of 400 mm2) subjected to a sinusoidal stress in alternating simple shear at a frequency of 10 Hz, under variable temperature conditions, in particular at 0 ° C and 23 ° C, 40 ° C and 100 ° C according to ASTM D 1349-99. A peak to peak strain sweep of 0.1 to 50% (forward cycle) followed by 50% to 1% (return cycle) is performed. . The results exploited are the complex dynamic shear modulus (G *) and the loss factor (tan Ô). For the return cycle, the maximum value of tan 8 observed (tan (8) max), as well as the complex modulus difference (4G *) between the values at 0.1% and at 50% of deformation (effect Payne). For the value of tan (δ) max at 0 ° C, the higher the value, the better the composition will allow good wet adhesion. For the value of tan (δ) max at 100 ° C, the higher the value, the more the composition will allow a good adhesion on dry ground. For values of tan (δ) max at 23 ° C and 40 ° C, the lower the value, the lower the composition will have a low hysteresis and thus a low rolling resistance. EXAMPLES [00112] The compositions are manufactured with an introduction of all the constituents on an internal mixer, with the exception of the vulcanization system. The vulcanizing agents (sulfur and accelerator) are introduced on an external mixer at low temperature (the constituent rolls of the mixer being at about 30 ° C.). The examples presented in Table 1 are intended to compare the different rubber properties of control compositions (T1 to T9) compositions C1 to C4 according to the invention. The measurement results of the properties measured before and after firing are shown in Table 2. Table 1 Composition Cl C2 C3 C4 T1 T2 T3 T4 T5 T6 T7 T8 T9 SBR (1) 70 70 70 100 70 70 70 70 70 70 70 70 70 BR (2) 30 Carbon black (3) 4 4 4 4 4 4 4 4 4 4 4 4 4 Silica (4) 90 90 90 90 90 90 90 90 55 90 30 150 55 Total Load 94 94 94 94 94 94 94 94 94 94 94 154 154 Resin low Tg (5) 47 35 30 47 0 62 10 25 25 15 15 47 47 High resin Tg (6) 15 12 25 15 62 0 52 5 5 2 2 15 15 Oil (7) 0 0 7 0 0 0 0 0 0 0 0 0 0 Total Plasticizer 62 47 62 62 62 62 62 30 30 17 17 62 62 Coupling agent (8) 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 Antioxidant (9) 2.5 2.5 2.5 2.5 2 , 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stearic acid (10) 3 3 3 3 3 3 3 3 3 3 3 3 3 Accelerator 1 (11) 3 , 9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 Accelerator 2 (12) 1.8 1.8 1 , 8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Sulfur 1.1 1.1 1.1 1.1 1.1 1 1 1,1 1,1 1,1 1,1 1,1 1,1 1,1 Zinc oxide (13) 1,2 1,2 1,2 1,2 1,2 1,2 1,2 1,2 1,2 1,2 1, 2 1.2 1.2 C / P 1.52 2.00 1.52 1.52 1.52 1.52 1.52 3.13 1.97 5.53 2.00 2.48 0.95 ( 1) SBR (Sn star) with 25% styrene unit and 57% 1.2 unit of butadiene (Tg = -24 ° C) (2) BR with 0.5% 1,2; 98.3% cis 1,4 and 1.2% 1,4 trans unit (Tg = -108 ° C) (3) ASTM N234 grade (Cabot company) (4) Rhodia "Zeosil 1165 MP" silica type "HDS" (5) hydrocarbon resin low Tg "Novares C30" Rütgers Chemical Company -27- (6) Hydrocarbon resin high Tg C5 / C9 "Escorez 2173" company EXXON (Mn 810 g / mol) ( 7) Trioleate of glycerol, sunflower oil 85% by weight of oleic acid "Lubrirob Tod 1880" from Novance (8) coupling agent: TESPT ("Si69" from Evonik-Degussa) (9) N - (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (Santoflex 6-PPD) from Flexsys and anti-ozone wax (10) Stearin "Pristerene 4931" from Uniqema (11) N-cyclohexyl -2-benzothiazol-sulfenamide ("Santocure CBS" from Flexsys) (12) Diphenylguanidine "Perkacit DPG" from Flexsys (13) Industrial grade zinc oxide - Umicore company Table 2 Composition Cl C2 C3 C 4 Q1 Q2 Q3 Q4 Q5 Q6 T7 T8 Q8 T9 Mooney 54 69 55 59 62 54 59 112 57 155 46 104 34 Shore hardness A 55.7 60.8 57.2 56.8 59.0 56.7 57.2 70, 4 59.2 76.9 56.3 83.4 48.0 Tan (3) max 0 ° C 0.8 0.8 0.8 1.4 1.0 0.8 1.1 0.6 0, 0 0.6 0.3 0.6 0.7 Tan (3) max 23 ° C 0.36 0.34 0.36 0.44 0.53 0.33 0.47 0.35 0.19 0, 37 0.10 0.50 0.19 Tan (6) max 40 ° C 0.25 0.27 0.28 0.24 0.35 0.27 0.32 0.28 0.15 0.29 0, 08 0.37 0.14 Tan (3) max 100 ° C 0.14 0.13 0.15 0.12 0.15 0.14 0.14 0.14 0.08 0.15 0.04 0, 0.07 [00114] Compared to the control compositions, it is noted that the compositions according to the invention have the best performance compromise between the Mooney, the hardness and the various measurements of Tan (8) max at 0 ° C. 23 ° C, 40 ° C and 100 ° C. Indeed, all the compositions in accordance with the invention make it possible to improve at least one property with respect to the controls taken separately. These results show that the compositions of the invention allow good performance on the essential aspects of processability, road behavior, adhesion on dry ground, adhesion on wet ground and rolling resistance. None of the control compositions allow such a good compromise of all these performances at the same time.
    权利要求:
    Claims (29)
    [0001]
    REVENDICATIONS1. A rubber composition based on at least one diene elastomer, a reinforcing filler, a vulcanization system and a combination of plasticizers, said combination of plasticizers comprising more than 15 phr (parts by weight per hundred parts by weight of elastomer) of hydrocarbon resin with a glass transition temperature (Tg) of between -40 ° C. and 20 ° C. and a Tg resin of greater than 20 ° C., the total plasticizer content being greater than or equal to 40 phr, and the levels of reinforcing filler and of plasticizer being such that the ratio of the total charge rate and the total plasticizer content is in a range from 1.3 to
    [0002]
    2. The composition according to claim 1, wherein said diene elastomer is selected from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. .
    [0003]
    3. The composition of any one of the preceding claims wherein said diene elastomer is selected from the group consisting of polybutadienes, butadiene and styrene copolymers, and mixtures of these elastomers.
    [0004]
    4. Composition according to any one of the preceding claims wherein the reinforcing filler is selected from the group consisting of silicas, carbon blacks and mixtures thereof. 25
    [0005]
    5. Composition according to any one of the preceding claims wherein the level of reinforcing filler is in a range from 30 to 200 phr, preferably from 30 to 150 phr. 30
    [0006]
    6. Composition according to any one of the preceding claims wherein the majority reinforcing filler is carbon black.
    [0007]
    7. Composition according to any one of the preceding claims wherein the carbon black content is in a range from 50 to 140 phr, preferably from 60 to 110 phr.
    [0008]
    8. Composition according to any one of claims 1 to 5 wherein the majority reinforcing filler is silica.
    [0009]
    9. The composition of claim 8 wherein the silica content is in a range from 50 to 140 phr, preferably from 70 to 120 phr.
    [0010]
    10. Composition according to any one of the preceding claims wherein the total level of plasticisers is greater than or equal to 50 phr, preferably in a range from 50 to 120 phr.
    [0011]
    11. Composition according to any one of the preceding claims wherein the total content of plasticizers is in a range from 50 to 100 phr, preferably from 50 to 80 phr.
    [0012]
    12. Composition according to any one of the preceding claims wherein the hydrocarbon resin content of Tg between -40 ° C and 20 ° C is in a range from 15 to 70 phr, preferably from 15 to 50 phr.
    [0013]
    13. The composition of claim 12 wherein the hydrocarbon resin content of Tg between -40 ° C and 20 ° C is in a range of 20 to 40 phr.
    [0014]
    14. Composition according to any one of the preceding claims wherein the hydrocarbon resin previously mentioned as a hydrocarbon resin with a Tg between -40 ° C and 20 ° C has a Tg between -20 ° C and 0 ° C.
    [0015]
    15. Composition according to any one of the preceding claims, in which the hydrocarbon resin previously mentioned as a hydrocarbon resin with a Tg of between -40 ° C. and 20 ° C. has a number-average molecular mass of less than 800 g / mol, preferably less than 800 g / mol. at 600 g / mol.
    [0016]
    16. The composition of claim 15 wherein the hydrocarbon resin previously mentioned as a hydrocarbon resin of Tg between -40 ° C and 20 ° C has a number average molecular weight of less than 400 g / mol.
    [0017]
    17. Composition according to any one of the preceding claims, in which the hydrocarbon resin previously mentioned as a hydrocarbon resin with a Tg of between -40 ° C. and 20 ° C. has a softening point in a range from 0 to 40. ° C, preferably from 10 to 30 ° C.
    [0018]
    18. Composition according to any one of the preceding claims, in which the hydrocarbon resin previously mentioned as a hydrocarbon resin with a Tg of between -40 ° C. and 20 ° C. has a polymolecularity index (Ip) of less than 3, preferably less than 2.
    [0019]
    19. Composition according to any one of the preceding claims, in which the level of hydrocarbon resin with a Tg greater than 20 ° C is in a range from 5 to 50 phr, preferably from 7 to 40 phr.
    [0020]
    20. The composition of claim 14 wherein the hydrocarbon resin content of Tg greater than 20 ° C is in a range from 10 to 15 phr.
    [0021]
    21. Composition according to any one of the preceding claims wherein the hydrocarbon resin previously mentioned as a hydrocarbon resin of Tg greater than 20 ° C has a Tg greater than 30 ° C. 20
    [0022]
    22. Composition according to any one of the preceding claims, in which the hydrocarbon resin previously mentioned as a hydrocarbon resin with a Tg greater than 20 ° C has a number-average molecular mass of between 400 and 2000 g / mol, preferably between 500 and 1500. g / mol. 25
    [0023]
    23. Composition according to any one of the preceding claims, in which the hydrocarbon resin previously mentioned as a hydrocarbon resin with a Tg greater than 20 ° C. has a polymolecularity index (Ip) of less than 3, preferably less than 2.
    [0024]
    24. Composition according to any one of the preceding claims, in which the ratio of the total charge rate and the total plasticizer content is in a range from 1.3 to 1.8, preferably from 1.4 to 1, 7. 35
    [0025]
    25. Composition according to any one of the preceding claims further comprising in the combination of plasticizers, a plasticizing oil.
    [0026]
    26. A composition according to claim 25 wherein the plasticizing oil is selected from the group consisting of naphthenic oils, paraffinic oils, MES (Medium Extracted Solvates) oils, Treated Distillate Aromatic Extracts (TDAE) oils, mineral oils, vegetable oils, ethers plasticizers, ester plasticizers, phosphate plasticizers, sulphonate plasticizers and mixtures of these compounds.
    [0027]
    27. Composition according to any one of claims 25 or 26 wherein the level of plasticizing oil is in a range from 2 to 80 phr, preferably from 5 to 60 phr.
    [0028]
    28. A tire comprising a composition according to any one of claims 1 to 27.
    [0029]
    29. A tire according to the preceding claim comprising said composition according to any one of claims 1 to 27 in all or part of the tread.
    类似技术:
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    同族专利:
    公开号 | 公开日
    FR3017870B1|2016-02-19|
    WO2015124681A1|2015-08-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP0524164A1|1991-07-18|1993-01-20|Semperit Reifen Aktiengesellschaft|Pneumatic vehicle tyre|
    WO2013092096A1|2011-12-22|2013-06-27|Compagnie Generale Des Etablissements Michelin|Rubber composition|US20170145195A1|2015-11-20|2017-05-25|The Goodyear Tire & Rubber Company|Pneumatic tire|
    GB201615606D0|2016-09-14|2016-10-26|Apollo Tyres Global R & D Bv|Rubber composition for tyres with improved winter performance and abrasion resistance|
    FR3061186B1|2016-12-22|2019-05-24|Compagnie Generale Des Etablissements Michelin|RUBBER COMPOSITION COMPRISING A SPECIFIC HYDROCARBON RESIN|
    FR3061184A1|2016-12-22|2018-06-29|Compagnie Generale Des Etablissements Michelin|RUBBER COMPOSITION COMPRISING A SPECIFIC HYDROCARBON RESIN|
    FR3061185A1|2016-12-22|2018-06-29|Compagnie Generale Des Etablissements Michelin|RUBBER COMPOSITION COMPRISING A SPECIFIC HYDROCARBON RESIN|
    NL2020806B1|2018-04-20|2019-10-28|Apollo Tyres Global R & D Bv|Rubber composition for tyres with good wet grip and rolling resistance properties|
    US10947368B2|2019-03-04|2021-03-16|The Goodyear Tire & Rubber Company|Pneumatic tire|
    法律状态:
    2015-02-19| PLFP| Fee payment|Year of fee payment: 2 |
    2016-02-18| PLFP| Fee payment|Year of fee payment: 3 |
    2017-02-17| PLFP| Fee payment|Year of fee payment: 4 |
    2018-02-23| PLFP| Fee payment|Year of fee payment: 5 |
    2019-10-25| ST| Notification of lapse|Effective date: 20191006 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1451386A|FR3017870B1|2014-02-21|2014-02-21|RUBBER COMPOSITION COMPRISING A PLASTICIZING SYSTEM BASED ON A CUTTING OF HYDROCARBONATED RESIN OF LOW AND HIGH TEMPERATURE OF VITREOUS TRANSITION|FR1451386A| FR3017870B1|2014-02-21|2014-02-21|RUBBER COMPOSITION COMPRISING A PLASTICIZING SYSTEM BASED ON A CUTTING OF HYDROCARBONATED RESIN OF LOW AND HIGH TEMPERATURE OF VITREOUS TRANSITION|
    PCT/EP2015/053519| WO2015124681A1|2014-02-21|2015-02-19|Rubber composition comprising a plasticising system based on a blend of hydrocarbonated resin having a low and a high glass transition temperature|
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