WO2014095590A1

WO2014095590A1 - Tyre comprising a composition essentially free of guanidine derivative and comprising a thiazole compound and an alkaline-earth or alkaline metal hydroxide

Info

Publication number: WO2014095590A1
Application number: PCT/EP2013/076432
Authority: WO
Inventors: Karine Longchambon; Christelle DARNAUD; Anne Veyland
Original assignee: Compagnie Generale Des Etablissements Michelin; Michelin Recherche Et Technique S.A.
Priority date: 2012-12-19
Filing date: 2013-12-12
Publication date: 2014-06-26
Also published as: FR2999584B1; FR2999584A1

Abstract

The invention relates to a tyre comprising a rubber composition containing at least one diene elastomer, a reinforcing filler including primarily silica, a curing system comprising a thiazole compound having general formula (I), and an alkaline-earth or alkaline metal hydroxide, said composition being essentially free of guanidine derivative.

Description

The invention relates to tires and more particularly to those whose composition comprises a particular thiazole compound and an alkali metal hydroxide. or alkaline earth.

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 into the mixtures as a reinforcing filler.

Also, the Applicants have already described that the use of a vulcanization system comprising a particular thiazole derivative makes it possible to reduce the hysteresis of the compositions and therefore to improve the rolling resistance, as described in the documents FR 2951 180 and FR 2974096.

Nevertheless, the manufacturers are still seeking solutions to further reduce the rolling resistance of the tires and it is in this context that the applicants have surprisingly discovered that the introduction of an alkali metal or alkaline earth metal hydroxide instead of Guanidine derivatives makes it possible to reduce the hysteresis of the diene rubber compositions comprising silica as the majority reinforcing filler.

Moreover, this solution has many other advantages over the compositions of the prior art and in particular the use of a lower cost compound and improving the environmental footprint.

Alkali or alkaline earth metal hydroxides have already been used in tire compositions different from those of the invention and for other purposes than to reduce the hysteresis of the compositions. For example, EP 0599643 discloses the use of basic compounds comprising sodium to improve the high temperature rigidity of a mixture comprising an SBR elastomer and black of carbon.

Nevertheless these alkali metal or alkaline earth metal hydroxides have never been used as proposed by the applicants to replace the guanidine derivatives in diene elastomer mixtures comprising silica as the majority filler, with the advantages presented above.

The invention therefore relates to a tire comprising a rubber composition based on at least one diene elastomer, a reinforcing filler mainly comprising silica, a vulcanization system, a thiazole compound of general formula (I)

in which

R 1 and R ₂ independently represent a hydrogen atom or a C 1 -C 25 hydrocarbon-based group chosen from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups, and optionally interrupted by one or more heteroatoms; , Ri and R ₂ may together form a non-aromatic ring, but can not together form an aromatic ring,

A is selected from

a hydrogen atom,

a radical of formula

in which

R ₃ , R ₄ and R ₅ independently represent a C 1 -C 18 hydrocarbon group, optionally interrupted by one or more heteroatoms,

y is an integer greater than or equal to 1, preferably less than or equal to 10, more preferably less than or equal to 8 and most preferably less than or equal to 6; a radical of formula

in which

R ₆ is a hydrocarbon group having Ci _8, optionally interrupted by one or more heteroatoms;

a radical of formula

in which

R ₇ is a hydrocarbon group having Ci _8, optionally interrupted by one or more heteroatoms;

a radical of formula

in which

Y is a C 1 -C ₈ hydrocarbon-based chain, optionally interrupted, substituted with one or more heteroatoms,

R ₈ is a hydrocarbon group having Ci _8, optionally interrupted by one or more heteroatoms;

a radical of formula

OFL

X - ^ - OR ₁₀

O

in which

X is a hydrocarbon chain Ci C _8, optionally interrupted or substituted by one or more heteroatoms,

R ₉ and R ₁₀ independently represent a hydrocarbon group having Ci _8, optionally interrupted by one or more heteroatoms, and

a radical of formula

in which

R11 is a hydrogen atom or a hydrocarbon group having Ci _8, optionally interrupted by one or more heteroatoms.

a radical of formula

- NH R12 in which

R12 represents a C1-C25 linear or branched, optionally interrupted by one or more heteroatoms, optionally substituted with one or more cyclic alkyl C3-C10 aryl or C ₆ -C _2, or

R12 represents a cyclic alkyl C3-C10, optionally interrupted by one or more heteroatoms, optionally substituted by one or more linear alkyl groups, branched or cyclic C 1 -C 25 aryl or C ₆ -C _2, optionally interrupted by one or a plurality of heteroatoms, said composition further comprising an alkali metal or alkaline earth metal hydroxide, said composition being devoid of or comprising less than 0.5 phr of guanidine derivative. Preferably, the invention relates to a tire as defined above wherein said composition comprises a thiazole compound of general formula (I), characterized in that R 1 and R ₂ independently represent a hydrogen atom or a methyl group, more preferably R 1 and R ₂ each represent a hydrogen atom, and according to an alternative mode, which is also preferential, R 1 and R ₂ each represent a methyl group.

Preferably, the invention relates to a tire as defined above wherein the groups R ₃ to Ru are independently selected from linear, branched or cyclic alkyl groups, aryl groups, aralkyl groups and alkylaryl groups.

Preferably also, the invention relates to a tire as defined above in which the groups X and Y are independently selected from among the linear, branched or cyclic alkylene groups, arylene groups and alkylarylene groups.

According to a first preferred embodiment, the invention relates to a tire as defined above in which A is chosen from

a radical of formula

a radical of formula

According to a second embodiment, more preferential, the invention relates to a tire as defined above in which A is a radical of formula

NH Ri2 in which

R-I2 is a C1-C25 linear or branched, optionally interrupted by one or more heteroatoms, optionally substituted with one or more cyclic alkyl C3-C10 aryl or C ₆ -C _2, or R12 represents uun cyclic alkyl C3-C1 _0, optionally interrupted by one or more heteroatoms, optionally substituted by one or more linear alkyl groups, branched or cyclic C 1 -C 25 aryl or C ₆ -C ₂ optionally interrupted by one or more heteroatoms. Preferentially, R ₁₂ represents a cyclohexyl group or a tert-butyl group. More preferably still; R12 represents a cyclohexyl group and

R 1 and R ₂ represent a methyl group, or

Ri and R ₂ represent H, or

R 1 is methyl, R ₂ is H, or R 1 represents H, R ₂ represents a methyl group.

Preferably, the invention relates to a tire as defined above in which the thiazole compound represents from 0.1 to 10 phr, preferably from 0.1 to 7 phr, preferably from 0.2 to 7 phr, more preferably from 0.5 to 7 phr, more preferably from 0.5 to 5 phr (parts by weight per cent of diene elastomer).

Preferably, the invention relates to a tire as defined above, in which the composition comprising the alkali metal or alkaline earth metal hydroxide contains less than 0.45 phr of guanidine derivative, and preferably less than 0.4 phr. .

Preferably also, the invention relates to a tire as defined above, in which the level of alkali metal or alkaline earth metal hydroxide is from 0.05 to 3 phr, preferably from more than 0.1 phr to 2 phr. pc.

More preferably, the invention relates to a tire as defined above, wherein the alkali metal or alkaline earth metal hydroxide is selected from the group consisting of sodium hydroxide, potassium hydroxide, hydroxide lithium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide and mixtures thereof. More preferably still, the alkali or alkaline earth metal hydroxide is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, and mixtures thereof. Alternatively, and more preferably also, the alkali or alkaline earth metal hydroxide is selected from the group consisting of magnesium hydroxide, calcium hydroxide, barium hydroxide and mixtures thereof. Even more preferably, the invention relates to a tire as defined above, wherein the alkali or alkaline earth metal hydroxide is sodium hydroxide or potassium hydroxide. Preferably, the invention relates to a tire as defined above, in which the silica content is from 30 to 150 phr.

Also preferably, the invention relates to a tire as defined above, wherein the reinforcing filler comprises carbon black, in a minority. Preferably, the carbon black content is from 0.5 to 50 phr. More preferably, the invention relates to a tire as defined above, in which the diene elastomer is chosen from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers and copolymers. of isoprene (such as butadiene-styrene copolymers, isoprene-butadiene copolymers, isoprene-styrene copolymers or isoprene-butadiene-styrene copolymers) and mixtures of these elastomers.

According to a preferred embodiment, the invention relates to a tire as defined above, in which the diene elastomer is predominantly composed of non-isoprene diene elastomer.

Preferably, the invention relates to a tire as defined above, in which the diene elastomer is composed of 100 phr of non-isoprene diene elastomer.

Preferably also, the invention relates to a tire as defined above, in which the non-isoprene diene elastomer is chosen from the group consisting of polybutadienes, butadiene copolymers and isoprene copolymers (such as copolymers of butadiene-styrene, isoprene-butadiene copolymers, isoprene-styrene copolymers or isoprene-butadiene-styrene copolymers) and mixtures of these elastomers.

More preferably, the invention relates to a tire as defined above, wherein the composition further comprises a plasticizer, preferably selected from plasticizing resins, extension oils and mixtures thereof.

Preferably, the invention relates to a tire as defined above, in which the level of plasticizer is from 5 to 100 phr. Preferably, the invention relates to a tire as defined above, wherein the composition is further free of zinc or contains less than 0.5 phr, preferably less than 0.3 phr.

Also preferably, the invention relates to a tire as defined above, further comprising a coupling agent. Preferably, the invention relates to a tire as defined above in which the coupling agent is a hydroxysilane polysulfide corresponding to the general formula (IV):

(HO) _a R (3- _a) Si-R'-S _x -R'-Si R _(3- _b ) (OH) _b (IV)

in which :

the radicals R, which are identical or different, are hydrocarbon groups preferably comprising from 1 to 15 carbon atoms;

the radicals R ', which may be identical or different, are divalent linking groups preferably comprising from 1 to 18 carbon atoms;

a and b, identical or different, are 1 or 2;

x is a number greater than or equal to 2.

More preferentially, the invention relates to a tire as defined above in which the coupling agent is a monohydroxysilane in which a and b are equal to 1.

Even more preferably, the invention relates to a tire as defined above in which the R radicals are chosen from linear or branched C ₁ -C ₆ alkyls, C ₅ -C ₈ cycloalkyls or a phenyl radical; the radicals R 'are selected from alkylene Ci C ₈ arylene or C ₆ -C _2. More particularly, the radicals R are chosen from C ₁ -C ₆ alkyls and R 'radicals from C 1 -C 10 alkylenes.

Very preferably, the invention relates to a tire as defined above in which the hydroxysilane is a polysulfide of monohydroxysilane of formula (V):

HO- ^ i- R ^* - Sx ^" - Si-OH

RR (V) in which the R radicals are C1-C3 alkyls, preferably methyl; the R 'radicals of the C1-C4 alkylenes, preferably methylene, ethylene or propylene; x is greater than or equal to 2. More particularly, the hydroxysilane is a polysulfide of bis (propyldimethylsilanol) of particular formula (Va):

Preferably, the invention relates to a tire as defined above, in which the composition comprising the thiazole compound of formula (I) and the alkali metal or alkaline earth metal hydroxide is the composition of a tire layer chosen from the group consisting of all or part of the tread, all or part of the tire belt and combinations thereof.

Preferably, the invention relates to a tire as defined above, in which the composition comprising the thiazole compound of formula (I) and the alkali metal or alkaline earth metal hydroxide is that of all or part of the tread .

The tire according to the invention may comprise the composition described above in one or more of its different layers, such as, for example, the tread, the plies of the tire belt, the carcass ply or any other layer. For the purposes of the present application, the tire tread designates the rubber layer in contact with the ground, wholly (that is to say throughout its thickness) or a part of the latter (including the underlayer ), especially when it is composed of several layers.

Preferably, the invention relates to a tire as defined above in which the composition comprising the thiazole compound of formula (I) and the alkali metal or alkaline earth metal hydroxide is the composition of a tire layer chosen from group consisting of all or part of the tread, all or part of the tire belt and combinations thereof.

Preferably, the invention relates to a tire as defined above in which the composition specified is that of all or part of the tread.

Preferably, the tire according to the invention will be chosen from tires intended to equip a two-wheeled vehicle, a passenger vehicle, or a so-called "heavy vehicle" (ie metro, bus, off-road vehicles, road transport equipment such as trucks, tractors, trailers), or aircraft, engineering machinery civil, agrarian, or handling.

I- Constituents of the composition

The rubber compositions according to the invention are based on the following constituents: at least one diene elastomer, a reinforcing filler comprising mainly silica, a vulcanization system comprising a thiazole compound of general formula (I), and a metal hydroxide alkaline or alkaline earth, said composition being free or comprising less than 0.5 phr of guanidine derivative. In the formulas which precede and which follow, the arrow (->) designates the point of attachment of the groups A on the sulfur atom of the formula (I).

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 with one another, at least partially, during the various phases of manufacture of the composition, or during 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 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 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 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 will be recalled here that it is to be understood in known manner that one or more elastomers derived from at least a part (ie, a homopolymer or copolymer) of diene monomers (monomers bearing two carbon-carbon double bonds, conjugated or otherwise).

The diene elastomers can be classified into two "essentially unsaturated" or "essentially saturated" categories. 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%.

As these definitions are given, the term "diene elastomer" can be understood more particularly to 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 oolefin 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 hexadiene-1,4, 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 It will be appreciated that the present invention is preferably implemented with substantially unsaturated diene elastomers, particularly of the type (a) or (b) above. As conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C ₅ alkyl) -1,3-butadienes, such as for example 2, are particularly suitable. 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 "vinyl-toluene" commercial mixture, para-tertiarybutylstyrene, methoxystyrenes, chlorostoises, 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, sequenced, microsequenced, 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, an elastomer can be used functionalized silanol or polysiloxane having a silanol end, in mixture with a coupled elastomer and / or starred tin (described in WO 11/042507), the latter representing a rate of 5 to 50%, for example from 25 to 50%. Suitable polybutadienes and in particular those having a content (mol%) in units -1, 2 of between 4% and 80% or those having a content (mol%) in cis-1, 4 greater than 80%, polyisoprenes, copolymers of butadiene-styrene and in particular those having a Tg (glass transition temperature (Tg, measured according to ASTM D3418) of 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%) of -1,2 bonds of the butadiene part of between 4% and 75%, a content ( mol%) in trans-1,4 bonds 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 of -40 ° C. to At -80 ° C., the isoprene-styrene copolymers and in particular those having a styrene content of between 5% and 50% by weight and a Tg included at -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 between 10% and 40% are especially suitable. 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 units -1, 2 of the butadiene part of between 4% and 85%, a content (mol%) in trans-1,4 units of the butadiene part of between 6% and 80%, a content (% molar) 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 isoprenic part of between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg of 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 "BR"), synthetic polyisoprenes (IR), natural rubber (NR), copolymers butadiene, 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 copolymers acrylonitrile (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 a 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) blend. ).

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 35 to 35% by weight, is used in particular. 45%, a vinyl 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 a synthetic cis-1,4 polyisoprene; of these synthetic polyisoprenes, polyisoprenes having a level (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 (i.e. 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 (ie, a homopolymer or a copolymer) from monomers dienes (monomers bearing two carbon-carbon double bonds) other than isoprene. Thus, non-isoprenic diene elastomers as defined herein also include copolymers comprising isoprene as a comonomer. 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 referred to as "high Tg" having a Tg of between -70 ° C. and 0 ° C. and one (or more) diene elastomers known as "low Tg" between -1 10 ° 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 molar ratio (% molar) of cis- 1, 4 preferably greater than 95%), BIR, SIR, SBIR, 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 Tg elastomer.

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 rate (mol%) of cis chains -1, 4 greater than 90%, with one or more S-SBR or E-SBR (as elastomer (s) high Tg).

1-2 Reinforcing filler

The tire according to the invention comprises a composition which contains, predominantly, silica as a reinforcing filler. By majority 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%. The physical state under 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 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 in 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.

According to a preferred embodiment of the invention, a reinforcing filler comprising from 30 to 150 phr of silica, more preferably from 50 to 130 phr of silica, and optionally carbon black, is used; the carbon black, when present, is used in combination with silica more preferably at a level of 0.5 to 50 phr, more preferably from 1 to 20 phr (especially between 1 and 10 phr).

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 / g. As highly dispersible precipitated silicas (called "HDS"), there may be mentioned for example the silicas "Ultrasil 7000" and "Ultrasil 7005" from the company Degussa, the silicas "Zeosil" 1 165MP, 1 135MP and 1 1 15MP of the Rhodia company, the "Hi-Sil EZ150G" silica of the PPG company, the "Zeopol" 8715, 8745 and 8755 silicas of the Huber Company, treated precipitated silicas, such as, for example, the "aluminum doped" silicas described in FIG. EP-A-0735088 or high surface area silicas 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 can be used in a known manner, thanks to an improvement in the dispersion of the filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to implement in the green state, these agents being, for example, hydrolysable silanes such as alkylalkoxysilanes, polyols, fatty acids, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes. In particular, polysulfide silanes, called "symmetrical" or "asymmetrical" silanes according to their particular structure, are used, as described for example in the applications WO03 / 002648 (or US 2005/016651) and WO03 / 002649 (or US 2005/016650). In particular, polysulphide silanes known as "symmetrical" silanes having the following general formula (III) are suitable in the following non-limiting definition:

(III) Z - A - S _x - A - Z, wherein: - x is an integer of 2 to 8 (preferably 2 to 5);

- A is a divalent hydrocarbon radical (preferably alkylene groups C1-C18 or arylene groups, C ₆ -C _2, more particularly alkylene C1-C1 _0, in particular C1-C4, particularly propylene);

Z is one of the following formulas:

R1 R1 R2

-Si-R1; - Si- R2; - Si- R2,

R2 R2 in which:

- the radicals R ^1, substituted or unsubstituted, identical or different, represent an alkyl group C 1 -C 18 cycloalkyl, C ₅ -C ₈ aryl or C ₆ -C ₈ (preferably alkyl, CrC ₆ , cyclohexyl or phenyl, especially C1-C4 alkyl groups, more particularly methyl and / or ethyl).

- the radicals R ^2, substituted or unsubstituted, identical or different, represent an alkoxy group C1-C18 cycloalkoxy or C ₅ -C ₈ (preferably a group selected from alkoxyls C ₈ and C cycloalkoxyls ₅ -C ₈ , more preferably still a group selected from C ₁ -C ₄ alkoxyls, in particular methoxyl and ethoxyl).

In the case of a mixture of polysulfurized alkoxysilanes corresponding to the formula (III) above, especially common commercially available mixtures, Isoudea 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 implemented for example with disulfide alkoxysilanes (x = 2). As examples of polysulphide silanes, mention may be made more particularly of polysulfides (in particular disulfides, trisulphides or tetrasulfides) of bis- (alkoxy (CiC ₄ ) -alkyl (Ci-C ₄ ) silyl-alkyl (CrC ₄ )), as for example polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl). Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated to TESPT, of formula [(C ₂ H ₅ O) ₃ Si (CH ₂ ) 3 S 2] 2 or bis (triethoxysilylpropyl) disulfide, in abbreviated form, is especially used. TESPD, of formula [(C2H ₅ O) 3 Si (CH ₂ ) 3 S] 2. Also suitable as preferred examples polysulphides (especially disulphides, trisulphides or tetrasulphides) bis- (monoalkoxyl (Ci-C ₄₎ -dialkyl (CrC ₄₎ silylpropyl), more particularly of bis-monoethoxydimethylsilylpropyl as described in the patent application WO 02/083782 (or US 2004/132880).

As coupling agent other than polysulfurized 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 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 patent applications WO 2006/125532. , WO 2006/125533, WO 2006/125534.

In particular, and preferably, the coupling agent may be a hydroxysilane polysulfide (as described in the documents cited above) corresponding to the general formula (IV): (HO) a R (3-a Si-R'-S _x -R'-Si R _(3-b) (OH) _b (IV) in which:

the radicals R ', which are identical or different, are divalent linking groups preferably comprising from 1 to 18 carbon atoms;

a and b, identical or different, are equal to 1 or 2;

x is a number greater than or equal to 2. The radicals R, which are identical or different, linear or branched, comprising preferably from 1 to 15 carbon atoms, are more preferably chosen from alkyls, cycloalkyls or aryls, in particular from C ₁ -C ₆ alkyls, C ₅ -C ₈ cycloalkyls and the phenyl radical. Among these radicals, mention may be made, for example, of those selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl and neopentyl. , n-hexyl, 2-ethylhexyl, n-octyl, isooctyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, phenyl, toluyl, benzyl.

More preferably still, the radicals R, which may be identical or different, are C1-C3 alkyls (namely methyl, ethyl, n-propyl or isopropyl), chosen in particular from methyl and ethyl.

The radicals R ', identical or different, substituted or unsubstituted, are preferably hydrocarbon radicals, saturated or unsaturated, containing from 1 to 18 carbon atoms, these radicals R' being able to be interrupted within the hydrocarbon chain by at least one heteroatom such as O, S or N. Particularly suitable are C 1 -C ₈ alkylene groups or C ₆ -C ₁₂ arylene groups, more particularly C ₁ -C 10 alkylenes, especially C ₁ -C ₄ alkylenes, in particular those chosen from methylene, ethylene and propylene.

Preferably in the hydroxysilane polysulfides having the general formula (IV), the hydroxysilane is a monohydroxysilane that is to say that a and b are equal to 1. Also preferably, the radicals R are chosen from linear or branched C ₁ -C ₆ alkyls, C ₅ -C ₈ cycloalkyls or a phenyl radical; the radicals R 'are selected from alkylene C1-C18 or arylene C ₆ -C _2, more particularly, the radicals R are selected from alkyl and -C ₆ the radicals R' from alkylene C1-C10 .

Thus, very preferably, the hydroxysilane is a monosiloxysilane polysulfide of formula (V):

RR (V) in which the R radicals are C1-C3 alkyls, preferably methyl; the R 'radicals of C1-C4 alkylenes, preferably methylene, ethylene or propylene; x is greater than or equal to 2. More particularly, the hydroxysilane may be a bis (propyldimethylsilanol) polysulfide of particular formula (Va):

This product of formula (Va) corresponds to the product D in the aforementioned document WO 02/31041 (or US 2004/051210).

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 10 phr.

In addition to the silica, it is possible to use 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 alumina, or a blend of these two types of filler.

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 blacks N 15, N 134, N 234, N 326, N330, N 339, N 347 or N375, or else, according to the targeted applications, the blacks of higher series (for example 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 functionalized polyvinyl organic fillers as described in applications WO-A-2006/069792, WO-A-2006/069793, WO-A-2008/003434 and WO-A-2008/003435. The person skilled in the art will understand that, as the equivalent filler of the silica described in this paragraph, it would be possible to use a reinforcing filler of another nature, in particular organic, since this reinforcing filler would be covered with a layer of silica, 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.

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).

Sulfur is used at a preferential 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 method. of the invention to constitute a tire tread.

According to the invention, the vulcanization system comprises, as primary vulcanization accelerator, one or more thiazole compounds chosen from the compounds of formula (I) below:

in which

R 1 and R ₂ independently represent a hydrogen atom or a C 1 -C 25 hydrocarbon-based group chosen from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups, and optionally interrupted by a or more heteroatoms, Ri and R ₂ may together form a non-aromatic ring, but can not together form a ring aromatic, selected from

a hydrogen atom

a radical of formula

in which

y is an integer greater than or equal to 1, preferably less than or equal to 10, more preferably less than or equal to 8 and most preferably less than or equal to 6;

a radical of formula

in which

R ₆ is a C1-C18 hydrocarbon group, optionally interrupted by more than one heteroatom;

a radical of formula

in which

R ₇ is a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms;

a radical of formula

in which

Y is a C1-C18 hydrocarbon chain, optionally interrupted or substituted by one or more heteroatoms;

R ₈ is a hydrocarbon group having Ci _8, optionally interrupted by one or several heteroatoms;

a radical of formula

X - ^ - OR ₁₀ O

in which

X is a hydrocarbon chain Ci C _8, optionally interrupted or substituted by one or more heteroatoms;

a radical of formula

in which

Ru is a hydrogen atom or a hydrocarbon group having Ci _8, optionally interrupted by one or more heteroatoms,

a radical of formula

- NH R12 in which

R12 represents a C1-C25 linear or branched, optionally interrupted by one or more heteroatoms, optionally substituted with one or more cyclic alkyl C3-C10 aryl or C ₆ -C _2, or R12 represents a cyclic alkyl C3-C10, optionally interrupted by one or more heteroatoms, optionally substituted by one or more linear alkyl groups, branched or cyclic C 1 -C 25 aryl or C ₆ -C ₂ optionally interrupted by one or more heteroatoms . By cyclic alkyl group is meant an alkyl group consisting of one or more rings.

By hydrocarbon group or chain (e) interrupted by one or more heteroatoms is meant a group or chain comprising one or more heteroatoms, each heteroatom being between two carbon atoms of said group or of said chain, or between a carbon atom of said group or said chain and another heteroatom of said group or said chain or between two other hetero atoms of said group or said chain. The heteroatom (s) may be a nitrogen, sulfur or oxygen atom.

Preferentially, R 1 and R ₂ independently represent a hydrogen atom or a methyl group. More preferably, R 1 and R ₂ each represent a hydrogen atom and according to a very preferred alternative, R 1 and R ₂ each represent a methyl group. The R ₃ to Ru groups may be independently selected from linear, branched or cyclic alkyl groups, aryl groups, aralkyl groups and alkylaryl groups. Groups X and Y may be independently selected from linear, branched or cyclic alkylene groups, arylene groups and alkylarylene groups.

The compound (s) of formula (I) are advantageously chosen from compounds whose group A is chosen from

the radical of formula

the radical of formula

and the radical of formula

Preferably, R ₃ , R ₄ and R ₅ represent a methyl group. Also preferably, R ₆ represents a C ₁ -C ₄ alkyl, more preferably a C ₁ -C ₃ alkyl and very preferably a methyl group or an ethyl group. Preferentially also, R ₇ represents a C ₁ -C ₄ alkyl, more preferably a C ₃ -C ₃ alkyl and very preferably a methyl group or an ethyl group, or R ₇ represents an aralkyl group such as for example a benzyl group.

Preferably, Y is an alkylene C 1 -C 4, more preferably an alkylene C1-C3 and very preferably a propylene group or an ethylene group and R ₈ represents a C1-C4 alkyl, more preferably alkyl, d- C ₃ and most preferably a methyl group or an ethyl group. Also preferably, X represents a C1-C4 alkylene, more preferably a C1-C3 alkylene and very preferably a methylene group or an ethylene group and R ₉ and R ₁₀ independently represent a C1-C4 alkyl, more preferably a C1-C3 alkyl and very preferably a methyl group or an ethyl group. Also preferably, Ru represents a hydrogen atom.

As a compound of formula (I) in particular, mention may be made of the following compounds:

Also preferably, A is a radical of formula

- NH R12 in which

R-I2 is a C1-C25 linear or branched, optionally interrupted by one or more heteroatoms, optionally substituted with one or more cyclic alkyl C3-C10 aryl or C ₆ -C _2, or R12 represents a cyclic alkyl C3-C1 _0, optionally interrupted by one or more heteroatoms, optionally substituted by one or more linear alkyl groups, branched or cyclic C 1 -C 25 aryl or C ₆ -C ₂ optionally interrupted by one or more heteroatoms. More preferentially, R ₁₂ represents a cyclohexyl group or a tert-butyl group. Very preferably, R12 represents a cyclohexyl group and:

Ri and R ₂ represent a methyl group, or

Ri and R ₂ represent H, or

R 1 is methyl, R ₂ is H, or

R 1 represents H, R ₂ represents a methyl group. Thus, a preferred compound of formula (I) is that wherein R 1 and R ₂ are methyl and R ₃ is cyclohexyl. In this case, the thiazole compound of formula (I) is N-cyclohexyl-4,5-dimethyl-2-thiazolesulfenamide.

A second compound of formula (I) is preferred wherein R 1 and R ₂ are H and R ₃ is cyclohexyl. In this case, the thiazole compound of formula (I) is N-cyclohexyl-2-thiazolesulfenamide.

A third compound of formula (I) is preferred wherein R 1 is methyl, R ₂ is H and R ₃ is cyclohexyl. In this case, the thiazole compound of formula (I) is N-cyclohexyl-4-methyl-2-thiazolesulfenamide.

A fourth compound of formula (I) is preferred wherein R 1 is H, R ₂ is methyl and R ₃ is cyclohexyl. According to another preferred embodiment, R ₃ represents a tert-butyl group. Thus, a particularly preferred compound of formula (I) is that wherein R 1 and R ₂ are methyl and R ₃ is tert-butyl. In this case, the thiazole compound of formula (I) is N-tert-butyl-4,5-dimethyl-2-thiazole sulfenamide.

The synthesis of the compounds of formula (I) is described in documents FR 2951 180 and FR 2974096, incorporated by reference with regard to these methods of preparation. The compound of formula (I), that is to say the compound (s) of formula (I) if there are several, generally represent from 0.1 to 10 phr, preferentially from 0.1 to 7 phr, preferably from 0.2 to 7 phr, more preferably from 0.5 to 7 phr, more preferably from 0.5 to 5 phr. The compounds of formula (I) may advantageously replace all or part of the accelerator compounds conventionally used.

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 (provided that they contain less than 0.5 phr) 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 "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated "CBS"), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (abbreviated "DCBS"), N-tert-butyl-2-benzothiazylsulfenamide (abbreviated "TBBS"), N-tert-butyl-2-benzothiazylsulfenimide (abbreviated "TBSI"), zinc dibenzyldithiocarbamate (in abbreviated "ZBEC") and mixtures of these compounds. Preferably, a primary accelerator of the sulfenamide type is used.

On the other hand, in the tires according to the invention, the composition comprising the thiazole compound of formula (I) and the alkali metal or alkaline-earth metal hydroxide required for the purposes of the invention is devoid of guanidine derivative or contains less than 0.5 phr. Preferably, the composition is either totally devoid of such compounds, or it contains less than 0.45 phr, preferably less than 0.4 phr, more preferably less than 0.3 phr, preferably less than 0, 2 phr and very preferably less than 0.1 phr. The term "guanidine derivative" is understood to mean the organic compounds bearing as their main function a guanidine function, such as those known in tire compositions, in particular as vulcanization accelerators, for example diphenylguanidine (DPG) or diorthotolylguanidine (DOTG). According to a preferred embodiment, in the tire according to the invention, the composition comprising the thiazole compound of formula (I) and the alkali metal or alkaline-earth metal hydroxide required for the purposes of the invention is also free of zinc or contains less than 0.5 phr, preferably less than 0.3 phr, more preferably less than 0.2 phr and very preferably less than 0.1 phr.

1-4 Alkaline or alkaline earth metal hydroxide

In order to advantageously replace the guanidine derivatives mentioned above, the tire according to the invention comprises an alkali metal or alkaline earth metal hydroxide.

In a known manner, the alkali and alkaline earth metals are those of the first two columns of the periodic table of the elements, such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) or barium (Ba).

Preferably, the alkali metal hydroxide or alkaline earth metal hydroxide is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, calcium hydroxide and the like. barium hydroxide and mixtures thereof.

According to a first embodiment and preferably, the alkali metal or alkaline earth metal hydroxide is chosen from the group consisting of alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, potassium hydroxide and the like. lithium hydroxide and mixtures thereof. More preferably, sodium hydroxide (or sodium hydroxide) or potassium hydroxide (potassium hydroxide) is used. In another embodiment, the alkali metal or alkaline earth metal hydroxide is selected from the group consisting of alkaline earth metal hydroxides, such as magnesium hydroxide, calcium hydroxide, hydroxide, and the like. barium and their mixtures.

For example, the alkali or alkaline earth metal hydroxide is sodium hydroxide. Soda is commercially available from many suppliers, for example in the form of pellets at Sigma-Aldrich. It can be introduced after rough grinding with mortar; it can also be dissolved in a small amount of water and preimpregnated silica with this solution before introduction into the mixer. The two modes of introduction give the same results.

Preferably, the level of alkali metal or alkaline earth hydroxide in the composition is in a range from 0.05 to 3 phr, more preferably from 0.1 to 2 phr, preferably more than 0.15 phr. at 1, 6 phr and more preferably from 0.2 to 1, 2 phr.

I-5 Other possible additives

The rubber compositions according to the invention optionally also include all or part of the usual additives usually used in elastomer compositions intended in particular for the production of treads, such as, for example, pigments, protective agents such as waxes, ozone, chemical antioxidants, anti-oxidants, plasticizers such as those proposed hereinafter, anti-fatigue agents, reinforcing resins, acceptors (for example phenolic novolak resin) or methylene donors (for example HMT or H3M). According to a preferred embodiment, the composition according to the invention further comprises a plasticizer. Preferably this plasticizer is a solid hydrocarbon resin (or plasticizing resin), an extender oil (or plasticizing oil), or a mixture of both. When it is included in the composition, the level of total plasticizer is preferably greater than or equal to 5 phr, more preferably 5 to 100 phr, in particular from 10 to 80 phr, for example from 15 to 70 phr.

According to a first preferred embodiment of the invention, the plasticizer is a liquid extension oil at 20 ° C, said to "low Tg", that is to say that by definition has a Tg lower than -20 ° C, preferably below -40 ° C.

Any extender oil, whether aromatic or non-aromatic in 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.

Particularly 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), oils TDAE (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 triesters above, there may be mentioned include glycerol triesters, preferably consisting predominantly (for more than 50%, more preferably more than 80% by weight) of an unsaturated fatty acid Ci ₈ is that is to say 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. Preferably, the extender oil content is between 2 and 50 phr, more preferably between 3 and 40 phr, more preferably between 5 and 35 phr.

According to another preferred embodiment of the invention, this plasticizer is a thermoplastic hydrocarbon resin whose Tg is greater than 0 ° C, preferably greater than 20 ° C. This resin is a solid at room temperature (23 ° C), as opposed to a liquid plasticizer such as an oil.

Preferably, the thermoplastic hydrocarbon plasticizing resin has at least one of the following characteristics: a Tg greater than 20 ° C, more preferably greater than 30 ° C;

a number-average molecular weight (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 / l; flow rate 1 ml / min; filtered solution on 0.45 μηη porosity filter before injection; Moore calibration with polystyrene standards; set of 3 "WATERS" columns 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). Suitable aromatic monomers are, for example, styrene, alpha-methylstyrene, ortho-, meta-, para-methylstyrene, vinyl-toluene, para-methylstyrene and the like. tert-butylstyrene, methoxystyrenes, the chl orostyrènes, vinylmesitylene, divinylbenzene, vinylnaphthalene, any vinylaromatic monomer derived from a C ₉ (or more generally from a C ₈ to C 1 _0). Preferably the vinylaromatic monomer is styrene or a vinylaromatic monomer resulting from a C ₉ (or more generally from a C ₈ to C 1 _0). 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), terpene homopolymer or copolymer resins, terpene phenol homopolymer or copolymer resins, homopolymer or C5 cut copolymer resins, homopolymer or C9 cut copolymer resins, alpha-methyl-styrene homopolymer and copolymer resins and blends of these resins, 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, lp = 1.6, Tg = 72 ° C.) or by the company ARIZONA under the name "Sylvagum TR7125C" (Mn = 630 g / mol;

Mw = 950 g / mol; lp = 1.5; Tg = 70 ° C);

C ₅ / vinylaromatic copolymer resins, in particular C ₅ / styrene or C ₅ / C ₉ cuts: by Neville Chemical Company under the names "Super Nevtac 78", "Super Nevtac 85" or "Super Nevtac 99", by Goodyear Chemicals under the name "Wingtack Extra", by Kolon sous denominations "Hikorez T1095" and "Hikorez TU 00", 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 "ZT1 15LT" and "ZT5100".

As 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-methylstyrene 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).

According to a particular embodiment of the invention, when it is included in the composition, the level of plasticizing hydrocarbon resin is between 5 and 50 phr, preferably between 7 and 40 phr, more preferably between 10 and 35 phr. Preferentially also, the content of plasticizing resin is between 5 and 20 phr, and more preferably between 5 and 15 phr.

Of course, the compositions according to the invention can be used alone or in a blend (i.e., in a mixture) with any other rubber composition that can be used for the manufacture of tires.

It goes without saying that the invention relates to the rubber compositions described above both in the so-called "raw" or uncrosslinked state (ie, before firing) in the so-called "cooked" or crosslinked state, or vulcanized ( ie, after crosslinking or vulcanization).

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 referred to as "non-phase" phase). at high temperature, up to a maximum temperature of between 110.degree. C. and 190.degree. C., preferably between 130.degree. C. and 180.degree. C., followed by a second phase of mechanical work (sometimes referred to as at lower temperature, typically below 10 ° C., for example between 60 ° C. and 100 ° C., a finishing phase during which the crosslinking or vulcanization system is incorporated, such phases have been described by US Pat. for example in EP-A-0501227, EP-A-0735088, EP-A-0810258, WO00 / 05300 or WO00 / 05301.

The first (non-productive) phase is preferably carried out in several thermomechanical steps. In a first step, the elastomers and the reinforcing fillers (and optionally the coupling agents and / or other ingredients) are introduced into a suitable mixer such as a conventional internal mixer at a temperature of between 20.degree. ° 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 of semi-finished products. finished in order to obtain products such as sidewalls, carcass ply, crown plies (or tire belt), tread, bead filler, tread underlayer or other layers of elastomers, preferentially the rolling. 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 cooking) is conducted in a known manner at a temperature generally between 130 ° C and 200 ° C, under pressure, for a sufficient time which can 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 following examples illustrate the invention without limiting it.

III- Examples of embodiment of the invention

111-1 Preparation of examples

In the following examples, the rubber compositions were made as described above. 111-2 Characterization of examples

In the examples, the rubber compositions are characterized before and / or after firing as indicated below.

- Mooney viscosity or Mooney plasticity (before cooking):

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 raw composition (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. Mooney plasticity (ML 1 +4) is expressed in "Mooney unit" (UM, with 1 UM = 0.83 Newton meter). For more readability the results will be indicated in base 100, the value 100 being attributed to the witness. 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.

- Dynamic properties (after cooking):

The dynamic properties G ^* and tan (5) 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 (4 mm cylindrical test specimen) is recorded. thickness and 400 mm ² section), subjected to sinusoidal stress in simple shear alternately, at the frequency of 10Hz, under normal temperature conditions (23 ° C) according to ASTM D 1349-99. A peak to peak deformation amplitude sweep of 0.1 to 50% (one-way cycle) is performed. then from 50% to 1% (return cycle). The results exploited are the complex dynamic shear modulus (G ^* ) and the loss factor (tan δ). For the return cycle, the maximum value of tan δ observed (tan (δ) _max ), as well as the complex modulus difference (ΔΘ *) between the values at 0.1% and at 50% of deformation (effect Payne). For more readability the results will be indicated in base 100, the value 100 being attributed to the witness. 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.

III-3 Examples

111-3-1 Example I

This example is intended to compare the different rubber properties of control compositions with compositions according to the invention, that is to say comprising a diene elastomer, a reinforcing filler mainly comprising silica, a vulcanization system comprising a thiazole compound of general formula (I), and an alkali metal or alkaline earth metal hydroxide, the compositions being free of or containing less than 0.5 phr of guanidine derivative.

In particular the compositions T-1 to T-3 and C-1 to C-4 were prepared and tested. The T1 composition does not include the thiazole compound of formula (I), or the alkali or alkaline earth metal hydroxide. The compositions T-2 and T-3 vary with respect to the first control only by replacing the CBS with a thiazole compound of formula (I) (in an isomolar amount) for T-2 and by replacing the DPG with sodium hydroxide for T-3, as shown in Table 1. The compositions C-1 to C-4 are in accordance with the invention. Composition C-1 comprises replacing CBS with a thiazole compound of formula (I) (in an isomolar amount) and replacing the DPG with the alkali and alkaline earth metal hydroxide with respect to control T-1 . Composition C-2 illustrates an embodiment in which the composition is free of zinc. Composition C-3, for its part, is identical to composition C-1 in which a preferred coupling agent is used. The composition C-4, for its part, is identical to the composition C-3 in which the zinc oxide has been removed.

Table 1

(1) SBR (Sn star) with 27% of styrene unit and 24% of 1,2-butadiene unit (Tg = -48 ° C) carrying a silanol function at the end of the elastomeric chain

(2) ASTM N234 grade (Cabot company)

(3) "Zeosil 1,165 MP" silica of Rhodia type "HDS"

(4) Coupling Agent: TESPT ("Si69" from Evonik - Degussa)

(5) Coupling agent: bis (propyldimethylsilanol) polysulfide as described in WO 02/31041 (or US 2004/051210)

(6) N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (Santoflex 6-PPD) from the company Flexsys and anti-ozone wax

(7) Sunflower oil 85% by weight of oleic acid "Lubrirob Tod 1880" from the company Novance

(8) Resin C5 / C9 "Escorez 1273" from the company Exxon

(9) Diphenylguanidine ("Perkacit" DPG from Flexsys)

(10) N-cyclohexyl-2-benzothiazol sulfenamide ("Santocure CBS") from the company Flexsys)

(1 1) N-cyclohexyl-4,5-dimethyl-2-thiazolesulfenamide

The compositions are made with an introduction of all the components 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.).

Table 2 below gives the properties measured before and after cooking. For a better understanding and comparison of the tests, the results are given in base 100, that is to say that the experimental value for the control is brought back to the value 100 then the values of the tests are given according to this base of 100 for the witness.

Table 2

Compared to the control compositions, it is noted that the compositions C-1 to C-4 have a reduced hysteresis, as attested by values of tan (δ) max and ΔΘ ^* which are substantially reduced, and / or a compromise hysteresis / processability improved raw (Mooney value lower).

Claims

1. A tire comprising a rubber composition based on at least one diene elastomer, a reinforcing filler predominantly composed of silica, and a vulcanization system co of the general formula (I)

in which

A is selected from

a hydrogen atom,

a radical of formula

in which

R ₃ , R ₄ and R ₅ independently represent a hydrocarbon group at dC optionally interrupted by one or more heteroatoms,

y is an integer greater than or equal to 1, preferably less than or equal to 1, more preferably less than or equal to 8 and most preferably less than 6;

a radical of formula

O

in which

R ₆ is a C 1 -C 18 hydrocarbon group, optionally interrupted by several heteroatoms;

a radical of formula

in which

R ₇ is a hydrocarbon group having Ci _8, optionally interrupted by one heteroatom;

a radical of formula

O

Ύ CT

in which

a radical of formula

OR _D

10

O

in which

X is a C 1 -C ₈ hydrocarbon-based chain, optionally interrupted, substituted by one or more heteroatoms,

R ₉ and io independently represent a hydrocarbon group d- 'optionally interrupted by one or more heteroatoms, and

a radical of formula

in which

Ru is a hydrogen atom or a hydrocarbon group having Ci _8, optionally interrupted by one or more heteroatoms.

a radical of formula - NH R12 in which

R-I2 is a C1-C25 linear or branched, optionally interrupted by one or more heteroatoms, optionally substituted with one or more cyclic alkyl C3-C10 aryl or C ₆ -C _2, or

R12 represents a cyclic alkyl C3-C10, optionally interrupted by one or more heteroatoms, optionally substituted by one or more linear alkyl groups, branched or cyclic C 1 -C 25 aryl or C ₆ -C _2, optionally interrupted by one or a plurality of heteroatoms, said composition further comprising an alkali metal or alkaline earth metal hydroxide, said composition being devoid of or comprising less than 0.5 phr of guanidine derivative.

2. A tire according to claim 1, wherein said composition comprises a thiazole compound of general formula (I) characterized in that R 1 and R ₂ independently represent a hydrogen atom or a methyl group.

3. Pneumatic tire according to claim 2, characterized in that R 1 and R ₂ each represent a hydrogen atom.

4. A tire according to claim 2, characterized in that R 1 and R ₂ each represent a methyl group.

5. A tire according to any one of the preceding claims, characterized in that the groups R ₃ to Ru are independently selected from linear, branched or cyclic alkyl groups, aryl groups, aralkyl groups and alkylaryl groups.

Pneumatic tire according to any one of the preceding claims, characterized in that the X and Y groups are independently selected from linear, branched or cyclic alkylene groups, arylene groups and alkylarylene groups.

Pneumatic tire according to any one of the preceding claims, characterized in that A is selected from

a radical of formula

R ₄

R ₅

radical of formula

8. A tire according to any one of claims 1 to 4, characterized in that A is a radical of formula

- NH R12 in which

R-I2 is a C1-C25 linear or branched, optionally interrupted by one or more heteroatoms, optionally substituted with one or more cyclic alkyl C3-C10 aryl or C ₆ -C _2, or R12 represents a cyclic alkyl C3-C1 _0, optionally interrupted by one or more heteroatoms, optionally substituted by one or more linear alkyl groups, branched or cyclic C 1 -C 25 aryl or C ₆ -C ₂ optionally interrupted by one or more heteroatoms.

9. A tire according to claim 8 characterized in that R12 represents a cyclohexyl group or a tertbutyl group.

10. A tire according to claim 9 characterized in that R12 represents a cyclohexyl group and:

R 1 and R ₂ represent a methyl group, or

Ri and R ₂ represent H, or

11. A tire according to any one of the preceding claims, characterized in that the thiazole compound represents from 0.1 to 10 phr, preferably from 0.1 to 7 phr, preferably from 0.2 to 7 phr, more preferably from 0.5 to 7 phr, more preferably from 0.5 to 5 phr (parts by weight per cent of diene elastomer).

12. A tire according to any one of the preceding claims, wherein said composition contains less than 0.45 phr of guanidine derivative, and preferably less than 0.4 phr.

13. A tire according to any one of the preceding claims wherein the level of alkali metal or alkaline earth metal hydroxide is 0.05 to 3 phr, preferably more than 0.1 phr to 2 phr.

A tire according to any one of the preceding claims wherein the alkali or alkaline earth metal hydroxide is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, lithium hydroxide and the like. magnesium hydroxide, calcium hydroxide, barium hydroxide and mixtures thereof.

A tire according to any one of the preceding claims wherein the alkali or alkaline earth metal hydroxide is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, and their salts. mixtures.

A tire according to any one of claims 1 to 14 wherein the alkali or alkaline earth metal hydroxide is selected from the group consisting of magnesium hydroxide, calcium hydroxide, barium hydroxide and their mixtures.

17. A tire according to one of the preceding claims wherein the silica content is 30 to 150 phr.

18. A tire according to any one of the preceding claims, wherein the reinforcing filler comprises carbon black, in a minority.

19. A tire according to claim 18 wherein the carbon black content is from 0.5 to 50 phr.

20. A tire according to any one of the preceding claims wherein the diene elastomer is selected from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and these elastomers.

21. A tire according to any one of the preceding claims wherein the diene elastomer is predominantly composed of non-isoprene diene elastomer.

22. A tire according to claim 21 wherein the diene elastomer is composed of 100 phr of non-isoprene diene elastomer.

Tire according to one of claims 21 or 22, wherein the non-isoprene diene elastomer is selected from the group consisting of polybutadienes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.

24. Tire according to one of the preceding claims wherein the composition further comprises a plasticizer, preferably selected from plasticizing resins, extension oils and mixtures thereof.

25. A tire according to claim 24 wherein the level of plasticizer is 5 to 100 phr.

26. Tire according to one of the preceding claims wherein the composition is further free of zinc or contains less than 0.5 phr, preferably less than 0.3 phr.

27. The tire according to one of the preceding claims further comprising a coupling agent.

28. The tire according to claim 27 wherein the coupling agent is a hydroxysilane polysulfide corresponding to the general formula (IV): (HO) _a R (3- _a) Si-R'-S _x -R'-Si R _(3- _b ) (OH) _b (IV)

in which :

a and b, identical or different, are 1 or 2;

x is a number greater than or equal to 2.

The tire of claim 28 wherein the coupling agent is a monohydroxysilane wherein a and b are 1.

30. A tire according to any one of claims 28 or 29 wherein the radicals R are chosen from C1-C6 alkyls, C5-C8 cycloalkyls or a phenyl radical; the radicals R 'are chosen from C 1 -C 18 alkylenes or C 6 -C 12 arylenes.

31. A tire according to any one of claims 28 to 30 wherein the radicals R are chosen from C1-C6 alkyls and R 'radicals from C1-C10 alkylenes.

Pneumatic tire according to any one of claims 28 to 31, in which the hydroxysilane is a polysulfide of monohydroxysilane of formula (V):

RR (V) wherein the R radicals are C ₁ -C ₃ alkyls, preferably methyl; the R 'radicals of the C ₁ -C ₄ alkylenes, preferably methylene, ethylene or propylene; x is greater than or equal to 2.

33. A tire according to any one of claims 28 to 32 wherein the hydroxysilane is a bis (propyldimethylsilanol) polysulfide of particular formula (Va):

Tire according to one of the preceding claims, in which the composition comprising the thiazole compound of formula (I) and the alkali or alkaline earth metal hydroxide is the composition of a tire layer selected from the group consisting of or part of the tread, all or part of the tire belt and their combinations.

35. A tire according to claim 34 wherein the composition comprising the thiazole compound of formula (I) and the alkali metal or alkaline earth metal hydroxide is that of all or part of the tread.