WO2011073186A1

WO2011073186A1 - Winter tyre with improved grip on ice

Info

Publication number: WO2011073186A1
Application number: PCT/EP2010/069621
Authority: WO
Inventors: Masayuki Maesaka; Salvatore Pagano
Original assignee: Societe De Technologie Michelin; Michelin Recherche Et Technique S.A.
Priority date: 2009-12-18
Filing date: 2010-12-14
Publication date: 2011-06-23
Also published as: FR2955584B1; EA201290524A1; CA2784412A1; JP2013514398A; JP5778171B2; FR2955584A1; EP2512825A1

Abstract

Winter tyre with improved grip on melting ice, the tread of which comprises a composition comprising at least one diene elastomer such as natural rubber and/or a polybutadiene, more than 30 phr of a liquid plasticizing agent, between 50 and 150 phr of a reinforcing filler such as silica and/or carbon black, and between 35 and 50 phr of hollow microparticles of at least one metal oxide such as an aluminosilicate, having a weight-based median size of between 2 and 500 μm.

Description

WINTER PNEUMATIC WITH IMPROVED ICE ADHESION

1. DOMAIN OF THE INVENTION

The invention relates to rubber compositions used as treads of tires for vehicles, in particular tires "winter" able to roll on floors covered with ice or ice without being provided with nails (also called "studless" tires).

It is more particularly related to treads of winter tires which are specifically adapted for running under so-called "melting ice" conditions encountered in a temperature range typically between -5 ° C and 0 ° C. It is recalled that, in such a field, the pressure of the tires at the passage of a vehicle causes a superficial melting of the ice which is covered with a thin film of water detrimental to the adhesion of these tires.

2. STATE OF THE ART

To avoid the harmful effects of nails, in particular their strong abrasive action on the floor covering itself and a markedly degraded road behavior on dry ground, the tire manufacturers have proposed various solutions consisting in modifying the formulation of the rubber compositions constituting their treads.

Thus, it has been proposed first of all to incorporate solid particles of high hardness, such as, for example, silicon carbide (see, for example, US Pat. No. 3,878,147), some of which are flush with the surface of the tread. as it wears, and thus come into contact with the ice. Such particles, able to act finally as micro-nails on hard ice, thanks to a well known "claw" effect, remain relatively aggressive vis-à-vis the ground; they are not well adapted to driving conditions on melting ice. Other solutions have therefore been proposed, including incorporating water-soluble powders (ie, which can dissolve in water) in the constitutive composition of the tread. Such powders solubilize more or less in contact with snow or melted ice, which allows on the one hand the creation on the surface of the tread of porosities likely to improve the attachment of the tread on the ground and on the other hand the creation of throats acting as evacuation channels of the liquid film created between the pneumatic and soil. Examples of such water-soluble powders include, for example, the use of cellulose powder, PVA (polyvinyl alcohol) or starch, or powders of guar gum or xanthan gum (see for example, patent application JP 3-159803, JP 2002-211203, EP 940,435, WO 2008/080750, WO 2008/080751).

In all these examples, the solubility at very low temperature and in a very short time of the powder used is an essential factor for the proper functioning of the tread. If the powder is not soluble in the conditions of use of the tire, the aforementioned functions (creation of microporosities and water discharge channels) are not met and the adhesion is not improved. Another known drawback of these solutions is that they can strongly penalize the reinforcement of the rubber compositions (and therefore their resistance to wear) or their hysteresis (and therefore their rolling resistance).

3. BRIEF DESCRIPTION OF THE INVENTION

Continuing their research, the Applicants have discovered a rubber composition capable of generating an effective surface microroughness by means of specific microparticles, and which makes it possible to greatly improve the ice adhesion of the treads and tires comprising them, under conditions of melting ice, without penalizing the strengthening and hysteresis properties.

Consequently, the present invention relates to a tire whose tread comprises a rubber composition comprising at least one diene elastomer, more than 30 phr of a liquid plasticizer, and between 50 and 150 phr of a reinforcing filler, characterized in that that said composition further comprises 35 to 50 phr of hollow microparticles of at least one metal oxide having a median size by weight of between 2 and 500 μιη.

Initially, these hollow microparticles which are protruding on the surface of the tread, fulfill the claw function described above without the disadvantage of being highly abrasive vis-à-vis the asphalt used as a road surface. Then, in a second step, after crushing by breaking of their hollow structure and progressive expulsion of the rubbery matrix, said microparticles create microcavities which act as storage volume and drainage channel of the water film on the surface. ice ; under these conditions, the contact between the surface of the tread and the ice is no longer lubricated and the coefficient of friction is thus improved.

The tires of the invention are particularly intended to equip tourism-type motor vehicles, including 4x4 vehicles (four-wheel drive) and SUV vehicles ("Sport Utility Vehicles"), two-wheel vehicles (including motorcycles) as industrial vehicles chosen in particular from vans and "heavy goods vehicles" (ie, metro, buses, road transport vehicles such as trucks, tractors).

The invention as well as its advantages will be readily understood in the light of the description and the following exemplary embodiments.

4. MEASUREMENTS AND TESTS USED The treads and rubber compositions constitutive of these treads are characterized, before and after cooking, as indicated below.

4.1 - Mooney plasticity An oscillating consistometer is used as described in the French standard NF T 43-005 (November 1980). 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. The Mooney plasticity (ML 1 + 4) is expressed in "Mooney unit" (UM, with 1 UM = 0.83 Newton.meter).

4.2 - Toasting time The measurements are carried out at 130 ° C., in accordance with the French standard NF T 43-005. The evolution of the consistency index as a function of time makes it possible to determine the toasting time of the rubber compositions, evaluated according to the above-mentioned standard by the parameter T5 (case of a large rotor), expressed in minutes, and defined as being the time required to obtain an increase in the consistometric index (expressed in MU) of 5 units above the minimum value measured for this index.

4.3 - Rheometry

The measurements are carried out at 150 ° C. with an oscillating chamber rheometer according to DIN 53529 - Part 3 (June 1983). The evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization reaction. The measurements are processed according to DIN 53529 - Part 2 (March 1983): Ti is the induction time, that is to say the time required for the beginning of the vulcanization reaction; T _a (for example T ₉₀ ) is the time required to achieve a cc% conversion, i.e., cc% (eg 90%) of the difference between the minimum and maximum torque. 4.4 - Traction tests

These tensile tests make it possible to determine the elastic stress and the properties at break. Unless otherwise indicated, they are carried out in accordance with the French standard NF T 46-002 of September 1988. The second elongation is measured (ie, after an accommodation cycle at the extension rate provided for the measurement itself). nominal secants (or apparent stresses, in MPa) at 10% elongation (denoted M 10), 100% elongation (denoted M 100) and 300% elongation (denoted M300). The breaking stresses (in MPa) and the elongations at break (in%) are also measured. All these tensile measurements are carried out under normal conditions of temperature (23 ± 2 ° C.) and hygrometry (50 ± 5% relative humidity), according to the French standard NF T 40-101 (December 1979). 4.5 - Shore A Hardness

The Shore A hardness of the compositions after curing is assessed according to ASTM D 2240-86. 4.6 - Dynamic Properties

Dynamic properties are measured on a viscoanalyzer (Metravib VA4000) according to ASTM D5992-96. The response of a sample of vulcanized composition (cylindrical specimen of 4 mm thickness and 400 mm ² section), subjected to a sinusoidal stress in alternating simple shear, at the frequency of 10 Hz, at a temperature of 0, is recorded. ° C. A strain amplitude sweep of 0.1% to 50%> (forward cycle) is performed, followed by 50%> to 1% (return cycle). The exploited results are the loss factor tan (6); for the return cycle, the maximum value of tan (δ) observed (denoted tan (δ) _max ) is given between the values at 0.15% and at 50%> deformation (Payne effect).

5. DETAILED DESCRIPTION OF THE INVENTION

In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight. The abbreviation "pce" means parts by weight per hundred parts of elastomer (of the total elastomers if several elastomers are present).

On the other hand, any range of values designated by the expression "between a and b" represents the range of values greater than "a" and less than "b" (i.e., terminals a and b excluded). while that any range of values designated by the term "from a to b" means the range of values from "a" to "b" (i.e. including the strict limits a and b).

The rubber composition of the tread according to the invention, at least for the portion (therefore carved) tread which is intended to come into contact with the road during the rolling of the tire, is therefore based on at least one diene elastomer, a plasticizer system, a reinforcing filler and specific hollow microparticles, components which are described in detail hereinafter. 5.1 - Diene elastomer

By elastomer (or rubber, the two terms being synonymous) of the "diene" type, it is recalled that must be understood an elastomer derived at least in part (ie a homopolymer or a copolymer) of monomers dienes (monomers carrying two double bonds carbon - carbon, conjugated or not).

The diene elastomers can be classified in known manner into two categories: those known as "essentially unsaturated" and those known as "essentially saturated". Butyl rubbers, such as, for example, copolymers of dienes and alpha-olefins of the EPDM type, fall into the category of essentially saturated diene elastomers having a diene origin ratio which is low or very low, always less than 15. % (mole%). By contrast, essentially unsaturated diene elastomer is understood to mean a diene elastomer derived at least in part from conjugated diene monomers having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%). ). 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%.

It is preferred to use at least one diene elastomer of the highly unsaturated type, in particular a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), polybutadienes (BR) and butadiene copolymers, copolymers of isoprene 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) and mixtures of such copolymers.

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 a coupling with carbon black, there may be mentioned for example functional groups comprising a C-Sn bond or amino functional groups such as benzophenone for example; for coupling to a reinforcing inorganic filler such as silica, mention may be made, for example, of silanol or polysiloxane functional groups having a silanol end (as described, for example, in US Pat. No. 6,013,718), alkoxysilane groups (as described, for example, in US 5,977,238), carboxylic groups (as described, for example, in US 6,815,473 or US 2006/0089445) or polyether groups (as described for example in US 6,503,973). By way of other examples of such functionalized elastomers, mention may also be made of elastomers (such as SBR, BR, NR or IR) of the epoxidized type.

Polybutadienes, and in particular those having a 1,2-unit content of between 4% and 80%, or those having a cis-1,4 content of greater than 80%, polyisoprenes and copolymers of butadiene- styrene and in particular those having a styrene content of between 5% and 50% by weight and more particularly between 20% and 40%, a 1,2-butadiene content of the butadiene part of between 4% and 65%. %, a trans-1,4-linkage content of between 20% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a glass transition temperature. ("Tg" - measured according to ASTM D3418-82) 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 between -25 ° C and -50 ° C.

In the case of butadiene-styrene-isoprene copolymers are especially suitable those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60%. by weight and more particularly between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly between 20% and 40%, a content of -1,2 units of the butadiene part between 4% and 85%, a content of trans-1,4 units of the butadiene part of between 6% and 80%, a content of -1,2 units plus -3,4 of the isoprenic part of between 5% and 70% % and a trans-1,4-unit content of the isoprene portion of between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg of between -20 ° C and -70 ° C.

According to a particularly preferred embodiment of the invention, the diene elastomer is chosen from the group consisting of natural rubber, synthetic polyisoprenes and polybutadienes having a cis-1,4 bond ratio of greater than 90%, copolymers of butadiene-styrene and mixtures of these elastomers.

According to a more particular and preferred embodiment, the rubber composition comprises 50 to 100 phr of natural rubber or synthetic polyisoprene, said natural rubber or synthetic polyisoprene which can be used in particular in cutting (mixture) with not more than 50 phr of a polybutadiene having a cis-1,4 bond ratio of greater than 90%.

According to another particular and preferred embodiment, the rubber composition comprises 50 to 100 phr of a polybutadiene having a cis-1,4 bond ratio greater than 90%, said polybutadiene being able to be used in particular in a blend with at most 50 pce of natural rubber or synthetic polyisoprene.

To the diene elastomers of the treads according to the invention could be associated, in a minor amount, synthetic elastomers other than diene, or even polymers other than elastomers, for example thermoplastic polymers.

5.2 - Plasticizer System Another essential feature of the rubber composition according to the invention is that it comprises at least 30 phr of a liquid plasticizer (at 20 ° C.) whose function is to soften the matrix by diluting the elastomer and the reinforcing filler; its Tg is by definition less than -20 ° C, preferably less than -40 ° C. Any extender oil, whether aromatic or non-aromatic, any liquid plasticizer known for its plasticizing properties vis-à-vis diene elastomers, is usable. At ambient temperature (20 ° C.), these plasticizers or these oils, more or less viscous, are liquids (that is to say, as a reminder, substances having the capacity to eventually take on the shape of their container) , in contrast to, in particular, hydrocarbon plasticizing resins which are inherently solid at room temperature.

Particularly suitable liquid plasticizers selected from the group consisting of naphthenic oils (low or high viscosity, including hydrogenated or not), paraffinic oils, MES oils (Medium Extracted Solvates), Treated Distillate Aromatic Extracts (TDAE) oils, mineral oils, vegetable oils, ethers plasticizers, ester plasticizers, phosphate plasticizers, sulphonate plasticizers and mixtures of these compounds.

As phosphate plasticizers, for example, mention may be made of those containing from 12 to 30 carbon atoms, for example trioctyl phosphate. As examples of 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- lates, sebacates, tri-esters, glycerol and mixtures of these compounds. Among the triesters above, mention may be made in particular of glycerol triesters, preferably consisting mainly (for more than 50%>, more preferably for more than 80% by weight) of a unsaturated fatty acid Ci _8, 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. The level of liquid plasticizer in the composition according to the invention is preferably greater than 40 phr, more preferably within a range of 50 to 100 phr.

According to another preferred embodiment, the compositions according to the invention may also comprise, as solid plasticizer (at 20 ° C.), a hydrocarbon resin having a Tg greater than + 20 ° C., preferably greater than + 30 ° C. C, as described for example in applications WO 2005/087859, WO 2006/061064 and WO 2007/017060.

Hydrocarbon resins are polymers that are well known to those skilled in the art, essentially based on carbon and hydrogen, and therefore inherently miscible in diene (s) elastomer compositions when they are further qualified as "plasticisers". ". They have been described, for example, in the book "Hydrocarbon Resins" by R. Mildenberg, M. Zander and G. Collin (New York, VCH, 1997, ISBN 3-527-28617-9), chapter 5 of which is devoted their applications, in particular pneumatic rubber (5.5 "Rubber Tires and Mechanical Goods"). They may be aliphatic, aromatic or 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). They are preferably exclusively hydrocarbon-based, that is to say they contain only carbon and hydrogen atoms.

Preferably, the plasticizing hydrocarbon resin has at least one, more preferably all, of the following characteristics: a Tg greater than 20 ° C (more preferably between 40 and 100 ° 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). The Tg is measured in a known manner by DSC (Differential Scanning Calorimetry), according to the ASTM D3418 (1999) standard. 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 / 1; flow rate 1 ml / min; filtered solution on 0.45 μιη 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"). According to a particularly preferred embodiment, the plasticizing hydrocarbon resin is chosen from the group consisting of cyclopentadiene homopolymer or copolymer resins (abbreviated to CPD), dicyclopentadiene homopolymer or copolymer resins (abbreviated to DCPD), homopolymer or terpene copolymer resins, C5 homopolymer or copolymer resins, C9 homopolymer or copolymer resins, and mixtures of these resins. Among the above copolymer resins are more preferably used those selected from the group consisting of (D) CPD / vinylaromatic copolymer resins, (D) CPD / terpene copolymer resins, copolymer resins (D) CPD / C5 cut, (D) CPD / C9 cut copolymer resins, terpene / vinylaromatic copolymer resins, terpene / phenol copolymer resins, C5 / vinylaromatic cut copolymer resins, C9 / vinylaromatic cut copolymer resins, and mixtures of these resins.

The term "terpene" here combines in a known manner the alpha-pinene, beta-pinene and limonene monomers; preferably, a limonene monomer is used which is present in a known manner in the form of three possible isomers: L-limonene (laevorotatory enantiomer), D-limonene (dextrorotatory enantiomer), or the dipentene, racemic of the dextrorotatory and levorotatory enantiomers. . Suitable vinylaromatic monomers are, for example, styrene, alpha-methylstyrene, ortho-, meta-, para-methylstyrene, vinyltoluene, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, hydroxystyrenes, vinylmesitylene, and the like. , divinylbenzene, vinylnaphthalene, any vinylaromatic monomer from a C ₉ cut (or more generally from a C ₈ to C ₁₀ cut). Preferably, the vinyl-aromatic compound is styrene or a vinylaromatic monomer derived from a C ₉ cut (or more generally from a C ₈ to C ₁₀ cut). Preferably, the vinylaromatic compound is the minor monomer, expressed as a mole fraction, in the copolymer under consideration.

The content of hydrocarbon resin is preferably between 3 and 60 phr, more preferably between 3 and 40 phr, especially between 5 and 30 phr. The level of total plasticizer (ie, liquid plasticizer plus, if appropriate, solid hydrocarbon resin) is preferably between 40 and 100 phr, more preferably in a range of 50 to 80 phr. 5.3 - Charge

Any type of reinforcing filler known for its ability to reinforce a rubber composition that can be used for manufacturing tires, for example an organic filler such as carbon black, or a reinforcing inorganic filler such as silica to which is associated in a known manner a coupling agent.

Such a reinforcing filler typically consists of nanoparticles whose average size (in mass) is less than 500 nm, most often between 20 and 200 nm, in particular and preferably between 20 and 150 nm.

Suitable carbon blacks are all carbon blacks, especially blacks conventionally used in tires or treads of tires (so-called pneumatic grade blacks). Among these, the reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades), for example blacks NI15, N134, N234, N326, N330, N339, N347, N375, will be mentioned more particularly. The carbon blacks could for example already be incorporated into the 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 and WO-A-2006/069793, WO-A-2008/003434. and WO-A-2008/003435.

"Reinforcing inorganic filler" means any inorganic or mineral filler, irrespective of its color and origin (natural or synthetic), also called "white" filler, "clear" filler or even "non-black" filler. "As opposed to carbon black, capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition for the manufacture of tires, in other words able to replace, in its function of reinforcement, a conventional carbon black of pneumatic grade; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.

Suitable reinforcing inorganic fillers are in particular siliceous type mineral fillers, in particular silica (SiO ₂₎ , or aluminous type, in particular alumina (Al ₂ O ₃ ), The silica used may be any reinforcing silica known from the person skilled in the art, in particular any precipitated or fumed silica having a BET surface, and that a CTAB specific surface area both less than 450 m ² / g, preferably 30 to 400 m ² / g, especially between 60 and 300 m ² / g. As highly dispersible precipitated silicas (called "HDS"), mention may be made, for example, of the "Ultrasil" 7000 and "Ultrasil" 7005 silicas of the Degussa company, the "Zeosil" 1165MP, 1135MP and 1115MP silicas of the Rhodia company. Silica "Hi-Sil" EZ150G from the company PPG, the silicas "Zeopol" 8715, 8745 and 8755 from the Huber Company. Examples of reinforcing aluminas include "Baikalox" A 125 or CRI 25 aluminas from Baikowski, "APA-100RDX" from Condea, "Aluminoxid C" from Degussa or "AKP-G015" from Sumitomo Chemicals. Preferably, the total reinforcing filler content (carbon black and / or reinforcing inorganic filler) is between 60 and 120 phr, in particular between 70 and 100 phr.

According to a particular embodiment, the filler comprises silica, carbon black or a mixture of carbon black and silica.

According to another particular embodiment, the reinforcing filler comprises predominantly carbon black; in such a case, the carbon black is present at a level preferably greater than 60 phr, associated or not with a reinforcing inorganic filler such as silica in a minority amount.

According to another particular embodiment, the reinforcing filler comprises an inorganic filler, in particular silica, as a majority; in such a case, the inorganic filler, in particular silica, is present at a rate preferably greater than 70 phr, associated or not with carbon black in a minor amount; the carbon black, when present, is preferably used at a level of less than 20 phr, more preferably less than 10 phr (for example between 0.1 and 10 phr).

Independently of the first aspect of the invention, namely the search for an optimized adhesion on melting ice, the majority use of a reinforcing inorganic filler such as silica is also advantageous from the point of view of adhesion. on wet or snowy ground.

According to another possible embodiment of the invention, the reinforcing filler comprises a blend of carbon black and reinforcing inorganic filler such as silica in similar amounts; in such a case, the level of inorganic filler, in particular silica, and the level of carbon black are preferably each between 25 and 75 phr, more particularly each between 30 and 50 phr.

To couple the reinforcing inorganic filler to the diene elastomer, a well-known at least bifunctional coupling agent (or bonding agent) is well known for ensure a sufficient chemical and / or physical connection between the inorganic filler (surface of its particles) and the diene elastomer. In particular, organosilanes or bifunctional polyorganosiloxanes are used. 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).

Particularly suitable, without the following definition being limiting, so-called "symmetrical" polysulfide silanes having the following general formula (I):

(I) 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

C 18 or C ₆ -C ₁₂ arylene groups, more particularly C ₁ -C ₁₀ alkylenes, especially C ₁ -C ₄ alkylenes, in particular 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, which may be substituted or unsubstituted, which are identical to or different from one another, represent a Ci-Cs alkyl, C ₅ -C ₈ cycloalkyl or C ₆ -C ₁₈ aryl group (preferably C ₁ -C ₈ alkyl groups); -C ₆ , cyclohexyl or phenyl, especially C ₁ -C ₄ alkyl groups, more particularly methyl and / or ethyl).

- the R radicals, substituted or unsubstituted, identical or different, represent an alkoxyl group Ci-Cig cycloalkoxy or C ₅ -C ₈ (preferably a group selected from Ci-Cg alkoxyls and C ₅ cycloalkoxyls -C ₈ , more preferably still a group selected from C ₁ -C ₄ alkoxyls, in particular methoxyl and ethoxyl).

As examples of polysulphide silanes, mention may be made more particularly of polysulfides of bis (3-trimethoxysilylpropyl) or of bis (3-triethoxysilylpropyl). Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated as TESPT, or bis (triethoxysilylpropyl) disulfide, abbreviated as TESPD, is especially used. Mention may also be made, by way of preferred examples, of polysulfides (in particular disulphides, trisulphides or tetrasulfides) (monoalkoxyl (C ₁ -C ₄ ) -dialkyl (C ₁ -C ₄ ) silylpropyl), more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide as described in patent application WO 02/083782 (or US 2004/132880). As coupling agent other than polysulfurized alkoxysilane, there may be mentioned in particular bifunctional POS (polyorganosiloxanes) or hydroxysilane polysulfides (R ² = OH in the formula (I) above) as described in the 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 12 phr, more preferably between 3 and 8 phr. Those skilled in the art will understand that, as the equivalent filler of the reinforcing inorganic filler described in this paragraph, it would be possible to use a reinforcing filler of another nature, in particular an organic filler, since this reinforcing filler would be covered with a filler. inorganic layer such as 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.

5.4 - Hollow microparticles of metal oxide

The rubber composition according to the invention has the essential feature of comprising 35 to 50 phr of hollow microparticles (or microspheres) of at least one metal oxide, the term oxide including, of course, hydroxides; these microparticles have a median size by weight of between 2 and 500 μιη.

By microparticles is meant by definition and generally micrometric size particles, that is to say whose average size or median size (both expressed by weight) are between 1 μιη and 1 mm.

Below the minima indicated above, the intended technical effect (namely the creation of a suitable micro-roughness) may be insufficient, whereas beyond the maximum values indicated, there are various disadvantages, especially when the rubber composition is used as a tread: in addition to a possible loss of aesthetics (particles too visible on the surface of the tread) and a risk of loosening, during rolling, relatively large tread elements it was found that the melting ice adhesion performance could be degraded. For all these reasons, it is preferred that the hollow microparticles have a median size (by weight) within a range of 5 to 200 μιη. This area of particularly preferred size seems to correspond to an optimized compromise between on the one hand the desired surface roughness and on the other hand a good contact between the rubber composition and the ice.

According to a preferred embodiment, the metal of the metal oxide is selected from the group consisting of aluminum, silicon, zirconium, transition metals and mixtures of such metals. By transition metal is meant more particularly the metals of the fourth period ranging from scandium to zinc, preferably titanium and zinc. Aluminum, silicon, titanium, zirconium and zinc are even more preferable.

According to a more preferred embodiment, the metal oxide is chosen from the group consisting of aluminum oxides and / or hydroxides, oxides and / or hydroxides of silicon, oxides and / or hydroxides of aluminum and silicon, and mixtures of such oxides and / or hydroxides. More preferably still, the metal oxide used is an aluminosilicate. For the analysis of the particle size and the calculation of the median size of the microparticles (or median diameter for microparticles supposed to be substantially spherical), various known methods are applicable, for example by laser diffraction (see, for example, ISO-8130-13 or JIS standard K5600-9-3). It is also possible to use, in a simple and preferably preferential way, an analysis of the particle size by mechanical sieving; the operation consists in sieving a defined quantity of sample (for example 200 g) on a vibrating table for 30 min with different sieve diameters (for example, according to a progression reason equal to 1.26, with meshes of 1000, 800, 630, 500, 400, ... 100, 80, 63 μιη); the refusals collected on each sieve are weighed on a precision scale; we deduce the% of refusal for each mesh diameter with respect to the total weight of product; the median (or median diameter) or mean (or mean diameter) size is finally calculated in a known manner from the histogram of the particle size distribution. 5.5 - Miscellaneous additives

The rubber compositions according to the invention also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tire treads, in particular for winter tires, such as, for example, protective agents such as waxes. anti-ozone, anti-ozonants chemicals, antioxidants, reinforcing resins, acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M), a crosslinking system based on either sulfur or sulfur donors and / or peroxide and / or bismaleimides, vulcanization accelerators, vulcanization activators.

These compositions may also contain coupling activators when a coupling agent is used, inorganic filler recovery agents or, more generally, processing aid agents that are capable in a known manner, by means of an improvement of 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 are for example hydrolysable silanes such as alkyl-alkoxysilanes, polyols, polyethers, amines, hydroxylated or hydrolysable polyorganosiloxanes.

5.6 - Manufacture of rubber compositions and treads

The rubber compositions according to the invention are manufactured in appropriate mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first thermomechanical working or mixing phase (sometimes referred to as a "no" phase). -productive ") at high temperature, up to a maximum temperature of between 130 ° C and 200 ° C, preferably between 145 ° C and 185 ° C, followed by a second phase of mechanical work (sometimes called phase" Producer ") at a lower temperature, typically below 120 ° C, for example between 60 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system or vulcanization.

A method that can be used for the manufacture of such compositions comprises, for example, and preferably the following steps: incorporating into the diene elastomer, in a mixer, more than 30 phr of a liquid plasticizer, between 50 and 150 phr of a reinforcing filler , 35 to 50 phr of hollow microparticles of a metal oxide having a median weight of between 2 and 500 μιη, by thermomechanically kneading the whole, in one or more times, until a maximum temperature of between 130 ° C. and 200 ° C;

- cool all at a temperature below 100 ° C;

then incorporate a crosslinking system;

mix everything up to a maximum temperature below 120 ° C; extruding or calendering the rubber composition thus obtained, especially in the form of a tire tread. By way of example, the first (non-productive) phase is carried out in a single thermomechanical step during which all the necessary constituents, the possible coating agents, are introduced into a suitable mixer such as a conventional internal mixer. or other complementary additives and other additives, with the exception of the crosslinking system. After cooling the mixture thus obtained during the first non-productive phase, the low temperature crosslinking system is then incorporated, generally in an external mixer such as a roll mill; the whole is then mixed (productive phase) for a few minutes, for example between 5 and 15 min.

The actual crosslinking system is preferably based on sulfur and a primary vulcanization accelerator, in particular a sulfenamide type accelerator. To this vulcanization system are added, incorporated during the first non-productive phase and / or during the productive phase, various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives (especially diphenylguanidine), etc. The sulfur content is preferably between 0.5 and 3.0 phr, that of the primary accelerator is preferably between 0.5 and 5.0 phr.

As accelerator (primary or secondary) can be used any compound capable of acting as an accelerator of vulcanization of diene elastomers in the presence of sulfur, in particular thiazole-type accelerators and their derivatives, accelerators of thiuram type, zinc dithiocarbamates. 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 ("DCBS"), N-tert-butyl-2-benzothiazylsulfenamide ("TBBS"), N-tert-butyl-2-benzothiazylsulfenimide ("TBSI"), zinc dibenzyldithiocarbamate ("ZBEC") and mixtures thereof. these compounds.

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 else extruded in the form of a rubber profile that can be used directly as a tread of a tire. winter.

The vulcanization (or cooking) is conducted in a known manner at a temperature generally between 130 ° C and 200 ° C, for a sufficient time which may vary for example between 5 and 90 min depending in particular on the cooking temperature, the system of vulcanization adopted and the kinetics of vulcanization of the composition under consideration.

In the case of a composite type tread formed of several rubber compositions of different formulations, the rubber compositions according to the invention previously described may constitute only part of the tread according to the invention, at least for the portion (therefore carved) of the tread intended to come into contact with the road during the rolling of the tire. The invention relates to the tires previously described both in the green state (ie, before firing) and in the fired state (ie, after crosslinking or vulcanization).

6. EXAMPLES OF CARRYING OUT THE INVENTION

6.1 - Preparation of rubber compositions

For the manufacture of these compositions, the following procedure was carried out: the reinforcing filler (carbon black, silica and its agent) was successively introduced into an internal mixer, the initial batch temperature of which was approximately 60 ° C. associated coupling), the liquid plasticizer, the hollow microparticles of metal oxide, the diene elastomer (or diene elastomer cutting) and the various other ingredients with the exception of the vulcanization system; the mixer is thus filled to about 70% (% by volume). Theromechanical work (non-productive phase) is then carried out in one step, which lasts a total of about 3 to 4 minutes, until a maximum temperature of "fall" of 165 ° C is reached. The mixture thus obtained is recovered, cooled and then sulfur and a sulfenamide-type accelerator are incorporated on an external mixer (homo-fmisseur) at 30 ° C., mixing the whole (productive phase) for a suitable time (for example between 5 and 12 minutes).

6.2 - Rubber and ice friction tests

In these tests, two compositions (denoted Cl and C-2) based on diene elastomers (NR and BR cleavage with a cis-1,4 bond ratio of greater than 95%) are compared, reinforced by a silica and silica blend. carbon black, which are associated or not 40 pce hollow microparticles aluminosilicate.

Tables 1 and 2 give the formulation of the two compositions (Table 1 - rate of the various products expressed in phr), their properties before and after curing (30 min at 150 ° C.); the vulcanization system is sulfur and sulfenamide.

Firstly, the examination of the different results in Table 2 reveals no significant degradation of the rubber properties for the composition according to the invention (C-2) despite the presence of a high level of metal oxide microparticles, which is already an unexpected result for the person skilled in the art: the processability in the raw state (Mooney plasticity) is certainly increased, but weakly; the rheometric properties (cooking) are not appreciably modified; after cooking, the modules in extension remain close; surprisingly, the Shore hardness is slightly increased compared to the amount of microparticles used; finally, the hysteresis (tan (δ) _max ) is not increased.

The two compositions are then subjected to a laboratory test consisting in measuring their coefficient of friction on ice. The principle is based on a rubber composition slider sliding at a given speed (for example 5 km / h) on an ice track with an imposed load (for example equal to 3 kg / cm ² ). Prior to the test, the surface of the test pad is lapped by planing to a thickness of 0.5 mm, followed by a series of repeated sliding friction on real dry soil (asphalt) under the said imposed load (for example 3 kg / cm ² ). The forces generated in the direction of advance (Fx) of the pad and perpendicular to the advance (Fz) are measured. The Fx Fz ratio determines the coefficient of friction of the specimen on the ice. The temperature during the measurement is set at -2 ° C.

This test, the principle of which is well known to those skilled in the art (see, for example, patent applications EP 1052270 and EP 1505112) makes it possible to evaluate, under representative conditions, the adhesion on melting ice that would be obtained after a rolling test on vehicle equipped with tires whose tread is made of the same rubber compositions.

The results are shown in Table 3. A value greater than that of the control (composition C1), arbitrarily set at 100, indicates an improved result, that is to say an aptitude for a shorter braking distance. It is found that the composition C-2 according to the invention has a very clear increase (23%) of the coefficient of friction on ice, compared to the control composition C1 devoid of aluminosilicate microparticles. In conclusion, the compositions according to the invention offer the tires and their treads a melting ice adhesion which is significantly improved.

Table 1

BR with 4.3% of 1-2; 2.7% trans; 97% cis 1-4 (Tg Natural rubber (peptized);

"Zeosil 1115MP" silica from Rhodia, type "HDS" (BET and CTAB: about 120 m 7 g);

coupling agent TESPT ("Si69" from Degussa); aluminosilicate ("Fillite 200/7" from Japan Fillite) (median particle size: about 90 μιη);

ASTM N234 grade (Cabot company);

MES oil ("Catenex SNR" from Shell);

diphenylguanidine ("Perkacit DPG" from Flexsys); N-1,3-dimethylbutyl-N-phenylparaphenylenediamine ("Santoflex 6-PPD" from Flexsys);

N-dicyclohexyl-2-benzothiazol sulfenamide

("Santocure CBS" from the company Flexsys).

Table 2

Table 3

Rubber composition: C-1 C-2

Friction on ice (-2 ° C) 100 123

Claims

1. A tire whose tread comprises a rubber composition comprising at least one diene elastomer, more than 30 phr of a liquid plasticizer, and between 50 and 150 phr of a reinforcing filler, characterized in that said composition further comprises 35 to 50 phr of hollow microparticles of at least one metal oxide having a median size by weight of between 2 and 500 μιη.

The tire of claim 1, wherein the diene elastomer is selected from the group consisting of natural rubber, synthetic polyisoprenes, polybutadienes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.

3. A tire according to claim 2, said composition comprising 50 to 100 phr of natural rubber or synthetic polyisoprene.

4. A tire according to claim 3, the natural rubber or the synthetic polyisoprene being used in a blend with at most 50 phr of a polybutadiene having a cis-1,4 bond ratio greater than 90%.

5. A tire according to claim 2, said composition comprising 50 to 100 phr of a polybutadiene having a cis-1,4 bond ratio greater than 90%.

6. A tire according to claim 5, the polybutadiene being used in a blend with at most 50 phr of natural rubber or synthetic polyisoprene.

7. A tire according to any one of claims 1 to 6, wherein the level of liquid plasticizer is greater than 40 phr, preferably within a range of 50 to

100 pce.

8. A tire according to any one of claims 1 to 7, wherein the liquid plasticizer is selected from the group consisting of naphthenic oils, paraffinic oils, MES oils, TDAE oils, mineral oils, vegetable oils, ethers plasticizers, ester plasticizers, phosphate plasticizers, sulphonate plasticizers and mixtures of these compounds.

9. A tire according to any one of claims 1 to 8, wherein the reinforcing filler comprises predominantly carbon black, the carbon black content is preferably greater than 60 phr.

10. A tire according to any one of claims 1 to 8, wherein the reinforcing filler comprises predominantly a reinforcing inorganic filler, the level of reinforcing inorganic filler preferably being greater than 70 phr.

11. A tire according to any one of claims 1 to 10, wherein the total reinforcing filler content is between 60 and 120, preferably between 70 and 100 phr.

Tire according to any of claims 1 to 11, wherein the metal of the metal oxide is selected from the group consisting of aluminum, silicon, zirconium, transition metals and mixtures of such metals. .

Tire according to claim 12, wherein the metal oxide is selected from the group consisting of aluminum oxides and / or hydroxides, silicon oxides and / or hydroxides, aluminum oxides and / or hydroxides and silicon, and mixtures of such oxides and / or hydroxides.

The tire of claim 13, wherein the metal oxide is an aluminosilicate.

15. A tire according to any one of claims 1 to 14, wherein the hollow microparticles of metal oxide have a median size in a range of 5 to 200 μιη.