WO2011086061A1

WO2011086061A1 - Rubber composition for a snow-tire tread

Info

Publication number: WO2011086061A1
Application number: PCT/EP2011/050268
Authority: WO
Inventors: Masayuki Maesaka; Salvatore Pagano
Original assignee: Societe De Technologie Michelin; Michelin Recherche Et Technique S.A.
Priority date: 2010-01-18
Filing date: 2011-01-11
Publication date: 2011-07-21
Also published as: CA2786223A1; JP2013517356A; EP2526145A1; EA201290670A1; FR2955328B1; JP5778176B2; FR2955328A1

Abstract

The invention relates to a rubber composition usable in particular as a tread for a snow tire having improved grip on melting ice, comprising at least one diene elastomer such as natural rubber and/or polybutadiene, more than 40 pce of a liquid plasticizer, 50 to 150 pce of a reinforcing filler such as silica and/or carbon black, 2 to 50 pace of water-soluble metal salt microparticles such as magnesium sulfate and 2 to 50 pce of hollow microparticles of at least one metal oxide such as aluminosilicate. The invention also relates to snow tires, the tread of which comprises such a composition.

Description

RUBBER COMPOSITION

FOR TIRE TREAD OF PNEUMATIC WINTER

1. DOMAIN OF THE INVENTION

The invention relates to rubber compositions that can be used as tire treads for vehicles, in particular "winter tires" capable of rolling 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.

3. BRIEF DESCRIPTION OF THE INVENTION Continuing their research, the Applicants have discovered a new rubber composition, capable of generating an effective surface micro-roughness and which makes it possible to greatly improve the ice adhesion of the treads and pneumatic tires. including, under conditions of melting ice. Consequently, the present invention relates to a rubber composition that can be used in particular as a tread of a winter tire, comprising at least one diene elastomer, more than 40 phr of a liquid plasticizer, and between 50 and 150 phr of a reinforcing filler. , characterized in that it further comprises between 2 and 50 phr of microparticles of water-soluble metal salt and between 2 and 50 phr of hollow microparticles of at least one metal oxide.

At first, these various microparticles, protruding on the surface of the tread, fulfill the claw function previously described without the disadvantage of being highly abrasive vis-à-vis the asphalt used as a road surface. Then, in a second step, after progressive expulsion of the rubbery matrix, on the one hand by at least partial hydrosolubilization of the water-soluble microparticles, on the other hand by breaking the hollow structure of the metal oxide microparticles, all these microparticles release microcavities that act as storage volume and drain channel of the water film on the surface of the 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 invention also relates to a tire whose tread, at least for the portion (therefore carved) tread which is intended to enter contact with the road during the rolling of the tire, comprises a composition according to the invention.

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. 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 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 invention is based on at least one diene elastomer, a plasticizer system, a reinforcing filler, water-soluble metal salt microparticles and hollow metal oxide microparticles, which components are described in detail below. after. 4.1 - 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 level of origin patterns. diene which is weak or very weak, always less than 15% (mol%). 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 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 content of trans-1,4 bonds 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 of between -25 ° C. and -50 ° C. In the case of butadiene-styrene-isoprene copolymers, those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, and an isoprene content of between 15% and 60%> by weight 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 in units -1 , 2 of the butadiene part of 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 content of the isoprene part of between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg included 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 greater than 90%, butadiene-styrene copolymers 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 blending (mixing) with at most 50 phr a polybutadiene having a cis-1,4 bond ratio 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 especially in a blend with at most 50 phr 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.

4.2 - Plasticizer System Another essential feature of the rubber composition of the invention is that it comprises more than 40 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. By way of 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, azelates, sebacates, glycerol 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.

The level of liquid plasticizer in the composition of the invention is preferably in a range of 50 to 100 phr.

According to another preferred embodiment, the compositions of 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 well known to those skilled in the art, essentially based on carbon and hydrogen, which are therefore inherently miscible in the diene (s) elastomer compositions (s) when they are further qualified as "plasticizers". 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 (i.e., liquid plasticizer plus, where appropriate, solid hydrocarbon resin) is preferably between 40 and 100 phr, more preferably in a range of 50 to 80 phr. 4.3 - 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 preferably 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. Carbon blacks could for example be already incorporated in the isoprene elastomer in the form of a masterbatch (see for example applications 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 those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m ² / g, preferably from 30 to 400 m ² / g, especially between 60 and 300 m ² / g As highly dispersible precipitated silicas (called "HDS"), mention may be made, for example, of the silicas "Ultrasil" 7000 and "Ultrasil" 7005 from the company Degussa, the silicas "Zeosil" 1165MP, 1135MP and 1115MP of the Rhodia, the "Silicone" silica EZ150G from PPG, the "Zeopol" silicas 8715, 8745 and 8755 from Huber As examples of reinforcing aluminas, mention may be made of "Baikalox" Al 25 aluminas. or "CR125" from Baikowski, "APA-1 Condea's "00RDX", Degussa's "Aluminoxid C" or Sumitomo Chemicals "AKP-G015". 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.

In order to couple the reinforcing inorganic filler to the diene elastomer, an at least bifunctional coupling agent (or bonding agent) is used in a well-known manner to 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

IC8 or arylene groups, C ₆ -C _2, especially in Cl- Cio alkylene, in particular C ₁ -C 4, particularly propylene);

Z is one of the following formulas: R1 R1 R2

I I

Si- -Si R2 Si-

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 polysulfurized silanes, mention may be made more particularly of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl) polysulfides. 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 tetrasulphides) of bis- (C ₁ -C ₄ monoalkoxyl) -dialkyl (C ₁ -C ₄ ) silylpropyl), more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide, such 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 have on its surface functional sites, in particular hydroxyls, requiring the use of a coupling agent to establish the bond between the filler and the elastomer.

4.4 - Water-soluble microparticles and hollow microparticles of metal oxide

The rubber compositions of the invention have the essential characteristic of comprising between 2 and 50 phr of hydrosulfide metal salt microparticles and between 2 and 50 phr of hollow microparticles (or microspheres) of at least one metal oxide, the term oxide including, of course, hydroxides.

These microparticles may be, for example, in the form of powder, microbeads, granules, beads or any other suitable densified form. A powder form is preferred for both types of microparticles. By microparticles is meant by definition and in general size particles (ie, larger dimension in the case of anisometric particles) micrometer, that is to say, whose average size or median size (both expressed in weight) are between 1 μιη and 1 mm. Preferably, the median size is between 2 μιη and 800 μιη, more preferably in a range from 5 to 200 μιη.

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 microparticles have a median size between 2 μιη and 500 μιη, more preferably still in a range from 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. On the other hand, for the same reasons as those set out above, the level of each type of microparticles (water-soluble microparticles on the one hand and metal oxide hollow microparticles on the other hand) is preferably between 5 and 40.degree. pce, more preferably between 10 and 35 phr. According to a preferred embodiment, the salt of the water-soluble microparticles is selected from the group consisting of chlorides, carbonates (including in particular hydroxycarbonates, bicarbonates), sulphates and mixtures of such salts. Even more preferentially, the salt chosen is a sulphate.

According to another preferred embodiment, which can be combined in particular with the preceding one, the metal of the metal salt is an alkaline or alkaline-earth metal. It will be recalled here simply that the group of alkali metals is that of the univalent chemical elements located in the first column of the Periodic Table and not including hydrogen (H); in order of increasing atomic number, the alkali metals are lithium, sodium, potassium, rubidium, cesium and francium. The group of alkaline earth metals is that of the chemical elements of group 2 (or Ha) of the periodic table; in order of increasing atomic number, the alkaline earth metals are beryllium, magnesium, calcium, strontium, barium and radium.

Preferably, the metal of the water-soluble metal salt is selected from the group consisting of Na (sodium), K (potassium), Mg (magnesium), Ca (calcium) and mixtures of such metals. More preferably still, the metal is magnesium. 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 a simple and preferential 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.

4.5 - Various additives The rubber compositions of the invention also comprise all or part of the usual additives normally used in elastomer compositions intended for the manufacture of tire treads, in particular for winter tires, such as for example such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants, reinforcing resins, acceptors (eg phenolic novolac resin) or methylene donors (eg HMT or H3M), a crosslinking system based either of sulfur, either of sulfur and / or peroxide and / or bismaleimide donors, 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.

4.6 - Manufacture of rubber compositions and treads

The rubber compositions of the invention are manufactured in suitable mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes referred to as "non-phase" 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: to incorporate into the diene elastomer, in a mixer, more than 40 phr of a liquid plasticizer, between 50 and 150 phr of a reinforcing filler, between 2 and 50 phr of hydrosulfide metal salt microparticles and between 2 and 50 phr hollow microparticles of at least one metal oxide, by thermomechanically kneading the whole, in one or more times, until a maximum temperature of between 130 ° C and 200 ° C is reached;

cool the assembly to 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.

It is possible to use as accelerator (primary or secondary) any compound capable of acting as accelerator for vulcanization of diene elastomers in the presence of sulfur, in particular thiazole-type accelerators and their derivatives, accelerators of the thiuram type, zinc dithiocarbamates. These accelerators are 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 described above may constitute only part of the tread of the tire 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 rubber and tire compositions described above both in the green (i.e., before firing) and the fired (i.e., after crosslinking or vulcanization) state.

EXAMPLES OF CARRYING OUT THE INVENTION 5.1 Preparation of Rubber Compositions

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 with which are associated or not, on the one hand 15 phr of magnesium sulfate microparticle powder and on the other hand 15 phr of aluminosilicate hollow microparticle powder. Table 1 gives the formulation of the two compositions (rate of the different products expressed in phr).

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 magnesium sulfate microparticles, the hollow aluminosilicate microparticles, 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). We then conduct a thermomechanical work (phase non-productive) in one step, which lasts in total about 3 to 4 minutes, until reaching a maximum temperature of "fallen" of 165 ° C. The mixture thus obtained is recovered, cooled and then sulfur and a sulfenamide type accelerator are incorporated on an external mixer (homo-finisher) at 30 ° C., mixing the whole (productive phase) for a suitable time (for example between 5 and 12 minutes).

5.2 - Friction tests on ice

These 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 ratio Fx / Fz 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 expressed in Table 2; a value greater than that of the control (composition C-1), arbitrarily set at 100, indicates an improved result, that is to say an aptitude at a shorter braking distance. It is found that the composition of the invention C-2 shows a significant improvement (gain of 10%) in the coefficient of friction on ice, compared to the control composition C-1.

In conclusion, the compositions according to the invention offer the tires and their treads an adhesion on melting ice which is improved. Table 1

BR with 0.3% of 1-2; 2.7% trans; 97% cis 1-4 (Tg = -104 ° C); Natural rubber (peptized);

silica "Zeosil 1115MP" from Rhodia, type "HDS"

(BET and CTAB: approximately 120 m 7 g);

coupling agent TESPT ("Si69" from Degussa);

ASTM N234 grade (Cabot company);

magnesium sulphate powder

(Aldrich company, median particle size: about 100 μιη); aluminosilicate powder ("Fillite 200/7" from Japan Fillite Company) (median particle size: about 90 μιη);

MES oil ("Catenex SNR" from Shell);

diphenylguanidine (Perkacit DPG from Flexsys);

N-l, 3-dimethylbutyl-N-phénylparaphénylènediamine

(Santoflex 6-PPD from Flexsys);

N-dicyclohexyl-2-benzothiazol sulfenamide

("Santocure CBS" from the company Flexsys).

Table 2

Rubber composition: C-1 C-2

Ice friction test (-2 ° C): 100 110

Claims

1. A rubber composition that can be used in particular as a tread of a winter tire, comprising at least one diene elastomer, more than 40 phr of a liquid plasticizer, and between 50 and 150 phr of a reinforcing filler, characterized in that it also comprises between 2 and 50 phr of hydrosulfide metal salt microparticles and between 2 and 50 phr of hollow microparticles of at least one metal oxide.

The composition 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. Composition according to claim 2, comprising 50 to 100 phr of natural rubber or synthetic polyisoprene.

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

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

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

7. Composition according to any one of claims 1 to 6, wherein the level of liquid plasticizer is in a range of 50 to 100 phr.

8. Composition 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. Composition 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. Composition according to any one of claims 1 to 6, wherein the reinforcing filler comprises predominantly a reinforcing inorganic filler, the level of reinforcing inorganic filler preferably being greater than 70 phr.

11. Composition 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.

12. The composition of claim 11, wherein the total reinforcing filler content is 70 and 100 phr.

13. Composition according to any one of claims 1 to 12, wherein the water-soluble metal salt is selected from the group consisting of chlorides, carbonates, sulfates and mixtures of such salts.

14. Composition according to any one of claims 1 to 13, wherein the metal of the metal salt is an alkaline or alkaline-earth metal, preferably chosen from Na, K, Mg,

Ca and mixtures of such metals.

The composition of claim 14 wherein the water-soluble metal salt is magnesium sulfate.

16. Composition according to any one of claims 1 to 15, wherein the water-soluble metal salt microparticles have a median size (by weight) of between 2 and 500 μιη.

17. Composition according to any one of claims 1 to 16, wherein the metal of the metal oxide is selected from the group consisting of aluminum, silicon, zirconium, transition metals and mixtures of such metals .

The composition of claim 17, 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 composition of any one of claims 1 to 18, wherein the metal oxide is an alumino silicate.

20. Composition according to any one of claims 1 to 19, wherein the hollow microparticles of metal oxide have a median size (by weight) of between 2 and 500 μιη.

21. Winter tire whose tread comprises a rubber composition according to any one of claims 1 to 20.