CA2709846A1 - Rubber composition for the tread of a winter tire - Google Patents

Abstract

A rubber composition that can be used as a tread of a winter tire, with a high adhesion to melting ice, comprising at least one diene elastomer such as natural rubber and / or polybutadiene, more than 30 phr of a liquid plasticizer, between 50 and 150 phr of a reinforcing filler such as silica and / or carbon black and between 5 and 40 phr of wheat semolina microparticles. The invention also relates to the use of such a composition for the manufacture of treads for winter tires, as well as these treads and tires themselves.

Description

RUBBER COMPOSITION
FOR TIRE TREAD OF PNEUMATIC WINTER

Ifivention is relative to usable rubber compositions especially as treads of winter tires suitable for rolling on floors covered with ice or ice without being provided with nails (also called studless tires).

It is more particularly related to the treads of winter tires specifically adapted for driving under so-called "ice conditions"
slush "
encountered in a temperature range typically between -5 C and 0 C. On recalls that, in such a field, tire pressure at passage of a vehicle causes a superficial melting of ice that overlaps with a thin film of water harmful to the adhesion of these tires.
To avoid the harmful effects of nails, especially their strong action abrasive on the of the soil itself and significantly degraded road dry soil, manufacturers of tires proposed different solutions consisting of modify the formulation of the rubber compositions themselves.
Thus, it has been proposed first of all to incorporate solid particles into great hardness, such silicon carbide (see, for example, US Pat. No. 3,878,147), some flush the surface of the tread as and when the wear of this last, and thus come into contact with the ice. Such particles, able to act in definitive like micro-nails on hard ice, thanks to an effect of "claw" well known, remain relatively aggressive vis-à-vis the ground; they are not well adapted to the conditions rolling on a melting ice.

Other solutions have therefore been proposed, including incorporating powders water-soluble in the constitutive composition of the tread. Of such powders solubilize more or less on contact with snow or melted ice, which allows for a share the creation at the surface of the tire tread of porosities likely improve the attachment of the tread on the ground and secondly the creation of throats acting as evacuation channels for the liquid film created between the pneumatic and ground. By way of examples of such water-soluble powders, mention may be made example the use of cellulose powder, vinyl alcohol or starch (see for example JP patent 3-159803, JP 2002-211203).

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 rolling. If the

-2-powder is not soluble in the conditions of use of the tire, the functions above mentioned (creation of microporosities and drainage channels) are not fulfilled and the adhesion is not improved. Another known disadvantage of these solutions is that they can strongly penalize the reinforcement of the rubber compositions (and so their resistance to wear) or their hysteresis (and therefore their resistance to rolling).

Pursuing their research, the Claimants discovered a composition of new rubber, able to generate an effective surface micro-roughness thanks to microparticles that are neither high-hard nor water-soluble, and improve ice adhesion of treads and tires comprising, under melting ice conditions, without significantly penalizing the properties reinforcement and hysteresis.

Thus, a first object of the invention relates to a rubber composition usable as tread of a winter tire, comprising at least one elastomer diene, more than 30 phr of a liquid plasticizer, between 50 and 150 phr of a reinforcing filler, said composition being characterized in that it further comprises between and 40 pce of microparticles of wheat semolina.

At first, these microparticles of wheat, protruding at the surface of the band bearing, fulfill the previously described claw function without the disadvantage of being abrasive. Then, in a second step, after progressive expulsion from the matrix rubbery, they release microcavities that act as a channel evacuation of the film water on the surface of the ice; in these circumstances, the contact between surface of the band of bearing and the ice is no longer lubricated and the coefficient of friction is thus improved.

The subject of the invention is also the use of such a composition of rubber for the manufacture of treads for winter tires, that the latter are intended for new tires such as retreading used tires.
The subject of the invention is also these treads and these tires themselves when they comprise a rubber composition according to the invention.

The tires of the invention are particularly intended for equipping vehicles to tourism-type engine, including 4x4 vehicles (four-wheel drive) and vehicles SUV ("Sport Utility Vehicles"), two-wheeled vehicles (including motorcycles) like the industrial vehicles chosen in particular from light trucks and heavy "(ie, subway, buses, road transport equipment (trucks, tractors, trailers), vehicles off-the-road such agricultural or civil engineering

-3-The invention and its advantages will be easily understood in the light of the description and examples of embodiments that follow.

I. MEASUREMENTS AND TESTS USED

The treads and rubber compositions that make up these bands of rolling are characterized, before and after cooking, as indicated below.
I-1. Mooney Plasticity An oscillating consistometer is used as described in the French standard (November 1980). The measure of Mooney plasticity is according to the principle next:
composition in the raw state (ie, before cooking) is molded in a chamber cylindrical heated at 100 C. After one minute of preheating, the rotor rotates within the test tube 2 revolutions / minute and we measure the useful torque to maintain this movement after 4 minutes of rotation. Mooney plasticity (ML 1 + 4) is expressed in "Mooney unit" (UM, with 1 UM =
0.83 Newton.meter).
I-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 consistometric index as a function of time allows determine the time roasting of the rubber compositions, evaluated according to the standard aforementioned by the parameter T5 (case of a large rotor), expressed in minutes, and defined as being the time necessary to obtain an increase in the consistometric index (expressed in UM) of 5 units above the minimum value measured for this index.

I-3. rheometry The measurements are carried out at 150 C with an oscillating chamber rheometer, according to standard DIN 53529 - Part 3 (June 1983). The evolution of the rheometric torque in time function describes the evolution of the stiffening of the composition as a result of reaction of vulcanization. Measurements are processed according to DIN 53529 - Part 2 (March 1983): Ti is the induction delay, that is the time required at the beginning of the reaction of vulcanization; T, (for example T90) is the time needed to reach a conversion of a%, that is to say a% (for example 90%) of the difference between the minimum and maximum.

-4-I-4. Traction tests These tensile tests make it possible to determine the elasticity stresses and the properties at the break. Unless otherwise indicated, they shall be carried out in accordance with french standard NF T
46-002 of September 1988. We measure in second elongation (ie, after a cycle the rate of expansion provided for the measure itself).
secant modules Nominal (or apparent stresses, in MPa) at 10% elongation (denoted M10), 100%
of elongation (denoted M100) and 300% elongation (denoted M300). Constraints to the rupture (in MPa) and elongations at break (in%) are also measures. All of these tensile measurements are made 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).

I-5. Shore A hardness The Shore A hardness of the compositions after firing is assessed in accordance with Standard ASTM D 2240-86.

I-6. Dynamic Properties Dynamic properties are measured on a viscoanalyzer (Metravib VA4000), according to the ASTM D5992-96. The response of a composition sample is recorded vulcanized (cylindrical specimen 4 mm thick and 400 mm2 in section), submitted to one sinusoidal stress in alternating simple shear, at the frequency of 10Hz, at a temperature of 0 C. A sweep in amplitude of deformation of 0.1% to 50%
(go cycle), then from 50% to 1% (return cycle). The exploited results are the loss factor tan (s); for the return cycle, we indicate the maximum value of tan (s) observed (denoted tan (S) max) between the values at 0.15% and at 50% deformation (Payne effect).

I-7. Tire tests A) Ice braking:

The tires are mounted on a motor vehicle ("Toyota Camry") equipped with a anti-lock braking system (ABS system) and traction control system.
acceleration (TCS system for Traction Control System). We measure the distance needed to pass from 20 to 5 km / h during a sudden longitudinal braking (activated ABS) on a track covered with ice cream. A value greater than that of the control, arbitrarily set at 100, indicates a result improved, that is to say a shorter braking distance.

WO 2009/08312

5 PCT / EP2008 / 010650 B) Acceleration on ice:

We measure the time needed to go from 5 to 20 km / h during a full acceleration regime, under the control of the activated TCS system. A value greater than of the witness, arbitrarily set to 100, indicates an improved result ie a acceleration more fast.

II. DETAILED DESCRIPTION OF THE INVENTION

The rubber composition of the invention is based on at least one diene elastomer, a plasticizer system, a reinforcing filler and microparticles of semolina wheat, components which are described in detail below.
In this description, unless expressly indicated otherwise, all percentages (%) indicated are% by mass. On the other hand, any designated range of values by the expression "between a and b" represents the range of values from more than a to less than b (that is to say terminals a and b excluded) while any range of values designated by the expression "from a to b"
means the range of values from a to b (that is, including the strict bounds has and b).

II-1. Diene elastomer By elastomer or rubber "diene", it is recalled that must be heard a elastomer at least in part (ie a homopolymer or copolymer) of diene monomers (monomers carrying two carbon-carbon double bonds, conjugated or no).

The diene elastomers can be classified in known manner into two categories: those so-called "essentially unsaturated" and those termed "essentially saturated". By example, butyl rubbers and copolymers of dienes and alpha-olefins type EPDM
enter the category of essentially saturated diene elastomers with a original reasons diene which is weak or very weak, always less than 15% (mol%).
On the contrary, essentially unsaturated diene elastomer means a diene elastomer from at least in part conjugated diene monomers having a rate of units or units of dienic origin (conjugated dienes) which is greater than 15% (mol%). In the category of elastomers Dienic "essentially unsaturated", in particular means elastomer diene "highly unsaturated" a diene elastomer having a level of origin diene (dienes conjugates) which is greater than 50%.

-6-It is preferred to use at least one diene elastomer of the type strongly unsaturated, in particular a diene elastomer selected from the group consisting of polybutadienes (BR), the synthetic polyisoprenes (NRs), natural rubber (NR), copolymers of butadiene, the copolymers of isoprene (other than IIR) and mixtures of these elastomers. Of such copolymers are more preferably selected from the group consisting of copolymers butadiene-styrene (SBR), isoprene-butadiene (BIR) copolymers, copolymers of isoprene-styrene (SIR), isoprene-butadiene-styrene copolymers (SBIR) and the mixtures of such copolymers.

The elastomers can be for example blocks, statistics, sequenced, microsequenced, and be prepared in dispersion or in solution; they can be coupled and / or starred or even functionalized with a coupling agent and / or starring or functionalization. For a coupling with carbon black, there may be mentioned, for example, groups functional comprising a C-Sn bond or amino functional groups such as benzophenone by example; for coupling to a reinforcing inorganic filler such as silica, mention may be made for example, silanol or polysiloxane functional groups having a silanol end (such described, for example, in US 6,013,718), alkoxysilane groups (such as as described by US Pat. No. 5,977,238), carboxylic groups (as described by US Pat.
example in US 6,815,473 or US 2006/0089445) or else polyether groups (such as described by example in US 6,503,973). As other examples of such elastomers functionalized, we mention may also be made of elastomers (such as SBR, BR, NR or IR) of the type epoxides.

Polybutadienes, and in particular those having a content units -1.2 between 4% and 80% or those with a cis-1,4 content greater than 80%, polyisoprenes, butadiene-styrene copolymers and in particular those having a content styrene content of between 5% and 50% by weight and more particularly between 20% and 40%, one 1,2-linkage content of the butadiene part of between 4% and 65%, a content in trans-1,4 bonds between 20% and 80%, the butadiene copolymers isoprene and especially those having an isoprene content of between 5% and 90% by weight and an glass transition temperature ("Tg" - measured according to ASTM D3418-82) of -40 C at -80 C, isoprene-styrene copolymers and especially those having a styrene content range between 5% and 50% by weight and a Tg between -25 C and -50 C.

In the case of butadiene-styrene-isoprene copolymers are suitable especially those having a styrene content of between 5% and 50% by weight and more particularly between 10% and 40%, an isoprene content of between 15% and 60%
weight and more particularly between 20% and 50%, a butadiene content between 5% and 50%
by weight and more particularly between 20% and 40%, a content of units -1.2 from the butadiene part between 4% and 85%, a content of trans -1,4 units Of the game butadiene content between 6% and 80%, a content of -1,2 units plus -3,4 the part

-7-between 5% and 70% and a trans-1,4 content of the part isoprenic between 10% and 50%, and more generally any copolymer butadiene styrene-isoprene having a Tg between -20 C and -70 C.

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

According to a more particular and preferred embodiment, the elastomer diene used is mostly, that is to say for more than 50 pce (for reminder, "pce"
meaning parts in weight per hundred parts of elastomer), natural rubber (NR) or polyisoprene synthesis (IR). More preferentially, said natural rubber or synthetic polyisoprene is then used in blending with a polybutadiene (BR) having a cis-1,4 bonds that is preferably greater than 90%.

According to another particular and preferred embodiment, the elastomer diene used is for the most part, that is to say for more than 50 phr, a polybutadiene (BR) having a rate of cis-1,4 bonds greater than 90%. More preferentially, said polybutadiene is then used in cutting with natural rubber or synthetic polyisoprene.

According to another particular and preferred embodiment, the elastomer diene used is a binary blend (mixture) of NR (or IR) and BR, or a ternary blend of NR (or IR), BR and SBR. Preferably, in the case of such cuts, the composition has between 25 and 75 phr of NR (or IR) and between 75 and 25 phr of BR, to which can be associated or not a third elastomer (ternary cutting) at a rate of less than 30 phr, especially less than 20 pc. This third elastomer is preferably an SBR elastomer, especially a SBR
solution (called "SSBR"). More preferentially still, in the case of such cutting, the composition comprises 35 to 65 phr of NR (or IR) and 65 to 35 phr of BR. The BR used is preferably a BR having a cis-1,4 bond ratio greater than 90%, more preferably greater than 95%.

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

II-2. Plasticizing system The rubber composition of the invention has another characteristic essential of contain at least 30 phr of a liquid plasticizing agent (at 23 C) function is to

-8-soften the matrix by diluting the elastomer and the reinforcing filler; his Tg is by definition less than -20 C, preferably less than -40 C.

Any extension oil, whether aromatic or non-aromatic, any agent liquid plasticizer known for its plasticizing properties vis-à-vis of diene elastomers, is usable ; are particularly suitable liquid plasticizers chosen in the group consisting of naphthenic oils, paraffmic oils, oils MES, oils TDAE, ester plasticizers and mixtures of these compounds.

As ester plasticizers, mention may be made in particular of triesters of glycerol, preferably majority (for more than 50%, more preferably for more than 80% in weight) of a C18 unsaturated fatty acid, that is to say selected from the group constituted by the acid oleic acid, linoleic acid, linolenic acid and mixtures of these acids. More preferentially, whether of synthetic or natural origin (case by example of oils of sunflower or rapeseed), the fatty acid used is more than 50% in weight, more preferably still for more than 80% by weight of acid oleic. Such triesters (trioleates) with a high oleic acid content are well known, they have been described by example in the application WO 02/088238, as plasticizers in bands of bearing for tires.
The level of liquid plasticizer in the composition of the invention is preference greater than 40 phr, more preferably in a range of 50 to 100 phr.

According to another preferred embodiment, the compositions of the invention also include, as a solid plasticizer (at 23 C), a resin hydrocarbon having a Tg greater than +20 C, preferably greater than +30 C, as described for example in WO 2005/087859, WO 2006/061064 and WO 2007/017060.

Hydrocarbon resins are polymers well known to humans profession, miscible therefore by nature in the elastomer (s) diene (s) compositions when they are qualified in addition to "plasticizers". They have been described for example in the book entitled "Hydrocarbon Resins" by R. Mildenberg, M. Zander and G. Collin (New York, VCH, 1997, ISBN 3-527-28617-9) whose chapter 5 is devoted to their applications, especially in Rubber Tires and Mechanical Goods.
can be aliphatic, aromatic or aliphatic / aromatic type that is say based on aliphatic and / or aromatic monomers. They can be natural or synthetic, oil-based or not (if so, also known as petroleum resins). They are preferentially exclusively hydrocarbon-based, that is to say they do not include that carbon and hydrogen atoms.

-9 Preferably, the hydrocarbon plasticizing resin has at least one, more preferentially all, of the following characteristics a Tg greater than 20 C;
a number-average molecular mass (Mn) of between 400 and 2000 g / mol;
a polymolecularity index (Ip) of less than 3 (recall: Ip = Mw / Mn with Mw mass molecular weight average).

The Tg is measured in a known manner by DSC (Differential Scanning Calorimetry), according to the ASTM D3418 (1999). The macrostructure (Mw, Mn and Ip) of the resin hydrocarbon is determined by steric exclusion chromatography (SEC): solvent tetrahydrofuran;
temperature 35 C; concentration 1 g / l; flow rate 1 ml / min; filtered solution on porosity filter 0.45 m before injection; Moore calibration with polystyrene standards ; set of 3 "WATERS" columns in series ("STYRAGEL" HR4E, HR1 and HRO.5); detection by differential refractometer ("WATERS 2410") and its operating system partner ("WATERS
Empower ").

According to a particularly preferred embodiment, the resin hydrocarbon plasticizer is selected from the group consisting of homopolymer resins or copolymer of cyclopentadiene (abbreviated as CPD) or dicyclopentadiene (abbreviated as DCPD), resins of homopolymer or terpene copolymer, homopolymer or copolymer resins cutting C5, and mixtures of these resins. Of the copolymer resins above are preferentially used those selected from the group consisting of resins of copolymer (D) CPD / vinylaromatic, copolymer resins (D) CPD / terpene, the resins of copolymer (D) CPD / C5 cut, terpene copolymer resins /
vinylaromatic, C5 / vinylaromatic cut copolymer resins, and mixtures of these resins.

The term "terpene" here combines in a known manner the alpha-pinene monomers, beta-pinene and limonene; preferentially is used a limonene monomer, consisting of presenting known manner in the form of three possible isomers: L-limonene (enantiomer levorotatory), D-limonene (dextrorotatory enantiomer), or dipentene, racemic enantiomers dextrorotatory and levorotatory. As vinylaromatic monomer agree by styrene, phenol, alpha-methylstyrene, ortho-, meta-, para-methylstyrene, the vinyl-toluene, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, the vinylmesitylene, divinylbenzene, vinylnaphthalene, any monomer vinylaromatic issued a C9 cut (or more generally a C8 cut CIO). Preferably, the compound aromatic vinyl is styrene or a vinylaromatic monomer derived from a C9 cut (or more generally a C8 to C10 cut). Preferably, the compound vinylaromatic is the minor monomer, expressed as a mole fraction, in the copolymer considered.

-10-The content of hydrocarbon resin is preferably between 5 and 60 pce, in particular between 5 and 40 phr, more preferably still between 10 and 30 phr.

The level of total plasticizer (ie, more liquid plasticizer, the case appropriate, resin solid hydrocarbon) is preferably between 40 and 100 phr, more preferably included in a range of 50 to 80 phr.

II-3. Reinforcing charge Any type of reinforcing filler known for its ability to strengthen a rubber composition usable for the manufacture of tires, for example example a organic load such as carbon black, or a load reinforcing inorganic such as silica to which is associated in a known manner coupling.

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

Suitable carbon blacks are all carbon blacks, especially those black type HAF, ISAF, SAF conventionally used in the treads of pneumatic (black called pneumatic grade). Among these, we will mention more especially blacks 100, 200 or 300 series of reinforcing carbon (ASTM grades), as example N115, N134, N234, N326, N330, N339, N347, N375. Carbon blacks could be for example already 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, it is possible to quote organic functionalized polyvinylaromatic fillers as described in the WO-A-2006/069792 and WO-A-2006/069793.
By "reinforcing inorganic filler" must be understood here any load inorganic or mineral, whatever its color and origin (natural or synthesis), again called "white charge" or sometimes "clear" charge as opposed to black carbon, capable to reinforce on its own, without any means other than a coupling agent intermediate, a rubber composition for use in the manufacture of tires, other words apt to replace, in its reinforcing function, a carbon black conventional grade pneumatic; such a charge is generally characterized, in a known manner, over there presence of hydroxyl groups (-OH) on its surface.

-11-Inorganic reinforcing fillers are particularly suitable minerals from siliceous type, in particular silica (SiO 2), or aluminous type, particular of alumina (Al 2 O 3). The silica used can be any reinforcing silica known to the man from especially any precipitated or fumed silica having a surface BET as well CTAB surface area both less than 450 m2 / g, preferably from 30 to 400 m2 / g, especially between 60 and 300 m2 / g. As precipitated silicas highly dispersible (say "HDS"), for example, Ultrasil 7000 silicas and Ultrasil 7005 of society Degussa, the Zeosil 1165MP, 1135MP and 1115MP silicas from Rhodia, the Hi-Sil silica EZ150G from PPG, the company's Zeopol 8715, 8745 and 8755 silicas Huber.
As examples of reinforcing aluminas, mention may be made of "Baikalox" aluminas "A125" or "CR125" from Baikowski, "APA-10ORDX" from Condea, "Aluminoxid C" from Degussa or "AKP-GO15" from Sumitomo Chemicals.

Preferably, the total reinforcing filler content (black of carbon and / or load reinforcing inorganic substance) is between 60 and 120 phr, especially between 70 and 100 pce.
According to one particular embodiment, the reinforcing filler comprises carbon black to majority title; in such a case, the carbon black is present at a rate preferably greater than 60 phr, associated or not with a reinforcing inorganic that silica in minority quantity.

According to another particular embodiment, the reinforcing filler comprises a charge inorganic, 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 pce, associate or no to carbon black in minority quantity; 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).

Regardless of the primary aspect of the invention, namely the search for a adherence optimized on melting ice, the use of a majority load reinforcing inorganic such as silica is also advantageous from the point of view of adhesion to wet soil or snowy.

According to another possible embodiment of the invention, the load reinforcement includes a cutting of carbon black and reinforcing inorganic filler such as silica in neighboring quantities; in such a case, the level of inorganic filler, in particular silica, and the rate carbon black are preferably each between 25 and 75 phr, more especially each between 30 and 50 phr.

-12-To couple the reinforcing inorganic filler to the diene elastomer, uses so well known at least one bifunctional coupling agent (or linker) intended for ensure a sufficient chemical and / or physical connection between the charge inorganic (surface of its particles) and the diene elastomer. We use especially organosilanes or bifunctional polyorganosiloxanes.

In particular, polysulfurized silanes, called "symmetrical" or "asymmetrical" according to their particular structure, as described for example in the applications W003 / 002648 (or US 2005/01665 1) and W003 / 002649 (or US 2005/016650).
In particular, without the following definition being limiting, silanes so-called "symmetrical" polysulfides corresponding to the following general formula (I):

(I) Z - A - S - A - Z, wherein:
x is an integer of 2 to 8 (preferably 2 to 5);
- A is a divalent hydrocarbon radical (preferably groups alkylene in C1-C18 or C6-C12 arylene groups, more particularly alkylene in C-Clo, especially C1-C4, in particular propylene);
Z is one of the following formulas:

-Si-RI-Si-R2; -Si-R2 in which:
- the radicals RI, substituted or unsubstituted, identical or different between them, are C 1 -C 18 alkyl, C 5 -C 18 cycloalkyl or C 6 -C 6 aryl C18 (from preferably C 1 -C 6 alkyl, cyclohexyl or phenyl groups, especially C1-C4 alkyl groups, more particularly methyl and / or ethyl).
the radicals R2, substituted or unsubstituted, identical or different between them, represent a C 1 -C 18 alkoxyl or C 5 -C 18 cycloalkoxyl group (from preferably a a group selected from C 1 -C 8 alkoxyls and C 5 -C 8 cycloalkoxyls, plus preferably still a group chosen from C 1 -C 4 alkoxyls, in particular methoxyl and ethoxyl).

As examples of polysulphide silanes, mention will be made more particularly the polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl). Among these compounds, we use in particular bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT, or disulfide

-13-bis- (triethoxysilylpropyl), abbreviated as TESPD. We will also mention examples polysulfides (especially disulfides, trisulphides or tetrasulfides) (monoalkoxyl (C1-C4) -dialkyl (C1-C4) silylpropyl), more particularly the bis-tetrasulfide monoethoxydimethylsilylpropyl as described in the patent application WO
02/083782 (or US 2004/132880).

As a coupling agent other than polysulfurized alkoxysilane, mention may be made including POS
bifunctional polyorganosiloxanes or polysulfides of hydroxysilane (R2 = OH
in formula (I) above) as described in the patent applications WO
02/30939 (or US 6,774,255) and WO 02/31041 (or US 2004/051210), or else silanes or POS
carriers of azo-dicarbonyl functional groups, as described by example in 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 4 and 12 phr, more preferably between 3 and 8 pce.
Those skilled in the art will understand that as an equivalent load load inorganic reinforcement described in this paragraph could be used reinforcing filler of another nature, particularly organic, since this reinforcing would be covered with an inorganic layer such as silica, or its surface of functional sites, in particular hydroxyls, requiring the use of an agent coupling for establish the connection between the load and the elastomer.

II-4. Wheat microparticles The rubber compositions of the invention have the characteristic essential of have between 5 and 40 phr of wheat semolina microparticles.

By microparticles, the definition of particles of size micrometric, that is, say larger than a micrometer; preferentially, their size average and their size median (both expressed in weight) are between 1 m and 1 mm. Of preference, the median size is between 50 m and 1 mm.

Below the minima indicated above, the intended technical effect (ie the creation of a adapted micro-roughness) may be insufficient when beyond indicated, exposed to various disadvantages, in particular when the composition of rubber is used as tread: in addition to a loss of aesthetics (too much particles visible on the surface of the tread) and a risk of decohesion, when driving, of relatively large carving elements, it has been found that the performance adhesion on melting ice could be degraded.

-14-For all these reasons, it is preferred that the microparticles have a size median included between 100 m and 800 m, more preferably still included in a area from 300 to 600 m. This particularly preferred size domain seems to correspond has a 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 reasons identical to those set out above, the rate of microparticles is preferably between 5 and 35 phr, more preferentially understood between 10 and 30 phr.

Preferably, microparticles of wheat intended for human consumption, made from ordinary wheat grains, by milling processes or grinding in which the sound and the germ are largely eliminated. take in account the sizes of microparticles recommended here, it is about semolina (or flours that we could qualify to "coarse") consisting of crushed wheat grains, coarsely ground, form any and generally having relatively salient angles.

For the analysis of particle size and the calculation of the median size of microparticles (or average diameter for microparticles supposed to be substantially spherical), different known methods are applicable, for example by laser diffraction (see standard example ISO-8130-13 or JIS standard K5600-9-3).

It is also possible to use a simple analysis of the granulometry by sieving mechanical ; the operation consists of sieving a defined quantity of sample (for example 200 g) on a vibrating table for 30 min with sieve diameters different (by example, with a progression ratio of 1.26, with stitches of 1000, 800, 630, 500, 400, ... 100, 80, 63 m); the refusals collected on each sieve are weighed on a scale precision; we deduce the% of refusal for each diameter of mesh by weight ratio total product; the median size (or median diameter) is finally calculated so known from the histogram of the particle size distribution.

II-5. Various additives The rubber compositions of the invention also include all or part of usual additives usually used in elastomer compositions intended for manufacture of treads for tires, in particular for winter tires, such as protective agents such as anti-ozone waxes, anti-antiozonants chemicals, antioxidants, reinforcing resins, acceptors (eg example resin phenolic novolak) or methylene donors (eg HMT or H3M), a

-15-crosslinking system based on either sulfur or sulfur donors and / or peroxide and / or bismaleimides, vulcanization accelerators, activators of vulcanization.
These compositions may also contain coupling activators when an agent coupling is used, inorganic filler or more generally, implementation support agents who are likely to known, thanks to improving the dispersion of the filler in the rubber matrix and a lowering the viscosity of the compositions, to improve their ability to the raw state; these agents are, for example, hydrolysable silanes such as alkoxysilanes, polyols, polyethers, amines, hydroxylated polyorganosiloxanes or hydrolysable.

II-6. Manufacture of rubber compositions and treads The rubber compositions of the invention are manufactured in mixers appropriate, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first phase of work or mixing thermomechanical (sometimes referred to as a "non-productive" phase) at high temperature, up to a maximum temperature of between 130 ° C. and 200 ° C., preferably between 145 C and 185 C, followed by a second phase of mechanical work (sometimes referred to as phase "productive") at a lower temperature, typically below 120 C, by example between 60 C and 100 C, finishing phase during which the system is incorporated crosslinking or vulcanization.

A process which can be used for the manufacture of such compositions comprises example and preferably the following steps:

- to incorporate in the diene elastomer, in a mixer, more than 30 phr of a liquid plasticizer, between 50 and 150 phr of a reinforcing filler, between 5 and 40 pce microparticles of semolina of wheat, thermomechanically kneading the whole, one or more times until reaching 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;
extrude or calendering the rubber composition thus obtained, in particular in the form of a tire tread.

For example, the first (non-productive) phase is conducted in one single step Thermomechanical during which is introduced, in a suitable mixer such as usual internal mixer, all the necessary constituents, the possible agents of

-16-additional recovery or implementation and other miscellaneous additives, the exception of crosslinking system. After cooling the mixture thus obtained course of the first non-productive phase, the crosslinking system is then incorporated into low temperature, usually in an external mixer such as a blender.
cylinders; all 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 an accelerator sulfenamide type. AT
this vulcanization system are added, incorporated during the first phase productive and / or during the productive phase, various accelerators secondary or known vulcanization activators such as zinc oxide, stearic acid, guanidic 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 likely to act as a vulcanization accelerator for diene elastomers in the presence of sulfur, including thiazole accelerators and their derivatives, accelerators thiuram types, zinc dithiocarbamates. These accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (in abstract "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated "CBS"), N, N-dicyclohexyl-2-benzothiazyl sulfenamide ("DCBS"), N-tert-butyl-2-benzothiazyl sulfenamide ("TBBS"), N-ter-butyl-2-benzothiazyl sulfenimide ("TBSI"), dibenzyldithiocarbamate zinc ("ZBEC") and mixtures of these compounds.
The final composition thus obtained is then calendered, for example under the form of a leaf or plate, in particular for laboratory characterization, or again extruded in the form of a rubber profile directly usable as Band winter tire bearing.
The vulcanization (or cooking) is conducted in a known manner at a temperature usually between 130 C and 200 C, for a sufficient time which may vary by example between 5 and 90 min depending in particular on the cooking temperature, the heating system vulcanization adopted and the kinetics of vulcanization of the composition under consideration.
The rubber compositions according to the invention may constitute the whole or part only the tread according to the invention, in the case of a Band composite-type bearing formed of several rubber compositions of formulations different.

-17-The invention relates to rubber compositions and treads previously described both in the raw state (ie, before cooking) and in the cooked state (ie, after crosslinking or vulcanization).

III. EXAMPLES OF CARRYING OUT THE INVENTION

III-1. Preparation of rubber compositions and treads The following tests are carried out as follows:
in a blender internal, whose initial tank temperature is about 60 C, successively the charge reinforcement (for example a reinforcing inorganic filler such as silica and his agent associated coupling), the liquid plasticizer, the semolina microparticles wheat, elastomer diene (or diene elastomer blending) as well as the various other ingredients to the exception of the vulcanization system; the mixer is thus filled to about 70% (%
volume). We then conduct a thermomechanical work (non-productive phase) in a step, which lasts in total about 3 to 4 minutes, until reaching a temperature maximum of "fallen" of 165 C. The resulting mixture is recovered, cooled and then we incorporate sulfur and a sulfenamide type accelerator on an external mixer (homo-finisher) at 30 C, by mixing the whole (productive phase) for a suitable time (by example between 5 and 12 min).

The compositions thus obtained are then calendered either in the form of plates (2-3 mm thick) or thin sheets of rubber for the measurement of their properties physical or mechanical, extruded as treads of winter tires for passenger cars.

III-2. Rubber Testing In this test, three compositions based on diene elastomers are compared (NR cutting and BR with a cis-1,4 bond ratio greater than 95%), reinforced by a blend of silica and black of carbon with or without a fraction (20 phr) of microparticles of wheat presenting in the form of a food semolina (Fuji Seifun); two sizes (medians) of semolina are analyzed here (about 200 m and about 440 m).

Tables 1 and 2 give the formulation of the three compositions (Table 1 -rate of different products expressed in phr, that is to say parts by weight per cent elastomer parts (total elastomer)), their properties before and after cooking (30 min at 150 ° C.) ; the system of vulcanization is sulfur and sulfenamide.

-18-First of all, the examination of the different results in Table 2 reveals no degradation noticeable rubber properties despite the presence of relatively high wheat microparticles:
- the processability in the raw state (Mooney plasticity) is unexpectedly slightly improved for the compositions of the invention;
the rheometric properties (cooking) are not modified in a manner sensitive, the roasting safety (T5) being even increased by 4 min;
- after cooking, Shore hardness and modules in extension remain constant, this who is favorable to the mechanical behavior of the tread, road behavior of the tire;
- the decrease in properties at break, in particular from the stress to the break, if it can be described as expected, but remains in a non crippling for the skilled person;
- finally, the hysteresis is not increased, which is the recognized indicator a resistance undegraded roll.

This is actually only during actual taxi tests conducted on tires that reveals itself the unexpected result of the invention, as clearly evidenced by the following essay.

III-3. Tire tests The compositions C-1, C-2 and C-3 previously tested are then used as bands of winter tire tires with radial carcass, noted respectively P-1 (control tires), P-2 and P-3 (tires according to the invention), of dimensions conventionally manufactured and identical in all respects except for compositions of rubber constituents of their tread.

All tires are mounted on the front and rear of a vehicle automobile, under nominal inflation pressure, and they are run on a circuit (about 2000 km), on dry ground, for break-in and early wear.

Then the tires thus lapped are subjected to the adhesion test on ice as described in paragraph I-7 above, according to different temperature conditions.

The results of the rolling tests are reported in Table 3, in units relative, the base 100 being selected for the P-1 control tire (as a reminder, a value greater than 100 indicates improved performance).

-19-It is firstly noted that braking on melting ice (-2 C) is significantly improved for the tires according to the invention (P-2 and P-3) whereas no effect is visible for a temperature below -5 C. This is the proof that ice adhesion melting is a specific problem that requires solutions well specific.
In addition, the net superiority of P-3 tires in concerns no only the braking on melting ice (-2 C) but also the performance acceleration, improvements that can only be attributed to a median size superior of microparticles of wheat semolina compared to P-2 tires.
In summary, P-3 tires whose tread includes microparticles of wheat semolina whose median size is included in the particularly preferential from 300 to 600 m, are clearly the ones displaying the best performance combined grip and acceleration on ice.

-20-Table 1 Composition N ': C-1 C-2 C-3 BR (1) 60 60 60 NR (2) 40 40 40 silica (3) 80 80 80 coupling agent (4) 5 5 5 microparticles of wheat (5) - 20 -wheat microparticles (6) - - 20 carbon black (7) 5 5 5 non-aromatic oil (8) 65 65 65 DPG (9) 1.5 1.5 1.5 ZnO 1.2 1.2 1.2 stearic acid 1 1 1 anti-ozone wax 1.5 1.5 1.5 antioxidant (10) 2 2 2 sulfur 2 2 2 accelerator 11 1.7 1.7 1.7 (1) BR with 4.3% of 1-2; 2.7% trans; 97% cis 1-4 (Tg = -104 C);
(2) Natural rubber (peptized);
(3) "Zeosil 1115MP" silica from Rhodia, type "HDS"
(BET and CTAB: approximately 120 m2 / g);
(4) coupling agent TESPT ("Si69" from Degussa);
(5) wheat semolina (median particle size: about 200 m);
(6) wheat semolina (median particle size: about 440 m);
(7) ASTM grade N234 (Cabot company);
(8) MES oil ("Catenex SNR" from Shell);
(9) diphenylguanidine (Perkacit DPG from Flexsys);
(10) N-1,3-Dimethylbutyl-N-phenylparaphenylenediamine (Santoflex 6-PPD from Flexsys);
(11) N-dicyclohexyl-2-benzothiazol sulfenamide ("Santocure CBS" from the company Flexsys).

-21-Table 2 Composition N: C-1 C-2 C-3 Properties before cooking:
Mooney (UM) 54 47 47 T5 (min) 13 17 17 Ti (min) 2.1 2.3 3.0 T90 (min) 15.8 16.8 18.4 T90 - Ti (min) 13.7 14.5 15.4 Properties after cooking:
Shore A 55 56 56 MI 0 (MPa) 3.4 3.5 3.5 MI 00 (MPa) 1.1 1.2 1.2 M300 (MPa) 1.0 1.0 1.0 breaking strain (MPa) 13.9 10.4 9.3 elongation at break (%) 540 520 490 tan (S) R, a ,, (0 C) 0.280 0.280 0.280 Table 3 Inflatable: P-1 P-2 P-3 Ice braking (-2 C) 100 107 111 Ice braking (-6 C) 100 99 99 Acceleration on ice (-4 C) 100 101 106

Claims (28)

-22- 1. A rubber composition usable as a tread of a pneumatic winter, comprising at least one diene elastomer, more than 30 phr of a liquid plasticizer, between 50 and 150 phr of a reinforcing filler, characterized in that has between 5 and 40 parts of wheat semolina microparticles. 2. The composition according to claim 1, wherein the microparticles have a size median weight between 50 microns and 1 mm. 3. The composition according to claim 2, wherein the microparticles have a size median weight between 100 microns and 800 microns. The composition of claim 3, wherein the microparticles have a size median by weight in a range of 300 to 600 μm. The composition of claim 4, wherein the rate of microparticles is between 5 and 35 phr. The composition of claim 5, wherein the rate of microparticles is between 10 and 30 phr. The composition of any one of claims 1 to 6, wherein semolina wheat is a food semolina. 8. Composition according to any one of claims 1 to 7, wherein elastomer diene is selected from the group consisting of natural rubber, polyisoprenes of synthesis, polybutadienes, butadiene copolymers, copolymers isoprene and mixtures of these elastomers. The composition of claim 8, wherein the diene elastomer is chosen in the group consisting of natural rubber, synthetic polyisoprenes, the polybutadienes having a cis-1,4 bond ratio greater than 90%, the copolymers of butadiene-styrene and mixtures of these elastomers. The composition of claim 9 wherein the diene elastomer is For the most part, that is to say for more than 50 pce, natural rubber or polyisoprene of synthesis. The composition of claim 10, wherein the natural rubber where the synthetic polyisoprene is used in blending with a polybutadiene having a rate cis-1,4 bonds greater than 90%. The composition of claim 9 wherein the diene elastomer is for the most part, that is to say for more than 50 phr, a polybutadiene having a link rate cis-1,4 greater than 90%. The composition of claim 12, wherein the polybutadiene is used in cutting with natural rubber or synthetic polyisoprene. 14. Composition according to any one of Claims 1 to 13, in which charge Reinforcing agent contains mainly carbon black. The composition of claim 14, wherein the black level of carbon is greater than 60 pce. 16. Composition according to any one of Claims 1 to 13, in which charge The reinforcing agent mainly comprises a reinforcing inorganic filler. 17. The composition of claim 16, wherein the charge rate inorganic reinforcing is greater than 70 phr. 18. The composition of claim 17, wherein the inorganic filler reinforcing is silica. 19. Composition according to any one of Claims 1 to 18, in which charge reinforcement comprises a blend of carbon black and silica. 20. Composition according to any one of claims 1 to 19, in which the rate of total reinforcing filler is between 60 and 120 phr. 21. Composition according to any one of claims 1 to 20, in which the liquid plasticizer is selected from the group consisting of oils naphthenic oils paraffins, MES oils, TDAE oils, ester plasticisers and mixtures of these compounds. 22. The composition of claim 21, wherein the rate of liquid plasticizer is included in a range of 50 to 100 phr. 23. Composition according to any one of claims 1 to 22, comprising a resin hydrocarbon having a Tg greater than 20 ° C. 24. The composition of claim 23, wherein the resin hydrocarbon is chosen in the group consisting of homopolymer or copolymer resins of cyclopentadiene or dicyclopentadiene, terpene homopolymer or copolymer resins, resins homopolymer or C5 cutting copolymer, and mixtures of these resins. 25. Composition according to claims 23 or 24, wherein the rate of resin hydrocarbon is between 5 and 60 phr. 26. Use of a composition in accordance with any one of Claims 1 to 25, for the manufacture of tire treads winter. 27. Winter tire tread having a composition in accordance with any of claims 1 to 25. 28. Pneumatic winter comprising a tread according to the claim 27.