EP2257593A1 - Composition de caoutchouc pour bande de roulement de pneumatique hiver - Google Patents

Composition de caoutchouc pour bande de roulement de pneumatique hiver

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Publication number
EP2257593A1
EP2257593A1 EP09719830A EP09719830A EP2257593A1 EP 2257593 A1 EP2257593 A1 EP 2257593A1 EP 09719830 A EP09719830 A EP 09719830A EP 09719830 A EP09719830 A EP 09719830A EP 2257593 A1 EP2257593 A1 EP 2257593A1
Authority
EP
European Patent Office
Prior art keywords
phr
composition according
composition
microparticles
diene elastomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09719830A
Other languages
German (de)
English (en)
French (fr)
Inventor
Hiroko Fukasawa
Salvatore Pagano
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Compagnie Generale des Etablissements Michelin SCA
Michelin Recherche et Technique SA France
Original Assignee
Michelin Recherche et Technique SA Switzerland
Societe de Technologie Michelin SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Michelin Recherche et Technique SA Switzerland, Societe de Technologie Michelin SAS filed Critical Michelin Recherche et Technique SA Switzerland
Publication of EP2257593A1 publication Critical patent/EP2257593A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products

Definitions

  • the invention relates to rubber compositions useful in particular as treads of "winter tires” capable of rolling on floors covered with ice or ice without being provided with nails (also called “studless” tires).
  • compositions solid particles having a high hardness, such as, for example, silicon carbide (see for example US Pat. No. 3,878,447).
  • Such particles flush with the surface of the tread as and when the wear of the latter, certainly act effectively, like micro-nails, on hard ice, but these compositions are not well adapted driving conditions on melting ice.
  • microparticles of powders such as for example cellulose powders, vinyl alcohol, starch or cereals. such as corn (see, for example, JP Patent Applications 3-159803, JP 2002-1 1203, US Patents 2,607,386, US 5,246,985, US 7,249,621).
  • powders once solubilized in contact with the melted ice (in the case of water-soluble powders) or expelled from the rubbery matrix (in the case of insoluble powders) lead, in a known manner, to the surface of the strip.
  • a first subject of the invention relates to a rubber composition that can be used as a tread of a winter tire, comprising at least one diene elastomer, between 50 and 150 phr of a reinforcing filler, and more than 40 phr of a liquid plasticizer, between 1 and 30 phr of a nonionic surfactant and between 5 and 40 phr of microparticles.
  • the invention also relates to the use of such a rubber composition for the manufacture of tire treads winter, that they are intended for new tires as retreading tires used.
  • the invention also relates to these treads and winter tires themselves when they comprise a rubber 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, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering vehicles).
  • 4x4 vehicles four-wheel drive
  • SUV vehicles Sport Utility Vehicles
  • two-wheel vehicles including motorcycles
  • industrial vehicles chosen in particular from vans and "heavy goods vehicles” (ie, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering vehicles).
  • treads and rubber compositions constituting these treads are characterized, before and after cooking, as indicated below.
  • Mooney plasticity (November 1980).
  • the measurements are carried out at 130 ° C., in accordance with the French standard NF T 43-005.
  • the evolution of the consistency index as a function of time makes it possible to determine the toasting time of the rubber compositions, evaluated according to the above-mentioned standard by the parameter T5 (case of a large rotor), expressed in minutes, and defined as being the time required to obtain an increase in the consistometric index (expressed in MU) of 5 units above the minimum value measured for this index.
  • the measurements are carried out at 150 ° C. with an oscillating chamber rheometer according to DIN 53529 - Part 3 (June 1983).
  • the evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization reaction.
  • the measurements are processed according to DIN 53529 - Part 2 (March 1983): Ti is the induction time, that is to say the time required for the beginning of the vulcanization reaction, T ⁇ (for example T 90 ) is the time necessary to reach a conversion of ⁇ %, that is to say ⁇ % (for example 90%) of the difference between the minimum and maximum couples.
  • Dynamic properties are measured on a viscoanalyzer (Metravib VA4000) according to ASTM D5992-96.
  • the response of a sample of vulcanized composition (cylindrical specimen 4 mm in thickness and 400 mm 2 in section), subjected to a sinusoidal stress in alternating simple shear, at the frequency of 10 Hz, at a temperature of 0 C. scans in 0.1% strain amplitude 50%
  • the tires are mounted on a motor vehicle (“Toyota Camry") equipped with anti-lock braking system (ABS) and traction control system (TCS system for Traction Control System).
  • ABS anti-lock braking system
  • TCS system for Traction Control System traction control system
  • the rubber composition of the invention is based on at least one diene elastomer, a reinforcing filler, a plasticizer system, a nonionic surfactant and microparticles, components which are described in detail below.
  • any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e., limits 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 limits a and b).
  • elastomer or "diene” rubber it is recalled that must be understood an elastomer derived at least in part (i.e. a homopolymer or a copolymer) of monomers dienes (monomers bearing two carbon-carbon double bonds, 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 and copolymers of dienes and alpha-olefins EPDM type, for example, fall into the category of substantially saturated diene elastomers, having a diene origin ratio which is low or very low, always less than 15. % (mole%).
  • 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%). .
  • 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%.
  • At least one diene elastomer of the highly unsaturated type in particular a diene elastomer chosen from the group consisting of polybutadienes (BR), synthetic polyisoprenes (IR), natural rubber (NR), butadiene copolymers, isoprene copolymers (other than HR) and mixtures of these elastomers.
  • a diene elastomer chosen from the group consisting of polybutadienes (BR), synthetic polyisoprenes (IR), natural rubber (NR), butadiene copolymers, isoprene copolymers (other than HR) 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.
  • SBR butadiene-styrene copolymers
  • BIR isoprene-butadiene copolymers
  • SIR isoprene-styrene copolymers
  • SBIR isoprene-copolymers of butadiene-styrene
  • the elastomers can be for example block, statistical, sequence, microsequential, and be prepared in dispersion or in solution; they can be coupled and / or star or functionalized with a coupling agent and / or starring or functionalization.
  • a coupling agent for example, there may be mentioned for example functional groups comprising a C-Sn bond or amino functional groups such as benzophenone for example;
  • 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.
  • alkoxysilane groups such 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).
  • elastomers such as SBR, BR, NR or IR of the epoxidized type.
  • Polybutadienes and in particular those having a 1,2-unit content of between 4% and 80%, or those having a cis-1,4 content of greater than 80%, polyisoprenes and copolymers of butadiene- styrene and in particular those having a styrene content of between 5% and 50% by weight and more particularly between 20% and 40%, a 1,2-butadiene content of the butadiene part of between 4% and 65%, a trans-1,4 bond content of between 20% and 80%, butadiene-isoprene copolymers and especially 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.
  • Tg glass transition temperature
  • 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.
  • butadiene-styrene-isoprene copolymers are especially suitable those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60%.
  • the diene elastomer is chosen from the group consisting of natural rubber, synthetic polyisoprenes and polybutadienes having a cis-1,4 bond ratio of greater than 90%, copolymers of butadiene-styrene and mixtures of these elastomers.
  • the diene elastomer used is predominantly, that is to say for more than 50 phr (as a reminder, "phr” meaning parts by weight per hundred parts of elastomer), natural rubber (NR) or synthetic polyisoprene (IR). More preferably, said natural rubber or synthetic polyisoprene is then used in blending with a polybutadiene (BR) having a cis-1,4 bond ratio which is preferably greater than 90%.
  • the diene elastomer used is predominantly, that is to say for more than 50 phr, a polybutadiene (BR) having a cis-1,4 bond ratio greater than 90% . More preferably, said polybutadiene is then used in a blend with natural rubber or synthetic polyisoprene.
  • the diene elastomer used is a binary (mixing) blend of NR (or IR) and BR, or a ternary blend of NR (or
  • the composition comprises between 25 and 75 phr of NR (or IR) and between 75 and 25 phr of BR, to which may be associated or not a third elastomer (ternary cutting) at a lower rate. at 30 phr, especially less than 20 phr.
  • This third elastomer is preferably an SBR elastomer, in particular an SBR solution (called "SSBR").
  • the composition comprises from 35 to 65 phr of NR (or IR) and from 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%.
  • 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.
  • reinforcing filler known for its ability to reinforce a rubber composition that can be used for manufacturing tires, for example an organic filler such as carbon black, or a reinforcing inorganic filler such as silica to which is associated in a known manner a coupling agent.
  • Such a reinforcing filler typically consists of nanoparticles whose average size (in mass) is less than 500 nm, most often between 20 and 200 nm, in particular and preferably between 20 and 150 nm.
  • Suitable carbon blacks are all carbon blacks, especially blacks of the HAF, ISAF, SAF type conventionally used in tire treads (so-called pneumatic grade blacks).
  • the reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades), for example Nl 15, N134, N234, N326, N330, N339, N347 or N375, will be mentioned more particularly.
  • the carbon blacks could for example already be incorporated into the isoprene elastomer in the form of a masterbatch (see for example WO 97/36724 or WO 99/16600).
  • organic fillers other than carbon blacks mention may be made of the organic functionalized polyvinylaromatic fillers as described in applications WO-A-2006/069792 and WO-A-2006/069793.
  • Reinforcing inorganic filler means any inorganic or mineral filler, irrespective of its color and origin (natural or synthetic), also called “white” filler or sometimes “clear” filler as opposed to carbon black. capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires, in other words able to replace, in its reinforcing function, a conventional carbon black pneumatic grade; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
  • -OH hydroxyl groups
  • Suitable reinforcing inorganic fillers are mineral fillers of the siliceous type, in particular silica (SiO 2), or of the aluminous type, in particular alumina (Al 2 O 3).
  • the silica used may be any reinforcing silica known to those skilled in the art, especially any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably 30 to
  • HDS highly dispersible precipitated silicas
  • the content of total reinforcing filler is between 60 and 120 phr, in particular between 70 and 100 phr.
  • the reinforcing filler comprises predominantly carbon black; in such a case, the carbon black is present at a preferential rate higher than 60 phr, associated or not with a reinforcing inorganic filler such as silica in a minority amount.
  • 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; carbon black, when it is 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).
  • 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.
  • the reinforcing filler comprises a cutting of carbon black and reinforcing inorganic filler such as silica in neighboring amounts or not; 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.
  • 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.
  • organosilanes or bifunctional polyorganosiloxanes are used.
  • 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).
  • x is an integer of 2 to 8 (preferably 2 to 5);
  • - A is a divalent hydrocarbon radical (preferably alkylene groups Ci-Ci 8 or arylene groups, C 6 -C) 2, more particularly alkylene Ci-Ci 0, in particular Ci-C 4, especially the propylene);
  • the radicals R ' substituted or unsubstituted, which are identical to or different from each other, represent a Ci-Ci 8 alkyl, C 5 -C 8 cycloalkyl or C 6 -C 8 aryl group (preferably alkyl groups containing C 1 -C 6 , cyclohexyl or phenyl, especially C 1 -C 4 alkyl groups, more particularly methyl and / or ethyl).
  • R.2 radicals substituted or unsubstituted, identical or different, represent an alkoxy group or Ci-Ci 8 cycloalkoxy, C 5 -C 8 (preferably a group selected from alkoxyls and C 8 cycloalkoxyls C 5 -C 8 , more preferably still a group selected from C 1 -C 4 alkoxyls, in particular methoxyl and ethoxyl).
  • polysulfurized silanes mention may be made more particularly of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl) polysulfides.
  • bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated as TESPT, or bis (triethoxysilylpropyl) disulfide, abbreviated as TESPD is especially used.
  • polysulfides in particular disulphides, trisulphides or tetrasulfides
  • polysulfides of bis- (monoalkoxyl (Ci-C 4 ) -dialkyl (Ci-C 4 ) silylpropyl), more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide.
  • polysulfides in particular disulphides, trisulphides or tetrasulfides
  • bis-monoethoxydimethylsilylpropyl tetrasulfide as described in patent application WO 02/083782 (or US 2004/132880).
  • the content of coupling agent is preferably between 4 and 12 phr, more preferably between 3 and 8 phr.
  • the essential characteristic of the rubber composition of the invention is that it comprises a liquid plasticizer (at 23 ° C.) whose function is, in particular, 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.
  • Particularly suitable liquid plasticizers selected from the group consisting of naphthenic oils, paraffinic oils, MES oils, TDAE oils, ester plasticizers, phosphate plasticizers and mixtures of these compounds.
  • Phosphate plasticizers include those containing from 12 to 30 carbon atoms, for example trioctyl phosphate.
  • ester plasticizers that may be mentioned include compounds selected from the group consisting of trimellitates, pyromellitates, phthalates, 1,2-cyclohexane dicarboxylates, adipates, azela- lates, sebacates, glycerol triesters and mixtures of these compounds.
  • glycerol triesters those composed predominantly (for more than 50%, more preferably more than 80% by weight) of an unsaturated fatty acid Ci 8 is that is, a fatty acid 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 are well known, they have been described for example in the application WO 02/088238 (or US 2004/0127617), as plasticizers in treads for tires.
  • the level of liquid plasticizer recommended for the composition of the invention is particularly high, greater than 40 phr, preferably in a range of 50 to 100 phr. . This area has proven to correspond to an optimum rigidity for a tread according to the invention, particularly for the low temperatures and conditions of use that are targeted.
  • compositions of the invention may include also, as a solid plasticizer (23 ° C), a hydrocarbon resin having a Tg greater than 20 0 C, preferably greater than 30 0 C, as described for example in applications WO 2005/087859, WO 2006/061064 and WO 2007/017060.
  • a solid plasticizer 23 ° C
  • a hydrocarbon resin having a Tg greater than 20 0 C, preferably greater than 30 0 C, as described for example in applications WO 2005/087859, WO 2006/061064 and WO 2007/017060.
  • Hydrocarbon resins are polymers that are well known to those skilled in the art, which are therefore inherently miscible in diene (s) elastomer compositions when they are qualified. in addition to “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.
  • the plasticizing hydrocarbon resin has at least one, more preferably all, of the following characteristics:
  • 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 porosity filter
  • the plasticizing hydrocarbon resin is chosen from the group consisting of homopolymer or copolymer resins of cyclopentadiene (abbreviated as CPD) or dicyclopentadiene (abbreviated as DCPD), terpene homopolymer or copolymer resins, C5 homopolymer or copolymer resins, and mixtures of these resins.
  • CPD cyclopentadiene
  • DCPD dicyclopentadiene
  • terpene homopolymer or copolymer resins C5 homopolymer or copolymer resins, and mixtures of these resins.
  • copolymer resins are preferably used those selected from the group consisting of copolymer resins (D) CPD / vinylaromatic, copolymer resins (D) CPD / terpene, copolymer resins (D) CPD / cut C5, terpene / vinylaromatic copolymer resins, C5 / vinylaromatic cut copolymer resins, and mixtures of these resins.
  • pene here combines in a known manner the alpha-pinene, beta-pinene and limonene monomers; preferentially, a limonene monomer, a compound presenting with known manner in the form of three possible isomers: L-limonene (laevorotatory enantiomer), D-limonene (dextrorotatory enantiomer), or the dipentene, racemic enantiomers dextrorotatory and levorotatory.
  • L-limonene laevorotatory enantiomer
  • D-limonene diextrorotatory enantiomer
  • dipentene racemic enantiomers dextrorotatory and levorotatory.
  • Suitable vinylaromatic monomers are, for example, styrene, phenol, alpha-methylstyrene, ortho-, meta-, para-methylstyrene, vinyl-toluene, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, and the like. , divinylbenzene, vinylnaphthalene, any vinylaromatic monomer derived from a C 9 (or more generally from a C 8 to Ci 0).
  • the vinyl aromatic compound is styrene or a vinylaromatic monomer resulting from a C 9 (or more generally from a C 8 to Ci 0).
  • 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 5 and 60 phr, especially between 5 and 40 phr, more preferably between 10 and 30 phr.
  • the level of total plasticizer i.e., liquid plasticizer plus, where appropriate, solid hydrocarbon resin
  • the level of total plasticizer is preferably between 40 and 100 phr, more preferably in a range of 50 to 80 phr.
  • composition of the invention comprises between 1 and 30 phr of a surfactant (or "surfactant") of the nonionic type.
  • polyalkoxylated phenols for example ethoxylated, propoxylated, ethopropoxylated
  • polyalkoxylated phenols for example ethoxylated, propoxylated, ethopropoxylated
  • alcohols or fatty acids C 6 -C 22 optionally polyalkoxylated (for example ethoxylated, propoxylated, ethopropoxylated); polyalkoxylated triglycerides (for example ethoxylated, propoxylated, ethopropoxylated), in particular of plant or animal origin;
  • the nonionic surfactant is selected from the group consisting of sorbitan esters, especially sorbitan monoesters.
  • R is a hydrocarbon radical containing from 1 to 25 atoms, in particular an alkyl having from 6 to 20 (in particular from 1 to 17) carbon atoms or an alkenyl containing from 10 to 22 (in particular from 13 to 19) carbon atoms.
  • sorbitan monoesters selected from the group consisting of monolaurate (C 1 -C alkyl), monopalmitate (C 15 alkyl), monostearate (C 1-4 alkyl), monooleate (R alkenyl C] 7 ) and mixtures of such esters.
  • the level of nonionic surfactant is between 1 and 30 phr. Below the minimum indicated, the wetting effect is insufficient while beyond the maximum recommended, one exposes a limit of compatibility between surfactant and elastomer matrix, combined with a problem of implementation (processability) of the composition. For these reasons, the level of surfactant is preferably between 1 and 20 phr, more preferably between 2 and 10 phr.
  • the rubber compositions of the invention have another essential feature of having between 5 and 40 phr of microparticles.
  • these protruding microparticles on the surface of the tread fulfill a "claw" function. Then, in a second step, after gradual elimination of the rubbery matrix, they release microcavities which act as a channel for evacuating the film of water on the surface of Ice cream; 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.
  • microparticles is meant by definition micrometric size particles, that is to say, whose average size and median size (both expressed by weight) are between 1 micron and 1 mm. Their size is such that, in known manner, they can not be described as reinforcing unlike previously described nanoparticles.
  • the median size is between 50 microns and 1 mm.
  • the intended technical effect namely the creation of a suitable micro-roughness
  • 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.
  • the microparticles have a median size of between 100 ⁇ m and 800 ⁇ m, more preferably still within a range of 150 to 600 ⁇ m. 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.
  • the level of microparticles is preferably between 5 and 35 phr, more preferably between 5 and 20 phr, in particular between 5 and 15 phr.
  • the invention is applicable to any type of microparticle, whether solid or hollow, in the form of a powder or in any other form, for example to microparticles with high hardness, water-soluble microparticles or cereal microparticles such as as described in the introduction to this memo.
  • microparticles of cereal are used.
  • Such microparticles have proved to be particularly suitable for generating an effective surface microroughness, without the disadvantage of being abrasive, as are very high-hardness particles such as, for example, silicon carbide (described for example in US Pat. No. 3,878). 147), nor the risk of having insufficient solubility at very low temperature and in a very short time, under the conditions of use of the tire, as may be the case for water-soluble particles such as, for example, cellulose powders, of vinyl alcohol or starch.
  • cereal microparticles intended for human consumption made from ordinary cereal grains are used by milling or grinding processes in which the bran and germ are largely removed. Given the size of microparticles recommended here, it is not flour but more or less coarse semolina with grains of crushed cereals, crushed coarsely, of any shape and generally having relatively salient angles.
  • These cereals include wheat, barley, rice, rye, oats, buckwheat or buckwheat, corn. More preferably, microparticles of wheat are used.
  • 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 ⁇ m); 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 size (or median diameter) is finally calculated in a known manner from the histogram of the particle size distribution.
  • the rubber compositions of the invention also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tire treads, in particular for winter tires, such as, for example, protective agents such as waxes.
  • protective agents such as waxes.
  • 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 at a lowering 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.
  • 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 between 130 ° C and 200 ° C, preferably between 145 ° C and 185 0 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 0 C and 100 0 C, finishing phase during which is incorporated the crosslinking system or vulcanization.
  • a first phase of work or thermomechanical mixing (sometimes referred to as "non-phase” phase).
  • -productive ) at high temperature, up to a maximum temperature between 130 ° C and 200 ° C, preferably between 145 ° C and 185 0 C
  • a second phase of mechanical work sometimes called phase” Producer ”
  • a method that can be used for the manufacture of such compositions comprises, for example, and preferably the following steps:
  • 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.
  • a suitable mixer such as a conventional internal mixer. or other complementary additives and other additives, with the exception of the crosslinking system.
  • 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.
  • 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.
  • accelerator primary or secondary
  • any compound capable of acting as an accelerator of vulcanization of diene elastomers in the presence of sulfur in particular thiazole-type accelerators and their derivatives, accelerators of thiuram type, zinc dithiocarbamates.
  • These accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated “CBS”), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (“DCBS”), N-tert-butyl-2-benzothiazylsulfenamide (“TBBS”), N-tert-butyl-2-benzothiazylsulfenimide (“TBS1”), zinc dibenzyldithiocarbamate (“ZBEC”) and mixtures thereof. these compounds.
  • MBTS 2-mercaptobenzothiazyl disulfide
  • CBS N-cyclohexyl-2-benzothiazyl sulfenamide
  • DCBS N-dicyclohexyl-2-benzothiazyl sulfenamide
  • 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.
  • the rubber compositions according to the invention can constitute all or only part of the tread according to the invention, in the case of a composite type tread formed of several rubber compositions of different formulations.
  • the invention relates to the rubber compositions and treads previously described both in the green state (ie, before firing) and in the fired state (ie, after crosslinking or vulcanization).
  • the reinforcing filler for example carbon black and / or silica and its agent
  • the initial vessel temperature of which is approximately 60 ° C. associated coupling the liquid plasticizer, the 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).
  • Theromechanical work (non-productive phase) is then carried out in one step, which lasts a total of about 3 to 4 minutes, until a maximum temperature of "fall" of 165 ° C is reached.
  • the mixture thus obtained is recovered, cooled and then sulfur and a sulfenamide type accelerator are incorporated on an external mixer (homo-finisher) at 30 ° C., mixing the whole (productive phase) for a suitable time (for example between 5 and 12 minutes).
  • compositions thus obtained are then calendered either in the form of plates (thickness of 2 to 3 mm) or thin sheets of rubber for the measurement of their physical or mechanical properties, or extruded in the form of tire treads winter vehicle tourism.
  • Tables 1 and 2 give the formulation of the three compositions (Table 1 - rate of the different products expressed in phr), their properties before and after curing (30 min at 150 ° C.); the vulcanization system is sulfur and sulfenamide.
  • the control composition CI contains neither surfactant nor microparticles.
  • the composition C-2 also not in accordance with the invention, comprises only the surfactant but it is devoid of microparticles. Only the composition C-3 comprising, in addition to a high level of liquid plasticizer, both a nonionic surfactant and microparticles, is therefore in accordance with the invention.
  • the amount of plasticizing oil was slightly reduced (minus 4 phr) compared with the control composition CI, so as to keep the rigidity of the composition substantially constant (shown in Table 2 by the Shore A hardness parameter).
  • the Mooney plasticity (raw processability indicator) is even reduced for the composition C-3; the rheometric properties (cooking) are not appreciably modified; after cooking, Shore hardness and modules in extension remain substantially constant, which is favorable to the mechanical behavior of the tread, and therefore to the road behavior of the tire; the reduction of the properties at break, in particular of the stress at break, if it can be described as expected, nevertheless remains in a non-prohibitive range for the skilled person; it is the same for the hysteresis (indicator of rolling resistance).
  • compositions CI, C-2 and C-3 tested above are then used as treads for winter tire tires with radial carcass, denoted respectively PI, P-2 (control tires) and P-3 (tires compliant with FIG. invention) of dimensions 205/65 Rl 5 conventionally manufactured and identical in all respects, except the rubber compositions constitutive of their tread.
  • All tires are mounted at the front and rear of a motor vehicle, under nominal inflation pressure, and are run on a circuit (about 2000 km), on dry ground, for running-in and beginning of wear.
  • the P-3 tires of the invention are clearly superior in the presence non-ionic surfactant and microparticles, with regard not only to braking capacity (improved by 22%) but also acceleration performance (also improved by
  • compositions of the invention incorporating in combination a particularly high level of liquid plasticizer, a nonionic surfactant and microparticles, particularly cereal microparticles, give the treads of winter tires a significantly improved performance in terms of adhesion and acceleration capacity on melting ice, without undesirably penalizing the other properties, in particular those of wear resistance and rolling resistance.
  • wheat semolina (median particle size: about 200 ⁇ m);

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
EP09719830A 2008-03-13 2009-03-09 Composition de caoutchouc pour bande de roulement de pneumatique hiver Withdrawn EP2257593A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0851629A FR2928647B1 (fr) 2008-03-13 2008-03-13 Composition de caoutchouc pour bande de roulement de pneumatique hiver
PCT/EP2009/001662 WO2009112220A1 (fr) 2008-03-13 2009-03-09 Composition de caoutchouc pour bande de roulement de pneumatique hiver

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EP2257593A1 true EP2257593A1 (fr) 2010-12-08

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EP (1) EP2257593A1 (enExample)
JP (1) JP5535947B2 (enExample)
CA (1) CA2716617A1 (enExample)
EA (1) EA201071070A1 (enExample)
FR (1) FR2928647B1 (enExample)
WO (1) WO2009112220A1 (enExample)

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FR2952645B1 (fr) 2009-10-27 2011-12-16 Michelin Soc Tech Bandage pneumatique dont la paroi interne est pourvue d'une couche de caoutchouc thermo-expansible
FR2956118B1 (fr) * 2009-12-18 2013-03-08 Michelin Soc Tech Composition de caoutchouc pour bande de roulement de pneumatique hiver.
FR2955584B1 (fr) * 2009-12-18 2014-08-22 Michelin Soc Tech Composition de caoutchouc pour bande de roulement de pneumatique hiver.
KR101153384B1 (ko) * 2009-12-22 2012-06-05 한국타이어 주식회사 타이어 트레드용 고무 조성물 및 이를 이용하여 제조한 타이어
FR2955328B1 (fr) * 2010-01-18 2013-03-08 Michelin Soc Tech Composition de caoutchouc pour bande de roulement de pneumatique hiver
DE102010017805A1 (de) * 2010-07-08 2012-01-12 Continental Reifen Deutschland Gmbh Kautschukmischung
FR2966157B1 (fr) * 2010-10-18 2012-12-14 Michelin Soc Tech Composition de caoutchouc pour bande de roulement de pneumatique
FR2975999B1 (fr) 2011-06-01 2014-07-04 Michelin Soc Tech Pneu dont la bande de roulement comporte une composition de caoutchouc thermo-expansible reduisant les bruits de roulage
FR2975997B1 (fr) 2011-06-01 2013-06-14 Michelin Soc Tech Pneumatique pour vehicule dont la bande de roulement comporte une composition de caoutchouc thermo-expansible
FR2979076B1 (fr) 2011-07-28 2013-08-16 Michelin Soc Tech Pneumatique pour vehicule dont la bande de roulement comporte une composition de caoutchouc thermo-expansible
JP5890679B2 (ja) * 2011-12-26 2016-03-22 株式会社ブリヂストン ゴム組成物の製造方法
PT3156445T (pt) * 2012-02-24 2018-03-20 Amyris Inc Composição de borracha e pneu
FR2992322B1 (fr) 2012-06-22 2015-06-19 Michelin & Cie Pneumatique pour vehicule dont la bande de roulement comporte une composition de caoutchouc thermo-expansible
FR2997407B1 (fr) 2012-10-30 2015-01-23 Michelin & Cie Bandage pour vehicule dont la bande de roulement comporte une composition de caoutchouc thermo-expansible
FR2998510A1 (fr) 2012-11-29 2014-05-30 Michelin & Cie Pneumatique pour vehicule dont la bande de roulement comporte une composition de caoutchouc thermo-expansible
WO2014084404A1 (ja) * 2012-11-30 2014-06-05 コンパニー ゼネラール デ エタブリッスマン ミシュラン 空気入りタイヤ用トレッド及びこのトレッドを有する空気入りタイヤ
US8813802B1 (en) * 2013-11-13 2014-08-26 The Goodyear Tire & Rubber Company Pneumatic tire with rubber component containing thermoplastic/filler composite
FR3015503B1 (fr) 2013-12-19 2016-02-05 Michelin & Cie Pneu dont la bande de roulement comporte des elements de sculpture avec des parois laterales rigides comportant des microparticules d'oxyde ou carbure metallique.
FR3015502B1 (fr) 2013-12-19 2016-02-05 Michelin & Cie Pneu dont la bande de roulement comporte des elements de sculpture avec des parois laterales rigides contenant des microparticules hydrosolubles.
FR3015501B1 (fr) 2013-12-19 2017-05-26 Michelin & Cie Pneu dont la bande de roulement comporte des elements de sculpture avec des parois laterales rigides comportant un caoutchouc thermo-expansible a l'etat cru, ou caoutchouc mousse a l'etat cuit.
JP6464596B2 (ja) * 2014-07-30 2019-02-06 横浜ゴム株式会社 ウインター用空気入りタイヤ
CN107001714A (zh) * 2014-12-15 2017-08-01 米其林集团总公司 具有包含橡胶组合物的胎面的雪地轮胎
EP3289011B1 (en) 2015-04-30 2019-03-20 Compagnie Générale des Etablissements Michelin A heat-expandable rubber composition
US10179479B2 (en) 2015-05-19 2019-01-15 Bridgestone Americas Tire Operations, Llc Plant oil-containing rubber compositions, tread thereof and race tires containing the tread
US10836884B2 (en) 2015-10-22 2020-11-17 Bridgestone Corporation Rubber composition and tire obtained therefrom
WO2017083082A1 (en) 2015-11-11 2017-05-18 Bridgestone Americas Tire Operations, Llc Saturated triglyceride-containing rubber composition, tires and tire components containing the rubber composition, and related methods
JP6613887B2 (ja) * 2015-12-28 2019-12-04 日本ゼオン株式会社 ゴム組成物、ゴム架橋物およびタイヤの製造方法
JP7009868B2 (ja) * 2017-01-31 2022-01-26 横浜ゴム株式会社 スタッドレスタイヤ用ゴム組成物およびスタッドレスタイヤ
JP7275804B2 (ja) * 2019-04-22 2023-05-18 横浜ゴム株式会社 ゴム組成物及びスタッドレスタイヤ
JP2022554014A (ja) * 2019-11-06 2022-12-27 ブリヂストン アメリカズ タイヤ オペレーションズ、 エルエルシー 特定のゴム組成物のトレッドを有するタイヤ及び関連方法
US20240117159A1 (en) * 2020-12-30 2024-04-11 Bridgestone Americas Tire Operations, Llc Tire Having Tread Of Specified Rubber Composition And Related Methods

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Also Published As

Publication number Publication date
JP2011513559A (ja) 2011-04-28
FR2928647A1 (fr) 2009-09-18
EA201071070A1 (ru) 2011-04-29
CA2716617A1 (fr) 2009-09-17
JP5535947B2 (ja) 2014-07-02
FR2928647B1 (fr) 2011-11-25
WO2009112220A1 (fr) 2009-09-17

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