WO2012146611A1 - Pneumatique a adhérence sur glace améliorée - Google Patents

Pneumatique a adhérence sur glace améliorée Download PDF

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Publication number
WO2012146611A1
WO2012146611A1 PCT/EP2012/057545 EP2012057545W WO2012146611A1 WO 2012146611 A1 WO2012146611 A1 WO 2012146611A1 EP 2012057545 W EP2012057545 W EP 2012057545W WO 2012146611 A1 WO2012146611 A1 WO 2012146611A1
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WIPO (PCT)
Prior art keywords
phr
oils
tire according
tire
rubber
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PCT/EP2012/057545
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English (en)
French (fr)
Inventor
Hiroko Fukasawa
Salvatore Pagano
Original Assignee
Compagnie Generale Des Etablissements Michelin
Michelin Recherche Et Technique S.A.
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Priority to JP2014506844A priority Critical patent/JP2014513182A/ja
Publication of WO2012146611A1 publication Critical patent/WO2012146611A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/32—Properties characterising the ingredient of the composition containing low molecular weight liquid component
    • C08L2207/324—Liquid component is low molecular weight polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof

Definitions

  • the invention relates to rubber compositions used as treads of tires for vehicles, in particular tires “winter” able to roll on floors covered with ice or ice without being provided with nails (also called “studless” tires).
  • treads of winter tires which are specifically adapted for driving under conditions called “dry ice” or “cold ice” corresponding to a temperature range below -5 ° C, while also satisfying the so-called “melting ice” conditions encountered in a temperature range typically between -5 ° C and 0 ° C, in which domain in known manner, the pressure of the tires at the passage of a vehicle causes a superficial melting of the ice which is covered with a thin film of water harmful to the adhesion of these tires.
  • solid particles of high hardness such as, for example, silicon carbide (see, for example, US Pat. No. 3,878,147), some of which are flush with the surface of the tread. as it wears, and thus come into contact with the ice.
  • Such particles capable of acting finally as micro-nails on hard ice, thanks to a well known "claw" effect, however remain relatively aggressive vis-à-vis the ground, besides they are not not well adapted to driving conditions on melting ice.
  • the present invention relates to a tire whose tread comprises a rubber composition based on at least one diene elastomer, more than 30 phr of a liquid plasticizer, between 50 and 150 phr of a non-reinforcing filler. black, optionally carbon black at a rate less than 3 phr, and between 5 and 50 phr of a photocurable liquid polymer resin.
  • the tires of the invention are particularly intended to equip tourism-type motor vehicles, including 4x4 vehicles (four-wheel drive) and SUV vehicles ("Sport Utility Vehicles"), two-wheel vehicles (including motorcycles) as industrial vehicles chosen in particular from vans and "heavy goods vehicles” (ie, metro, buses, road transport vehicles such as trucks, tractors).
  • 4x4 vehicles four-wheel drive
  • SUV vehicles Sport Utility Vehicles
  • two-wheel vehicles including motorcycles
  • industrial vehicles chosen in particular from vans
  • "heavy goods vehicles” ie, metro, buses, road transport vehicles such as trucks, tractors.
  • the invention applies in the case where the tire and said polymer resin are both in the green (i.e., uncrosslinked) state as in the crosslinked state (i.e., after crosslinking or vulcanization)
  • any range of values designated by the expression “between a and b” represents the range of values greater than “a” and less than “b” (i.e., terminals a and b excluded). while any range of values designated by the term “from a to b” means the range of values from “a” to "b” (i.e. including the strict limits a and b).
  • the rubber composition of the invention is therefore based on at least one diene elastomer, a plasticizer system, a reinforcing inorganic filler, a photocrosslinkable liquid polymer resin, components which are described in detail below.
  • composition comprising the mixture of the various constituents used or, where appropriate, their reaction product, some of these basic constituents being in particular capable of or intended to react with each other. at least partly during the various phases of manufacture of the composition, in particular during its crosslinking or vulcanization.
  • diene Elastomer or rubber, the two terms being synonymous
  • diene elastomer or rubber, the two terms being synonymous
  • elastomer derived at least in part (ie a homopolymer or a copolymer) from monomers dienes (monomers carrying two double carbon-carbon 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 as well as, for example, copolymers of dienes and alpha-olefins of the EPDM type, fall into the category of essentially saturated diene elastomers, with a level of diene origin units 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%. It is preferred to use at least one diene elastomer of the highly unsaturated type, in particular a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), polybutadienes (BR) and butadiene copolymers, copolymers of isoprene and mixtures of these elastomers.
  • NR natural rubber
  • IR synthetic polyisoprenes
  • BR polybutadienes
  • butadiene copolymers copolymers of isoprene and mixtures of these elastomers.
  • Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene-copolymers of butadiene-styrene (SBIR) and mixtures of such copolymers.
  • SBR butadiene-styrene copolymers
  • BIR isoprene-butadiene copolymers
  • SIR isoprene-styrene copolymers
  • SBIR isoprene-copolymers of butadiene-styrene
  • Polybutadienes and in particular those having a content of 1,2-units of between 4% and 80%, or those having a cis-1,4 content of greater than 80%, the polyisoprenes and the butadiene copolymers, are preferably used.
  • 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 > and 65%>, a content of trans-1,4 bonds of between 20%> and 80%>, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a glass transition temperature ("Tg" - measured according to ASTM D3418-82) from -40 ° C to -80 ° C, isoprene-styrene copolymers and in particular those having a styrene content of between 5%> and 50%> in weight and a Tg between -25 ° C and -50 ° C.
  • Tg glass transition temperature
  • butadiene-styrene-isoprene copolymers those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40% are especially suitable, an isoprene content of between 15% and 50% by weight.
  • the diene elastomer is chosen from the group consisting of natural rubber, synthetic polyisoprenes and polybutadienes having a cis-1,4 bond ratio greater than 90%, butadiene-styrene copolymers and mixtures of these elastomers.
  • the diene elastomer used is predominantly, and more preferably for more than 50 phr (for recall, "phr” or “phr” in English meaning parts by weight per hundred parts of elastomer or rubber), natural rubber (NR) or synthetic polyisoprene (IR). More preferably still, 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%.
  • BR polybutadiene
  • 50 to 100 phr of a polybutadiene having a cis-1,4 bond ratio of greater than 90%, in particular in a blend with at most 50 phr of natural rubber or polyisoprene, are used. synthesis.
  • the diene elastomer used is predominantly, and more preferably for more than 50 phr, a polybutadiene (BR) having a cis-1,4 bond ratio greater than 90%. More preferably still, said polybutadiene is then used in a blend with natural rubber or synthetic polyisoprene.
  • BR polybutadiene
  • the diene elastomer used is a binary (mixing) blend of NR (or IR) and BR, or a ternary blend of NR (or IR), BR and SBR.
  • 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 compositions of the invention could be associated, in a minor amount, with synthetic elastomers other than dienes, or even polymers other than elastomers, for example thermoplastic polymers.
  • Another essential feature of the rubber composition of the invention is that it comprises more than less than 30 phr of a liquid plasticizer (at 23 ° C.) whose function is to soften the matrix by diluting the elastomer and the reinforcing filler; its Tg is preferably less than -20 ° C, more preferably less than -40 ° C.
  • any extender oil whether of aromatic or non-aromatic nature, any liquid plasticizing agent known for its plasticizing properties with respect to diene elastomers, is usable.
  • these plasticizers or these oils are liquids (that is to say, as a reminder, substances having the capacity to eventually take on the shape of their container) , in contrast to, in particular, hydrocarbon plasticizing resins which are by nature solid at ambient temperature.
  • Liquid plasticizers selected from the group consisting of polyolefin oils, naphthenic oils, paraffinic oils, DAE (Distillate Aromatic Extracts) oils, MES (Medium Extracted Solvates) oils, Treated Distillate Aromatic Extracts (TDAE) oils are particularly suitable. ), Residual Aromatic Extracts (RAE) oils, Treated Residual Aromatic Extracts (TREE) oils, Safety Residual Aromatic Extracts (SRAE) oils, mineral oils, vegetable oils, ethers plasticizers, ester plasticizers, phosphate plasticizers sulphonate plasticizers and mixtures of these compounds.
  • the liquid plasticizer is selected from the group consisting of MES oils, TDAE oils, naphthenic oils, vegetable oils and mixtures of these oils.
  • the liquid plasticizer in particular petroleum oil, is of the non-aromatic type.
  • a liquid plasticizer is described as non-aromatic if it has a content of polycyclic aromatic compounds, determined with the extract in DMSO according to the IP 346 method, of less than 3% by weight, relative to the total weight of the plasticizer.
  • a liquid plasticizer chosen from the group consisting of MES oils, TDAE oils, naphthenic oils (at low or high viscosity, especially hydrogenated), paraffinic oils and mixtures of these oils.
  • RAE oils, TRAE oils and SRAE oils or mixtures thereof which contain low levels of polycyclic compounds.
  • phosphate plasticizers for example, mention may be made of those containing from 12 to 30 carbon atoms, for example trioctyl phosphate.
  • ester plasticizers mention may be made in particular of compounds selected from the group consisting of trimellitates, pyromellitates, phthalates, 1,2-cyclohexane dicarboxylates, adipates, azelates, sebacates, glycerol and mixtures of these compounds.
  • glycerol triesters preferably consisting predominantly (for more than 50%, more preferably more than 80% by weight) of an unsaturated fatty acid Ci 8 is that is to say selected from the group consisting of oleic acid, linoleic acid, linolenic acid and mixtures of these acids. More preferably, whether of synthetic or natural origin (for example vegetable oils of sunflower or rapeseed), the fatty acid used is more than 50% by weight, more preferably still more than 80% by weight. % by weight of oleic acid.
  • Such triesters (trioleates) with a high oleic acid content are well known, they have been described for example in WO 02/088238, as plasticizers in tire treads.
  • the level of liquid plasticizer in the composition of the invention is preferably greater than 40 phr, more preferably within a range of 50 to 100 phr.
  • compositions of the invention may also comprise, as solid plasticizer (at 23 ° C.), a hydrocarbon resin having a Tg greater than + 20 ° C., preferably greater than + 30 ° C. C, as described for example in applications WO 2005/087859, WO 2006/061064 and WO 2007/017060.
  • Hydrocarbon resins are polymers that are well known to those skilled in the art, essentially based on carbon and hydrogen, and therefore inherently miscible in diene (s) elastomer compositions when they are further qualified as “ plasticizing ". 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.
  • the plasticizing hydrocarbon resin has at least one, more preferably all, of the following characteristics: a Tg greater than 20 ° C (more preferably between 40 and 100 ° C);
  • Mn a number-average molecular weight (Mn) of between 400 and 2000 g / mol (more preferentially between 500 and 1500 g / mol);
  • the Tg of this resin is measured in a known manner by DSC (Differential Scanning Calorimetry), according to the ASTM D3418 standard.
  • the macro structure (Mw, Mn and Ip) of the hydrocarbon resin is determined by steric exclusion chromatography (SEC): tetrahydroiuran solvent; temperature 35 ° C; concentration 1 g / 1; flow rate 1 ml / min; filtered solution on 0.45 ⁇ porosity filter before injection; Moore calibration with polystyrene standards; set of 3 "WATERS” columns in series (“STYRAGEL” HR4E, HR1 and HR0.5); differential refractometer detection ("WATERS 2410") and its associated operating software (“WATERS EMPOWER”).
  • the plasticizing hydrocarbon resin is chosen from the group consisting of cyclopentadiene homopolymer or copolymer resins (abbreviated to CPD), dicyclopentadiene homopolymer or copolymer resins (abbreviated to DCPD), terpene homopolymer or copolymer resins, homopolymer or C5 cut copolymer resins, homopolymer or C9 cut copolymer resins, alpha-methyl-styrene homopolymer or copolymer resins and mixtures thereof. resins.
  • CPD cyclopentadiene homopolymer or copolymer resins
  • DCPD dicyclopentadiene homopolymer or copolymer resins
  • terpene homopolymer or copolymer resins homopolymer or C5 cut copolymer resins
  • homopolymer or C9 cut copolymer resins homopolymer or C9 cut copolymer resins
  • copolymer resins are more preferably used those selected from the group consisting of (D) CPD / vinylaromatic copolymer resins, (D) CPD / terpene copolymer resins, copolymer resins (D) CPD / C5 cut, (D) CPD / C9 cut copolymer resins, terpene / vinylaromatic copolymer resins, terpene / phenol copolymer resins, C5 / vinylaromatic cut copolymer resins, C9 / vinylaromatic cut copolymer resins, and mixtures of these resins.
  • pene here combines in a known manner the alpha-pinene, beta-pinene and limonene monomers; preferably, a limonene monomer is used which is present in a known manner in the form of three possible isomers: L-limonene (laevorotatory enantiomer), D-limonene (dextrorotatory enantiomer), or the dipentene, racemic of the dextrorotatory and levorotatory enantiomers. .
  • Suitable vinylaromatic monomers are, for example, styrene, alpha-methylstyrene, ortho-, meta-, para-methylstyrene, vinyltoluene, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, hydroxystyrenes, vinylmesitylene, and the like. , divinylbenzene, vinylnaphthalene, any vinylaromatic monomer from a C 9 cut (or more generally from a C 8 to C 10 cut).
  • the vinyl-aromatic compound is styrene or a vinylaromatic monomer derived from a C 9 cut (or more generally from a C 8 to C 10 cut).
  • the vinylaromatic compound is the minor monomer, expressed as a mole fraction, in the copolymer under consideration.
  • the content of hydrocarbon resin is preferably between 3 and 60 phr, more preferably between 3 and 40 phr, especially between 5 and 30 phr.
  • the level of total plasticizer i.e., liquid plasticizer plus, where appropriate, solid hydrocarbon resin
  • non-black reinforcing filler must be understood here any inorganic or organic filler other than carbon black, regardless of its color (other than black) and its origin (natural or synthetic), sometimes called “mineral” filler “white charge” or “clear” charge as opposed to carbon black, which non-black charge is capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition for manufacturing a tire tread, in other words able to replace, in its reinforcing function, a conventional tire grade carbon black for tread; such a filler is generally characterized, in known manner, by the presence of functional groups, in particular hydroxyl groups, at its surface, thereby requiring the use of a coupling agent intended to ensure a stable chemical bond between the diene elastomer and said charge.
  • the non-black reinforcing filler is an inorganic filler, more particularly a filler of the siliceous or aluminous type, or a mixture of these two types of filler.
  • the silica (SiO 2 ) used may be any reinforcing silica known to those skilled in the art, in particular any precipitated silica or pyro-hindered silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
  • Highly dispersible precipitated silicas are preferred, in particular when the invention is used for the manufacture of tires having a low rolling resistance; examples of such silicas are Ultrasil 7000 silicas from Degussa, Zeissil 1165 MP, 1135 MP and 1115 MP silicas from Rhodia, Hi-Sil EZ150G silica from PPG, Zeopol 8715 silicas, 8745 or 8755 of the Huber Company, the silicas as described in the application WO 03/016387.
  • the reinforcing alumina (Al 2 O 3) preferably used is a highly dispersible alumina having a BET surface area ranging from 30 to 400 m 2 / g, more preferably from 60 to 250 m 2 / g, an average particle size of at most 500 nm. more preferably at most equal to 200 nm.
  • Such reinforcing aluminas mention may in particular be made of "Baikalox Al 25" or "CRI 25" aluminas (Baikowski company), "APA-100RDX” (Congrua), "Aluminoxid C” (Degussa) or "AKP- G015 (Sumitomo Chemicals).
  • inorganic filler suitable for use in the rubber compositions of the invention mention may also be made of aluminum (oxide) hydroxides, aluminosilicates, titanium oxides, carbides or nitrides of silicon, all of the reinforcing type as described for example in the applications WO 99/28376, WO 00/73372, WO 02/053634, WO 2004/003067, WO 2004/056915.
  • the non-black reinforcing filler used in particular if it is a reinforcing inorganic filler such as silica, preferably has a BET surface area between 60 and 350 m2 / g.
  • An advantageous embodiment of the invention consists in using a non-black filler, in particular a reinforcing inorganic filler such as silica, having a high BET specific surface area, in a range of 130 to 300 m 2 / g, because of of the high reinforcing power recognized such charges.
  • a non-black filler having a BET specific surface area of less than 130 m 2 / g, preferably in such a case between 60 and 130 ⁇ / g (see for example WO03 / 002648 and WO03 / 002649 applications cited above).
  • non-black reinforcing filler is indifferent whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
  • non-black reinforcing filler is also understood to mean mixtures of different non-black reinforcing fillers, in particular inorganic fillers such as highly dispersible siliceous and / or aluminous fillers as described above.
  • such a reinforcing inorganic filler consists of nanoparticles whose average mass size is less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 ⁇ .
  • This average size can be measured in a well-known manner, after dispersion by ultrasonic deagglomeration of the load to be analyzed in water (or aqueous solution containing a surfactant), for example by means of a centrifugal sedimentometer with X-ray detection type "XDC” (X-rays Disk Centrifuge), marketed by Brookhaven Instruments, according to the following procedure: a suspension of 3.2 g of inorganic filler sample to be analyzed in 40 ml of water, by action for 8 minutes, at 60% power (60% of the maximum position of the "output control"), a 1500 W ultrasound probe (3/4 "Vibracell soniflator marketed by Bioblock); after sonification, 15 ml of the suspension is introduced into the rotating disc; after sedimentation for
  • the BET surface area is determined in a known manner by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society” Vol. 60, page 309, February 1938, more precisely according to the French standard NF ISO 9277 of December 1996 (multipoint volumetric method (5 points) - gas: nitrogen - degassing: 1 hour at 160 ° C. - relative pressure range p / po: 0.05 to 0.17).
  • the CTAB specific surface is the external surface determined according to the French standard NF T 45-007 of November 1987 (method B).
  • carbon black could be used if it were covered with a non-black layer, in particular inorganic such as silica, having on its surface functional sites (especially hydroxyl) in known manner requiring the use of a coupling agent to establish the bond between the filler (the surface of its particles) and the diene elastomer.
  • a non-black layer in particular inorganic such as silica, having on its surface functional sites (especially hydroxyl) in known manner requiring the use of a coupling agent to establish the bond between the filler (the surface of its particles) and the diene elastomer.
  • the non-black reinforcing filler is a reinforcing inorganic filler, more preferably silica.
  • the level of non-black reinforcing filler in particular of silica, is between 60 and 120 phr, in particular between 70 and 100 phr.
  • a bifunctional coupling agent intended to ensure a sufficient chemical and / or physical connection between the charge (surface of its particles) and the diene elastomer.
  • bifunctional organosilanes or 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 or groups -C IC8 arylene C 6 -C 2, especially in Cl- Cio alkylene, in particular C 1 -C 4, particularly propylene);
  • the radicals R 1 which may be substituted or unsubstituted, which are identical to or different from one another, represent a Ci-C18 alkyl, C 5 -C 8 cycloalkyl or C 6 -C 18 aryl group (preferably C 1 -C 8 alkyl groups); C 6 , cyclohexyl or phenyl, especially C 1 -C 4 alkyl groups, more particularly methyl and / or ethyl).
  • the R radicals substituted or unsubstituted, identical or different, represent an alkoxyl group Ci-Cig cycloalkoxy or C 5 -C 8 (preferably a group selected from Ci-Cg alkoxyls and C 5 cycloalkoxyls -C 8 , more preferably still a group selected from C 1 -C 4 alkoxyls, in particular methoxyl and ethoxyl).
  • 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 2 and 12 phr, more preferably between 3 and 8 phr.
  • the rubber composition of the tread of the tire of the invention is devoid of carbon black or has less than 3 phr, in order to prevent carbon black from playing, because of its anti-UV properties. known, an antagonistic role therefore undesirable compared to the photocrosslinking of the photocurable liquid polymer resin.
  • carbon black is used in a very small amount, between 0.05 and 2.0 phr, in particular between 0.05 and 1.5 phr, a narrow concentration range in which the black retains its function of black coloration of the composition but no longer fills that of anti-UV agent.
  • Suitable carbon blacks are all carbon blacks capable of bringing a black color to the rubber compositions, in particular blacks of the HAF, ISAF and SAF type known to those skilled in the art and conventionally used in tires.
  • the reinforcing carbon blacks of the series (ASTM grades) 100, 200 or 300 used in the treads of these tires for example NI 15, N134, N234, N326, N330, N339, N347, N375
  • those of the non-reinforcing (because less structured) type of the higher series 400 to 700 for example the blacks N660, N683, N772.
  • Non-reinforcing blacks called "ink blacks" used as black pigments in printing inks and paints could also be used as examples.
  • the carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used.
  • the heart of the present invention lies in the use of a photocurable liquid polymer resin in the rubber composition forming at least the surface or extreme surface of the tread of the invention, that is to say the portion of the tread which is intended to come into contact with the road during the rolling of the tire.
  • This polymer may be an oligomer, a prepolymer, a homopolymer or a copolymer. Its essential characteristic is that it is on the one hand liquid (at ambient temperature, ie 23 ° C) in the non (photo) crosslinked state and on the other functionalized that is to say carrying one or several groups or functions crosslinkable (polymerizable) under the action of UV radiation. The consequence is a hardening of the rubber matrix comprising this type of polymer, when this matrix, at least its surface, is exposed to UV.
  • this polymer is an oligomer, typically having 3 to 20 monomer units.
  • the number of functions capable of reacting under the action of UV is preferably within a range of 1 to 4 per oligomeric hydrocarbon backbone.
  • the crosslinkable function or functions are more preferably in the telechelic position, that is to say at the ends of said oligomeric hydrocarbon backbone.
  • a photocrosslinkable resin of the radical type (radical polymerizing) or cationic (cationic polymerizing) type is used. More preferably, the photocrosslinkable resin is chosen from the group consisting of acrylate, methacrylate, epoxy, oxetane, unsaturated polyester, vinyl ether, vinylester resins, and mixtures thereof. Such denominations refer in a well-known manner to the nature of the photo-crosslinkable (or photo-polymerizable) functional groups carried by the polymer (or preferably oligomer) constituting the hydro-carbon skeleton of these resins.
  • the photocrosslinkable resin used is an acrylate resin (for example, monoacrylate, diacrylate, triacrylate, epoxy-acrylate, epoxy-diacrylate, urethane-acrylate, urethane-diacrylate) or a methacrylate resin (for example: monomethacrylate, diamethacrylate, urethane-monomethacrylate, urethane-dimethacrylate).
  • an acrylate resin for example, monoacrylate, diacrylate, triacrylate, epoxy-acrylate, epoxy-diacrylate, urethane-acrylate, urethane-diacrylate
  • a methacrylate resin for example: monomethacrylate, diamethacrylate, urethane-monomethacrylate, urethane-dimethacrylate.
  • fumarate resins for example monofumarate, difumarate
  • maleate for example monomaleate, dimaleate
  • mixtures of such resins include fumarate resins (for example monofumarate, difumarate), maleate (for example monomaleate, dimaleate), and mixtures of such resins.
  • the liquid polymer or oligomer constituting the resin is a diene-type polymer; in particular, this diene polymer, by liquid definition, is a polybutadiene or polyisoprene bearing the photo-crosslinkable functional group.
  • the photocurable liquid polymer resin is a poly (butadiene-acrylate) or a poly (butadiene-methacrylate) or a mixture of both.
  • the weight average mass (denoted Mw) of the liquid polymer described above, in particular when it is a liquid diene polymer, is preferably between 200 and 5000 g / mol.
  • This size is well known to those skilled in the art, available especially from polymer suppliers, also measurable by conventional techniques such as GPC ("Gel Permeation Chromatography") or SEC ("Size Exclusion Chromatography”).
  • GPC Gel Permeation Chromatography
  • SEC Size Exclusion Chromatography
  • the sample to be analyzed is simply solubilized beforehand in a suitable solvent, for example tetrahydrofuran at a concentration of 1 g / liter. Then the solution is filtered on a filter, for example porosity 0.45 ⁇ , before injection into the apparatus.
  • a suitable solvent for example tetrahydrofuran at a concentration of 1 g / liter.
  • the equipment used is for example a graphic chromato chain "Waters alliance”.
  • the elution solvent is for example tetrahydrofuran
  • the flow rate is 0.7 ml / min
  • the system temperature is 35 ° C.
  • a set of 4 "Waters" columns in series decominations "Styragel HMW7", “Styragel HMW6E", and two "Styragel HT6E" are used.
  • the injected volume of the solution of the polymer sample is for example 100 ⁇ .
  • the detector is a differential refractometer (for example "Waters 2410") that can be equipped with associated data exploitation software (for example “Waters Millenium”).
  • a Moore calibration is conducted with a series of low Ip (less than 1.2) polystyrene commercial standards of known molar masses covering the field of masses to be analyzed.
  • the rubber composition may also comprise, in combination with the photo-crosslinkable liquid polymer resin previously described, a photoinitiator intended to promote, accelerate the process of surface photocrosslinking of the tread when the latter is exposed to UV radiation. .
  • the photoinitiators are stable compounds able to release, when exposed to a light of appropriate wavelength, radical or ionic species which will favor and accelerate photocrosslinking or photooxidation processes.
  • These usable photoinitiators are preferably of the radical or cationic type. Such compounds are commonly used in the fields of photopolymerization of multifunctional monomers, surface treatment of materials with protective coatings, graphic arts and electronics for the production of microcircuits. They have also been described (see patent application WO 2006/077059) in treads of photo-oxidizable tires having improved adhesion on a wet road.
  • cationic initiators are onium salts, more particularly sulphonium salts such as triarylsulphonium salts or iodonium salts such as diaryliodonium salts.
  • a photoinitiator of the radical type is preferably used, in particular those chosen from the group consisting of benzal ketals (especially diketals), benzoins (in particular benzoin ethers) and ⁇ , ⁇ -dialkoxy. acetophenones, ⁇ -hydroxyalkylphenones, ⁇ -aminoaromatic ketones (or ⁇ -aminoalkylphenones), acylphosphine oxides, benzophenones or thioxanthones in combination with a hydrogen donor (eg, a tertiary amine), and mixtures of such compounds.
  • a hydrogen donor eg, a tertiary amine
  • photoinitiator adjusts the amount of photoinitiator according to the particular applications targeted. This amount is preferably between 0.1 and 10 phr, more preferably between 0.2 and 5 phr.
  • the photoinitiators previously described may be used alone when exposed to UV radiation or, when exposed to visible light, in combination with photo sensitizers capable of activating their own photo-oxidant action.
  • Such sensitizing photos are, for example, dyes such as phthalenes (eosin, erythrosine, ethyl eosin, phloxine, bengal rose) and thiazines (thionine and methylene blue).
  • the photoinitiators will preferably be chosen in such a way that their UV absorption spectrum and the emission spectrum of the light source (whether natural or artificial) responsible for photooxidation. of the tread, have a recovery zone. 4.5.
  • the photoinitiators will preferably be chosen in such a way that their UV absorption spectrum and the emission spectrum of the light source (whether natural or artificial) responsible for photooxidation. of the tread, have a recovery zone. 4.5.
  • the rubber compositions used in the treads according to the invention may also comprise all or part of the usual additives normally used in elastomer compositions intended for the manufacture of treads for tires, in particular for winter tires, for example protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, reinforcing resins, acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M), a crosslinking system based on either sulfur, or sulfur and / or peroxide and / or bismaleimide donors, vulcanization accelerators, vulcanization activators.
  • protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, reinforcing resins, acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M), a crosslinking system based on either sulfur, or sulfur and / or peroxide and / or bismaleimide donors, vulcanization accelerators
  • compositions may also contain coupling activators when a coupling agent is used, inorganic filler recovery agents or, more generally, processing aid agents that are capable in a known manner, by means of an improvement of the dispersion of the filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to implement in the green state; these agents are for example hydrolysable silanes such as alkyl-alkoxysilanes, polyols, polyethers, amines, hydroxylated or hydrolysable polyorganosiloxanes.
  • coupling activators when a coupling agent is used
  • inorganic filler recovery agents or, more generally, processing aid agents that are capable in a known manner, by means of an improvement of the dispersion of the filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to implement in the green state
  • these agents are for example hydrolysable silanes such as alkyl-alkoxysilane
  • the rubber compositions 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 a "non-productive" phase) at high temperature, up to a maximum temperature between 130 ° C and 200 ° C, preferably between 145 ° C and 185 ° C, followed by a second phase of mechanical work (sometimes called “productive" phase) at a lower temperature, typically less than 120 ° C, for example between 60 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system or vulcanization.
  • a first phase of work or thermomechanical mixing sometimes referred to as a "non-productive" phase
  • a second phase of mechanical work sometimes called “productive” phase
  • a method that can be used for the manufacture of such compositions, capable of exhibiting, after photooxidation of their surface, an improved adhesion on ice comprises for example and preferably the following steps: - Incorporate into the diene elastomer (or the diene mixture) diene elastomers), in a mixer, more than 30 phr of a liquid plasticizer, between 50 and 150 phr of a non-black reinforcing filler, optionally carbon black at a rate of less than 3 phr, between 5 and 50 phr of a photocrosslinkable liquid polymer resin, by thermomechanically kneading the whole, in one or more times, until a maximum temperature of between 130 ° C. and 200 ° C. is reached; cool the assembly to a temperature below 100 ° C;
  • 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.
  • a primary vulcanization accelerator in particular a sulfenamide type accelerator.
  • various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives (especially diphenylguanidine), etc.
  • the sulfur content is preferably between 0.5 and 3.0 phr, that of the primary accelerator is preferably between 0.5 and 5.0 phr.
  • accelerator any compound capable of acting as accelerator for vulcanization of diene elastomers in the presence of sulfur, in particular thiazole-type accelerators and their derivatives, accelerators of the thiuram type, zinc dithiocarbamates.
  • accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated “CBS”), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (“DCBS”) , N-tert-butyl-2-benzothiazylsulfenamide (“TBBS”), N-tert-butyl-2-benzothiazylsulfenimide (“TBSI”), zinc dibenzyldithiocarbamate (“ZBEC”) and mixtures thereof.
  • MBTS 2-mercaptobenzothiazyl disulfide
  • CBS N-cyclohexyl-2-benzothiazyl sulfenamide
  • DCBS N-dicyclohexyl-2-benzothiazyl sulfenamide
  • TBBS N
  • 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, for example in the form of a rubber profile that can be used directly as a strip of tire rolling.
  • 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.
  • a final step of photo-oxidation of the surface of the tread gives the latter improved adhesion on dry ice as on melting ice.
  • This complementary step may consist of a simple natural exposure to UV-visible radiation or preferably an accelerated artificial aging, for example using one or more lamp (s) emitting in the UV-visible (eg steam lamp mercury, xenon lamp, fluorescent lamp, metal halide lamps), or in an accelerated photoaging chamber which may comprise one or more of said lamps.
  • the rubber composition described above may constitute all or only a part of the tread of the tire according to the invention, in the case of a tread of composite type which would be formed of several rubber compositions of different formulations, it being understood that, in this second case, the previously described composition based on the photocurable liquid polymer resin, is that constituting the surface or extreme surface of the tread portion intended to come into contact with the ground (ice) during the rolling of the tire, in new condition as during its subsequent use.
  • the reinforcing inorganic filler (silica), its associated coupling agent, is introduced successively into an internal mixer, the initial vessel temperature of which is approximately 60 ° C. carbon, the liquid plasticizer, the photocurable liquid polymer resin in the case of the invention, 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 thin sheets or sheets of rubber for the measurement of their physical or mechanical properties, or extruded in the form of treads of winter tires for passenger vehicles.
  • Mooney plasticity using an oscillating consistometer as described in the French standard NF T 43-005 (November 1980).
  • the Mooney plasticity measurement is carried out according to the following principle: the raw composition (i.e., before firing) is molded in a cylindrical chamber heated to 100 ° C. After one minute of preheating, the rotor rotates within the test tube at 2 revolutions / minute and the useful torque is measured to maintain this movement after 4 minutes of rotation.
  • Shore A hardness The Shore A hardness of the compositions after curing is assessed according to ASTM D 2240-86;
  • dynamic properties they are measured on a viscoanalyzer (Metravib VA4000), according to the ASTM D5992-96 standard.
  • the response of a sample of vulcanized composition (cylindrical specimen with a thickness of 4 mm and a section thickness of 400 mm 2 ) is recorded, subjected to a sinusoidal stress in alternating simple shear, at a frequency of 10 Hz; during a temperature sweep under a fixed stress of 0.7 MPa, the value of tan ( ⁇ ) observed at 60 ° C. is recorded. It is recalled that this value of tan ( ⁇ ) at 60 ° C is representative of the hysteresis of the material and therefore of the rolling resistance (the lower it is, the lower the hysteresis).
  • Tables 1 and 2 give the formulation of the two compositions (Table 1 - rate of the various products expressed in phr), their properties before and after curing (30 min at 150 ° C.); the vulcanization system is sulfur and sulfenamide.
  • Composition C-1 is the reference composition, it comprises 80 phr of silica, 5 phr of carbon black and 60 phr of liquid plasticizer, conventionally used as tread of tires of the "studless” type; it is devoid of photocurable liquid polymer resin.
  • the composition C-2 is the composition according to the invention. It is distinguished from the control composition C-1 by the addition of 10 phr of photocrosslinkable liquid polymer resin (Mw equal to about 1000 g / mol) which, combined with a very low level of carbon black (1 phr), possesses a high photo-crosslinking capability which is assumed to be a posteriori - at least that is what the following rolling tests seem to show - as being particularly favorable for ice adhesion.
  • the level of liquid plasticizer was adjusted in the composition of the invention C-2 in order to maintain the rigidity at the same level as that of the control composition C-1 (Shore A hardness equal to about 52): in a known manner, identical rigidity is the necessary condition for a rigorous comparison of ice driving performance.
  • compositions C1 and C-2 previously tested are then used as treads for winter tire tires with a radial carcass, denoted respectively P-1 (control tires) and P-2 (tires in accordance with the invention), of dimensions 205 / 65 RI 5 conventionally manufactured and in all respects identical, except the rubber compositions constitutive of their tread. All tires are mounted at the front and rear of a motor vehicle, under rated inflation pressure, and are first run on a circuit (about 2000 km), on dry ground , for break-in and start of wear.
  • the tires P-1 and P-2 are then subjected to a UV treatment (natural exposure to ultraviolet radiation) of a duration of three days to stiffen the surface, at least the extreme surface, of their tread by photocrosslinking of the liquid polymer resin.
  • a UV treatment naturally exposure to ultraviolet radiation
  • the tires were exposed to the outside, in a static position, in a south orientation, these tires being rotated around their axis by 1/3 of a turn each day, so as to expose their tire strip. rolling in a homogeneous way.
  • - braking on ice one measures the distance necessary to pass from 20 to 5 km / h during sudden longitudinal braking (activated ABS) on an ice-covered runway. A value greater than that of the control, arbitrarily set at 100, indicates an improved result, that is to say a shorter braking distance;

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WO2015090974A1 (fr) 2013-12-19 2015-06-25 Compagnie Generale Des Etablissements Michelin 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
WO2015090975A1 (fr) 2013-12-19 2015-06-25 Compagnie Generale Des Etablissements Michelin Pneu dont la bande de roulement comporte des elements de sculpture avec des parois laterales rigides contenant des microparticules hydrosolubles
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WO2015090976A1 (fr) 2013-12-19 2015-06-25 Compagnie Generale Des Etablissements Michelin Pneu dont la bande de roulement comporte des elements de sculpture avec des parois laterales rigides comportant des microparticules d'oxyde ou carbure metallique
WO2015090974A1 (fr) 2013-12-19 2015-06-25 Compagnie Generale Des Etablissements Michelin 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
WO2015090975A1 (fr) 2013-12-19 2015-06-25 Compagnie Generale Des Etablissements Michelin Pneu dont la bande de roulement comporte des elements de sculpture avec des parois laterales rigides contenant des microparticules hydrosolubles
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
EP3234001A4 (en) * 2014-12-15 2018-05-30 Compagnie Générale des Etablissements Michelin A snow tire having a tread comprising a 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

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