EP1915422A1 - Plasticizing system for a rubber composition - Google Patents

Plasticizing system for a rubber composition

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Publication number
EP1915422A1
EP1915422A1 EP06776284A EP06776284A EP1915422A1 EP 1915422 A1 EP1915422 A1 EP 1915422A1 EP 06776284 A EP06776284 A EP 06776284A EP 06776284 A EP06776284 A EP 06776284A EP 1915422 A1 EP1915422 A1 EP 1915422A1
Authority
EP
European Patent Office
Prior art keywords
phr
composition according
composition
resin
terpene
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Withdrawn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
EP06776284A
Other languages
German (de)
French (fr)
Inventor
Pierre Robert
Stéphanie DE LANDTSHEER
Jean-Michel Favrot
Garance Lopitaux
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
Michelin Recherche et Technique SA France
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, Michelin Recherche et Technique SA France, Societe de Technologie Michelin SAS filed Critical Michelin Recherche et Technique SA Switzerland
Publication of EP1915422A1 publication Critical patent/EP1915422A1/en
Withdrawn legal-status Critical Current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
    • 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
    • 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
    • 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
    • C08K5/01—Hydrocarbons
    • 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

Definitions

  • the present invention relates to rubber compositions intended in particular for the manufacture of tires or semi-finished products for tires, it relates more particularly to the plasticizer systems used for the plasticization of such compositions.
  • the tire rubber compositions comprise in a known manner plasticizing agents used for the preparation or synthesis of certain diene elastomers, to improve the implementation (or "processability") of said compositions in the green state, as well as some of their properties.
  • use in the fired state such as, for example, in the case of treads of tires, their adhesion on wet ground or their resistance to abrasion and cuts.
  • DAE oils for "Distillate Aromatic Extracts”
  • MES for “Medium Extracted Solvates”
  • TDAE Treated Distillate Aromatic Extracts
  • “Chipping” ("chipping” or “scaling" is a known mechanism of damage which corresponds to superficial lamellar tearing - in the form of flakes - of the "gum” (or rubber composition) constituting the treads, under certain aggressive driving conditions.
  • This problem is particularly encountered on tires for off-the-road vehicles or construction site or civil engineering, having to ride on different types of soil, for some stony and relatively aggressive; For example, it has been described, as well as some remedies, in EP-A-0 030 579 (or AU-A-6429780) and FR-A-2 080 661 (or GB-AI 343 487).
  • the invention also relates to a method for preparing a rubber composition having improved abrasion and cut resistance, this composition being based on a diene elastomer, a reinforcing filler, a plasticizer system and of a crosslinking system, said method comprising the following steps:
  • the invention also relates, in itself, to a plasticizer system useful for plasticizing a diene rubber composition, said system comprising in combination a MES or TDAE oil and a terpene / vinylaromatic copolymer resin, as well as the use of such a system for plasticizing a diene rubber composition.
  • the invention also relates to the use of a composition according to the invention for the manufacture of a finished article or a semi-finished rubber product for any tire or tire / motor vehicle connection system such as internal safety support for tire, wheel, rubber spring, elastomeric joint, other suspension element and anti-vibration.
  • the subject of the invention is particularly the use of a composition according to the invention for the manufacture of tires or semi-finished rubber products intended for these tires, these semi-finished products being preferably chosen from the group consisting of treads, crown reinforcement plies, sidewalls, carcass reinforcement plies, beads, guards, underlayments, rubber blocks and other internal rubbers, in particular decoupling erasers, intended to provide the connection or interface between the aforementioned zones of the tires.
  • the invention more particularly relates to the use of a composition according to the invention for the manufacture of a tire tread having improved resistance to cuts and peeling.
  • the invention also relates to finished articles and semi-finished products of rubber themselves, in particular tires and semi-finished products for tires, when they comprise an elastomeric composition according to the invention.
  • the tires according to the invention are particularly intended for passenger vehicles such as two-wheeled vehicles (motorcycles, bicycles), industrial vehicles chosen from vans, "heavy trucks” - ie, metro, buses, road transport vehicles (trucks tractors, trailers), off-the-road vehicles -, agricultural or civil engineering machinery, airplanes, other transport or handling vehicles.
  • composition according to the invention which can be used in particular for the manufacture of a tire or a tire tread, is based on at least one diene elastomer, a reinforcing filler, a crosslinking system and a system specific plasticizer.
  • composition based on is meant a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being 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.
  • elastomer or “diene” rubber it is to be understood in a known way (one or more elastomers), at least in part (ie, a homopolymer or a copolymer) of diene monomers (monomers bearing two carbon-to-carbon double bonds). , conjugated or not).
  • diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”.
  • the term “essentially unsaturated” is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%);
  • diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated” diene elastomers ( low or very low diene origin, always less than 15%).
  • 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%.
  • iene elastomer can be understood more particularly to be used in the compositions according to the invention:
  • diene elastomer any type of diene elastomer
  • the person skilled in the tire art will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b). ) above.
  • 1,3-butadiene, 2-methyl-1,3-butadiene and 2,3-di (C 1 -C 5 alkyl) -1,3-butadienes such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl- 1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
  • Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.
  • the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units.
  • the elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used.
  • 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.
  • Suitable polybutadienes and in particular those having a content in units -1.2 of between 4% and 80% or those having a content of cis-1,4 greater than 80%, polyisoprenes, butadiene-styrene copolymers and in especially those having a styrene content of between 5% and 50% by weight and more particularly between 20% and 40%, a 1,2-butadiene content of the butadiene part of between 4% and 65%, a content of trans-1,4 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) from -40 ° C to -80 ° C, the isoprene-styrene copolymers and especially those having a styrene content of between 5% and 50% by weight and a Tg 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 of the composition according to the invention is preferably selected from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated as "BR"), polyisoprenes (IR) and natural rubber (NR). , butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
  • BR polybutadienes
  • IR polyisoprenes
  • NR natural rubber
  • butadiene copolymers isoprene copolymers 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) and isoprene-copolymers.
  • SBR butadiene-styrene
  • the diene elastomer is predominantly (that is to say for more than 50 phr) an SBR, whether it is a SBR prepared in emulsion ("E-SBR") or a SBR prepared in solution (“S-SBR”), or a blend (mixture) SBR / BR, SBR / NR (or SBR / IR), or BR / NR (or BR / IR).
  • E-SBR SBR prepared in emulsion
  • S-SBR SBR prepared in solution
  • an SBR elastomer use is made in particular of an SBR having a styrene content of between 20% and 30% by weight, a vinyl bond content of the butadiene part of between 15% and 65%, a bond content of trans-1,4 between 15% and 75% and a Tg of between -20 ° C and -55 ° C; such an SBR can be advantageously used in admixture with a BR preferably having more than 90% cis-1,4 bonds.
  • the diene elastomer is predominantly (for more than 50 phr) an isoprene elastomer.
  • the compositions of the invention are intended to constitute, in tires, the rubber matrices of certain treads (for example for industrial vehicles), crown reinforcing plies (for example work webs, protective webs or hoop webs), carcass reinforcement plies, flanks, beads, protectors, underlayments, rubber blocks and other internal gums providing the interface between aforementioned areas of the tires.
  • isoprene elastomer in known manner a homopolymer or copolymer of isoprene, in other words a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), different isoprene copolymers and mixtures of these elastomers.
  • NR natural rubber
  • IR synthetic polyisoprenes
  • isobutene-isoprene copolymers butyl rubber-HR
  • isoprene-styrene copolymers SIR
  • isoprene-butadiene copolymers BIR
  • isoprene-butadiene-styrene copolymers SBIR
  • This isoprene elastomer is preferably natural rubber or synthetic cis-1,4 polyisoprene; of these synthetic polyisoprenes, polyisoprenes having a content (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used.
  • the composition according to the invention may contain less than an essentially saturated diene elastomer, in particular at least one EPDM copolymer or a butyl rubber (optionally chlorinated or brominated), that these copolymers are used alone or in admixture with highly unsaturated diene elastomers as mentioned above, in particular NR or IR, BR or SBR.
  • the rubber composition comprises a blend of one (or more) diene elastomers called "high Tg” having a Tg between -65 ° C and -10 0 C and of a (one or more) diene elastomer called "at low Tg” between -HO 0 C and -80 0 C, more preferably between -105 0 C and -80 0 C.
  • the high Tg elastomer is chosen from preferably in the group consisting of S-SBR, E-SBR, natural rubber, synthetic polyisoprenes (having a level of cis-1,4 chains preferably greater than 95%), BIRs, SIRs, SBIR, and mixtures of these elastomers.
  • the low Tg elastomer preferably comprises butadiene units at a content of at least 70%; it consists preferably of a polybutadiene (BR) having a degree of cis-1,4 chains higher than 90%.
  • the rubber composition comprises, for example, from 40 to 100 phr, in particular from 50 to 100 phr, of a high Tg elastomer in a blend with 0 to 60 phr, in particular 0 to 50 phr of a low Tg elastomer, for example 100 phr of one or more copolymers of styrene and butadiene prepared in solution.
  • the diene elastomer of the composition according to the invention comprises a blend of a BR (as low elastomer Tg) having a rate of cis-1,4 linkages. greater than 90%, with S-SBR or E-SBR (as high elastomer Tg).
  • compositions of the invention may contain a single diene elastomer or a mixture of several diene elastomers, wherein the diene elastomer (s) may be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers.
  • reinforcing filler known for its capacity 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 with a coupling agent.
  • Carbon blacks are suitable for all carbon blacks, in particular blacks of the HAF, ISAF, SAF type conventionally used in tires (so-called pneumatic grade blacks).
  • the reinforcing carbon blacks of the 100, 200 or 300 series for example blacks Nl 15, N134, N234, N326, N330, N339, N347 or N375, or else, according to the targeted applications, the blacks of higher series (for example N660, N683, N772).
  • any inorganic or mineral filler (regardless of its color and origin (natural or synthetic), also called “white” filler, “clear” filler or “non-black load”, as opposed to carbon black, capable of reinforcing on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires, in particular other words capable of replacing, in its reinforcing function, a conventional carbon black of pneumatic grade, such a charge is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
  • -OH hydroxyl groups
  • the physical state in which the reinforcing inorganic filler is present is indifferent whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
  • the term "reinforcing inorganic filler” also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.
  • Suitable reinforcing inorganic fillers are, in particular, 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
  • HD highly dispersible precipitated silicas
  • Ultrasil 7000 and Ultrasil 7005 silicas from Degussa
  • Hi-SiI silica EZ150G from PPG
  • Zeopol 8715, 8745 and 8755 silicas from Huber high surface area silicas as described in application WO 03/16837 .
  • reinforcing aluminas examples include the "Baikalox”"A125” or “CR125” aluminums from the Baikowski company, "APA-100RDX” from Condea, "Aluminoxid C” from Degussa or “AKP-GOl 5" from Sumitomo Chemicals.
  • inorganic filler By way of other examples of inorganic filler that may be used, mention may be made of aluminum (oxide) hydroxides, titanium oxides or reinforcing silicon carbides (see, for example, application WO 02/053634 or US 2004 / 030,017).
  • the reinforcing inorganic filler used in particular if it is silica, preferably has a BET surface area of between 45 and 400. m 2 / g, more preferably between 60 and 300 m 2 / g.
  • the content of total reinforcing filler is between 20 and 200 phr, more preferably between 30 and 150 phr, the optimum being in a known manner different according to the specific applications referred to.
  • the level of reinforcement expected on a bicycle tire is of course lower than that required on a tire capable of running at high speed in a sustained manner, for example a motorcycle tire, a tire for a passenger vehicle or for a commercial vehicle such as Heavyweight.
  • an at least bifunctional coupling agent is used in known manner to ensure a sufficient chemical and / or physical connection between the inorganic filler ( surface of its particles) and the diene elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
  • 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).
  • n is an integer of 2 to 8 (preferably 2 to 5);
  • - A is a divalent hydrocarbon radical (preferably C 1 -C 18 alkylene or arylene groups groups C 6 -C 2, especially alkylenes CpCio, including Ci-C 4, especially propylene);
  • radicals R 1 substituted or unsubstituted, identical or different, represent an alkyl group Ci-8 cycloalkyl, C 5 -C] 8 aryl or C 6 -C 8 (preferably alkyl C 1 -C 6 , cyclohexyl or phenyl, especially C 1 -C 4 alkyl groups, more particularly methyl and / or ethyl).
  • radicals R 2 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).
  • n is a fractional number preferably between 2 and 5, more preferably close to 4.
  • silane polysulfides are more particularly the bis (mono, trisulfide or tetrasulfide) of bis (alkoxyl (Ci-C4) alkyl (Ci -C 4) SiIyI- alkyl (Ci-C 4) ), such as polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl).
  • TESPT bis (3-triethoxysilylpropyl) tetrasulfide
  • TESPD bis (3-triethoxysilylpropyl) tetrasulfide
  • TESPD bis-disulfide ( triethoxysilylpropyl)
  • polysulfides in particular disulfides, trisulphides or tetrasulfides
  • bis- (monoalkoxyl (Ci-C 4 ) -dialkyl (Ci-C 4 ) silylpropyl) more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide.
  • the content of coupling agent is preferably between 4 and 12 phr, more preferably between 3 and 8 phr.
  • the coupling agent could be grafted beforehand on the diene elastomer or on the reinforcing inorganic filler. However, it is preferred, especially for reasons of better implementation of the compositions in the green state, to use the coupling agent is grafted onto the reinforcing inorganic filler, or in the free state (i.e., ungrafted).
  • MES and TDAE oils are well known to those skilled in the art, see for example the recent publication KGK (Kautschuk für Kunstoffe) 52. Jahrgang, Nr. 12/99, pp. 799-805, entitled "Safe Process Oils for Tires with Low Environmental Impact”.
  • Patent applications describing the use of such oils in substitution of conventional aromatic oils are, for example, EP-A1 179 560 (or US2002 / 0045697) or EP-A1 270 657.
  • MES oils are well known to those skilled in the art, see for example the recent publication KGK (Kautschuk Gummi Kunstoffe) 52. Gonzgang, Nr. 12/99, pp. 799-805, entitled "Safe Process Oils for Tires with Low Environmental Impact”.
  • Patent applications describing the use of such oils in substitution of conventional aromatic oils are, for example, EP-A1 179 560 (or US2002 / 0045697) or EP-A1 270 657.
  • MES oils are well known to those skilled in the art, see for example
  • resins are well known; they have been mainly used until now for their application as tackifiers in the food industry, or as plasticizers or processing aids in rubber tire compositions.
  • Suitable vinylaromatic monomers are, for example, styrene, ortho-, meta-, para-methylstyrene, vinyl-toluene, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.
  • the vinyl aromatic compound is styrene.
  • pene here combines in a known manner the alpha-pinene, beta-pinene and limonene monomers.
  • a limonene monomer is used which is 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. .
  • a monomer mixture consisting of 196 g of styrene and 204 g of limonene (or 4-isopropenyl-1-methyl-1-cyclohexene, Fluka product, purity> 99%) is added to the suspension dropwise for 5 minutes. .
  • the temperature of the reaction medium increases to 58 ° C. After polymerization for 15 minutes, the reaction is quenched with 250 ml of deionized water.
  • the content of terpene / vinylaromatic copolymer resin must be between 5 and 35 phr. Below the minimum indicated, the technical effect targeted is insufficient, whereas beyond 35 phr, the stickiness of the compositions in the green state, on the mixing tools, becomes unacceptable from the industrial point of view. For this reason, this level of resin is preferably between 5 and 25 phr, more preferably between 5 and 20 phr.
  • That of the MES or TDAE oil is preferably between 10 and 30 phr, more preferably between 10 and 25 phr, while the total plasticizer system rate of the invention comprising the MES oil and / or TDAE and the resin, is preferably between 15 and 45 phr, more preferably between 20 and 40 phr.
  • the terpene / vinylaromatic copolymer resin, in particular terpene / styrene has at least one (more preferably all) of the following preferred characteristics:
  • a Tg greater than 25 ° C (more preferably greater than 30 0 C); a number-average molecular mass (Mn) of between 400 and 2000 g / mol; a polymolecularity index (Ip) of less than 3 (booster: Ip Mw / Mn with Mw weight average molecular weight); a rate of units derived from terpene monomer (in particular limonene) and a level of units derived from vinylaromatic monomer (in particular styrene) which are each between 5% and 95% (more particularly each between 10% and 90%) ).
  • this resin has at least one (more preferably all) of the following preferred characteristics:
  • Tg of between 30 ° C. and 80 ° C. (more particularly between 35 ° C. and 60 ° C.); a molecular weight Mn of between 600 and 1500 g / mol; a polymolecularity index Ip of less than 2.5; a level of units derived from vinylaromatic monomer (in particular styrene) greater than 40% (more particularly between 40% and 90%).
  • the glass transition temperature 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 terpene / vinylaromatic copolymer is determined by steric exclusion chromatography (SEC): solvent tetrahydrofuran; temperature
  • the plasticizer system of the invention further comprises between 5 and 35 phr (more preferably between 10 and 30 phr) of an unsaturated (Ci 2 -C 22 ) fatty acid triester of glycerol, in particular a glycerol trioleate (derived from oleic acid and glycerol), present for example in the form of a vegetable oil sunflower or rapeseed.
  • glycerol unsaturated fatty acid triester of glycerol
  • a glycerol trioleate derived from oleic acid and glycerol
  • Such a triester makes it possible to minimize, in said tread, on the one hand the exudation in compression rolling of the total plasticizer system and, on the other hand, the migration of said plasticizer towards mixtures adjacent to the tread.
  • the fatty acid (or all of the fatty acids if several are present) comprises oleic acid in a mass fraction of at least 60%.
  • the overall rate of plasticizer system in the rubber composition of the The invention is preferably between 20 and 70 phr, more preferably between 30 and 60 phr.
  • the plasticizer system of the invention could also comprise other non-aromatic or very weakly aromatic plasticizing agents, for example naphthenic, paraffinic, other hydrocarbon plasticizing resins having a high Tg preferably greater than 25 ° C, in combination with the terpene / vinylaromatic copolymer resin and the MES or TDAE oil previously described.
  • non-aromatic or very weakly aromatic plasticizing agents for example naphthenic, paraffinic, other hydrocarbon plasticizing resins having a high Tg preferably greater than 25 ° C, in combination with the terpene / vinylaromatic copolymer resin and the MES or TDAE oil previously described.
  • the rubber compositions in accordance with the invention also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tires, in particular treads, such as, for example, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, antioxidants, anti-fatigue agents, reinforcing resins, acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M) as described, for example, in the US Pat. WO 02/10269 (or US 2003/212185), a crosslinking system based on either sulfur, or sulfur and / or peroxide donors and / or bismaleimides, vulcanization accelerators, vulcanization activators.
  • additives usually used in elastomer compositions intended for the manufacture of tires, in particular treads, such as, for example, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, antioxidants, anti-fatigue agents, reinforcing resins, accept
  • compositions may also contain, in addition to the coupling agents, coupling activators, inorganic charge-covering agents or, more generally, processing aids that can be used in a known manner, thanks to an improvement in the dispersion. of the charge in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to use in the green state, these agents being for example hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes.
  • hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes.
  • compositions are manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (so-called “non-productive” phase) at high temperature, up to a maximum of maximum temperature between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, followed by a second phase of mechanical work (so-called “productive” phase) to a lower temperature, typically less than 110 0 C, for example between 40 0 C and 100 0 C, finishing phase during which is incorporated the crosslinking system.
  • a first phase of work or thermomechanical mixing at high temperature, up to a maximum of maximum temperature between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C
  • a second phase of mechanical work so-called “productive” phase
  • the method according to the invention for preparing a rubber composition having improved abrasion and cut resistance comprises the following steps:
  • a MES or TDAE oil between 5 and 35 phr of a MES or TDAE oil; between 5 and 35 phr of a terpene / vinylaromatic copolymer resin (preferably terpene / styrene, in particular limonene / styrene).
  • a terpene / vinylaromatic copolymer resin preferably terpene / styrene, in particular limonene / styrene.
  • the non-productive phase is carried out in a single thermomechanical step during which all the necessary basic constituents (diene elastomer) are introduced into a suitable mixer such as a conventional internal mixer. , reinforcing filler and coupling agent if necessary, plasticizing system), then in a second step, for example after one to two minutes of kneading, the other additives, any additional coating or processing agents, with the exception of of the crosslinking system. After cooling the mixture thus obtained, it is then incorporated in an external mixer such as a roll mill, maintained at low temperature (for example between 40 0 C and 100 0 C), the crosslinking system. The whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
  • a suitable mixer such as a conventional internal mixer.
  • reinforcing filler and coupling agent if necessary, plasticizing system then in a second step, for example after one to two minutes of kneading, the other additives, any additional coating or processing agents, with the exception
  • the crosslinking system is preferably a vulcanization system based on sulfur and an accelerator.
  • Any compound capable of acting as an accelerator for vulcanization of diene elastomers in the presence of sulfur in particular those selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated “CBS”), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (abbreviated to " DCBS "), N-tert-butyl-2-benzothiazylsulfenamide (abbreviated” TBBS “), N-tert-butyl-2-benzothiazylsulfenimide (abbreviated” TBSI ”) and mixtures of these compounds.
  • a primary accelerator of the sulfenamide type is used.
  • the sulfur content is for example between 0.5 and 3.0 phr, that of the primary accelerator between 0.5 and 5.0 pce.
  • the final composition thus obtained can then be calendered, for example in the form of a sheet, a plate or extruded, for example to form a rubber profile used for the manufacture of a semi-finished tire product, such as treads, webs or other webs, underlays, various rubber blocks, reinforced or not with textile or metal reinforcements, intended to form a part of the tire structure, particularly its tread.
  • a semi-finished tire product such as treads, webs or other webs, underlays, various rubber blocks, reinforced or not with textile or metal reinforcements, intended to form a part of the tire structure, particularly its tread.
  • the vulcanization (or firing) may then be carried out in a known manner at a temperature generally of between 130 ° C. and 200 ° C., preferably under pressure, for a sufficient time which may vary, for example, between 5 and 90 min, depending in particular on the firing temperature, the vulcanization system adopted and the vulcanization kinetics of the composition under consideration.
  • the invention relates to the rubber compositions described above both in the so-called “raw” state (i.e., before firing) and in the so-called “cooked” or vulcanized state (i.e. after vulcanization).
  • composition according to the invention (hereinafter noted C-3) was compared with two control compositions (denoted C-I and C-2), the three compositions tested being identical, with the following differences:
  • C-I control according to prior art with aromatic oil (37 phr);
  • C-2 control with MES oil alone (31.5 phr);
  • composition with plasticizer system according to the invention (combination of 12 phr of MES oil and 19.5 phr of limonene / styrene copolymer resin). These three compositions, with the exception of their plasticizer system, have a customary formulation for a tire tread rubber composition, namely essentially a mixture of diene elastomers (SSBR 70 pce / BR 30 pce), silica (78 phr), carbon black (4 phr) and a vulcanization system.
  • Compositions CI and C-2 were formulated with iso-volume of plasticizing oil.
  • about 2/3 (ie 19.5 phr) of MES oil were replaced by the limonene / styrene resin (19.5 phr) previously synthesized, compared with the control composition C-2.
  • the three compositions were tested as treads of passenger tires with radial carcass, dimension 195/65 Rl 5 (speed index H), conventionally manufactured and in all respects identical except for the constitutive rubber composition of the tread.
  • These tires are noted respectively PI, P-2 and P-3, they were mounted on a passenger vehicle (Citro ⁇ n model "C5" vehicle - front and rear pressure: 2.2 bars - tested tires mounted on the front of the vehicle - ambient temperature 25 ° C) to be subjected to an endurance test to assess the resistance to cuts and chipping of rubber compositions.
  • the test was conducted at a moderate driving speed (less than 60 km / h), on two successive circuits:
  • a first driving on a stony clay circuit (coarse grained stones), intended to weaken the tread, in the form of cuts and other superficial aggressions of the gum rolls constituting his sculpture;
  • the state of the treads is evaluated on the one hand visually (photographs) by the attribution of a note (according to a gravity scale of 1 to 10), on the other hand by the measurement of weight loss. Resistance to peeling is finally appreciated by a relative overall score (base 100 on a reference product).

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Abstract

The invention relates to a plasticizing system that can be used for plasticizing a diene rubber composition, characterized in that it is based on an MES or TDAE oil and on a terpene/vinyl aromatic copolymer resin, in particular, limonene and styrene copolymer. The rubber composition exhibits an improved resistance to wear and to cuts, said composition being based on at leas tone diene elastomer, a reinforcing filler, a cross-linking system and a plasticizing system comprising between 5 and 35 pce of an MES or TDAE oil and between 5 and 35 pce of a terpene/vinyl aromatic copolymer resin (pce = parts by weight per 100 parts of elastomers). The invention also relates to a method for preparing a composition of the aforementioned type, to the use of this composition for producing a finished article or semi-finished product for use in a tire or a tire/motor vehicle connecting system, particularly a tire tread.

Description

SYSTEME PLASTIFIANT POUR COMPOSITION DE CAOUTCHOUC PLASTICIZING SYSTEM FOR RUBBER COMPOSITION
La présente invention se rapporte aux compositions de caoutchouc destinées notamment à la fabrication de pneumatiques ou de produits semi-finis pour pneumatiques, elle est plus particulièrement relative aux systèmes plastifiants utilisables pour la plastification de telles compositions.The present invention relates to rubber compositions intended in particular for the manufacture of tires or semi-finished products for tires, it relates more particularly to the plasticizer systems used for the plasticization of such compositions.
Les compositions de caoutchouc pour pneumatiques comportent de manière connue des agents plastifiants utilisés pour la préparation ou synthèse de certains élastomères diéniques, pour améliorer la mise en œuvre (ou "processabilité") desdites compositions à l'état cru ainsi que certaines de leurs propriétés d'usage à l'état cuit comme par exemple, dans le cas de bandes de roulement de pneumatiques, leur adhérence sur sol mouillé ou encore leur résistance à l'abrasion et aux coupures.The tire rubber compositions comprise in a known manner plasticizing agents used for the preparation or synthesis of certain diene elastomers, to improve the implementation (or "processability") of said compositions in the green state, as well as some of their properties. use in the fired state such as, for example, in the case of treads of tires, their adhesion on wet ground or their resistance to abrasion and cuts.
Depuis fort longtemps, ce sont essentiellement des huiles dérivées du pétrole et fortement aromatiques, connues sous le nom d'huiles DAE (pour "Distillate Aromatic Extracts"), qui ont été utilisées pour remplir cette fonction d'agent plastifiant. Nombre de manufacturiers de pneumatiques, pour des raisons environnementales, envisagent aujourd'hui de remplacer progressivement ces huiles DAE par des huiles de substitution du type "non-aromatiques", en particulier par des huiles dites MES (pour "Médium Extracted Solvates") ou TDAE ("Treated Distillate Aromatic Extracts") se caractérisant par un très faible taux de polyaromatiques (environ 20 à 50 fois moins).Since a very long time, it is essentially oils derived from petroleum and strongly aromatic, known under the name DAE oils (for "Distillate Aromatic Extracts"), which have been used to fulfill this function of plasticizer. Many manufacturers of tires, for environmental reasons, are now considering gradually replacing these DAE oils with "non-aromatic" type of replacement oils, in particular with oils called MES (for "Medium Extracted Solvates") or Treated Distillate Aromatic Extracts (TDAE) is characterized by a very low level of polyaromatics (about 20 to 50 times less).
Les Demanderesses ont constaté que le remplacement, dans des compositions de caoutchouc pour pneumatique, des huiles aromatiques DAE par ces huiles MES ou TDAE se traduisait de manière inattendue par une diminution de la résistance à l'abrasion et aux coupures desdites compositions, cette diminution pouvant être même rédhibitoire pour certaines applications, notamment vis-à-vis du problème d'écaillement des bandes de roulement de pneumatiques.The Applicants have found that the replacement, in pneumatic rubber compositions, of DAE aromatic oils with these MES or TDAE oils unexpectedly resulted in a reduction in the abrasion and cut resistance of said compositions, this reduction being possible. even be unacceptable for certain applications, especially vis-à-vis the problem of peeling tire treads.
L' « écaillement » (en anglais "chipping" ou "scaling") est un mécanisme d'endommagement connu qui correspond à des arrachements lamellaires superficiels - en forme d'écaillés - de la "gomme" (ou composition de caoutchouc) constitutive des bandes de roulement, sous certaines conditions de roulage agressives. Ce problème est notamment rencontré sur des pneumatiques pour véhicule hors-la-route ou de type chantier ou génie civil, ayant à rouler sur différents types de sols, pour certains caillouteux et relativement agressifs ; il a été par exemple décrit, ainsi que certaines solutions pour y remédier, dans les documents de brevet EP-A-O 030 579 (ou AU-A-6429780) et FR- A-2 080 661 (ou GB-A-I 343 487). Poursuivant leurs recherches, les Demanderesses ont découvert que le remplacement d'une partie de ces huiles MES ou TDAE par un autre agent plastifiant spécifique permettait non seulement de résoudre le problème ci-dessus, mais, ce qui est encore plus surprenant, d'améliorer encore la résistance à l'abrasion et aux coupures des compositions de caoutchouc utilisant des huiles conventionnelles aromatiques à titre d'agent plastifiant."Chipping"("chipping" or "scaling") is a known mechanism of damage which corresponds to superficial lamellar tearing - in the form of flakes - of the "gum" (or rubber composition) constituting the treads, under certain aggressive driving conditions. This problem is particularly encountered on tires for off-the-road vehicles or construction site or civil engineering, having to ride on different types of soil, for some stony and relatively aggressive; For example, it has been described, as well as some remedies, in EP-A-0 030 579 (or AU-A-6429780) and FR-A-2 080 661 (or GB-AI 343 487). Continuing their research, the Applicants have discovered that the replacement of a portion of these MES or TDAE oils by another specific plasticizing agent not only made it possible to solve the problem above, but, what is even more surprising, to improve still the abrasion and cut resistance of rubber compositions using conventional aromatic oils as a plasticizer.
En conséquence, un premier objet de l'invention concerne une composition de caoutchouc à base d'au moins un élastomère diénique, une charge renforçante, un système plastifiant et un système de réticulation, caractérisée en ce que ledit système plastifiant comporte (pce = parties en poids pour cent parties d'élastomère) :Accordingly, a first subject of the invention relates to a rubber composition based on at least one diene elastomer, a reinforcing filler, a plasticizer system and a crosslinking system, characterized in that said plasticizing system comprises (pce = parts in weight per hundred parts of elastomer):
entre 5 et 35 pce d'une huile MES ou TDAE ; entre 5 et 35 pce d'une résine de copolymère terpène/ vinylaromatique.between 5 and 35 phr of a MES or TDAE oil; between 5 and 35 phr of a terpene / vinylaromatic copolymer resin.
L'invention a également pour objet un procédé pour préparer une composition de caoutchouc ayant une résistance à l'abrasion et aux coupures améliorée, cette composition étant à base d'un élastomère diénique, d'une charge renforçante, d'un système plastifiant et d'un système de réticulation, ledit procédé comportant les étapes suivantes :The invention also relates to a method for preparing a rubber composition having improved abrasion and cut resistance, this composition being based on a diene elastomer, a reinforcing filler, a plasticizer system and of a crosslinking system, said method comprising the following steps:
• incorporer à un élastomère diénique, au cours d'une première étape dite "non- productive", au moins une charge renforçante et un système plastifiant, en malaxant thermomécaniquement le tout, en une ou plusieurs fois, jusqu'à atteindre une température maximale comprise entre 110°C et 190°C ; • refroidir l'ensemble à une température inférieure à 100°C ;• Incorporating at least one reinforcing filler and a plasticizer system into a diene elastomer during a first so-called "nonproductive" step, by thermomechanically kneading the whole, in one or more times, until a maximum temperature is reached. between 110 ° C and 190 ° C; • cool the assembly to a temperature below 100 ° C;
• incorporer ensuite, au cours d'une seconde étape dite "productive", le système de réticulation ;• then incorporate, during a second so-called "productive" step, the crosslinking system;
• malaxer le tout jusqu'à une température maximale inférieure à 110°C,• mix everything up to a maximum temperature of less than 110 ° C,
et étant caractérisé en ce que ledit système plastifiant comporte :and being characterized in that said plasticizer system comprises:
entre 5 et 35 pce d'une huile MES ou TDAE ; entre 5 et 35 pce d'une résine de copolymère terpène/ vinylaromatique.between 5 and 35 phr of a MES or TDAE oil; between 5 and 35 phr of a terpene / vinylaromatic copolymer resin.
L'invention concerne également, en soi, un système plastifiant utilisable pour la plastification d'une composition de caoutchouc diénique, ledit système comportant en combinaison une huile MES ou TDAE et une résine de copolymère terpène/ vinylaromatique, ainsi que l'utilisation d'un tel système pour la plastification d'une composition de caoutchouc diénique. L'invention a également pour objet l'utilisation d'une composition selon l'invention pour la fabrication d'un article fini ou d'un produit semi-fini en caoutchouc destiné à tout pneumatique ou système de liaison pneu/ véhicule automobile tel que appui interne de sécurité pour pneumatique, roue, ressort en caoutchouc, articulation élastomérique, autre élément de suspension et anti- vibratoire.The invention also relates, in itself, to a plasticizer system useful for plasticizing a diene rubber composition, said system comprising in combination a MES or TDAE oil and a terpene / vinylaromatic copolymer resin, as well as the use of such a system for plasticizing a diene rubber composition. The invention also relates to the use of a composition according to the invention for the manufacture of a finished article or a semi-finished rubber product for any tire or tire / motor vehicle connection system such as internal safety support for tire, wheel, rubber spring, elastomeric joint, other suspension element and anti-vibration.
L'invention a particulièrement pour objet l'utilisation d'une composition selon l'invention pour la fabrication de pneumatiques ou de produits semi-finis en caoutchouc destinés à ces pneumatiques, ces produits semi-finis étant de préférence choisis dans le groupe constitué par les bandes de roulement, les nappes d'armature de sommet, les flancs, les nappes d'armature de carcasse, les bourrelets, les protecteurs, les sous-couches, les blocs de caoutchouc et autres gommes internes, notamment les gommes de découplage, destinés à assurer la liaison ou l'interface entre les zones précitées des pneumatiques.The subject of the invention is particularly the use of a composition according to the invention for the manufacture of tires or semi-finished rubber products intended for these tires, these semi-finished products being preferably chosen from the group consisting of treads, crown reinforcement plies, sidewalls, carcass reinforcement plies, beads, guards, underlayments, rubber blocks and other internal rubbers, in particular decoupling erasers, intended to provide the connection or interface between the aforementioned zones of the tires.
L'invention a plus particulièrement pour objet l'utilisation d'une composition selon l'invention pour la fabrication d'une bande de roulement de pneumatique présentant une résistance aux coupures et à l'écaillement améliorée.The invention more particularly relates to the use of a composition according to the invention for the manufacture of a tire tread having improved resistance to cuts and peeling.
L'invention a également pour objet les articles finis et produits semi-finis en caoutchouc eux- mêmes, en particulier les pneumatiques et produits semi-finis pour pneumatiques, lorsqu'ils comportent une composition élastomérique conforme à l'invention. Les pneumatiques conformes à l'invention sont notamment destinés à des véhicules tourisme comme à des véhicules deux roues (moto, vélo), véhicules industriels choisis parmi camionnettes, "Poids- lourd" - i.e., métro, bus, engins de transport routier (camions, tracteurs, remorques), véhicules hors-la-route - , engins agricoles ou de génie civil, avions, autres véhicules de transport ou de manutention.The invention also relates to finished articles and semi-finished products of rubber themselves, in particular tires and semi-finished products for tires, when they comprise an elastomeric composition according to the invention. The tires according to the invention are particularly intended for passenger vehicles such as two-wheeled vehicles (motorcycles, bicycles), industrial vehicles chosen from vans, "heavy trucks" - ie, metro, buses, road transport vehicles (trucks tractors, trailers), off-the-road vehicles -, agricultural or civil engineering machinery, airplanes, other transport or handling vehicles.
L'invention ainsi que ses avantages seront aisément compris à la lumière de la description détaillée et des exemples de réalisation qui suivent.The invention as well as its advantages will be readily understood in the light of the detailed description and the following exemplary embodiments.
DESCRIPTION DETAILLEE DE L'INVENTIONDETAILED DESCRIPTION OF THE INVENTION
La composition de caoutchouc selon l'invention, utilisable notamment pour la fabrication d'un pneumatique ou d'une bande de roulement de pneumatique, est à base d'au moins un élastomère diénique, une charge renforçante, un système de réticulation et un système plastifiant spécifique. Par l'expression composition "à base de", il faut entendre une composition comportant le mélange et/ou le produit de réaction des différents constituants utilisés, certains de ces constituants de base étant susceptibles de, ou destinés à réagir entre eux, au moins en partie, lors des différentes phases de fabrication de la composition, en particulier au cours de sa réticulation ou vulcanisation.The rubber composition according to the invention, which can be used in particular for the manufacture of a tire or a tire tread, is based on at least one diene elastomer, a reinforcing filler, a crosslinking system and a system specific plasticizer. By the term "composition based on" is meant a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being 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.
Dans la présente description, sauf indication expresse différente, tous les pourcentages (%) indiqués sont des % en masse.In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight.
Elastomère diéniqueDiene elastomer
Par elastomère ou caoutchouc "diénique", doit être compris de manière connue un (on entend un ou plusieurs) elastomère issu au moins en partie (i.e., un homopolymère ou un copolymère) de monomères diènes (monomères porteurs de deux doubles liaisons carbone- carbone, conjuguées ou non).By elastomer or "diene" rubber, it is to be understood in a known way (one or more elastomers), at least in part (ie, a homopolymer or a copolymer) of diene monomers (monomers bearing two carbon-to-carbon double bonds). , conjugated or not).
Ces élastomères diéniques peuvent être classés dans deux catégories : "essentiellement insaturés" ou "essentiellement saturés". On entend en général par "essentiellement insaturé", un elastomère diénique issu au moins en partie de monomères diènes conjugués, ayant un taux de motifs ou unités d'origine diénique (diènes conjugués) qui est supérieur à 15% (% en moles) ; c'est ainsi que des élastomères diéniques tels que les caoutchoucs butyle ou les copolymères de diènes et d'alpha-oléfines type EPDM n'entrent pas dans la définition précédente et peuvent être notamment qualifiés d'élastomères diéniques "essentiellement saturés" (taux de motifs d'origine diénique faible ou très faible, toujours inférieur à 15%). Dans la catégorie des élastomères diéniques "essentiellement insaturés", on entend en particulier par elastomère diénique "fortement insaturé" un elastomère diénique ayant un taux de motifs d'origine diénique (diènes conjugués) qui est supérieur à 50%.These diene elastomers can be classified into two categories: "essentially unsaturated" or "essentially saturated". The term "essentially unsaturated" is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%); Thus, diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated" diene elastomers ( low or very low diene origin, always less than 15%). In the category of "essentially unsaturated" diene elastomers, the term "highly unsaturated" diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
Ces définitions étant données, on entend plus particulièrement par elastomère diénique susceptible d'être utilisé dans les compositions conformes à l'invention:These definitions being given, the term "diene elastomer" can be understood more particularly to be used in the compositions according to the invention:
(a) - tout homopolymère obtenu par polymérisation d'un monomère diène conjugué ayant de 4 à 12 atomes de carbone;(a) - any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms;
(b) - tout copolymère obtenu par copolymérisation d'un ou plusieurs diènes conjugués entre eux ou avec un ou plusieurs composés vinyle aromatique ayant de 8 à 20 atomes de carbone;(b) - any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms;
(c) - un copolymère ternaire obtenu par copolymérisation d'éthylène, d'une α-oléfine ayant 3 à 6 atomes de carbone avec un monomère diène non conjugué ayant de 6 à 12 atomes de carbone, comme par exemple les élastomères obtenus à partir d'éthylène, de propylène avec un monomère diène non conjugué du type précité tel que notamment l'hexadiène-1,4, l'éthylidène norbornène, le dicyclopentadiène;(c) - a ternary copolymer obtained by copolymerization of ethylene, an α-olefin having 3 to 6 carbon atoms with a non-conjugated diene monomer having from 6 to 12 carbon atoms, for example elastomers obtained from ethylene, propylene with a non-conjugated diene monomer of the aforementioned type, such as in particular 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene;
(d) - un copolymère d'isobutène et d'isoprène (caoutchouc butyle), ainsi que les versions halogénées, en particulier chlorées ou bromées, de ce type de copolymère.(d) - a copolymer of isobutene and isoprene (butyl rubber), as well as the halogenated versions, in particular chlorinated or brominated, of this type of copolymer.
Bien qu'elle s'applique à tout type d'élastomère diénique, l'homme du métier du pneumatique comprendra que la présente invention est de préférence mise en œuvre avec des élastomères diéniques essentiellement insaturés, en particulier du type (a) ou (b) ci-dessus.Although it applies to any type of diene elastomer, the person skilled in the tire art will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b). ) above.
A titre de diènes conjugués conviennent notamment le butadiène-1,3, le 2-méthyl-l,3- butadiène, les 2,3-di(alkyle en C!-C5)-l,3-butadiènes tels que par exemple le 2,3-diméthyl- 1,3-butadiène, le 2,3-diéthyl-l,3-butadiène, le 2-méthyl-3-éthyl-l,3-butadiène, le 2-méthyl-3- isopropyl-l,3-butadiène, un aryl-l,3-butadiène, le 1,3-pentadiène, le 2,4-hexadiène. A titre de composés vinylaromatique conviennent par exemple le styrène, l'ortho-, meta-, para- méthylstyrène, le mélange commercial "vinyle-toluène", le para-tertiobutylstyrène, les méthoxystyrènes, les chlorostyrènes, le vinylmésitylène, le divinylbenzène, le vinylnaphtalène.As conjugated dienes, 1,3-butadiene, 2-methyl-1,3-butadiene and 2,3-di (C 1 -C 5 alkyl) -1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl- 1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene. Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.
Les copolymères peuvent contenir entre 99% et 20% en poids d'unités diéniques et entre 1% et 80% en poids d'unités vinylaromatique. Les élastomères peuvent avoir toute microstructure qui est fonction des conditions de polymérisation utilisées, notamment de la présence ou non d'un agent modifiant et/ou randomisant et des quantités d'agent modifiant et/ou randomisant employées. Les élastomères peuvent être par exemple à blocs, statistiques, séquences, microséquencés, et être préparés en dispersion ou en solution ; ils peuvent être couplés et/ou étoiles ou encore fonctionnalisés avec un agent de couplage et/ou d'étoilage ou de fonctionnalisation.The copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units. The elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used. 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.
Conviennent les polybutadiènes et en particulier ceux ayant une teneur en unités -1,2 comprise entre 4% et 80% ou ceux ayant une teneur en cis-1,4 supérieure à 80%, les polyisoprènes, les copolymères de butadiène-styrène et en particulier ceux ayant une teneur en styrène comprise entre 5% et 50% en poids et plus particulièrement entre 20% et 40%, une teneur en liaisons -1,2 de la partie butadiénique comprise entre 4% et 65%, une teneur en liaisons trans-1,4 comprise entre 20% et 80%, les copolymères de butadiène-isoprène et notamment ceux ayant une teneur en isoprène comprise entre 5% et 90% en poids et une température de transition vitreuse (Tg, mesurée selon ASTM D3418) de -40°C à -80°C, les copolymères isoprène-styrène et notamment ceux ayant une teneur en styrène comprise entre 5% et 50% en poids et une Tg comprise entre -25°C et -50°C. Dans le cas des copolymères de butadiène-styrène-isoprène conviennent notamment ceux ayant une teneur en styrène comprise entre 5% et 50% en poids et plus particulièrement comprise entre 10% et 40%, une teneur en isoprène comprise entre 15% et 60% en poids et plus particulièrement entre 20% et 50%, une teneur en butadiène comprise entre 5% et 50% en poids et plus particulièrement comprise entre 20% et 40%, une teneur en unités -1,2 de la partie butadiénique comprise entre 4% et 85%, une teneur en unités trans -1,4 de la partie butadiénique comprise entre 6% et 80%, une teneur en unités -1,2 plus -3,4 de la partie isoprénique comprise entre 5% et 70% et une teneur en unités trans -1,4 de la partie isoprénique comprise entre 10% et 50%, et plus généralement tout copolymère butadiène-styrène-isoprène ayant une Tg comprise entre -20°C et -70°C.Suitable polybutadienes and in particular those having a content in units -1.2 of between 4% and 80% or those having a content of cis-1,4 greater than 80%, polyisoprenes, butadiene-styrene copolymers and in especially those having a styrene content of between 5% and 50% by weight and more particularly between 20% and 40%, a 1,2-butadiene content of the butadiene part of between 4% and 65%, a content of trans-1,4 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) from -40 ° C to -80 ° C, the isoprene-styrene copolymers and especially those having a styrene content of between 5% and 50% by weight and a Tg between -25 ° C and -50 ° C. In the case of butadiene-styrene-isoprene copolymers are especially suitable those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60%. by weight and more particularly between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly between 20% and 40%, a 1,2-butadiene content of the butadiene part of between 4% and 85%, a content of trans -1,4 units of the butadiene part of between 6% and 80%, a content of -1,2 units plus -3,4 of the isoprene part of between 5% and 70% and a content of trans-units , 4 of the isoprenic portion of between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg between -20 ° C and -70 ° C.
En résumé, l'élastomère diénique de la composition conforme à l'invention est choisi préférentiellement dans le groupe des élastomères diéniques fortement insaturés constitué par les polybutadiènes (en abrégé "BR"), les polyisoprènes (IR), le caoutchouc naturel (NR), les copolymères de butadiène, les copolymères d'isoprène et les mélanges de ces élastomères. De tels copolymères sont plus préférentiellement choisis dans le groupe constitué par les copolymères de butadiène-styrène (SBR), les copolymères d'isoprène-butadiène (BIR), les copolymères d'isoprène-styrène (SIR) et les copolymères d'isoprène-butadiène-styrèneIn summary, the diene elastomer of the composition according to the invention is preferably selected from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated as "BR"), polyisoprenes (IR) and natural rubber (NR). , butadiene copolymers, isoprene copolymers 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) and isoprene-copolymers. butadiene-styrene
(SBIR).(SBIR).
Selon un mode de réalisation particulier, l'élastomère diénique est majoritairement (c'est-à- dire pour plus de 50 pce) un SBR, qu'il s'agisse d'un SBR préparé en émulsion ("E-SBR") ou d'un SBR préparé en solution ("S-SBR"), ou un coupage (mélange) SBR/BR, SBR/NR (ou SBR/IR), ou encore BR/NR (ou BR/IR). Dans le cas d'un élastomère SBR, on utilise notamment un SBR ayant une teneur en styrène comprise entre 20% et 30% en poids, une teneur en liaisons vinyliques de la partie butadiénique comprise entre 15% et 65%, une teneur en liaisons trans- 1,4 comprise entre 15% et 75% et une Tg comprise entre -20°C et -55°C ; un tel SBR peut être avantageusement utilisé en mélange avec un BR possédant de préférence plus de 90% de liaisons cis-1,4.According to a particular embodiment, the diene elastomer is predominantly (that is to say for more than 50 phr) an SBR, whether it is a SBR prepared in emulsion ("E-SBR") or a SBR prepared in solution ("S-SBR"), or a blend (mixture) SBR / BR, SBR / NR (or SBR / IR), or BR / NR (or BR / IR). In the case of an SBR elastomer, use is made in particular of an SBR having a styrene content of between 20% and 30% by weight, a vinyl bond content of the butadiene part of between 15% and 65%, a bond content of trans-1,4 between 15% and 75% and a Tg of between -20 ° C and -55 ° C; such an SBR can be advantageously used in admixture with a BR preferably having more than 90% cis-1,4 bonds.
Selon un autre mode de réalisation particulier, l'élastomère diénique est majoritairement (pour plus de 50 pce) un élastomère isoprénique. C'est le cas en particulier lorsque les compositions de l'invention sont destinées à constituer, dans les pneumatiques, les matrices de caoutchouc de certaines bandes de roulement (par exemple pour véhicules industriels), de nappes d'armature de sommet (par exemple de nappes de travail, nappes de protection ou nappes de frettage), de nappes d'armature de carcasse, de flancs, de bourrelets, de protecteurs, de sous-couches, de blocs de caoutchouc et autres gommes internes assurant l'interface entre les zones précitées des pneumatiques.According to another particular embodiment, the diene elastomer is predominantly (for more than 50 phr) an isoprene elastomer. This is particularly the case when the compositions of the invention are intended to constitute, in tires, the rubber matrices of certain treads (for example for industrial vehicles), crown reinforcing plies (for example work webs, protective webs or hoop webs), carcass reinforcement plies, flanks, beads, protectors, underlayments, rubber blocks and other internal gums providing the interface between aforementioned areas of the tires.
Par "élastomère isoprénique", on entend de manière connue un homopolymère ou un copolymère d'isoprène, en d'autres termes un élastomère diénique choisi dans le groupe constitué par le caoutchouc naturel (NR), les polyisoprènes de synthèse (IR), les différents copolymères d'isoprène et les mélanges de ces élastomères. Parmi les copolymères d'isoprène, on citera en particulier les copolymères d'isobutène-isoprène (caoutchouc butyle - HR), d'isoprène-styrène (SIR), d'isoprène-butadiène (BIR) ou d'isoprène-butadiène-styrène (SBIR). Cet élastomère isoprénique est de préférence du caoutchouc naturel ou un polyisoprène cis-1,4 de synthèse; parmi ces polyisoprènes de synthèse, sont utilisés de préférence des polyisoprènes ayant un taux (% molaire) de liaisons cis-1,4 supérieur à 90%, plus préférentiellement encore supérieur à 98%.By "isoprene elastomer" is meant in known manner a homopolymer or copolymer of isoprene, in other words a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), different isoprene copolymers and mixtures of these elastomers. Among the copolymers of isoprene, mention will be made in particular of isobutene-isoprene copolymers (butyl rubber-HR), isoprene-styrene copolymers (SIR), isoprene-butadiene copolymers (BIR) or isoprene-butadiene-styrene copolymers (SBIR) . This isoprene elastomer is preferably natural rubber or synthetic cis-1,4 polyisoprene; of these synthetic polyisoprenes, polyisoprenes having a content (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used.
Selon un autre mode de réalisation particulier, notamment lorsqu'elle est destinée à un flanc de pneumatique, à une gomme intérieure étanche de pneumatique sans chambre (ou autre élément imperméable à l'air), la composition conforme à l'invention peut contenir au moins un élastomère diénique essentiellement saturé, en particulier au moins un copolymère EPDM ou un caoutchouc butyle (éventuellement chloré ou brome), que ces copolymères soient utilisés seuls ou en mélange avec des élastomères diéniques fortement insaturés tels que cités précédemment, notamment NR ou IR, BR ou SBR.According to another particular embodiment, especially when it is intended for a tire sidewall, a tubeless tire sealing inner liner (or other airtight element), the composition according to the invention may contain less than an essentially saturated diene elastomer, in particular at least one EPDM copolymer or a butyl rubber (optionally chlorinated or brominated), that these copolymers are used alone or in admixture with highly unsaturated diene elastomers as mentioned above, in particular NR or IR, BR or SBR.
Selon un autre mode préférentiel de réalisation de l'invention, la composition de caoutchouc comprend un coupage d'un (un ou plusieurs) élastomère diénique dit "à haute Tg" présentant une Tg comprise entre -65°C et -100C et d'un (un ou plusieurs) élastomère diénique dit "à basse Tg" comprise entre -HO0C et -800C, plus préférentiellement entre -1050C et -9O0C. L'élastomère à haute Tg est choisi de préférence dans le groupe constitué par les S-SBR, les E-SBR, le caoutchouc naturel, les polyisoprènes de synthèse (présentant un taux d'enchaînements cis-1,4 de préférence supérieur à 95%), les BIR, les SIR, les SBIR, et les mélanges de ces élastomères. L'élastomère à basse Tg comprend de préférence des unités butadiène selon un taux au moins égal à 70% ; il consiste de préférence en un polybutadiène (BR) présentant un taux d'enchaînements cis- 1 ,4 supérieur à 90%.According to another preferred embodiment of the invention, the rubber composition comprises a blend of one (or more) diene elastomers called "high Tg" having a Tg between -65 ° C and -10 0 C and of a (one or more) diene elastomer called "at low Tg" between -HO 0 C and -80 0 C, more preferably between -105 0 C and -80 0 C. The high Tg elastomer is chosen from preferably in the group consisting of S-SBR, E-SBR, natural rubber, synthetic polyisoprenes (having a level of cis-1,4 chains preferably greater than 95%), BIRs, SIRs, SBIR, and mixtures of these elastomers. The low Tg elastomer preferably comprises butadiene units at a content of at least 70%; it consists preferably of a polybutadiene (BR) having a degree of cis-1,4 chains higher than 90%.
Selon un mode particulier de réalisation de l'invention, la composition de caoutchouc comprend par exemple de 40 à 100 pce, en particulier de 50 à 100 pce, d'un élastomère à haute Tg en coupage avec 0 à 60 pce, en particulier de 0 à 50 pce, d'un élastomère à basse Tg, par exemple 100 pce d'un ou plusieurs copolymères de styrène et de butadiène préparés en solution.According to one particular embodiment of the invention, the rubber composition comprises, for example, from 40 to 100 phr, in particular from 50 to 100 phr, of a high Tg elastomer in a blend with 0 to 60 phr, in particular 0 to 50 phr of a low Tg elastomer, for example 100 phr of one or more copolymers of styrene and butadiene prepared in solution.
Selon un autre mode particulier de réalisation de l'invention, l'élastomère diénique de la composition selon l'invention comprend un coupage d'un BR (à titre d'élastomère basse Tg) présentant un taux d'enchaînements cis-1,4 supérieur à 90%, avec un S-SBR ou un E-SBR (à titre d'élastomère haute Tg).According to another particular embodiment of the invention, the diene elastomer of the composition according to the invention comprises a blend of a BR (as low elastomer Tg) having a rate of cis-1,4 linkages. greater than 90%, with S-SBR or E-SBR (as high elastomer Tg).
Les compositions de l'invention peuvent contenir un seul élastomère diénique ou un mélange de plusieurs élastomères diéniques, le ou les élastomères diéniques pouvant être utilisés en association avec tout type d'élastomère synthétique autre que diénique, voire avec des polymères autres que des élastomères, par exemple des polymères thermoplastiques.The compositions of the invention may contain a single diene elastomer or a mixture of several diene elastomers, wherein the diene elastomer (s) may be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers.
Charge renforçanteReinforcing charge
On peut utiliser tout type de charge renforçante connue pour ses capacités à renforcer une composition de caoutchouc utilisable pour la fabrication de pneumatiques, par exemple une charge organique tel que du noir de carbone, ou encore une charge inorganique renforçante telle que de la silice à laquelle est associé un agent de couplage.Any type of reinforcing filler known for its capacity 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 with a coupling agent.
Comme noirs de carbone conviennent tous les noirs de carbone, notamment les noirs du type HAF, ISAF, SAF conventionnellement utilisés dans les pneumatiques (noirs dits de grade pneumatique). Parmi ces derniers, on citera plus particulièrement les noirs de carbone renforçants des séries 100, 200 ou 300 (grades ASTM), comme par exemple les noirs Nl 15, N134, N234, N326, N330, N339, N347, N375, ou encore, selon les applications visées, les noirs de séries plus élevées (par exemple N660, N683, N772).Carbon blacks are suitable for all carbon blacks, in particular blacks of the HAF, ISAF, SAF type conventionally used in tires (so-called pneumatic grade blacks). Among these, the reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades), for example blacks Nl 15, N134, N234, N326, N330, N339, N347 or N375, or else, according to the targeted applications, the blacks of higher series (for example N660, N683, N772).
Par "charge inorganique renforçante", doit être entendu dans la présente demande, par définition, toute charge inorganique ou minérale (quelles que soient sa couleur et son origine (naturelle ou de synthèse), encore appelée charge "blanche", charge "claire" voire "charge non noire" ("non-blackβller") par opposition au noir de carbone, capable de renforcer à elle seule, sans autre moyen qu'un agent de couplage intermédiaire, une composition de caoutchouc destinée à la fabrication de pneumatiques, en d'autres termes apte à remplacer, dans sa fonction de renforcement, un noir de carbone conventionnel de grade pneumatique ; une telle charge se caractérise généralement, de manière connue, par la présence de groupes hydroxyle (-OH) à sa surface.By "reinforcing inorganic filler" is meant in this application, by definition, any inorganic or mineral filler (regardless of its color and origin (natural or synthetic), also called "white" filler, "clear" filler or "non-black load", as opposed to carbon black, capable of reinforcing on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires, in particular other words capable of replacing, in its reinforcing function, a conventional carbon black of pneumatic grade, such a charge is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
L'état physique sous lequel se présente la charge inorganique renforçante est indifférent, que ce soit sous forme de poudre, de microperles, de granulés, de billes ou toute autre forme densifiée appropriée. Bien entendu on entend également par charge inorganique renforçante des mélanges de différentes charges inorganiques renforçantes, en particulier de charges siliceuses et/ou alumineuses hautement dispersibles telles que décrites ci-après.The physical state in which the reinforcing inorganic filler is present is indifferent whether in the form of powder, microbeads, granules, beads or any other suitable densified form. Of course, the term "reinforcing inorganic filler" also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.
Comme charges inorganiques renforçantes conviennent notamment des charges minérales du type siliceuse, en particulier de la silice (SiÛ2), ou du type alumineuse, en particulier de l'alumine (AI2O3). La silice utilisée peut être toute silice renforçante connue de l'homme du métier, notamment toute silice précipitée ou pyrogénée présentant une surface BET ainsi qu'une surface spécifique CTAB toutes deux inférieures à 450 m2/g, de préférence de 30 àSuitable reinforcing inorganic fillers are, in particular, 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
400 m2/g. A titres de silices précipitées hautement dispersibles (dites "HD"), on citera par exemple les silices Ultrasil 7000 et Ultrasil 7005 de la société Degussa, les silices Zeosil 1165MP, 1135MP et 1115MP de la société Rhodia, la silice Hi-SiI EZ150G de la société PPG, les silices Zeopol 8715, 8745 et 8755 de la Société Huber, les silices à haute surface spécifique telles que décrites dans la demande WO 03/16837. Comme exemples d'alumines renforçantes, on peut citer les alumines "Baikalox" "A125" ou "CR125" de la société Baïkowski, "APA-100RDX" de Condea, "Aluminoxid C" de Degussa ou "AKP-GOl 5" de Sumitomo Chemicals.400 m 2 / g. As highly dispersible precipitated silicas (referred to as "HD"), mention may be made of, for example, Ultrasil 7000 and Ultrasil 7005 silicas from Degussa, Zeosil silicas. 1165MP, 1135MP and 1115MP from Rhodia, Hi-SiI silica EZ150G from PPG, Zeopol 8715, 8745 and 8755 silicas from Huber, high surface area silicas as described in application WO 03/16837 . Examples of reinforcing aluminas that may be mentioned are the "Baikalox""A125" or "CR125" aluminums from the Baikowski company, "APA-100RDX" from Condea, "Aluminoxid C" from Degussa or "AKP-GOl 5" from Sumitomo Chemicals.
A titre d'autres exemples de charge inorganique susceptible d'être utilisée peuvent être encore cités des (oxyde-)hydroxydes d'aluminium, des oxydes de titane ou des carbures de silicium renforçants (voir par exemple demande WO 02/053634 ou US 2004/030017).By way of other examples of inorganic filler that may be used, mention may be made of aluminum (oxide) hydroxides, titanium oxides or reinforcing silicon carbides (see, for example, application WO 02/053634 or US 2004 / 030,017).
Lorsque les compositions de l'invention sont destinées à des bandes de roulement de pneumatique à faible résistance au roulement, la charge inorganique renforçante utilisée, en particulier s'il s'agit de silice, a de préférence une surface BET comprise entre 45 et 400 m2/g, plus préférentiellement comprise entre 60 et 300 m2/g.When the compositions of the invention are intended for tire treads with a low rolling resistance, the reinforcing inorganic filler used, in particular if it is silica, preferably has a BET surface area of between 45 and 400. m 2 / g, more preferably between 60 and 300 m 2 / g.
De manière préférentielle, le taux de charge renforçante totale (noir de carbone et/ou charge inorganique renforçante) est compris entre 20 et 200 pce, plus préférentiellement entre 30 et 150 pce, l'optimum étant de manière connue différent selon les applications particulières visées : le niveau de renforcement attendu sur un pneumatique vélo, par exemple, est bien sûr inférieur à celui exigé sur un pneumatique apte à rouler à grande vitesse de manière soutenue, par exemple un pneu moto, un pneu pour véhicule de tourisme ou pour véhicule utilitaire tel que Poids lourd.Preferably, the content of total reinforcing filler (carbon black and / or reinforcing inorganic filler) is between 20 and 200 phr, more preferably between 30 and 150 phr, the optimum being in a known manner different according to the specific applications referred to. : the level of reinforcement expected on a bicycle tire, for example, is of course lower than that required on a tire capable of running at high speed in a sustained manner, for example a motorcycle tire, a tire for a passenger vehicle or for a commercial vehicle such as Heavyweight.
Pour coupler la charge inorganique renforçante à l'élastomère diénique, on utilise de manière connue un agent de couplage (ou agent de liaison) au moins bifonctionnel destiné à assurer une connexion suffisante, de nature chimique et/ou physique, entre la charge inorganique (surface de ses particules) et l'élastomère diénique, en particulier des organosilanes ou des polyorganosiloxanes bifonctionnels .In order to couple the reinforcing inorganic filler to the diene elastomer, an at least bifunctional coupling agent (or bonding agent) is used in known manner to ensure a sufficient chemical and / or physical connection between the inorganic filler ( surface of its particles) and the diene elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
On utilise notamment des silanes polysulfurés, dits "symétriques" ou "asymétriques" selon leur structure particulière, tels que décrits par exemple dans les demandes WO03/002648 (ou US 2005/016651) et WO03/002649 (ou US 2005/016650).In particular, polysulfide silanes, called "symmetrical" or "asymmetrical" silanes according to their particular structure, are used, as described for example in the applications WO03 / 002648 (or US 2005/016651) and WO03 / 002649 (or US 2005/016650).
Conviennent en particulier, sans que la définition ci-après soit limitative, des silanes polysulfurés dits "symétriques" répondant à la formule générale (I) suivante:Particularly suitable, without the following definition being limiting, so-called "symmetrical" polysulfide silanes having the following general formula (I):
(I) Z - A - Sn - A - Z , dans laquelle:(I) Z - A - S n - A - Z, wherein:
- n est un entier de 2 à 8 (de préférence de 2 à 5) ; - A est un radical hydrocarboné divalent (de préférence des groupements alkylène en C1-C18 ou des groupements arylène en C6-Ci2, plus particulièrement des alkylènes en CpCio, notamment en Ci-C4, en particulier le propylène) ;n is an integer of 2 to 8 (preferably 2 to 5); - A is a divalent hydrocarbon radical (preferably C 1 -C 18 alkylene or arylene groups groups C 6 -C 2, especially alkylenes CpCio, including Ci-C 4, especially propylene);
- Z répond à l'une des formules ci-après:Z is one of the following formulas:
R1 R1 R2R 1 R1 R2
— Si— R1 ; — Si— R2 ; — Si— R2 , R2 R2 R2- Si- R1; - Si- R2; - Si- R2, R2 R2 R 2
dans lesquelles:in which:
- les radicaux R1, substitués ou non substitués, identiques ou différents entre eux, représentent un groupe alkyle en Ci-Ci8, cycloalkyle en C5-C]8 ou aryle en C6-Ci8 (de préférence des groupes alkyle en Ci-C6, cyclohexyle ou phényle, notamment des groupes alkyle en Ci-C4, plus particulièrement le méthyle et/ou l'éthyle).- the radicals R 1, substituted or unsubstituted, identical or different, represent an alkyl group Ci-8 cycloalkyl, C 5 -C] 8 aryl or C 6 -C 8 (preferably alkyl C 1 -C 6 , cyclohexyl or phenyl, especially C 1 -C 4 alkyl groups, more particularly methyl and / or ethyl).
- les radicaux R2, substitués ou non substitués, identiques ou différents entre eux, représentent un groupe alkoxyle en Ci-Ci8 ou cycloalkoxyle en C5-Ci8 (de préférence un groupe choisi parmi alkoxyles en Ci-C8 et cycloalkoxyles en C5-C8, plus préférentiellement encore un groupe choisi parmi alkoxyles en Ci-C4, en particulier méthoxyle et éthoxyle).- the radicals R 2, 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).
Dans le cas d'un mélange d'alkoxysilanes polysulfurés répondant à la formule (I) ci-dessus, notamment des mélanges usuels disponibles commercialement, la valeur moyenne des "n" est un nombre fractionnaire de préférence compris entre 2 et 5, plus préférentiellement proche de 4. Mais l'invention peut être aussi avantageusement mise en œuvre par exemple avec des alkoxysilanes disulfurés (n = 2).In the case of a mixture of polysulfurized alkoxysilanes corresponding to formula (I) above, in particular common commercially available mixtures, the average value of "n" is a fractional number preferably between 2 and 5, more preferably close to 4. But the invention can also be advantageously implemented for example with disulfide alkoxysilanes (n = 2).
A titre d'exemples de silanes polysulfurés, on citera plus particulièrement les polysulfurés (notamment disulfurés, trisulfures ou tétrasulfures) de bis-(alkoxyl(Ci-C4)-alkyl(Ci -C4)SiIyI- alkyl(Ci-C4)), comme par exemple les polysulfurés de bis(3-triméthoxysilylpropyl) ou de bis(3-triéthoxysilylpropyl). Parmi ces composés, on utilise en particulier le tétrasulfure de bis(3-triéthoxysilylpropyl), en abrégé TESPT, de formule [(C2H5O)3Si(CH2)3S2]2 ou le disulfure de bis-(triéthoxysilylpropyle), en abrégé TESPD, de formule [(C2H5O)3Si(CH2)3S]2. On citera également à titre d'exemples préférentiels les polysulfurés (notamment disulfurés, trisulfures ou tétrasulfures) de bis-(monoalkoxyl(Ci-C4)-dialkyl(Ci-C4)silylpropyl), plus particulièrement le tétrasulfure de bis-monoéthoxydiméthylsilylpropyl tel que décrit dans la demande de brevet WO 02/083782 (ou US 2004/132880) .As examples of silane polysulfides, are more particularly the bis (mono, trisulfide or tetrasulfide) of bis (alkoxyl (Ci-C4) alkyl (Ci -C 4) SiIyI- alkyl (Ci-C 4) ), such as polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl). Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated to TESPT, of formula [(C 2 H 5 O) 3 Si (CH 2 ) 3 S 2 ] 2 or bis-disulfide ( triethoxysilylpropyl), abbreviated TESPD, of formula [(C 2 H 5 O) 3 Si (CH 2 ) 3 S] 2 . Mention may also be made, by way of preferred examples, of polysulfides (in particular disulfides, trisulphides or tetrasulfides) of bis- (monoalkoxyl (Ci-C 4 ) -dialkyl (Ci-C 4 ) silylpropyl), more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide. as described in patent application WO 02/083782 (or US 2004/132880).
A titre d'agent de couplage autre qu'alkoxysilane polysulfuré, on citera notamment des POS (polyorganosiloxanes) bifonctionnels ou encore des polysulfurés d'hydroxysilane (R2 = OH dans la formule I ci-dessus) tels que décrits dans les demandes de brevet WO 02/30939 (ou US 6774255) et WO 02/31041 (ou US 2004/051210).As coupling agent other than polysulfurized alkoxysilane, there may be mentioned in particular bifunctional POS (polyorganosiloxanes) or polysulfides of hydroxysilane (R 2 = OH in formula I above) as described in patent applications WO 02/30939 (or US 6774255) and WO 02/31041 (or US 2004/051210).
Dans les compositions de caoutchouc conformes à l'invention, la teneur en agent de couplage est préférentiellement comprise entre 4 et 12 pce, plus préférentiellement entre 3 et 8 pce.In the rubber compositions according to the invention, the content of coupling agent is preferably between 4 and 12 phr, more preferably between 3 and 8 phr.
L'agent de couplage pourrait être préalablement greffé sur l'élastomère diénique ou sur la charge inorganique renforçante. On préfère toutefois, notamment pour des raisons de meilleure mise en œuvre des compositions à l'état cru, utiliser l'agent de couplage soit greffé sur la charge inorganique renforçante, soit à l'état libre (i.e., non greffé).The coupling agent could be grafted beforehand on the diene elastomer or on the reinforcing inorganic filler. However, it is preferred, especially for reasons of better implementation of the compositions in the green state, to use the coupling agent is grafted onto the reinforcing inorganic filler, or in the free state (i.e., ungrafted).
Système plastifiantPlasticizing system
Les compositions de caoutchouc de l'invention ont donc pour caractéristique essentielle d'utiliser un système plastifiant comportant au moins :It is therefore essential for the rubber compositions of the invention to use a plasticizer system comprising at least:
entre 5 et 35 pce d'une huile MES ou TDAE ; entre 5 et 35 pce d'une résine de copolymère d'au moins un monomère terpène et d'au moins un monomère vinylaromatique.between 5 and 35 phr of a MES or TDAE oil; between 5 and 35 phr of a copolymer resin of at least one terpene monomer and at least one vinylaromatic monomer.
Les huiles MES et TDAE sont bien connues de l'homme du métier, on se reportera par exemple à la publication récente KGK (Kautschuk Gummi Kunstoffe) 52. Jahrgang, Nr. 12/99, pp. 799-805, intitulée "Safe Process OiIs for Tires with Low Environmental Impact". Des demandes de brevet décrivant l'emploi de telles huiles, en substitution d'huiles aromatiques conventionnelles, sont par exemple EP-A-I 179 560 (ou US2002/0045697) ou EP-A-I 270 657. A titre d'exemples d'huiles MES (qu'elles soient du type "extraites" ou "hydrotraitées") ou d'huiles TDAE, on peut citer par exemple les produits commercialisés sous les dénominations "Flexon 683" de ExxonMobil, "Vivatec 200" ou "Vivatec 500" de H&R European, "Plaxolene MS" de Total, ou encore "Catenex SNR" de Shell.MES and TDAE oils are well known to those skilled in the art, see for example the recent publication KGK (Kautschuk Gummi Kunstoffe) 52. Jahrgang, Nr. 12/99, pp. 799-805, entitled "Safe Process Oils for Tires with Low Environmental Impact". Patent applications describing the use of such oils in substitution of conventional aromatic oils are, for example, EP-A1 179 560 (or US2002 / 0045697) or EP-A1 270 657. As examples of MES oils. (whether of the "extracted" or "hydrotreated" type) or of TDAE oils, mention may be made, for example, of the products marketed under the names "Flexon 683" by ExxonMobil, "Vivatec 200" or "Vivatec 500" by H & R European, "Plaxolene MS" from Total, or "Catenex SNR" from Shell.
Les résines (on rappelle que l'appellation "résine" est réservée par définition à un composé de départ solide à température ambiante) de copolymère terpène/ vinylaromatique, en particulier terpène/ styrène, sont bien connues ; elles ont été essentiellement utilisées jusqu'ici pour leur application comme agents adhésifs ("tackifiers") dans l'industrie alimentaire, ou comme plastifiants ou agents de mise en œuvre ("processing aids") dans des compositions de caoutchouc pour pneumatiques.The resins (it will be remembered that the term "resin" is by definition reserved for a solid starting compound at room temperature) of terpene / vinylaromatic copolymer, in particular terpene / styrene, are well known; they have been mainly used until now for their application as tackifiers in the food industry, or as plasticizers or processing aids in rubber tire compositions.
A titre de monomère vinylaromatique conviennent par exemple le styrène, l'ortho-, meta-, para-méthylstyrène, le vinyle-toluène, le para-tertiobutylstyrène, les méthoxystyrènes, les chlorostyrènes, le vinylmésitylène, le divinylbenzène, le vinylnaphtalène. De préférence, le composé vinyle-aromatique est du styrène.Suitable vinylaromatic monomers are, for example, styrene, ortho-, meta-, para-methylstyrene, vinyl-toluene, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene. Preferably, the vinyl aromatic compound is styrene.
Le terme "terpène" regroupe ici de manière connue les monomères alpha-pinène, beta-pinène et limonène. Préférentiellement est utilisé un monomère limonène, composé se présentant de manière connue sous la forme de trois isomères possibles : le L-limonène (énantiomère lévogyre), le D-limonène (énantiomère dextrogyre), ou bien le dipentène, racémique des énantiomères dextrogyre et lévogyre.The term "terpene" here combines in a known manner the alpha-pinene, beta-pinene and limonene monomers. Preferably, a limonene monomer is used which is 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. .
A titre d'exemples de résines de copolymère limonène/ styrène commercialement disponibles peuvent être cités par exemple les produits "Dercolyte TS 105" de la société DRT, "ZTl 15LT" et "ZT5100" de la société ARIZONA Chemical Company.By way of examples of commercially available limonene / styrene copolymer resins, mention may be made, for example, of the products "Dercolyte TS 105" from the company DRT, "ZTl 15LT" and "ZT5100" from the company ARIZONA Chemical Company.
De telles résines peuvent être également préparées selon des procédés de polymérisation connus, par exemple comme suit : un réacteur est chargé avec 1380 ml de toluène et 6 g de trichlorure d'aluminium (produit Aldrich, pureté = 99%). La suspension est portée à 25°C.Such resins can also be prepared according to known polymerization processes, for example as follows: a reactor is charged with 1380 ml of toluene and 6 g of aluminum trichloride (Aldrich product, purity = 99%). The suspension is brought to 25 ° C.
Un mélange de monomères constitué de 196 g de styrène et de 204 g de limonène (ou 4- isopropenyl-1-méthyl-l-cyclohéxène ; produit Fluka ; pureté > 99%) est ajouté à la suspension goutte à goutte, pendant 5 min. La température du milieu réactionnel augmente à 58°C. Après 15 min de polymérisation la réaction est stoppée avec 250 ml d'eau permutée.A monomer mixture consisting of 196 g of styrene and 204 g of limonene (or 4-isopropenyl-1-methyl-1-cyclohexene, Fluka product, purity> 99%) is added to the suspension dropwise for 5 minutes. . The temperature of the reaction medium increases to 58 ° C. After polymerization for 15 minutes, the reaction is quenched with 250 ml of deionized water.
La phase organique est récupérée. A la résine en solution peut être ajoutée un anti-oxydantThe organic phase is recovered. To the resin in solution can be added an antioxidant
(par exemple 1,6 g de 2,2'-méthylène-bis(4-méthyl-6-tertiobutylphénol). La majorité du toluène est éliminé à l'évaporateur rotatif à 700C sous pression réduite. Le produit final est obtenu après séchage en étuve à 200°C sous pression réduite. On obtient ainsi une résine de copolymère limonène-styrène (Tg = 52°C ; Mn = 720 ; Ip = 1 ,4) sous forme d'un matériau de couleur beige, dur, cassant et friable à température ambiante, avec une conversion des monomères complète (99 à 100%, d'après chromatographie en phase gazeuse).(For example 1.6 g of 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) The majority of toluene is removed on a rotary evaporator at 70 ° C. under reduced pressure. After drying in an oven at 200 ° C. under reduced pressure, a limonene-styrene copolymer resin (Tg = 52 ° C., Mn = 720, Ip = 1.4) is obtained in the form of a beige-colored, hard-colored material. brittle and brittle at room temperature, with complete monomer conversion (99-100%, based on gas chromatography).
Le taux de résine de copolymère de terpène/ vinylaromatique doit être compris entre 5 et 35 pce. En dessous du minimum indiqué, l'effet technique visé est insuffisant alors qu'au- delà de 35 pce, le pouvoir collant des compositions à l'état cru, sur les outils de mélangeage, devient rédhibitoire du point de vue industriel. Pour cette raison, ce taux de résine est de préférence compris entre 5 et 25 pce, plus préférentiellement entre 5 et 20 pce.The content of terpene / vinylaromatic copolymer resin must be between 5 and 35 phr. Below the minimum indicated, the technical effect targeted is insufficient, whereas beyond 35 phr, the stickiness of the compositions in the green state, on the mixing tools, becomes unacceptable from the industrial point of view. For this reason, this level of resin is preferably between 5 and 25 phr, more preferably between 5 and 20 phr.
Celui de l'huile MES ou TDAE est de préférence compris entre 10 et 30 pce, plus préférentiellement compris entre 10 et 25 pce, tandis que le taux de système plastifiant total de l'invention comportant l'huile MES et/ou TDAE et la résine, est compris préférentiellement entre 15 et 45 pce, plus préférentiellement entre 20 et 40 pce. La résine de copolymère terpène/ vinylaromatique, en particulier terpène/styrène, présente au moins une (plus préférentiellement l'ensemble) des caractéristiques préférentielles suivantes :That of the MES or TDAE oil is preferably between 10 and 30 phr, more preferably between 10 and 25 phr, while the total plasticizer system rate of the invention comprising the MES oil and / or TDAE and the resin, is preferably between 15 and 45 phr, more preferably between 20 and 40 phr. The terpene / vinylaromatic copolymer resin, in particular terpene / styrene, has at least one (more preferably all) of the following preferred characteristics:
une Tg supérieure à 25°C (plus particulièrement supérieure à 300C) ; - une masse moléculaire moyenne en nombre (Mn) comprise entre 400 et 2000 g/mol ; un indice de polymolécularité (Ip) inférieur à 3 (rappel : Ip = Mw/Mn avec Mw masse moléculaire moyenne en poids) ; un taux d'unités dérivées de monomère terpène (en particulier limonène) et un taux d'unités dérivées de monomère vinylaromatique (en particulier styrène) qui sont chacun compris entre 5% et 95% (plus particulièrement chacun compris entre 10% et 90%).a Tg greater than 25 ° C (more preferably greater than 30 0 C); a number-average molecular mass (Mn) of between 400 and 2000 g / mol; a polymolecularity index (Ip) of less than 3 (booster: Ip = Mw / Mn with Mw weight average molecular weight); a rate of units derived from terpene monomer (in particular limonene) and a level of units derived from vinylaromatic monomer (in particular styrene) which are each between 5% and 95% (more particularly each between 10% and 90%) ).
Encore plus préférentiellement, cette résine présente au moins une (plus préférentiellement l'ensemble) des caractéristiques préférentielles suivantes :Even more preferentially, this resin has at least one (more preferably all) of the following preferred characteristics:
- une Tg comprise entre 300C et 800C (plus particulièrement entre 35°C et 600C) ; une masse moléculaire Mn comprise entre 600 et 1500 g/mol ; un indice de polymolécularité Ip inférieur à 2,5 ; un taux d'unités dérivées de monomère vinylaromatique (en particulier styrène) supérieur à 40% (plus particulièrement compris entre 40% et 90%).a Tg of between 30 ° C. and 80 ° C. (more particularly between 35 ° C. and 60 ° C.); a molecular weight Mn of between 600 and 1500 g / mol; a polymolecularity index Ip of less than 2.5; a level of units derived from vinylaromatic monomer (in particular styrene) greater than 40% (more particularly between 40% and 90%).
La température de transition vitreuse Tg est mesurée de manière connue par DSC (Differential Scanning Calorimetry), selon la norme ASTM D3418 (1999).The glass transition temperature Tg is measured in a known manner by DSC (Differential Scanning Calorimetry), according to the ASTM D3418 (1999) standard.
La macrostructure (Mw, Mn et Ip) du copolymère terpène/ vinylaromatique est déterminée par chromatographie d'exclusion stérique (SEC) : solvant tétrahydrofurane ; températureThe macrostructure (Mw, Mn and Ip) of the terpene / vinylaromatic copolymer is determined by steric exclusion chromatography (SEC): solvent tetrahydrofuran; temperature
35°C ; concentration 1 g/1 ; débit 1 ml/min ; solution filtrée sur filtre de porosité 0,45 μm avant injection ; étalonnage de Moore avec des étalons de polystyrène ; jeu de 3 colonnes35 ° C; concentration 1 g / 1; flow rate 1 ml / min; filtered solution on 0.45 μm porosity filter before injection; Moore calibration with polystyrene standards; set of 3 columns
"WATERS" en série ("STYRAGEL" HR4E, HRl et HR0.5) ; détection par réfractomètre différentiel ("WATERS 2410") et son logiciel d'exploitation associé ("WATERS EMPOWER")."WATERS" in series ("STYRAGEL" HR4E, HR1 and HR0.5); differential refractometer detection ("WATERS 2410") and its associated operating software ("WATERS EMPOWER").
Selon un mode préférentiel de réalisation de l'invention, notamment lorsque la composition de l'invention est destinée à une bande de roulement de pneumatique, le système plastifiant de l'invention comprend en outre entre 5 et 35 pce (plus préférentiellement entre 10 et 30 pce) d'un triester d'acide gras insaturé (Ci2-C22) de glycérol, en particulier un trioléate de glycérol (dérivé de l'acide oléique et du glycérol), présent par exemple sous forme d'une huile végétale de tournesol ou de colza. Un tel triester permet de minimiser, dans ladite bande de roulement, d'une part l'exsudation en roulage par compression du système plastifiant total et, d'autre part, la migration dudit plastifiant vers des mélanges adjacents à la bande de roulement. Ceci se traduit par un tassement et un durcissement également minimisés pour la bande de roulement et, par conséquent, par une conservation dans le temps des performances d'adhérence. Dans un tel cas, de préférence, l'acide gras (ou l'ensemble des acides gras si plusieurs sont présents) comporte de l'acide oléique selon une fraction massique au moins égale à 60%.According to a preferred embodiment of the invention, especially when the composition of the invention is intended for a tire tread, the plasticizer system of the invention further comprises between 5 and 35 phr (more preferably between 10 and 30 phr) of an unsaturated (Ci 2 -C 22 ) fatty acid triester of glycerol, in particular a glycerol trioleate (derived from oleic acid and glycerol), present for example in the form of a vegetable oil sunflower or rapeseed. Such a triester makes it possible to minimize, in said tread, on the one hand the exudation in compression rolling of the total plasticizer system and, on the other hand, the migration of said plasticizer towards mixtures adjacent to the tread. This results in a settlement and hardening also minimized for the rolling and, therefore, by a retention in time of adhesion performance. In such a case, preferably, the fatty acid (or all of the fatty acids if several are present) comprises oleic acid in a mass fraction of at least 60%.
Lorsque le système plastifiant de l'invention comprend un tel triester d'acide gras de glycérol en complément de l'huile MES ou TDAE et de la résine de copolymère terpène/ vinylaromatique, le taux global de système plastifiant dans la composition de caoutchouc de l'invention est de préférence compris entre 20 et 70 pce, plus préférentiellement compris entre 30 et 60 pce.When the plasticizer system of the invention comprises such a triester of glycerol fatty acid in addition to the oil MES or TDAE and the terpene / vinylaromatic copolymer resin, the overall rate of plasticizer system in the rubber composition of the The invention is preferably between 20 and 70 phr, more preferably between 30 and 60 phr.
Le système plastifiant de l'invention pourrait également comporter d'autres agents plastifiants non aromatiques ou très faiblement aromatiques, par exemple des huiles naphténiques, paraffiniques, d'autres résines plastifiantes hydrocarbonées présentant une haute Tg de préférence supérieure à 25°C, en combinaison avec la résine de copolymère terpène/ vinylaromatique et l'huile MES ou TDAE précédemment décrits.The plasticizer system of the invention could also comprise other non-aromatic or very weakly aromatic plasticizing agents, for example naphthenic, paraffinic, other hydrocarbon plasticizing resins having a high Tg preferably greater than 25 ° C, in combination with the terpene / vinylaromatic copolymer resin and the MES or TDAE oil previously described.
Additifs diversVarious additives
Les compositions de caoutchouc conformes à l'invention comportent également tout ou partie des additifs usuels habituellement utilisés dans les compositions d'élastomères destinées à la fabrication de pneumatiques, notamment de bandes de roulement, comme par exemple des pigments, des agents de protection tels que cires anti-ozone, anti-ozonants chimiques, antioxydants, des agents anti-fatigue, des résines renforçantes, des accepteurs (par exemple résine phénolique novolaque) ou des donneurs de méthylène (par exemple HMT ou H3M) tels que décrits par exemple dans la demande WO 02/10269 (ou US 2003/212185), un système de réticulation à base soit de soufre, soit de donneurs de soufre et/ou de peroxyde et/ou de bismaléimides, des accélérateurs de vulcanisation, des activateurs de vulcanisation.The rubber compositions in accordance with the invention also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tires, in particular treads, such as, for example, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, antioxidants, anti-fatigue agents, reinforcing resins, acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M) as described, for example, in the US Pat. WO 02/10269 (or US 2003/212185), a crosslinking system based on either sulfur, or sulfur and / or peroxide donors and / or bismaleimides, vulcanization accelerators, vulcanization activators.
Ces compositions peuvent également contenir, en complément des agents de couplage, des activateurs de couplage, des agents de recouvrement des charges inorganiques ou plus généralement des agents d'aide à la mise en œuvre susceptibles de manière connue, grâce à une amélioration de la dispersion de la charge dans la matrice de caoutchouc et à un abaissement de la viscosité des compositions, d'améliorer leur faculté de mise en œuvre à l'état cru, ces agents étant par exemple des silanes hydrolysables tels que des alkylalkoxysilanes, des polyols, des polyéthers, des aminés primaires, secondaires ou tertiaires, des polyorganosiloxanes hydroxylés ou hydrolysables.These compositions may also contain, in addition to the coupling agents, coupling activators, inorganic charge-covering agents or, more generally, processing aids that can be used in a known manner, thanks to an improvement in the dispersion. of the charge in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to use in the green state, these agents being for example hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes.
Préparation des compositions de caoutchouc Les compositions sont fabriquées dans des mélangeurs appropriés, en utilisant deux phases de préparation successives bien connues de l'homme du métier : une première phase de travail ou malaxage thermomécanique (phase dite "non-productive") à haute température, jusqu'à une température maximale comprise entre 110°C et 190°C, de préférence entre 130°C et 180°C, suivie d'une seconde phase de travail mécanique (phase dite "productive") jusqu'à une plus basse température, typiquement inférieure à 1100C, par exemple entre 400C et 1000C, phase de finition au cours de laquelle est incorporé le système de réticulation.Preparation of rubber compositions The compositions are manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (so-called "non-productive" phase) at high temperature, up to a maximum of maximum temperature between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, followed by a second phase of mechanical work (so-called "productive" phase) to a lower temperature, typically less than 110 0 C, for example between 40 0 C and 100 0 C, finishing phase during which is incorporated the crosslinking system.
Le procédé conforme à l'invention pour préparer une composition de caoutchouc présentant une résistance à l'abrasion et aux coupures améliorée, comporte les étapes suivantes :The method according to the invention for preparing a rubber composition having improved abrasion and cut resistance comprises the following steps:
• incorporer à un élastomère diénique, au cours d'une première étape (dite "non- productive"), au moins une charge renforçante et un système plastifiant, en malaxant thermomécaniquement le tout, en une ou plusieurs fois, jusqu'à atteindre une température maximale comprise entre 1100C et 1900C ;Incorporating in a diene elastomer, during a first step (so-called "nonproductive"), at least one reinforcing filler and a plasticizer system, thermomechanically kneading the whole, in one or more times, to reach a maximum temperature between 110 0 C and 190 0 C;
• refroidir l'ensemble à une température inférieure à 1000C ;• cool the assembly to a temperature below 100 0 C;
• incorporer ensuite, au cours d'une seconde étape (dite "productive"), le système de réticulation ;• then incorporate, during a second stage (called "productive"), the crosslinking system;
• malaxer le tout jusqu'à une température maximale inférieure à 1100C,• mix everything up to a maximum temperature below 110 0 C,
et il est caractérisé en ce que ledit système plastifiant comporte :and it is characterized in that said plasticizer system comprises:
entre 5 et 35 pce d'une huile MES ou TDAE ; entre 5 et 35 pce d'une résine de copolymère terpène/ vinylaromatique (de préférence terpène/styrène, en particulier limonène/ styrène).between 5 and 35 phr of a MES or TDAE oil; between 5 and 35 phr of a terpene / vinylaromatic copolymer resin (preferably terpene / styrene, in particular limonene / styrene).
A titre d'exemple, la phase non-productive est conduite en une seule étape thermomécanique au cours de laquelle on introduit, dans un mélangeur approprié tel qu'un mélangeur interne usuel, dans un premier temps tous les constituants de base nécessaires (élastomère diénique, charge renforçante et agent de couplage si nécessaire, système de plastification), puis dans un deuxième temps, par exemple après une à deux minutes de malaxage, les autres additifs, éventuels agents de recouvrement ou de mise en œuvre complémentaires, à l'exception du système de réticulation. Après refroidissement du mélange ainsi obtenu, on incorpore alors dans un mélangeur externe tel qu'un mélangeur à cylindres, maintenu à basse température (par exemple entre 400C et 1000C), le système de réticulation. L'ensemble est alors mélangé (phase productive) pendant quelques minutes, par exemple entre 2 et 15 min.By way of example, the non-productive phase is carried out in a single thermomechanical step during which all the necessary basic constituents (diene elastomer) are introduced into a suitable mixer such as a conventional internal mixer. , reinforcing filler and coupling agent if necessary, plasticizing system), then in a second step, for example after one to two minutes of kneading, the other additives, any additional coating or processing agents, with the exception of of the crosslinking system. After cooling the mixture thus obtained, it is then incorporated in an external mixer such as a roll mill, maintained at low temperature (for example between 40 0 C and 100 0 C), the crosslinking system. The whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
Le système de réticulation est préférentiellement un système de vulcanisation à base de soufre et d'un accélérateur. On peut utiliser tout composé susceptible d'agir comme accélérateur de vulcanisation des élastomères diéniques en présence de soufre, en particulier ceux choisis dans le groupe constitué par disulfure de 2-mercaptobenzothiazyle (en abrégé "MBTS"), N-cyclohexyl-2-benzothiazyle sulfénamide (en abrégé "CBS"), N,N-dicyclohexyl- 2-benzothiazyle sulfénamide (en abrégé "DCBS"), N-ter-butyl-2-benzothiazyle sulfénamide (en abrégé "TBBS"), N-ter-butyl-2-benzothiazyle sulfénimide (en abrégé "TBSI") et les mélanges de ces composés. De préférence, on utilise un accélérateur primaire du type sulfénamide.The crosslinking system is preferably a vulcanization system based on sulfur and an accelerator. Any compound capable of acting as an accelerator for vulcanization of diene elastomers in the presence of sulfur, in particular those selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated "CBS"), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (abbreviated to " DCBS "), N-tert-butyl-2-benzothiazylsulfenamide (abbreviated" TBBS "), N-tert-butyl-2-benzothiazylsulfenimide (abbreviated" TBSI ") and mixtures of these compounds. Preferably, a primary accelerator of the sulfenamide type is used.
A ce système de vulcanisation viennent s'ajouter, incorporés au cours de la première phase non-productive et/ou au cours de la phase productive, divers accélérateurs secondaires ou activateurs de vulcanisation connus tels que oxyde de zinc, acide stéarique, dérivés guanidiques (en particulier diphénylguanidine), etc. Dans le cas d'une utilisation de la composition de l'invention en bande de roulement de pneumatique, le taux de soufre est par exemple compris entre 0,5 et 3,0 pce, celui de l'accélérateur primaire entre 0,5 et 5,0 pce.To this vulcanization system are added, incorporated during the first non-productive phase and / or during the productive phase, various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives ( especially diphenylguanidine), etc. In the case of a use of the composition of the invention in tread tire, the sulfur content is for example between 0.5 and 3.0 phr, that of the primary accelerator between 0.5 and 5.0 pce.
La composition finale ainsi obtenue peut ensuite être calandrée, par exemple sous la forme d'une feuille, d'une plaque ou encore extrudée, par exemple pour former un profilé de caoutchouc utilisé pour la fabrication d'un produit semi-fini pour pneumatique, tel que bandes de roulement, nappes ou autres bandes, sous-couches, divers blocs de caoutchouc, renforcés ou non de renforts textiles ou métalliques, destinés à former une partie de la structure du pneumatique, tout particulièrement sa bande de roulement.The final composition thus obtained can then be calendered, for example in the form of a sheet, a plate or extruded, for example to form a rubber profile used for the manufacture of a semi-finished tire product, such as treads, webs or other webs, underlays, various rubber blocks, reinforced or not with textile or metal reinforcements, intended to form a part of the tire structure, particularly its tread.
La vulcanisation (ou cuisson) peut ensuite être conduite de manière connue à une température généralement comprise entre 130°C et 200°C, de préférence sous pression, pendant un temps suffisant qui peut varier par exemple entre 5 et 90 min en fonction notamment de la température de cuisson, du système de vulcanisation adopté et de la cinétique de vulcanisation de la composition considérée.The vulcanization (or firing) may then be carried out in a known manner at a temperature generally of between 130 ° C. and 200 ° C., preferably under pressure, for a sufficient time which may vary, for example, between 5 and 90 min, depending in particular on the firing temperature, the vulcanization system adopted and the vulcanization kinetics of the composition under consideration.
L'invention concerne les compositions de caoutchouc précédemment décrites tant à l'état dit "cru" (i.e. avant cuisson) qu'à l'état dit "cuit" ou vulcanisé (i.e. après vulcanisation).The invention relates to the rubber compositions described above both in the so-called "raw" state (i.e., before firing) and in the so-called "cooked" or vulcanized state (i.e. after vulcanization).
Tests de résistance aux coupures et à l'écaillementCut and peel resistance tests
Une composition selon l'invention (notée ci-après C-3) a été comparée à deux compositions témoins (notées C-I et C-2), les trois compositions testées étant identiques aux différences près qui suivent :A composition according to the invention (hereinafter noted C-3) was compared with two control compositions (denoted C-I and C-2), the three compositions tested being identical, with the following differences:
C-I : témoin selon art antérieur avec huile aromatique (37 pce) ; C-2 : témoin avec huile MES seule (31,5 pce);C-I: control according to prior art with aromatic oil (37 phr); C-2: control with MES oil alone (31.5 phr);
C-3 : composition avec système plastifiant selon l'invention (combinaison de 12 pce d'huile MES et de 19,5 pce de résine de copolymère limonène/ styrène). Ces trois compositions, à l'exception de leur système plastifiant, possèdent une formulation usuelle pour une composition de caoutchouc pour bande de roulement de pneumatique, à savoir essentiellement un mélange d'élastomères diéniques (SSBR 70 pce/BR 30 pce), de la silice (78 pce), du noir de carbone (4 pce) et un système de vulcanisation. Les compositions C-I et C-2 ont été formulées à iso-volume d'huile plastifiante. Dans la composition C-3, 2/3 environ (soit 19,5 pce) d'huile MES ont été remplacés par la résine limonène/ styrène (19,5 pce) précédemment synthétisée, comparativement à la composition témoin C-2.C-3: Composition with plasticizer system according to the invention (combination of 12 phr of MES oil and 19.5 phr of limonene / styrene copolymer resin). These three compositions, with the exception of their plasticizer system, have a customary formulation for a tire tread rubber composition, namely essentially a mixture of diene elastomers (SSBR 70 pce / BR 30 pce), silica (78 phr), carbon black (4 phr) and a vulcanization system. Compositions CI and C-2 were formulated with iso-volume of plasticizing oil. In the composition C-3, about 2/3 (ie 19.5 phr) of MES oil were replaced by the limonene / styrene resin (19.5 phr) previously synthesized, compared with the control composition C-2.
Les trois compositions ont été testées comme bandes de roulement de pneumatiques tourisme à carcasse radiale, de dimension 195/65 Rl 5 (indice de vitesse H), conventionnellement fabriqués et en tous points identiques hormis la composition de caoutchouc constitutive de la bande de roulement. Ces pneumatiques sont notés respectivement P-I, P-2 et P-3, ils ont été montés sur un véhicule tourisme (véhicule Citroën modèle "C5" - pression avant et arrière : 2,2 bars - pneus testés montés à l'avant du véhicule - température ambiante 25°C) pour être soumis à un test d'endurance permettant d'apprécier la résistance aux coupures et à l'écaillement des compositions de caoutchouc.The three compositions were tested as treads of passenger tires with radial carcass, dimension 195/65 Rl 5 (speed index H), conventionally manufactured and in all respects identical except for the constitutive rubber composition of the tread. These tires are noted respectively PI, P-2 and P-3, they were mounted on a passenger vehicle (Citroën model "C5" vehicle - front and rear pressure: 2.2 bars - tested tires mounted on the front of the vehicle - ambient temperature 25 ° C) to be subjected to an endurance test to assess the resistance to cuts and chipping of rubber compositions.
Le test a été conduit à vitesse de roulage modérée (inférieure à 60 km/h), sur deux circuits successifs :The test was conducted at a moderate driving speed (less than 60 km / h), on two successive circuits:
un premier roulage sur un circuit en terre battue caillouteux (cailloux à grosse granulométrie), destiné à fragiliser la bande de roulement, sous forme de coupures et autres agressions superficielles des pains de gomme constitutifs de sa sculpture ; - un second roulage sur un circuit goudronné fortement virageux, destiné à "révéler" l'écaillement, suite à l'arrachement de morceaux de caoutchouc (en forme d'écaillés), selon les plans fragilisés.a first driving on a stony clay circuit (coarse grained stones), intended to weaken the tread, in the form of cuts and other superficial aggressions of the gum rolls constituting his sculpture; - A second run on a tarred circuit highly virulent, intended to "reveal" the peeling, following the tearing of rubber pieces (shaped flakes), according to the weakened planes.
A la sortie du test de roulage, l'état des bandes de roulement est évalué d'une part visuellement (photographies) par l'attribution d'une note (selon une échelle de gravité de 1 à 10), d'autre part par le mesurage de la perte de poids. La résistance à l'écaillement est finalement appréciée par un note globale relative (base 100 sur un produit de référence).At the end of the rolling test, the state of the treads is evaluated on the one hand visually (photographs) by the attribution of a note (according to a gravity scale of 1 to 10), on the other hand by the measurement of weight loss. Resistance to peeling is finally appreciated by a relative overall score (base 100 on a reference product).
Si les propriétés usuelles des compositions, avant et après cuisson, sont sensiblement identiques, seul le test de résistance à l'écaillement démontre tout l'intérêt de la composition selon l'invention par rapport aux deux compositions témoins.If the usual properties of the compositions, before and after curing, are substantially identical, only the test for resistance to peeling demonstrates all the advantages of the composition according to the invention with respect to the two control compositions.
Les résultats sont rapportés dans le tableau ci-dessous, en unités relatives, la base 100 ayant étant retenue pour le pneu témoin P-I dont la bande de roulement comporte l'huile aromatique conventionnelle (une valeur supérieure à 100 indique une performance améliorée par rapport au témoin de base 100):The results are reported in the table below, in relative units, the base 100 being selected for the control tire PI whose tread comprises the oil conventional flavor (greater than 100 indicates improved performance over base control 100):
TableauBoard
On note tout d'abord que le remplacement de l'huile aromatique par l'huile MES (pneus P-2 comparés aux pneus P-I) se traduit par une chute inattendue de 15% de la résistance à l'écaillement, ce qui est tout à fait notable et peut être considéré comme rédhibitoire pour certains usages des pneumatiques.First of all, the replacement of the aromatic oil with MES oil (P-2 tires compared to PI tires) results in an unexpected 15% drop in the resistance to flaking, which is all noticeable and may be considered unacceptable for certain uses of tires.
Par contre, le remplacement d'une partie de l'huile MES par la résine polymérique terpène/ styrène se traduit, de manière surprenante, par une remontée spectaculaire de performance (+ 34% pour les pneus P-3 comparativement aux pneus P-2), la résistance observée sur les pneus P-3 de l'invention étant même supérieure de 14% à celle des pneumatiques P-I constituant la référence de départ. On the other hand, the replacement of a part of the MES oil by the terpene / styrene polymer resin surprisingly results in a spectacular increase in performance (+ 34% for P-3 tires compared to P-2 tires). ), the resistance observed on the tires P-3 of the invention being even 14% higher than that of the tires PI constituting the starting reference.

Claims

REVENDICATIONS
1. Composition de caoutchouc à base d'au moins un élastomère diénique, une charge renforçante, un système plastifiant et un système de réticulation, caractérisée en ce que ledit système plastifiant comporte (pce = parties en poids pour cent parties d'élastomère) :1. A rubber composition based on at least one diene elastomer, a reinforcing filler, a plasticizer system and a crosslinking system, characterized in that said plasticizer system comprises (phr = parts by weight per hundred parts of elastomer):
entre 5 et 35 pce d'une huile MES ou TDAE ; - entre 5 et 35 pce d'une résine de copolymère terpène/ vinylaromatique.between 5 and 35 phr of a MES or TDAE oil; between 5 and 35 phr of a terpene / vinylaromatic copolymer resin.
2. Composition selon la revendication 1 , ledit copolymère étant un copolymère de terpène et de styrène.2. Composition according to claim 1, said copolymer being a terpene-styrene copolymer.
3. Composition selon la revendication 2, ledit copolymère étant un copolymère de limonène et de styrène.3. Composition according to claim 2, said copolymer being a copolymer of limonene and styrene.
4. Composition selon l'une quelconque des revendications 1 à 3, la température de transition vitreuse de la résine étant supérieure à 25°C.4. Composition according to any one of claims 1 to 3, the glass transition temperature of the resin being greater than 25 ° C.
5. Composition selon la revendication 4, la température de transition vitreuse de la résine étant supérieure à 30°C.5. The composition of claim 4, the glass transition temperature of the resin being greater than 30 ° C.
6. Composition selon la revendication 5, la température de transition vitreuse de la résine étant comprise entre 30°C et 800C.6. Composition according to claim 5, the glass transition temperature of the resin being between 30 ° C and 80 0 C.
7. Composition selon l'une quelconque des revendications 1 à 6, la masse moléculaire moyenne en nombre de la résine étant comprise entre 400 et 2000 g/mol.7. Composition according to any one of claims 1 to 6, the number-average molecular weight of the resin being between 400 and 2000 g / mol.
8. Composition selon la revendication 7, la masse moléculaire moyenne en nombre de la résine étant comprise entre 600 et 1500 g/mol.8. Composition according to claim 7, the number-average molecular weight of the resin being between 600 and 1500 g / mol.
9. Composition selon l'une quelconque des revendications 1 à 8, l'indice de polymolécularité de la résine étant inférieur à 3.9. Composition according to any one of claims 1 to 8, the polymolecularity index of the resin being less than 3.
10. Composition selon la revendication 9, l'indice de polymolécularité de la résine étant inférieur à 2,5. 10. Composition according to claim 9, the polymolecularity index of the resin being less than 2.5.
11. Composition selon l'une quelconque des revendications 1 à 10, le taux d'unités dérivées de monomère terpène et le taux d'unités dérivées de monomère vinylaromatique étant chacun compris entre 5% et 95% (% en poids).11. Composition according to any one of claims 1 to 10, the level of units derived from terpene monomer and the level of units derived from vinylaromatic monomer being each between 5% and 95% (% by weight).
12. Composition selon la revendication 11, le taux d'unités dérivées de monomère terpène et le taux d'unités dérivées de monomère vinylaromatique étant chacun compris entre 10% et 90%.12. The composition of claim 11, the terpene monomer derived unit rate and the vinylaromatic monomer derived unit level being each between 10% and 90%.
13. Composition selon la revendication 12, le taux d'unités dérivées de monomère vinylaromatique étant supérieur à 40%.13. Composition according to claim 12, the units derived from vinylaromatic monomer being greater than 40%.
14. Composition selon la revendication 13, le taux d'unités dérivées de monomère vinylaromatique étant compris entre 40% et 90%.14. The composition of claim 13, the units derived from vinylaromatic monomer being between 40% and 90%.
15. Composition selon l'une quelconque des revendications 1 à 14, le taux de résine étant compris entre 5 et 25 pce.15. Composition according to any one of claims 1 to 14, the resin content being between 5 and 25 phr.
16. Composition selon la revendication 15, le taux de résine étant compris entre 5 et 20 pce.16. The composition of claim 15, the resin content being between 5 and 20 phr.
17. Composition selon l'une quelconque des revendications 1 à 16, le taux d'huile MES ou TDAE étant compris entre 10 et 30 pce.17. Composition according to any one of claims 1 to 16, the MES or TDAE oil content being between 10 and 30 phr.
18. Composition selon la revendication 17, le taux d'huile MES ou TDAE étant compris entre 10 et 25 pce.18. The composition of claim 17, the MES or TDAE oil content being between 10 and 25 phr.
19. Composition selon l'une quelconque des revendications 1 à 18, le taux de système plastifiant total étant compris entre 15 et 45 pce.19. Composition according to any one of claims 1 to 18, the total plasticizer system content being between 15 and 45 phr.
20. Composition selon la revendication 19, le taux de système plastifiant total étant compris entre 20 et 40 pce.20. The composition of claim 19, the total plasticizer system being between 20 and 40 phr.
21. Composition selon l'une quelconque des revendications 1 à 20, le système plastifiant comportant en outre entre 5 et 35 pce d'un triester d'acide gras insaturé (Ci2-C22) de glycérol.21. Composition according to any one of claims 1 to 20, the plasticizer system further comprising between 5 and 35 phr of a triester of unsaturated fatty acid (Ci 2 -C 22 ) glycerol.
22. Composition selon la revendication 21, le triester étant un trioléate de glycérol.22. Composition according to claim 21, the triester being a glycerol trioleate.
23. Composition selon la revendication 22, le trioléate de glycérol étant une huile végétale de tournesol ou de colza. 23. A composition according to claim 22, the glycerol trioleate being a vegetable oil of sunflower or rapeseed.
24. Composition selon l'une quelconque des revendications 21 à 23, le taux de système plastifiant total étant compris entre 20 et 70 pce.24. Composition according to any one of claims 21 to 23, the total plasticizer system being between 20 and 70 phr.
25. Composition selon la revendication 24, le taux de système plastifiant total étant compris entre 30 et 60 pce.25. The composition of claim 24, the total plasticizer system ratio being between 30 and 60 phr.
26. Composition selon l'une quelconque des revendications 1 à 25, Pélastornère diénique étant choisi dans le groupe constitué par les polybutadiènes, le caoutchouc naturel, les polyisoprènes de synthèse, les copolymères de butadiène, les copolymères d'isoprène et les mélanges de ces élastomères.26. Composition according to any one of claims 1 to 25, the diene elastomer being chosen from the group consisting of polybutadienes, natural rubber, synthetic polyisoprenes, butadiene copolymers, isoprene copolymers and mixtures thereof. elastomers.
27. Composition selon l'une quelconque des revendications 1 à 26, la charge renforçante étant présente à un taux compris entre 20 et 200 pce.27. Composition according to any one of claims 1 to 26, the reinforcing filler being present at a rate of between 20 and 200 phr.
28. Procédé pour préparer une composition de caoutchouc présentant une résistance à l'abrasion et aux coupures améliorée, cette composition étant à base d'un élastomère diénique, d'une charge renforçante, d'un système plastifiant et d'un système de réticulation, ledit procédé comportant les étapes suivantes : incorporer à un élastomère diénique, au cours d'une première étape dite "non- productive", au moins une charge renforçante et un système plastifiant, en malaxant thermomécaniquement le tout, en une ou plusieurs fois, jusqu'à atteindre une température maximale comprise entre 110°C et 190°C ;28. A process for preparing a rubber composition having improved abrasion and cut resistance, this composition being based on a diene elastomer, a reinforcing filler, a plasticizer system and a crosslinking system. said process comprising the following steps: incorporating in a diene elastomer, during a so-called "nonproductive" first step, at least one reinforcing filler and a plasticizer system, by thermomechanically kneading the whole, in one or more times, until reaching a maximum temperature of between 110 ° C and 190 ° C;
• refroidir l'ensemble à une température inférieure à 1000C ;• cool the assembly to a temperature below 100 0 C;
• incorporer ensuite, au cours d'une seconde étape dite "productive", le système de réticulation ;• then incorporate, during a second so-called "productive" step, the crosslinking system;
• malaxer le tout jusqu'à une température maximale inférieure à 110°C,• mix everything up to a maximum temperature of less than 110 ° C,
et étant caractérisé en ce que ledit système plastifiant comporte (pce = parties en poids pour cent parties d'élastomère) :and being characterized in that said plasticizer system comprises (phr = parts by weight per hundred parts of elastomer):
entre 5 et 35 pce d'une huile MES ou TDAE ; entre 5 et 35 pce d'une résine de copolymère terpène/ vinylaromatique.between 5 and 35 phr of a MES or TDAE oil; between 5 and 35 phr of a terpene / vinylaromatic copolymer resin.
29. Utilisation d'une composition selon l'une quelconque des revendications 1 à 27, pour la fabrication d'un article fini ou d'un produit semi-fini destiné à un pneumatique ou un système de liaison pneu/ véhicule automobile.29. Use of a composition according to any one of claims 1 to 27, for the manufacture of a finished article or a semi-finished product for a tire or a tire / motor vehicle connection system.
30. Article fini ou produit semi-fini destiné à destiné à un pneumatique ou un système de liaison pneu/ véhicule automobile, comportant une composition selon l'une quelconque des revendications 1 à 27. 30. Finished article or semi-finished product intended for use in a tire or a tire / motor vehicle connection system, comprising a composition according to any one of Claims 1 to 27.
31. Pneumatique comportant une composition de caoutchouc selon l'une quelconque des revendications 1 à 27.31. A tire comprising a rubber composition according to any one of claims 1 to 27.
32. Bande de roulement de pneumatique comportant une composition de caoutchouc selon l'une quelconque des revendications 1 à 27.Tire tread comprising a rubber composition according to any one of claims 1 to 27.
33. Système plastifiant utilisable pour la plastification d'une composition de caoutchouc diénique, caractérisé en ce qu'il comporte une huile MES ou TDAE et une résine de copolymère terpène/ viny laromatique .33. Plasticizer system that can be used for the plasticization of a diene rubber composition, characterized in that it comprises a MES or TDAE oil and a terpene / vinyl laromatic copolymer resin.
34. Système plastifiant selon la revendication 33, caractérisé en ce que la résine de copolymère terpène/ vinylaromatique est une résine de copolymère limonène/ styrène.34. Plasticizer system according to claim 33, characterized in that the terpene / vinylaromatic copolymer resin is a limonene / styrene copolymer resin.
35. Système plastifiant selon les revendications 33 ou 34, caractérisé en ce qu'il comprend en outre un triester d'acide gras insaturé (Ci2-C22) de glycérol.35. Plasticizer system according to claims 33 or 34, characterized in that it further comprises an unsaturated fatty acid triester (Ci 2 -C 22 ) of glycerol.
36. Système plastifiant selon la revendication 35, le triester étant un trioléate de glycérol.36. Plasticizer system according to claim 35, the triester being a glycerol trioleate.
37. Utilisation d'un système plastifiant selon l'une quelconque des revendications 33 à 36, pour la plastification d'une composition de caoutchouc diénique. 37. Use of a plasticizer system according to any one of claims 33 to 36 for the plasticization of a diene rubber composition.
EP06776284A 2005-08-08 2006-07-18 Plasticizing system for a rubber composition Withdrawn EP1915422A1 (en)

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FR2889538B1 (en) 2007-09-14
FR2889538A1 (en) 2007-02-09
BRPI0614237A2 (en) 2016-11-22
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WO2007017060A1 (en) 2007-02-15
JP2009504810A (en) 2009-02-05

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