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    • 专利摘要:
    The present invention relates to a tire tread which comprises a rubber composition based on at least: an elastomer matrix comprising more than 50% by weight of a first diene elastomer which carries a silanol function and a pendant amine function a silica present at a level of between 120 and 140 phr; a coupling agent; a plasticizer system comprising: comprising, in a content A ranging from 5 to 60 phr, a hydrocarbon resin having a Tg greater than 20 ° C .; - A content B ranging from 0 to 60 phr a liquid plasticizer; it being understood that the total level A + B is at least equal to 60 phr, preferably ranging from 60 to 90 phr. The tread according to the invention makes it possible to improve the compromise between the adhesion on wet ground and the adhesion on dry ground of a tire with low rolling resistance.
    公开号:FR3014443A1
    申请号:FR1362332
    申请日:2013-12-10
    公开日:2015-06-12
    发明作者:Philippe Labrunie；Gaudemaris Benoit De
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:

    [0001] The field of the invention is that of rubber tire compositions, more specifically rubber tread compositions. A tire tread must obey in a known manner to a large number of technical requirements, often antithetical, among which a low rolling resistance, a high wear resistance, as well as a high adhesion on a dry road 10 as wet. This compromise of properties, in particular from the point of view of rolling resistance and wear resistance, has been improved in recent years on "green tires" with low energy consumption, especially for passenger vehicles. , thanks in particular to the use of new low-hysteretic rubber compositions having the characteristic of being reinforced mainly by specific inorganic fillers qualified as reinforcing agents, in particular highly dispersible "HDS" (Highly Dispersible Silica) silicas, capable of competing, from the point of view of reinforcing power, with conventional pneumatic grade carbon blacks. The use of high levels of silica and plasticizer in a low hysteretic rubber composition based on functional diene elastomer and interactive with silica is described in patent application WO 2012/069567. Such a rubber composition makes it possible to provide a tire which contains a tread 25 comprising such a rubber composition an improved compromise with respect to rolling resistance and wet grip. In return, the use of a low hysteretic rubber composition may be accompanied by a reduction in dry-wall adhesion performance, since the hysteretic potential of the rubber composition has been decreased. This is why the improvement of the adhesion properties, both in dry and wet conditions, of tires with low rolling resistance remains a constant concern for tire designers. Continuing their research, the Applicants have unexpectedly discovered that the specific choice of a functional and interactive elastomer with respect to silica, a certain amount of silica associated with a specific choice of the plasticizer system makes it possible to Achieve an improved performance compromise over dry grip and wet grip of a tire with low rolling resistance. Thus, the subject of the invention is a tire tread which comprises a rubber composition based on at least: an elastomer matrix comprising more than 50% by weight of a first diene elastomer which carries a silanol function and a pendant amine function; a silica present at a level of between 120 and 140 phr; a coupling agent; a plasticizer system comprising: in a content A ranging from 5 to 60 phr, a hydrocarbon resin having a Tg greater than 20 ° C .; - A content B ranging from 0 to 60 phr a liquid plasticizer; - It being understood that the total rate A + B is at least equal to 60 phr, preferably 60 to 90 phr. The invention also relates to a tire which comprises a tread as defined above.
    [0002] The invention also relates to a method for preparing a tread according to the invention. The tires of the invention are particularly intended for equipping tourism-type motor vehicles, including 4x4 vehicles (four-wheel drive) and SUV vehicles ("Sport Utility Vehicles"), as well as two-wheeled vehicles (especially motorcycles). . The invention as well as its advantages will be readily understood in the light of the description and the following exemplary embodiments.
    [0003] DETAILED DESCRIPTION OF THE INVENTION In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight. The abbreviation "pce" means parts by weight per hundred parts of the elastomeric matrix which consists of all of the elastomers present in the rubber composition. All values of glass transition temperature "Tg" are measured in a known manner by DSC (Differential Scanning Calorimetry) according to ASTM D3418 (1999). On the other hand, any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term "from a to b" means the range from a to b (i.e., including the strict limits a and b). I-1. Diene elastomer P10-3215 - By elastomer (or indistinctly "rubber", the two terms being considered synonymous) of the "diene" type, must be understood in a known manner (one or more) elastomer derived from at least one of part (ie, a homopolymer or a copolymer) of monomers dienes (monomers bearing two carbon-carbon double bonds, conjugated or not). 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%).
    [0004] 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%. Although it is applicable to any type of diene elastomer, those skilled in the art of pneumatics will understand that the invention is preferably carried out with essentially unsaturated diene elastomers. These definitions being given, the term "diene elastomer" that may be used in the compositions according to the invention is understood to mean: (a) - any homopolymer obtained by polymerization of a conjugated diene monomer, preferably having from 4 to 12 carbon atoms; (b) - any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinyl aromatic compounds preferably having from 8 to 20 carbon atoms. As conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 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, "vinyl-toluene" commercial mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene. P10-3215 - 4 - According to one embodiment of the invention, the first diene elastomer is an SBR, preferably an SBR solution. According to this embodiment of the invention, the glass transition temperature, Tg, of the diene and vinylaromatic copolymer, in particular styrene, is advantageously between -55 ° and -40 ° C. In general, a function carried by a diene elastomer may be located on the elastomeric chain either at the end of the chain or inside the chain (that is to say outside the chain ends). The first case occurs for example when the diene elastomer is prepared using a polymerization initiator bearing the function or using a functionalising agent. The second case occurs for example when the diene elastomer is modified by the use of a coupling agent or starring carrying the function.
    [0005] According to a preferred embodiment of the invention, the silanol function and the pendant amine function are located outside the chain ends of the first diene elastomer.
    [0006] The amine function carried by the first diene elastomer is a pendant group. The pendant position of the amine function means, in known manner, that the nitrogen atom of the amine function does not interconnect between the carbon-carbon bonds of the elastomer chain of the first diene elastomer.
    [0007] According to a first variant of the invention, the silanol function carried by the first diene elastomer is a pendant group, which is to say that the silicon atom of the silanol function does not interconnect between the carbon-carbon bonds of the elastomeric chain of the first diene elastomer. A diene elastomer carrying a silanol pendant function may, for example, be prepared by hydrosilylation of the elastomeric chain with a silane carrying an alkoxysilane group, followed by hydrolysis of the alkoxysilane function in silanol function. According to a second variant of the invention, the silanol function carried by the first diene elastomer is not a pendant group, but is located in the elastomeric chain, which is to say that the silicon atom of the silanol function is intercalates between the carbon-carbon bonds of the elastomeric chain of the first diene elastomer. Such a diene elastomer may be prepared by coupling reaction of the elastomeric chains with a coupling agent carrying an alkoxysilane function and an amine function, followed by hydrolysis of the alkoxysilane function in silanol function. Suitable coupling agents are, for example, N, N-dialkylaminopropyltrialkoxysilanes, the P10-3215-dialkyl groups being C1-C10, preferably C1-C4, the compounds 3- (N, N-dimethylaminopropyl) trimethoxysilane, the 3- (N, N-dimethylaminopropyl) triethoxysilane, 3 - (N, N -diethylaminopropyl) trimethoxy silane, 3 - (N, N -diethylaminopropyl) triethoxy silane being more particularly preferred whatever the embodiment. of the invention. This second variant is preferred and applies to any embodiment of the invention. According to the first or the second variant, the hydrolysis of the alkoxysilane function carried by a diene elastomer in silanol function can be carried out according to the procedure described in the patent application EP 2,266,819 A1 or by a stripping step of the solution containing the diene elastomer. According to a preferred embodiment of the invention, the amine function is a tertiary amine. As tertiary amine function, there may be mentioned amines substituted with alkyl radicals C1-C10, preferably C1-C4 alkyl, more preferably a methyl or ethyl radical regardless of the embodiment of the invention. According to a particularly preferred embodiment of the invention, the first diene elastomer is predominantly in a linear form, that is to say if it contains starred or branched chains, these represent a minority weight fraction. in this elastomer, that is to say that the amount of star chains and branched chains present in the first diene elastomer is in a range from 0% to less than 50% by weight of the total weight of the first diene elastomer . It is understood that the first diene elastomer may consist of a mixture of elastomers which differ from each other by the chemical nature of the amine function, by their microstructure or by their macrostructure. When the elastomer matrix of the composition of the tread according to the invention comprises a second elastomer, this second elastomer is a diene elastomer. The second diene elastomer is different from the first diene elastomer in that it does not carry both silanol function and pendant amine function. However, this second elastomer may have a microstructure or a macrostructure which may be identical to or different from those of the first diene elastomer. It is used in a proportion of between 0 and 50%, preferably between 0 and 25%, more preferably between 0 and 10%. In other words, the elastomer matrix comprises more than 50%, preferably more than 75%, more preferably more than 90% by weight of the first diene elastomer, the 100% complement being constituted by a second diene elastomer. The second diene elastomer may be a polybutadiene, a natural rubber, a synthetic polyisoprene, a butadiene copolymer, an isoprene copolymer or a mixture of these elastomers.
    [0008] Reinforcing filler As another essential characteristic, the rubber composition of the tread according to the invention comprises between 120 and 140 phr of a silica.
    [0009] The silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g, especially between 60 and 300 m2 / g. As highly dispersible precipitated silicas (called "HDS"), mention may be made, for example, of the "Ultrasil" 7000 and "Ultrasil" 7005 silicas of the Degussa company, the "Zeosil" 1165MP, 1135MP and 1115MP silicas of the Rhodia company. "Hi-Sil" silica EZ150G from the company PPG, the "Zeopol" silicas 8715, 8745 and 8755 from the Huber Company, the silicas with a high specific surface area as described in the application WO 03/16387.
    [0010] The person skilled in the art will understand that, as the equivalent silica filler described in this paragraph, could be used a reinforcing filler of another nature, in particular organic such as carbon black, since this reinforcing filler would be covered of a silica. By way of example, mention may be made, for example, of carbon blacks for tires as described for example in documents WO 96/37547 and WO 99/28380. Advantageously, the silica content is in a range from 125 to 135 phr. According to one embodiment of the invention, the rubber composition of the tread according to the invention may comprise carbon black. The carbon black, when present, is preferably used at a level of less than 20 phr, more preferably less than 10 phr (for example between 0.5 and 20 phr, in particular between 2 and 10 phr). In the ranges indicated, it benefits from the coloring properties (black pigmentation agent) and anti-UV carbon blacks, without otherwise penalizing the typical performance provided by the reinforcing inorganic filler. In order to couple the silica to the diene elastomer, a coupling agent, generally a silane (or binding agent), is used in a well-known manner to ensure a sufficient chemical and / or physical connection between the inorganic filler. (surface of its P10-3215 - 7 - particles) and the diene elastomer. This coupling agent is at least bifunctional. In particular, organosilanes or at least bifunctional polyorganosiloxanes are used. In particular, polysulfide silanes, called "symmetrical" or "asymmetrical" silanes according to their particular structure, are used, as described, for example, in claims WO 03/002648 (or US 2005/016651) and WO 00/002649 (or US 2005/016650). Particularly suitable, but not limited to, polysulfide silanes having the following general formula (I): (I) Z - A - S8 - A - Z, wherein: - x is an integer of 2 at 8 (preferably from 2 to 5); the symbols A, which are identical or different, represent a divalent hydrocarbon radical (preferably a C1-C18 alkylene group or a C6-C12 arylene group, more particularly a C1-C10 alkylene, especially a C1-C4 alkylene, in particular propylene); the symbols Z, which are identical or different, correspond to one of the following three formulas: ## STR1 ## in which: the radicals R 1, substituted or unsubstituted, identical or are C 1 -C 18 alkyl, C 5 -C 18 cycloalkyl or C 6 -C 18 aryl (preferably C 1 -C 6 alkyl, cyclohexyl or phenyl, especially C 1 -C 4 alkyl groups, more preferably especially methyl and / or ethyl). the radicals R2, substituted or unsubstituted, which are identical to or different from one another, represent a C1-C18 alkoxyl or C5-C18 cycloalkoxyl group (preferably a group chosen from C1-C8 alkoxyls and C5-C8 cycloalkoxyls, plus still more preferably a group selected from C1-C4 alkoxyls, in particular methoxyl and ethoxyl). In the case of a mixture of polysulfurized alkoxysilanes corresponding to formula (I) above, in particular common commercially available mixtures, the average value of "x" is a fractional number preferably of between 2 and 5, more preferably However, the invention can also be advantageously used for example with disulfide alkoxysilanes (x = 2). By way of examples of polysulphide silanes, mention may be made more particularly of bis (C 1 -C 4 alkoxy-C 1 -C 4 alkylsilyl-C 1 -C 4 alkyl) polysulfides (especially disulfides, trisulphides or tetrasulfides), as for example polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl). Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT, of formula [(C2H50) 3Si (CH2) 3S212 or bis (triethoxysilylpropyl) disulfide, abbreviated TESPD, of formula (C2H50) 3Si (CH2) 3S] 2. Mention may also be made, by way of preferred examples, of polysulfides (in particular disulphides, trisulphides or tetrasulfides) of bis- (C 1 -C 4 monoalkoxyl) dialkyl (C 1 -C 4) silylpropyl), more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide as described in US Pat. patent application WO 02/083782 cited above (or US 7,217,751).
    [0011] By way of examples of coupling agents other than a polysulfurized alkoxysilane, mention may be made in particular of bifunctional POS (polyorganosiloxanes) or hydroxysilane polysulfides (R 2 = OH in formula I above) as described, for example in patent applications WO 02/30939 (or US Pat. No. 6,774,255), WO 02/31041 (or US 2004/051210), and WO2007 / 061550, or else silanes or POS bearing functional azo-dicarbonyl groups, such as described for example in patent applications WO 2006/125532, WO 2006/125533, WO 2006/125534. As examples of other sulphurized silanes, mention may be made, for example, of silanes carrying at least one thiol function (-SH) (called mercaptosilanes) and / or of at least one blocked thiol function, as described for example in patents or patent applications US 6,849,754, WO 99/09036, WO 2006/023815, WO 2007/098080. Of course, it would also be possible to use mixtures of the coupling agents described above, as described in particular in the aforementioned application WO 2006/125534. The content of coupling agent is advantageously less than 20 phr, it being understood that it is generally desirable to use as little as possible. Typically the level of coupling agent is from 0.5% to 15% by weight relative to the amount of silica. Its level is preferably between 0.5 and 15 phr, more preferably between 3 and 12 phr. This level is easily adjusted by those skilled in the art according to the level of silica used in the composition. .1-3. Another essential characteristic of the rubber composition of the tread according to the invention is to comprise a specific plasticizer system comprising, in a content A ranging from 5 to 60 phr, a resin. hydrocarbon containing a Tg greater than 20 ° C, and a content B ranging from 0 to 60 phr a liquid plasticizer, it being understood that the total A + B is at least equal to 60 phr. The term "resin" is hereby reserved, by definition known to those skilled in the art, to a compound which is solid at room temperature (23 ° C) as opposed to a liquid plasticizer such as an oil.
    [0012] Hydrocarbon resins are polymers well known to those skilled in the art, essentially based on carbon and hydrogen but may include other types of atoms, used in particular as plasticizers or tackifying agents in polymeric matrices. They are inherently miscible (i.e., compatible) with the levels used with the polymer compositions for which they are intended, so as to act as true diluents. They have been described, for example, in the book "Hydrocarbon Resins" by R. Mildenberg, M. Zander and G. Collin (New York, VCH, 1997, ISBN 3-527-28617-9), chapter 5 of which is devoted their applications, in particular pneumatic rubber (5.5 "Rubber Tires and Mechanical Goods"). They can be aliphatic, cycloaliphatic, aromatic, hydrogenated aromatic, aliphatic / aromatic type that is to say based on aliphatic and / or aromatic monomers. They may be natural or synthetic, whether or not based on petroleum (if so, also known as petroleum resins). Their Tg is preferably greater than 0 ° C., especially greater than 20 ° C. (most often between 30 ° C. and 95 ° C.).
    [0013] In a known manner, these hydrocarbon resins can also be described as thermoplastic resins in that they soften by heating and can thus be molded. They can also be defined by a point or softening point (in English, "softening point"). The softening temperature of a hydrocarbon resin is generally about 50 to 60 ° C. higher than its Tg value. The softening point is measured according to ISO 4625 ("Ring and Ball" method). The macrostructure (Mw, Mn and Ip) is determined by size exclusion chromatography (SEC) as indicated below.
    [0014] As a reminder, the SEC analysis, for example, consists in separating the macromolecules in solution according to their size through columns filled with a porous gel; the molecules are separated according to their hydrodynamic volume, the larger ones being eluted first. The sample to be analyzed is simply solubilized beforehand in a suitable solvent, tetrahydrofuran at a concentration of 1 g / liter. The solution is then filtered through a 0.45 nm porosity filter prior to injection into the apparatus. The equipment used is for example a "Waters alliance" chromatographic chain according to the following conditions: elution solvent: tetrahydrofuran, temperature 35 ° C .; - concentration 1 g / liter; flow rate: 1 ml / min; - injected volume: 100 n1; - Moore calibration with polystyrene standards; - set of 3 columns "Waters" in series ("Styragel HR4E", "Styragel HR1" and "Styragel HR 0.5"); - Differential refractometer detection (for example "WATERS 2410") that can be equipped with operating software (for example "Waters Millenium"). A Moore calibration is conducted with a series of low Ip (less than 1.2) polystyrene commercial standards of known molar masses covering the field of masses to be analyzed. The mass-averaged molecular weight (Mw), the number-average molecular weight (Mn) and the polymolecularity index (Ip = Mw / Mn) are deduced from the recorded data (mass distribution curve of the molar masses).
    [0015] All the molar mass values indicated in the present application are therefore relative to calibration curves made with polystyrene standards. According to a preferred embodiment of the invention, the hydrocarbon resin has at least any one, more preferably all of the following characteristics: a Tg greater than 25 ° C. (in particular between 30 ° C. and 100 ° C.) more preferably greater than 30 ° C (in particular between 30 ° C and 95 ° C); a softening point greater than 50 ° C. (in particular between 50 ° C. and 150 ° C.); a number-average molar mass (Mn) of between 400 and 2000 g / mol, preferably between 500 and 1500 g / mol; - A polymolecularity index (Ip) of less than 3, preferably 2 (recall: Ip = Mw / Mn with Mw weight average molar mass). By way of examples of such hydrocarbon resins, mention may be made of homopolymer or copolymer resins of cyclopentadiene (abbreviated as CPD), homopolymer or copolymer resins of dicyclopentadiene (abbreviated to DCPD), homopolymer or copolymer resins terpene, C5 homopolymer or copolymer resins, C9 homopolymer or copolymer resins, alpha-methyl-styrene homopolymer or copolymer resins, or mixtures of these resins.
    [0016] Among the above copolymer resins, mention may be made more particularly of P10-3215 copolymer (D) CPD / vinylaromatic resins, copolymer resins (D) CPD / terpene, terpene phenol copolymer resins, copolymer resins (D) CPD / C5 cut, (D) CPD / C9 cut copolymer resins, terpene / vinylaromatic copolymer resins, terpene / phenol copolymer resins, C5 / vinylaromatic cut copolymer resins, or blends thereof resins. The term "terpene" here combines in a known manner the alpha-pinene, betapinene and limonene monomers; preferably, a limonene monomer is used which is present in a known manner in the form of three possible isomers: L-limonene (laevorotatory enantiomer), D-limonene (dextrorotatory enantiomer), or the dipentene, racemic of the dextrorotatory and levorotatory enantiomers. . Examples of suitable vinyl aromatic monomers are styrene, alpha-methylstyrene, ortho-methylstyrene, metamethylstyrene, para-methylstyrene, vinyl-toluene, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes and hydroxystyrenes. vinylmesitylene, divinylbenzene, vinylnaphthalene, any vinylaromatic monomer from a C9 cut (or more generally from a Cs to Cm cut). More particularly, mention may be made of homopolymer resins (D) CPD, copolymer resins (D) CPD / styrene, polylimonene resins, limonene / styrene copolymer resins, limonene / D copolymer resins (CPD) , C5 / styrene cut copolymer resins, C5 / C9 cut copolymer resins, or mixtures of these resins. All the resins above are well known to those skilled in the art and commercially available, for example sold by the company DRT under the name "Dercolyte" for polylimonene resins, by the company Neville Chemical Company under the name "Super Nevtac ", by Kolon under the name" Hikorez "or by the company Exxon Mobil under the name" Escorez "with regard to C5 / styrene resins or C5 / C9 cut resins or by Struktol under the name" 40 MS "or" 40 NS "(mixtures of aromatic and / or aliphatic resins). According to any of the embodiments of the invention, the resin is preferably a terpene resin such as a homopolymer or a copolymer of limonene, or a C5 cutting and C9 cutting copolymer.
    [0017] The liquid plasticizer preferably has a glass transition temperature below -20 ° C, more preferably below -40 ° C. As liquid plasticizer, any extender oil, whether of aromatic or non-aromatic nature, any liquid plasticizer known for its plasticizing properties vis-à-vis deuelic elastomers, is usable. At room temperature (23 ° C.), these plasticizers or these oils, more or less viscous, are liquids (that is to say, as a reminder, substances having the capacity to eventually take on the shape of their container) , in contrast in particular to hydrocarbon plasticizing resins which are inherently solid at room temperature. Particularly suitable as liquid plasticizers are naphthenic oils, paraffinic oils, DAE oils, MES (Medium Extracted Solvates) oils, Treated Distillate Aromatic Extracts (TDAE) oils, Residual Aromatic Extract oils (RAE), TREE oils. (Treated Residual Aromatic Extract) and SRAE (Safety Residual Aromatic Extract Oils) oils, mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulphonate plasticizers and mixtures of these compounds.
    [0018] According to any one of the embodiments of the invention, the liquid plasticizer is preferably a vegetable oil or glycerol trioleate. Particularly particularly suitable vegetable oil rich in oleic acid, that is to say that the fatty acid (or all of the fatty acids if several are present) which it derives, comprises oleic acid in a fraction mass at least equal to 60%, preferably in a mass fraction of at least 70%, more preferably at least 80%. As a suitable vegetable oil, mention may be made of a sunflower oil which is such that all of the fatty acids from which it is derived comprise oleic acid in a mass fraction equal to or greater than 60%, preferably 70%. and, according to a particularly advantageous embodiment of the invention, in a mass fraction equal to or greater than 80%. When all of the fatty acids from which it is derived comprises oleic acid in a mass fraction greater than 80%, sunflower oil is called oleic sunflower oil. Alternatively to the vegetable oil, glycerol trioleate, a triester of fatty acid which is generally contained in sunflower oil, can be used as the liquid plasticizer. According to any of the embodiments of the invention, the total A + B content of hydrocarbon resin and liquid plasticizer is preferably in a range from 60 to 90 phr, more preferably in a range from 60 to 80 phr According to a preferred embodiment of the invention, the level A of hydrocarbon resin is in a range from 35 to 60 phr and the level B of liquid plasticizer is in a range from 0 to at 35 pce. More preferably, A is greater than 40 phr and less than or equal to 60 phr, and B is in a range from 0 to 30 phr. According to another preferred embodiment of the invention, the level of liquid plasticizer is between 15 and 30 phr.
    [0019] According to one particular embodiment of the invention, the ratio of A to B is greater than 1, preferably greater than or equal to 2. According to another particular embodiment of the invention, the mass ratio of (A + B) ) on the reinforcing inorganic filler mass, in particular silica, is in a range from 40 to 60%, preferably from 50 to 60%. I-4. Various additives: The rubber compositions of the treads of the tires in accordance with the invention may also comprise all or part of the usual additives normally used in elastomer compositions intended for the manufacture of treads of tires, in particular pneumatic tires, fillers other than those mentioned above, for example non-reinforcing fillers such as chalk or lamellar fillers such as kaolin, talc, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, oxidizing agents, reinforcing resins (such as resorcinol or bismaleimide), acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M) as described, for example, in the application WO 02/10269, a crosslinking based on either sulfur or sulfur and / or peroxide donors and / or bismaleimides, accelerators or retarders. vulcanization agents, vulcanization activators. These compositions may also contain coupling activators when a coupling agent is used, inorganic filler recovery agents or, more generally, processing aid agents capable in a known manner, by means of an improvement of the dispersion of the filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to implement in the green state; these agents are for example hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, amines, hydroxyl or hydrolysable polyorganosiloxanes. I-5. Preparation of rubber compositions: The compositions used in the treads of the tires of the invention may be manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work 40 or thermomechanical mixing (so-called "non-productive" phase) at high temperature, up to a maximum temperature of 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 ° C, for example between 40 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system.
    [0020] The process for preparing such compositions comprises for example the following steps: thermomechanically kneading (for example in one or more times) the first diene elastomer, the silica, the coupling agent, the plasticizing system, until a temperature is reached maximum between 110 ° C and 190 ° C (so-called "non-productive" phase); - cool all at a temperature below 100 ° C; - Then incorporate, in a second step (called "productive"), a crosslinking system; - mix everything up to a maximum temperature of less than 110 ° C.
    [0021] By way of example, the non-productive phase is carried out in a single thermomechanical step in the course of which, in a suitable mixer such as a conventional internal mixer, all the basic constituents (the diene elastomers, the plasticizer system, the reinforcing inorganic filler and the coupling agent), then in a second step, for example after one to two minutes of mixing, the other additives, any agents for recovering the charge or for setting the complementary work, with the exception of the crosslinking system. The total mixing time in this non-productive phase is preferably between 1 and 15 minutes.
    [0022] 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 ° C and 100 ° C), the crosslinking system. The whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
    [0023] The actual crosslinking system is preferably based on sulfur and a primary vulcanization accelerator, in particular a sulfenamide type accelerator. To this vulcanization system are added, incorporated during the first non-producing phase and / or during the production phase, various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives (especially diphenylguanidine), etc. The sulfur content is preferably between 0.5 and 3.0 phr, that of the primary accelerator is preferably between 0.5 and 5.0 phr. It is possible to use as accelerator (primary or secondary) any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur, in particular thiazole accelerators and their derivatives, thiuram type accelerators. , zinc dithiocarbamates. These accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated "CBS"), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (abbreviated "DCBS"), N-tert-butyl-2-benzothiazylsulfenamide (abbreviated "TBBS"), N-tert-butyl-2-benzothiazylsulfenimide (abbreviated "TBSI"), zinc dibenzyldithiocarbamate (in abbreviated "ZBEC") and mixtures of these compounds. Preferably, a primary accelerator of the sulfenamide type is used.
    [0024] The final composition thus obtained can then be calendered, for example in the form of a sheet, a plate especially for a characterization in the laboratory, or extruded, for example to form a rubber profile used for the manufacture of a tire tread, especially for passenger vehicles.
    [0025] The invention relates to the previously described treads both in the green state (that is to say, before firing) and in the fired state (that is, after crosslinking or vulcanization). The invention also relates to a method for preparing the tread according to the invention, which method comprises the following steps: thermomechanically kneading the first diene elastomer, the silica, the coupling agent and the plasticizer system, up to reach a maximum temperature between 110 ° C and 190 ° C; - cool all at a temperature below 100 ° C; - Then incorporate, in a second step, a crosslinking system; - mix everything up to a maximum temperature below 110 ° C; - Calender or extrude the composition thus obtained. The invention also relates to tires which comprise a tread previously described.
    [0026] The invention also applies to cases where the rubber compositions described above form only part of composite or hybrid type treads, in particular those consisting of two radially superposed layers of different formulations ("cap-base" structure). , both carved and intended to come into contact with the road during the rolling of the tire, during the life of the latter. The portion based on the previously described formulation may then constitute the radially outer layer of the tread intended to come into contact with the ground from the beginning of the rolling of the new tire, or on the contrary its radially inner layer intended to come into contact with the ground later.
    [0027] II-EXAMPLES OF CARRYING OUT THE INVENTION II.1 - Preparation of Compositions C1, C2, C3 and C4: The formulations (in phr) of compositions C1, C2, C3 and C4 are described in the table I.
    [0028] The composition C1, according to the invention, is characterized by an elastomer matrix which comprises more than 50% by weight of an SBR which carries a silanol function and an amine function, in particular tertiary, which functions are positioned outside the ends of the the elastomeric chain. Composition C1 also contains 130 phr of silica, 23 phr of oleic sunflower oil and 47 phr of polylimonene resin. In this composition the rate A + B is equal to 70 phr, greater than 45 phr. Composition C2, which does not conform to the invention, differs from Cl only in the nature of the elastomer which constitutes the elastomer matrix. The elastomer matrix of the composition C2 comprises more than 50% by weight of an elastomer bearing a silanol function at the end of the elastomeric chain. The compositions C3 and C4 are not in accordance with the invention, since the filler content is 110 phr in C3 and C4 and the elastomer carries a silanol function at the chain end in C4.
    [0029] The compositions are prepared as follows: an internal mixer (final filling ratio: about 70% by volume) is introduced, the initial temperature of which is approximately 60 ° C., the elastomers successively, silica, coupling agent, plasticizers and various other ingredients with the exception of the vulcanization system. Thermomechanical work (non-productive phase) is then carried out in one step, which lasts a total of 5 minutes, until a maximum temperature of 165 ° C is reached. The mixture thus obtained is recovered, cooled, and sulfur and a sulfenamide type accelerator are incorporated on a mixer (homo-finisher) at 23 ° C., mixing the whole (productive phase) for a suitable time (for example between 5 hours). and 12 min). The properties of compositions C1 and C2 after firing are shown in Table II. 11.2 - Results: The results are shown in Table II. The dynamic properties tan (fl) max are measured on a viscoanalyzer (Metravib VA4000), according to ASTM D 5992-96. The response of a sample of vulcanized composition (cylindrical specimen of 4 mm thickness and 400 mm 2 of P10-3215 section) is recorded, subjected to sinusoidal stress in alternating simple shear, at the frequency of 10 Hz. at 0 ° C or 100 ° C. For measurements at 100 ° C, a strain amplitude sweep of 0 to 50% (forward cycle) and then 50% to 0% (return cycle) are performed. For the return cycle, we measure the maximum value of tan (S) observed, tan (S). The value of tan (s). at 100 ° C is higher, the better the adhesion of the tire on dry ground. For measurements at 0 ° C, a constant strain strain sweep is performed at 0.7MPa. The higher the value of tan (S) at 0 ° C, the better the grip of the tire on wet ground.
    [0030] The results show that the composition C1 according to the invention has an improved compromise of performance between adhesion on wet and dry ground, compared to the composition C2 not according to the invention. Indeed the composition C1 has tan values at 0 ° C and 100 ° C both higher than those of the composition C2. It is observed that the improvement of this compromise can not be obtained if the combination based on the choice of a specific functional elastomer and a specific charge rate associated with a plasticizer system is not in accordance with the invention. Indeed, it can be seen that at a feed rate which is not in accordance with the invention, in this case 110 phr, both the values at 0 ° C. and at 100 ° C. of the composition C3 are significantly lower than those of the composition Cl. The same is also true for the composition C4 not in accordance with the invention. It is even noted that the composition C3 is less interesting than the composition C4 from the point of view of the performance compromise between adhesion on wet ground and on dry ground, the values of tans at 0 ° C. and at 100 ° C. being lower than those of the composition C4. Improving the performance compromise between wet grip and dry grip is made possible by the judicious choice of the functional elastomer and the silica ratio associated with a plasticizer system. Such a result is unexpected.
    [0031] P10-3215 - 18 - Table I Composition No: C1 C2 C3 C4 Non-compliant Non compliant SBR1 compliant (1) 100 - 100 - SBR2 (2) - 100 - 100 Carbon black (3) 3 3 3 3 Silica (4) 130 130 110 110 Coupling agent 10 10 10 10 (5) Liquid plasticizer (6) 23 23 37 37 Resin (7) 47 47 20 20 Stearic acid 3 3 3 3 Anti-ozone wax 2 2 2 2 Antioxidant ( 8) 3 3 3 3 DPG (9) 2 2 2 2 ZnO 1 1 1 1 Accelerator (10) 2 2 2 2 Sulfur 1 1 1 1 (1) SBR1: SBR with 27% of styrene unit and 24% of unit 1 , 2 of the butadiene part (Tg = -48 ° C) carrying a silanol function and a tertiary amine pendant function, which functions are located for the majority of the weight of the elastomer chains (more than 50% by mass of the mass elastomer) outside the ends of the elastomeric chain; (2) SBR with 27% styrene and 24% 1,2-butadiene moiety (Tg = -48 ° C) carrying a silanol function at the end of the elastomeric chain (3) ASTM grade N234 (company) Cabot); (4) "Zeosil 1165 MP" silica of Rhodia type "FIDS" (5) TESPT ("Si69" from Degussa); (6) Sunflower oil 85% by weight of oleic acid, "Lubrirob Tod 1880" from Novance (7) Resin C5 / C9 ECR-373 from Exxon; (8) N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, from Flexsys (9) Diphenylguanidine ("Perkacit" DPG from Flexsys); (10) N-cyclohexyl-2-benzothiazol sulfenamide ("Santocure CBS" from Flexsys). Table II Composition: Cl C2 C3 C4 tans at 0 ° C 0.728 0.705 0.333 0.354 tan5max at 100 ° C 0.168 0.164 0.155 0.156 P10-3215
    权利要求:
    Claims (19)
    [0001]
    REVENDICATIONS1. Tire tread comprising a rubber composition based on at least: an elastomer matrix comprising more than 50% by weight of a first diene elastomer bearing a silanol functional group and a pendant amine function; at a rate of between 120 and 140 phr; a coupling agent; a plasticizer system comprising: - comprising at a content A ranging from 5 to 60 phr a hydrocarbon resin having a Tg greater than 20 ° C; - A content B ranging from 0 to 60 phr a liquid plasticizer; it being understood that the total level A + B is at least equal to 60 phr, preferably ranging from 60 to 90 phr.
    [0002]
    2. A tread according to claim 1, wherein the silanol function and the pendant amine function are located outside the chain ends of the first diene elastomer.
    [0003]
    3. A tread according to claim 1 or 2 wherein the first diene elastomer is a diene elastomer obtainable by a coupling reaction with a coupling agent carrying an alkoxysilane function and an amine function, followed by hydrolysis. of the alkoxysilane function in silanol function.
    [0004]
    4. Tread according to any one of claims 1 to 3, wherein the first diene elastomer is an SBR, preferably an SBR solution.
    [0005]
    The tread of claim 4 wherein the diene vinylaromatic copolymer has a glass transition temperature of from -55 ° C to -40 ° C.
    [0006]
    6. A tread according to any one of claims 1 to 5 wherein the amine function is a tertiary amine function.
    [0007]
    7. Tread according to any one of claims 1 to 6 wherein the amount of star chains and branched chains present in the first diene elastomer is in a range of 0% to less than 50% by weight of the weight total of the first diene elastomer. P10-3215 25 35 40- 20 -
    [0008]
    8. tread according to any one of claims 1 to 7, wherein the elastomeric matrix comprises more than 75%, preferably more than 90% by weight of the first diene elastomer.
    [0009]
    9. Tread according to any one of claims 1 to 8, wherein A is in a range from 35 to 60 phr and B is in a range from 0 to 35 phr.
    [0010]
    10. Tread according to claim 9 wherein A is greater than 40 phr and less than or equal to 60 phr and B is in a range from 0 to 30 phr.
    [0011]
    11. Tread according to any one of claims 1 to 10, wherein B is between 15 and 30 phr.
    [0012]
    The tread of any one of claims 1 to 11, wherein the ratio of A to B is greater than 1.
    [0013]
    The tread of claim 12 wherein the ratio of A to B is greater than or equal to 2.
    [0014]
    A tread according to any one of claims 1 to 13, wherein the hydrocarbon resin is a terpene resin or a C5 cutting and C9 cutting copolymer.
    [0015]
    15. Tread according to any one of claims 1 to 14 wherein the plasticizer is glycerol trioleate or a vegetable oil, preferably a sunflower oil, more preferably an oleic sunflower oil.
    [0016]
    16. Tread according to any one of claims 1 to 15 wherein the silica content is 125 to 135 phr.
    [0017]
    17. Tread according to any one of claims 1 to 16, wherein the mass ratio of (A + B) on the weight of reinforcing inorganic filler is in a range from 40 to 60%, preferably 50 at 60%.
    [0018]
    18. A tire which comprises a tread according to any one of claims 1 to 17.
    [0019]
    19. A process for preparing a tread according to any one of claims 1 to 17 which comprises the following steps: thermomechanically kneading the first diene elastomer, the silica, the coupling agent, the system plasticizer, until a maximum temperature of between 110 ° C and 190 ° C is reached; - cool all at a temperature below 100 ° C; - Then incorporate, in a second step, a crosslinking system; - mix everything up to a maximum temperature below 110 ° C; - Calender or extrude the composition thus obtained. P10-3215
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    同族专利:
    公开号 | 公开日
    WO2015086586A1|2015-06-18|
    JP6495919B2|2019-04-03|
    FR3014443B1|2016-01-15|
    CN105813853A|2016-07-27|
    EP3105066A1|2016-12-21|
    EP3105066B1|2018-02-07|
    JP2017500402A|2017-01-05|
    CN105813853B|2017-07-21|
    US20160319116A1|2016-11-03|
    引用文献:
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    FR2930554A1|2008-04-29|2009-10-30|Michelin Soc Tech|ELASTOMERIC MIXTURE COMPRISING MAJORITARILY A DIAGNOSTIC ELASTOMER COUPLED BY AN AMINO-ALCOXYSILANE GROUP, RUBBER COMPOSITION COMPRISING SAME AND METHODS OF OBTAINING SAME|
    WO2012069567A1|2010-11-26|2012-05-31|Societe De Technologie Michelin|Tyre tread|
    WO2012076456A1|2010-12-08|2012-06-14|Societe De Technologie Michelin|Tread for a tyre|
    WO2013092096A1|2011-12-22|2013-06-27|Compagnie Generale Des Etablissements Michelin|Rubber composition|EP3214111A4|2014-10-27|2017-09-06|Bridgestone Corporation|Method for producing rubber composition, rubber composition, and tire|
    WO2018079800A1|2016-10-31|2018-05-03|Compagnie Generale Des Etablissements Michelin|A tire comprising a tread|
    WO2018115761A1|2016-12-22|2018-06-28|Compagnie Generale Des Etablissements Michelin|Rubber composition with a good dispersion of large amounts of reinforcing inorganic filler|
    WO2019073145A1|2017-10-09|2019-04-18|Compagnie Generale Des Etablissements Michelin|Tyre provided with a tread including at least one butyl rubber and a butadiene and styrene copolymer|
    WO2019122604A1|2017-12-19|2019-06-27|Compagnie Generale Des Etablissements Michelin|Tyre tread, the crosslinking system of which is based on organic peroxide|
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    CN111433047A|2017-11-30|2020-07-17|米其林集团总公司|High modulus rubber compositions comprising an effective sulfur crosslinking system|US5936038A|1996-08-09|1999-08-10|The University Of Akron|Vulcanizable elastomeric composition and thermoplastic vulcanizate employing the same|
    US7137423B2|2003-06-06|2006-11-21|The Goodyear Tire & Rubber Company|Tire with component comprised of amine functionalized styrene/diene copolymer elastomer, silanol functionalized carbon black and coupling agent|
    FR2974808B1|2011-05-06|2013-05-03|Michelin Soc Tech|PNEUMATIC TIRE COMPRISING SBR EMULSION AT HIGH TRANS RATE.|
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    WO2013040425A1|2011-09-14|2013-03-21|Compagnie Generale Des Etablissements Michelin|Tread with ultra efficient vulcanization system|FR3038320A1|2015-07-02|2017-01-06|Michelin & Cie|RUBBER COMPOSITION COMPRISING A VERY HIGH SPECIFIC SURFACE SILICA AND A HYDROCARBONATED RESIN WITH LOW VITREOUS TRANSITION TEMPERATURE|
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    FR3061184A1|2016-12-22|2018-06-29|Compagnie Generale Des Etablissements Michelin|RUBBER COMPOSITION COMPRISING A SPECIFIC HYDROCARBON RESIN|
    JP6957126B2|2017-07-19|2021-11-02|コンパニー ゼネラール デ エタブリッスマン ミシュラン|Rubber composition based on silicone oil|
    EP3674357A4|2017-08-25|2021-05-05|Bridgestone Corporation|Rubber composition and tire|
    法律状态:
    2015-12-21| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-22| PLFP| Fee payment|Year of fee payment: 4 |
    2017-12-21| PLFP| Fee payment|Year of fee payment: 5 |
    2019-09-27| ST| Notification of lapse|Effective date: 20190906 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362332A|FR3014443B1|2013-12-10|2013-12-10|TIRE TREAD TIRE|FR1362332A| FR3014443B1|2013-12-10|2013-12-10|TIRE TREAD TIRE|
    PCT/EP2014/077027| WO2015086586A1|2013-12-10|2014-12-09|Tyre tread|
    US15/103,139| US20160319116A1|2013-12-10|2014-12-09|Tire tread|
    CN201480067334.9A| CN105813853B|2013-12-10|2014-12-09|Tire tread|
    JP2016538747A| JP6495919B2|2013-12-10|2014-12-09|Tire tread|
    EP14814693.9A| EP3105066B1|2013-12-10|2014-12-09|Tyre tread|
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