法国专利FR3029139A1 ELASTOMER LAMINATE COMPRISING 3 LAYERS

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专利摘要:
The present invention relates to an elastomeric laminate comprising three layers, the first layer consisting of a diene rubber composition comprising a first elastomer matrix, the second layer consisting of a diene rubber composition comprising a second elastomer matrix, which second elastomer matrix comprises a second elastomer comprising ethylene units and diene units having a carbon-carbon double bond, which units are statistically distributed within the second elastomer, the third layer consisting of a diene rubber composition comprising a third diene elastomer having a mass rate of unity diene greater than 50%, the second layer being disposed between the first layer and the third layer. Such a laminate has good resistance to the separation of the layers that constitute it.
公开号:FR3029139A1
申请号:FR1461755
申请日:2014-12-02
公开日:2016-06-03
发明作者:Da Silva Jose Carlos Araujo；Mathilde Abad；Aurelie Triguel
申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；Michelin Recherche et Technique SA France；
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专利说明:

[0001] The present invention is that of elastomeric laminates comprising 3 layers of diene rubber composition, in particular for use in a tire. A tire usually comprises a tread, two sidewalls, two beads, a carcass reinforcement passing in both flanks and anchored to the two beads, and a crown reinforcement disposed circumferentially between the tread and the carcass reinforcement. The tread is intended to come into contact with the running surface of the tire. The tire may further comprise an underlayer to the tread, the underlayer being disposed circumferentially between the tread and the carcass reinforcement, preferably between the tread and the crown reinforcement, the tread underlayer to the tread band being generally adjacent to the tread. In the tire, the underlayer at the tread must adhere sufficiently to the tread to prevent the underlayer at the surface of the tread from becoming disengaged from the tread during the entire duration of the tread. tire life. The underlayer generally adheres to the tread by means of physical or chemical phenomena, such as the phenomena of interpenetration, entanglement or crosslinking of the diene rubber compositions constituting respectively the tread and the tread. -layer to the tread. Under the appropriate conditions for carrying out and firing the diene rubber compositions placed against each other, these compositions are firmly bonded together and the resulting complex makes it possible to endure the stresses related to the field of application in question. , especially that of the tire.
[0002] Compositions which may be used in tread may contain an elastomeric matrix which is weakly unsaturated or which comprises a terpolymer elastomer of ethylene, an α-olefin and a nonconjugated diene. An elastomeric matrix is considered as weakly unsaturated when it contains less than 10% by weight of diene unit. Generally, the rubber composition of a tread underlayer is generally based on an elastomeric matrix which comprises natural rubber as a highly unsaturated elastomer. However, the level of adhesion between firstly a composition based on an elastomer matrix which is weakly unsaturated or which contains a terpolymer elastomer of ethylene, an α-olefin and a non-conjugated diene, and on the other hand a second composition based on an elastomer matrix containing a highly unsaturated elastomer may be considered insufficient, especially for pneumatic application of the first composition as P10-3482 tread of the tire and the second composition as a sub-layer to the tread. To remedy this, it is possible to resort to the use of a material which will serve as glue or gum binding between the first composition and the second composition, in particular used respectively as tread of a tire and sub-component. layer to the tread. In this case, the sub-layer to the tread is no longer adjacent its entire length to the tread, but is separated by the connecting rubber.
[0003] The Applicants have solved the problem by using a diene rubber composition which serves as a gum binding between these two compositions. Used as an intermediate layer between the two compositions each constituting a layer in a laminate, it significantly improves the resistance of the laminate to the separation of the layers that constitute it. Thus, a first subject of the invention is an elastomer laminate comprising 3 layers, the first layer consisting of a diene rubber composition comprising a first elastomer matrix, the second layer consisting of a diene rubber composition comprising a second elastomer matrix, which second elastomeric matrix comprises a second elastomer comprising ethylene units and diene units having a carbon-carbon double bond, which units are statistically distributed within the second elastomer, the third layer consisting of a diene rubber composition comprising a third diene elastomer having a diene unit mass ratio greater than 50%, the second layer being disposed between the first layer and the third layer.
[0004] Another object of the invention is the use of the laminate according to the invention in a tire. The invention also relates to a tire which comprises the laminate according to the invention.
[0005] The invention also relates to the use of an adhesive composition identical to the diene rubber composition constituting the second layer of the laminate according to the invention for bonding a diene rubber composition identical to that constituting the first layer of the laminate according to the invention to a diene rubber composition identical to that constituting the third layer of the laminate according to the invention. P10-3482 I. DETAILED DESCRIPTION OF THE INVENTION By the term "composition-based" 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 one another at least in part during the various phases of manufacture of the composition, in particular during its crosslinking or vulcanization. By the expression "part by weight per hundred parts by weight of elastomer" (or phr), is meant within the meaning of the present invention, the proportion by mass per hundred parts of elastomer present in the rubber composition considered and constituting a layer. In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are percentages (%) by mass. 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).
[0006] A laminate is a product made of several layers of flat or non-planar shape, as defined by the International Patent Classification. The elastomeric laminate according to the invention comprises 3 layers, the first layer consisting of a diene rubber composition comprising a first elastomer matrix, the second layer consisting of a diene rubber composition comprising a second elastomer matrix, which second elastomer matrix comprises a second elastomer comprising ethylene units and diene units having a carbon-carbon double bond, which units are statistically distributed within the second elastomer, the third layer consisting of a diene rubber composition comprising a third diene elastomer having a mass ratio of diene unit greater than 50%, the second layer being disposed between the first layer and the third layer.
[0007] The laminate according to the invention is called elastomer because it comprises 3 layers consisting of diene rubber compositions. Preferably, the laminate consists of 3 layers defined according to any of the embodiments of the invention. Because of the nature of the elastomers of which it is composed, the diene rubber composition which constitutes the second layer is different from the diene rubber composition of the first layer and is different from the diene rubber composition of the third layer.
[0008] By "elastomer" (or indistinctly "rubber", the two terms being considered as synonymous) "diene", must be understood in a known manner (one or more) elastomer derived at least in part (ie, a homopolymer or a copolymer) monomers dienes (monomers carrying two carbon-carbon double bonds, conjugated or not). The term "highly unsaturated diene elastomer" is understood to mean an elastomer having a diene unit mass ratio greater than 50%.
[0009] The term "weakly unsaturated diene elastomer" is understood to mean an elastomer having a diene unit mass ratio of less than 10%. The proportion of diene unit which relates to an elastomer is expressed in percent by weight per 100 g of the elastomer. It is therefore a mass rate. For example, a diene unit mass ratio of x% in an elastomer A means that the diene units represent xg in 100 g of elastomer A, x being a number of 0 to 100, for example equal to 5. This formulation is equivalent to to that which consists in saying that the elastomer A contains x% of diene unit, or that the elastomer A has x% of diene unit, or that the elastomer A has a diene unit%.
[0010] By diene unit is meant a monomeric unit resulting from the insertion of a monomer unit resulting from the polymerization of a conjugated diene monomer or of a non-conjugated diene monomer, the diene unit comprising a carbon-carbon double bond.
[0011] By elastomeric matrix is meant a rubber composition all the elastomers contained in the rubber composition. The term "highly unsaturated elastomer matrix" is understood to mean an elastomer matrix having a diene unit mass ratio greater than 50%. A highly unsaturated elastomer matrix typically contains one (or more) highly unsaturated diene elastomer having a diene unit mass ratio of greater than 50%. By way of example, mention may be made of homopolymeric elastomers and copolymers of 1,3-diene, especially butadiene or isoprene.
[0012] P10-3482 A weakly unsaturated elastomer matrix is understood to mean an elastomer matrix having a diene unit mass ratio of less than 10%. A weakly unsaturated elastomer matrix typically contains one (or more) weakly unsaturated diene elastomer having a diene unit mass ratio of less than 10%. The weakly unsaturated elastomer matrix may nevertheless contain a highly unsaturated diene elastomer in a proportion such that the mass ratio of diene units present in the elastomer matrix is less than 10%. The proportion of diene unit which relates to an elastomer matrix is expressed in percent by weight per 100 g of the elastomer matrix. It is therefore a mass rate. For example, a diene unit mass ratio of y% in an elastomer matrix B means that all the diene units present in the elastomer matrix B represent yg in 100 g of elastomer matrix B, y being a number of from 0 to 100, by This formulation is equivalent to that which consists in saying that the elastomer matrix B contains y% of diene unit or that the elastomer matrix B has y% of diene unit. Second elastomeric matrix: The second elastomer matrix has the essential characteristic of comprising a second elastomer comprising ethylene units and diene units comprising a carbon-carbon double bond, which units are statistically distributed within the second elastomer. According to any one of the embodiments of the invention, the diene units comprising a carbon-carbon double bond and present in the second elastomer are preferably 1,3-diene units having 4 to 12 carbon atoms, especially 1,3-butadiene units. According to one embodiment of the invention, the ethylene units present in the second elastomer represent at least 50 mol% of all the monomer units of the second elastomer. According to a particular embodiment of the invention, the second elastomer comprises the following units UA, UB, UC and UD statistically distributed within the second elastomer, UA) -CH2-CH2 - in a molar percentage of m% UB). a molar percentage of n% P10-3482 UC) R1 according to a molar percentage of 0% I -CH2-C-1C-R2 II CH2 UD) CH2-CI-12 according to a molar percentage of p% cFi / 2 Wherein R 1 and R 2, which may be identical or different, denote a hydrogen atom, a methyl radical or a phenyl radical which may or may not be substituted in the ortho, meta or para position with a methyl radical; m 50 - 0 < o + p 25 - n + o> 0 - m, n, o and p being numbers ranging from 0 to 100 - the respective molar percentages of m, n, o, and p being calculated on the basis of the sum of m + n + o + p which is equal to 100.
[0013] According to another particular embodiment of the invention, the second elastomer contains statistically distributed units UE within the second elastomer: UE) / CH 2 -CH 2 CHCH 2 in a molar percentage of q% CH 2 -CH 2 - o + p + q 10 - q 0 - the respective molar percentages of m, n, o, p and q being calculated on the basis of the sum of m + n + o + p + q which is equal to 100. While the The unit unit UD forms a bivalent hydrocarbon ring with 6 carbon atoms of 1,2-cyclohexane type, the unit unit unit EU forms a divalent hydrocarbon ring with 6 carbon atoms of 1,4-cyclohexane type. P10-3482 According to another embodiment of the invention, the second elastomer contains UF units statistically distributed within the second elastomer, UF) -CH2-CH5- in a molar percentage of r 1, R 3 -R 3 denoting a radical alkyl having 1 to 4 carbon atoms or an aryl radical, preferably 25, preferably 10, the molar percentages of m, n, o, p and r being calculated on the basis of based on the sum of m + n + o + p + r which is equal to 100. According to this particular embodiment of the invention, the second elastomer may comprise q% of UE units statistically distributed within the second elastomer, to which in which case the respective molar percentages of m, n, o, p, q and r are calculated on the basis of the sum of m + n + o + p + q + r which is equal to 100. It is understood that the second elastomer can be constituted by a mixture of elastomers which contain the units UA, UB, UC, UD, EU and UF according to the mol percentages respective areas m, n, o, p, q and r as defined above and which differ from each other by their macrostructure or their microstructure, in particular by the respective molar ratio of the units UA, UB, UC, UD, UE and UF.
[0014] According to any one of the embodiments of the invention, preferably the second elastomer does not contain a UF unit. According to one embodiment of the invention, at least one of the two molar percentages p and q is preferably different from 0. In other words, preferably the second diene elastomer contains at least one of the units which are a ring. bivalent hydrocarbon with 6 carbon atoms of 1,2-cyclohexane type and a divalent hydrocarbon ring with 6 carbon atoms of 1,4-cyclohexane type. More preferably, p is strictly greater than 0.
[0015] According to one embodiment of the invention, the second elastomer has at least one of the following criteria, and preferably all: - m 65 - n + o + p + ci 15, more preferably 20 - 10 p + q 2 - 1 n / (o + p + q) - when q is non-zero, 20 / q 1 P10-3482 According to another preferred embodiment of the invention, the second elastomer contains as monomer units only the units UA, UB, UC , UD and UE according to their respective molar percentage m, n, o, p and q, preferably all different from 0.
[0016] According to another preferred embodiment of the invention, the second elastomer contains as monomeric units only the units UA, UB, UC and UD according to their respective molar percentage m, n, o and p, preferably all different from 0.
[0017] According to any of the embodiments of the invention, the UB units present in the second elastomer preferably have the trans configuration represented by the following formula: ## STR1 ## In any of the embodiments of the invention, the second elastomer preferably has a number average molecular weight (Mn) of at least 60,000 g / mol and at most 1,500,000 g / mol. The starting diene polymer useful for the purposes of the invention preferably has a polydispersity index lp equal to Mw / Mn (Mw being the average molecular weight by weight) of between 1.20 and 3.00. The values of Mn, Mw and lp are measured according to the method described in section II.2-b). The second elastomer can be obtained according to various synthesis methods known to those skilled in the art, in particular according to the target values of m , n, o, p, q and r. Generally, the second elastomer may be prepared by copolymerization of at least one conjugated diene monomer and ethylene and according to known synthetic methods, in particular in the presence of a catalyst system comprising a metallocene complex. Catalyst systems based on metallocene complexes, which catalytic systems are described in documents EP 1 092 731 A1, EP 1 554 321 A1, EP 1 656 400 A1, EP 1 829 901 A1, EP 1 954, are described. 705 A1, EP 1 957 506 A1, on behalf of the Applicants. As conjugated diene monomer is suitable in particular a conjugated diene having from 4 to 12 carbon atoms. 1,3-Butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1-aryl-1,3-butadiene and 1,3-pentadiene may be mentioned. In a preferred aspect, the diene monomer is 1,3-butadiene or 2-methyl-1,3-butadiene, more preferably 1,3-butadiene, in which case R 1 and R 2 are each hydrogen.
[0018] Thus, according to some of these methods of synthesis, the second elastomer can be obtained by copolymerization of at least one conjugated diene monomer and ethylene, in P10-3482 presence of a catalyst system comprising a metallocene lanthanide complex with ansa ligands of fluorenyl type. The metallocene complexes described in documents EP 1 092 731 A1, EP 1 554 321 A1 and EP 1 954 705 A1 can be cited as such.
[0019] The second elastomer which contains UF units according to a particular embodiment of the invention can be obtained by copolymerization of at least one conjugated diene monomer and two olefins, such as ethylene and an alpha-olefin, in the presence of a catalyst system comprising a metallocene lanthanide complex with ansa cyclopentadienyl fluorenyl type ligands. As alpha-olefin monomer suitable for example an alpha-olefin having 3 to 18 carbon atoms, preferably having 3 to 6 carbon atoms. There may be mentioned propylene, butene, pentene, hexene or a mixture of these compounds. As a termonomer associated with at least one conjugated diene monomer and ethylene, there may also be mentioned a styrene derivative. Catalyst systems based on metallocene complexes may be those described in documents EP 1 092 731 A1, EP 1 656 400 A1, EP 1 829 901 A1, EP 1 957 506 A1, in the name of the Applicants. The second elastomer can be prepared in accordance with the documents cited above, by adapting the polymerization conditions by means known to those skilled in the art, so as to reach values of number average molecular weight (Mn) of at least 60,000 g / mol. By way of illustration, the polymerization time can be significantly increased so that the conversion to monomer is greater, thus leading to the obtaining of molar masses of at least 60,000 g / mol. By way of illustration, during the preparation of the catalytic systems according to the documents cited above, the stoichiometry of the alkylating agent with respect to the metallocene complex (s) is decreased, so as to reduce the chain transfer reactions and to obtain molar masses of at least 60 000 g / mol. In addition to the second elastomer, the second elastomer matrix may comprise another diene elastomer, in particular a highly unsaturated diene elastomer. As a highly unsaturated elastomer, mention may be made of those containing monomeric conjugated diene units, in particular 1,3 dienes having 4 to 12 carbon atoms. More particularly homopolymers and copolymers of butadiene and isoprene are suitable. Advantageously, this other diene elastomer is a polyisoprene, preferably a high cis polyisoprene having a 1,4-cis bond ratio greater than 90%, more preferably natural rubber. When the second elastomer matrix comprises another highly unsaturated diene elastomer, the weight fraction of this other diene elastomer in the second diene elastomer matrix preferably varies from 10 to 70% (of the mass of the second elastomer matrix). P10-3482 According to a particular embodiment of the invention, the second elastomer matrix consists of the second elastomer and this other highly unsaturated diene elastomer.
[0020] According to another embodiment of the invention, the second elastomer represents more than 50% by weight of the second elastomer matrix, preferably more than 90% by weight of the second elastomer matrix, better the whole of the second elastomer matrix. First elastomeric matrix: According to one embodiment of the invention, the first elastomer matrix comprises a terpolymer of ethylene, an α-olefin and a non-conjugated diene, hereinafter referred to as the first elastomer or also called the first terpolymer elastomer of ethylene, an α-olefin and a nonconjugated diene.
[0021] According to a particular embodiment of the invention, the first elastomer has at least one of the following characteristics, preferably all: the ethylene units represent between 20 and 90%, preferably between 30 and 70% by weight of the second elastomer, the α-olefin units represent between 10 and 80%, preferably 15 to 70% by weight of the second elastomer, the non-conjugated diene units represent between 0.5 and 10% by weight of the first elastomer. According to a preferred embodiment of the invention, the first elastomer has a mass ratio of diene unit lower than the mass ratio of diene unit of the second elastomer. According to a more preferred embodiment of the invention, the first elastomer has a diene unit mass ratio of less than 10%.
[0022] According to one embodiment of the invention, the first elastomer represents more than 50% by weight of the first elastomer matrix, preferably all of the first elastomer matrix.
[0023] According to another embodiment of the invention, the first elastomer matrix has a mass ratio of diene unit lower than the mass ratio of diene unit of the second elastomer. For example, according to this embodiment of the invention, if the mass ratio of diene unit of the second elastomer is 14%, the mass ratio of diene unit of the first elastomer matrix is less than 14%, for example is about 5%.
[0024] P10-3482 According to a particular embodiment of the invention, the first elastomer matrix has a diene unit mass ratio lower than the diene unit mass ratio of the second elastomer and comprises the first ethylene terpolymer elastomer, a α-olefin and a non-conjugated diene. According to another embodiment of the invention, the first elastomer matrix has less than 10% by weight of diene unit and preferably comprises the first terpolymer elastomer of ethylene, an α-olefin and a non-diene diene. conjugate. The elastomeric matrix is considered a weakly unsaturated matrix. It is understood that the first elastomer may be a mixture of terpolymers of ethylene, α-olefin and non-conjugated diene which differ from each other by their macrostructure or their microstructure, in particular by the respective mass ratio of the units ethylene, α-olefin and non-conjugated diene. The α-olefin whose monomeric units constitute the first elastomer may be a mixture of alpha olefins. The α-olefin generally comprises 3 to 16 carbon atoms. Suitable α-olefins are, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-dodecene. Advantageously, the α-olefin is propylene, to which 20 cases the terpolymer is commonly called an EPDM (in English "EPDM rubber"). The non-conjugated diene whose monomeric units constitute the first elastomer or the second elastomer generally comprises 6 to 12 carbon atoms. As non-conjugated diene, there may be mentioned dicyclopentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1,5-cyclooctadiene. Advantageously, the non-conjugated diene is 5-ethylidene-2-norbornene. Preferably, the first elastomer is a terpolymer of ethylene, propylene and 5-ethylidene-2-norbornene. Third Diene Elastomer: The essential characteristic of the third diene elastomer is that it has a diene unit mass ratio of greater than 50%. The third diene elastomer may be an elastomer containing monomeric conjugated diene units, in particular 1,3 dienes containing 4 to 12 carbon atoms, advantageously isoprene. It is understood that the third diene elastomer may be a mixture of elastomers which differ from each other by their macrostructure or their microstructure. According to a preferred embodiment of the invention, the third diene elastomer is a polyisoprene. Polyisoprene as the third diene elastomer is preferably a polyisoprene having a 1,4-cis bond ratio greater than 90%, calculated on the basis of the weight of the polyisoprene. Advantageously, the third diene elastomer is natural rubber.
[0025] According to one embodiment of the invention, the third diene elastomer, advantageously polyisoprene or very advantageously natural rubber, represents at least 95% by weight, preferably all of the elastomer matrix which constitutes the diene rubber composition of the third layer.
[0026] The microstructure of the elastomers is determined by 1 H NMR analysis, supplemented by 1 H NMR analysis when the resolution of the 1 H NMR spectra does not allow the assignment and quantification of all the species. Measurements are made using a 500 MHz BRUKER NMR spectrometer at frequencies of 500.43 MHz for proton observation and 125.83 MHz for carbon observation.
[0027] For measurements on mixtures or insoluble elastomers but having the ability to swell in a solvent, is used a probe HRMAS 4mm z-grad for observing the proton and carbon decoupled proton mode. The spectra are acquired at rotation speeds of 4000Hz to 5000Hz. For measurements on soluble elastomers, a liquid NMR probe is used to observe the proton and the carbon in decoupled mode of the proton. The preparation of insoluble samples is done in rotors filled with the analyzed material and a deuterated solvent for swelling, generally deuterated chloroform (CDCl3). The solvent used must always be deuterated and its chemical nature can be adapted by those skilled in the art. The amounts of material used are adjusted to obtain spectra with sufficient sensitivity and resolution. The soluble samples are dissolved in a deuterated solvent (approximately 25 mg of elastomer in 1 ml), generally deuterated chloroform (CDCl 3). The solvent or solvent cut used must always be deuterated and its chemical nature can be adapted by those skilled in the art.
[0028] In both cases (soluble sample or swollen sample): For the proton NMR, a single pulse sequence of 30 ° is used. The spectral window is set to observe all of the resonance lines belonging to the analyzed molecules. The accumulation number is set to obtain a signal-to-noise ratio sufficient for the quantization of each pattern. The recycle time between each pulse is adapted to obtain a quantitative measurement. For carbon NMR a 30 ° single pulse sequence is used with decoupling of the proton only during acquisition to avoid "Nuclear Overhauser" (NOE) effects and remain quantitative. The spectral window is set to observe all of the resonance lines belonging to the analyzed molecules. The accumulation number is set to obtain a signal-to-noise ratio sufficient for quantization of each P10-3482 pattern. The recycle time between each pulse is adapted to obtain a quantitative measurement. NMR measurements are carried out at 25 ° C.
[0029] Reinforcing filler: The diene rubber composition constitutive of any one of the 3 layers preferably comprises a reinforcing filler, particularly when the laminate is used in a tire.
[0030] The reinforcing filler can be any type of so-called reinforcing filler known for its ability to reinforce a diene rubber composition that can be used for the manufacture of tires, for example an organic filler such as carbon black, preferably a reinforcing inorganic filler such as silica to which is associated in a known manner a coupling agent, or a mixture of these two types of filler. Such a reinforcing filler typically consists of nanoparticles whose average size (in mass) is less than one micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm. Suitable carbon blacks are all carbon blacks, especially blacks conventionally used in tires or their treads (so-called pneumatic grade blacks). Among the latter, there will be mentioned more particularly the reinforcing carbon blacks of the series 100, 200, 300, or the series blacks 500, 600 or 700 (ASTM grades), such as, for example, the blacks N115, N134, N234, N326, N330. , N339, N347, N375, N550, N683, N772). These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used.
[0031] "Reinforcing inorganic filler" means any inorganic or mineral filler, irrespective of its color and origin (natural or synthetic), also called "white" filler, "clear" filler or even "non-black" filler. "As opposed to carbon black, capable of reinforcing on its own, with no other means than an intermediate coupling agent, a diene rubber composition for the manufacture of pneumatic tires, in other words able to replace, in its reinforcement function, a conventional carbon black of pneumatic grade; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
[0032] P10-3482 As inorganic reinforcing fillers are particularly suitable mineral fillers of the siliceous type, preferably silica (SiO 2). 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 high surface area silicas as described in the application WO 03/016387. In the present disclosure, the BET surface area is determined in a known manner by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society" Vol. 60, page 309, February 1938, more precisely according to the French standard NF ISO 9277 of December 1996 (multipoint volumetric method (5 points) - gas: nitrogen - degassing: 1 hour at 160 ° C - relative pressure range p / po: 0.05 at 0.17). The CTAB specific surface is the external surface determined according to the French standard NF T 45-007 of November 1987 (method B).
[0033] The physical state under which the reinforcing inorganic filler is present is indifferent, whether in the form of powder, microbeads, granules or beads. Of course, reinforcing inorganic filler is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of highly dispersible silicas as described above.
[0034] Those skilled in the art will understand that, as an equivalent load of the reinforcing inorganic filler described in this paragraph, it would be possible to use a reinforcing filler of another nature, in particular an organic filler such as carbon black, provided that this filler reinforcing would be covered with an inorganic layer such as silica, or would comprise on its surface functional sites, including hydroxyl, requiring the use of a coupling agent to establish the connection between the filler and the elastomer. 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.
[0035] In order to couple the reinforcing inorganic filler to the diene elastomer, a coupling agent is used in a well-known manner, in particular an at least bifunctional silane (or bonding agent) intended to ensure a sufficient connection, of a chemical and / or physical nature. , between the inorganic filler (surface of its particles) and the diene elastomer.
[0036] In particular, organosilanes or at least bifunctional polyorganosiloxanes are used. P10-3482 In particular, polysulfide silanes, called "symmetrical" or "asymmetrical" silanes according to their particular structure, are used, as described for example in the applications W003 / 002648 (or US 2005/016651) and W003 / 002649 (or US 2005 / 016650).
[0037] In particular, polysulfides silanes having the general formula (V) Z - A - Sx - A - Z (V) in which: - x is an integer of 2 to 8 ( preferably from 2 to 5); the symbols A, which may be identical or different, represent a divalent hydrocarbon radical (preferably a C1-C18 alkylene group or a C6-C12 arylene group, more particularly a C1-C18 alkylene, in particular a C1-C4 alkylene, in particular propylene); the symbols Z, which are identical or different, correspond to one of the following three formulas: ## STR2 ## in which: the radicals R 1, substituted or unsubstituted , which are identical or different from one another, represent a C1-C18 alkyl, C5-C18 cycloalkyl or C6-C18 aryl group (preferably C1-C6 alkyl, cyclohexyl or phenyl groups, especially C1-C4 alkyl groups); more particularly methyl and / or ethyl). the radicals R2, substituted or unsubstituted, which are identical to or different from each other, represent a C5-C18 alkoxyl or C5-C18 cycloalkoxyl group (preferably a group chosen from C1-C8 alkoxyls and C5-cycloalkoxyls); C8, more preferably still a group selected from C1-C4 alkoxyls, in particular methoxyl and ethoxyl). In the case of a mixture of polysulfide alkoxysilanes corresponding to formula (I) above, in particular common commercially available mixtures, the average value of "x" is a fractional number preferably between 2 and 5, more preferably close to 4. But the invention can also be advantageously used for example with disulfide alkoxysilanes (x = 2).
[0038] By way of examples of polysulfide silanes, mention may be made more particularly of bis (C 1 -C 4 alkoxy) -alkyl (C 1 -C 4) alkylsilyl-P 10 -3482 alkyl (C 1 -C 4) polysulfides (especially disulfides, trisulphides or tetrasulfides). )), such as polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl). Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated to TESPT, of formula [(C2H50) 3Si (CH2) 352) 2 or bis (triethoxysilylpropyl) disulfide, abbreviated to TESPD, is preferably used. formula [(C2H50) 3Si (CH2) 35] 2.
[0039] As coupling agent other than polysulfide alkoxysilane, there may be mentioned in particular bifunctional POSS (polyorganosiloxanes) or hydroxysilane polysulfides as described in patent applications WO 02/30939 (or US Pat. No. 6,774,255), WO 02 / 31041 (or US 2004/051210) or silanes or POSS carrying azodicarbonyl functional groups, as described for example in patent applications WO 2006/125532, WO 2006/125533, WO 2006/125534. As coupling agent, there may also be mentioned alkoxysilanes carrying an unsaturated carbon group capable of reacting radical with a diene unit of the elastomeric matrix. By way of example, mention may be made of 3-butene-triethoxysilane and 3-methacryloxypropyltrimethoxysilane. The content of coupling agent is advantageously less than 20 phr (parts by weight per hundred parts of elastomer present in the rubber composition considered and constituting a layer), it being understood that it is generally desirable to use it. the least possible. Typically the level of coupling agent is from 0.5% to 15% by weight relative to the amount of inorganic filler. Its level is preferably between 0.5 and 12 phr, more preferably in a range from 3 to 10 phr. This level is easily adjusted by those skilled in the art according to the level of inorganic filler used in the diene rubber composition. According to a particular embodiment of the invention, each of the diene rubber compositions constituting respectively the 3 layers of the laminate comprises a reinforcing filler, preferably a carbon black.
[0040] Reinforcing filler content: The level of reinforcing filler in each of the diene rubber compositions of the laminate can vary to a large extent, for example according to the nature of the elastomer matrix or the reinforcing filler in the diene rubber composition or the amount of of plasticizer in the diene rubber composition. These variables are adjusted by those skilled in the art according to the use that is made of the laminate, especially in a tire. In the case of a use of the laminate in which the first layer of the laminate is constitutive of a tread intended to equip a tire and the third layer is constitutive of a sub-layer to the tread, the nature of the P10-3482 reinforcing filler in the diene rubber composition of the first layer and the third layer and its rate are chosen by those skilled in the art in accordance with the particular conditions of this use. For example, the reinforcing filler may be a carbon black, a silica or a mixture thereof, its content in the diene rubber composition may vary from 20 to 200 phr. According to any of the embodiments of the invention, the level of reinforcing filler in the diene rubber composition of the second layer preferably varies from 5 to 80 phr, more preferably from 5 to 50 phr.
[0041] According to a particular embodiment of the invention, the diene rubber composition of the second layer comprises a level of reinforcing filler less than or equal to the reinforcing filler content of the diene rubber composition of the first layer.
[0042] Other additives: The diene rubber composition constitutive of any one of the 3 layers may also contain, in addition to the coupling agents, coupling activators, inorganic charge-covering agents or, more generally, agents for assisting the in a known manner, by improving the dispersion of the filler in the rubber matrix and lowering the viscosity of the diene rubber composition, to improve its ability to implement in the state believed. It may also comprise all or part of the usual additives usually used in elastomer compositions intended to constitute mixtures of finished articles of rubber such as tires, for example pigments, protective agents such as anti-ozone waxes. Chemical antiozonants, anti-oxidants, anti-fatigue agents, a crosslinking system, vulcanization accelerators or retarders, vulcanization activators. When the elastomeric matrix contains a terpolymer of ethylene, α-olefin and non-conjugated diene, in particular EPDM, crosslinking coagents conventionally used in the crosslinking of EPDM can be used. As crosslinking agent, there may be mentioned triallyl isocyanurate, ethylene dimethacrylate, trimethylolpropane trimethacrylate. The crosslinking system is preferably based on sulfur, but it can also be based on sulfur donor, peroxide, bismaleimide or their mixtures. Preferably, the diene rubber compositions constituting respectively the first layer, the second layer and the third layer comprise a crosslinking system, preferably a vulcanization system.
[0043] P10-3482 The diene rubber compositions useful for the purposes of the invention may also comprise plasticizers, for example extender oils of aromatic or nonaromatic nature, in particular very slightly or non-aromatic oils (eg paraffinic oils). hydrogenated naphthenic, MES or TDAE oils), vegetable oils, in particular glycerol esters such as glycerol trioleates, hydrocarbon plasticizing resins having a high Tg, preferably greater than 30 ° C., as described, for example, in the WO 2005/087859, WO 2006/061064 and WO 2007/017060. The plasticizer content is adjusted by those skilled in the art depending on the viscosity and desired properties of the diene rubber composition which are determined by the use of the diene rubber composition. The viscosity of the diene rubber composition itself depends on many variables, such as the viscosity of the elastomeric matrix, the level of reinforcing filler, interactions that may exist between the elastomeric matrix and the reinforcing filler. Thus the skilled person with his general knowledge chooses the appropriate plasticizer rate taking into account these different variables. If the diene rubber composition of the second useful layer of the invention contains a plasticizer, it preferably contains at most 20 phr, more preferably less than 10 phr, even more preferably less than 5 phr.
[0044] These preferred embodiments make it possible to achieve very remarkable levels of adhesion between the first and third layers thanks to the interphase constituted by the second layer. According to another embodiment of the invention, the diene rubber composition of the second layer is devoid of plasticizer. This advantageous embodiment from the point of view of the adhesion performance is particularly suitable for diene rubber compositions constituting the second layer which are weakly charged, especially those comprising at most 50 phr of reinforcing filler.
[0045] Preparation of the diene rubber compositions: The diene rubber compositions useful for the purposes of the invention 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 temperature of between 130 ° C and 200 ° C, followed by a second phase of mechanical work (so-called "productive" phase) up to a more low temperature, typically less than 110 ° C, for example between 40 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system.
[0046] Preparation of the laminate: P10-3482 In the manufacture of the laminate according to the invention, the diene rubber compositions constituting the layers are affixed in the green state, one on the other. To facilitate interfacial adhesion, the layers are preferably applied hot, the layers being in the green state.
[0047] It will be readily understood that, depending on the specific fields of application, the laminate according to the invention may comprise several preferred ranges of thickness. Thus, for example, for passenger-type tires, the first and third layers may have a thickness of at least 2 mm, preferably between 3 and 10 mm. In another example, for tire tires of heavy goods vehicles or agricultural vehicles, the preferential thickness may be between 2 and 20 mm for the first and third layers. In another example, for tire tires of vehicles in the field of civil engineering or for aircraft, the preferred thickness of the first and third layers may be between 2 and 100 mm.
[0048] According to any one of the embodiments of the invention, the second layer preferably has a thickness ranging from 60 μm to a few millimeters, for example from 100 μm to 5 mm. The thickness is adjusted according to the particular conditions of use of the laminate.
[0049] For the smallest thicknesses, in particular of the order of a few hundred μm, the layers are preferably formed by applying the diene rubber composition in the form of a dissolution composed of a volume of solvent. For higher thicknesses, it is preferred to calendate or even extrude the diene rubber composition in the form of a layer.
[0050] In order to manufacture the laminate, the layers may be arranged one on the other by successive application of the layers, for example on a clothing drum conventionally used in the manufacture of a tire (or envelope) of a tire. For example, the first layer is deposited on the drum, the second layer on the first layer, the third layer on the second layer. The laminate can be either in the green state (before crosslinking or vulcanization) or in the fired state (after crosslinking or vulcanization).
[0051] In the manufacture of a tire containing the laminate, the laminate can be manufactured prior to the manufacture of the tire or during the manufacture of the tire. In the first case, the preformed laminate formed and in the green state can be applied to the tire by depositing it, for example, on the carcass or crown reinforcement of the tire, also in the green state. In the second case, the third layer may be deposited, for example, on the carcass or crown reinforcement of the tire, also in the green state, then the second layer on the third layer and the first layer on the second layer. layer, the first, second and third layers being in the green state. The laminate can be used in a tire, the tire comprising a tread, two sidewalls, two beads, a carcass reinforcement passing in both sides and anchored to the two beads, and a crown reinforcement arranged circumferentially between the tread and the carcass reinforcement. According to one embodiment of the invention, the laminate is used in a tire so that the first layer constitutes part or all of the tread of the tire and the third layer a part or all of a tire. under layer to the tread. According to a preferred embodiment of the invention in which the laminate is used in a tire, the first layer constitutes the entire tread and the third layer all of a sub-layer to the tread. When the third layer in the laminate is used as a sub-layer to the tread of a tire, it is preferably not intended to come into contact with the tread surface of the tire. The tire which is provided with the laminate and which represents another object of the invention may be in the baked state or in the green state.
[0052] The aforementioned features of the present invention, as well as others, will be better understood on reading the following description of several embodiments of the invention, given by way of illustration and not limitation. II. EXAMPLES OF CARRYING OUT THE INVENTION 11.1-Preparation of the Diene Rubber Compositions and Laminates: For the compositions whose formulation is shown in Table 1, the following procedure is carried out: The final filling rate is introduced into an internal mixer: approximately 70% by volume), whose initial tank temperature is approximately 80 ° C., successively the elastomer, the reinforcing filler, as well as the 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 about 3 to 4 minutes, until a maximum temperature of "fall" of 165 ° C is reached. The mixture thus obtained is recovered, cooled, and sulfur and a sulfenamide type accelerator are incorporated on a mixer P10-3482 (homo-finisher) at 30 ° C, mixing the whole (productive phase) for a suitable time (by example about ten minutes). The compositions thus obtained are then calendered either in the form of a plate (thickness 2 to 3 mm) or layer for the measurement of their respective adhesion levels. Compositions C1, C2 and C3 differ in the nature of the elastomer matrix which composes them respectively. Composition C1 represents the first layer of the laminate and contains a weakly unsaturated EPDM El elastomer having 5% by weight of diene unit. The composition C2 represents the second layer of the laminate and contains an elastomer E2 comprising ethylene units and diene units comprising a carbon-carbon double bond, which units are statistically distributed within the second elastomer.
[0053] Composition C3 represents the third layer of the laminate and contains a highly unsaturated E3 elastomer, natural rubber. 11.2-Measurements and tests used: II.2-a) Size Exclusion Chromatography Size Exclusion Chromatography (SEC) is used. The SEC makes it possible to separate the macromolecules in solution according to their size through columns filled with a porous gel. The macromolecules are separated according to their hydrodynamic volume, the larger ones being eluted first. Without being an absolute method, the SEC allows to apprehend the distribution of the molar masses of a polymer. From commercial standard products, the various average molar masses (Mn) and weight (Mw) can be determined and the polymolecularity index (lp = Mw / Mn) calculated via a so-called calibration of MOORE. Preparation of the polymer: There is no particular treatment of the polymer sample before analysis. This is simply solubilized in (tetrahydrofuran + 1% vol diisopropylamine + 1% vol triethylamine + 1% vol distilled water) or in chloroform at a concentration of about 1 g / I . Then the solution is filtered on 0.45um porosity filter before injection. SEC analysis: The equipment used is a "WATERS alliance" chromatograph. The elution solvent is tetrahydrofuran + 1% vol. of diisopropylamine + 1% vol. triethylamine or chloroform depending on the solvent used for dissolving the polymer. The flow rate is 0.7 ml / min, the system temperature 35 ° C and the analysis time 90 min. A set of four WATERS columns in series, trade names "STYRAGEL HMW7", "STYRAGEL HMW6E" and two "STYRAG EL HT6E" are used. P10-3482 The injected volume of the solution of the polymer sample is 100 μl. The detector is a differential refractometer ((WATERS 2410)> and the chromatographic data exploitation software is the "WATERS EMPOWER" system.The calculated average molar masses relate to a calibration curve made from commercial standard polystyrene " PSS READY CAL-KIT II.2-b) Adhesion test The adhesion measurement is carried out by a so-called T-coat or also called a 180 ° peel test. The peel test pieces are made by contacting the two layers (the constituent compositions of the layers being in the green state) whose adhesion must be tested. A rupture primer is inserted between the two layers. Each of the layers is reinforced by a composite web which limits the deformation of said layers under traction.
[0054] The test piece once assembled is heated to 150 ° C. under a pressure of 16 bar for 30 minutes. Strips of 30 mm width are then cut to the cutter. Both sides of the breakout primer were then placed in the jaws of an "Instron" brand traction machine. The tests are carried out at 20 ° C. and at a tensile speed of 100 mm / min. The tensile forces are recorded and these are standardized by the width of the specimen. A force curve is obtained per unit of width (in N / mm) as a function of the displacement of the moving beam of the traction machine (between 0 and 200 mm). The adhesion value retained corresponds to the propagation of the rupture within the test piece and therefore to the average stabilized value of the curve. The adhesion values of the examples are standardized with respect to a control (base 100).
[0055] The adhesion is measured between the two layers C1 and C3, between the two layers C1 and C2 and between the two layers C2 and C3. The value of the adhesion measurement between the two layers C1 and C3 is retained as the control value, since the laminate comprising the only two layers C1 and C3 is not in accordance with the invention because of the absence of the layer C2.
[0056] Table 2 shows the results obtained after peel tests at room temperature. The results are expressed in performance index. An index greater than 100 indicates a greater improvement in membership. It is found that the adhesion performance indexes on the one hand between the first layer and the second layer, on the other hand between the second layer and the third layer are the highest (respectively 700 and 625) relative to the control. The presence in a laminate of the second layer between the first layer and the third layer of the laminate greatly increases the resistance of the laminate to the separation of the layers that constitute it, compared to the control laminate comprising only the layers C1 and C3. P10-3482 Table 1 C1 C2 C3 E1 (1) 100 E2 (2) 100 E3 (3) 100 Carbon black (4) 30 30 Antioxidant (5) 1.5 1.5 1.5 Stearic acid (6) 2.5 2.5 2.5 Zinc Oxide (7) 3 3 3 Accelerator (8) 2.0 2.0 2.0 Sulfur 1.0 1.0 1.0 (1) EPDM Nordel IP 4570 from the Dow Company (2) Elastomer containing 71% UA unit, 8% UB unit, 14% UC unit and 7% UD unit (% molar), prepared according to a process for the polymerization of ethylene and butadiene according to Example 4 2 of patent EP 1 954 705 B1 in the name of the Applicants, the polymerization time being adjusted so as to obtain a molar mass Mn = 153 000 g / mol with a polydispersity index equal to 1.9; the mass content of diene unit being 45% by mass (3) Natural rubber (4) Carbon black of grade N234 according to ASTM D-1765 (5) N-1,3-dimethylbutyl-N-phenylparaphenylenediamine "Santoflex 6-PPD "from Flexsys (6) Stearin" Pristerene 4931 "from Uniqema (7) Industrial grade zinc oxide from Umicore (8) N-cyclohexyl-2-benzothiazyl sulfenamide" Santocure CBS "from the company Flexsys company Table 2 Interface between layers tested Cl / C3 C2 / C3 C2 / C1 Level of adhesion 100 625 700 P10-3482

权利要求:
Claims (37)
[0001]
REVENDICATIONS1. An elastomeric laminate comprising 3 layers, the first layer consisting of a diene rubber composition comprising a first elastomeric matrix, the second layer consisting of a diene rubber composition comprising a second elastomeric matrix, which second elastomer matrix comprises a second elastomer comprising ethylene units and diene units having a carbon-carbon double bond, which units are statistically distributed within the second elastomer, the third layer consisting of a diene rubber composition comprising a third diene elastomer having a diene unit mass ratio greater than 50% the second layer being disposed between the first layer and the third layer.
[0002]
2. Laminate according to claim 1 wherein the ethylene units representing at least 50 mol% of all the monomer units of the second elastomer.
[0003]
A laminate according to claim 2 wherein the second elastomer comprises the following UA, UB, UC and UD units statistically distributed within the second elastomer, AU) -CH2-CH2- at a molar percentage of m% UB) as a percentage. molar ratio of n% UC) 130 to a molar percentage of 0% -CH2-C-1C-R2 CH2 40 UD) CH2-CI-12 in a molar percentage of p% cH2 / CH2 CH CH / P10-3482 R1 and R2, which may be identical or different, denoting a hydrogen atom, a methyl radical or a phenyl radical which may or may not be substituted in the ortho, meta or para position by a methyl radical, - m 50 - 0 <o + p 25 - n + o> 0 - m, n, o and p being numbers ranging from 0 to 100 - the respective molar percentages of m, n, o, and p being calculated on the basis of the sum of m + n + o + p which is equal to 100.
[0004]
A laminate according to claim 3 wherein the second elastomer contains units UE statistically distributed within the second elastomer, UE) CH2- according to a molar percentage of q% / CH CH2 CH2 -O + p + q 10 q 0 - the respective molar percentages of m, n, o, p and q being calculated on the basis of the sum of m + n + o + p + q which is equal to 100.
[0005]
5. The laminate according to claim 3, wherein the second elastomer contains UF units statistically distributed within the second elastomer, UF) -CH 2 -CH-I R 3 in a molar percentage of r% -R 3 denoting a alkyl radical having 1 to 4 carbon atoms or an aryl radical, - 0 <r <25. the respective molar percentages of m, n, o, p, q and r being calculated on the basis of the sum of m + n + o + p + q + r which is equal to 100.
[0006]
The laminate of claim 5 wherein r is 0. P10-3482
[0007]
Laminate according to any one of claims 3 to 6 wherein at least one of the two molar percentages p and q is other than 0.
[0008]
8. A laminate according to any one of claims 3 to 7 wherein p is strictly greater than 0.
[0009]
9. Laminate according to any one of claims 3 to 8 wherein the second elastomer has at least one of the following criteria, and preferably all: - m 65 - n + o + p + q 15, preferably 20 - 10 p + q 2 to 1 n / (o + p + q) - when q is not zero, 20 p / q 1.
[0010]
A laminate according to any one of claims 3 to 9 wherein the second elastomer contains as monomeric units only the units UA, UB, UC, UD and UE according to their respective molar percentage m, n, o, p and q, of preferably all different from 0.
[0011]
A laminate according to claim 3 or any one of claims 5 to 9 wherein the second elastomer contains as monomeric units only the units UA, UB, UC and UD according to their respective molar percentage m, n, o and p, of preferably all different from 0.
[0012]
12. A laminate according to any one of claims 3 to 11 wherein R1 and R2 are identical and denote a hydrogen atom.
[0013]
A laminate according to any one of claims 1 to 12 wherein the first elastomeric matrix comprises a first terpolymer elastomer of ethylene, an α-olefin and a nonconjugated diene.
[0014]
The laminate of claim 13 wherein the first elastomer is an EPDM, preferably a terpolymer of ethylene, propylene and 5-ethylidene-2-norbornene.
[0015]
15. Laminate according to any one of claims 13 to 14 wherein the first elastomer has a mass ratio of diene unit lower than the mass ratio of diene unit of the second elastomer.
[0016]
16. Laminate according to any one of claims 13 to 15 wherein the first elastomer has a diene unit mass ratio of less than 10%. P10-3482
[0017]
17. A laminate according to any one of claims 13 to 16 wherein the first elastomer represents more than 50% by weight of the first elastomeric matrix, preferably the entirety of the first elastomeric matrix.
[0018]
18. Laminate according to any one of claims 1 to 17 wherein the first elastomer matrix has a diene unit mass ratio lower than the diene unit mass ratio of the second elastomer.
[0019]
19. Laminate according to any one of claims 1 to 18 wherein the first elastomer matrix has less than 10% by weight of diene unit.
[0020]
20. A laminate according to any one of claims 1 to 19 wherein the second elastomeric matrix comprises another highly unsaturated diene elastomer which preferably represents from 10 to 70% by weight of the second elastomer matrix.
[0021]
The laminate of claim 20 wherein the second elastomeric matrix consists of the second elastomer and the other highly unsaturated diene elastomer.
[0022]
22. A laminate according to claim 20 or 21 wherein the other highly unsaturated diene elastomer is a polyisoprene, preferably a high cis polyisoprene having a 1,4-cis bond ratio greater than 90%, more preferably preferential natural rubber.
[0023]
23. Laminate according to any one of claims 1 to 22 wherein the second elastomer represents more than 50%, preferably more than 90% by weight of the second elastomer matrix in mass of the second elastomer matrix.
[0024]
24. A laminate according to any one of claims 1 to 19 wherein the second elastomer represents the entire second elastomeric matrix.
[0025]
25. A laminate according to any one of claims 1 to 24 wherein the third diene elastomer contains 1,3-diene monomer units, preferably isoprene.
[0026]
26. The laminate of claim 25 wherein the third diene elastomer is a polyisoprene preferably having a 1,4-cis bond ratio greater than 90%, preferably natural rubber.
[0027]
27. A laminate according to any one of claims 1 to 26 wherein the third diene elastomer is at least 95% by weight, preferably all of the elastomeric matrix which constitutes the diene rubber composition of the third layer. P10-3482
[0028]
28. A laminate according to any one of claims 1 to 27 wherein the diene rubber composition constitutive of any of the 3 layers comprises a reinforcing filler, preferably a carbon black.
[0029]
29. A laminate according to claim 28 wherein the diene rubber compositions constituting respectively the first layer, the second layer and the third layer comprise a reinforcing filler, preferably a carbon black.
[0030]
30. A laminate according to any one of claims 1 to 29 wherein the diene rubber composition constitutive of any one of the 3 layers comprises a crosslinking system, preferably a vulcanization system. 15
[0031]
31. A laminate according to claim 30 wherein the diene rubber compositions constituting respectively the first layer, the second layer and the third layer comprise a crosslinking system, preferably a vulcanization system. 20
[0032]
32. Laminate according to any one of claims 1 to 31 wherein the diene rubber composition of the second layer contains at most 20 phr of plasticizer, preferably less than 10 phr.
[0033]
33. A laminate according to any one of claims 1 to 32 wherein the diene rubber composition of the second layer is free of plasticizer.
[0034]
34. Use in a tire of a laminate defined according to any one of claims 1 to 33. 30
[0035]
35. A tire comprising a tread, two sidewalls, two beads, a carcass reinforcement passing in both flanks and anchored to the two beads, and a crown reinforcement disposed circumferentially between the tread and the carcass reinforcement, which pneumatic tire comprises a laminate according to any one of claims 1 to 33.
[0036]
Tire according to claim 35 wherein the first layer of the laminate constitutes part or all of the tread of the tire and the third layer of the laminate constitutes part or all of a tread underlayer. . 40 P10-3482 10
[0037]
37. Use of an adhesive composition for bonding two compositions, characterized in that the adhesive composition is identical to the diene rubber composition constituting the second layer defined according to any one of claims 1 to 33, and that the two compositions are respectively identical to the diene rubber compositions constituting the first layer and the third layer defined according to any one of claims 1 to 33. P10-3482

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FR3001223B1|2013-01-22|2015-03-06|Michelin & Cie|RUBBER COMPOSITION COMPRISING A HIGHLY SATURATED DIENIC ELASTOMER|CN110713646A|2018-07-13|2020-01-21|杭州星庐科技有限公司|Rubber composition and tire using the same|

FR3088328B3|2018-11-09|2020-12-04|Michelin & Cie|FUNCTIONAL DIENIC ELASTOMER AND RUBBER COMPOSITION|

FR3099766B1|2019-08-07|2021-07-30|Michelin & Cie|Ethylene-rich diene block polymer having a statistical block and a polyethylene block.|

WO2021256123A1|2020-06-15|2021-12-23|住友ゴム工業株式会社|Tire|

法律状态:
2015-12-21| PLFP| Fee payment|Year of fee payment: 2 |

2016-06-03| PLSC| Publication of the preliminary search report|Effective date: 20160603 |

2016-12-22| PLFP| Fee payment|Year of fee payment: 3 |

2017-12-21| PLFP| Fee payment|Year of fee payment: 4 |

2019-09-27| ST| Notification of lapse|Effective date: 20190906 |

优先权:

申请号 | 申请日 | 专利标题

FR1461755A|FR3029139B1|2014-12-02|2014-12-02|ELASTOMER LAMINATE COMPRISING 3 LAYERS|FR1461755A| FR3029139B1|2014-12-02|2014-12-02|ELASTOMER LAMINATE COMPRISING 3 LAYERS|

BR112017010810-0A| BR112017010810B1|2014-12-02|2015-11-23|ELASTOMERIC LAMINATE COMPRISING 3 LAYERS|

CN201580064835.6A| CN107000395B|2014-12-02|2015-11-23|Elastomeric laminate comprising three layers|

US15/532,305| US20170327617A1|2014-12-02|2015-11-23|Elastomer laminate comprising three layers|

EP15798416.2A| EP3227106B1|2014-12-02|2015-11-23|Elastomer laminate comprising three layers|

PCT/EP2015/077350| WO2016087248A1|2014-12-02|2015-11-23|Elastomer laminate comprising three layers|

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