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    • 专利摘要:
    The present invention relates to an elastomeric laminate comprising a layer A consisting of a diene rubber composition, a layer B comprising a highly unsaturated diene elastomer B, n layers Ci disposed between the layer A and the layer B, n being an integer ≥ 2 , i being an integer ranging from 1 to n, the layer C1 being disposed between the layer A and the layer C2, the layer Cn being disposed between the layer B and the layer Cn-1, the layer Ci being disposed between the layer Ci-1 and the layer Ci + 1 for the values of i ranging from 2 to n-1 when n> 2, the layer C1 comprises a diene elastomer E comprising ethylene units and more than 10% by weight of diene units, the Cn layer comprises a highly unsaturated N diene elastomer, the level expressed in N diene elastomer pce being higher in the Cn layer than in the C1 layer, the level expressed in diene elastomer pce E being higher in the layer;C1 that in the Cn layer, for n> 2, the layers Ci comprise a diene elastomer I chosen from the group consisting of homopolymers and diene copolymers having more than 10% by weight of diene unit, for the values of i ranging from 2 to n-1. Such a laminate has good resistance to the separation of the layers that constitute it.
    公开号:FR3029837A1
    申请号:FR1462227
    申请日:2014-12-11
    公开日:2016-06-17
    发明作者:Da Silva José-Carlos Araujo；Xavier Deparis；Baptiste FOGLIENI
    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 present invention is that of elastomeric laminates comprising more than 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, in particular for a pneumatic application of the first composition as a tread of the tire and the second composition as under layer to the tread. To remedy this, use may be made of a material which will act as glue or rubber binding between the first composition and the second composition, in particular used respectively as tread of a tire and under -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] Applicants have solved the problem by using a laminate which acts as a bonding gum between these two compositions. Used between the two compositions each constituting a layer to be bonded, it makes it possible to significantly improve the resistance to separation of the layers, in particular by better bonding of each of the layers to be bonded. Thus, a first object of the invention is an elastomeric laminate comprising a layer A, a layer B, n layers Ci disposed between the layer A and the layer B, n being an integer greater than or equal to 2, i being a number integer ranging from 1 to n, wherein the layer C1 (i = 1) being disposed between the layer A and the layer C2 (i = 2), where the layer Cn (i = n) being arranged between the layer B and the layer Cn-1, where the layer Ci is disposed between the layer Ci-1 and the layer Ci + 1 for the values of i ranging from 2 to n-1 when n is greater than 2, in which the layer A consists of a diene rubber composition, the layer B consists of a diene rubber composition comprising a diene elastomer B having a mass content of diene unit greater than 50%, the n layers Ci for i ranging from 1 to n each consist of a composition of diene rubber, the layer C1 comprises a diene elastomer E comprising ethylene units and dienic units, the diene units representing more than 10% by weight of the monomer units of the diene elastomer E, the Cn layer comprises from 50 to less than 100 phr of an N diene elastomer having a higher diene unit mass ratio at 50%, the level expressed in pce of diene elastomer N being higher in the layer Cn than in the layer C1, the level expressed in pce of diene elastomer E being higher in the layer C1 than in the layer Cn for n greater than 2, the layers Ci comprise a diene elastomer I selected from the group consisting of homopolymers and diene copolymers having more than 10% by weight of diene unit, for the values of i ranging from 2 to n-1.
    [0004] Another object of the invention is the use of the elastomer laminate according to the invention in a tire.
    [0005] The invention also relates to a tire which comprises the elastomeric laminate according to the invention. The invention also relates to an adhesive laminate which consists of the layers C1, Cn and Ci as defined in the elastomeric laminate according to the invention, with the difference that the layer C1 and the layer Cn have a single interface with a layer , respectively with the layer C2 and the layer Cn-1, for i ranging from 2 to n-1 with n greater than or equal to 2. The invention also relates to the use of the adhesive laminate according to the invention for bonding two layers A 'and B' of identical composition respectively to layers A and B as defined in the elastomeric laminate according to the invention, by applying the layer C1 on the layer A 'and the layer Cn on the layer B'. I. DETAILED DESCRIPTION OF THE INVENTION By the term "base-based" composition is meant a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended to react with each other, at least 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.
    [0006] In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are percentages (%) by weight. 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 "from a to b" means the range from a to b (i.e., including the strict limits a and b). A laminate is a product made of several layers of flat or non-planar shape, as defined by the International Patent Classification.
    [0007] The elastomeric laminate according to the invention comprises a layer A, a layer B, n layers Ci disposed between the layer A and the layer B, n being an integer greater than or equal to 2, i being an integer ranging from from 1 to n, where the layer C1 (i = 1) is disposed between the layer A and the layer C2 (i = 2), where the layer Cn is disposed between the layer B and the layer Cn-1, where layer Ci being disposed between the layer Ci-1 and the layer Ci + 1 for the values of i ranging from 2 to n-1 when n is greater than 2, in which the layer A consists of a diene rubber composition, the layer B consists of a diene rubber composition comprising a diene elastomer B having a mass content of diene unit greater than 50%, the n layers Ci for i ranging from 1 to n each consist of a diene rubber composition, the layer C1 comprises a diene elastomer E comprising ethylene units and di enic, the dienic units representing more than 10% by weight of the monomer units of the diene elastomer E, the Cn layer comprises from 50 to less than 100 phr of an N diene elastomer having a mass content of diene unit greater than 50 %, the level expressed in pce of diene elastomer N being higher in the layer Cn than in the layer C1, the level expressed in pce of diene elastomer E being higher in the layer C1 than in the layer Cn, for n greater than 2, the layers Ci comprise a diene elastomer I chosen from the group consisting of homopolymers and copolymers of diene having more than 10% by weight of diene unit, for the values of i ranging from 2 to n- 1. The elastomeric laminate according to the invention is called elastomeric since it comprises several layers which consist of diene rubber compositions, in this case layer A, layer B and n layers.
    [0008] The layers are distinguished from their close neighbors by their respective diene rubber composition, preferably by the nature of their elastomeric matrix. By close neighbors of the layer Ci are meant the layers Ci + 1 and Ci-1 for the values of i ranging from 2 to n-1, the close neighbors of the layer C1 being the layer A and the layer C2, the close ones 35 adjacent to the Cn layer being the Cn-1 layer and the B layer. By "elastomer" (or indistinctly "rubber", the two terms being considered synonymous) "diene", must be understood in a known manner (one or more ) elastomer derived at least in part (ie, a homopolymer or a copolymer) of 40 diene monomers (monomers bearing two carbon-carbon double bonds, conjugated or otherwise).
    [0009] The term "highly unsaturated diene elastomer" is understood to mean an elastomer having a diene unit mass ratio greater than 50%. The term "weakly unsaturated diene elastomer" is understood to mean an elastomer having a diene unit mass ratio of less than 10%.
    [0010] The diene unit rate which refers 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 z% in an elastomer A means that the diene units represent zg in 100 g of elastomer A, z being a number from 0 to 100, for example equal to 5. This formulation is equivalent to to that which consists in saying that the elastomer A contains z% of diene unit, or that the elastomer A has z% of diene unit, or that the elastomer has az% of diene unit. By diene unit is meant a monomeric unit resulting from the insertion of a monomeric 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. By elastomeric matrix is meant a rubber composition all the elastomers contained in the rubber composition.
    [0011] 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. The term "weakly unsaturated elastomer matrix" is understood to mean an elastomer matrix which has 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 level of less than 10%. The weakly unsaturated elastomer matrix may, however, contain a highly unsaturated diene elastomer in a proportion such that the level of diene units present in the elastomeric matrix is less than 10%. The proportion of diene unit which refers to an elastomeric 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 z '% in an elastomer matrix B means that all the diene units present in the elastomer matrix B represent z' g in 100 g of elastomer matrix B, where z 'is a number of 0 at 100, for example equal to 10. This formulation is equivalent to that which consists in saying that the elastomer matrix B 40 contains z '% of diene unit or that the elastomer matrix B has z'% of diene unit.
    [0012] Layering of the layers: The essential characteristic of the elastomer laminate according to the invention is to comprise a layer A, a layer B and n layers Ci disposed between the layers A and B, n being an integer greater than or equal to 2, i being an integer ranging from 1 to n.
    [0013] When the elastomeric laminate contains layer A, layer B and two layers both disposed between layer A and layer B, layer C1 (i = 1) is disposed between layer A and layer C2 (i = 1). 2), while the layer C2 is arranged between the layer C1 and the layer B. This variant corresponds to the case where n is equal to 2.
    [0014] When the elastomeric laminate according to the invention contains the layer A, the layer B and more than two layers, in particular n layers (n being greater than 2), between the layer A and the layer B, each of the layers, called Ci, is disposed between the layer Ci-1 and the layer Ci + 1 for the values of i ranging from 2 to n-1, knowing that the layer C1 has a common interface with the layer A and that the layer Cn has a common interface with layer B. This variant corresponds to the case where n is greater than 2. The value of n is not limited by a maximum value from a technical point of view: it can vary to a large extent. Nevertheless, those skilled in the art understand that a large number of layers Ci may not be favorable for certain applications, for example because of the material cost and the weight which increase with the number of layers. For this reason, preferably n is 2. Composition of the layers: The layer C1 The elastomer laminate also has the essential feature that the layer C1 comprises a diene elastomer E comprising ethylene units and diene units, the diene units representing more than 10% by weight of the monomeric units of the diene elastomer E. The elastomers comprising ethylene units and diene units are well known to those skilled in the art and can be synthesized by polymerization in the presence of Ziegler Natta catalysts or catalytic systems comprising metallocenes. Mention may be made, by way of diene elastomer E, of ethylene and 1,3-diene copolymers, in particular butadiene or isoprene, terpolymers of ethylene, α-olefin and non-conjugated diene. , especially EPDM (ethylene-propylene-diene rubber). It is understood that the diene elastomer E may be a mixture of elastomers meeting the definition of the diene elastomer E, especially mixtures of terpolymers of ethylene, α-olefin and nonconjugated diene which differ from each other. from each other by their macrostructure or their microstructure, in particular by the respective mass ratio of the ethylene, α-olefin and non-conjugated diene units According to one variant of the invention, the diene elastomer E is a terpolymer of ethylene , Α-olefin and nonconjugated diene, the non-conjugated diene units being greater than 10% by weight of the second elastomer. According to this variant, the diene elastomer E preferably 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 diene elastomer E the α-olefin units represent between 10 and 80%, preferably from 15 to 70% by weight of the diene elastomer E.
    [0015] According to any of the embodiments of this variant, the diene elastomer E preferably contains between 10 and 40%, more preferentially between 10 and 20% by weight of diene unit. When the diene elastomer E has such a diene unit level, it differs from the terpolymers of ethylene, α-olefin and nonconjugated diene which are conventionally used in tire rubber compositions, especially in tire sidewalls for their resistance to aging and ozone, and which generally have a diene unit level of at most 10%. According to one particular embodiment of the invention, the level of diene elastomer E is 50 to 100 phr, preferably 50 to 100 phr in the Cl layer. The Cl layer may also contain another diene elastomer preferably having a diene unit mass ratio greater than 50%, in particular the diene elastomer N which is also present in the Cn layer, in which case the amount calculated in pce of diene elastomer N is lower in the layer C 1 than in the layer Cn. According to the invention, the content expressed as pce of diene elastomer E in the layer C1 is such that it is always greater than that in the layer Cn. In other words, the quantity calculated in pce of diene elastomer E is higher in the layer C1 than in the layer Cn. According to a particularly preferred embodiment of the invention, the layer C1 contains more than 90 phr of a mixture of elastomers consisting of the elastomer di nique N and the diene elastomer E, preferably 100 phr of this blend.
    [0016] Another essential feature of the elastomer laminate is that the Cn layer comprises from 50 to less than 100 phr, preferably from 50 to 90 phr of diene elastomer N, having a diene unit weight ratio greater than 100 to 100 phr. 50%.
    [0017] The diene elastomer N may be an elastomer containing conjugated diene monomer units, in particular 1,3 diene containing preferably 4 to 12 carbon atoms, advantageously isoprene. It is understood that the diene elastomer N may be a mixture of elastomers which differ from each other in their macrostructure or microstructure. According to a preferred embodiment of the invention, the diene elastomer N is a high cis polyisoprene having a 1,4-cis bond ratio greater than 90%, calculated on the basis of the weight of the polyisoprene.
    [0018] According to any of the embodiments of the invention, the diene elastomer is preferably natural rubber. In addition to the diene elastomer N, the Cn layer contains another elastomer 20 preferably selected from the group of diene elastomers having a diene unit mass ratio greater than 10%. This other diene elastomer is preferably the diene elastomer E, in which case the amount of diene elastomer E calculated in pce is lower in the Cn layer than in the Cl layer.
    [0019] According to a particularly preferred embodiment of the invention, the Cn layer contains more than 90 phr of a mixture of elastomers consisting of the diene elastomer N and the diene elastomer E, preferably 100 phr of this mixture. When two layers are arranged between the layers A and B, as already mentioned previously (n = 2), the layer C2 contains the diene elastomer N and can contain the diene elastomer E, while the layer C1 contains the elastomer diene E and can contain the diene elastomer N. The layers Ci for the values of i ranging from 2 to n-1, n being greater than 2: 35 When the laminate comprises more than 2 layers between the layers A and B (n being greater than 2), the layers Ci each comprise, of course, a diene elastomer I selected from the group consisting of homopolymers and diene copolymers having more than 10% by weight of diene unit, for values of i ranging from 2 to n-1. When n is equal to 3, the values taken by i varying from 2 to n-1 are of course limited to the only value 2.
    [0020] The diene elastomer I is preferably the diene elastomer E, the diene elastomer N or a mixture thereof. When the diene elastomer I is the diene elastomer E, the content expressed in terms of diene elastomer E is preferably lower in the layer Ci + 1 than in the layer Ci for at least one of the values of i ranging from 2 to n-1. In other words, the composition of at least one of the layers C 1 preferably has a diene elastomer level E which is lower than the constitutive rubber composition of the layer which is considered to be its close neighbor and which precedes it in the direction from layer 1 to layer n, for the values of i ranging from 2 to n-1. According to a particularly preferred embodiment of the invention (n being greater than 2), the level expressed in diene elastomer pce E is lower in the layer Ci + 1 than in the layer Ci for any value of i ranging from 2 to n-1. Since the layers are stacked one on top of the other and, given their respective concentration of diene elastomer E, the person skilled in the art understands that there is a gradient of diene elastomer level E in the elastomeric laminate, this decreasing rate in the direction going from layer 1 to layer n, the level of diene elastomer E being expressed in phr in each of the layers.
    [0021] According to one embodiment of the invention (where n is greater than 2), the level expressed in pce of diene elastomer N is lower in the layer Ci than in the layer Ci + 1 for at least one of the values of i. ranging from 2 to n-1. In other words, the composition of at least one of the layers C 1 preferably has a diene elastomer level E which is lower than the constitutive rubber composition of the layer which is considered to be its close neighbor and which follows it in the direction from layer 1 to layer n, for values of i ranging from 2 to n-1. According to another particularly preferred embodiment of the invention (where n is greater than 2), the level expressed in pce of diene elastomer N is lower in the layer Ci than in the layer Ci + 1 for any value of i. ranging from 2 to n-1. Since the layers are stacked one on top of the other and, given their respective concentration of diene elastomer N, the person skilled in the art understands that there is a gradient of levels of diene elastomer N in the elastomeric laminate, this increasing rate in the in the direction from layer 1 to layer n, the level of diene elastomer N being expressed in phr in each of the layers. A more preferred embodiment of the invention consists in combining the two particularly preferred embodiments described above, which leads to describe two gradients of diene elastomer content in the elastomeric laminate, a relative one 40 to the rate of the diene elastomer E and the other relating to the level of diene elastomer N ranging respectively decreasing and increasing in the elastomeric laminate in the direction from layer 1 to layer n. According to a particularly preferred embodiment of the invention, any one of the layers Ci, preferably all, for i ranging from 2 to n-1 (n being greater than 2), contains more than 90 phr of a elastomer mixture consisting of elastomer N and elastomer E, preferably 100 phr of this mixture. The B-layer The elastomeric laminate according to the invention has the essential feature of comprising a layer B, which layer B consists of a diene rubber composition comprising a diene elastomer B having a diene unit mass ratio greater than 50%.
    [0022] It is understood that the diene elastomer B may be a mixture of elastomers which differ from each other in their macrostructure or microstructure. The diene elastomer B may be an elastomer containing conjugated diene monomer units, in particular 1,3 diene containing 4 to 12 carbon atoms, advantageously isoprene. According to a preferred embodiment of the invention, the diene elastomer B is a high cis polyisoprene having a 1,4-cis bond ratio greater than 90%, preferably a natural rubber.
    [0023] According to any of the embodiments of the invention, the diene rubber composition of layer B preferably contains at least 95 phr, more preferably 100 phr of diene elastomer B.
    [0024] The layer A The elastomeric laminate according to the invention has the essential feature of comprising a layer A, which layer A consists of a diene rubber composition.
    [0025] According to any of the embodiments of the invention, the layer A preferably comprises a diene elastomer having a terpolymer of ethylene, an α-olefin and a non-conjugated diene having a diene unit level. less than 10% by weight. According to a particular embodiment of the invention, the diene elastomer A 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. diene elastomer A, the α-olefin units represent between 10 and 80%, preferably from 15 to 70% by weight of the diene elastomer A, the non-conjugated diene units represent between 0.5 and 10% by weight of Diene elastomer A. The level of diene elastomer A in layer A is preferably at least 95 phr, more preferably equal to 100 phr. These preferred ranges of values may apply to any of the embodiments of the invention. According to one embodiment of the invention, the elastomeric matrix which may be composed in part or in whole of the diene elastomer A and contained in the layer A itself has a mass content of diene unit of less than 10%. This characteristic implies that the elastomeric matrix is relatively poor in highly unsaturated elastomer and relatively rich in weakly unsaturated elastomer. The α-olefin whose monomeric units constitute the diene elastomer E or the diene elastomer A may be a mixture of alpha olefins. The α-olefin generally comprises 3 to 16 carbon atoms. Suitable olefins are, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-dodecene. Advantageously, the α-olefin is propylene, in which case the terpolymer is commonly called an EPDM (in English "EPDM rubber").
    [0026] The non-conjugated diene of which the monomeric units constitute the diene elastomer E or the diene elastomer A 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.
    [0027] According to any of the embodiments of the invention, the diene elastomer E or the diene elastomer A is preferably an EPDM, more preferably a terpolymer of ethylene, propylene and 5-ethylidene. 2-norbornene.
    [0028] According to any of the embodiments of this variant, the diene elastomer E and the diene elastomer A are preferably an EPDM, more preferably a terpolymer of ethylene, propylene and 5-ethylidene-2. -norbornène. The microstructure of the elastomers is determined by 1 H NMR analysis, supplemented by 13 C NMR analysis when the resolution of the 1E1 NMR spectra does not allow the assignment and quantification of all species. The measurements are carried out using a 500 MHz BRUKER NMR spectrometer at frequencies of 500.43 MHz for proton observation and 125.83 MHz for carbon observation. For measurements on mixtures or elastomers which are insoluble but have the capacity to swell in a solvent, a HRMAS 4mm z-grad probe is used to observe the proton and carbon in decoupled mode of the proton. 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, usually 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. Soluble samples are dissolved in a deuterated solvent (about 25mg of elastomer in 1mL), usually deuterated chloroform (CDCl3). The solvent or solvent cut used must always be deuterated and its chemical nature can be adapted by those skilled in the art. 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 single 30 ° pulse sequence is used with proton decoupling 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 the quantization of each pattern. The recycle time between each pulse is adapted to obtain a quantitative measurement. The measurements are carried out at 25 ° C. Reinforcing filler: The diene rubber composition constitutive of any one of the layers A, B and C 1, preferably all, preferably comprises a reinforcing filler, in particular when the elastomer laminate is used in a tire, i ranging from 1 at n with n greater than or equal to 2. 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 black carbon, a reinforcing inorganic filler such as silica with 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. By "reinforcing inorganic filler" is to be understood herein any inorganic or mineral filler whatever its color and origin (natural or synthetic), still called "white" filler, "clear" filler or even "non-filler" as opposed to carbon black, capable of reinforcing on its own, without any other means than an intermediate coupling agent, a diene rubber composition intended for the manufacture of pneumatic tires, in other words able to replace, in its reinforcing function, a conventional carbon black of pneumatic grade; such a filler is generally characterized, in a known manner, by the presence of hydroxyl groups (-OH) on its surface. Suitable reinforcing inorganic fillers are in particular mineral fillers of the siliceous type, preferentially 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 Degussa, the "Zeosil" 1165MP, 1135MP and 1115MP silicas of Rhodia, the "Hi-Sil" silica EZ150G from the PPG company, the "Zeopol" 8715, 8745 and 8755 silicas from the Huber Company, the high surface area silicas as described in the application WO 03/016387. In the present specification, 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 3029837 14 according to the French standard NF ISO 9277 of December 1996 (multipoint volumetric method (5 points) - gas: nitrogen - degassing: 1 hour at 160 ° C - relative pressure range p / po : 0.05 to 0.17). The CTAB specific surface is the external surface determined according to the French standard NF T 45-007 of November 1987 (method B).
    [0029] The physical state in which the reinforcing inorganic filler is present is indifferent whether in the form of powder, microbeads, granules or beads. Of course, the term "reinforcing inorganic filler" is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of highly dispersible silicas as described above. It will be understood by those skilled in the art that, as the equivalent filler of the reinforcing inorganic filler described in this paragraph, a reinforcing filler of another nature, in particular organic such as carbon black, could be used, provided that this reinforcing filler would be covered with an inorganic layer such as silica, or would comprise on its surface functional sites, especially 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. 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 nature and / or between the inorganic filler (surface of its particles) and the diene elastomer. In particular, organosilanes or at least bifunctional polyorganosiloxanes are used. Polysulphurized silanes, called "symmetrical" or "asymmetrical" silanes according to their particular structure, are especially used, as described, for example, in the claims W003 / 002648 (or US 2005/016651) and W003 / 002649 (or US 2005/016650). . Particularly suitable, but not limited to, polysulfide silanes having the general formula (V) Z - A - Sx - A - Z (V) wherein: - x is an integer of 2 to 8 (preferably from 2 to 5); the symbols A, 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 radical; , in particular propylene); the symbols Z, which may be identical or different, correspond to one of the following three formulas: ## STR2 ## wherein: ## STR2 ## in which: the radicals R1, which may be substituted or unsubstituted, which are identical to 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 C1-C13 alkoxyl or C5-C18 cycloalkoxyl group (preferably a group chosen from C1-C8 alkoxyls and C5-C8 cycloalkoxyls, more preferably still a group selected from C1-C4 alkoxyls, in particular methoxyl and ethoxyl).
    [0030] In the case of a mixture of polysulphurized alkoxysilanes of formula (I) above, especially commercially available mixtures, the average value of "x" is a fractional number preferably between 2 and 5, more Preferably, the invention can be advantageously used, for example, with disulfide alkoxysilanes (x = 2). As examples of polysulphide silanes, mention may be made more particularly of polysulfides (in particular disulphides, trisulphides or tetrasulfides) of bis- (C 1 -C 4 alkoxyl) -alkyl (C 1 -C 4) silylalkyl (C 1 -C 4) alkyl, as per 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. As coupling agent other than polysulfide alkoxysilane, there may be mentioned in particular bifunctional POSS 35 (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.
    [0031] Coupling agents that may also be mentioned are 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.
    [0032] 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 as little as possible. Typically the level of coupling agent is 0.5% to 15% by weight, based on 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.
    [0033] According to a particular embodiment of the invention, each of the diene rubber compositions respectively constituting the layers A, B and n layers of the elastomeric laminate comprises a reinforcing filler. Reinforcing filler content: The level of reinforcing filler in each of the diene rubber compositions of the elastomeric laminate can vary to a large extent, for example according to the nature of the elastomeric matrix or reinforcing filler in the diene rubber composition or according to the amount 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, in particular in a tire. In the case of a use of the laminate in which the layer A of the laminate is constitutive of a tread intended to equip a tire and the layer B is constitutive of a sub-layer to the tread, the nature of the The reinforcing filler in the diene rubber composition of the n layers and its level are selected 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.
    [0034] According to any of the embodiments of the invention, the level of reinforcing filler in the diene rubber composition of the n layers preferably varies from 5 to 80 phr, more preferably from 5 to 50 phr. According to a particular embodiment of the invention, the diene rubber composition of the n layers comprises a level of reinforcing filler less than or equal to the reinforcing filler content of the diene rubber composition of the layer A.
    [0035] Other additives: The diene rubber composition constitutive of any one of the layers A, B and n layers of the elastomeric laminate may also contain, in addition to the coupling agents, coupling activators, coating agents and the like. inorganic agents or, more generally, processing aids which can be used in a known manner by improving the dispersion of the filler in the rubber matrix and lowering the viscosity of the diene rubber composition, improve its ability to implement in the raw state.
    [0036] It may also include 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-corrosion waxes, ozone, 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 the crosslinking agent, mention may be made of triallyl isocyanurate, ethylene dimethacrylate and 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 respectively constituting the layers A, B and n layers comprise a crosslinking system, preferably a vulcanization system. 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, naphthenic oils). hydrogenated, MES or TDAE oils), vegetable oils, in particular glycerol esters such as glycerol trioleate, hydrocarbon plasticizing resins having a high Tg, preferably greater than 30 ° C, as described for example in the WO applications 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, the interactions that may exist between the elastomeric matrix and the reinforcing filler. Thus, the person skilled in the art with his general knowledge chooses the appropriate plasticizer content taking into account these different variables. If the diene rubber compositions constituting n layers useful in the invention contain a plasticizer, they preferably contain at most 20 phr, more preferably less than 10 phr, even more preferably less than 5 phr. . These preferred embodiments make it possible to achieve levels of adhesion between the very remarkable layers.
    [0037] According to another embodiment of the invention, the diene rubber composition of any one or more of the n layers, preferably all, is devoid of plasticizer. This advantageous embodiment from the point of view of the adhesion performance is particularly suitable for the diene rubber compositions constituting the n layers which are weakly loaded, in particular those which comprise at most 50 phr of reinforcing filler. Preparation of the diene rubber compositions: The diene rubber compositions useful for the purposes of the invention are manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or mixing thermomechanical (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 maximum lower temperature, typically less than 110 ° C, for example between 40 ° C and 100 ° C, finishing phase during which the crosslinking system is incorporated. Preparation of the laminate: In the manufacture of the elastomer laminate according to the invention, the diene rubber compositions constituting the layers are affixed in the green state, one on the other 30. To facilitate interfacial adhesion, the layers are preferably applied hot, the layers being in the green state. The hot application of the layers in the green state is carried out at a temperature which is compatible with the chemical nature of the layers, that is to say at a temperature which does not cause for example prematurely the crosslinking of the layers . Typically, a temperature above ambient (20 ° C) and not exceeding 80 ° C is entirely appropriate. It will be readily understood that, depending on the specific fields of application, the elastomeric laminate according to the invention may comprise several preferred ranges of thickness. Thus, for example, for passenger-type tires, the 40 layers A and B 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 layers A and B. According to another example, for tire tires of vehicles in the In the field of civil engineering or for aircraft, the preferential thickness of layers A and B can be between 2 and 100 mm.
    [0038] According to the particular conditions of use of the elastomeric laminate, the n layers may each have a thickness ranging from 60 μm to a few millimeters, for example from 100 μm to 5 mm.
    [0039] 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.
    [0040] In order to manufacture the elastomeric laminate, the layers may be arranged one on the other by successive application of the layers, for example on a construction drum conventionally used in the manufacture of a tire (or envelope) of a tire. For example, the layer A is deposited on the drum, the layer C1 on the layer A and so on until the application of the layer B on the layer Cn. The elastomer laminate can be either in the raw state. (before crosslinking or vulcanization), either in the cooked state (after crosslinking or vulcanization).
    [0041] In the manufacture of a tire containing the elastomeric laminate, the elastomeric laminate may be manufactured prior to the manufacture of the tire or during the manufacture of the tire. In the first case, the previously formed elastomeric laminate can be applied to the tire by depositing it, for example, on the carcass or crown reinforcement of the tire. In the second case, the layer B may be deposited for example on the carcass or crown reinforcement of the tire, then the layer Cn on the layer B and so on until the application of layer A on the layer Cl. The elastomeric laminate can be used in a tire, the 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. According to one embodiment of the invention, the elastomeric laminate is used in a tire so that the layer A forms part or all of the tire tread and the layer B a part or all of the tire tread. an under layer to the tread.
    [0042] According to a preferred embodiment of the invention in which the elastomer laminate is used in a tire, the layer A constitutes the entire tread and the layer B the entire tread layer to the tread .
    [0043] When the layer B in the elastomeric 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.
    [0044] The tire which is provided with the elastomeric laminate and which represents another object of the invention may be in the baked state or in the green state. The other object, the adhesive laminate, consists of the layers C1, Cn and Ci as defined in the elastomer laminate according to the invention, with the difference that the layer C1 and the layer Cn have a single interface with a layer , respectively with the layer C2 and the layer Cn-1, for i ranging from 2 to n-1 with n greater than or equal to 2. It can be used as a bonding rubber to bond two layers A 'and B' respectively of identical compositions to the layers A and B and thus form with the layers A 'and B' the elastomeric laminate according to the invention. The green adhesive laminate is disposed between the layers A 'and B' also in the green state to form the elastomeric laminate according to the invention, by applying the layer C1 to the layer A 'and the layer Cn on the layer B '. The aforementioned features of the present invention, as well as others, will be better understood on reading the following description of several exemplary embodiments of the invention, given by way of illustration and not limitation. II. EXAMPLES OF CARRYING OUT THE INVENTION II.1-Preparation of the Diene Rubber Compositions and Laminates: For the compositions whose formulation is shown in Table I, the procedure is as follows: final filling: about 70% by volume), whose initial tank temperature is about 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 (homo-finisher) at 30 ° C., mixing the whole (productive phase) for a suitable time (for example ten minutes).
    [0045] The compositions thus obtained are then calendered either in the form of a plate (thickness 2 to 3 mm) or as a layer for the measurement of their respective adhesion levels. The compositions A, B, Cl and C2 differ in the nature of the elastomer matrix which respectively composes them and respectively constitute the layers A, B, Cl and C2. The layer C1 is disposed between the layer A and C2; the layer C2 between the layer C1 and the layer B. The layer A comprises a weakly unsaturated EPDM elastomer at 5% by weight of diene unit; layer B comprises an elastomer having more than 50% by weight of diene unit, natural rubber. The elastomer matrix of the layer C1 and that of the layer C2 respectively comprise an elastomer EPDM with 14% by mass of diene unit and the natural rubber, elastomer having more than 50% by weight of diene unit, knowing that the the EPDM elastomer at 14% by weight of diene unit is higher in the Cl layer than in the C2 layer and the level of natural rubber is higher in the C2 layer than in the Cl layer, the elastomer levels being expressed in pce. II.2-Measurements and tests used: 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.
    [0046] 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 a "lnstron" 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 to a control (base 100). The adhesion is measured between the two layers A and B, between the two layers C1 and C2, between the two layers A and Cl and between the two layers B and C2. The value of the adhesion measurement between the two layers A and B is retained as the control value, since a laminate comprising the two layers A and B, the layer A being disposed on the layer B, does not comply with the invention.
    [0047] 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.
    [0048] It is found that the adhesion performance indices between the layer B and the layer C2, between the layer A and the layer C1 and between the layer C1 and the layer C2 are the highest (respectively 475, 570 and 500) by report to the witness. The presence of the layers C1 and C2 in a laminate comprising the layers A and B, the layers C1 and C2 being disposed between the layer A and the layer C2 and between the layer C1 and the layer B of the laminate makes it possible to increase very strongly. the resistance of the laminate to the separation of the layers that constitute it, compared to the control laminate comprising only the layers A and B.
    [0049] Table 1 AB Cl C2 NR (1) 100 10 70 EPDM (2) 100 EPDM (3) 90 Carbon Black (4) 30 Antioxidant (5) 1.5 1.5 1.5 1, 5 Stearic acid (6) 2.5 2.5 2.5 2.5 Zinc oxide (7) 3 3 3 3 Accelerator (8) 2.0 2.0 2.0 2.0 Sulfur 1.0 1, 0 1.0 1.0 (1) Natural Rubber (2) EPDM Nordel IP 4570 from Dow Company 15 (3) EPDM 9090M from Mitsui Corporation (4) Carbon black 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 20 (7) Industrial grade zinc oxide from Umicore ( 8) N-cyclohexyl-2-benzothiazyl sulfenamide "Santocure CBS" from the company Flexsys Table 2 Interface between layers tested A / BB / C2 A / C1 C1 / C2 Level of adhesion 100 475 570 500 5 10 25 30
    权利要求:
    Claims (31)
    [0001]
    REVENDICATIONS1. An elastomeric laminate comprising a layer A, a layer B, n layers Ci disposed between the layer A and the layer B, n being an integer greater than or equal to 2, i being an integer ranging from 1 to n, o the layer C1 being disposed between the layer A and the layer C2, where the layer Cn is disposed between the layer B and the layer Cn-1, where the layer Ci being disposed between the layer Ci-1 and the layer Ci + 1 for the values of i ranging from 2 to n-1 when n is greater than 2, wherein layer A consists of a diene rubber composition, layer B consists of a diene rubber composition comprising a diene elastomer B having a mass level of unity diene greater than 50%, the n layers Ci for i ranging from 1 to n each consist of a diene rubber composition, the layer C1 comprises a diene elastomer E comprising ethylene units and diene units, the diene units representing more than 10 % in the mass of the monomeric units of the diene elastomer E, the layer Cn comprises from 50 to less than 100 phr of an N-diene elastomer having a mass content of diene unit greater than 50%, the content expressed in terms of elastomer diene N being higher in the layer Cn than in the layer C1, the level expressed in pce of diene elastomer E being higher in the layer C1 than in the layer Cn, for n greater than 2, the layers Ci comprise an elastomer diene I selected from the group consisting of homopolymers and copolymers of diene having more than 10% by weight of diene unit, for the values of i ranging from 2 to n-1.
    [0002]
    2. An elastomeric laminate according to claim 1 wherein the diene elastomer N is a high cis polyisoprene having a 1,4-cis bond ratio greater than 90%, preferably a natural rubber.
    [0003]
    3. elastomeric laminate according to any one of claims 1 to 2 wherein the diene elastomer I is the diene elastomer E, the diene elastomer N or a mixture thereof.
    [0004]
    4. The elastomeric laminate according to claim 3, in which the level expressed in diene elastomer pce E is lower in the layer Ci + 1 than in the layer Ci for at least one of the values of i ranging from 2 to n-1, with n greater than 2. 3029837 25
    [0005]
    An elastomeric laminate according to any one of claims 3 to 4 wherein the level expressed as diene elastomer pce E is lower in the layer Ci + 1 than in the layer Ci for any value of i ranging from 2 to n. -1, with n greater than 2. 5
    [0006]
    6. An elastomeric laminate according to any one of claims 3 to 5 wherein the level expressed in pce diene elastomer N is lower in the layer Ci than in the layer Ci + 1 for at least one of the values of i ranging from 2 to n-1, with n greater than 2.
    [0007]
    An elastomeric laminate according to any one of claims 3 to 6 wherein the level expressed as pce of diene elastomer N is lower in the layer Ci than in the layer Ci + 1 for any value of i ranging from 2 to n-1, with n greater than 2.
    [0008]
    An elastomeric laminate according to any one of claims 1 to 7 wherein any one or more of the Ci layers contains more than 90 phr of a mixture of elastomers consisting of N elastomer and elastomer E, preferably 100 phr of this mixture, for i ranging from 2 to n-1, with n greater than 2.
    [0009]
    9. An elastomeric laminate according to any one of claims 1 to 8 wherein the Cn layer comprises another elastomer preferably selected from the group of diene elastomers having a diene unit mass ratio greater than 10%, preferably the elastomer diene E.
    [0010]
    10. An elastomeric laminate according to any one of claims 1 to 9 wherein the Cn layer contains more than 90 phr of a mixture of elastomers consisting of the diene elastomer N and the diene elastomer E, preferably 100 phr. of this mixture.
    [0011]
    11. An elastomeric laminate according to any one of claims 1 to 10 wherein the layer C1 comprises another diene elastomer preferably having a diene unit mass ratio greater than 50%, preferably the diene elastomer N.
    [0012]
    12. An elastomeric laminate according to any one of claims 1 to 11 wherein the level of diene elastomer E is 50 to 100 phr, preferably between 50 and 100 phr in the Cl layer.
    [0013]
    13. An elastomeric laminate according to any one of claims 1 to 12 wherein the C1 layer contains more than 90 phr of a mixture of elastomers consisting of the diene elastomer N and the diene elastomer E, preferably 100 phr of this mixture.
    [0014]
    14. Elastomeric laminate according to any one of claims 1 to 13 wherein 40 the rate expressed in pce diene elastomer N is 50 to 90 phr in the layer Cn 3029837 26
    [0015]
    15. An elastomeric laminate according to any one of claims 1 to 14 wherein the diene elastomer E contains between 10 and 40%, preferably between 10 and 20% by weight of diene unit. 5
    [0016]
    An elastomeric laminate according to any one of claims 1 to 15 wherein the diene elastomer E is a terpolymer of ethylene, an α-olefin and a nonconjugated diene, preferably an EPDM.
    [0017]
    17. An elastomeric laminate according to any one of claims 1 to 16 wherein the level of diene elastomer B in the diene rubber composition of layer B is at least 95 phr, preferably 100 phr.
    [0018]
    An elastomeric laminate according to any one of claims 1 to 17 wherein the diene elastomer B is a high cis polyisoprene having a 1,4-cis bond ratio greater than 90%, preferably a natural rubber. .
    [0019]
    An elastomeric laminate according to any one of claims 1 to 18 wherein layer A comprises a diene terpolymer elastomer of ethylene, an α-olefin and a nonconjugated diene having a lower diene unit level. at 10% by weight, preferably EPDM.
    [0020]
    20. An elastomeric laminate according to any one of claims 1 to 19 wherein the layer A contains an elastomeric matrix A having a diene unit mass ratio of less than 10%. 25
    [0021]
    21. An elastomeric laminate according to any one of claims 1 to 20 wherein the level of diene elastomer A in the layer A is at least 95 phr, preferably equal to 100 phr. 30
    [0022]
    22. An elastomeric laminate according to any one of claims 1 to 21 wherein any one of preferably A, B and C 1 layers comprises a reinforcing filler, preferably a carbon black, i ranging from 1 to n .
    [0023]
    An elastomeric laminate according to any one of claims 1 to 22 wherein any one of preferably A, B and C 1 comprises a crosslinking system, preferably a vulcanization system, varying from 1 to n.
    [0024]
    24. An elastomeric laminate according to any one of claims 1 to 23 wherein each of the n layers contains at most 20 phr of a plasticizer, preferably less than 40 phr. 3029837 27
    [0025]
    25. An elastomeric laminate according to any one of claims 1 to 24 wherein any one of n preferably all layers is free of plasticizer.
    [0026]
    26. An elastomeric laminate according to any one of claims 1 to 3 or 9 to 25 wherein n is 2.
    [0027]
    27. Use in a tire of an elastomeric laminate defined according to any one of claims 1 to 26. 10
    [0028]
    28. 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 an elastomeric laminate according to any one of claims 1 to 26.
    [0029]
    The tire of claim 28 wherein the layer A of the elastomeric laminate constitutes part or all of the tread of the tire and the layer B of the elastomeric laminate constitutes a part or all of a sub-layer to the web. rolling. 20
    [0030]
    30. adhesive laminate which consists of the layers C1, Cn and Ci as defined in claims 1 to 26, with the difference that the layer C1 and the layer Cn have a single interface with a layer, respectively with the layer C2 and the layer Cn-1, for i ranging from 2 to n-1 with n greater than or equal to 2. 25
    [0031]
    31. Use of a defined adhesive laminate according to claim 30 for bonding two layers A 'and B' of identical composition respectively to the layers A and B defined according to any one of claims 1 to 26, by applying the layer C1 on the layer A 'and the layer Cn on layer B'. 30
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    同族专利:
    公开号 | 公开日
    EP3230057A1|2017-10-18|
    EP3230057B1|2019-01-02|
    FR3029837B1|2016-12-30|
    WO2016091571A1|2016-06-16|
    US10414132B2|2019-09-17|
    US20170326844A1|2017-11-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP1880871A1|2005-05-09|2008-01-23|The Yokohama Rubber Co., Ltd.|Multilayer body and pneumatic tire using same|
    EP1940617B1|2005-10-27|2014-03-26|The Yokohama Rubber Co., Ltd.|Construction comprising tie layer|
    US4089360A|1975-09-22|1978-05-16|The Firestone Tire & Rubber Company|Pneumatic tire containing an irradiated laminated component|
    US4450252A|1982-09-30|1984-05-22|The Firestone Tire & Rubber Company|Contact adhesive and adhesive system for EPDM and related elastomers|
    JPH0455106B2|1985-02-21|1992-09-02|Mitsuboshi Belting Ltd|
    US4601935A|1985-05-06|1986-07-22|Gencorp Inc.|EPDM laminate|
    JPH05338079A|1992-06-11|1993-12-21|Fuji Porimatetsuku Kk|Gradient-structure synthetic rubber|
    WO2007050061A1|2005-10-27|2007-05-03|Exxonmobil Chemical Patents Inc.|Construction comprising tie layer|FR3029138B1|2014-12-02|2017-01-13|Michelin & Cie|ELASTOMER LAMINATE COMPRISING 3 LAYERS|
    FR3044008B1|2015-11-19|2017-12-08|Michelin & Cie|TIRE TREAD FOR TIRE AIRCRAFT|
    FR3044009B1|2015-11-19|2017-12-08|Michelin & Cie|TIRE TREAD FOR TIRE AIRCRAFT|
    FR3044010A1|2015-11-19|2017-05-26|Michelin & Cie|TIRE TREAD FOR TIRE AIRCRAFT|
    FR3044007B1|2015-11-19|2017-12-08|Michelin & Cie|TIRE TREAD FOR TIRE AIRCRAFT|
    CN111448062A|2017-12-06|2020-07-24|米其林集团总公司|Elastomeric laminate|
    EP3720700A1|2017-12-06|2020-10-14|Compagnie Générale des Etablissements Michelin|Elastomeric laminate|
    法律状态:
    2015-12-21| PLFP| Fee payment|Year of fee payment: 2 |
    2016-06-17| PLSC| Search report ready|Effective date: 20160617 |
    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
    FR1462227A|FR3029837B1|2014-12-11|2014-12-11|ELASTOMERIC LAMINATE COMPRISING MORE THAN 3 LAYERS|FR1462227A| FR3029837B1|2014-12-11|2014-12-11|ELASTOMERIC LAMINATE COMPRISING MORE THAN 3 LAYERS|
    EP15801729.3A| EP3230057B1|2014-12-11|2015-11-23|Elastomeric laminate comprising more than three layers|
    US15/533,916| US10414132B2|2014-12-11|2015-11-23|Elastomeric laminate comprising more than three layers|
    PCT/EP2015/077351| WO2016091571A1|2014-12-11|2015-11-23|Elastomeric laminate comprising more than three layers|
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