ELASTOMERLAMINAT

Description

[0001] The field of the present invention is that of rubber laminates comprising a highly saturated diene elastomer, in particular those intended for use in a tire.

[0002] A tire usually has two beads intended to come into contact with a rim, a crown composed of at least one crown reinforcement and a tread, two sidewalls, the tire being reinforced by a carcass reinforcement anchored in the two beads.

[0003] In conventional tire manufacturing, the various components of the crown, carcass reinforcement, beads, and sidewalls are assembled to form a tire. The assembly step is followed by a shaping step to give the assembly a toric shape before the press curing step.

[0004] When assembling the tire, the tread is arranged radially outside the crown reinforcement, and is generally separated from the latter by a tread sub-layer. The sidewalls, for their part, are elastomeric layers arranged outside the carcass reinforcement relative to the internal cavity of the tire, between the crown and the beads so as to totally or partially cover the area of ​​the carcass reinforcement extending from the crown to the beads.

[0005] The tread, which is intended to come into contact with the ground when the tire is rolling, must have very specific properties, including good grip on both dry and wet surfaces, low rolling resistance and good wear resistance. The sidewall of the tire is subject to deformation cycles such as bending during the rolling of the tire, the rubber composition constituting a tire sidewall must be both sufficiently flexible and low hysteretic, but also have good resistance to physical attacks, such as curb impacts, and chemical attacks such as ozone attack.As a result, the compositions of the treads and sidewalls of tires consist of a very specific composition, different from the layers of tires on which they are arranged, such as respectively the underlayer of the tread, or the carcass ply, which are often made of a composition comprising a highly unsaturated diene elastomer, such as natural rubber, and a reinforcing filler, such as carbon black.

[0006] This difference in composition can result in a decrease in the adhesion properties of the tread or sidewall of a tire with their respective adjacent layer.

[0007] Therefore, it remains important to develop compositions with good properties for the position (tread or sidewall for example) for which they are intended, while presenting good adhesion to their respective adjacent layer, in particular to improve the resistance of the cured interfaces.

[0008] FR 3089 976 A1 and FR 3078 973 A1 give examples of rubber compositions based on copolymers containing units of a 1,3-diene.

[0009] Continuing its research, the Applicant discovered that the use of a copolymer comprising ethylene units and units of a specific 1,3-diene makes it possible to further improve the adhesion of the composition to a diene composition.

[0010] Thus a first object of the invention is an elastomer laminate comprising at least two adjacent layers: the first layer consisting of a rubber composition based on: ∘ 20 to 100 pce of at least one copolymer comprising ethylene units and units of a 1,3-diene of formula (I), the ethylene units in the copolymer representing more than 50% by mole of the monomer units of the copolymer, CH2=CR-CH=CH2 (I) the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms; ∘ 0 to 80 pce of at least one diene elastomer having a mass content of diene unit greater than 50%; ∘ 10 to 100 pce of a plasticizing system comprising at least one plasticizer liquid at 23°C and / or at least one plasticizing resin having a glass transition temperature greater than 20°C; ∘ ​​a reinforcing filler; and ∘ a crosslinking system, the second layer consisting of a rubber composition based on a diene elastomer having a mass content of diene units greater than 50% and a crosslinking system.

[0011] Another subject of the invention is a rubber article, as well as a pneumatic or non-pneumatic tire comprising this laminate. I- DEFINITIONS

[0012] The expression "based on" used to define the constituents of a catalytic system means the mixture of these constituents, or the product of the reaction of some or all of these constituents with each other.

[0013] The expression "composition based on" means a composition comprising the mixture and / or the reaction product in situ of the different constituents used, some of these constituents being able to react and / or being intended to react with each other, at least partially, during the different phases of manufacturing the composition; the composition thus being able to be in a totally or partially crosslinked state or in a non-crosslinked state.

[0014] By “elastomer matrix” is meant all the elastomers in the composition, including the copolymer defined below.

[0015] Unless otherwise indicated, the rates of units resulting from the insertion of a monomer into a copolymer are expressed as a molar percentage relative to the total monomer units of the copolymer.

[0016] By the expression "part by weight per hundred parts by weight of elastomer" (or pce), it is meant, within the meaning of the present invention, the part, by mass per hundred parts of elastomer present in the rubber composition considered and constituting a layer.

[0017] On the other hand, any interval 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., excluding the limits a and b), while any interval of values ​​designated by the expression "from a to b" means the range of values ​​from a to b (i.e., including the strict limits a and b). In this document, when an interval of values ​​is designated by the expression "from a to b", the interval represented by the expression "between a and b" is also and preferably designated.

[0018] When a "majority" compound is referred to, within the meaning of the present invention, this compound is the majority among the compounds of the same type in the composition, that is to say that it is the one which represents the largest quantity by mass among the compounds of the same type. Thus, for example, a majority elastomer is the elastomer representing the largest mass relative to the total mass of the elastomers in the composition. In the same way, a so-called majority filler is the one representing the largest mass among the fillers in the composition. For example, in a system comprising a single elastomer, this is the majority within the meaning of the present invention; and in a system comprising two elastomers, the majority elastomer represents more than half of the mass of the elastomers. On the contrary, a "minority" compound is a compound which does not represent the largest mass fraction among the compounds of the same type.Preferably by majority, we mean present at more than 50% by mass, preferably more than 60%, 70%, 80%, 90%, and more preferably the “majority” compound represents 100% by mass.

[0019] The compounds mentioned in the description may be of fossil or bio-sourced origin. In the latter case, they may be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. Similarly, the compounds mentioned may also come from the recycling of materials already in use, that is to say, they may be, partially or totally, derived from a recycling process, or obtained from raw materials themselves derived from a recycling process.

[0020] All glass transition temperature “Tg” values ​​described herein are measured in a known manner by DSC (Differential Scanning Calorimetry) according to ASTM D3418 (1999). II- DESCRIPTION OF THE INVENTION II -1 Laminate

[0021] According to the invention, the laminate comprises at least two, preferably strictly two, adjacent layers, called "first layer" and "second layer".

[0022] By "adjacent layers" we mean that the layers are in contact, at least in part, with each other.

[0023] The first layer of the laminate according to the invention may have a thickness in a range from 0.2 to 120 mm, preferably from 0.3 to 15 mm.

[0024] Advantageously, the first layer of the laminate according to the invention has a thickness in a range from 0.5 to 120 mm, preferably from 1 to 15 mm. These dimensions are particularly advantageous when the first layer constitutes an external layer of the tire, such as a sidewall or a tire tread.

[0025] The first layer of the laminate according to the invention may also have a thickness in a range from 0.2 to 10 mm, preferably from 0.3 to 5 mm. These dimensions are particularly advantageous when the first layer constitutes a bonding layer between two tire layers.

[0026] Regardless of the thickness of the first layer, the second layer preferably has a thickness in the range of 0.2 to 10 mm, preferably 0.3 to 7 mm.

[0027] The first and second layers of the laminate can overlap completely or partially. II-2 Composition of the first layer of the laminate II-2.1 Elastomeric matrix

[0028] According to the invention, the first layer consists of a rubber composition based on: ∘ 20 to 100 pce of at least one copolymer comprising ethylene units and units of a 1,3-diene of formula (I), the ethylene units in the copolymer representing more than 50% by mole of the monomer units of the copolymer, CH 2 =CR-CH=CH 2 (I) the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms; ∘ 0 to 80 pce of at least one diene elastomer having a mass content of diene unit greater than 50%; ∘ 10 to 100 pce of a plasticizing system comprising at least one plasticizer liquid at 23°C and / or at least one plasticizing resin having a glass transition temperature greater than 20°C; ∘ ​​a reinforcing filler; and o a crosslinking system.

[0029] In this document, unless otherwise indicated, the expression "the copolymer" means "the at least one copolymer comprising ethylene units and units of a 1,3-diene of formula (I), the ethylene units in the copolymer representing more than 50% by mole of the monomer units of the copolymer, CH 2 =CR-CH=CH 2 (I), the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms" for the sake of simplification of wording.

[0030] Preferably, the copolymer contains ethylene units which represent between 50% and 95% by mole of the monomer units of the copolymer, i.e. between 50% and 95% by mole of the ethylene units and the 1,3-diene units. Very preferably, the copolymer contains ethylene units which represent from 60% to 90%, preferably from 70% to 85% by mole, of the monomer units of the copolymer.

[0031] 1,3-Diene of formula (I) is a substituted 1,3-diene, which can give rise to units of 1,2-configuration represented by formula (1), 3,4-configuration represented by formula (2) and 1,4-configuration whose trans form is represented below by formula (3).

[0032] As is also well known, the ethylene unit is a "-(CH 2 -CH 2 )-" motif unit.

[0033] The copolymer useful for the purposes of the invention is a copolymer comprising ethylene units and 1,3-diene of formula (I), which implies that monomer units of the copolymer are units resulting from the polymerization of ethylene and 1,3-diene of formula (I). The copolymer therefore comprises ethylene units and units of 1,3-diene of formula (I). According to the invention, the 1,3-diene may be a single compound, i.e. a single (in English "one") 1,3-diene of formula (I) or be a mixture of 1,3-dienes of formula (I), the 1,3-dienes of the mixture being differentiated from each other by the group represented by the symbol R.

[0034] The copolymer useful for the purposes of the invention is advantageously a statistical copolymer according to any one of the embodiments of the invention.

[0035] In formula (I) of 1,3-diene, the hydrocarbon chain represented by the symbol R is an unsaturated chain of 3 to 20 carbon atoms. Preferably, the symbol R represents a hydrocarbon chain having 6 to 16 carbon atoms.

[0036] The hydrocarbon chain represented by the symbol R may be a saturated or unsaturated chain. Preferably, the symbol R represents an aliphatic chain, in which case in formula (I) of 1,3-diene, the hydrocarbon chain represented by the symbol R is an aliphatic hydrocarbon chain. It may be a straight or branched chain, in which case the symbol R represents a straight or branched chain. Preferably, the hydrocarbon chain is acyclic, in which case the symbol R represents an acyclic chain. More preferably, the symbol R represents an unsaturated and branched acyclic hydrocarbon chain. Thus, the hydrocarbon chain represented by the symbol R is advantageously an unsaturated and branched acyclic chain containing from 3 to 20 carbon atoms, in particular from 6 to 16 carbon atoms. Very advantageously, the 1,3-diene is myrcene, β-farnesene or a mixture of myrcene and β-farnesene.

[0037] Advantageously, the copolymer contains 1,3-diene units of formula (I) which represent between 1% and 50%, preferably between 1% and 30%, preferably between 5% and 30%, in moles of the monomer units of the copolymer.

[0038] The copolymer may comprise a second 1,3-diene chosen from 1,3-butadiene, isoprene or a mixture thereof. In this case, the copolymer is a copolymer of ethylene, a 1,3-diene of formula (I) and a second 1,3-diene chosen from 1,3-butadiene, isoprene or a mixture thereof, the monomer units of the copolymer are units resulting from the polymerization of ethylene, the 1,3-diene of formula (I) and the second 1,3-diene. The copolymer may thus comprise ethylene units, units of the 1,3-diene of formula (I) and units of the second 1,3-diene. Advantageously, the second 1,3-diene of the copolymer is 1,3-butadiene.

[0039] Advantageously, the copolymer contains units of the second 1,3-diene which represent between 1% and 49%, preferably between 4% and 29%, preferably between 4% and 25%, in moles of the monomer units of the copolymer.

[0040] Preferably, the copolymer has a glass transition temperature of less than -35°C, preferably between -90°C and -35°C, more preferably between -70°C and -35°C.

[0041] The copolymer may be prepared by a process which comprises the copolymerization of ethylene, 1,3-diene of formula (I) and the optional second 1,3-diene, in the presence of a catalytic system based at least on one metallocene of formula (II) and an organomagnesium compound of formula (III) P(Cp 1< Cp 2< ) Nd(BH 4 ) (1+y)- L y -N x (II) MgR 1< R 2< (III) in which: Cp 1< and Cp 2< , identical or different, being chosen from the group consisting of the cyclopentadienyl group of formula C 5 H 4 , the unsubstituted fluorenyl group of formula C 13 H 8 and the substituted fluorenyl groups, P being a group bridging the two groups Cp 1< and Cp 2< and representing a group ZR 3< R 4< , Z representing a silicon or carbon atom, R 3< and R 4< , identical or different, each representing an alkyl group comprising from 1 to 20 carbon atoms, preferably a methyl, y, an integer, being equal to or greater than 0, x, an integer or not, being equal to or greater than 0, L representing an alkali metal chosen from the group consisting of lithium, sodium and potassium, N representing a molecule of an ether, preferably diethyl ether or tetrahydrofuran, R 1< and R 2< , identical or different, representing a carbon group.

[0042] Substituted fluorenyl groups include those substituted by alkyl radicals having 1 to 6 carbon atoms or by aryl radicals having 6 to 12 carbon atoms. The choice of radicals is also guided by the accessibility of the corresponding molecules, which are substituted fluorenes, because the latter are commercially available or easily synthesized.

[0043] As substituted fluorenyl groups, mention may be made more particularly of the 2,7-ditertiobutyl-fluorenyl and 3,6-ditertiobutyl-fluorenyl groups. Positions 2, 3, 6 and 7 respectively designate the position of the carbon atoms of the rings as shown in the diagram below, position 9 corresponding to the carbon atom to which the P bridge is attached.

[0044] The catalytic system can be prepared in a traditional manner by a process similar to that described in patent application WO 2007054224 or WO 2007054223. For example, the organomagnesium compound and the metallocene are reacted in a hydrocarbon solvent, typically at a temperature ranging from 20 to 80°C for a period of between 5 and 60 minutes. The catalytic system is generally prepared in a hydrocarbon solvent, aliphatic such as methylcyclohexane or aromatic such as toluene. Generally, after its synthesis, the catalytic system is used as is in the process for synthesizing the copolymer in accordance with the invention.

[0045] Alternatively, the catalytic system may be prepared by a process analogous to that described in patent application WO 2017093654 A1 or in patent application WO 2018020122 A1. According to this alternative, the catalytic system further contains a preformation monomer chosen from a conjugated diene, ethylene or a mixture of ethylene and a conjugated diene, in which case the catalytic system is based at least on the metallocene, the organomagnesium compound and the preformation monomer. For example, the organomagnesium compound and the metallocene are reacted in a hydrocarbon solvent, typically at a temperature of 20 to 80°C for 10 to 20 minutes to obtain a first reaction product, then with this first reaction product, the preformation monomer chosen from a conjugated diene, ethylene or a mixture of ethylene and a conjugated diene is reacted at a temperature of 40 to 90°C for 1 hour to 12 hours.The conjugated diene as pre-formation monomer is preferably a 1,3-diene such as 1,3-butadiene, isoprene or a 1,3-diene of formula (I), in particular myrcene or β-farnesene. The catalytic system thus obtained can be used immediately in the process according to the invention or can be stored under an inert atmosphere before its use in the process according to the invention.

[0046] The metallocene used to prepare the catalytic system may be in the form of a crystallized or non-crystalline powder, or in the form of single crystals. The metallocene may be in a monomeric or dimeric form, these forms depending on the method of preparation of the metallocene, as for example described in patent application WO 2007054224 or WO 2007054223. The metallocene may be prepared in a conventional manner by a process analogous to that described in patent application WO 2007054224 or WO 2007054223, in particular by reaction under inert and anhydrous conditions of the salt of an alkali metal of the ligand with a rare earth borohydride in a suitable solvent, such as an ether, such as diethyl ether or tetrahydrofuran or any other solvent known to those skilled in the art. After reaction, the metallocene is separated from the reaction by-products by techniques known to those skilled in the art, such as filtration or precipitation in a second solvent.The metallocene is finally dried and isolated in solid form.

[0047] Like any synthesis carried out in the presence of organometallic compounds, the synthesis of the metallocene and that of the catalytic system take place under anhydrous conditions under an inert atmosphere. Typically, the reactions are carried out from solvents and anhydrous compounds under anhydrous nitrogen or argon.

[0048] The organomagnesium compound useful for the purposes of the invention is of formula MgR 1< R 2< in which R 1< and R 2< , identical or different, represent a carbon group. A carbon group is understood to mean a group which contains one or more carbon atoms. Preferably, R 1< and R 2< contain 2 to 10 carbon atoms. More preferably, R 1< and R 2< each represent an alkyl. The organomagnesium compound is advantageously a dialkylmagnesium compound, better still butylethylmagnesium or butyloctylmagnesium, even better still butyloctylmagnesium.

[0049] According to any one of the embodiments of the invention, the molar ratio of the organomagnesium to the Nd metal constituting the metallocene is preferably within a range from 1 to 100, more preferably is greater than or equal to 1 and less than 10. The range of values ​​from 1 to less than 10 is in particular more favorable for obtaining copolymers with high molar masses.

[0050] When the copolymer useful for the purposes of the invention is a copolymer which has a microstructure as defined according to the first variant of the invention, it is prepared according to the process mentioned in the present application using a metallocene of formula (II) in which Cp 1< and Cp 2< , identical or different, are chosen from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula C 13 H 8 . For this variant, the following metallocenes are particularly suitable in which the symbol Flu has the fluorenyl group of formula C 13 H 8 : [{Me 2 SiFlu 2 Nd(µ-BH 4 ) 2 Li(THF)} 2 ] ; [Me 2 SiFlu 2 Nd(µ-BH 4 ) 2 Li(THF)] ; [Me 2 SiFlu 2 Nd(µ-BH 4 )(THF)] ; [{Me 2 SiFlu 2 Nd(µ-BH 4 )(THF)} 2 ]; [Me 2 SiFlu 2 Nd(µ-BH 4 )].

[0051] The skilled person also knows how to adapt the polymerization conditions and the concentrations of each of the reactants (components of the catalytic system, monomers) according to the equipment (tools, reactors) used to carry out the polymerization and the different chemical reactions. As is known to the skilled person, the copolymerization as well as the handling of the monomers, the catalytic system and the polymerization solvent(s) are carried out under anhydrous conditions and under an inert atmosphere. The polymerization solvents are typically hydrocarbon, aliphatic or aromatic solvents.

[0052] The polymerization is preferably carried out in solution, continuously or batchwise. The polymerization solvent may be a hydrocarbon, aromatic or aliphatic solvent. Examples of polymerization solvents include toluene and methylcyclohexane. The monomers may be introduced into the reactor containing the polymerization solvent and the catalytic system or, conversely, the catalytic system may be introduced into the reactor containing the polymerization solvent and the monomers. The copolymerization is typically carried out under anhydrous conditions and in the absence of oxygen, in the optional presence of an inert gas. The polymerization temperature generally varies within a range from 30 to 150°C, preferably from 30 to 120°C. Preferably, the copolymerization is carried out at constant ethylene pressure.

[0053] During the polymerization of ethylene, 1,3-diene of formula (I) and the optional second 1,3-diene, in a polymerization reactor, a continuous addition of ethylene and 1,3-diene of formula (I) and the optional second 1,3-diene, can be carried out in the polymerization reactor, in which case the polymerization reactor is a fed reactor. This embodiment is particularly suitable for the synthesis of random copolymer.

[0054] The polymerization can be stopped by cooling the polymerization medium. The polymer can be recovered using conventional techniques known to those skilled in the art, such as precipitation, evaporation of the solvent under reduced pressure or stripping with water vapor.

[0055] The elastomer matrix of the composition of the first layer of the laminate according to the invention may comprise mainly the copolymer comprising ethylene units and units of a 1,3-diene of formula (I). In this case, the content of the copolymer comprising ethylene units and units of a 1,3-diene of formula (I) in the composition of the first layer is advantageously within a range from more than 50 to 100 phr, preferably from 75 to 100 phr, more preferably from 90 to 100 phr. The rate of the copolymer comprising ethylene units and units of a 1,3-diene of formula (I) in the composition of the first layer may advantageously be 100 pce, that is to say that the elastomer matrix of the composition of the first layer of the laminate does not comprise any other elastomer than the copolymer comprising ethylene units and units of a 1,3-diene of formula (I).It is understood that the copolymer may consist of a mixture of copolymers which differ in their microstructure or in their macrostructure. When the elastomer matrix of the composition of the first layer mainly comprises the copolymer comprising ethylene units and units of a 1,3-diene of formula (I), the content of the diene elastomer having a mass content of diene unit greater than 50% in the composition of the first layer of the laminate according to the invention may be within a range from 0 to less than 50 phr, preferably from 0 to 25 phr, more preferably from 0 to 10 phr.

[0056] The elastomer matrix of the composition of the first layer of the laminate according to the invention advantageously comprises a mixture of the copolymer comprising ethylene units and units of a 1,3-diene of formula (I) and at least one diene elastomer having a mass content of diene units greater than 50%. Advantageously, the composition of the first layer of the laminate according to the invention comprises from 20 to 90 phr, preferably from 25 to 80 phr, more preferably from 30 to 80 phr, of the copolymer comprising ethylene units and units of a 1,3-diene of formula (I). It is understood that the copolymer may be constituted by a mixture of copolymers which differ by their microstructure or by their macrostructure.In this case, the rate of the diene elastomer having a mass rate of diene unit greater than 50% in the composition of the first layer of the laminate according to the invention is advantageously within a range from 10 to 80 phr, preferably from 20 to 75 phr, more preferably from 20 to 70 phr.

[0057] A diene unit is understood to mean a monomer unit resulting from the insertion of a monomer unit resulting from the polymerization of a conjugated diene monomer or a non-conjugated diene monomer, the diene unit comprising a carbon-carbon double bond.

[0058] Advantageously, the diene elastomer having a mass content of diene units greater than 50% of the composition of the first layer is chosen from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene copolymers, isoprene copolymers, and mixtures of these elastomers.

[0059] Preferably, the diene elastomer having a mass content of diene units greater than 50% of the composition of the first layer is chosen from the group consisting of isoprene elastomers.

[0060] By "isoprene elastomer" is meant, in a known manner, a homopolymer or a copolymer of isoprene, in other words a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), the various copolymers of isoprene and mixtures of these elastomers.

[0061] Advantageously, the isoprene elastomer is a polyisoprene comprising a mass content of 1,4-cis bonds of at least 90%, preferably at least 98%, of the mass of the polyisoprene.

[0062] Preferably, the polyisoprene is selected from the group consisting of natural rubber, synthetic polyisoprenes and their mixtures. More preferably, the polyisoprene is a natural rubber. II-2.2 Plasticizing system

[0063] The rubber composition of the first layer of the laminate according to the invention further comprises 10 to 100 phr of a plasticizing system comprising at least one plasticizer which is liquid at 23°C, called “low Tg”, i.e. which by definition has a Tg of less than -20°C, preferably less than -40°C and / or a plasticizing resin having a glass transition temperature of more than 20°C, called “high Tg”, (also referred to herein as “plasticizing resin” for the sake of simplification of wording).

[0064] Advantageously, the rate of the plasticizing system comprising at least one liquid plasticizer at 23°C and / or at least one plasticizing resin having a glass transition temperature greater than 20°C, in the composition of the first layer of the laminate according to the invention, is within a range from 35 to 100 phr, preferably from 50 to 95 phr, more preferably from 55 to 90 phr.

[0065] Advantageously, the plasticizing system of the composition of the first layer of the laminate according to the invention comprises at least one plasticizing resin having a glass transition temperature greater than 20°C, preferably it comprises both a liquid plasticizer at 23°C and a plasticizing resin having a glass transition temperature greater than 20°C. II-2.2.a Plasticizing resin

[0066] The term “resin” is reserved in the present application, by definition known to those skilled in the art, for a compound which is solid at room temperature (23°C), as opposed to a liquid plasticizing compound such as an oil.

[0067] Plasticizing resins are polymers well known to those skilled in the art, essentially based on carbon and hydrogen but which may contain other types of atoms, usable in particular as plasticizing agents or tackifying agents in polymer matrices. They are generally by nature miscible (i.e., compatible) at the rates used with the polymer compositions for which they are intended, so as to act as true diluting agents. They have been described for example in the work entitled " Hydrocarbon Resins" by R. Mildenberg, M. Zander and G. Collin (New York, VCH, 1997, ISBN 3-527-28617-9) of which chapter 5 is devoted to their applications, notably in pneumatic rubber (5.5. "Rubber Tires and Mechanical Goods ") .They can be aliphatic, cycloaliphatic, aromatic, hydrogenated aromatic, aliphatic / aromatic type i.e. based on aliphatic and / or aromatic monomers. They can be natural or synthetic, petroleum based or not (if so, also known as petroleum resins). Their Tg is preferably above 20°C (most often between 30°C and 95°C).

[0068] As is known, these plasticizing resins can also be called thermoplastic resins in the sense that they soften upon heating and can thus be molded. They can also be defined by a softening point or temperature (in English, "softening point"). The softening temperature of a plasticizing resin is generally about 50 to 60°C higher than its Tg value. The softening point is measured according to ISO 4625 (Ring and Ball method). The macrostructure (Mw, Mn and Ip) is determined by size exclusion chromatography (SEC) as shown below.

[0069] As a reminder, SEC analysis, for example, consists of separating macromolecules in solution according to their size through columns filled with a porous gel; the molecules are separated according to their hydrodynamic volume, the largest being eluted first. The sample to be analyzed is simply previously solubilized in an appropriate solvent, tetrahydrofuran at a concentration of 1 g / liter. Then the solution is filtered through a 0.45 µm porosity filter, before injection into the equipment. The equipment used is, for example, a "Waters alliance" chromatographic chain under the following conditions: elution solvent is tetrahydrofuran, temperature 35°C; concentration 1 g / liter; flow rate: 1 ml / min; injected volume: 100 µl; Moore calibration with polystyrene standards; set of 3 "Waters" columns in series ("Styragel HR4E", "Styragel HR1" and "Styragel HR 0.5"); detection by differential refractometer (e.g. "WATERS 2410") which can be equipped with operating software (e.g. "Waters Millennium").

[0070] A Moore calibration is carried out with a series of commercial polystyrene standards with low Ip (less than 1.2), of known molar masses, covering the mass range to be analyzed. The mass-average molar mass (Mw), the number-average molar mass (Mn), and the polydispersity index (Ip = Mw / Mn) are deduced from the recorded data (molar mass distribution curve).

[0071] All molar mass values ​​indicated in this application are therefore relative to calibration curves produced with polystyrene standards.

[0072] According to a preferred embodiment of the invention, the plasticizing resin has at least one, preferably 2 or 3, more preferably all, of the following characteristics: a Tg greater than 25°C (in particular between 30°C and 100°C), more preferably greater than 30°C (in particular between 30°C and 95°C); a softening point greater than 50°C (in particular between 50°C and 150°C); a number-average molar mass (Mn) between 300 and 2000 g / mol, preferably between 400 and 1500 g / mol; a polydispersity index (Ip) less than 3, preferably 2 (reminder: Ip = Mw / Mn with Mw weight-average molar mass).

[0073] The above preferred high Tg plasticizing resins are well known to those skilled in the art and commercially available, for example sold as: polylimonene resins: by the company DRT under the name "Dercolyte L120" (Mn=625 g / mol; Mw=1010 g / mol; Ip=1.6; Tg=72°C) or by the company ARIZONA under the name "Sylvagum TR7125C" (Mn=630 g / mol; Mw=950 g / mol; Ip=1.5; Tg=70°C); C5 / vinylaromatic cut copolymer resins, in particular C5 / styrene cut or C5 / C9 cut: by Neville Chemical Company under the names "Super Nevtac 78", "Super Nevtac 85" or "Super Nevtac 99", by Goodyear Chemicals under the name "Wingtack Extra", by Kolon under the names "Hikorez T1095" and "Hikorez T1100", by Exxon under the names "Escorez 2101" and "Escorez 1273"; limonene / styrene copolymer resins: by DRT under the name "Dercolyte TS 105" of the company DRT, by ARIZONA Chemical Company under the names "ZT115LT" and "ZT5100".

[0074] According to the invention, the plasticizing resin having a glass transition temperature greater than 20°C can be chosen from the group comprising or consisting of cyclopentadiene homopolymer or copolymer resins (abbreviated CPD), dicyclopentadiene homopolymer or copolymer resins (abbreviated DCPD), terpene homopolymer or copolymer resins, C5 cut homopolymer or copolymer resins, C9 cut homopolymer or copolymer resins, alpha-methyl-styrene homopolymer or copolymer resins and mixtures thereof.Preferably, the plasticizing resin is selected from the group comprising or consisting of (D)CPD / vinylaromatic copolymer resins, (D)CPD / terpene copolymer resins, terpene phenol copolymer resins, (D)CPD / C5 cut copolymer resins, (D)CPD / C9 cut copolymer resins, terpene / vinylaromatic copolymer resins, terpene / phenol copolymer resins, C5 cut / vinylaromatic copolymer resins, and mixtures thereof.

[0075] The term "terpene" here includes the monomers alpha-pinene, beta-pinene and limonene in a known manner; preferentially a limonene monomer is used, a compound which is present in a known manner in the form of three possible isomers: L-limonene (levorotatory enantiomer), D-limonene (dextrorotatory enantiomer), or dipentene, racemic of the dextrorotatory and levorotatory enantiomers. Suitable vinylaromatic monomers are, for example, styrene, alpha-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyltoluene, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, hydroxystyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene, any vinylaromatic monomer derived from a C9 cut (or more generally from a C8 to C10 cut).

[0076] More particularly, mention may be made of plasticizing resins chosen from the group consisting of (D)CPD homopolymer resins, (D)CPD / styrene copolymer resins, polylimonene resins, limonene / styrene copolymer resins, limonene / D(CPD) copolymer resins, C5 / styrene cut copolymer resins, C5 / C9 cut copolymer resins, and mixtures of these resins.

[0077] All of the above plasticizing resins are well known to those skilled in the art and commercially available, for example sold by the company DRT under the name "Dercolyte" for polylimonene resins, by the company Neville Chemical Company under the name "Super Nevtac", by Kolon under the name "Hikorez" or by the company Exxon Mobil under the name "Escorez" for C 5 / styrene cut resins or C 5 / C 9 cut resins, or by the company Struktol under the name "40 MS" or "40 NS" (mixtures of aromatic and / or aliphatic resins).

[0078] Advantageously, the level of plasticizing resin having a glass transition temperature above 20°C in the composition of the first layer of the laminate according to the invention is within a range from 1 to 99 phr, preferably from 5 to 95 phr, preferably from 10 to 90 phr, preferably from 15 to 85 phr. Those skilled in the art understand that when the level of the plasticizing resin having a glass transition temperature above 20°C is lower than the minimum level of the plasticizing system comprising at least one liquid plasticizer at 23°C and / or at least one plasticizing resin having a glass transition temperature above 20°C, the composition comprises at least the balance of the liquid plasticizer at 23°C.When the composition of the first layer of the laminate according to the invention does not comprise a liquid plasticizer at 23°C, the level of the resin having a glass transition temperature above 20°C in the composition is advantageously within a range from 10 to 90 pce, preferably from 15 to 85 pce, preferably from 20 to 80 pce. II-2.2.b Liquid plasticizer at 23°C

[0079] Any liquid plasticizer at 23°C (or extender oil), whether aromatic or non-aromatic, known for its plasticizing properties with respect to diene elastomers, can be used. At room temperature (23°C), these plasticizers or oils, more or less viscous, are liquids (that is to say, as a reminder, substances having the capacity to eventually take the shape of their container), in contrast in particular to plasticizing resins which are by nature solid at room temperature.

[0080] Particularly suitable are liquid plasticizers at 23°C chosen from the group comprising or consisting of liquid diene polymers, polyolefin oils, naphthenic oils, paraffinic oils, DAE oils, MES oils ( Medium Extracted Solvates ), TDAE oils ( Treated Distillate Aromatic Extracts ), RAE oils ( Residual Aromatic Extract oils ), TRAE oils ( Treated Residual Aromatic Extract ) and SRAE oils ( Safety Residual Aromatic Extract oils ), mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulfonate plasticizers and mixtures of these plasticizers liquid at 23°C.

[0081] For example, the liquid plasticizer at 23°C may be a petroleum oil, preferably non-aromatic. A liquid plasticizer is described as non-aromatic when it has a content of polycyclic aromatic compounds, determined with the extract in DMSO according to method IP 346, of less than 3% by weight, relative to the total weight of the plasticizer.

[0082] The liquid plasticizer at 23°C may also be a liquid polymer resulting from the polymerization of olefins or dienes, such as polybutenes, polydienes, in particular polybutadienes, polyisoprenes (also known as "LIR") or copolymers of butadiene and isoprene, or copolymers of butadiene or isoprene and styrene or mixtures of these liquid polymers. The number-average molar mass of such liquid polymers is preferably in a range from 500 g / mol to 50,000 g / mol, preferably from 1,000 g / mol to 10,000 g / mol. Examples include the "RICON" products from SARTOMER.

[0083] When the liquid plasticizer at 23°C is a vegetable oil, it may be, for example, an oil chosen from the group comprising or consisting of linseed, safflower, soybean, corn, cottonseed, rapeseed, castor, tung, pine, sunflower, palm, olive, coconut, peanut, grape seed oils and mixtures of these oils. The vegetable oil is preferably rich in oleic acid, that is to say that the fatty acid (or all the fatty acids if several are present) from which it is derived, comprises oleic acid in a mass fraction at least equal to 60%, even more preferably in a mass fraction at least equal to 70%.As vegetable oil, a sunflower oil is advantageously used which is such that all of the fatty acids from which it is derived comprise oleic acid in a mass fraction equal to or greater than 60%, preferably 70% and, according to a particularly advantageous embodiment of the invention, in a mass fraction equal to or greater than 80%.

[0084] According to another particular embodiment of the invention, the liquid plasticizer is a triester chosen from the group consisting of triesters of carboxylic acid, phosphoric acid, sulfonic acid and mixtures of these triesters.

[0085] Examples of phosphate plasticizers include those containing between 12 and 30 carbon atoms, for example trioctyl phosphate. Examples of carboxylic acid ester plasticizers include compounds selected from the group consisting of trimellitates, pyromellitates, phthalates, 1,2-cyclohexane dicarboxylates, adipates, azelates, sebacates, glycerol triesters and mixtures of these compounds. Among the above triesters, examples of glycerol triesters may be mentioned, preferably consisting predominantly (more than 50%, more preferably more than 80% by weight) of an unsaturated C 18 fatty acid, i.e. selected from the group consisting of oleic acid, linoleic acid, linolenic acid and mixtures of these acids. Glycerol triester is preferred.More preferably, whether of synthetic or natural origin (for example, sunflower or rapeseed vegetable oils), the fatty acid used consists of more than 50% by weight, and even more preferably more than 80% by weight, of oleic acid. Such triesters (trioleates) with a high oleic acid content are well known; they have been described, for example, in application WO 02 / 088238, as plasticizing agents in tire treads.

[0086] When the liquid plasticizer at 23°C is an ether plasticizer, it can be, for example, polyethylene glycol or polypropylene glycol.

[0087] Preferably, the liquid plasticizer at 23°C is chosen from the group comprising or consisting of MES oils, TDAE oils, naphthenic oils, vegetable oils and mixtures of these liquid plasticizers at 23°C. More preferably, the liquid plasticizer at 23°C is a vegetable oil, preferably a sunflower oil.

[0088] Advantageously also, the composition of the first layer of the laminate according to the invention does not comprise liquid polymer.

[0089] Advantageously, the level of liquid plasticizer at 23°C, in the composition of the first layer of the laminate according to the invention, is within a range from 1 to 49 phr, preferably from 5 to 40 phr. Those skilled in the art understand that when the level of liquid plasticizer at 23°C is lower than the minimum level of the plasticizing system comprising at least one liquid plasticizer at 23°C and / or at least one plasticizing resin having a glass transition temperature above 20°C, the composition comprises at least the balance of the plasticizing resin having a glass transition temperature above 20°C. When the composition of the first layer of the laminate according to the invention does not comprise a resin having a glass transition temperature above 20°C, the level of liquid plasticizer at 23°C in the composition is advantageously within a range from 20 to 49 phr, preferably from 30 to 49 phr. II-2.3 Reinforcing charge

[0090] The composition of the first layer of the laminate according to the invention may further comprise a reinforcing filler. Such a reinforcing filler typically consists of nanoparticles whose average size (by 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.

[0091] The reinforcing filler may comprise carbon black, silica or a mixture thereof. The composition of the first layer of the laminate according to the invention may consist mainly of silica. Alternatively, it may consist mainly, preferably exclusively, of carbon black.

[0092] The level of reinforcing filler is adjusted by a person skilled in the art depending on the use of the rubber composition. Advantageously, the level of reinforcing filler, in the composition of the first layer of the laminate according to the invention, is within a range from 30 to 200 phr, preferably from 40 to 190 phr, preferably from 50 to 180 phr.

[0093] Suitable carbon blacks are all carbon blacks, including those conventionally used in tires or their treads. Among the latter, we will particularly mention the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series (ASTM D-1765-2017 grades), such as for example 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. Carbon blacks could, for example, already be incorporated into the diene elastomer, in particular isoprene, in the form of a masterbatch (see, for example, applications WO97 / 36724-A2 or WO99 / 16600-A1).

[0094] Any type of precipitated silica is suitable as silica, in particular highly dispersible precipitated silicas (known as "HDS" for "highly dispersible" or "highly dispersible silica"). These precipitated silicas, whether highly dispersible or not, are well known to those skilled in the art. Examples include the silicas described in applications WO03 / 016215-A1 and WO03 / 016387-A1. Among the commercial HDS silicas, we can notably use the silicas “Ultrasil ®< 5000GR”, “Ultrasil ®< 7000GR” from the company Evonik, the silicas “Zeosil ®< 1085GR”, “Zeosil ®< 1115 MP”, “Zeosil ®< 1165MP”, “Zeosil ®< Premium 200MP”, “Zeosil ®< HRS 1200 MP” from the company Solvay.As non-HDS silica, the following commercial silicas can be used: silicas “Ultrasil ®< VN2GR”, “Ultrasil ®< VN3GR” from Evonik, silica “Zeosil ®< 175GR” from Solvay, silicas “Hi-Sil EZ120G(-D)”, “Hi-Sil EZ160G(-D)”, “Hi-Sil EZ200G(-D)”, “Hi-Sil 243LD”, “Hi-Sil 210”, “Hi-Sil HDP 320G” from PPG.

[0095] To couple the silica to the diene elastomer, it is possible to use, in a well-known manner, an at least bifunctional coupling agent (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. In particular, at least bifunctional organosilanes or polyorganosiloxanes are used. By "bifunctional", we mean a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the diene elastomer. For example, such a bifunctional compound may comprise a first functional group comprising a silicon atom, said first functional group being capable of interacting with the hydroxyl groups of an inorganic filler and a second functional group comprising a sulfur atom, said second functional group being capable of interacting with the diene elastomer.

[0096] Preferably, the organosilanes are chosen from the group consisting of polysulfurized organosilanes (symmetrical or asymmetrical) such as bis(3-triethoxysilylpropyl) tetrasulfide, abbreviated to TESPT, marketed under the name “Si69” by the company Evonik or bis-(triethoxysilylpropyl) disulfide, abbreviated to TESPD, marketed under the name “Si75” by the company Evonik, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, such as S-(3-(triethoxysilyl)propyl) octanethioate marketed by the company Momentive under the name “NXT Silane”. More preferably, the organosilane is a polysulfurized organosilane.

[0097] When silica is used, the coupling agent content in the composition of the first layer of the laminate of the invention can easily be adjusted by those skilled in the art. Typically the coupling agent content represents from 0.5% to 15% by weight relative to the amount of silica. II-2.4 Crosslinking system

[0098] The crosslinking system may be any type of system known to those skilled in the art in the field of tire rubber compositions. It may in particular be based on sulfur, and / or peroxide and / or bismaleimides.

[0099] Preferably, the crosslinking system is sulfur-based, in which case it is referred to as a vulcanization system. The sulfur can be provided in any form, in particular in the form of molecular sulfur, or a sulfur-donating agent. At least one vulcanization accelerator is also preferably present, and, optionally, also preferably, various known vulcanization activators can be used, such as zinc oxide, stearic acid or equivalent compounds such as stearic acid salts and transition metal salts, guanidine derivatives (in particular diphenylguanidine), or even known vulcanization retarders.

[0100] Sulphur is used at a preferential rate of between 0.3 pce and 10 pce, more preferably between 0.3 and 5 pce. The primary vulcanisation accelerator is used at a preferential rate of between 0.5 and 10 pce, more preferably between 0.5 and 5 pce.

[0101] Any compound capable of acting as an accelerator for the vulcanization of diene elastomers in the presence of sulfur may be used as an accelerator, in particular accelerators of the thiazole type and their derivatives, accelerators of the sulfenamide, thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthate types. Examples of such accelerators include, but are not limited to, the following compounds: 2-mercaptobenzothiazyl disulfide (abbreviated as "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide ("CBS"), N,N-dicyclohexyl-2-benzothiazyl sulfenamide ("DCBS"), N-tert-butyl-2-benzothiazyl sulfenamide ("TBBS"), N-tert-butyl-2-benzothiazyl sulfenimide ("TBSI"), tetrabenzylthiuram disulfide ("TBZTD"), zinc dibenzyldithiocarbamate ("ZBEC") and mixtures of these compounds. II-2.5 Possible additives

[0102] The composition of the first layer of the laminate useful for the purposes of the invention may also comprise all or part of the usual additives usually used in elastomer compositions intended to be used in a tire, such as for example processing agents, pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, antioxidants. II-3 Composition of the second layer of the laminate II-3.1 Elastomeric matrix

[0103] According to the invention, the second layer consists of a rubber composition based on a diene elastomer having a mass content of diene units greater than 50% and a crosslinking system.

[0104] Advantageously, the diene elastomer having a mass content of diene units greater than 50% of the composition of the second layer is chosen from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene copolymers, isoprene copolymers, and mixtures of these elastomers.

[0105] Preferably, the diene elastomer having a mass content of diene units greater than 50% of the composition of the second layer is chosen from the group consisting of isoprene elastomers.

[0106] Advantageously, the isoprene elastomer is a polyisoprene comprising a mass content of 1,4-cis bonds of at least 90%, preferably at least 98%, of the mass of the polyisoprene.

[0107] Preferably, the polyisoprene is selected from the group consisting of natural rubber, synthetic polyisoprenes and their mixtures. More preferably, the polyisoprene is a natural rubber.

[0108] Particularly advantageously, the diene elastomer having a mass content of diene units greater than 50% of the first layer and the diene elastomer having a mass content of diene units greater than 50% of the second layer are polyisoprenes, which may be identical or different. Preferably, the diene elastomer having a mass content of diene units greater than 50% of the first layer and the diene elastomer having a mass content of diene units greater than 50% of the second layer are polyisoprenes comprising a mass content of 1,4-cis bonds of at least 90%, preferably at least 98%, of the mass of the polyisoprene.

[0109] Advantageously, the elastomer matrix of the composition of the second layer of the laminate according to the invention comprises mainly the diene elastomer having a mass content of diene unit greater than 50%. The content of the diene elastomer having a mass content of diene unit greater than 50% in the composition of the second layer of the laminate according to the invention is advantageously within a range from 60 to 100 phr, preferably from 80 to 100 phr, more preferably from 90 to 100 phr. In a particularly advantageous manner, the content of the diene elastomer having a mass content of diene unit greater than 50% in the composition of the second layer of the laminate according to the invention is 100 phr. II-3.2 Reinforcing charge

[0110] The composition of the second layer of the laminate according to the invention may further comprise a reinforcing filler. The reinforcing filler of the second layer may comprise carbon black, silica or a mixture thereof. Advantageously, the composition of the second layer of the laminate according to the invention consists mainly, preferably exclusively, of carbon black. The composition of the second layer of the laminate according to the invention could alternatively consist mainly of silica.

[0111] The level of reinforcing filler is adjusted by a person skilled in the art depending on the use of the rubber composition. Advantageously, the level of reinforcing filler, in the composition of the second layer of the laminate according to the invention, is within a range from 20 to 80 phr, preferably from 25 to 70 phr, preferably from 30 to 60 phr.

[0112] The nature of the reinforcing filler may be as described previously for the composition of the first layer of the laminate, without the reinforcing filler of the first layer and that of the second layer necessarily being identical.

[0113] When silica is used in the second layer of the laminate according to the invention, the content of coupling agent in the composition of the second layer of the laminate of the invention can easily be adjusted by a person skilled in the art. Typically the level of coupling agent represents from 0.5% to 15% by weight relative to the quantity of silica. II-3.3 Crosslinking system

[0114] The crosslinking system may be any type of system known to those skilled in the art in the field of tire rubber compositions. It may in particular be based on sulfur, and / or peroxide and / or bismaleimides.

[0115] Preferably, the crosslinking system is sulfur-based, in which case it is referred to as a vulcanization system. The sulfur can be provided in any form, in particular in the form of molecular sulfur, or a sulfur-donating agent. At least one vulcanization accelerator is also preferably present, and, optionally, also preferably, various known vulcanization activators can be used, such as zinc oxide, stearic acid or equivalent compounds such as stearic acid salts and transition metal salts, guanidine derivatives (in particular diphenylguanidine), or even known vulcanization retarders.

[0116] Sulphur is used at a preferential rate of between 0.3 pce and 10 pce, more preferably between 0.3 and 5 pce. The primary vulcanisation accelerator is used at a preferential rate of between 0.5 and 10 pce, more preferably between 0.5 and 5 pce.

[0117] Any compound capable of acting as an accelerator for the vulcanization of diene elastomers in the presence of sulfur, those described previously for the composition of the first layer of the laminate, may be used as an accelerator, without these accelerators necessarily being identical. II-3.4 Possible additives

[0118] The composition of the second layer of the laminate useful for the purposes of the invention may also comprise all or part of the usual additives usually used in elastomer compositions intended to be used in a tire, such as for example processing agents, plasticizers, pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, antioxidants. II-4 Preparation of rubber compositions

[0119] The compositions usable in the laminate according to the invention can be manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art: a first phase of working or thermomechanical mixing (so-called "non-productive" phase), which can be carried out in a single thermomechanical step during which all the necessary constituents are introduced into a suitable mixer such as a conventional internal mixer (for example of the "Banbury" type), in particular the elastomer matrix, the reinforcing filler, any other various additives, with the exception of the crosslinking system. The incorporation of the possible filler into the elastomer can be carried out in one or more stages by thermomechanical mixing.In the case where the filler is already incorporated in whole or in part into the elastomer in the form of a masterbatch as described for example in applications WO 97 / 36724 or WO 99 / 16600, it is the masterbatch which is directly mixed and where appropriate the other elastomers or fillers present in the composition which are not in the form of a masterbatch are incorporated, as well as any various additives other than the crosslinking system. The non-productive phase can be carried out at high temperature, up to a maximum temperature of between 110°C and 200°C, preferably between 130°C and 185°C, for a duration generally of between 2 and 10 minutes.a second phase of mechanical work (so-called "productive" phase), which is carried out in an external mixer such as a roller mixer, after cooling the mixture obtained during the first non-productive phase to a lower temperature, typically below 120°C, for example between 40°C and 100°C. The crosslinking system is then incorporated, and everything is then mixed for a few minutes, for example between 5 and 15 min.

[0120] Such phases have been described for example in applications EP-A-0501227, EP-A-0735088, EP-A-0810258, WO00 / 05300 or WO00 / 05301.

[0121] The final composition thus obtained is then calendered, for example, in the form of a sheet or plate, in particular for laboratory characterization, or extruded (or co-extruded with another rubber composition) in the form of a semi-finished (or profiled) rubber. The first and second layers can be produced separately, then placed one on top of the other during the manufacture of the tire, according to techniques known to those skilled in the art.

[0122] The laminate compositions can be either in the raw state (before crosslinking or vulcanization) or in the cured state (after crosslinking or vulcanization). The laminate can be a semi-finished product that can be used in a tire.

[0123] Crosslinking (or curing), where appropriate vulcanization, is carried out in a known manner at a temperature generally between 130°C and 200°C, for a sufficient time which may vary, for example, between 5 and 90 min depending in particular on the curing temperature, the crosslinking system adopted and the crosslinking kinetics of the composition considered. II-5 Rubber article

[0124] The present invention also relates to a rubber article comprising at least one laminate according to the invention. The rubber article may be chosen from the group consisting of pneumatic tires, non-pneumatic tires, tracks, conveyor belts and anti-vibration articles. Preferably, the rubber article is chosen from the group consisting of pneumatic tires, non-pneumatic tires and conveyor belts. More preferably, the rubber article is a pneumatic or non-pneumatic tire.

[0125] More particularly, the invention also relates to a pneumatic or non-pneumatic tire provided with a tread comprising the composition of the first layer of the laminate according to the invention. Preferably, the first layer of the laminate constitutes part or all of the tread of the tire and the second layer of the laminate constitutes part or all of a sub-layer for the tread.

[0126] The invention also relates to a pneumatic tire in which the first layer of the laminate constitutes part or all of at least one sidewall of the tire and the second layer of the laminate constitutes part or all of a carcass ply.

[0127] The tire according to the invention can be intended to equip any type of vehicle, in particular motor vehicles, without any particular limitation. III- PREFERRED EMBODIMENTS

[0128] In view of the above, preferred embodiments of the invention are described below: 1. Elastomeric laminate comprising at least two adjacent layers: the first layer consisting of a rubber composition based on: ∘ 20 to 100 phr of at least one copolymer comprising ethylene units and units of a 1,3-diene of formula (I), the ethylene units in the copolymer representing more than 50% by mole of the monomer units of the copolymer, CH 2 =CR-CH=CH 2 (I) the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms; ∘ 0 to 80 phr of at least one diene elastomer having a mass content of diene units greater than 50%; ∘ 10 to 100 phr of a plasticizing system comprising at least one plasticizing resin having a glass transition temperature greater than 20°C and / or at least one plasticizer liquid at 23°C; ∘ a reinforcing filler; and ∘ a crosslinking system,the second layer being made up of a rubber composition based on a diene elastomer having a mass content of diene units greater than 50% and a crosslinking system. 2. Laminate according to embodiment 1, in which the copolymer of the first layer contains ethylene units which represent between 50% and 95%, preferably from 60% to 90%, preferably from 70% to 85%, by mole of the monomer units of the copolymer. 3. Laminate according to any one of the preceding embodiments, in which the symbol R of the copolymer of the first layer represents a hydrocarbon chain having 6 to 16 carbon atoms. 4. Laminate according to any one of the preceding embodiments, in which the symbol R of the copolymer of the first layer represents an aliphatic chain. 5. Laminate according to any one of the preceding embodiments,wherein the symbol R of the copolymer of the first layer represents an acyclic chain. 6. Laminate according to any one of the preceding embodiments, wherein the symbol R of the copolymer of the first layer represents a linear or branched chain. 7. Laminate according to any one of the preceding embodiments, wherein the 1,3-diene of formula (I) of the copolymer of the first layer is myrcene, β-farnesene or a mixture of myrcene and β-farnesene. 8. Laminate according to any one of the preceding embodiments, wherein the copolymer of the first layer contains units of the 1,3-diene of formula (I) which represent between 1% and 50%, preferably between 1% and 30%, preferably between 5% and 30%, by mole of the monomer units of the copolymer. 9. Laminate according to any one of the preceding embodiments, in which the copolymer is a copolymer further comprising a second 1,3-diene chosen from 1,3-butadiene,isoprene or a mixture thereof. 10. Laminate according to embodiment 9, wherein the second 1,3-diene of the copolymer is 1,3-butadiene. 11. Laminate according to any one of embodiments 9 to 10, wherein the copolymer of the first layer contains units of the second 1,3-diene which represent between 1% and 49%, preferably between 4% and 29%, preferably between 4% and 25%, by mole of the monomer units of the copolymer. 12. Laminate according to any one of the preceding embodiments, wherein the copolymer is a random copolymer. 13. Laminate according to any one of the preceding embodiments, wherein the copolymer of the first layer has a glass transition temperature below -35°C, preferably between -90°C and -35°C, preferably between -70°C and -35°C. 14. Laminate according to any one of the preceding embodiments, in which the rate of the copolymer of ethylene and a 1,3-diene of formula (I) in the composition of the first layer is comprised in a range from more than 50 to 100 phr, preferably from 75 to 100 phr, more preferably from 90 to 100 phr. 15. Laminate according to embodiment 14, in which the diene elastomer having a mass content of diene unit greater than 50% is present in the composition of the first layer at a rate comprised in a range from 0 to less than 50 phr, preferably from 0 to 25 phr, more preferably from 0 to 10 phr. 16. Laminate according to any one of embodiments 1 to 13, in which the content of the copolymer of ethylene and a 1,3-diene of formula (I) in the composition of the first layer is within a range from 20 to 90 phr, preferably from 25 to 80 phr, more preferably from 30 to 80 phr. 17. Laminate according to embodiment 16,in which the diene elastomer having a mass content of diene units greater than 50% is present in the composition of the first layer at a rate within a range of from 10 to 80 phr, preferably from 20 to 75 phr, more preferably from 20 to 70 phr. 18. Laminate according to any one of the preceding embodiments, in which the composition of the first layer does not comprise any other elastomer than the copolymer of ethylene and a 1,3-diene of formula (I) and the diene elastomer having a mass content of diene units greater than 50%. 19. Laminate according to any one of the preceding embodiments, in which the diene elastomer having a mass content of diene units greater than 50% of the composition of the first layer is chosen from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene copolymers, isoprene copolymers,and mixtures of these elastomers. 20. Laminate according to any one of the preceding embodiments, in which the diene elastomer having a mass content of diene units greater than 50% of the composition of the first layer is a polyisoprene, preferably comprising a mass content of 1,4-cis bonds of at least 90%, preferably at least 98%, of the mass of the polyisoprene. 21. Laminate according to embodiment 20, in which the polyisoprene of the composition of the first layer is chosen from the group consisting of natural rubber, synthetic polyisoprenes or mixtures thereof. 22. Laminate according to any one of the preceding embodiments, in which the rate of the plasticizing system comprising at least one liquid plasticizer at 23°C and / or at least one plasticizing resin having a glass transition temperature above 20°C, in the composition of the first layer, is within a range from 35 to 100 pce,preferably from 50 to 95 phr, more preferably from 55 to 90 phr. 23. Laminate according to any one of the preceding embodiments, in which the plasticizing system comprises a plasticizer which is liquid at 23°C and a plasticizing resin having a glass transition temperature above 20°C. 24. Laminate according to any one of the preceding embodiments, in which the plasticizer which is liquid at 23°C of the composition of the first layer is selected from the group consisting of liquid diene polymers, polyolefin oils, naphthenic oils, paraffinic oils, DAE oils, MES oils, TDAE oils, RAE oils, TRAE oils, SRAE oils, mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulfonate plasticizers and mixtures thereof. 25. Laminate according to any one of the preceding embodiments, in which the level of liquid plasticizer at 23°C,in the composition of the first layer, is comprised in a range from 1 to 49 pce, preferably from 5 to 40 pce. 26. Laminate according to any one of the preceding embodiments, in which the plasticizing resin having a glass transition temperature greater than 20°C of the composition of the first layer is chosen from the group consisting of cyclopentadiene homopolymer or copolymer resins, dicyclopentadiene homopolymer or copolymer resins, terpene homopolymer or copolymer resins, C 5 cut homopolymer or copolymer resins, C 9 cut homopolymer or copolymer resins, alpha-methyl-styrene homopolymer or copolymer resins and mixtures thereof. 27. Laminate according to any one of the preceding embodiments, in which the level of plasticizing resin having a glass transition temperature greater than 20°C, in the composition of the first layer,is comprised in a range from 1 to 99 phr, preferably from 5 to 95 phr. 28. Laminate according to any one of the preceding embodiments, in which the reinforcing filler of the composition of the first layer comprises carbon black, silica or a mixture thereof. 29. Laminate according to any one of the preceding embodiments, in which the level of reinforcing filler in the composition of the first layer is comprised in a range from 30 to 200 phr, preferably from 40 to 190 phr, preferably from 50 to 180 phr. 30. Laminate according to any one of the preceding embodiments, in which the crosslinking system of the first layer is a vulcanization system comprising molecular sulfur and / or at least one sulfur donor agent. 31. Laminate according to any one of the preceding embodiments,wherein the diene elastomer having a mass content of diene units greater than 50% of the composition of the second layer is chosen from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene copolymers, isoprene copolymers, and mixtures of these elastomers. 32. Laminate according to any one of the preceding embodiments, wherein the diene elastomer having a mass content of diene units greater than 50% of the composition of the second layer is a polyisoprene, preferably comprising a mass content of 1,4-cis bonds of at least 90%, preferably at least 98%, of the mass of the polyisoprene. 33. Laminate according to embodiment 32, wherein the polyisoprene of the composition of the second layer is selected from the group consisting of natural rubber, synthetic polyisoprenes or mixtures thereof. 34. Laminate according to any one of the preceding embodiments,wherein the diene elastomer having a mass content of diene units greater than 50% of the first layer and the diene elastomer having a mass content of diene units greater than 50% of the second layer are polyisoprenes. 35. Laminate according to any one of the preceding embodiments, wherein the diene elastomer having a mass content of diene units greater than 50% of the first layer and the diene elastomer having a mass content of diene units greater than 50% of the second layer are polyisoprenes comprising a mass content of 1,4-cis bonds of at least 90%, preferably at least 98%, of the mass of the polyisoprene. 36. Laminate according to any one of the preceding embodiments, in which the diene elastomer having a mass content of diene unit greater than 50% is present in the composition of the second layer at a rate within a range from 60 to 100 pce, preferably from 80 to 100 pce,preferably still from 90 to 100 pce. 37. Laminate according to any one of the preceding embodiments, in which the composition of the second layer comprises a reinforcing filler. 38. Laminate according to embodiment 37, in which the reinforcing filler of the composition of the second layer is predominantly, preferably exclusively, made of carbon black. 39. Laminate according to embodiment 37, in which the reinforcing filler of the composition of the second layer is predominantly made of silica. 40. Laminate according to any one of embodiments 37 to 39, in which the level of reinforcing filler in the composition of the second layer is within a range from 20 pce to 80 pce, preferably from 25 to 70 pce, preferably from 30 to 60 pce. 41. Laminate according to any one of the preceding embodiments,wherein the crosslinking system of the second layer is a vulcanization system comprising molecular sulfur and / or at least one sulfur donor agent. 42. Laminate according to any one of the preceding embodiments, wherein the first layer has a thickness in a range from 0.5 to 120 mm, preferably from 1 to 15 mm, or from 0.2 mm to 120 mm, preferably from 0.3 to 15 mm. 43. Laminate according to any one of embodiments 1 to 41, wherein the first layer has a thickness in a range from 0.2 to 10 mm, preferably from 0.3 to 5 mm. 44. Laminate according to any one of the preceding embodiments, wherein the second layer has a thickness in a range from 0.2 to 10 mm, preferably from 0.3 to 7 mm. 45. Rubber article comprising a laminate defined in any one of embodiments 1 to 43. 46. Rubber article according to embodiment 45,said article being selected from the group consisting of pneumatic tires, non-pneumatic tires, tracks, conveyor belts and anti-vibration articles, preferably from the group consisting of pneumatic tires, non-pneumatic tires and conveyor belts. 47. A pneumatic or non-pneumatic tire comprising a laminate defined in any one of embodiments 1 to 44, wherein the first layer of the laminate constitutes part or all of the tread of the tire and the second layer of the laminate constitutes part or all of a sub-layer to the tread. 48. A pneumatic tire comprising a laminate defined in any one of embodiments 1 to 44, wherein the first layer of the laminate constitutes part or all of at least one sidewall of the tire and the second layer of the laminate constitutes part or all of a carcass ply. IV- EXAMPLES IV-1 Measurements and tests used IV-1.1 Determination of the microstructure of elastomers : a) Determination of the microstructure of Ethylene-Butadiene copolymers (Elastomer E1):

[0129] The microstructure of ethylene and butadiene copolymers is determined by 1H NMR analysis, supplemented by 13C NMR analysis when the resolution of 1H NMR spectra does not allow the attribution and quantification of all species. Measurements are carried out using a BRUKER 500MHz NMR spectrometer at frequencies of 500.43 MHz for proton observation and 125.83MHz for carbon observation. For non-soluble elastomers but having the ability to swell in a solvent, a 4mm z-grad HRMAS probe is used to observe the proton and carbon in proton-decoupled mode. 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 carbon in proton-decoupled mode.The preparation of insoluble samples is done in rotors filled with the analyzed material and a deuterated solvent allowing swelling, generally deuterated chloroform (CDCl3). The solvent used must always be deuterated and its chemical nature can be adapted by the skilled person. The quantities of material used are adjusted to obtain spectra with sufficient sensitivity and resolution. Soluble samples are dissolved in a deuterated solvent (approximately 25mg of elastomer in 1mL), generally deuterated chloroform (CDCl3). The solvent or solvent blend used must always be deuterated and its chemical nature can be adapted by the skilled person. In both cases (soluble sample or swollen sample). For proton NMR, a single 30° pulse sequence is used. The spectral window is adjusted to observe all the resonance lines belonging to the analyzed molecules.The number of accumulations is adjusted to obtain a sufficient signal-to-noise ratio for the quantification of each pattern. The recycling 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 adjusted to observe all the resonance lines belonging to the analyzed molecules. The number of accumulations is adjusted to obtain a sufficient signal-to-noise ratio for the quantification of each pattern. The recycling time between each pulse is adapted to obtain a quantitative measurement. NMR measurements are carried out at 25°C. b) Determination of the microstructure of Ethylene-Myrcene copolymers (Elastomer E2):

[0130] Spectral characterization and microstructure measurements of Ethylene-Myrcene copolymers are performed by Nuclear Magnetic Resonance (NMR) spectroscopy. Spectrometer: For these measurements, a Bruker Avance III HD 400 MHz spectrometer is used, equipped with a Bruker cryo-BBFO z-grad 5 mm probe.

[0131] Experiments: 1H experiments are recorded using a radiofrequency pulse with a flip angle of 30°, the number of repetitions is 128 with a recycle delay of 5 seconds. 1H-13C HSQC (Heteronuclear Single Quantum Coherence) and HMBC (Heteronuclear Multiple-Bond Correlation) NMR correlation experiments are recorded with a number of repetitions of 128 and a number of increments of 128. The experiments are carried out at 25°C.

[0132] Sample preparation: 25 mg of sample is solubilized in 1 mL of deuterated chloroform (CDCl 3 ).

[0133] Sample calibration: The 1< H and 13< C chemical shift axes are calibrated relative to the protonated solvent impurity (CHCl 3 ) at δ 1H = 7.2 ppm (for the most deshielded signal) and δ 13C = 77 ppm (for the least deshielded signal).

[0134] Spectral assignment for ethylene and 1,3-myrcene copolymers: In representations A, B, C below, the symbols R1 and R2 represent the attachment points of the unit to the polymer chain. The signals of the insertion forms of 1,3-diene A, B and C were observed in the different recorded spectra. According to S. Georges et al., (Polymer 55 (2014) 3869-3878), the signal of the -CH= group n°8" characteristic of the C form has chemical shifts 1< H and 13< C identical to the - CH= group n°3. The chemical shifts of the characteristic signals of the A, B and C motifs are presented in Table 1. The A, B and C motifs correspond respectively to the 3,4-configuration, 1,2-configuration and 1,4-trans-configuration units. The quantifications were carried out from the integration of the 1D 1< H NMR spectra using the Topspin software. The integrated signals for the quantification of the different motifs are: Ethylene: signal at 1.2 ppm corresponding to 4 protons Total myrcene: signal n°1 (1.59 ppm) corresponding to 6 protons Form A: signal n°7 (4.67 ppm) corresponding to 2 protons Form B: signal n°8' (5.54 ppm) corresponding to 1 proton

[0135] The quantification of the microstructure is carried out in molar percentage (mol%) as follows: mol% of a motif = 1H integral of a motif * 100 / Σ (1H integrals of each motif). [Table 1] δ1H (ppm) δ13C (ppm) Group 5.54 146.4 8' 5.07 124.6 3 + 8" 4.97 - 4.79 112.0 9' 4.64 108.5 7 2.03 26.5 4 2.0 - 1.79 31.8 5 + 5' + 5'' 44.5 8 1.59 25.9 and 17.0 1 1.2 36.8 - 24.0 CH 2 ethylene c) Determination of the microstructure of Ethylene-Butadiene-Myrcene terpolymers (Elastomer E3):

[0136] Spectral characterization and microstructure measurements of Ethylene-Butadiene-Myrcene copolymer are performed by Nuclear Magnetic Resonance (NMR) spectroscopy.

[0137] For these measurements, a Bruker Avance III HD 400 MHz spectrometer is used, equipped with a Bruker cryo-BBFO z-grad 5 mm probe. 1H experiments are recorded using a radiofrequency pulse with a flip angle of 30°, the number of repetitions is 128 with a recycle delay of 5 seconds. 1H-13C HSQC (Heteronuclear Single Quantum Coherence) and HMBC (Heteronuclear Multiple-Bond Correlation) correlation NMR experiments are recorded with a number of repetitions of 128 and a number of increments of 128. The experiments are carried out at 25 °C. 25 mg of sample is solubilized in 1 mL of deuterated orthodichlorobenzene (ODCB). The 1H and 13C chemical shift axes are calibrated relative to the protonated solvent impurity at δ1H = 7.2 ppm (for the most deshielded signal) and δ13C = 127 ppm (for the least deshielded signal).

[0138] Possible monomeric units in the terpolymer are -CH 2 -CH(CH=CH 2 )-, -CH 2 -CH=CH-CH 2 -, -CH 2 -CH 2 -, the 1,2-cyclohexanediyl unit and the following structures, with R 1 and R 2 representing the polymer chain:

[0139] The 1,2-cyclohexanediyl unit has the following structure:

[0140] The signals of the insertion forms of myrcene A were observed on the different recorded spectra. According to S. Georges et al. (S.Georges, M.Bria, P. Zinck and M. Visseaux. Polymer 55 (2014) 3869-3878), the signal of the -CH= group n°8" characteristic of the C form presents chemical shifts 1< H and 13< C identical to the -CH= group n°3.

[0141] The chemical shifts of the characteristic signals of the polymer are presented in Table 2 (Assignment of the 1< H and 13< C signals of the Ethylene-Butadiene-Myrcene terpolymers other than those of the 1,3-butadiene units). [Table 2] δ1H (ppm) δ13C (ppm) Group 5.19 125.1 3 + 8" 4.86 109.0 7 1.59 and 1.68 247 and 17.6 1 1.3 37.5 - 24.0 CH2 ethylene

[0142] Quantifications were performed from the integration of 1D 1< H NMR spectra using Topspin software.

[0143] The integrated signals for quantification of the different patterns are: Ethylene: Total signals between 0.5 ppm and 3.0 ppm by subtracting the aliphatic contributions of the other units of the terpolymer. The calculation corresponds to 4 protons of the Ethylene unit. Form A: signal n°7 (4.86 ppm) corresponding to 2 protons. The proportion of form C is not directly accessible but can be calculated from signal n°3+8" by subtracting the contribution of form A. PB1-4: Signal between 5.71 ppm and 5.32 ppm corresponds to 2 protons (by removing the contribution of PB1-2). PB1-2: signal between 5.11 ppm and 4.92 ppm corresponds to 2 protons. Cyclohexane rings: signal between 1.80 ppm and 1.70 ppm corresponds to 2 protons.

[0144] Microstructure quantification is performed in molar percentage (mol%) as follows: % molaire d ′ un motif = intégrale H <mprescripts / > <none / > 1 d ′ un motif * 100 / ∑ intégrale H <mprescripts / > <none / > 1 de chaque motif . d) Determination of the microstructure of ethylene-butadiene-farnesene terpolymers (Elastomers E4 and E5):

[0145] Spectral characterization and microstructure measurements of Ethylene-butadiene-farnesene copolymer are performed by Nuclear Magnetic Resonance (NMR) spectroscopy. For these measurements, a Bruker Avance III HD 400 MHz spectrometer is used, equipped with a Bruker cryo-BBFO z-grad 5 mm probe. 1H experiments are recorded using a radiofrequency pulse with a flip angle of 30°, the number of repetitions is 128 with a recycle delay of 5 seconds. 1H-13C HSQC (Heteronuclear Single Quantum Coherence) and HMBC (Heteronuclear Multiple-Bond Correlation) NMR experiments are recorded with a number of repetitions of 128 and a number of increments of 128. The experiments are performed at 25 °C. 25 mg of sample are solubilized in 1 mL of deuterated orthodichlorobenzene (ODCB).The chemical shift axes 1< H and 13< C are calibrated relative to the protonated solvent impurity at δ 1H = 7.2 ppm (for the most deshielded signal) and δ 13C = 127 ppm (for the least deshielded signal).

[0146] The possible monomeric units in the terpolymer are -CH 2 -CH(CH=CH 2 )-, -CH 2 -CH=CH-CH 2 -, -CH 2 -CH 2 -, the 1,2-cyclohexanediyl unit and the following structures, and R 2 representing the polymer chain:

[0147] The signals of the insertion form of farnesene A were observed on the different recorded spectra. The signal of the -CH= group n°11" characteristic of the C form shows chemical shifts 1< H and 13< C identical to the -CH= groups n°3 and n°7.

[0148] The chemical shifts of the characteristic signals of the polymer are presented in Table 3 (Assignment of the 1< H and 13< C signals of the Ethylene-Butadiene-Farnesene terpolymers other than those of the 1,3-butadiene units). [Table 3] δ1H (ppm) δ13C (ppm) Group 5.25 125.0 7 5.15 125.0 3, 11" 4.87 109.0 14 1.59 and 1.67 24.6 and 17.5 1, 13 1.28 38 - 24.0 CH2 ethylene

[0149] Quantifications were performed from the integration of 1D 1< H NMR spectra using Topspin software.

[0150] The integrated signals for quantification of the different patterns are: Farnesene motif form A from signal n°14 CH 2 = for 2 protons, Farnesene motif form C from the signals No. 3, 11" and No. 7 CH= (subtracting the contribution of form A), for 2 protons, Farnesene motif form B: from the signal n°11', specific to this form, for 1 proton. PB1-4: Signal between 5.71 ppm and 5.32 ppm corresponds to 2 protons (removing the PB1-2 contribution). PB1-2: signal between 5.11 ppm and 4.92 ppm corresponds to 2 protons. Cyclohexane rings: signal between 1.80 ppm and 1.70 ppm corresponds to 2 protons. Ethylene unit by integrating all aliphatic signals (from ~ 0.5 to 3 ppm) and subtracting the contribution of all other aliphatic units (PB1-4, PB1-2, EBR ring, farnesene forms A and C).

[0151] Microstructure quantification is performed in molar percentage (mol%) as follows: % molaire d'un motif = intégrale 1 H d'un motif * 100 / ∑ intégrales 1 H de chaque motif IV-1.2 Determination of the glass transition temperature of polymers:

[0152] The glass transition temperature is measured using a differential scanning calorimeter according to ASTM D3418 (1999). IV-1.3 Determination of the macrostructure of polymers by size exclusion chromatography (SEC) : a) Principle of measurement:

[0153] Size exclusion chromatography (SEC) separates macromolecules in solution according to their size using columns filled with a porous gel. Macromolecules are separated according to their hydrodynamic volume, with the largest being eluted first.

[0154] Combined with 3 detectors (3D), a refractometer, a viscometer and a 90° light scattering detector, SEC allows the absolute molar mass distribution of a polymer to be understood. The various number-average (Mn), weight-average (Mw) absolute molar masses and the dispersity (D = Mw / Mn) can also be calculated. b) Preparation of the polymer:

[0155] Each sample is solubilized in tetrahydrofuran at a concentration of approximately 1 g / L. The solution is then filtered through a 0.45µm porosity filter before injection. c) 3D SEC analysis:

[0156] To determine the number-average molar mass (Mn), and where appropriate the weight-average molar mass (Mw) and the polydispersity index (Ip) of polymers, the method below is used.

[0157] The number-average molar mass (Mn), weight-average molar mass (Mw) and polydispersity index of the polymer (hereinafter referred to as sample) are determined absolutely by triple detection size exclusion chromatography (SEC). Triple detection size exclusion chromatography has the advantage of measuring average molar masses directly without calibration.

[0158] The refractive index increment dn / dc value of the sample solution is measured online using the peak area detected by the refractometer (RI) of the liquid chromatography equipment. To apply this method, it must be ensured that 100% of the sample mass is injected and eluted through the column. The RI peak area depends on the sample concentration, the RI detector constant and the dn / dc value.

[0159] To determine the average molar masses, the previously prepared and filtered 1g / l solution is used and injected into the chromatographic system. The equipment used is a "WATERS alliance" chromatographic chain. The elution solvent is tetrahydrofuran containing 250 ppm of BHT (2,6-diter-butyl 4-hydroxy toluene), the flow rate is 1 mL.min -1< , the system temperature is 35° C and the analysis time is 60 min. The columns used are a set of three AGILENT columns with the trade name "PL GEL MIXED B LS". The injected volume of the sample solution is 100 µL. The detection system is composed of a Wyatt differential viscometer with the trade name “VISCOSTAR II”, a Wyatt differential refractometer with the trade name “OPTILAB T-REX” with a wavelength of 658 nm, a Wyatt multi-angle static light scattering detector with a wavelength of 658 nm and the trade name “DAWN HELEOS 8+”.

[0160] For the calculation of the number-average molar masses and the polydispersity index, the value of the refractive index increment dn / dc of the sample solution obtained above is integrated. The software for processing the chromatographic data is the “ASTRA de Wyatt” system. IV-2 Synthesis of polymers:

[0161] In polymer synthesis, all reagents are obtained commercially except for metallocenes. BOMAG butylloctylmagnesium (20% in heptane, C = 0.88 mol.L -1< ) ​​is obtained from Chemtura and is stored in a Schlenk tube under an inert atmosphere. Ethylene, grade N35, is obtained from Air Liquide and is used without prior purification. Myrcene (purity ≥ 95%) and farnesene (purity ≥ 95%) are obtained from Sigma-Aldrich.

[0162] The following polymers are synthesized according to the procedure described below: copolymer of ethylene and 1,3-butadiene: elastomer E1 (not in accordance with the invention) copolymer of ethylene and myrcene: elastomer E2 (in accordance with the invention) copolymer of ethylene, butadiene and farnesene: elastomer E3 (in accordance with the invention) copolymers of ethylene, butadiene and myrcene: elastomers E4 and E5 (in accordance with the invention)

[0163] In a reactor containing methylcyclohexane at 80°C, as well as ethylene (Et) and butadiene (Bd) and / or myrcene (Myr) and / or farnesene (Far) in the proportions indicated in Table 4, butyloctylmagnesium (BOMAG) is added to neutralize the impurities in the reactor, then the catalytic system (see Table 4). At this point, the reaction temperature is regulated at 80°C and the polymerization reaction starts. The polymerization reaction proceeds at a constant pressure of 8 bar. The reactor is supplied throughout the polymerization with ethylene and butadiene (Bd) and / or myrcene (Myr) and / or farnesene (Far) in the proportions defined in Table 4. The polymerization reaction is stopped by cooling, degassing the reactor and adding ethanol. An antioxidant is added to the polymer solution. The copolymer is recovered by drying in a vacuum oven to constant mass. The catalytic system is a preformed catalytic system.It is prepared in methylcyclohexane from a metallocene, [Me 2 SiFlu 2 Nd(µ-BH 4 ) 2 Li(THF)], a co-catalyst, butyloctylmagnesium (BOMAG), and a preformation monomer, 1,3-butadiene, in the contents indicated in Table 4. It is prepared according to a preparation method in accordance with paragraph II.1 of patent application WO 2017 / 093654 A1.

[0164] The microstructure of elastomers E1 to E5 and their properties are shown in Tables 5 and 6. For the microstructure, Table 5 shows the molar ratios of ethylene units (Eth), 1,3-butadiene units, 1,2-cyclohexanediyl units (ring), β-farnesene units or myrcene units. Also shown is the molar ratio of β-farnesene or myrcene units according to whether they are of 1,4 configuration, 1,2 configuration or 3,4 configuration. [Table 4] Synthesis E1 E2 E3 E4 E5 Metallocene concentration (mmol / L) 0,07 0,09 0,09 0,09 0,09 Alkylating agent concentration (mmol / L) 0,36 0,17 0,25 0,2 0,33 Preformation monomer / Nd metal molar ratio 90 90 90 90 90 Diet composition (%mol Et / Bd) 80 / 20 - - - - Diet composition (%mol Et / Myr) - 60 / 40 - - - Feed composition (%mol Eth / Btd / Far) - - 81 / 9 / 10 - - Feed composition (%mol Eth / Btd / Myr) - - - 79 / 14 / 7 70 / 20 / 10 [Table 5] Elastomer E1 E2 E3 E4 E5 And (%mol) 77 74 76 75 68 Bd (mol%) 15 - 8 13 19 1,2-cyclohexanediyl (mol%) 8 - 5 6 7 Far or Myr (%mol) - 26 11 6 6 Far or Myr 1.4 (%mol / %mol Far or Myr) - 31 36 33 33 Far or Myr 1.2 (%mol / %mol Far or Myr) - 4 <1 <1 <1 Far or Myr 3.4 (%mol / %mol Far or Myr) - 65 64 67 67 [Table 6] Elastomer E1 E2 E3 E4 E5 Tg (°C) -40 -60 -61 -49 -49 Mn (g / mol) 128 888 367 400 200 800 298 000 179 500 IV-3 Preparation of compositions of rubber :

[0165] In the following examples, the rubber compositions were produced as described in point II-4 above. In particular, the “non-productive” phase was carried out in a 3-liter mixer for 5 minutes, for an average paddle speed of 50 revolutions per minute until a maximum drop temperature of 160°C was reached. The “productive” phase was carried out in a cylinder tool at 23°C for 10 minutes. IV-4 Rubber tests:

[0166] The adhesion of several rubber compositions comprising a copolymer containing ethylene and 1,3-diene units to a natural rubber-based composition was compared depending on the nature of the copolymer and the level of plasticizer in the composition.

[0167] The natural rubber-based layer on which the adhesion of compositions T1 to T6 (not in accordance with the invention) and compositions C1 to C4 (in accordance with the invention) was tested corresponds to a composition conventionally used as an internal layer of a tire, such as a carcass ply or a tread sub-layer. The composition (T0) of this natural rubber-based layer is presented in Table 7 below.

[0168] The adhesion of compositions T1 to T6 and C1 to C4 to composition T0 was compared. Control compositions T1 and T6 are not in accordance with the invention because elastomer E1 comprising more than 50 mol% of ethylene unit does not comprise a 1,3-diene unit of formula (I). Control compositions T1 to T5 are not in accordance with the invention because they do not comprise a plasticizing system in accordance with the invention. Compositions T6, C1, C2, C3 and C4 differ respectively from compositions T1, T2, T3, T4 and T5 only by the presence of a plasticizing system in accordance with the invention.It may be noted that the silica content has been adjusted in order to maintain the volume fraction of filler constant, the volume fraction of filler in a rubber composition being defined as the ratio of the volume of the filler to the volume of all the constituents of the composition, it being understood that the volume of all the constituents is calculated by adding the volume of each of the constituents of the composition.

[0169] The adhesion measurements were carried out by a so-called T-peel test or also called 180° peel. The peel specimens were produced by bringing the two layers into contact (the constituent compositions of the layers being in the raw state) whose adhesion was to be tested. A fracture incipient was inserted between the two layers. Each of the layers was reinforced by a composite sheet which limits the deformation of said layers under tension. The assembled specimen was heated to 150°C under a pressure of 16 bars for 30 minutes. 30 mm wide strips were then cut with a guillotine. Both sides of the fracture incipient were then placed in the jaws of an “Instron” brand tensile testing machine. The tests were carried out at 20°C and at a tensile speed of 100 mm / min. The tensile forces were recorded and standardized by the width of the specimen.A force curve per unit width (in N / mm) was obtained as a function of the displacement of the moving crosshead of the tensile machine (between 0 and 200 mm). The adhesion value retained corresponds to the propagation of the fracture within the specimen and therefore to the average stabilized value of the curve. The adhesion values ​​of the examples were also normalized (base 100) compared to the control T1 for compositions T2 to T5 or compared to the control T6 for compositions C1 to C4. An index greater than 100 indicates a greater improvement in adhesion.

[0170] Table 7 shows the compositions tested (in pce), as well as the results obtained. [Table 7] Compositions T0 T1 T2 T3 T4 T5 T6 C1 C2 C3 C4 Natural rubber 100 - - - - - - - - - - Elastomer E1(1) - 100 - - - - 100 - - - - Elastomer E2(1) - - 100 - - - - 100 - - - Elastomer E3(1) - - - 100 - - - - 100 - - Elastomer E4(1) - - - - 100 - - - - 100 - Elastomer E5(1) - - - - - 100 - - - - 100 N330(2) 35 - - - - - - - - - - Silica(3) 10 48 48 48 48 48 80.5 80.5 80.5 80.5 80.5 Fraction of charge vol. NC 16% 16% 16% 16% 16% 16% 16% 16% 16% 16% Coupling agent(4) 1 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 Resin(5) 1 - - - - - - - - - - Resin(6) 0.5 - - - - - - - - - - Resin(7) - - - - - - 38 38 38 38 38 Oil(8) - - - - - - 38 38 38 38 38 DPG(9) - 1 1 1 1 1 1 1 1 1 1 Ozone wax (10) - 1 1 1 1 1 1 1 1 1 1 Antioxidant(11) 1 2 2 2 2 2 2 2 2 2 2 Stearic acid 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 ZnO(12) 4.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Accelerator(13) 1.5 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 Sulfur 1.7 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Adhesion (N / mm) - 10 8 4 5 3 14 16 25 25 25 Membership (base 100 / E1) - 100 80 40 50 30 100 115 180 180 180 (1) Elastomers E1 to E5 prepared according to the process described in point IV-2 above (2) Carbon black N330 according to standard ASTM D-1765-2017 (3) Silica “Zeosil 1165MP” marketed by Solvay (4) Liquid silane triethoxysilylpropyltetrasulfide (TESPT) “Si69” from the company Evonik (5) Gum Rosin (rosin GEM SPE1) from the company Diamanto Malho (6) Tackifying resin “Escorez 1102” from the company EXXON (Mn 1370 g / mol; Ip= 2.3) (7) Petroleum hydrocarbon resin “Escorez 5000 series” from the company Exxon Mobil (Tg = 52°C) (8) MES oil “Catenex SNR” marketed by the company Shell (9) Diphenylguanidine “ Perkacit DPG » from Flexsys (10) Anti-ozone wax « VARAZON 4959 » from Sasol Wax (11) N-1,3-dimethylbutyl-N-phenyl-para-phenyldiamine « Santoflex 6-PPD » from Flexsys (12) Industrial grade Zinc Oxide from Umicore (13) N-cyclohexyl-2-benzothiazol-sulfenamide « Santocure CBS » from Flexsys

[0171] These results show that the use of a rubber composition in accordance with the invention comprising the combination of a copolymer containing ethylene units and units of a 1,3-diene of formula (I) and a plasticizing system in accordance with the invention makes it possible to improve the adhesion to a diene composition, compared to a rubber composition comprising a copolymer containing ethylene and 1,3-diene units different from the 1,3-diene units of formula (I) and / or compared to a composition not comprising the plasticizing system in accordance with the invention. The improvement in adhesion is much greater for copolymers which are copolymers of ethylene, a 1,3-diene of formula (I) and a second 1,3-diene chosen from 1,3-butadiene, isoprene or their mixture in accordance with the invention.

Claims

1. Elastomer laminate comprising at least two adjacent layers: - the first layer consisting of a rubber composition based on: ∘ 20 to 100 phr of at least one copolymer comprising ethylene units and units of a 1,3-diene of formula (I), the ethylene units in the copolymer representing more than 50 mol% of the monomer units of the copolymer,         CH2=CR-CH=CH2     (I) the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms; ∘ 0 to 80 phr of at least one diene elastomer having a weight content of diene units of greater than 50%; ∘ 10 to 100 phr of a plasticizing system comprising at least one plasticizing resin having a glass transition temperature above 20°C and / or at least one plasticizer that is liquid at 23°C; ∘ a reinforcing filler; and ∘ a crosslinking system, - the second layer consisting of a rubber composition based on a diene elastomer having a weight content of diene units of greater than 50% and a crosslinking system.

2. Laminate according to Claim 1, wherein the 1,3-diene of formula (I) of the copolymer of the first layer is myrcene, β-farnesene or a mixture of myrcene and β-farnesene.

3. Laminate according to either one of the preceding claims, wherein the copolymer further comprises a second 1,3-diene selected from 1,3-butadiene, isoprene or a mixture thereof, preferably the second 1,3-diene of the copolymer is 1,3-butadiene.

4. Laminate according to any one of Claims 1 to 3, wherein the content of the copolymer of ethylene and of a 1,3-diene of formula (I) in the composition of the first layer is within a range extending from 20 to 90 phr, preferably from 25 to 80 phr, more preferably from 30 to 80 phr, and wherein the diene elastomer having a weight content of diene units of greater than 50% is present in the composition of the first layer at a content within a range extending from 10 to 80 phr, preferably from 20 to 75 phr, more preferably from 20 to 70 phr.

5. Laminate according to any one of the preceding claims, wherein the diene elastomer having a weight content of diene units of greater than 50% of the composition of the first layer is selected from the group consisting of polybutadienes (BRs), natural rubber (NR), synthetic polyisoprenes (IRs), butadiene copolymers, isoprene copolymers and the mixtures of these elastomers.

6. Laminate according to any one of the preceding claims, wherein the plasticizing system comprises a plasticizer that is liquid at 23°C and a plasticizing resin having a glass transition temperature above 20°C.

7. Laminate according to any one of the preceding claims, wherein the plasticizer that is liquid at 23°C of the composition of the first layer is selected from the group consisting of liquid diene polymers, polyolefin oils, naphthenic oils, paraffinic oils, DAE oils, MES oils, TDAE oils, RAE oils, TRAE oils, SRAE oils, mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulfonate plasticizers and mixtures thereof.

8. Laminate according to any one of the preceding claims, wherein the content of plasticizer that is liquid at 23°C, in the composition of the first layer, is within a range extending from 1 to 49 phr, preferably from 5 to 40 phr.

9. Laminate according to any one of the preceding claims, wherein the plasticizing resin having a glass transition temperature above 20°C of the composition of the first layer is selected from the group consisting of cyclopentadiene homopolymer or copolymer resins, dicyclopentadiene homopolymer or copolymer resins, terpene homopolymer or copolymer resins, C5 fraction homopolymer or copolymer resins, C9 fraction homopolymer or copolymer resins, α-methylstyrene homopolymer or copolymer resins and mixtures thereof.

10. Laminate according to any one of the preceding claims, wherein the content of plasticizing resin having a glass transition temperature above 20°C, in the composition of the first layer, is within a range extending from 1 to 99 phr, preferably from 5 to 95 phr.

11. Laminate according to any one of the preceding claims, wherein the content of reinforcing filler in the composition of the first layer is within a range extending from 30 to 200 phr, preferably from 40 to 190 phr, preferably from 50 to 180 phr.

12. Laminate according to any one of the preceding claims, wherein the diene elastomer having a weight content of diene units of greater than 50% of the composition of the second layer is selected from the group consisting of polybutadienes (BRs), natural rubber (NR), synthetic polyisoprenes (IRs), butadiene copolymers, isoprene copolymers and the mixtures of these elastomers.

13. Laminate according to any one of the preceding claims, wherein the diene elastomer having a weight content of diene units of greater than 50% of the first layer and the diene elastomer having a weight content of diene units of greater than 50% of the second layer are polyisoprenes comprising a weight content of 1,4-cis bonds of at least 90%, preferably of at least 98%, of the weight of the polyisoprene.

14. Laminate according to any one of the preceding claims, wherein the first layer has a thickness within a range extending from 0.2 to 120 mm, preferably from 0.3 to 15 mm, and wherein the second layer has a thickness within a range extending from 0.2 to 10 mm, preferably from 0.3 to 7 mm.

15. Rubber article comprising a laminate defined in any one of Claims 1 to 14, said article preferably being selected from the group consisting of pneumatic tyres, non-pneumatic tyres, caterpillar tracks, conveyor belts and anti-vibratory articles, more preferably from the group consisting of pneumatic tyres, non-pneumatic tyres and conveyor belts.