CN111448062A

CN111448062A - Elastomeric laminate

Info

Publication number: CN111448062A
Application number: CN201880079284.4A
Authority: CN
Inventors: J-C·阿劳约达席尔瓦; T·费兰德
Original assignee: Compagnie Generale des Etablissements Michelin SCA
Current assignee: Compagnie Generale des Etablissements Michelin SCA
Priority date: 2017-12-06
Filing date: 2018-12-05
Publication date: 2020-07-24
Also published as: WO2019110926A1

Abstract

The present invention relates to an elastomeric laminate comprising a layer a, a layer B, and n layers Ci disposed between layer a and layer B, n being an integer greater than or equal to 2, i being an integer from 1 to n, a layer C1 disposed between layer a and layer C2, a layer Cn disposed between layer B and layer Cn-1, and when n is greater than 2, for i from 2 to n-1, a layer Ci disposed between layer Ci-1 and layer Ci + 1. Said layer A comprising a diene elastomer matrix having structural repeating units comprising more than 75 mol% of hydrocarbon-based units, and said layer B comprising a polar elastomer comprising ethylene units and vinyl acetate units. For i from 1 to n, the layer Ci comprises a highly saturated diene elastomer having more than 50 mol% of ethylene units and from 0 to less than 100phr of a polar elastomer. In layer C1, the content of highly saturated diene elastomer is higher than the content of polar elastomer. In the layer Cn, the content of polar elastomer is higher than the content of highly saturated diene elastomer. The elastomeric laminate has good resistance to separation of the layers comprising the elastomeric laminate.

Description

Elastomeric laminate

Technical Field

The field of the invention is that of elastomeric laminates comprising more than three layers of diene rubber composition, said elastomeric laminates being intended in particular for use in tyres.

Background

A tire generally comprises a tread, two sidewalls, two beads, a carcass reinforcement passing through the two sidewalls and anchored to the two beads, and a crown reinforcement arranged circumferentially between the tread and the carcass reinforcement. The tread is intended to be in contact with the surface on which the tire is running. The tire may also comprise a tread underlayer circumferentially arranged between the tread and the carcass reinforcement, preferably between the tread and the crown reinforcement, said tread underlayer being generally adjacent to the tread.

In a tire, the undertread must be sufficiently bonded to the tread to avoid the undertread of the tread surface from becoming detached from the tread throughout the life of the tire. The under layer is generally attached to the tread by a physical phenomenon or a chemical phenomenon, such as a phenomenon of interpenetration, entanglement, or crosslinking of diene rubber compositions constituting the tread and the under tread, respectively. These compositions are firmly bonded together under conditions suitable for processing and curing diene rubber compositions placed in close proximity to each other, and the compounds obtained enable stresses related to the field of application considered, in particular the field of tyres.

The compositions useful as treads may contain an elastomeric matrix comprising an elastomer comprising ethylene units and vinyl acetate units, as described for example in patent application FR 16/63180. The presence of vinyl acetate units in the elastomer makes it possible to characterize the elastomer as a polar elastomer.

In general, the rubber composition of the undertread is typically based on a highly hydrocarbon-based elastomer matrix, since the elastomer matrix is typically composed of greater than 75 mole percent of hydrocarbon-based structural repeat units. However, the level of adhesion between a first composition based on a highly hydrocarbon-based elastomeric matrix on the one hand and a second composition based on an elastomeric matrix comprising a polar elastomer containing vinyl acetate units on the other hand may be considered insufficient, in particular for tire applications where the first composition is used as a tire tread and the second composition is used as an undertread.

To overcome this problem, a material may be used that will act as a bonding rubber or adhesive that bonds between the first and second compositions, which are used in particular as tire tread and undertread, respectively. In this case, the undertread is no longer adjacent to the tread over its entire length, but is separated from the tread by the bonding rubber.

The applicant has solved this problem by using a laminate acting as a bonding rubber between these two compositions. The use between the two compositions each constituting the layer to be bonded makes it possible to improve the resistance of the layer to separation considerably, in particular by making the layers to be bonded better.

Disclosure of Invention

A first subject of the invention is therefore an elastomeric laminate comprising a layer a, a layer B and n layers Ci arranged between layer a and layer B, n being an integer greater than or equal to 2, i being an integer from 1 to n,

○ layer C1 is disposed between layer a and layer C2,

○ layer Cn is disposed between layer B and layer Cn-1,

○ when n is greater than 2, for values of i from 2 to n-1, the layer Ci is arranged between the layer Ci-1 and the layer Ci +1,

wherein

■ the layer A consisting of a diene rubber composition comprising a diene elastomer matrix whose structural repeating units contain more than 75 mol% of hydrocarbon-based units,

■ said layer B consisting of a rubber composition comprising an elastomer matrix comprising a polar elastomer comprising ethylene units and vinyl acetate units,

■ for i ranging from 1 to n, the layer Ci consisting of a rubber composition comprising an elastomeric matrix containing a highly saturated diene elastomer containing more than 50 mol% of ethylene units and from 0 to less than 100phr of a polar elastomer,

■ in layer C1, the content of highly saturated diene elastomer is higher than the content of polar elastomer,

■ the content of polar elastomer in the layer Cn is higher than the content of highly saturated diene elastomer.

Another subject of the present invention is the use of the elastomeric laminate according to the present invention in a tire.

The invention also relates to a tire comprising an elastomeric laminate according to the invention.

The invention also relates to an adhesive laminate consisting of a layer C1, a layer Cn and a layer Ci defined in the elastomeric laminate according to the invention, with n being greater than or equal to 2, in addition to the fact that the layer C1 and the layer Cn have a single interface with one layer (with the layer C2 and the layer Cn-1, respectively), for a range of i from 2 to n-1.

The invention also relates to the use of the adhesive laminate according to the invention for bonding two layers a 'and B' having the same composition to a layer a and a layer B, respectively, defined in the elastomeric laminate according to the invention, by applying layer C1 to layer a 'and layer Cn to layer B'.

Detailed Description

I. Detailed description of the invention:

the expression composition "based on" is understood to mean that the composition comprises a mixture and/or reaction product of the various components used, some of these essential components being capable of reacting or intended to react at least partially with each other during the various stages of production of the composition, in particular during its crosslinking or vulcanization.

In the context of the present invention, the expression "parts by weight per hundred parts by weight of elastomer" (or phr) is understood to mean parts by weight per hundred parts by weight of elastomer present in the rubber composition considered and constituting the layer.

In the present specification, all percentages (%) shown are percentages by weight (%), unless otherwise indicated. Furthermore, any interval of values denoted by the expression "between a and b" represents a range of values extending from more than a to less than b (i.e. excluding the limits a and b), whereas any interval of values denoted by the expression "from a to b" means a range of values extending from a up to b (i.e. including the strict limits a and b).

"laminate" is intended to mean a product made of several layers of planar or non-planar shape according to the definition given by the international patent classification.

The elastomeric laminate according to the present invention comprises a layer a, a layer B and n layers Ci disposed between layer a and layer B, n being an integer greater than or equal to 2, i being an integer from 1 to n,

○ layer C1 is disposed between layer a and layer C2,

○ layer Cn is disposed between layer B and layer Cn-1,

wherein

■ the layer A consisting of a diene rubber composition comprising a diene elastomer matrix whose structural repeating units comprise more than 75 mol% of hydrocarbon-based units,

Since the elastomeric laminate according to the invention comprises several layers (in the case of layer a, layer B and n layers) consisting of a diene rubber composition, the elastomeric laminate according to the invention is referred to as elastomeric.

These layers differ from their adjacent counterparts by virtue of their respective diene rubber compositions, preferably by virtue of the nature of their elastomer matrix. The "adjacent corresponding layers" of layers Ci are intended to mean layers Ci +1 and Ci-1, where i has a value of 2 to n-1, the adjacent corresponding layers of layer C1 are layer a and layer C2, and the adjacent corresponding layers of layer Cn are layer Cn-1 and layer B.

"diene" elastomer (or equivalently "rubber", the two terms being considered synonymous) is understood in a known manner to mean one (understood as one or more) elastomer(s) derived at least in part (i.e. a homopolymer or a copolymer) from diene monomers (monomers bearing two carbon-carbon double bonds, which may be conjugated or non-conjugated).

The elastomer matrix of the rubber composition is all of the elastomers contained in the rubber composition.

Diene units are intended to mean the monomer units resulting from the insertion of a monomer subunit resulting from the polymerization of a conjugated diene monomer or of a non-conjugated diene monomer, the diene unit comprising a carbon-carbon double bond.

The content of a given structural repeating unit of the elastomer is equal to the ratio between the number of moles of this structural repeating unit present in the elastomer and the number of moles of all the structural repeating units of the elastomer. In particular, the diene unit content of the elastomer is the ratio between the number of moles of diene units present in the elastomer and the number of moles of all the structural repeating units of the elastomer. This definition of the diene unit content of a given elastomer E falls within the formula τ (Ud)_E＝Ud_(E)/ΣU_(E)Therein, symbol Ud_(Ed)Denotes the structural weight in elastomer ENumber of moles of polydiene units, Σ U_(E)Is the sum of the moles of all structural repeat units in elastomer E. For a given elastomer E, the content of hydrocarbon-based structural repeating units may be determined by replacing the symbol Ud with the symbol U_HCAnd fall within the formula in the same way, the symbol U_HCRepresents the number of moles of the repeating unit having a hydrocarbon-based structure in the elastomer E.

The content of structural repeating units of the elastomer is expressed in mole percent.

The content of a given structural repeat unit of the elastomer matrix is equal to the sum of the contents of structural repeat units associated with each elastomer in the elastomer matrix, weighted by the mass fraction of the respective elastomer in the elastomer matrix. For example, in the case of diene units, this definition falls within the formula τ (Ud)_M＝Στ(Ud)_Ex F_EInner, middle symbol tau (Ud)_EDenotes the content (in mol%) of structural diene units in the elastomer E constituting the elastomer matrix, symbol F_ERepresenting the mass fraction of the elastomer E in the elastomer matrix, the symbol Σ representing the summation operator for the product τ (Ud) to be obtained for each elastomer E constituting the elastomer matrix_Ex F_EAnd (4) adding.

Microstructure of elastomer through¹H NMR analysis determined when¹When the resolution of the H NMR spectrum is not capable of assigning and quantifying all entities, by¹³C NMR analysis was compensated. Measurements were made using a Bruker 500MHz NMR spectrometer at 500.43MHz for proton observation and 125.83MHz for carbon observation.

For the measurement of insoluble but solvent-swellable mixtures or elastomers, HRMAS z-gradient 4mm probes were used so that protons and carbon could be observed in proton decoupled mode. Spectra were obtained at rotation speeds of 4000Hz to 5000 Hz.

For the measurement of soluble elastomers, liquid NMR probes were used so that protons and carbon could be observed in a proton decoupled mode.

The insoluble sample is loaded with an assay material and a deuterated solvent, typically deuterated chloroform (CDCl)₃) Prepared in a rotor ofThe deuterated solvents enable swelling. The solvent used must always be deuterated and its chemical nature can be adjusted by the person skilled in the art. The amount of material used is adjusted to obtain a spectrum with sufficient sensitivity and resolution.

The soluble sample was dissolved in a deuterated solvent (about 25mg elastomer in 1 ml), typically deuterated chloroform (CDCl)₃). The solvent or solvent blend used must always be deuterated and its chemical nature can be adjusted by the person skilled in the art.

In both cases (soluble or swollen samples):

for proton NMR, a simple 30 ° pulse sequence was used. The spectral window is adjusted to observe all resonance lines belonging to the molecule analyzed. The accumulated number is adjusted to obtain a signal-to-noise ratio sufficient to quantize each sub-unit. The cyclic delay between each pulse is adjusted to obtain a quantitative measurement.

For carbon NMR, protons are only decoupled during acquisition using a simple 30 ° pulse sequence to avoid the "austenite core" effect (NOE) and to maintain quantitation. The spectral window is adjusted to observe all resonance lines belonging to the molecule analyzed. The accumulated number is adjusted to obtain a signal-to-noise ratio sufficient to quantize each sub-unit. The cyclic delay between each pulse is adjusted to obtain a quantitative measurement.

The measurement was carried out at 25 ℃.

The polar elastomers which may be used in the requirements of the present invention are elastomers containing ethylene units and vinyl acetate units. Due to the presence of vinyl acetate units in the elastomer, it is referred to as a polar elastomer. Preferably, the polar elastomer contains more than 50 mole% of ethylene units, preferably at least 55 mole% of ethylene units. Preferably, the polar elastomer contains at least 10 mole% of vinyl acetate units. More preferably, the polar elastomer contains more than 50 mole% of ethylene units and at least 10 mole% of vinyl acetate units. Even more preferably, the polar elastomer contains at least 55 mol% of ethylene units and at least 10 mol% of vinyl acetate units. Advantageously, the polar elastomer is a copolymer of ethylene and vinyl acetate, also known as EVA.

It is understood that the polar elastomers useful for the requirements of the present invention may be mixtures of polar elastomers whose macrostructures or microstructures, in particular their respective molar contents of structural repeat units, are different from one another.

Highly saturated diene elastomers which can be used for the purposes of the present invention are diene elastomers containing more than 50 mol% of ethylene units randomly distributed in the elastomer.

Preferably, the highly saturated diene elastomer comprises units UA, UB, UC, UD, where appropriate unit UE, having the following formulae in the following indicated molar percentages:

UA)-CH₂-CH₂-mole percentage in m%

UB)-CH₂-CH＝CH-CH₂-mole percentage in terms of n%

UC)-CH₂-CH(CH＝CH₂) Mol% in terms of o%

UD)

In terms of mole percent of p%

UE)

In terms of mole percent of q%

■ m, n, o, p and q are numbers from 0 to 100,

■m>50

■n+o>0

■p>0

■q≥0，

■ m, n, o, p and q are each calculated on the basis of the sum of m + n + o + p + q equal to 100.

More preferably still, the first and second liquid crystal compositions are,

■0<o+p≤25

■o+p+q≥5

■n+o>0

■q≥0，

Even more preferably, the highly saturated diene elastomer meets at least one and preferably all of the following requirements:

■m≥65

■ n + o + p + q.gtoreq.15, preferably n + o + p + q.gtoreq.20

■12≥p+q≥2

■1≥n/(o+p+q)

■ when q is nonzero, 20 ≧ p/q ≧ 1.

Advantageously, q is equal to 0.

According to another preferred embodiment of the invention, the highly saturated diene elastomer comprises as monomer units only the units UA, UB, UC, UD and UE in accordance with their respective molar percentages m, n, o, p and q, preferably all of these percentages being other than 0.

According to another preferred embodiment of the invention, the highly saturated diene elastomer comprises as monomer units only the units UA, UB, UC, UD corresponding to their respective molar percentages m, n, o and p, preferably all of these percentages being different from 0.

According to any one of the embodiments of the present invention, the ethylene units UA present in the highly saturated diene elastomer preferably represent more than 70 mol% of all the monomer units of the highly saturated diene elastomer.

According to any one of the embodiments of the present invention, the diene units comprising a carbon-carbon double bond and present in the highly saturated diene elastomer are preferably 1, 3-diene units having from 4 to 12 carbon atoms, in particular 1, 3-butadiene units. More preferably, the highly saturated diene elastomer is a copolymer of ethylene and 1, 3-butadiene.

It is understood that the highly saturated diene elastomer which can be used for the requirements of the present invention may be a mixture of highly saturated diene elastomers whose macrostructures or microstructures, in particular their respective molar contents of structural repeat units, are different from one another.

The highly saturated diene elastomers can be obtained according to various synthetic methods known to the person skilled in the art, in particular according to variations in the target values m, n, o, p, q and r. In general, highly saturated diene elastomers can be prepared by copolymerization of at least one conjugated diene monomer with ethylene and according to known synthesis methods, in particular in the presence of a catalytic system comprising a metallocene complex. In this connection, mention may be made of catalytic systems based on metallocene complexes, which are described in the documents EP 1092731 a1, EP 1554321 a1, EP 1656400 a1, EP 1829901 a1, EP 1954705 a1 and EP 1957506 a1 of the applicant.

Highly saturated diene elastomers can be prepared according to the above-mentioned documents, by adjusting the polymerization conditions, according to methods known to those skilled in the art, so as to preferably reach a number average molar mass (Mn) value of at least 60000 g/mol (generally determined by Size Exclusion Chromatography (SEC) in combination with differential refractometric detection calibrated with polystyrene standards). By way of example, the polymerization time can be increased significantly, leading to a greater monomer conversion, resulting in a molar mass of at least 60000 g/mol being obtained. By way of example, during the preparation of the catalytic system according to the above-mentioned document, the stoichiometry of the alkylating agent with respect to the metallocene complex is reduced, thereby reducing the chain transfer reactions and enabling a molar mass of at least 60000 g/mol to be obtained.

Arrangement of layers:

the elastomeric laminate according to the present invention has the following basic features: comprising a layer A, a layer B and n layers Ci arranged between the layer A and the layer B, n being an integer greater than or equal to 2 and i being an integer from 1 to n.

When the elastomeric laminate comprises layer a, layer B and two layers disposed between layer a and layer B, layer C1(i ═ 1) is disposed between layer a and layer C2(i ═ 2) and layer C2 is disposed between layer C1 and layer B. This variant corresponds to the case where n is equal to 2.

When the elastomeric laminate according to the present invention comprises a layer a, a layer B and more than 2 layers between layer a and layer B, in particular n layers (then n is greater than 2), each layer, called Ci, is arranged between a layer Ci-1 and a layer Ci +1 (where i has a value of 2 to n-1), layer C1 being known to have a common interface with layer a and layer Cn with layer B. This variant corresponds to the case where n is greater than 2.

From a technical point of view, the value of n is not limited by the maximum value: which can vary to a large extent. However, those skilled in the art will appreciate that a larger number of layers Ci may not be suitable for certain applications, for example due to material cost and weight (which increases with increasing number of layers). This is why n is preferably equal to 2.

Layer A

The elastomeric laminate according to the present invention is essentially characterized in that it comprises a layer a consisting of a diene rubber composition comprising a diene elastomer matrix whose structural repeating units are greater than 75 mol% of hydrocarbon-based units.

The elastomeric matrix of the rubber composition constituting layer a is a diene elastomeric matrix in that it comprises one or more diene elastomers. Hereinafter, this elastomeric matrix is referred to as matrix a. Since more than 75 mol% of the repeating units constituting the matrix a are hydrocarbon-based units, the matrix a is essentially characterized as being highly hydrocarbon-based. The structural repeating units of matrix a are generally the monomeric units of the elastomer constituting matrix a and are also the units resulting from the modification of the monomeric units in the case where one or more elastomers of matrix a have been modified after the polymerization reaction. Preferably, the structural repeat units of matrix a are greater than 90 mole percent of the hydrocarbyl units.

Preferably, matrix a contains a molar content of diene units higher than the molar content of diene of the elastomeric matrix of layer C1.

Preferably, since matrix a preferably has a molar content of diene units greater than 50%, matrix a is also a highly unsaturated elastomeric matrix.

As the diene elastomer which can be used in the invention to form the requirements of the matrix A, mention may be made of homopolymers and copolymers of 1, 3-dienes, in particular butadiene or isoprene.

Preferably, matrix a is an elastomer selected from the following diene elastomers: polybutadiene, polyisoprene, butadiene copolymers, isoprene copolymers and mixtures thereof. In other words, the elastomer is present in the matrix a in a content of preferably 100phr, said elastomer being chosen from the following diene elastomers: polybutadiene, polyisoprene, butadiene copolymers, isoprene copolymers and mixtures thereof, which means that the elastomer alone forms the matrix a. More preferably, the matrix A is a highly unsaturated diene elastomer, i.e.an elastomer containing more than 50 mol% of diene units. Even more preferably, matrix a is a polyisoprene with a high cis content (with a degree of 1, 4-cis bonding of more than 90%), preferably natural rubber. In other words, the content of this polyisoprene (whether synthetic or natural) in matrix A is preferably 100 phr. This more preferred embodiment is particularly applicable where the laminate is used in a tire, more particularly when layer a constitutes part or all of the undertread.

Layer B:

the elastomeric laminate according to the present invention is essentially characterized in that it comprises a layer B consisting of a rubber composition comprising an elastomeric matrix containing a polar elastomer. The polar elastomer is an elastomer comprising ethylene units and vinyl acetate units and is as defined above. Hereinafter, the elastomeric matrix of the layer B is denoted matrix B.

According to a preferred embodiment of the invention, the polar elastomer is present in the matrix B in a quantity greater than 50 phr. Preferably, matrix B comprises more than 90phr of a polar elastomer. More preferably, the content of polar elastomer in layer B is 100 phr.

Layers Ci with i from 1 to n

Hereinafter, the elastomer matrix of the rubber composition of the layer Ci is denoted as matrix Ci. The matrix Ci contains a highly saturated diene elastomer as defined above. Layer Ci contains from 0 to less than 100phr of a polar elastomer as defined above.

The matrix C1 is also essentially characterized by a content of highly saturated diene elastomer which is higher than the content of polar elastomer. The presence of a highly saturated diene elastomer at a higher level than the polar elastomer allows good adhesion between layer a and layer C1, which helps to provide a laminate with good peel strength.

According to a preferred embodiment of the invention, the matrix C1 contains more than 50 mol% of ethylene units.

According to another preferred embodiment of the invention, the matrix C1 contains more than 50phr of a highly saturated diene elastomer. The content of highly saturated diene elastomer in layer C1 in contact with layer a, greater than 50phr, provides good adhesion between layer C1 and layer a, which makes it possible to provide a laminate having good peel strength.

According to one embodiment of the invention, the laminate satisfies all of the following conditions, i being from 1 to n-1:

the content of highly saturated diene elastomer in the layer Ci is higher than that in the layer Ci +1,

the content of polar elastomer in the layer Ci is lower than in the layer Ci +1,

the polar elastomer is present in a higher amount in layer B than in layer Cn.

The matrix Cn is also essentially characterized by a content of polar elastomer higher than that of highly saturated diene elastomer. The presence of the polar elastomer in the matrix Cn in a higher content than the highly saturated diene elastomer allows good adhesion between layer B and layer Cn, which helps to provide a laminate with good peel strength.

Preferably, the elastomeric matrix of layer Cn contains more than 50phr of polar elastomer. The content of polar elastomer in the layer Cn in contact with layer B is greater than 50phr, making it possible to impart good peel strength on the laminate due to good adhesion to layer B.

As described above, when 2 layers are arranged between layer a and layer B (n ═ 2), the elastomer matrix of the rubber compositions of layer C1 and layer C2 each preferably consists of a mixture of a highly saturated diene elastomer and a polar elastomer.

Reinforcing filler:

the diene rubber composition constituting any one (preferably all) of layers a, B and Ci preferably comprises a reinforcing filler, in particular when the elastomeric laminate is used in a tyre, i is from 1 to n, and n is greater than or equal to 2.

The reinforcing filler may be any type of "reinforcing" filler known to be capable of reinforcing diene rubber compositions usable for the manufacture of tires, such as an organic filler (for example carbon black), a reinforcing inorganic filler (for example silica) or a mixture of these two types of filler, said reinforcing filler being combined in a known manner with a coupling agent.

Such reinforcing fillers generally consist of nanoparticles, the (weight-) average size of which is less than a micron, generally less than 500nm, most often between 20 and 200nm, particularly and more preferably between 20 and 150 nm.

All carbon blacks, in particular carbon blacks conventionally used in tires or treads thereof ("tire-grade" carbon blacks), are suitable as carbon blacks. In the latter, mention is made more particularly of reinforcing blacks of the series 100, 200 and 300, or blacks of the series 500, 600 or 700 (ASTM grades), such as, for example, the blacks N115, N134, N234, N326, N330, N339, N347, N375, N550, N683 and N772. These carbon blacks may be used in the isolated state, which is commercially available, or in any other form, for example as a carrier for some of the rubber additives used.

The term "reinforcing inorganic filler" is understood herein to mean any inorganic or mineral filler, whatever its colour and its origin (natural or synthetic), also known as "white filler", "clear filler" or even "non-black filler" with respect to carbon black, which is capable of reinforcing alone, without a process other than an intermediate coupling agent, a diene rubber composition intended for the manufacture of pneumatic tires, in other words which is capable of replacing, in its reinforcing role, a conventional tire-grade carbon black; such fillers are generally characterized in a known manner by the presence of hydroxyl groups (-OH) on their surface.

Mineral fillers of siliceous type, preferably Silica (SiO)₂) Particularly suitable as reinforcing inorganic fillers. The silica used may be any reinforcing silica known to the person skilled in the art, in particular having a BET surface area and a CTAB specific surface area both of which are less than 450m²G, preferably from 30 to 400m²In particular in the range from 60 to 300m²Between/g of precipitated silica or pyrogenic silica. As highly dispersible precipitated silicas ("HDS"), mention may be made, for example, of Ultrasil7000 from DegussaAnd Ultrasil 7005 silica, Zeosil 1165MP, 1135MP and 1115MP silica from Rhodia, Hi-Sil EZ150G silica from PPG, Zeopol 8715, 8745 and 8755 silica from Huber or silica with a high specific surface area as described in application WO 03/016387.

In this context, The BET specific surface area is determined in a known manner by gas adsorption using The Brunauer-Emmett-Teller method described in The Journal of The American chemical Society, volume 60, page 309, month 2 1938, more particularly according to French standard NF ISO 9277 (multipoint (5 points) volumetric method-gas: nitrogen-degassing: 1 hour at 160 ℃ relative pressure p/p₀The range is as follows: 0.05 to 0.17). The CTAB specific surface area is the external surface determined according to French standard NF T45-007 (method B) at 11 months 1987.

It is not important in what physical state the reinforcing inorganic filler is provided, whether in powder, microbead, granule or bead form. Of course, reinforcing inorganic filler is also understood to mean a mixture of different reinforcing inorganic fillers, in particular of highly dispersible silicas as described above.

It will be understood by those skilled in the art that reinforcing fillers having another property, in particular an organic property, such as carbon black, can be used as fillers equivalent to the reinforcing inorganic fillers described in this section, provided that the reinforcing filler is covered with an inorganic layer, such as silica, or comprises on its surface functional sites, in particular hydroxyl sites, which require the use of coupling agents in order to establish a bond between the filler and the elastomer. For example, mention may be made, for example, of carbon blacks for tires, as described, for example, in patent documents WO 96/37547 and WO 99/28380.

For coupling the reinforcing inorganic filler to the diene elastomer, use is made, in a known manner, of an at least bifunctional coupling agent (in particular a silane) (or bonding agent) intended to provide a linkage of satisfactory chemical and/or physical characteristics between the inorganic filler (its particle surface) and the diene elastomer. In particular, at least bifunctional organosilanes or polyorganosiloxanes are used.

In particular, use is made of what is termed "symmetrical" according to its particular structure"or" unsymmetrical "silane polysulphides, for example as described in patent applications WO 03/002648 (or US 2005/016651) and WO 03/002649 (or US 2005/016650). As examples of polysulfide silanes, bis ((C) will be mentioned more particularly₁-C₄) Alkoxy (C)₁-C₄) Alkylsilyl (C)₁-C₄) Alkyl) polysulfides (in particular disulfides, trisulfides or tetrasulfides), for example bis (3-trimethoxysilylpropyl) polysulfide or bis (3-triethoxysilylpropyl) polysulfide. Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide (abbreviated to TESPT, of formula [ (C)₂H₅O)₃Si(CH₂)₃S₂]₂) Or bis (triethoxysilylpropyl) disulfide (abbreviated TESPD, formula [ (C)₂H₅O)₃Si(CH₂)₃S]₂)。

As coupling agents it is also possible to use silanes bearing at least one activated ethylenic double bond, which are combined with free-radical initiators by thermal initiation, as described, for example, in documents WO 01/49781, US 4370448 and US 4603158. The double bond is preferably activated by carbonyl CO. The silane bearing at least one activated ethylenic double bond is preferably a silane bearing a methacrylate functional group, such as 3- (trimethoxysilyl) propyl methacrylate or 3- (triethoxysilyl) propyl methacrylate.

The content of coupling agent is advantageously less than 20phr (parts by weight per hundred parts of elastomer present in the rubber composition considered to constitute a layer), it being understood that it is generally desirable to use as little coupling agent as possible. Generally, the content of the coupling agent is 0.5 to 15% by weight relative to the amount of the inorganic filler. The content of coupling agent is preferably between 0.5 and 12phr, more preferably in the range from 3 to 10 phr. The content is easily adjusted by those skilled in the art according to the content of the inorganic filler used in the diene rubber composition.

For coupling the inorganic filler, in particular silica, to the elastomer matrix containing the polar elastomer, it is possible to use, as coupling agent, a polymer bearing functional groups reactive with the acetate groups of the polar elastomer, for example epoxy or carboxyl functional groups, it being possible in this way to use copolymers containing monomeric units of a terminal olefin, for example ethylene or α -olefin, and monomeric units of a monomer bearing epoxy or carboxyl functional groups, for example certain acrylate or methacrylate monomers, most particularly suitable are copolymers of ethylene and glycidyl acrylate, copolymers of ethylene and glycidyl methacrylate, copolymers of ethylene, vinyl acetate and glycidyl methacrylate, and copolymers of ethylene, vinyl acetate and glycidyl acrylate, these polymers being commercially available, in particular under the name L otader from Arkema, Elvaloy from Du Pont and "Ingetabond" from Sumitomo, these polymers being used as agents in rubber compositions, the content of which is generally adjusted according to the amount of inorganic filler, in particular silica, and generally ranging from 30% to 5% by weight relative to the weight of the inorganic reinforcing filler, in particular silica.

When they are elastomers (e.g., L otader AX8900), they form part of the elastomeric matrix in the layer in which they are used with polar elastomers, when they are elastomers, they preferably constitute at most 25%, more preferably at most 15%, of the elastomeric matrix of the rubber composition in which they are used.

According to a particular embodiment of the invention, each of the diene rubber compositions constituting layer a and layer B and the n layers, respectively, of the elastomeric laminate comprises a reinforcing filler, preferably carbon black or silica, or a mixture of carbon black and silica. When layer B is used for a tire tread, the reinforcing filler of layer B preferably comprises silica, and the reinforcing filler of the rubber composition of the other layer is carbon black or a mixture of carbon black and silica.

Content of reinforcing filler:

the content of reinforcing filler in each diene rubber composition of the elastomeric laminate may vary within wide limits, for example depending on the nature of the elastomeric matrix or of the reinforcing filler in the diene rubber composition or depending on the amount of plasticizer in the diene rubber composition. These variables are adjusted by the person skilled in the art according to the use of the laminate, in particular in tyres.

In the case of use of a laminate in which layer a of the laminate constitutes the tread intended to be fitted on a tire and layer B constitutes the undertread, the nature of the reinforcing filler in the diene rubber composition of the n layers and its content are chosen by the person skilled in the art to suit the particular conditions of this use. For example, the reinforcing filler may be carbon black, silica or a mixture thereof, and the content of the reinforcing filler in the diene rubber composition can be from 20 to 200 phr.

According to any one of the embodiments of the present invention, the content of the reinforcing filler in the n-layer diene rubber composition is preferably 5 to 80phr, more preferably 5 to 50 phr.

According to a particular embodiment of the invention, the diene rubber compositions of the n layers comprise a content of reinforcing filler less than or equal to the content of reinforcing filler of the diene rubber compositions of layer a.

Other additives：

In addition to the coupling agent, the diene rubber composition constituting layer a and layer B and any of the n layers of the elastomeric laminate may also comprise a coupling activator, an agent covering the inorganic filler or, more generally, a processing aid capable of improving its processability in the uncured state in a known manner by improving the dispersion of the filler in the rubber matrix and reducing the viscosity of the diene rubber composition.

It may also comprise all or part of the usual additives usually used in elastomer compositions intended for mixtures constituting finished rubber articles (for example tyres), such as, for example, pigments, protective agents (for example antiozone waxes, chemical antiozonants, antioxidants), antifatigue agents, crosslinking systems based on sulfur, peroxides or bismaleimides.

The constituent rubber compositions of layer a and layer B and any of the n layers of the elastomeric laminate preferably comprise a crosslinking system. Preferably, the rubber composition of all layers comprises a crosslinking system.

When the elastomeric matrix is a diene matrix, it is preferable to use a crosslinking system based on sulfur, commonly known as a vulcanization system, or a crosslinking system based on peroxides. When the elastomer matrix comprises a polar elastomer, the crosslinking system is preferably a peroxide-based crosslinking system.

The rubber compositions which can be used for the purposes of the present invention can also comprise plasticizers, such as extender oils of aromatic or non-aromatic nature, in particular oils which are very slightly aromatic or non-aromatic (for example paraffinic or hydrogenated naphthenic oils, or MES or TDAE oils), vegetable oils (in particular glycerol esters such as glycerol trioleate), hydrocarbon-based plasticizing resins having a high Tg (preferably higher than 30 ℃) (such as those described, for example, in applications WO 2005/087859, WO 2006/061064 and WO 2007/017060). The content of plasticizer is adjusted by those skilled in the art according to the viscosity and the properties sought for the rubber composition, depending on the use for which the rubber composition is to be used. The viscosity of the rubber composition itself depends on many variables, such as the viscosity of the elastomeric matrix, the content of reinforcing filler and possible interactions between the elastomeric matrix and the reinforcing filler. The person skilled in the art therefore selects, on his own general knowledge, the appropriate plasticizer content taking into account these various variables.

If the diene rubber compositions constituting the n layers for the purposes of the present invention comprise plasticizers, they preferably comprise up to 20phr, more preferably less than 10phr and even more preferably less than 5phr of plasticizers. These preferred embodiments make it possible to achieve very significant adhesion levels between the layers.

According to another embodiment of the present invention, the diene rubber composition of any one (preferably all) of the n layers does not contain a plasticizer. This embodiment, which is advantageous from the standpoint of adhesion properties, is particularly suitable for constituting n layers of diene rubber compositions having a relatively low filler content, in particular those comprising up to 50phr of reinforcing filler.

Preparation of diene rubber composition:

the diene rubber compositions which can be used for the requirements of the present invention can be prepared in suitable mixers using two successive preparation stages known to those skilled in the art: a first stage of thermomechanical working or kneading at high temperature (up to a maximum temperature between 130 ℃ and 200 ℃) ("non-productive" stage), followed by a second stage of mechanical working at a reduced temperature (generally less than 110 ℃, for example between 40 ℃ and 100 ℃) ("productive" stage), during which a crosslinking system is introduced.

Preparation of the laminate:

in the manufacture of the elastomeric laminate according to the present invention, the diene rubber compositions constituting the layers adhere to each other in the uncured state. To promote interfacial adhesion, it is preferred to apply the layer in an uncured state under thermal conditions. The application of the layer in the uncured state under thermal conditions is carried out at a temperature compatible with the chemical nature of the layer, that is to say, for example, at a temperature which does not cause premature crosslinking of the layer. Generally, temperatures above ambient (20 ℃) but not exceeding 80 ℃ are most suitable.

It will be readily appreciated that the elastomeric laminate according to the present invention may comprise several preferred thickness ranges depending on the particular field of application. Thus, for example, for a pneumatic tire of the passenger vehicle type, layers a and B may have a thickness of at least 2mm, preferably between 3 and 10 mm. According to another embodiment, for pneumatic tires for heavy goods or agricultural vehicles, the preferred thickness of layers a and B may be between 2 and 20 mm. According to another embodiment, the preferred thickness of layers a and B may be between 2 and 100mm for pneumatic tires for vehicles in the civil engineering field or pneumatic tires for aircraft.

Depending on the particular conditions of use of the elastomeric laminate, the thickness of the n layers may each be from 60 μm to several millimeters, for example from 100 μm to 5 mm.

For minimum thicknesses, in particular of the order of a few hundred microns, the layer is preferably formed by applying the diene rubber composition in dissolved form containing a volume of solvent. For greater thicknesses, it is preferred to calender or even extrude the diene rubber composition in the form of a layer.

To manufacture elastomeric laminates, the layers can be arranged one on top of the other by applying them in succession, for example on a building drum usually used for manufacturing pneumatic tires (or tire casings). For example, layer a is placed on the drum, layer C1 is placed on layer a, and so on until layer B is applied to layer Cn.

The elastomeric laminate may be in an uncured state (before crosslinking or curing) or in a cured state (after crosslinking or curing).

In the manufacture of tires comprising elastomeric laminates, the elastomeric laminates may be manufactured prior to or during the manufacture of the tire. In the former case, it may be applied to the tire by, for example, placing a preformed elastomeric laminate on the carcass reinforcement or crown reinforcement of the tire. In the second case, layer B may be placed, for example, on the carcass reinforcement or crown reinforcement of the tyre, then layer Cn on layer B and so on until layer a is applied to layer C1.

The elastomeric laminate may be used in a tire comprising a tread, two sidewalls, two beads, a carcass reinforcement passing through the two sidewalls and anchored to the two beads, and a crown reinforcement arranged circumferentially between the tread and the carcass reinforcement.

According to one embodiment of the invention, the elastomeric laminate is used in a tire such that layer a constitutes a portion or all of the tire tread and layer B constitutes a portion or all of the undertread.

According to a preferred embodiment of the elastomeric laminate of the present invention for use in a tire, layer a constitutes the entirety of the tread and layer B constitutes the entirety of the undertread layer.

When layer B in the elastomeric laminate is used as the tire tread underlayer, it is preferably not in contact with the surface on which the tire is running.

A tyre provided with an elastomeric laminate and representing another subject of the present invention can be in a cured state or in an uncured state.

Another subject of the invention is an adhesive laminate consisting of the layers C1, Cn and Ci defined in the elastomeric laminate according to the invention, apart from the fact that the layer C1 and the layer Cn have a single interface with one of the layers (layer C2 and layer Cn-1, respectively), for i ranging from 2 to n-1, where n is greater than or equal to 2. The bonded laminate may be used as a bonding rubber for bonding two layers a 'and B' having the same composition to layer a and layer B, respectively, and thus forming an elastomeric laminate according to the invention with layer a 'and layer B'. By applying layer C1 to layer a 'and layer Cn to layer B', the bonded laminate in the uncured state is disposed between layer a 'and layer B', also in the uncured state, to form an elastomeric laminate in accordance with the present invention.

The above-mentioned and other characteristics of the invention will be better understood on reading the following several exemplary embodiments of the invention, described by way of illustration and not by way of limitation.

Exemplary embodiments of the invention

Compositions of the formulations shown in table 1 were prepared according to the methods described below.

In addition to the vulcanization system, the elastomer, the reinforcing filler and the various other ingredients are introduced into an internal mixer in succession (final degree of filling: about 70% by volume) at an initial vessel temperature of about 80 ℃. Thermomechanical working (non-productive phase) is then carried out in one step, which lasts about 3 to 4 minutes in total, until a maximum "tapping" temperature of 180 ℃ is reached. The mixture thus obtained is recovered and cooled, then the crosslinking system (in this case sulphur) and the vulcanization accelerator or peroxide are introduced into a mixer (homogeneous finisher) at 40 ℃ while mixing all the substances (production stage) at a temperature lower than 110 ℃ for a suitable time (for example about 10 minutes).

Composition a (1) is the composition of layer a of the laminate according to the invention, since the elastomeric matrix is natural rubber.

Composition B (4) is the composition of layer B of the laminate according to the invention, since the elastomeric matrix is a copolymer of ethylene and vinyl acetate.

Composition C1(2) is the composition of layer C1 of the laminate according to the invention, since the elastomeric matrix is a mixture of 60phr of a copolymer of ethylene and of highly saturated 1, 3-butadiene and 40phr of a copolymer of ethylene and of vinyl acetate.

Composition C2(3) is the composition of layer C2 of the laminate according to the invention, since the elastomeric matrix is a mixture of 40phr of a copolymer of ethylene and of highly saturated 1, 3-butadiene and 60phr of a copolymer of ethylene and of vinyl acetate.

An adhesion test (peel test) was performed to test the ability of adhesive layer B to adhere to layer C2 after curing, the ability of this same layer C3 to adhere to layer C2 after curing, and the ability of layer C2 to adhere to layer a after curing.

Adhesion was measured between the two layers a and C1, between layer C1 and layer C2, and between layer C2 and layer B. The value of the adhesion measured between the two layers a and B is retained as a control value, and therefore the laminate does not comply with the present invention. By convention, the control value for the adhesion measured (i.e. the value of the adhesion measured between the two layers a and B) is 100. The results are expressed as performance indices. An index greater than 100 indicates a greater improvement in adhesion.

Adhesion was measured according to the peel test described below.

II-1 description of the Peel test:

a peel test specimen (180 ℃ peel type) was prepared by stacking the following products:

b adhesion to C2:

passenger vehicle carcass ply-type fabric

Layer C2 (thickness between 2 and 3 mm)

Layer B (thickness between 2 and 3 mm)

Layer C2 (thickness between 2 and 3 mm)

Passenger vehicle carcass ply-type fabric

Adhesion of C2 to C1:

passenger vehicle carcass ply-type fabric

Layer C1 (thickness between 2 and 3 mm)

Layer C2 (thickness between 2 and 3 mm)

Layer C3 (thickness between 2 and 3 mm)

Passenger vehicle carcass ply-type fabric

C1 adhesion on a:

passenger vehicle carcass ply-type fabric

Layer A (thickness between 2 and 3 mm)

Layer C1 (thickness between 2 and 3 mm)

Layer A (thickness between 2 and 3 mm)

Passenger vehicle carcass ply-type fabric

An initial crack is provided at the interface between one of the rubber layers and the adhesive layer.

The test specimens were then cured in a plate press at 170 ℃ and 16 bar for 20 minutes.

Strips with a width of 30mm were cut using a cutter. Subsequently, both sides of the initial crack were placed in the jaws of a tensile testing apparatus under the brand name Instron. After curing the specimens for 30 minutes, the test was carried out at 60 ℃. The drawing speed was 100 mm/min. The tensile stress was recorded and normalized by the width of the specimen. A curve of the strength per unit width (in N/mm) as a function of the displacement of the movable crosshead (between 0 and 200 mm) of the tensile testing machine was obtained. The retained adhesion values correspond to the mean values calculated on the curve.

II-2. results:

the results are shown in Table 2.

Note that the adhesion performance index was highest between layer a and layer C1, between layer C1 and layer C2, and between layer C2 and layer B, compared to the control. They were even more than ten times higher than the control.

The presence of layers C2 and C3 (between layers a and B of the laminate) in the laminate enables a great increase in the resistance of the layers of the laminate constituting the laminate to separation, compared to a control laminate comprising only layers a and B.

The results of the peel test demonstrate the advantage of using an adhesive laminate consisting of layer C1 and layer C2 to bond layer a to layer B.

TABLE 1

(1) Natural rubber

(2) Polybutadiene comprising 98% of 1, 4-cis units

(3) Copolymer of styrene and 1, 3-butadiene comprising 25% by weight of styrene and 58% of 1,2 units of the butadiene fraction

(4) An ethylene/vinyl acetate (EVA) copolymer sold by Arlanxeo under the reference L EVAPREN 500, having a molar percentage of ethylene monomers equal to 75% and a molar percentage of vinyl acetate monomers equal to 25%

(5) Copolymer of ethylene and 1, 3-butadiene comprising 76% of UA units, 6.4% of UB units, 10% of UC units and 7.6% of UD units (mol%) and prepared according to the polymerization process of ethylene and butadiene according to example 4-2 of patent EP 1954705B 1

(6) ASTM grade N683(Cabot)

(7) ASTM grade N234(Cabot)

(8) Silica "160 MP" sold by Solvay and having a BET specific surface area of 160m²The BET specific surface area is measured according to the method described in section I-2)

(9) 3- (trimethoxysilyl) propyl methacrylate sold by Gelest (CAS:2530-85-0)

(10) TESPT sold by Evonik with reference to "SI 69

(11) C5/C9 resin ("Escorez ECR-373" from Exxon corporation)

(12) Non-aromatic oil (MES "Catenex" SNR from Shell company)

(13) N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine from Flexsys

(14) Diphenylguanidine (DPG Perkacit from Flexsys, Inc.)

(15) N-Cyclohexylthiophthalimide ("Vulkalent G" from L anxess Co.)

(16) N-cyclohexyl-2-phenylthiazolesulfamide ("Santocure" from Flexsys).

TABLE 2

Adhesive force	C1-1/C4-1	C4-1/C3-1	C3-1/C2-1	C2-1/C1-1
					Performance index	100	1550	1150	1650

Claims

1. An elastomeric laminate comprising a layer A, a layer B, and n layers Ci disposed between layer A and layer B, n being an integer greater than or equal to 2, i being an integer from 1 to n,

a. layer C1 is disposed between layer a and layer C2,

b. layer Cn is disposed between layer B and layer Cn-1,

c. when n is greater than 2, for values of i from 2 to n-1, the layer Ci is arranged between the layer Ci-1 and the layer Ci +1,

wherein

■ the layer A consisting of a diene rubber composition comprising a diene elastomer matrix having structural repeating units of greater than 75 mol% of hydrocarbon-based units,

2. The laminate of claim 1, wherein the highly saturated diene elastomer comprises units UA, UB, UC, UD, where appropriate UE, having the formula,

UA)-CH₂-CH₂-mole percentage in m%

UB)-CH₂-CH＝CH-CH₂-mole percentage in terms of n%

UC)-CH₂-CH(CH＝CH₂) Mol% in terms of o%

UD)

In terms of mole percent of p%

UE)

In terms of mole percent of q%

■ m, n, o, p and q are numbers from 0 to 100,

■m≥50

■n+o>0

■p>0

■q≥0，

3. The laminate of claim 2, wherein:

■0<o+p≤25

■o+p+q≥5

■n+o>0

■q≥0，

4. Laminate according to any one of claims 2 and 3, wherein the highly saturated diene elastomer contains as monomer units only units UA, UB, UC, UD and UE in accordance with their respective molar percentages m, n, o, p and q, preferably all of these percentages being different from 0.

5. The laminate according to any one of claims 2 to 4, wherein q is equal to 0.

6. The laminate of any one of claims 1 to 5, wherein the highly saturated diene elastomer is a copolymer of ethylene and 1, 3-butadiene.

7. The laminate according to any one of claims 1 to 6, wherein the polar elastomer contains more than 50 mol% of ethylene units, preferably at least 55 mol% of ethylene units.

8. The laminate of any one of claims 1 to 7, wherein the polar elastomer contains at least 10 mole% of vinyl acetate units.

9. The laminate of any one of claims 1 to 8, wherein the polar elastomer is a copolymer of ethylene and vinyl acetate.

10. The laminate of any one of claims 1 to 9, wherein the elastomeric matrix of layer a contains a molar content of diene units that is greater than the molar content of diene units of the elastomeric matrix of layer C1.

11. The laminate of any one of claims 1 to 10, wherein the elastomeric matrix of layer a contains a molar content of diene units greater than 50%.

12. The laminate of any one of claims 1 to 11, wherein the structural repeat units of the elastomeric matrix of layer a are greater than 90 mole percent hydrocarbon-based units.

13. The laminate according to any one of claims 1 to 12, wherein the elastomeric matrix of layer a contains 100phr of an elastomer selected from the group consisting of polybutadiene, polyisoprene, butadiene copolymers, isoprene copolymers and mixtures thereof.

14. The laminate according to any one of claims 1 to 13, wherein the elastomeric matrix of layer a contains 100phr of a high cis content polyisoprene with a degree of 1, 4-cis bonding of more than 90%, preferably 100phr of natural rubber.

15. The laminate of any one of claims 1 to 14, wherein for i from 1 to n-1,

i. the content of highly saturated diene elastomer in the layer Ci is higher than that in the layer Ci +1,

the content of polar elastomer in the layer Ci is lower than that in the layer Ci +1,

the content of polar elastomer in layer B is higher than in layer Cn.

16. The laminate of any one of claims 1 to 15, wherein the elastomeric matrix of layer C1 contains greater than 50 mole% of ethylene units.

17. The laminate of any one of claims 1 to 16, wherein the elastomeric matrix of layer C1 contains greater than 50phr of a highly saturated diene elastomer.

18. The laminate according to any one of claims 1 to 17, wherein the elastomeric matrix of layer B contains more than 50phr of a polar elastomer, preferably more than 90phr of a polar elastomer.

19. The laminate according to any one of claims 1 to 18, wherein the content of polar elastomer in layer B is 100 phr.

20. The laminate of any one of claims 1 to 19, wherein the elastomeric matrix of the layer Cn contains more than 50phr of a polar elastomer.

21. The elastomeric laminate of any one of claims 1 to 20, wherein any one of, preferably all of, layer a, layer B and layer Ci comprises a reinforcing filler, preferably carbon black or silica or a mixture of carbon black and silica, i being from 1 to n.

22. The elastomeric laminate of any one of claims 1 to 21, wherein any one of layer a, layer B and layer Ci, preferably all, comprises a crosslinking system, i being from 1 to n.

23. The elastomeric laminate according to any one of claims 1 to 22, wherein each of the n layers contains at most 20phr, preferably less than 10phr, of plasticizer.

24. The elastomeric laminate of any one of claims 1 to 22, wherein any one, preferably all, of the n layers does not comprise a plasticizer.

25. The laminate of any one of claims 1 to 24, wherein n is equal to 2.

26. Use of the elastomeric laminate as defined in any one of claims 1 to 25 in a tire.

27. A tire comprising a tread, two sidewalls, two beads, a carcass reinforcement passing through the two sidewalls and anchored to the two beads, and a crown reinforcement arranged circumferentially between the tread and the carcass reinforcement, the tire comprising the elastomeric laminate of any one of claims 1 to 25.

28. The tire of claim 27, wherein layer B of the elastomeric laminate comprises a portion or all of a tire tread and layer C of the elastomeric laminate comprises a portion or all of an undertread.

29. Adhesive laminate, with i ranging from 2 to n-1, wherein n is greater than or equal to 2, consisting of a layer C1, a layer Cn and a layer Ci as defined in claims 1 to 25, apart from the fact that the layer C1 and the layer Cn have a single interface with one layer, respectively with the layer C2 and the layer Cn-1.

30. Use of an adhesive laminate as defined in claim 29 for bonding two layers a 'and B' having the same composition to a layer a and a layer B, respectively, as defined in any one of claims 1 to 25 by applying layer C1 to layer a 'and layer Cn to layer B'.