FR3058677A1 - PNEUMATIC READY TO RECEIVE AN ORGAN ON ITS SURFACE - Google Patents

Abstract

The invention relates to a tire having an inner and / or outer surface with a receiving area, an adhesive part disposed on said receiving area and a unitary protective film or a stack of protective films arranged on said adhesive portion, characterized in that the protective film or the stack of protective films represents a rigidity and a thickness such that the equation (E1) is satisfied, equation (E1) in which: Ei represents the modulus of Young of a film i in GPa, hi represents the thickness of a film i in mm.

Description

Holder (s): COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN Limited partnership with shares, MICHELIN RECHERCHE ET TECHNIQUE S.A. Limited company.

Extension request (s)

Agent (s): MANUFACTURE FRANÇAISE DES PNEUMATIQUES MICHELIN.

TIRE READY TO RECEIVE AN ORGAN AT ITS SURFACE.

FR 3 058 677 - A1 (5 /) The invention relates to a tire comprising an internal and / or external surface with a reception zone, an adhesive part disposed on said reception zone and a unitary protective film or a stack protective films, arranged on said adhesive part, characterized in that the protective film or the stack of protective films represents a rigidity and a thickness such that the equation (E1) is verified,

Σ (^. / Ι ³ )> 0.4 (El) equation (1 = 1) in which:

E, represents the Young's modulus of a film i in GPa, h, represents the thickness of a film i in mm.

The present invention relates to tires, and more particularly to tires ready to receive a member, for example electronic, fixed to their inner and / or outer surface.

The recent development of tire pressure monitoring systems for a running vehicle (in English "Tire Pressure Monitoring Systems" or "TPMS") is limited by the difficulty of quickly and lastingly fixing an object to the surface of a tire.

Document US2012 / 0248274 proposes a tire comprising an interior and / or exterior surface with a reception area, an adhesive layer disposed on this reception area and a protective film disposed on the adhesive layer, in which the adhesive layer consists of a fabric embedded in a thermoplastic material. This document gives no indication as to the nature of the materials usable for the protective film.

[0004] Also, the document EPI070580 proposes a tire comprising an interior and / or exterior surface with a reception area, an adhesive strip placed on this reception area and a protective film placed on the adhesive strip before its use, to fix an object inside the tire via the use of acrylic adhesive tapes, requiring the handling of these acrylic adhesive tapes both in the tire and on the object to be fixed. The protective film used is a polyester film.

Finally, document WO2016 / 097257 describes a tire comprising an interior and / or exterior surface with a reception area, an adhesive layer comprising a saturated thermoplastic elastomer (TPE), disposed on this reception area and a film. 25 µm protection of a fluorinated ethylene-propylene copolymer (FEP).

Given the applications under development which are based on the attachment of objects, in particular electronic on tires, it is advantageous for manufacturers to develop fastening solutions which are quick, efficient and durable, while being striving to have a simple and economical manufacture of tires capable of receiving these

-2 fixed objects. In particular, it is advantageous to satisfy these conditions of ease of use with regard to the protective film used on the reception area of the tire, by allowing easier handling of the tire provided with the protective film, including during its exit from the baking mold, and also easy removal of the film, without deformation of the surface of the reception area under the protective film.

The invention relates to a tire comprising an interior and / or exterior surface with a reception area, an adhesive portion disposed on said reception area and a unitary protection film or a stack of protection films, disposed on said adhesive part, characterized in that the protective fdm or the stack of protective fdms represents a rigidity and a thickness such that the equation (El) is verified,

Σ (Ε _ί ./ι _ί ³ )> 0.4 (El) equation (El) in which:

Ej represents the Young's modulus of a film i in GPa, hj represents the thickness of a film i in mm.

The use of such a protective fdm has the advantage of making it possible not to deform the adhesive layer or the adhesive strip (for example by creating bubbles in the layer) during the manufacture of the tire and in particular during the removal of the tire from the baking mold, and in particular during the operation of removing the baking membrane at the end of baking; or when removing the protective film. During these operations, the reception area of the tire of the invention must separate from the baking membrane of the mold, and the protective film must separate from the reception area, without the reception area not is degraded. Thus, with the specific protective film of the invention, this separation of the protective film from the reception area and from the curing membrane is optimal, whether at the temperature at which the tire cures, which temperature can vary according to the nature and dimensions of the tire, as well known to those skilled in the art, and which can in particular be 150 ° C. or 175 ° C., or at ambient temperature, temperature at which the film

-3 protection can be removed from the reception area. Also, this removal of the protective film facilitated and without deformation of the adhesive part (adhesive strip or adhesive layer of TPE) makes it possible to ensure good adhesion of the object (or organ) to the tire, even when hot during the use of tires.

Another object of the invention is a method of fixing a member provided with a fixing zone, to the surface of a tire according to the invention described above, in which:

- all or part of the protective film is removed;

if the tire includes an adhesive layer as an adhesive part, the adhesive layer is brought to a temperature higher than the softening temperature of the thermoplastic blocks of the block thermoplastic elastomer (s);

the contact area of the member and the adhesive part of the tire are brought into contact, by applying pressure.

The fixing of the organ is thus carried out very quickly and very simply. In particular, the removal of the protective fdm is easy and does not deform the adhesive part of the tire.

The invention relates more particularly to tires intended to equip motor vehicles of the touring type, SUV ("Sports Utility Vehicles"), two wheels (in particular motorcycles), airplanes, such as industrial vehicles chosen from vans, "Weight "heavy" - ie metro, bus, road transport equipment (trucks, tractors, trailers), off-road vehicles such as agricultural or civil engineering vehicles -, other transport or transport vehicles handling.

Detailed description of the invention In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by mass.

-4 By "one" means "one or more", for example, "a thermoplastic elastomer" is equivalent to "one or more thermoplastic elastomers".

On the other hand, any range of values designated by the expression "between a and b" represents the range of values ranging from more than a to less than b (that is to say limits a and b excluded ) while any range of values designated by the expression "from a to b" means the range of values from a to b (ie including the strict bounds a and b).

The details of the invention will be explained below by the description, firstly, of the specific constituents of the tire according to one of the objects of the invention, then by the description of the method of manufacturing the tire and characterization tests performed.

The tire according to the invention has the essential characteristics of having an interior and / or exterior surface with a reception area, an adhesive portion disposed on said reception area and a protective fdm or a stack of films of protection, arranged on said adhesive part, characterized in that the protective film or the stack of protective films have rigidities and thicknesses such as equation (El).

Reception area of the tire The tire of the invention has an interior and / or exterior surface with a reception area on which an adhesive part is disposed and a protective film disposed on said adhesive part.

According to a preferred arrangement of the invention, the reception area may consist only of said adhesive part, and, when it is in place, of the protective film.

According to another preferred arrangement of the invention, the reception area further comprises a layer, noted as an under-layer, positioned between the adhesive part and the interior and / or exterior surface of the tire carrying the reception area. .

The adhesive part can be an adhesive strip, or an adhesive layer, the composition of which comprises a thermoplastic elastomer (TPE), these two embodiments being preferred.

The preferences concerning the adhesive strip and adhesive layer, the composition of which comprises a thermoplastic elastomer (TPE) are described in detail below.

Composition of the adhesive layer of the tire The adhesive layer of the tire according to the invention preferably comprises a thermoplastic block elastomer (TPE) as defined below, with all the preferences and all the embodiments.

The TPE elastomer (s) can alone constitute an adhesive layer composition of the tire.

Optionally, the presence of the polyphenylene ether in the adhesive composition could increase the temperature viscosity of the adhesive composition and thus penalize the interpenetration of the adhesive layer and the rubbery layer of the tire surface, limiting the adhesion of these two layers. However, very surprisingly, on the contrary, there is an improvement in adhesion at operating temperatures below 100 ° C.

In a minority, the composition of the adhesive layer may comprise a usual diene elastomer such as an SBR, a polybutadiene or a natural or synthetic polyisoprene. Very preferably, the level of diene elastomer in the composition is less than 20 parts per hundred parts by mass of elastomers of the composition (phr). Of course, the TPE (s) of the composition are taken into account in the elastomers of the composition.

In addition, according to a preferred embodiment of the invention, the composition of the adhesive layer may also include, as plasticizer, an extension oil

-6 (or plasticizing oil) whose function is to facilitate the placing of the adhesive layer and the fixing layer of the member, in particular by lowering the module and increasing the tackifying power.

One can use any extension oil, weakly polar in character, capable of extending, plasticizing elastomers, in particular thermoplastics. At room temperature (23 ° C), these oils, more or less viscous, are liquids (that is to say, substances having the capacity to eventually take the form of their container), by contrast in particular to resins or rubbers which are by nature solid.

Preferably, the extension oil is chosen from the group consisting of polyolefin oils (that is to say derived from the polymerization of olefins, monoolefins or diolefins), paraffinic oils, naphthenic oils (low or high viscosity), aromatic oils, mineral oils, and mixtures of these oils. A person skilled in the art will be able to adjust the nature and the amount of extension oil according to the particular conditions of use of the adhesive layer.

Preferably an oil of the liquid isoprene rubber type (“LIR”) is used. For example, the LIR 30 and 50, respectively of number average molecular weights of 30,000 and 50,000 g / mol, are sold by Kuraray.

The composition of the adhesive layer may also include the various additives usually present in compositions based on block thermoplastic elastomers known to those skilled in the art. Examples that may be mentioned are reinforcing fillers such as carbon black or silica, non-reinforcing or inert or even fibrillar fillers, coloring agents advantageously usable for coloring the composition, plasticizers other than the aforementioned extension oils , tackifying resins, protective agents such as antioxidants or antiozonants, anti-UV, various implementing agents or other stabilizers, or alternatively promoters capable of promoting adhesion to the rest of the structure of the tire.

-7 The use of tackifying resins can be particularly advantageous for adjusting the softening temperatures as well as the necessary levels of adhesion of the adhesive or fixing layers.

Thermoplastic elastomer Thermoplastic elastomers (abbreviated as "TPE") have an intermediate structure between thermoplastic polymers and elastomers. These are block copolymers, made up of rigid, thermoplastic blocks, connected by flexible, elastomeric blocks.

The thermoplastic elastomer used for the implementation of the invention is a block copolymer whose chemical nature of the thermoplastic blocks and elastomer blocks can vary, and which can optionally be functionalized, that is to say carrying a reactive chemical function.

Structure of the TPE The number-average molecular mass (denoted Mn) of the TPE is preferably between 30,000 and 500,000 g / mol, more preferably between 40,000 and 400,000 g / mol. Below the minimums indicated, the cohesion between the TPE elastomer chains, in particular due to its possible dilution (in the presence of an extension oil), is likely to be affected; on the other hand, an increase in the temperature of use risks affecting the mechanical properties, in particular the properties at break, with the consequence of a reduced performance when hot. Furthermore, an excessively high mass Mn can be penalizing for the implementation. Thus, it has been found that a value within a range of 50,000 to 300,000 g / mol is particularly well suited, in particular to the use of TPE in a composition for a tire tread.

The number-average molecular mass (Mn) of the TPE elastomer is determined in known manner, by size exclusion chromatography (SEC). For example, in the case of styrenic thermoplastic elastomers, the sample is dissolved beforehand in

-8 tetrahydrofuran at a concentration of about 1 g / 1; then the solution is filtered through a filter with a porosity of 0.45 μm before injection. The equipment used is a "WATERS alliance" chromatographic chain. The elution solvent is tetrahydrofuran, the flow rate of 0.7 ml / min, the system temperature of 35 ° C and the analysis time of 90 min. We use a set of four WATERS columns in series, with trade names "STYRAGEL" ("HMW7", "HMW6E" and two "HT6E"). The volume injected with the polymer sample solution is 100 µl. The detector is a "WATERS 2410" differential refractometer and its associated software for processing chromatographic data is the "WATERS MILLENIUM" system. The calculated average molar masses are relative to a calibration curve carried out with polystyrene standards. The conditions are adaptable by a person skilled in the art.

The value of the polydispersity index Ip (reminder: Ip = Mw / Mn with Mw weight average molecular weight and Mn number average molecular weight) of the TPE is preferably less than 3; more preferably less than 2 and even more preferably less than 1.5.

In known manner, the TPEs have two glass transition temperature peaks (Tg, measured according to ASTM D3418), the lowest temperature being relative to the elastomer part of the TPE, and the highest temperature being relating to the thermoplastic part of TPE. Thus, the flexible blocks of TPEs are defined by a Tg lower than ambient temperature (25 ° C), while the rigid blocks have a Tg greater than 80 ° C.

In the present application, when reference is made to the glass transition temperature of the TPE, it is the Tg relating to the elastomer block. The TPE preferably has a glass transition temperature (Tg) which is preferably less than or equal to 25 ° C, more preferably less than or equal to 10 ° C. A value of

Tg greater than these minima can reduce the performance of the tread when used at very low temperatures; for such use, the Tg of TPE is more

-9 preferably still less than or equal to -10 ° C. Also preferably, the Tg of the TPE is greater than -100 ° C.

To be both elastomeric and thermoplastic in nature, the TPE must be provided with sufficiently incompatible blocks (that is to say different due to their mass, their polarity or their respective Tg) to keep their specific properties of elastomeric or thermoplastic block.

The TPEs can be copolymers with a small number of blocks (less than 5, typically 2 or 3), in which case these blocks preferably have high masses, greater than 15000 g / mol. These TPEs can be, for example, diblock copolymers, comprising a thermoplastic block and an elastomer block. They are also often triblock elastomers with two rigid segments connected by a flexible segment. The rigid and flexible segments can be arranged linearly, in a star or branched. Typically, each of these segments or blocks often contains at least more than 5, generally more than 10 base units (for example styrene units and butadiene units for a styrene / butadiene / styrene block copolymer).

The TPEs can also include a large number of smaller blocks (more than 30, typically from 50 to 500), in which case these blocks preferably have low masses, for example from 500 to 5000 g / mol, these TPE will be called multiblock TPE afterwards, and are a chain of elastomeric blocks - thermoplastic blocks.

According to a first variant, the TPE is in a linear form. For example, TPE is a diblock copolymer: thermoplastic block / elastomer block. The TPE can also be a triblock copolymer: thermoplastic block / elastomer block / thermoplastic block, that is to say a central elastomer block and two terminal thermoplastic blocks, at each of the two ends of the elastomer block. Also, the multiblock TPE can be a linear sequence of elastomeric blocks - thermoplastic blocks.

According to another variant of the invention, the TPE useful for the needs of the invention is in a star shape with at least three branches. For example, the TPE can then

-10 consist of a star-shaped elastomer block with at least three branches and a thermoplastic block, located at the end of each of the branches of the elastomer block. The number of branches of the central elastomer can vary, for example from 3 to 12, and preferably from 3 to

6.

According to another variant of the invention, the TPE is in a branched or dendrimer form. The TPE can then consist of a branched elastomer block or dendrimer and a thermoplastic block, located at the end of the branches of the elastomer dendrimer block.

Nature of the Elastomeric Blocks The elastomeric blocks of the TPE for the purposes of the invention may be any of the elastomers known to those skilled in the art. They preferably have a Tg of less than 25 ° C, preferably of less than 10 ° C, more preferably of less than 0 ° C and very preferably of less than -10 ° C. Also preferably, the Tg elastomer block of the TPE is greater than -100 ° C.

For elastomer blocks with a carbon chain, if the elastomer part of the TPE does not contain ethylenic unsaturation or comprises a molar level of unsaturated units of less than 10%, preferably less than 5% and more preferably less than 2% relatively to all of the patterns of the elastomer block, we will speak of a saturated or essentially saturated elastomer block. If the elastomer block of TPE contains 10 mol% and more of ethylenic unsaturations (that is to say carbon-carbon double bonds), we will then speak of an unsaturated or diene elastomer block.

A saturated elastomer block consists of a polymer block obtained by the polymerization of at least one (that is to say one or more) ethylenic monomer, that is to say comprising a double bond carbon - carbon. Among the blocks originating from these ethylenic monomers, mention may be made of polyalkylene blocks such as random ethylene-propylene or ethylene-butylene copolymers, mention may also be made in particular of polyisobutylenes, polyethylenes, polypropylenes, polybutylenes as preferential for the needs of the invention. These preferred saturated elastomer blocks

they can also be obtained by hydrogenation of unsaturated elastomeric blocks. Also preferably, it may also be aliphatic blocks from the family of polyethers, polyesters, or polycarbonates, and in particular polyethers.

An unsaturated elastomer block consists of a polymer block obtained by the polymerization of at least one (that is to say one or more) diene monomers conjugated to C4 - Cm, the latter being able to be copolymerized with vinyl aromatic monomers. In this case, these are random copolymers. Preferably, these conjugated dienes are chosen from the group consisting of isoprene, butadiene, isoprene copolymers, butadiene copolymers and their mixtures. In this context, the isoprene copolymers and the butadiene copolymers are preferably and respectively copolymers of isoprene and styrene and copolymers of butadiene and styrene.

According to a preferred embodiment of the invention, the elastomeric blocks of TPE have in total a number-average molecular mass (Mn) ranging from 25,000 g / mol to 350,000 g / mol, preferably 35,000 g / mol to 250,000 g / mol so as to give the TPE good elastomeric properties and sufficient mechanical strength compatible with the use in tires.

The elastomer block can also be made up of several elastomer blocks as defined above.

Nature of the thermoplastic blocks The glass transition temperature (Tg) characteristic of the rigid thermoplastic block will be used for the definition of the thermoplastic blocks. This characteristic is well known to those skilled in the art. It allows in particular to choose the temperature of industrial implementation (transformation). In the case of an amorphous polymer (or block of polymer), the processing temperature is chosen to be substantially higher than the Tg. In the specific case of a semi-polymer (or block of polymer) -crystalline, one can observe a melting temperature then higher than the glass transition temperature. In this case, it is rather the melting temperature (Tf) which makes it possible to choose the setting temperature

- 12work of the polymer (or polymer block) considered. So, later, when we talk about "Tg (or Tf, if applicable)", it will be necessary to consider that this is the temperature used to choose the processing temperature.

For the purposes of the invention, the TPE elastomers comprise one or more thermoplastic block (s) preferably having a Tg (or Tf, if applicable) greater than or equal to 80 ° C. and constituted (s) ) from polymerized monomers. Preferably, this thermoplastic block has a Tg (or Tf, if applicable) comprised in a range varying from 80 ° C to 250 ° C. Preferably, the Tg (or Tf, if applicable) of this thermoplastic block is preferably from 80 ° C to 200 ° C, more preferably from 80 ° C to 180 ° C.

The proportion of the thermoplastic blocks relative to the TPE, as defined for the implementation of the invention, is determined on the one hand by the thermoplastic properties that said copolymer must have. The thermoplastic blocks having a Tg (or Tf, where appropriate) greater than or equal to 80 ° C. are preferably present in sufficient proportions to preserve the thermoplastic nature of the elastomer according to the invention. The minimum level of thermoplastic blocks having a Tg (or Tf, if applicable) greater than or equal to 80 ° C. in the TPE can vary depending on the conditions of use of the copolymer. On the other hand, the capacity of the TPE to deform during the preparation of the tire can also contribute to determining the proportion of the thermoplastic blocks having a Tg (or Tf, if applicable) greater than or equal to 80 ° C.

Thermoplastic blocks having a Tg (or Tf, where appropriate) greater than or equal to 80 ° C can be made from polymerized monomers of various kinds, in particular, they can constitute the following blocks or their mixtures:

polyolefins (polyethylene, polypropylene) polyurethanes;

- polyamides;

polyesters; polyacetals;

- 13 polyethers (polyethylene oxide, polyphenylene ether); phenylene polysulfides; polyfluorinated (FEP, PF A, ETFE); polystyrenes (detailed below);

- polycarbonates;

polysulfones; polymethylmethacrylate polyetherimide thermoplastic copolymers such as acrylonitrile-butadiene10 styrene copolymer (ABS).

Thermoplastic blocks having a Tg (or Tf, where appropriate) greater than or equal to 80 ° C can also be obtained from monomers chosen from the following compounds and their mixtures:

acenaphthylene: a person skilled in the art may for example refer to the article by Z.

Fodor and J.P. Kennedy, Polymer Bulletin 1992 29 (6) 697-705;

indene and its derivatives such as for example 2-methylindene, 3-methylindene, 4methylindene, dimethylindene, 2-phenylindene, 3-phenylindene and 4phenylindene; those skilled in the art may for example refer to patent document US4946899, by the inventors Kennedy, Puskas, Kaszas and Hager and to documents J. E.

Puskas, G. Kaszas, JP Kennedy, WG Hager Journal of Polymer Science Part A: Polymer Chemistry (1992) 30, 41 and JP Kennedy, N. Meguriya, B. Keszler, Macromolecules (1991) 24 (25), 6572-6577 ;

isoprene, then leading to the formation of a number of 1,4-trans polyisoprene units and of cyclized units according to an intramolecular process; those skilled in the art may for example refer to the documents G. Kaszas, J.E. Puskas, .P. Kennedy Applied Polymer Science (1990) 39 (1) 119-144 and J.E. Puskas, G. Kaszas, J.P. Kennedy, Macromolecular Science, Chemistry A28 (1991) 65-80.

- The polystyrenes are preferred thermoplastic blocks for the invention according to a preferred embodiment, and are obtained from styrenic monomers, the TPEs comprising this type of styrenic blocks are then called styrenic thermoplastic elastomers (TPS). By styrenic monomer should be understood in the present description any monomer comprising styrene, unsubstituted as substituted; among the substituted styrenes, mention may be made, for example, of methylstyrenes (for example o-methylstyrene, m-methylstyrene or p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha-4- dimethylstyrene or diphenylethylene), para-tertio-butylstyrene, chlorostyrenes (for example o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,410 dichlorostyrene, 2,6-dichlorostyrene or 2,4, 6-trichlorostyrene), bromostyrenes (for example o-bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene or 2,4,6-tribromostyrene), fluorostyrenes (for example ofluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6difluorostyrene or 2,4,6-trifluorostyrene) or para-hydroxy-styrene.

According to a preferred embodiment of the invention, the weight content of styrene in the TPS elastomer is between 5% and 50%. Below the minimum indicated, the thermoplastic nature of the elastomer may decrease significantly while above the recommended maximum, the elasticity of the tread may be affected. For these reasons, the level of styrene is more preferably between 10% and 40%.

In the preferred embodiments where the TPE is saturated and comprises a thermoplastic block of polystyrene type (TPS), the elastomer block of TPS is chosen from the group consisting of polyisobutylenes, polyethylenes, polypropylenes, polybutylenes, and their mixtures. More preferably, the TPS elastomer block is a polyisobutylene block.

In the preferred embodiments where the TPE is unsaturated and comprises a thermoplastic block of polystyrene type (TPS), the elastomer block of TPS is chosen from the group consisting of polymers based on isoprene, butadiene, copolymers

- 15 statistics of isoprene and styrene and statistical copolymers of butadiene and styrene and their mixtures.

Also preferably according to the invention, the TPE thermoplastic blocks are non-styrenic blocks, chosen from polyamide blocks, polyesters, and mixtures thereof. Very preferably in this embodiment of the invention, the thermoplastic blocks are chosen from the group consisting of polyamides of type PA6, PA11 or PA12, or polyesters of type PET or PBT and mixtures of the latter. In this preferred embodiment, the elastomeric blocks essentially consist of polymers chosen from the group consisting of polyisobutylenes, polyethylenes, polypropylenes, polybutylenes, polyethers and their mixtures; preferably in the group of polyethers and their mixtures.

The particular TPEs in which the non-styrenic thermoplastic blocks are polyamides are usually denoted TPE-A or TPA (thermoplastic copolyamide) or PEBA (copolyether block amide), and they are particularly preferred for the purposes of the invention.

The particular TPEs in which the non-styrenic thermoplastic blocks are polyesters are usually denoted TPE-E or TPC (thermoplastic copolyester) or else COPE (ether-ester block copolymer), and they are also particularly preferred for the requirements of the invention. 'invention.

According to the invention, the thermoplastic blocks of TPE have a total number-average molecular mass (Mn) ranging from 5,000 g / mol to 150,000 g / mol, so as to give TPE good elastomeric properties and sufficient mechanical strength compatible with use as a tire tread.

The thermoplastic block can also be made up of several thermoplastic blocks as defined above.

16 Hot viscosity of TPE The dynamic hot viscosity (η) of TPE is measured using an apparatus allowing the measurement of the viscoelastic properties of polymers and rubbers, the Rubber Process Analyzer 2000 from Alpha Technologies. The samples are prepared by hot transformation in a press between 150 ° C and 180 ° C depending on the material, for 3 minutes at 1.5 bar pressure in a sheet of silicone release paper. A viscosity measurement according to a temperature sweep is carried out on a 5 g sample according to the following protocol. The sample is molded in the air gap for 1 min at 180 ° C after which the temperature is lowered to 40 ° C. Starts scanning at 40 ° C

200 ° C under a stress frequency of 10 Hz with an imposed angle deformation of

5%. The dynamic viscosity values at 150 ° C and 175 ° C are then noted on the rheogram obtained.

This hot viscosity of the TPEs is variable, in particular according to the molecular mass, the polydispersity index, the connection rate, the length ratio of the elastomer blocks / thermoplastic blocks, the nature of the monomers constituting the blocks. Some viscosities of commercially available TPE are given for example in the table below.

Viscosity at 150 ° C Viscosity at 175 ° C SIS (1) 1000 Pa.s 1800 Pa.s SIS (2) 1000 Pa.s 1800 Pa.s PEBA (2) 2200 Pa.s 1000 Pa.s SEBS (3) 5000 Pa.s 3500 Pa.s

(1) SIS "Dl 161" from Kraton (2) SIS "Dl 163" from Kraton

- 17 (3) ΡΕΒΑ "Pebax 3533" from the company Arkema (4) SEBS-MA "FG1901" from the company Kraton, functional methacrylate Preferably, whatever the structure and chemical nature of TPE, such as described above, the TPE used for the adhesive layer of the tire (and also preferably used for the fixing layer of the member), has a viscosity greater than 2000 Pa.s at the baking temperature of the tire, in particular 150 ° C or 175 ° C.

Preferably, the viscosity is greater than 2200 Pa.s at the baking temperature of the tire, in particular at 150 ° C or 175 ° C.

More preferably, the viscosity is greater than 3000 Pa.s at the tire curing temperature, in particular at 150 ° C or 175 ° C.

Examples of TPE For example, TPE is a copolymer in which the elastomer part is saturated, and comprising styrene blocks and alkylene blocks. The alkylene blocks are preferably ethylene, propylene or butylene. More preferably, this TPE elastomer is chosen from the following group, consisting of diblock, linear or star triblock copolymers: styrene / ethylene / butylene (SEB), styrene / ethylene / propylene (SEP), styrene / ethylene / ethylene / propylene (SEEP) ), styrene / ethylene / butylene / styrene (SEB S), styrene / ethylene / propylene / styrene (SEPS), styrene / ethylene / ethylene / propylene / styrene (SEEPS), styrene / isobutylene (SIB), styrene / isobutylene / styrene (SIBS) and mixtures of these copolymers. These TPEs can also carry reactive functions, such as methacrylate groups as in the case of styrene / ethylene / butylene / styrene copolymers functionalized methacrylate (SEBS-MA).

For example also, the TPE is a copolymer whose elastomer part is unsaturated, and which comprises diene blocks and advantageously styrene blocks, these diene blocks being in particular isoprene or butadiene blocks. More preferably, this

- 18 TPS elastomer is chosen from the following group, consisting of diblock, linear or star triblock copolymers: styrene / butadiene (SB), styrene / isoprene (SI), styrene / butadiene / isoprene (SBI), styrene / butadiene / styrene ( SBS), styrene / isoprene / styrene (SIS), styrene / butadiene / isoprene / styrene (SBIS) and mixtures of these copolymers.

Among the multiblock TPEs, mention may be made of copolymers comprising random copolymer blocks of ethylene and propylene / polypropylene, polyether / polyester (COPE), polyether / polyamide (PEBA).

It is also possible that the TPEs given in the example above are mixed together within the tread according to the invention.

As examples of commercially available saturated or essentially saturated TPE elastomers, mention may be made of the elastomers of the SEPS, SEEPS or SEBS type marketed by the company Kraton under the name Kraton G (eg products G1650, G1651, G1654 , G1730) or the company Kuraray under the name Septon (eg "Septon 2007", "Septon 4033", "Septon 8004"). Mention may also be made of the elastomers of the SEBS-MA type marketed by the company Kraton under the trade names “FG1901” or “FG1924”, or the elastomers of the SIBS type marketed by the company Kaneka under the trade name “SIBSTAR” (eg “ SIBSTAR 102T ";" SIBSTAR 103T "). Among the multiblock TPEs, there may be mentioned the “Vistamaxx” TPE marketed by the company Exxon; TPE COPE marketed by DSM under the name "Arnitel", or by Dupont under the name "Hytrel", or by Ticona under the name "Riteflex"; PEPE PEBA marketed by Arkema under the name "PEBAX" (e.g. "PEBAX 3533").

- 19 Miscellaneous additives The composition of the adhesive layer can optionally comprise, in combination with the TPE elastomer previously described, at least one polyphenylene ether (abbreviated as "PPE").

PPEs are well known to those skilled in the art, they are resins that are solid at room temperature (23 ° C.) compatible with styrenic polymers, which are used in particular to increase the Tg of TPS elastomers (see for example "Thermal, Mechanical and Morphological Analyzes of Poly (2,6-dimethyl-1,4-phenylene oxide) / Styrene-ButadieneStyrene Blends", Tucker, Barlow and Paul, Macromolecules, 1988, 21, 1678-1685).

Preferably, the PPE used here has a glass transition temperature (hereinafter referred to as Tg) which is greater than 150 ° C., more preferably greater than 180 ° C. As for its number-average molecular mass (Mn), it is preferably between 5,000 and 100,000 g / mol.

The number-average molecular mass (Mn) is determined in a known manner, by size exclusion chromatography (SEC). The sample is dissolved beforehand in tetrahydrofuran at a concentration of approximately 1 g / 1; then the solution is filtered on a filter with a porosity of 0.45 μm before injection. The equipment used is a "WATERS alliance" chromatographic chain. The eluting solvent is tetrahydrofuran, the flow rate of 0.7 ml / min, the system temperature of 35 ° C and the analysis time of 90 min. We use a set of four WATERS columns in series, with trade names "STYRAGEL" ("HMW7", "HMW6E" and two "HT6E"). The volume injected with the polymer sample solution is 100 μΐ. The detector is a "WATERS 2410" differential refractometer and its associated software for processing chromatographic data is the "WATERS MILLENIUM" system. The calculated average molar masses are relative to a calibration curve carried out with polystyrene standards.

As non-limiting examples of PPE polymers which can be used in the waterproof composition according to an object of the invention, mention may in particular be made of those chosen from the group consisting of poly (2,6-dimethyl-1, 4-phenylene-ether), poly (2,6-dimethyl-co-2,3,6trimethyl-1,4- phenylene-ether), poly- (2,3,6-trimethyl-1,4-phenylene-ether ), poly (2,6-diethyl5 1,4- phenylene ether), poly (2-methyl-6-ethyl-l, 4-phenylene-ether), poly (2-methyl-6-propyl1,4-phenylene -ether), poly- (2,6-dipropyl-1,4-phenylene ether), poly (2-ethyl-6-propyl-1,4phenylene ether), poly (2,6-dilauryl-1,4 - phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly (2,6-dimethoxy-1,4-phenylene ether), poly (1,6-diethoxy-1,4) phenylene ether), poly (2-methoxy-6-ethoxy-1,4-phenylene ether), poly (2-ethyl-6-stearyloxy-1,4-phenylene10 ether), poly (2,6-dichloro- 1,4-phenylene ether), poly (2-methyl- 6-phenyl-1,4-phenylene ether), poly (2-ethoxy-l , 4-phenylene-ether), poly (2-chloro-1,4-phenylene-ether), poly (2,6dibromo-1,4- phenylene-ether), poly (3-bromo-2,6-dimethyl- 1,4-phenylene ether), their respective copolymers, and mixtures of these homopolymers or copolymers.

According to a particular and preferred embodiment, the PPE used is poly (2,6-dimethyl-1,4-phenylene-ether). Such commercially available PPEs are, for example, "Xyron S202" from the company Asahi Kasei, or "Noryl S Al 20" from the company Sabic.

Band-Aid

The adhesive tape 'used as a fixing zone on the member or as an adhesive part on the tire), can be any type of known adhesive tape, sometimes called "scotch" ("tape" in English) or PSA ("Pressure Sensitive" Adhesive ”).

As known to those skilled in the art of adhesives, the term "Pressure Sensitive Adhesive" is used to designate materials which are intrinsically tacky or which have been made tacky by the addition of tackifying resins. There are several methods to identify a PSA, including the following three:

-21- a PSA can be described by the Dahlquist criteria from the mechanical and viscoelastic point of view,

- a PSA is a material which has tackiness (or "tack") permanently and aggressively at room temperature and strongly adheres to various surfaces by simple contact without the need for pressure greater than that applicable by hand,

- a PSA is a material whose conservation modulus is between 0.02 MPa and 0.04 MPa at a frequency of 0.1 rad / s (0.017Hz) and 0.2 MPa at 0.8 MPa at a frequency of 100 rad / s (17Hz).

Preferably for the invention, an adhesive tape is used

PSA says "acrylic", known to those skilled in the art ("Technology of Pressure Sensitive Adhesives and Products", by I.Benedek and M.F. Feldstein, chapter 5 "Acrylic adhesives" by

P.B.Foreman) comprising 50 to 100% by mass of so-called “primary” monomers. These monomers are acrylic acid esters obtained with primary or secondary alcohols, the alkyl parts of which are C4-C20, and preferably these monomers are chosen from the group consisting of 2-ethylhexylacrylate, iso-octyl acrylate, n-butyl acrylate and mixtures thereof. These primary monomers have a low Tg, preferably less than 0 ° C., imparting the soft and tacky nature of the adhesive strip. Optionally, the acrylic composition comprises from 0 to 35% by mass of so-called “secondary” monomers, of Tg greater than 0 ° C. which are known to those skilled in the art and preferably chosen from the group consisting of methyl acrylate, methyl methacrylate, vinyl acetate, styrene and their mixtures. More preferably, methyl acrylate is used. These secondary monomers make it possible to improve the cohesion of the adhesive mass. They have the effect of increasing the modulus and the Tg. Optionally, the acrylic composition comprises from 0 to 15% of polar and functional monomers, which can be of any type other than the primary and secondary monomers previously described. Preferably, these monomers are chosen from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl acrylate, acrylamides (such as

-22butyl acrylamide or octyl acrylamide), methacrylamides, N-vinyl pyrrolidone, Nvinyl caprolactam and their mixtures. More preferably, acrylic acid is used. These monomers can increase adhesion by setting up Van der Waals-type interactions on polar supports. On the other hand, they can also contribute to the cohesion of the mass by dipole-dipole interactions or hydrogen bridges.

The adhesive strip may in particular be foamed, that is to say obtained by the dispersion of a gas in a condensed phase, whether the gas phase is supplied directly or by means of solids (gas-generating compounds , expandable polymer beads, glass microbeads). It may for example be a crosslinked acrylic foam taken between two crosslinked acrylic adhesive masses, the foam effect being obtained by the use of glass microbeads. The main methods of obtaining “foamed” PSAs are therefore for example the direct injection of gas, the addition of expandable polymer microspheres, the addition of glass microbeads (porous or not), the addition of foaming agents chemicals, solvent evaporation.

PSAs known under the designation "VHB" (Very High Bond) are offered by the company 3M, are conformable to non-planar surfaces and can be used for the needs of the invention, such as for example "VHB4955". "VHB" high performance adhesive tapes are assembly tapes made of a homogeneous mass of foamed acrylic adhesive. Traditionally used in construction, they offer high adhesion on a variety of substrates and offer thicknesses up to 3 mm. The stress being distributed over the entire thickness, these products absorb a maximum of energy during shocks, vibrations, or mechanical stresses. They are indicated for applications with flatness or roughness defects as well as for outdoor applications and requiring sealing.

-23 Protective film The protective film or the stack of protective films for the needs of the invention has a rigidity and a thickness such that the equation (El) is verified,

Σ (Ε _ί ./ι?)>0,4 (El) equation (El) in which:

Ej represents the Young's modulus of a film i (constituting the stack of protective films or, where appropriate, only protective film) in GPa, hj represents the thickness of a film i (constituting the stack of protective films or, where appropriate, single protective film) in mm.

Preferably, said reception area comprises a unitary protective film, disposed on said adhesive part having a rigidity and a thickness such that the equation (E2) is verified,

E * h ³ > 0.4 (E2) equation (E2) in which:

- E represents the Young's modulus of the film in GPa, h represents the thickness of the film in mm.

The equations El and E2 represent the fact that the more rigid a material, the less the thickness will have to be important for the film to be usable for the invention. Table 1 below provides some examples of materials and the thickness required depending on their Young's modulus.

Table 1

Young's module minimum unit thickness PTFE 0.5 GPa 0.93mm Aluminum 69 GPa 0.18mm Brass 110 GPa 0.15mm Fiberglass 69 GPa 0.18mm

The skilled person will understand that the minimum unit thickness indicated in Table 1 represents the case where the protective film is a single film, unit. This unit film thickness can be lower in the case of a stack of films, provided that the equation (El) is verified.

Table 2 below provides some examples of minimum Young's modulus to be used depending on the thickness desired for a unitary film.

Table 2

thickness desired Minimum Young's Modulus 1 mm 0.4 Gpa 0.5mm 3.2 Gpa 0.25mm 25.6 Gpa

Thus, preferably, the Young's modulus of the material of the unitary protective film or of at least one of the films in the stack of protective films is greater than 0.4 GPa so as to be able to use layers less than 1mm thick. Preferably, in particular for very thin protective films, it will be preferable to use materials in the unitary protective film or in at least one of the films in the stack of protective films, which have a Young modulus greater than 25 , 6 GPa.

According to a preferred embodiment, the reception area comprises a stack of protective films having a rigidity and a thickness such that the equation (Elbis) is verified,

Σ (£; Λ ^? )> 1 (Elbis) equation (Elbis) in which:

Ej represents the Young's modulus of a film i (constituting the stack of protective films or, where appropriate, only protective film) in GPa,

-25 hj represents the thickness of a film i (constituting the stack of protective films or, where appropriate, single protective film) in mm.

[0092] Preferably according to another embodiment, the reception area comprises a unitary protective film having a rigidity and a thickness such that the equation (E2bis) is verified,

E * h ³ > 1 (E2bis) equation (E2bis) in which:

E represents the Young's modulus of the film in GPa, h represents the thickness of the film in mm.

The Ibis table below provides some examples of materials and the thickness required as a function of their Young's modulus according to the preferred embodiment.

Ibis painting

Young's module minimum unit thickness PTFE 0.5 GPa 1.26mm Aluminum 69 GPa 0.24mm Brass 110 GPa 0.21mm Fiberglass 69 GPa 0.24mm

Table 2bis below provides some examples of minimum Young's modulus to be used as a function of the thickness desired for a unitary film, according to the preferred embodiment.

Table 2bis

thickness desired Minimum Young's Modulus 1 mm 1 Gpa 0.5mm 8 Gpa 0.25mm 64 Gpa

Preferably, said unitary protection film is an aluminum film or a canvas comprising glass fibers and more preferably an aluminum film.

Alternatively and preferably also, said reception area comprises a stack of protective films. Preferably, said stack comprises at least one aluminum film or a fabric comprising glass fibers, and more preferably an aluminum film.

Still in the embodiment in which said reception zone comprises a stack of protective films, said stack comprises a thermoplastic film in contact with the adhesive part chosen so that the peeling force of said film from the part adhesive is less than 1 N / mm and preferably less than 0.5 N / mm, at 20 ° C. This allows the thermoplastic film to be a flexible heat resistant film which additionally has limited adhesion to the adhesive layer so that it can be easily peeled off.

This thermoplastic film protects the surface of the adhesive layer during tire assembly operations and its vulcanization in the mold.

This thermoplastic film is advantageously chosen from the group of polyesters and films comprising at least one fluoropolymer. A person skilled in the art will know how to choose its thickness to obtain the best compromise between its flexibility and its mechanical strength. This thickness is advantageously between 10 and 300 μm.

The nature of the thermoplastic film may be incompatible with that of the TPE of the adhesive layer to obtain an appropriate limited adhesion.

Preferably, the Tg (or Tf, if applicable) of the thermoplastic film is higher than the baking temperature of the rubber mixture in the reception area of the tire surface. A temperature of 200 ° C for Tg (or Tf, if applicable) allows the film to withstand the usual temperatures for vulcanizing tires for passenger vehicles.

We can choose for example as a thermoplastic polyester film, we can use the films sold under the brand Mylar with a thickness between 0.03 and 0.2 mm. Such polyester fdm has a melting temperature above 230 ° C.

One can choose for example as thermoplastic a film of fluorinated polymers ethylene-propylene fluorinated copolymers (FEP). Advantageously, the fdm comprises a copolymer of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP). These polymers have remarkable anti-sticking properties.

An example of a suitable thermoplastic film is the A5000 film from Aerovac Systèmes France. This fdm contains a fluorinated ethylene-propylene or FEP copolymer. This film has a maximum use temperature of around 204 ° C and has an elongation at break greater than 300%. Its thickness is 25 µm. These characteristics allow it to be placed directly on the tire building drum in the specific case of a reception area placed on the surface of the sealed inner layer of the tire.

The following table indicates examples of thermoplastic films suitable for the invention, in the embodiment where the reception area comprises a stack of protective films.

Denomination Provider nature thickness T max elongation A5000 Aerovac FEP 25 pm 260 ° C > 300% A6000 Aerovac ETFE 12.15 and 20 pm 230 ° C > 200% MR Film Aerovac PTFE 25 pm 315 ° C > 550% FEP100 Dupont FEP 25 pm 260 ° C > 300% FEP100 Dupont FEP 12.5 pm 260 ° C > 300% Norton FEP 0.001 Saint Gobain FEP 25 pm 260 ° C > 300% Norton FEP 0.0005 Saint Gobain FEP 12.5 pm 260 ° C > 300%

In a preferred use, the protective film or the stack of protective films is removed just before placing the member on the surface of the tire to

-28 avoid any pollution of the surface of the adhesive layer. The protective film or the stack of protective films then has the advantage of protecting the adhesive layer during all the transport and storage phases of the tires.

The protective film or the stack of protective films makes it possible to separate the adhesive layer from any contact with the tire manufacturing drum and then with the curing membrane of the vulcanization mold.

The preferentially incompatible nature of the protective film or of the stack of protective films relative to the adhesive layer allows it to be removed from the inner surface of the tire after vulcanization. The removal of this protective film or this stack of protective films restores the adhesive layer to all its properties. The protective film or the stack of protective films can be removed without tearing.

Method for fixing the member to the tire The invention also relates to the fixing of a member provided with a fixing zone, to the surface of a tire as described above and also subject of the invention, in which:

all or part of the protective film is removed;

if the tire has an adhesive layer as an adhesive part, the adhesive layer is brought to a temperature higher than the softening temperature of the thermoplastic blocks of the block thermoplastic elastomer (s);

the contact area of the member and the adhesive part of the tire are brought into contact, by applying pressure.

Manual fixing pressure is sufficient. The fixation of the organ is thus carried out very quickly and very simply. The fixation is effective and lasting. It also has the advantage of being completely reversible.

Organ designed to be fixed to the tire. The organ can be a housing capable of receiving an electronic device. The organ can also be an electronic device. It can also be a marking on the tire or a decoration. The organ is fixed to the tire thanks to the fixing zone present on the organ.

Organ fixing zone The organ fixing zone is an adhesive strip, or a fixing layer, the composition of which comprises a thermoplastic elastomer (TPE).

According to a first preferred embodiment, the attachment zone of the member is a fixing layer, the composition of which comprises one or more thermoplastic elastomer (s) (TPE), said fixing layer being brought to a temperature higher than the softening temperature of the thermoplastic blocks of the block thermoplastic elastomer or elastomers, before contacting with the adhesive zone. All the TPEs as described above for the adhesive layer of the tire can be used and the preferences apply mutatis mutandis.

Preferably, the thermoplastic blocks of the TPEs of the fixing layer are compatible (that is to say similar due to their masses, their polarities or their Tg) with the thermoplastic blocks of the thermoplastic elastomer (s) of the composition of the adhesive layer of the tire. Preferably, the thermoplastic blocks of the TPE (s) of the composition of the fixing layer of the member are identical to the thermoplastic blocks of the TPE (s) of the composition of the adhesive layer of the tire. Very preferably, the TPEs of the fixing and adhesive layers are identical. The composition of the fixing layer of the member may also include saturated or unsaturated diene elastomers, in the minority, oils or various additives as previously described for the adhesive layer of the tire.

According to a second preferred embodiment, the area for fixing the member is an adhesive strip. All the adhesive strips as described above for the adhesive part of the tire can be used and the preferences apply mutatis mutandis. In particular, the adhesive strip can preferably be an acrylic adhesive strip. Also preferably, the adhesive strip can be a foam adhesive strip.

EXAMPLES OF EMBODIMENTS Additional elements of the invention are now described with the aid of the 10 accompanying drawings, presented without limitation, in which:

FIG. 1 very schematically represents (without respecting a specific scale), a radial section of a tire according to an embodiment of the invention;

FIG. 2 shows in partial radial section a tire blank according to an embodiment of the invention;

FIG. 3 illustrates a member with a fixing zone; and FIG. 4 shows the member fixed to the surface of the tire.

Figure 1 schematically shows a radial section of a pneumatic or pneumatic tire incorporating in a reception area 13 given an adhesive portion with a protective film according to an embodiment of the invention. It will be recalled here that another preferred embodiment consists in using a stack of protective films.

This tire 1 has a crown 2 reinforced by a crown reinforcement or belt 6, two sidewalls 3 and two beads 4, each of these beads 4 being reinforced with a bead wire 5. The crown frame 6 is surmounted radially externally of a rubber tread 9. A carcass reinforcement 7 is wound around the two rods 5 in each bead 4, the reversal 8 of this reinforcement 7 being for example

-31 disposed towards the outside of the tire 1. The carcass reinforcement 7 is in a manner known per se consisting of at least one ply reinforced by so-called “radial” cables, for example textile or metal, that is to say -to say that these cables are arranged practically parallel to each other and extend from one bead to the other so as to form an angle between 80 ° and 90 ° with the median circumferential plane (plane perpendicular to the axis of rotation of the tire which is located midway between the two beads 4 and passes through the middle of the crown reinforcement 6). A tight layer 10 extends from one bead to the other radially internally relative to the carcass reinforcement 7.

The tire 1 is such that its inner wall has in a reception area

13 given an adhesive part 11. The adhesive part 11 is radially covered internally by a protective film (or a stack of protective films) 12. The thickness of the adhesive part is preferably between 0.1 and 4 mm, and very preferably between 0.2 and 2 mm. Those skilled in the art will be able to adapt this thickness according to the nature, geometry and mass of the organ as well as the thickness of the area for fixing the organ.

The surface of the reception area 13 and therefore of the adhesive part 11 is suitable for obtaining a robust attachment of the member, the person skilled in the art will be able to adjust the dimension of the adhesive part as a function of the size and of the mass of the organ to be fixed.

The adhesive part 11 consists of an adhesive strip or an adhesive layer, the composition of which comprises a TPE, as described above.

The separable protective film (or stack of protective films) 12 is an aluminum film or a stack of aluminum films and a thermoplastic film, the latter being in contact with the part adhesive and comprising, for example, a fluoropolymer. The thermoplastic film is stretchable with low rigidity and has a plastic behavior. This thermoplastic film preferably has a Tg (or Tf, if applicable) higher than the vulcanization temperature of the tire. An example of a suitable film is Aerovac Systems France's A5000 film. This film includes for example a

-32 fluorinated ethylene-propylene copolymer or FEP. This film has a maximum use temperature of around 204 C and has an elongation at break greater than 300%. Its thickness is 25 µm. These characteristics allow it, in an exemplary embodiment of the invention, to be placed directly either on the tire making drum.

As shown in FIG. 2, the protective film (or the stack of protective films) 12 extends beyond the reception area of the adhesive part. The overflow is preferably greater than 2 mm to guarantee the non-contamination of this adhesive part during the vulcanization of the tire.

The protective film (or the stack of protective films) 12 makes it possible to protect the adhesive part from any contact with the tire manufacturing drum and then with the curing membrane of the vulcanization mold. The particular nature of this protective film (or stack of protective films) allows it to be removed from the interior surface of the tire after vulcanization. The removal of this protective film (or stack of protective films) restores all of its properties to the surface of the adhesive part. Preferably, the protective film (or the stack of protective films) 12 can be removed without tearing.

The pneumatic tire of FIG. 1 can be manufactured, as indicated in FIG. 2, by integrating the adhesive part into an unvulcanized tire blank 1 using a manufacturing drum and the other usual techniques in the manufacture of pneumatic tires. More specifically, the protective film (or the stack of protective films) 12 arranged radially inward is applied first to the manufacturing drum 15. The adhesive part 11 is then put in place. Then applied , successively, all the other usual components of the tire.

After shaping, the crown plies and the tread are placed on the tire blank. The blank thus completed is placed in a mold.

-33 baking and is vulcanized. During vulcanization, the protective film protects the baking membrane of the mold from contact with the adhesive layer.

At the outlet of the baking mold, the protective film (or the stack of protective films) 12 is always fixed to the adhesive part 11. The specific nature of the protective film (or stack of protective films) used allows the adhesive part not to deform (for example by creating bubbles) during the manufacture of the tire and in particular when the tire is removed from the baking mold. During this operation, the reception area of the tire of the invention separates from the baking membrane of the mold, without the reception area being degraded. Thus, with the protective film (or stack of protective films) specific to the invention, this separation of the reception area and the curing membrane is optimal, at the temperature at which the tire cures.

The protective film (or stack of protective films) 12 can be easily removed at the outlet from the vulcanization mold of the tire. It is also possible and preferable to leave this protective film in place until the organ is fixed.

The protective film (or stack of protective films) and the adhesive part can also be applied to the chosen reception area on the surface of the tire after the tire blank has been shaped and before the introduction of this in the vulcanization mold.

Figure 3 schematically shows a member 20 comprising a housing 22 and a fixing area 24. The fixing area of the member can be an adhesive strip or a fixing layer whose composition comprises a TPE thermoplastic elastomer, such as previously described. The thickness of the attachment zone is preferably between 0.5 and 4 mm, and very preferably between 1 and 3 mm. Those skilled in the art will be able to adapt the thickness of the attachment zone according to that of the adhesive layer and of the size and mass of the organ.

Figure 4 shows the assembly of the tire of Figure 1 and the member 20 fixed on its inner surface on the sealed inner layer.

-34 [00132] The fixing of the member 20 to the surface of the tire is carried out easily and quickly:

all or part of the protective film is removed;

if the tire has an adhesive layer as an adhesive part, the adhesive layer is brought to a temperature higher than the softening temperature of the thermoplastic blocks or of the thermoplastic block elastomers;

the contact area of the member and the adhesive part of the tire are brought into contact, by applying pressure.

if the tire has an adhesive layer as an adhesive part, contact is preferably maintained until the layer cools below the Tg (or Tf if applicable) of the TPE.

The contact pressure is preferably greater than 0.05 bar. Those skilled in the art will be able to adjust it according to the fixing zones and adhesive parts used.

In the examples discussed above, the member is fixed to the interior surface of the tire; it is also possible to place it on an external surface of the tire, for example on the sidewall of the tire.

Tests [00135] Pneumatic tires are produced according to the mode presented in FIG. 1. Before the tire is cured, an adhesive layer (11) is applied to the raw inner rubber (or waterproof inner layer). A protective film (12) is applied to this adhesive layer in accordance with the invention. The inner gum of this bandage is then subjected to the application of a non-stick product, then the bandage is placed in a baking mold.

After this cooking and after removal of the cooking membrane, the bandage is removed from the mold. Thereafter, the protective film or stack of films is removed and the facies of the adhesive layer is observed. A rating is then established visually. This notation

-35 translates the surface condition of the adhesive layer according to the following codification: “+” represents a predominantly smooth and non-degraded surface with a macroscopic roughness rate sufficiently low for reliable use, “-” corresponds to a rate of 'higher roughness and "-" corresponds to a surface mainly presenting macroscopic roughness.

According to a similar process, a macroscopic roughness rate is measured by image analysis. A photograph of the adhesive layer is taken and the image is processed using "imageJ" software. This makes it possible to define the total surface of the adhesive layer on the one hand and to add up the surfaces of the zones having a defect (most often the defect is in the form of a concave element of crater type). The ratio of the sum of the defect areas to the total area of the adhesive layer represents the defect rate, expressed as a percentage. Examples of protective films:

Table 3 below presents the protective films tested (conforming and not conforming to the invention). Aluminum films are used in combination with an FEP film placed between the adhesive layer and the aluminum film to facilitate peeling off the stack of protective films. In the following table are presented the thicknesses of the films used, the Young's modulus of the material used. The figures represent the number of layers of the same film used for example, for test n ° 4 the stack of protective films is composed of a thickness of 0.025mm FEP film and 3 thicknesses of aluminum film 1 ( 0.06mm thick) or a total of 0.18mm thick aluminum.

Table 3

Nature of the film Thickness (mm) Young's module (GPa) 1 2 3 4 FEP 0.025 0.5 1 1 1 1 Aluminum 1 0.06 70 1 3 Aluminum 2 0.3 70 1 ΣΟυ © 7.10 * 0.015 1.89 0.41

-36Results of the tests Table 4 below presents the results obtained.

1 2 3 4 Σ (^ Λ ^? ) 7.10 * 0.015 1.89 0.41 Visual note - - + + Default rate (%) 32 18 8 11

The comparison of tests 3 and 4 with tests 1 and 2 show that the use of a protective film or a stack of protective films meeting the criterion makes it possible to reduce the defect rate by 65% at minimum and gives access to acceptable surfaces for later use which is confirmed by the visual appearance.

The comparison between tests 3 with 4 shows that the rigid part of the protective film can be a single film or a film stack.

Claims (34)

1. A tire comprising an interior and / or exterior surface with a reception area, an adhesive part disposed on said reception area and a unitary protection film or a stack of protection films, disposed on said adhesive part , characterized in that the unitary protective film or the stack of protective films represents a rigidity and a thickness such that the equation (El) is verified, Z (Ei.h?)> 0.4 (El) equation (El) in which: E, represents the Young's modulus of a film i in GPa, hj represents the thickness of a film i in mm. 2. A tire according to claim 1, in which said reception area comprises a unitary protective film, disposed on said adhesive part having a rigidity and a thickness such that the equation (E2) is verified, E * h ³ > 0.4 (E2) equation (E2) in which: E represents the Young's modulus of the film in GPa, h represents the thickness of the film in mm. 3. A tire according to claim 2, in which the unitary protective film has a rigidity and a thickness such that the equation (E2bis) is verified, E * h ³ > 1 (E2bis). 4. Tire according to one of claims 1 to 3, wherein said unitary protective film is an aluminum film or a fabric comprising glass fibers and more preferably an aluminum film. 5. A tire according to claim 1, wherein said reception area comprises a stack of protective films. -386. A tire according to claim 5, in which the stack of protective films represents a rigidity and a thickness such that the equation (Elbis) is verified, Σ (£ ζΛ ^? )> 1 (Elbis). 7. Tire according to one of claims 1, 5 or 6, wherein said stack comprises at least one aluminum film or a fabric comprising glass fibers and more preferably an aluminum film. 8. A tire according to any one of claims 1, or 5 to 7, in which said stack comprises a thermoplastic film in contact with the chosen adhesive part so that the peel force of said film of the adhesive part is less than 1 N / mm and preferably less than 0.5 N / mm, at 20 ° C. 9. A tire according to claim 8, in which the thermoplastic film is chosen from the group of polyesters and films comprising at least one fluoropolymer. 10. Tire according to claim 9, in which the fluoropolymer comprises a fluorinated ethylene-propylene copolymer (FEP). 11. A tire according to any one of claims 8 to 10, in which the Tg (or Tf, if applicable) of the thermoplastic film is higher than the maximum baking temperature of the tire in the reception area. 12. Tire according to any one of the preceding claims, in which the adhesive part is an adhesive strip, or an adhesive layer, the composition of which comprises a thermoplastic elastomer (TPE). 13. The tire as claimed in claim 12, in which the elastomer block of the TPE of the composition of the adhesive layer is saturated or essentially saturated, that is to say comprising a molar level of unsaturated units of less than 10%, preferably less at 5%, more preferably less than 2%, relative to all of the patterns of the elastomer block. -3914. Tire according to any one of Claims 12 to 13, in which the TPE of the composition of the adhesive layer has thermoplastic blocks essentially consisting of polymers chosen from the group consisting of polyamides, polyesters and mixtures thereof. 15. Tire according to the preceding claim, in which the TPE of the composition of the adhesive layer has elastomeric blocks essentially consisting of polymers chosen from the group consisting of polyisobutylenes, polyethylenes, polypropylenes, polybutylenes, polyethers and their mixtures ; preferably in the group of polyethers and their mixtures. 16. A tire according to any one of claims 12 to 13, in which the TPE of the composition of the adhesive layer is a styrenic thermoplastic elastomer (TPS), that is to say the thermoplastic block of which essentially consists of styrenic monomers. 17. A tire according to the preceding claim, in which the thermoplastic block of the TPS of the composition of the adhesive layer is a polystyrene block. 18. A tire according to any one of claims 16 or 17, in which the TPS elastomer block of the composition of the adhesive layer is chosen from the group consisting of polyisobutylenes, polyethylenes, polypropylenes, polybutylenes, and their mixtures. 19. A tire according to any one of claims 12 or 16 to 17, in which the TPE of the composition of the adhesive layer is a styrenic thermoplastic elastomer (TPS), the elastomer block of which is unsaturated, that is to say comprising a molar rate of unsaturated units greater than or equal to 10% relative to all of the units of the elastomer block. -4020. Tire according to the preceding claim, in which the elastomer block of the TPE of the composition of the adhesive layer is chosen from the group consisting of polymers of dienes conjugated to C4-C14 and their mixtures, preferably from the group of polybutadienes, polyisoprenes, butadiene / styrene copolymers, isoprene / styrene copolymers and their mixtures. 21. A tire according to any one of claims 12 to 20 in which the adhesive part is an adhesive layer the composition of which comprises a TPE having a viscosity greater than 2000 Pa.s at the baking temperature of the tire, preferably a viscosity greater than 2000 Pa.s at 150 ° C, more preferably greater than 2000 Pa.s at 175 ° C. 22. A tire according to claim 21, in which the TPE of the composition of the adhesive layer has a viscosity greater than 2200 Pa.s at the baking temperature of the tire, preferably a viscosity greater than 2200 Pa s at 150 ° C, more preferably greater than 2200 Pa.s at 175 ° C. 23. A tire according to any one of claims 21 or 22, in which the TPE of the composition of the adhesive layer has a viscosity greater than 3000 Pa.s at the baking temperature of the tire, preferably a viscosity greater than 3000 Pa.s at 150 ° C, more preferably greater than 3000 Pa.s at 175 ° C. 24. A tire according to any one of claims 12 to 23, in which thermoplastic block telastomer of the composition of the adhesive layer is a mixture of TPE. 25. A tire according to any one of claims 12 to 24, in which the thermoplastic block elastomer (s) (TPE) of the composition of the adhesive layer are the only elastomers of said composition of the adhesive layer. 26. A tire according to any one of claims 12 to 25, in which the composition of the adhesive layer comprises one or more polyphenylene ethers (“PPE”). -41 27. The tire according to claim 12, in which the adhesive part is an acrylic adhesive strip. 28. Tire according to the preceding claim, in which the acrylic adhesive strip comprises - from 50 to 100% by mass of so-called “primary” monomers chosen from the group consisting of acrylic acid esters obtained with primary or secondary alcohols, the alkyl parts of which are C4-C20; - from 0 to 35% by mass of so-called "secondary" monomers chosen from the group consisting of methyl acrylate, methyl methacrylate, vinyl acetate, styrene and their mixtures; from 0 to 15% of polar and functional monomers, chosen from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl acrylate, acrylamides, methacrylamides, N-vinyl pyrrolidone, N-vinyl caprolactam and their mixtures. 29. A tire according to the preceding claim, in which the acrylic adhesive strip comprises: from 50 to 100% by mass of so-called “primary” monomers chosen from the group consisting of 2-ethylhexylacrylate, iso-octyl acrylate, n-butyl acrylate and their mixtures; - from 0 to 35% by mass of methyl acrylate; - from 0 to 15% acrylic acid. 30. A tire according to any one of claims 12 or 27 to 29 in which the adhesive strip of the fixed member is a foam adhesive strip. 31. Method for fixing a member provided with a fixing zone, to the surface of a tire according to any one of claims 1 to 30, in which: - all or part of the protective film is removed; If the tire has an adhesive layer as an adhesive part, the adhesive layer is brought to a temperature higher than the softening temperature of the thermoplastic blocks of the block thermoplastic elastomer (s); - the area of attachment of the member and the adhesive part of the tire are brought into contact, by applying pressure. 32. Method according to the preceding claim in which the attachment zone of the member is an adhesive strip, or a fixing layer, the composition of which comprises a thermoplastic elastomer (TPE). 33. Method according to one of claims 31 or 32 wherein the attachment zone of the member is a fixing layer whose composition comprises one or more thermoplastic elastomer (s) (TPE), said fixing layer being brought to a temperature higher than the softening temperature of the thermoplastic blocks of the block thermoplastic elastomer (s), before being brought into contact with the adhesive zone. 34. Method according to one of claims 31 or 32 wherein the attachment area of the member is an acrylic adhesive strip. 35. Method according to one of claims 31, 32 or 34 wherein the attachment area of the member is a foam adhesive tape. 36. Method according to any one of claims 31 to 35 wherein said member is a housing capable of receiving an electronic device. 37. Method according to any one of claims 31 to 35 wherein said member is an electronic device. 1/2