FR3052708A1 - PNEUMATIC HAVING AN ORGAN FIXED TO ITS SURFACE - Google Patents

Abstract

The invention relates to a tire provided with a member fixed on / in said tire, said member comprising an adhesive tape, said tire having an inner and / or outer surface with a receiving zone, an adhesive layer disposed on said zone receiving, and the composition of said adhesive layer being based on a thermoplastic block elastomer (TPE) whose thermoplastic blocks consist essentially of polymers selected from the group consisting of polyamides, polyesters and mixtures thereof, and the elastomeric blocks consist essentially of polymers selected from the group consisting of polyethers and mixtures thereof. The invention also relates to the method of manufacturing this tire provided with a member fixed on / in said tire.

Description

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

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

Document US 2012/0248274 proposes a tire comprising an inner and / or outer surface with a reception zone, an adhesive layer disposed on this reception zone and a protective film disposed on the adhesive layer, in which the adhesive layer consists of a fabric embedded in a thermoplastic material. After having removed the protective film from the surface of the adhesive layer, the adhesive layer is brought into contact with the reception area of the tire and the attachment layer of the body. The presence of the fabric allows a stable attachment of the adhesive layer to the surface of the tire during the vulcanization of the tire. The attachment layer of the member is also made of a thermoplastic material and the reversible attachment of the member to the surface of the tire is provided by contacting the two adhesive and fixing layers after softening thereof by heating . This document gives no indication as to the nature of the thermoplastic materials that can be used.

Also, the document EP 1070580 proposes the attachment of an object inside a tire via the use of acrylic adhesive tapes, requiring the handling of these acrylic adhesive tapes both in the tire and on the tire. object to fix. The acrylic adhesive tapes described are very flexible objects and not or little crosslinked. This causes a fragility of these materials that can be damaged by elongation or tear during handling during the manufacture of the tire especially before the cooking step. In order to limit this mechanical damage and to obtain the optimal properties related to the use of acrylic adhesive tapes, they must be supported on a release tape which generates the production of waste. In addition, the use of crosslinked adhesive tapes may limit the adhesion developed to the raw rubber composition during firing. Finally, the adhesion of an acrylic adhesive both in the tire and on the object to be fixed can reduce the reversibility of the operation, resulting in less flexibility of use.

[0005] In view of the applications currently being developed which are based on the fixation of objects, in particular electronic ones on tires, it is interesting for the manufacturers to develop fixing solutions which are fast, efficient and durable, while striving to have a simple and economical manufacture of tires suitable for receiving these fixed objects. In particular, it is interesting to satisfy these conditions without requiring the presence of a fabric at the interface.

The invention relates to a tire provided with a member fixed on / in said tire, said member comprising an adhesive tape, said tire having an inner and / or outer surface with a receiving zone, an adhesive layer disposed on said reception zone, characterized in that the composition of said adhesive layer is based on a thermoplastic block elastomer (TPE) whose thermoplastic blocks consist essentially of polymers selected from the group consisting of polyamides, polyesters and mixtures thereof, and the elastomeric blocks consist essentially of polymers selected from the group consisting of polyethers and mixtures thereof.

The use of such an assembly has the advantage of allowing rapid adhesion, effective and durable of the body on the tire provided with the receiving area, without the need for the presence of a tissue to the body. interface between the tire and the body attached to its surface.

[0008] Also, the specific materials used for the invention make it possible to maintain good adhesion of the object to the tire, including when the tire is in use when hot.

In addition, this method of attachment provides great freedom as to the geometry and functions of the body due to the attachment of the object after baking (vulcanization) of the tire.

The member may be a housing adapted to receive an electronic device. The organ can also be an electronic device. It can also be a marking on the tire or a decoration.

Another object of the invention is a method of fixing a member provided with an adhesive tape, on the surface of a tire as described above, with an adhesive layer, protected by a film of protection, and arranged on a reception area, in which: - all or part of a protective film is removed; the adhesive strip of the member and the adhesive layer of the tire are brought into contact by applying pressure.

Fixing the organ is thus performed very quickly and very simply. Fixation is effective and durable. It also has the advantage of being totally reversible.

The invention relates more particularly to tires for equipping tourism-type motor vehicles, SUV ("Sports Utility Vehicles"), two wheels (including motorcycles), aircraft, such as industrial vehicles chosen from light trucks, "weight "heavy" - that is to say metro, bus, road transport equipment (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering -, other transport vehicles or handling.

DETAILED DESCRIPTION OF THE INVENTION [0014] In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight.

By "one" is meant "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 from more than a to less than b (that is, terminals a and b excluded). ) while any range of values designated by the expression "from a to b" signifies the range of values from a to b (that is to say, including the strict limits a and b).

The details of the invention will be explained below by the description, in a first step, the specific constituents of the tire according to one of the objects of the invention, then by the description of the tire manufacturing method and characterization tests carried out.

The tire according to the invention has the essential characteristics of being provided with a member, said member comprising an adhesive tape, said tire having an inner and / or outer surface with a receiving zone, an adhesive layer disposed on said reception zone, said adhesive layer being based on a thermoplastic block elastomer (TPE) whose thermoplastic blocks consist essentially of polymers chosen from the group consisting of polyamides, polyesters and mixtures thereof, and the elastomeric blocks consist essentially of polymers selected from the group consisting of polyethers and mixtures thereof. Thermoplastic Elastomer Thermoplastic elastomers (abbreviated as "TPE") have an intermediate structure between thermoplastic polymers and elastomers. They are block copolymers, made up of rigid, thermoplastic blocks, connected by flexible blocks, elastomers.

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

The thermoplastic elastomer used for the implementation of the invention is a thermoplastic block elastomer (TPE) whose thermoplastic blocks consist essentially of polymers selected from the group consisting of polyamides, polyesters and mixtures thereof. latter, and the elastomeric blocks consist essentially of polymers selected from the group consisting of polyethers and mixtures thereof.

Structure of the TPE

The number-average molecular weight (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 minima indicated, the cohesion between the elastomer chains of the TPE, in particular because of 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 may affect the mechanical properties, including the properties at break, resulting in reduced performance "hot". Moreover, a mass Mn that is too high can be penalizing for the implementation. Thus, it has been found that a value in a range of 50,000 to 300,000 g / mol was particularly well suited, in particular to a use of TPE in a composition used in a tire.

The number-average molecular weight (Mn) of the TPE elastomer is determined in known manner, by steric exclusion chromatography (SEC). For example, in the case of styrenic thermoplastic elastomers, the sample is solubilized beforehand in tetrahydrofuran at a concentration of approximately 1 g / l; then the solution is filtered through a 0.45 μm porosity filter before injection. The apparatus used is a "WATERS alliance" chromatographic chain. The elution solvent is tetrahydrofuran, the flow rate 0.7 ml / min, the system temperature 35 ° C and the analysis time 90 min. A set of four WATERS columns in series, of trade names "STYRAGEL" ("HMW7", "HMW6E" and two "HT6E") is used. The injected volume of the solution of the polymer sample is 100 μl. The detector is a "WATERS 2410" differential refractometer and its associated software for the exploitation of chromatographic data is the "WATERS MILLENIUM" system. The calculated average molar masses relate to a calibration curve made with polystyrene standards. The conditions are adaptable by those skilled in the art.

The value of the polydispersity index Ip (booster: Ip = Mw / Mn with Mw weight average molecular weight and Mn 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 elastomeric portion of the TPE, and the highest temperature being relative to the thermoplastic part of the TPE. Thus, the soft blocks of the TPEs are defined by a Tg lower than the 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 relative 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 higher than these minima can reduce the performance when used at very low temperature; for such use, the Tg of the TPE is more preferably still less than or equal to -10 ° C. Also preferably, the Tg of the TPE is greater than -100 ° C.

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

The TPEs useful for the purposes of the invention comprise a large number of blocks (more than 30, typically from 50 to 500) smaller, in which case these blocks preferably have low masses, for example from 500 to 5000 g / mol, these TPE will be called multiblock TPE thereafter, and are a sequence of elastomeric blocks - thermoplastic blocks.

Nature of the Elastomeric Blocks The elastomeric blocks of the TPE for the purposes of the invention may be any polyether type elastomer known to those skilled in the art.

The polyether elastomer block fraction in the TPE is in a range from 1 to 95%, preferably from 10 to 92%, more preferably from 30 to 90%.

These polyether blocks preferably have a Tg (glass transition temperature) measured by DSC according to the ASTM D3418 standard of 1999, less than 25 ° C, preferably less than 10 ° C, more preferably less than 0 ° C and very preferably below -10 ° C. Also preferably, the T g of the polyether blocks is greater than -100 ° C. Polyether blocks having a Tg of between 20 ° C. and -70 ° C. and more particularly between 0 ° C. and -50 ° C. are particularly suitable.

For the purposes of the present invention, the polyether blocks may be composed of monomers chosen from cyclic alcohols or ethers, preferably aliphatic aliphatic alcohols or ethers, such as, for example, ethanol or tetrahydrofuran. Among the polyethers, those selected from the group consisting of polytetramethylene glycol (PTMG), polyethylene glycols (PEG), polypropylene ether glycol (PPG), polyhexamethylene ether glycol, polytrimethylenether glycol (PO 3 G), poly ( 3-alkyltetrahydrofuran), and mixtures thereof. Very preferably, the polyether is selected from the group consisting of polytetramethylene glycol (PTMG), polyethylene glycols (PEG) and mixtures thereof.

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

The elastomeric block may also consist of several elastomeric blocks as defined above.

Nature of the Thermoplastic Blocks The definition of the thermoplastic blocks will use the glass transition temperature characteristic (Tg) of the thermoplastic rigid block. 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 a polymer block), the implementation temperature is chosen to be substantially greater than the Tg. In the specific case of a polymer (or a polymer block) semi -crystalline, we 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 implementation temperature of the polymer (or polymer block) considered. Thus, later, when we speak of "Tg (or Tf, if any)", we must consider that this is the temperature used to choose the temperature of implementation.

For the purposes of the invention, the TPE elastomers have thermoplastic blocks essentially consisting of polymers selected from the group consisting of polyamides, polyesters and mixtures thereof.

Preferably, the thermoplastic blocks are chosen from the group consisting of polyamides of PA6, PA or PA12 type, or polyesters of PET or PB T type and mixtures thereof.

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

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

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

The thermoplastic block may also consist of several thermoplastic blocks as defined above.

Examples of TPE

As examples of TPE elastomers which are suitable for the invention and commercially available, mention may be made of PEBA elastomers of the "PEBAX" type, marketed by Arkema, for example under the name "PEBAX 4033", " PEBAX 6333 "," PEBAX 3533 "or COPE elastomers of the" Pelprene P "type, marketed by Toyobo, for example under the name" Pelprene P40B ".

Tire receiving zone [0043] The tire of the invention comprises an inner and / or an outer surface with a reception zone, on which an adhesive layer is placed and, after assembly, the member fixed on this zone of the tire. 'Home.

According to a preferred arrangement of the invention, the reception zone further comprises a layer denoted underlayer, positiormée between the adhesive layer and the inner surface and / or outside of the tire carrying the reception area.

Said sublayer may be of several types, it may be a local application of a surface preparation solution, as in the art, or a thin layer (for example from 0.01 to 1 mm) of an adhesion composition comprising for example a thermoplastic elastomer.

Composition of the adhesive layer of the tire The adhesive layer of the tire according to the invention has the essential characteristic of comprising a thermoplastic block elastomer (TPE) whose thermoplastic blocks consist essentially of polymers chosen from the group consisting of polyamides , the polyesters and mixtures thereof, and the elastomeric blocks consist essentially of polymers selected from the group consisting of polyethers and mixtures thereof; as defined above, with all the preferences and all the embodiments.

The term "one" must be understood as "at least one", that is to say one or more thermoplastic block elastomers.

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

Optionally, the presence of a polyphenylene ether (PPE) 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. Surprisingly, on the contrary, an improvement in adhesion is observed at operating temperatures below 100 ° C.

As a minority, the composition of the adhesive layer may comprise a conventional diene elastomer such as SBR, a polybutadiene or a natural or synthetic polyisoprene. Very preferably, the content of diene elastomer in the composition is less than 20 parts per hundred parts by weight 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 comprise, as plasticizer, an extender oil (or plasticizing oil) whose function is to facilitate placing the adhesive layer and the adhesive tape of the member in particular, particularly by lowering the modulus and increasing the tackifying power.

Can be used any extension oil, weakly polar character, capable of extending, plasticizing elastomers, especially thermoplastics. At room temperature (23 ° C), these oils, more or less viscous, are liquids (that is to say, as a reminder, substances having the ability to eventually take the shape of their container), as opposed in particular to resins or rubbers which are inherently solid.

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

Preferably used is an oil of the liquid isoprene rubber type ("LIR"). By way of example, the LIRs 30 and 50, respectively of number-average molecular weights of 30,000 and 50,000 g / mol, are marketed by Kuraray.

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

The use of tackifying resins can be particularly interesting for adjusting the softening temperatures and the necessary adhesion levels of the adhesive or fixing layers.

Body attached to the tire [0057] V member may be a housing adapted to receive an electronic device. The organ can also be an electronic device. It can also be a marking on the tire or a decoration. The member is attached to the tire with an adhesive tape on the body.

Adhesive tape of the organ

The adhesive tape of the organ can be any type of known adhesive tape, sometimes called "tape" ("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 refer to materials that are inherently tacky or have been made sticky by the addition of tackifying resins. Several methods make it possible to identify a PSA, in particular the following three: a PSA can be described by the Dahlquist criteria from the mechanical and viscoelastic point of view; a PSA is a material that possesses stickiness (or "tack") of permanently and aggressively at room temperature and strongly adheres to various surfaces by simple contact without the need for pressure greater than that applicable to the hand. a PSA is a material whose storage modulus is between 0.02 MPa and 0.04 MPa at a frequency of 0.1 rad / s (0.017 Hz) and 0.2 MPa at 0.8 MPa at a frequency of 100 rad / s (17 Hz).

Preferably, for the invention, a so-called "acrylic" PSA, known to those skilled in the art ("Technology of Pressure Sensitive Adhesives and Products", by I. Benedek and MFFeldstein, is used as adhesive tape. , Chapter 5 "Acrylic adhesives" PBForeman) comprising 50 to 100% by weight 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 and iso-octyl acrylate. n-butyl acrylate and mixtures thereof. These primary monomers have a low Tg, preferably less than 0 ° C, imparting the softness and tackiness of the adhesive tape. Optionally, the acrylic composition comprises from 0 to 35% by weight of so-called "secondary" monomers with a Tg greater than 0 ° C. which are known to those skilled in the art and preferably selected from the group consisting of methyl acrylate, methyl methacrylate, vinyl acetate, styrene and mixtures thereof. More preferably, the 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 may be of any type other than the primary and secondary monomers described above. Preferably, these monomers are selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl acrylate, acrylamides (such as butyl acrylamide or octyl acrylamide), methacrylamides, N-vinyl pyrrolidone, N-vinyl caprolactam and mixtures thereof. More preferably, acrylic acid is used. These monomers can increase the adhesion by setting up Van der Waals 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, the gas phase is provided directly or via solids (gas generating compounds , expandable polymer beads, glass microbeads). It may be for example a crosslinked acrylic foam sandwiched between two crosslinked acrylic adhesive masses, the foam effect being obtained by using glass microbeads. The main methods for obtaining "foamed" PSAs are therefore, for example, the direct injection of gas, the addition of expandable polymer microspheres, the addition of glass microspheres (porous or nonporous), the addition of foaming agents. chemical evaporation of solvent.

PSA known under the designation "VHB" (Very High Bond) are proposed by the company 3M, are conformable to non-planar surfaces and are used for the purposes of the invention, such as for example the "VHB4955". High performance "VHB" adhesive tapes are assembly tapes consisting 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 throughout the thickness, these products absorb a maximum of energy during shocks, vibrations, or mechanical stresses. They are suitable for applications with flatness or roughness defects as well as for outdoor applications requiring tightness.

Attaching the Body to the Tire Another object of the invention is a method of fixing a member provided with an adhesive tape, on the surface of a tire as described above, with a layer adhesive, itself being protected by a protective film, and arranged on a reception area, in which: - all or part of the protective film is removed; the adhesive strip and the adhesive layer are brought into contact by applying pressure.

Preferably, the invention relates to the method as defined above wherein the member is a member provided with an adhesive tape, as defined above.

Fixing the organ is thus performed very quickly and very simply. Fixation is effective and durable. It also has the advantage of being totally reversible.

Protective film [0065] For the method of the invention, it is necessary to use a protective film on the adhesion layer of the tire receiving zone before the body is attached to this film. area. This protective film allows the adhesive layer to be preserved during the preparation of the tire, its cooking and its possible handling and storage before the body is attached to its surface.

The protective film is preferably a heat-resistant flexible film which preferably has a limited adhesion to the adhesive layer to be peeled off. The peel strength of the film of the adhesive layer is preferably less than 1 N / mm at 20 ° C and very preferably less than 0.5 N / mm.

This film makes it possible to protect the surface of the adhesive layer during assembly operations of the tire and its vulcanization in a mold.

It may especially be a thermoplastic film. This thermoplastic film is advantageously chosen from the group of polyesters and films comprising at least one fluorinated polymer. Those skilled in the art will know how to choose their thickness in order to obtain the best compromise between their flexibility and their mechanical strength. This thickness is advantageously between 10 and 300 μm.

The nature of the protective film may be incompatible with that of the TPE of the adhesive layer to obtain a suitable limited adhesion.

In a preferred embodiment, this film is removed just before the establishment of the body on the surface of the tire to prevent pollution of the surface of the adhesive layer. The film then has the advantage of protecting the adhesive layer during all the transport and storage phases of the tires.

Preferably, the Tg (or Tf, if any) of the protective film is greater than the firing temperature of the rubber mix of the reception area of the tire surface. A temperature of 200 ° C for the Tg (or Tf, if applicable) allows the film to withstand the usual vulcanization temperatures of tires for passenger vehicles.

As an example of a polyester film, it is possible to use the films marketed under the trademark Mylar with a thickness of between 0.03 and 0.2 mm. Such a polyester film has a melting temperature above 230 ° C.

Fluorinated ethylene-propylene copolymers (FEP) may be chosen as fluoropolymers. Advantageously, the film comprises a copolymer of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP).

These polymers have remarkable anti-adhesive properties.

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

The following table shows examples of suitable films for the invention.

The protective film makes it possible to separate the adhesive layer from any contact with the pneumatic tire manufacturing drum and then with the vulcanization mold's cooking membrane. The incompatible nature of the protective film with respect to the adhesive layer allows it to be removed from the inner surface of the tire after vulcanization. The removal of this protective film gives back to the adhesive layer all its properties. The protective film can be removed without tearing.

Embodiments of the invention Complementary elements of the invention are now described with the aid of the accompanying drawings, presented in a non-limiting manner, in which: FIG. 1 represents very schematically (without respecting a specific scale) a radial section of a tire adapted to receive an element on its surface; Figure 2 shows a partial radial section a tire blank adapted to receive a member on its surface; Figure 3 illustrates a member with an adhesive tape; and FIG. 4 shows a tire according to the invention, with a member fixed on its surface.

FIG. 1 schematically represents a radial section of a pneumatic or pneumatic tire incorporating, in a given reception area, an adhesive layer with a protective film.

This tire 1 comprises a vertex 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 rod 5. The crown reinforcement 6 is surmounted radially outwardly of a rubbery tread 9. A carcass reinforcement 7 is wound around the two rods 5 in each bead 4, the upturn 8 of this armature 7 being for example disposed towards the outside of the tire 1. The carcass reinforcement 7 is in known manner constituted of at least one sheet reinforced by so-called "radial" cables, for example textile or metal, that is to say that these cables are arranged substantially parallel to each other and s' extend from one bead to the other so as to form an angle of between 80 ° and 90 ° with the median circumferential plane (plane perpendicular to the axis of rotation of the tire which is located in the middle of istance of the two beads 4 and passes through the middle of the crown reinforcement 6). A sealing layer 10 extends from one bead to the other radially inwardly relative to the carcass reinforcement 7.

The tire 1 is such that its inner wall comprises in an accommodating area 13 given an adhesive layer 11. The adhesive layer 11 is covered radially internally by a protective film 12. The thickness of the adhesive layer is preferably between 0.1 and 4 mm, and very preferably between 0.2 and 2 mm. Those skilled in the art will know how to adapt this thickness according to the nature, the geometry and the mass of the organ as well as the thickness of the adhesive strip of the organ.

The surface of the reception area 13 and therefore the adhesive layer 11 is adapted to obtain a robust attachment of the body, the skilled person will adjust the size of the adhesive layer depending on the size and of the mass of the organ to fix.

The adhesive layer 11 consists of a specific TPE, as described above and in particular chosen from those proposed in the examples below.

The separable protective film 12 is a thermoplastic film comprising, by way of example, a fluorinated polymer. The thermoplastic film is extensible with low rigidity and has a plastic behavior. This film preferably has a Tg (or Tf, where appropriate) greater than the vulcanization temperature of the tire. An example of a suitable film is Aerovac Systèmes France film A5000. This film comprises for example a fluorinated ethylene-propylene copolymer or FEP. This film has a maximum operating temperature of the order of 204 ° C. and has a breaking elongation greater than 300%. Its thickness is 25 pm. These characteristics allow it, in an exemplary embodiment of the invention, to be put in place directly on the drum or making the tire.

As shown in Figure 2, the protective film 12 extends beyond the reception area of the adhesive layer. The overflow is preferably greater than 2 mm to ensure the non-contamination of this adhesive layer during the vulcanization of the tire.

The protective film 12 makes it possible to protect the adhesive layer from any contact with the manufacturing drum of the tire and then with the baking membrane of the vulcanization mold. The particular nature of this protective film allows it to be removed from the inner surface of the tire after vulcanization. The removal of this protective film restores the surface of the adhesive layer all its properties. Preferably, the protective film 12 can be removed without tearing.

The tire of FIG. 1 can be manufactured, as indicated in FIG. 2, by integrating the adhesive layer into a non-vulcanized blank of tire 1 by using a manufacturing drum and the other techniques customary in the manufacture of pneumatic tires. More specifically, the radially innermost protective film 12 is applied first to the production drum 15. The adhesive layer 11 is then put in place. Then, all the other usual components of the adhesive layer are applied successively. pneumatic tire.

After shaping, the crown plies and the tread are put in place on the tire blank. The thus completed blank is placed in a baking mold and is vulcanized. During vulcanization, the protective film protects the mold's baking membrane from contact with the adhesive layer.

At the outlet of the baking mold, the protective film 12 is always attached to the adhesive layer 11. The protective film 12 can be easily removed at the outlet of the vulcanization mold of the tire. It is also possible, and preferable, to leave in place this protective film until the time of fixation of the organ.

The protective film and the adhesive layer may also be applied to the chosen reception zone on the surface of the tire after the conformation of the tire blank and before introducing it into the vulcanization mold. .

Figure 3 schematically shows a member 20 having a housing 22 and an adhesive strip 24. The material of the adhesive strip 24 is as described above and in particular an acrylic adhesive tape type "HBV". The adhesion and fixing layers consist of a TPE comprising a saturated or essentially saturated elastomeric block, as described previously and in particular chosen from those proposed in the examples below. The thickness of the adhesive strip 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 adhesive tape according to that of the adhesive layer and the size and mass of the organ.

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

The attachment of the member 20 to the tire surface is easily and quickly carried out: all or part of the protective film 12 is removed from the adhesive layer 11 of the tire 1; the adhesive strip and the adhesive layer are brought into contact by applying contact pressure (manual pressure is sufficient).

The contact pressure is preferably greater than 0.05 bar. Those skilled in the art will know how to adjust it depending on the adhesive layer and the adhesive tape used.

As soon as the cooling is effective, the member is firmly attached to the tire surface.

In the examples discussed above, the member is attached to the inner 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

Manual peel test [0097] Adhesion tests (peel tests) were conducted to test the ability of the adhesive layer to adhere after firing to a diene elastomer layer, more specifically to a conventional rubber composition for an inner waterproof layer (sometimes also called "inner liner") of tire, based on butyl rubber (isobutylene and isoprene copolymer) further comprising the usual additives (filler, sulfur, accelerator) , ZnO, stearic acid, antioxidant). Of course, this test can be adapted to the case where the member must be placed on the sidewall of the tire, in this case, it will be used to make the specimens a layer of rubbery sidewall mixture instead of a waterproof inner layer layer usual. This same test is used to measure the adhesion of the adhesive layer and the adhesive tape.

The peel test pieces (of the 180 ° peel type) were made by stacking the following products: a fabric of carcass carcass tourism type; a usual waterproof inner layer layer (1 mm); an adhesive layer to be tested (in particular TPE according to the invention) (1 mm); a usual waterproof inner layer layer (1 mm); and a fabric carcass tourism web.

[0099] A breaking primer is placed at the interface between one of the sealed inner layer layers and the adhesive layer.

The specimens are then vulcanized at 140 ° C for 50 minutes and at a pressure of 16 bar in a platen press.

[00101] Strips 30 mm wide were cut with a cutter. Both sides of the breakout primer were then placed in the jaws of an Instron® brand traction machine. The tests are carried out at ambient temperature and at a tensile speed of 100 mm / min. The tensile forces are recorded and these are standardized by the width of the specimen. A force curve is obtained per unit of width (in N / mm) as a function of the displacement of the moving beam of the traction machine (between 0 and 200 mm). The value of adhesion retained corresponds to the initiation of the rupture within the specimen and therefore to the maximum value of this curve.

The peel measurements are carried out at room temperature (23 ° C) and at 60 ° C or 80 ° C depending on the case.

Adhesion tests (peel tests) were also conducted to test the ability of the adhesive layer to adhere after firing to a fixing layer / adhesive tape as it is present on the body to be fixed to the tire. In this case, the test pieces are made by contacting the adhesive layer to be tested with the adhesive strip to be tested. Two similar half-test pieces are made according to the following stack in order to subsequently accommodate the adhesive strip: a fabric of carcass-like carcass type; a usual waterproof inner layer layer (1 mm); an adhesive layer to be tested (in particular TPE according to the invention for the tire) (1 mm).

The half-samples are then vulcanized at 140 ° C for 50 minutes and under a pressure of 16 bar in a platen press protecting the adhesive layer with a protective film.

After baking and removal of the protective film, the adhesive layer faces are brought into contact with the adhesive strip which is sandwiched between the two half-test pieces. A breaking primer is placed at one of the interfaces of the adhesive layers with the adhesive tape. Pressure is applied with an applicator roll passed in a round trip.

Both sides of the rupture primer were then placed in the jaws of an Instron® brand traction machine. The tests are carried out at ambient temperature and at a tensile speed of 100 mm / min. The tensile forces are recorded and these are standardized by the width of the specimen. A force curve is obtained per unit of width (in N / mm) as a function of the displacement of the moving beam of the traction machine (between 0 and 200 mm). The value of adhesion retained corresponds to the initiation of the rupture within the specimen and therefore to the maximum value of this curve.

The peel measurements are carried out at 60 ° C or 80 ° C.

EXAMPLES OF COMPOSITIONS: [00108] Table 1 below shows the compositions tested in which: C-1 is a usual composition of sealed inner layer; C-2 is a control composition comprising a TPE that is not suitable for the adhesive layer C-3 is a composition comprising a TPE that is suitable for the adhesive layer of the tire according to the invention C-4 is an adhesive tape

Table 1: compositions in pce

(1) brominated copolymer of isobutylene and isoprene "BROMOBUTYL 2222" marketed by the company EXXON CHEMICAL Co; (2) N-dicyclohexyl-2-benzothiazol sulfenamide ("Santocure CBS" from Flexsys); (3) SIS "DI 163" of the Kraton Company; (4) PEBA "PEBAX 3533" from Arkema; (5) acrylic PSA "VHB4955" from the 3M company. Test Results [00109] To represent the adhesion of the adhesive layer to the inner sealing layer of the tire provided with the receiving zone, the adhesion values are measured (peel test) for the C-2 layer assemblies. at C-4 on the C-1 layer and the results are shown in Table 2. In the case of the C-3 / C-1 assembly, an undercoat composed of a styrene-butadiene-styrene thermoplastic elastomer and a polyphenylene ether (66 phr) is interposed between the two layers C-3 and C-1.

Table 2

* nm: not measured [00110] The results presented in Table 2 show the advantage of using as adhesive layer a thermoplastic elastomer composition. These allow adhesion values of the adhesive layer on the inner liner greater than those proposed by the acrylic adhesive tape. At this stage, the nature of the thermoplastic elastomer used is not important, and the results obtained with compositions C-2 and C-3 are good.

To represent the adhesion of the member on the tire according to the invention, the adhesion values are measured (peel test) for the various assemblies presented below with the results in Table 3.

Table 3

The results presented in Table 3 illustrate the advantage of using as adhesive layer a thermoplastic block composition whose thermoplastic blocks consist essentially of polymers selected from the group consisting of polyamides, polyesters and mixtures thereof. latter, and the elastomeric blocks consist essentially of polymers selected from the group consisting of polyethers and mixtures thereof in combination with an acrylic adhesive tape on the member attached to this tire.

The result of adhesion of C-4 on C-4 is also good, but for the purposes of the invention, it is also necessary that the adhesion on the tight layer (C-1) is good, making C-3 the best solution between a C-1 type waterproof layer and a C-4 type adhesive tape on the object to be fixed. On the tire receiving zone, a C-3 type adhesive layer is preferred, rather than a C-4 type adhesive tape, because the handling of the adhesive strips in the tire is delicate, as indicated previously, because the fragility of these materials that can be damaged by elongation or tear during the manufacture of the tire especially before the firing step. Finally, the adhesion of an acrylic adhesive both in the tire and on the object to be fixed could reduce the reversibility of the operation, resulting in less flexibility of use of the invention.

[00114] Thus; the invention allows rapid and reversible attachment of members to the surface of a tire without the disadvantages associated with the preparation of the contact surface.

Finally, this method of attachment provides great freedom as to the geometry and functions of the body due to post vulcanization fixation.

Claims (21)

1. A tire provided with a member fixed on / in said tire, said member comprising an adhesive tape, said tire having an inner and / or outer surface with a receiving zone, an adhesive layer disposed on said reception zone, characterized in that the composition of said adhesive layer is based on a thermoplastic block elastomer (TPE) whose thermoplastic blocks consist essentially of polymers selected from the group consisting of polyamides, polyesters and mixtures thereof, and the elastomeric blocks consist essentially of polymers selected from the group consisting of polyethers and mixtures thereof. 2. A tire according to claim 1 wherein the one or more elastomeric blocks of the thermoplastic block elastomer (TPE) of the adhesive layer are chosen from polyethers having a glass transition temperature below 25 ° C. 3. A tire according to any preceding claim wherein the polyether elastomeric block or blocks are selected from the group consisting of polytetramethylene glycol (PTMG), polyethylene glycols (PEG), polypropylene ether glycol (PPG), polyhexamethylene ether glycol, polytrimethylenether glycol (PO3G), poly (3-alkyltetrahydrofuran), and mixtures thereof; preferably in the group consisting of polytetramethylene glycol (PTMG), polyethylene glycols (PEG), and mixtures thereof. 4. A tire according to any one of the preceding claims wherein the thermoplastic block or blocks of the thermoplastic block elastomer (TPE) of the adhesive layer are selected from the group consisting of polyamides PA6, PAA, PA12, polyesters type PET, PBT and mixtures thereof. A tire according to any one of the preceding claims, wherein the TPE of the adhesive layer is a polyether block copolymer (COPE). A tire according to any one of claims 1 to 4, wherein the TPE of the adhesive layer is a polyether polyamide block copolymer (PEBA). A tire according to any one of the preceding claims, wherein the one or more thermoplastic block elastomers of the adhesive layer composition are the only elastomers of said adhesive layer composition. 8. A tire according to any one of the preceding claims, wherein the receiving zone further comprises a layer denoted underlayer, positioned between the adhesive layer and the inner and / or outer surface of the tire carrying the receiving zone. . A tire according to any one of the preceding claims wherein the adhesive tape of the attached member is an acrylic adhesive tape. 10. A tire according to the preceding claim wherein the acrylic adhesive tape comprises from 50 to 100% by weight of so-called "primary" monomers selected from the group consisting of acrylic acid esters obtained with primary or secondary alcohols whose alkyl parts. are C4-C20; 0 to 35% by weight of so-called "secondary" monomers selected from the group consisting of methyl acrylate, methyl methacrylate, vinyl acetate, styrene and mixtures thereof; 0 to 15% of polar and functional monomers selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl acrylate, acrylamides, methacrylamides, N-vinyl pyrrolidone, N-vinyl caprolactam and their mixtures. 11. Tire according to the preceding claim wherein the acrylic adhesive tape comprises: from 50 to 100% by weight of so-called "primary" monomers selected from the group consisting of 2-ethylhexyl acrylate, iso-octyl acrylate, n-butyl acrylate and mixtures thereof; from 0 to 35% by weight of methyl acrylate; from 0 to 15% of acrylic acid. 12. A tire according to any preceding claim wherein said member is a housing adapted to receive an electronic device. 13. A tire according to any one of the preceding claims wherein said member is an electronic device. 14. A method of preparing a tire according to any one of claims 1 to 13 comprising a step of fixing the member to the inner and / or outer surface of the tire, in which: all or part of a tire is removed; protective film disposed on said adhesive layer; the adhesive strip of the member and the adhesive layer of the tire are brought into contact by applying pressure. 15. Method according to the preceding claim, wherein the tire was baked during a firing step, prior to the step of fixing the member to the surface of the tire. 16. A method according to any one of claims 14 to 15, wherein the protective film has been placed on the adhesive layer of the tire reception zone during its preparation, prior to the step of fixing the tire. member on the surface of the tire. 17. A method according to any one of claims 14 to 16, wherein the protective film has been placed on the adhesive layer of the tire receiving zone during its preparation, prior to the step of baking the tire. 18. A method according to any one of claims 14 to 17, wherein the protective film is a thermoplastic film selected such that the peel force of said film of the adhesive layer is less than 1 N / mm and preferably less than 1 N / mm. 0.5 N / mm at 20 ° C. 19. The method of claim 18, wherein the protective film is selected from the group of polyesters and films comprising at least one fluoropolymer. The method of claim 19, wherein the fluoropolymer comprises a fluorinated ethylene-propylene copolymer (FEP). 21. A method according to any one of claims 14 to 20, wherein the Tg (or Tf, if any) of the protective film is greater than the maximum cooking temperature of the rubbery mixture of the receiving zone.