WO2017220897A1

WO2017220897A1 - Tyre ready to receive a member on the surface thereof

Info

Publication number: WO2017220897A1
Application number: PCT/FR2017/051579
Authority: WO
Inventors: Jérémy DUCROT; José-Carlos ARAUJO DA SILVA
Original assignee: Compagnie Generale Des Etablissements Michelin
Priority date: 2016-06-21
Filing date: 2017-06-16
Publication date: 2017-12-28
Also published as: FR3052707A1

Abstract

The invention relates to a tyre comprising an inner and/or outer surface with a receiving region, an adhesive layer disposed on the receiving region, and a protective film disposed on the adhesive layer, characterised in that the composition of the adhesive layer is based on at least one block thermoplastic elastomer (TPE) having a viscosity greater than 2000 Pa.s at the curing temperature of the tyre. The invention also relates to an assembly comprising a tyre with a member secured to the surface thereof by the binding of the adhesive layer of the tyre and the object securing layer. The invention further relates to the method for producing said assembly.

Description

Pneumatic ready to receive an organ on its surface

The present invention relates to tires, and more particularly to tires ready to receive a member, for example electronic, attached 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.

[0004] Considering the applications currently being developed which are based on the fixation of objects, particularly electronic ones on tires, it is interesting for manufacturers to develop fastening solutions that 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, a fabric that imposes constraints of geometry, implementation.

The invention relates to a tire having an inner and / or outer surface with a receiving zone, an adhesive layer disposed on said receiving zone and a protective film disposed on said adhesive layer, characterized in that the composition of said adhesive layer is based on at least one thermoplastic block elastomer ΓΡΕ) having a viscosity greater than 2000 Pa.s at the baking temperature of the tire.

The use of such an adhesive layer has the advantage of allowing rapid adhesion, effective and durable an object on the tire with the receiving area, without the need for a tissue to the interface between the tire and the object attached to its surface. In addition, the specific viscosity of the TPEs used for the adhesive layer makes it possible for this layer not to deform (for example by creating bubbles in the layer) during the manufacture of the tire and in particular when the tire is released from the mold. during the removal of the protective film. During this operation, the reception area of the tire of the invention must separate from the baking membrane of the mold, without the reception area being degraded. Thus, with the specific TPEs of the invention, this separation of the reception zone and the baking membrane is optimal, at the end-of-firing temperature of the tire, which temperature may vary according to the nature and the dimensions of the tire. as well known to those skilled in the art, and which may especially be 150 ° C or 175 ° C. Thus, the specific materials used for the invention make it possible to preserve, even during the manufacturing steps of the tire equipped with the receiving zone, an undistorted surface of the adhesive layer, which promotes good adhesion of the object to the pneumatic, including hot when using the tire.

The invention also relates to a member (or object) intended to be fixed to the surface of a tire as defined above according to the invention, characterized in that said member comprises a fixing layer of which the composition is based on at least one thermoplastic block elastomer (TPE) having a viscosity greater than 2000 Pa.s at 150 ° C. 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.

The invention also relates to the assembly comprising a tire as defined above, wherein the protective film is removed in whole or part25 and a member fixed to said tire by a fixing zone, said organ being preferably an organ as defined above and hereinafter.

Another object of the invention is a method of fixing a member provided with a fixing zone, on the surface of a tire as described above, with an adhesive layer, protected by a film protection, and arranged on a reception area, in which:

- all or part of the protective film is removed;

if the attachment zone of the member is a fixing layer whose composition comprises a thermoplastic elastomer (TPE), the adhesive layer is raised to a temperature above the softening temperature of the thermoplastic blocks of the thermoplastic block elastomer (s).

- The pressure layer is brought into contact with the fixing layer and the adhesive layer. Preferably, the invention relates to the method as defined above wherein the member is a member as defined above, the attachment layer is raised to a temperature above the softening temperature of the thermoplastic blocks. of the thermoplastic block elastomer (s), before contacting with the adhesive layer.

Fixing the organ is thus performed very quickly and very simply. The fixing is effective and durable, and, in the case where the attachment zone of the member is a fixing layer whose composition comprises a thermoplastic elastomer (TPE), as soon as the The temperatures of the adhesion and fixation layers have fallen below the softening temperatures or Tg (or Tf, if any) of the TPEs. It also has the advantage of being totally reversible.

The invention relates more particularly to tires intended to equip 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

In the present description, unless otherwise expressly indicated, all the percentages (%) indicated are% by weight.

By "at least one" is meant "one or more", for example, "at least one 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, on a given reception area of its surface, with an adhesive layer whose composition is at base of at least one thermoplastic block elastomer ΓΡΕ) having a viscosity greater than 2000 Pa.s at the baking temperature of the tire, the adhesive layer being protected by a protective film as defined below.

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) having a viscosity greater than 2000 Pa.s at the baking temperature of the tire. This baking temperature of the tire may vary according to the nature and dimensions of the tire, as well known to those skilled in the art, and which may in particular be 150 ° C or 175 ° C.

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 included in a range of 50,000 to 300,000 g / mol was particularly well suited, especially to a use of TPE in a composition used in tires.

The number-average molecular weight (Mn) of the TPE elastomer is determined in a 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 on 0.45 μηι 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 μΐ. The detector is a differential refractometer "WATERS 2410" 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 (recall: 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 elastomeric block. The TPE presents preferably 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 TPE may 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 often also triblock elastomers with two rigid segments connected by a flexible segment. The rigid and flexible segments can be arranged linearly, star or connected. Typically, each of these segments or blocks often contains at least more than 5, usually more than 10 base units (e.g., styrene units and butadiene units for a styrene / butadiene / styrene block copolymer).

The TPE may also 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 TPEs will be called multiblock TPEs later, and are a sequence of elastomeric blocks - thermoplastic blocks.

In a first variant, the TPE is in a linear form. For example, TPE is a diblock copolymer: thermoplastic block / elastomeric 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 thermoplastic blocks terminals, at each of the two ends of the elastomeric 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 purposes of the invention is in a star shape at least three branches. For example, the TPE may then consist of a stellate elastomer block with at least three branches and a thermoplastic block, located at the end of each of the branches of the elastomeric 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 form or dendrimer. The TPE can then consist of a connected elastomeric block or dendrimer and a thermoplastic block, located at the end of the branches of the dendrimer elastomer block.

Nature of elastomeric blocks

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

For the elastomeric blocks with a carbon chain, if the elastomer part of the TPE does not contain any ethylenic unsaturation or comprises a molar content of unsaturated units of less than 10%, preferably less than 5% and more preferably less than 2%. relative to all the elastomeric block units, we will speak of a saturated or essentially saturated elastomeric block. If the elastomeric block of the TPE comprises 10 mol% and more ethylenic unsaturations (ie carbon-carbon double bonds), then we will 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 derived from these ethylenic monomers, mention may be made of polyalkylene blocks, such as the ethylene-propylene or ethylene-butylene random copolymers. Polyisobutylenes, polyethylenes, polypropylenes and polybutylenes may also be mentioned as being preferred for the invention. These preferred saturated elastomer blocks can also be obtained by hydrogenation of unsaturated elastomeric blocks. Also preferentially, it may also be aliphatic blocks from the family of polyethers, polyesters, or polycarbonates, and especially 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) conjugated diene monomers C4 - CM, the latter being copolymerizable with vinylaromatic monomers. In this case, it is a question of random copolymers. Preferably, these conjugated dienes are selected from the group consisting of isoprene, butadiene, isoprene copolymers, butadiene copolymers and mixtures thereof. 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 elastomer blocks of the 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 TPE good elastomeric properties and sufficient mechanical strength and compatible with use in pneumatic tires.

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

For the definition of the thermoplastic blocks, the glass transition temperature characteristic (Tg) of the thermoplastic rigid block will be used. 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 comprise one or more thermoplastic block (s) preferably having a Tg (or Tf, where appropriate) greater than or equal to 80 ° C. and consisting of ) from polymerized monomers. Preferably, this thermoplastic block has a Tg (or Tf, if applicable) in a range of 80 ° C to 250 ° C. Preferably, the Tg (or Tf, if appropriate) of this thermoplastic block is preferably from 80 ° C to 200 ° C, more preferably from 80 ° C to 180 ° C.

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

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

polyolefins (polyethylene, polypropylene)

polyurethanes;

polyamides;

polyesters;

polyacetals;

polyethers (polyethylene oxide, polyphenylene ether);

phenylene polysulfides;

polyfluorides (FEP, PFA, ETFE);

polystyrenes (detailed below);

polycarbonates;

polysulfones;

polymethyl methacrylate

polyetherimide

thermoplastic copolymers such as acrylonitrile-butadiene-styrene copolymer (ABS).

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

acenaphthylene: one skilled in the art can 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, 4-methylindene, dimethylindene, 2-phenylindene, 3-phenylindene and 4- phenylindene; those skilled in the art will for example be able to refer to the patent document US4946899, by the inventors Kennedy, Puskas, Kaszas and Hager and to the documents JE 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 cyclized units according to an intramolecular process; those skilled in the art can for example refer to the documents G. Kaszas, J. E. Puskas, .P. Kennedy Applied Polymer Science (1990) 39 (1) 1 19-144 and J. E. Puskas, G. Kaszas, J.P. Kennedy, Macromolecular Science, Chemistry A28 (1991) 65-80.

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 styrene monomer is to be understood in the present description any monomer comprising styrene, unsubstituted as substituted; among the substituted styrenes may be mentioned, for example, methylstyrenes (for example o-methylstyrene, m-methylstyrene or p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha-4- dimethylstyrene or diphenylethylene), para-tert-butylstyrene, chlorostyrenes (for example Γ-chloro-styrene, m-chlorostyrene, p-chlorostyrene, 2,4-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, α-fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6-difluorostyrene 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 layer including TPS may be affected. For these reasons, the styrene content is more preferably between 10% and 40%.

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

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

Also preferably according to the invention, the thermoplastic blocks of the TPE 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 PA6, PA11 or PA12 type, or polyesters of PET or PBT type and mixtures thereof. In this preferred embodiment, the elastomeric blocks consist essentially of polymers selected from the group consisting of polyisobutylenes, polyethylenes, polypropylenes, polybutylenes, polyethers and their mixtures; preferably in the group of polyethers 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 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 COPE (ether-ester block copolymer), 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.

Hot Viscosity of TPE

The hot dynamic viscosity (η) of the TPE is measured using an apparatus for measuring the viscoelastic properties of polymers and rubbers, the Rubber Process Analyzer 2000 from Alpha Technologies. The samples are prepared by hot-pressing in a press between 150 ° C. and 180 ° C., depending on the material, for 3 minutes under 1.5 bar pressure in a sheet of silicone release paper. A viscosity measurement according to a temperature sweep is carried out on a sample of 5 g 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. Begins the temperature sweep from 40 ° C to 200 ° C under a 10 Hz bias frequency with an imposed angle distortion of 5%. The dynamic viscosity values at 150 ° C. and 175 ° C. are then recorded on the rheogram obtained.

This hot viscosity of the TPE is variable, in particular according to the molecular weight, the polydispersity index, the branching rate, the length ratio of the elastomeric blocks / thermoplastic blocks, the nature of the constituent monomers of 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) 1800 Pa.s 1000 Pa.s

SIS (2) 1800 Pa.s 1000 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

(3) PEBA "Pebax 3533" from Arkema

(4) SEBS-MA "FG1901" from the company Kraton, methacrylate functional [0056] For the purposes of the invention and whatever the structure and the chemical nature of the TPE, as described above, the TPE used for the adhesive layer of the tire (and also preferably used for the attachment layer of the body), has a viscosity greater than 2000 Pa.s at the baking temperature of the tire, in particular at 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 baking temperature of the tire, in particular at 150 ° C or 175 ° C.

Examples of TPE

For example, the TPE is a copolymer whose elastomer portion is saturated, and comprising styrenic blocks and alkylene blocks. Alkylene blocks are preferably ethylene, propylene or butylene. More preferably, this TPE elastomer is chosen from the following group, consisting of diblock copolymers, linear or starred triblocks: styrene / ethylene / butylene (SEB), styrene / ethylene / propylene (SEP), styrene / ethylene / ethylene / propylene (SEEP ), styrene / ethylene / butylene / styrene (SEBS), 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 functionalized methacrylate (SEBS-MA) copolymers.

For example also, the TPE is a copolymer whose elastomer part is unsaturated, and which comprises diene blocks and preferably styrenic blocks, these diene blocks being in particular isoprene or butadiene blocks. More preferably, this TPS elastomer is chosen from the following group, consisting of diblock copolymers, linear or starred triblocks: 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, there may be mentioned copolymers comprising random copolymer blocks of ethylene and propylene / polypropylene, polyether / polyester (COPE), polyether / polyamide (PEBA).

It is also possible that the TPE given as examples above are mixed together in the layer according to the invention.

As examples of saturated or essentially saturated TPE elastomers that are commercially available, mention may be made of the elastomers of the SEPS, SEEPS or SEBS type marketed by the Kraton company under the name "Kraton G" or the Kuraray company under the name "Kraton G". denomination "Septon". Mention may also be made of the elastomers of SEBS-MA type sold by Kraton under the trade names "FG1901" or "FG1924", or the SIBS elastomers marketed by Kaneka under the name trade name "SIBSTAR". Among the multiblock TPEs, mention may be made of the "Vistamaxx" TPE marketed by Exxon; the COPE TPE marketed by the company DSM under the name "Arnitel", or by the company Dupont under the name "Hytrel", or by the company Ticona under the name "Riteflex"; PEBA PEPE marketed by Arkema under the name "PEBAX" (eg "PEBAX 3533").

Various additives

The composition of the adhesive layer may optionally comprise, in combination with the previously described TPE elastomer, at least one polyphenylene ether (abbreviated as "EPP").

PPE are well known to those skilled in the art, they are solid resins 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-Butadiene-Styrene Blends", Tucker, Barlow and Paul, Macromolecules, 1988, 21, 1678-1685).

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

The number-average molecular weight (Mn) is determined in a known manner by steric exclusion chromatography (SEC). The sample is first solubilized in tetrahydrofuran at a concentration of about 1 g / l; then the solution is filtered on 0.45 μπι 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. We uses a set of four WATERS columns in series, trade names "STYRAGEL"("HMW7","HMW6E" and two "HT6E"). The injected volume of the solution of the polymer sample is 100 μΐ. 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.

By way of non-limiting examples of PPE polymers that can be used in the sealed composition according to an object of the invention, mention may be made in particular of those selected from the group consisting of poly (2,6-dimethyl-1,4) phenylene ether), poly (2,6-dimethyl-co-2,3,6-trimethyl-1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether poly (2,6-diethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl), 4-phenylene ether), poly- (2,6-dipropyl-1,4-phenylene ether), poly (2-ethyl-6-propyl-1,4-phenylene 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 di-methoxy-1,4-phenylene ether), poly (2-methoxy-6-ethoxy-1,4-phenylene ether), poly (2-ethyl-6-stearyloxy-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether) , poly (2-ethoxy-1,4-phenylene ether), poly (2-chloro-1,4-phenylene ether), poly (2,6-dibromo-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 EPP used is poly (2,6-dimethyl-1,4-phenylene ether). Such commercially available PEPs are, for example, "Xyron S202" from Asahi Kasei or "Noryl S Al 20" from Sabic. Tire reception area

The tire of the invention comprises an inner and / or outer surface with a reception area, on which is disposed an adhesive layer and a protective film disposed on said adhesive layer.

According to a preferred arrangement of the invention, the reception zone may consist solely of said adhesive layer, and, when in place, the protective film.

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

Said sub-layer may be of several kinds, it may be a local application of a surface preparation solution, known to those skilled 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 feature of comprising a thermoplastic block elastomer ΓΡΕ) having a viscosity greater than 2000 Pa.s at the baking temperature of the tire as defined above, with all the preferences. and all embodiments.

By way of example, it is advantageous to use a mixture of TPEs, one of which has a number-average molecular weight Mn suitable for good temperature stability and a low-mass TPE Mn to promote good bonding between the adhesive layers of the tire and fixing the organ.

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 rubber 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 for the expression in unit phr.

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 the joining of the adhesive layer and the attachment layer of the member, particularly by a lowering of the module and an increase in the tackifying power.

Any extension oil, of a slightly polar nature, capable of extending, plasticizing elastomers, especially thermoplastics, may be used. 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. The skilled person 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 a liquid isoprene rubber type oil ("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 may be particularly advantageous for adjusting the softening temperatures and the necessary adhesion levels of the adhesive or fixing layers.

Protective film

The protective film is preferably a flexible heat-resistant film which preferably has a limited adhesion to the adhesive layer to be able 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 μηι.

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 use, 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 rubbery mixture of the zone of reception of the surface of the tire. 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-stick 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%. His thickness is 25 μηι. 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 drum for manufacturing the tire and then with the baking membrane of the vulcanization mold. 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.

Body intended to be attached to 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. The member is attached to the tire through the attachment layer on the body. Area of fixation of the organ

The attachment zone of the member may in particular and preferably be an adhesive tape, or a fastening layer whose composition comprises a thermoplastic elastomer (TPE).

According to a first preferred embodiment, the attachment zone of the member is a fixing layer whose composition comprises one or more thermoplastic elastomer (s) (TPE) having a viscosity greater than 2000 Pa. at 150 ° C. and preferably at 175 ° C. also, as defined above, with all the preferences and all the embodiments.

Preferably, the thermoplastic block elastomer (TPE) having a viscosity greater than 2000 Pa.s at 150 ° C. and preferably at 175 ° C. also, are chosen such that the adhesion strength, c that is, the force required to separate the two adhesive and fastening layers in a peel test is greater than 0.5 N / mm, preferably greater than 1 N / mm, more preferably greater than 2 N / mm at 60 ° C.

According to a preferred embodiment, the thermoplastic blocks of the TPE of the fixing layer are compatible (that is to say, similar because of their masses, their polarities or their Tg) with the thermoplastic blocks of the or thermoplastic block elastomers of the adhesive layer composition of the tire.

According to a preferred embodiment, the thermoplastic blocks of the TPE or the TPE of the composition of the attachment layer of the member are identical to the thermoplastic blocks of the TPE or the TPE of the composition of the adhesive layer of the tire.

According to a very preferred embodiment, the TPE of the attachment and adhesive layers are identical.

The composition of the attachment layer of the member may also comprise diene elastomers saturated or unsaturated, in a minority, various oils or additives such as previously described for the adhesive layer of the tire. According to a second preferred embodiment, the fastening zone of the member is an adhesive strip. The adhesive tape used as a fastening zone on the body or as an adhesive part on the tire) may be any type of known adhesive tape, sometimes called "tape" 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. There are several methods for identifying a PSA, including 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 has tack (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 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).

[00107] Preferably, for the invention, an "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 0 to 35% by weight of monomers said "secondary", of 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 is preferably 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.

[00109] 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 a power of adhesion high 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.

Fixing the body to the tire

The invention also relates to the assembly comprising a tire as defined above with a member attached to its surface by the connection of the adhesive layer of the tire and the attachment zone of the object, said object being preferably an object as defined above.

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

if the attachment zone of the member is a fixing layer whose composition comprises a thermoplastic elastomer (TPE), the adhesive layer is raised to a temperature above the softening temperature of the thermoplastic blocks of the thermoplastic block elastomer (s). ,

- The pressure layer is brought into contact with the fixing layer and the adhesive layer.

Preferably, the invention relates to the method as defined above wherein the member is a member as defined above, the attachment layer is raised to a temperature above the softening temperature of the thermoplastic blocks. of the thermoplastic block elastomer (s), before contacting with the adhesive layer.

Fixing the organ is thus performed very quickly and very simply. The fixing is effective and durable as soon as the temperatures of the adhesion and fixation layers have fallen back under the softening temperatures or Tg (or Tf, if any) of the TPEs. It also has the advantage of being totally reversible.

Examples of realization

[00114] Complementary elements of the invention are now described with the aid of the accompanying drawings, presented in a non-limiting manner, in which:

Figure 1 shows very schematically (without respecting a specific scale), a radial section of a tire according to one embodiment of the invention;

- Figure 2 shows a partial radial section of a tire blank according to one embodiment of the invention;

Figure 3 illustrates an organ with a fixation layer; and

Figure 4 shows the member attached to the tire surface.

[00115] Figure 1 schematically shows a radial section of a pneumatic or pneumatic tire incorporating in a reception area 13 given an adhesive layer with a protective film according to one embodiment of the invention.

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 tire which is located midway between 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 1 1 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 attachment layer of the organ.

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

The adhesive layer 1 1 consists of a specific TPE, as described above and in particular selected from those proposed in the examples below.

The separable protective film 12 is a thermoplastic film comprising, by way of example, a fluoropolymer. 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 μηι. 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 precisely, the radially innermost protective film 12 is applied first to the manufacturing drum 15. The adhesive layer 11 is then put into place. Next, all the other conventional components pneumatic tire.

After shaping, the crown plies and the tread are placed 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 specific viscosity of the TPEs used for the adhesive layer allows this layer not to be deformed (for example by creating bubbles in the layer) during the manufacture of the tire and in particular at the exit of the tire 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 specific TPEs of the invention, this separation of the reception zone and the baking membrane is optimal, at the end-of-firing temperature of the tire, which temperature may vary according to the nature and the dimensions of the tire. as well known to those skilled in the art, and which may especially be 150 ° C or 175 ° C. The protective film 12 can be easily removed at the outlet of the tire vulcanization mold. 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 area on the surface of the tire after the conformation of the tire blank and before introducing it into the vulcanization mold. .

FIG. 3 schematically shows a member 20 comprising a housing 22 and a fixing layer 24. The material of the fixing layer 24 is based on at least one thermoplastic elastomer TPE, which may especially be a TPE specific to high viscosity when hot as described above and in particular chosen from those proposed in the examples below, the rigid thermoplastic blocks are of the same nature as the rigid blocks of the TPE or the adhesive layer of the tire. The fixing layer is preferably based on the same TPE as that of the adhesive layer. 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 fixing layer 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 fixing layer according to that of the adhesive layer and the size and mass of the organ.

[00129] Figure 4 shows the entire 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 1 1 of the tire 1;

the tire adhesion layers 1 1 of the tire and the fastening 24 of the organ are heated to temperatures higher than the Tg (or Tf, if applicable) of the elastomers thermoplastic blocks; this heating can be achieved by any means (blowing hot air, infra-red radiation ...); the surface areas of the two adhesion and attachment layers are then beyond their operating temperatures and are thus softened; the fixing layer and the adhesive layer are brought into contact by applying a contact pressure; and

the contact is maintained until the two adhesion and fixation layers below the Tg (or Tf, if applicable) of the TPEs have cooled.

The contact pressure is preferably greater than 0.05 bar (more than the atmospheric pressure). Those skilled in the art will know how to adjust it depending on the attachment and adhesive layers used.

As soon as the cooling is effective, the member is fixed robustly 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

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 a tight inner layer. (sometimes also called "inner liner") of pneumatic, based on butyl rubber (isobutylene and isoprene copolymer) further comprising the usual additives (filler, sulfur, accelerator, ZnO, acid stearic, 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 rubber mix flank instead a usual waterproof inner layer layer. This same test is used to measure the adhesion of the adhesive layer and the fixing layer.

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 tissue carcass carcass type tourism.

A rupture 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.

[00138] 30 mm wide strips were cut with a cutter. Both sides of the breakout primer were then placed into 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 ambient temperature (23 ° C.) and at 60 ° C.

[00140] Adhesion tests (peel tests) were also conducted to test the ability of the adhesive layer to adhere after firing to a fastening layer as it is present on the body to be fixed to the tire. In this case, the specimens are made by contacting the adhesive layer to be tested with two similar half-specimens made according to the following stack:

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).

The half-samples are then vulcanized at 140 ° C for 50 minutes and at 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 for 30 seconds under a temperature of 200 ° C. and a pressure of 50 mbar with a rupture primer is placed at the interface between the two layers. adhesive.

[00143] 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. Tensile forces are recorded and these are determined 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.

Evaluation of the profile of the adhesion layer after the exit of the baking mold of the tire equipped with the reception area

[00145] Evaluation tests of the profile of the adhesion layer after the exit of the baking mold of the tire provided with the reception zone were conducted to evaluate the degradation of the adhesion layer after baking. To do this, the protective film, deposited on the adhesion layer before baking, is removed after baking at the desired temperature. The Degradation of the adhesion layer is visually evaluated according to the proportion of surface area that provides a degraded or bubbled appearance and the adhesion layer surface that provides a macroscopically smooth surface appearance. When this surface ratio is less than 10%, ie when less than 10% of the surface of the adhesion layer is degraded (absence of bubble), the evaluation is positive and noted (+) and when more than 10% of the adhesion layer is degraded the evaluation is negative and noted (-). This test can be carried out at variable cooking temperatures, and especially after cooking at 150 ° C. or 175 ° C.

Examples of compositions:

Table 1 below shows the compositions tested in which:

C-1 is a usual composition of waterproof inner layer;

C-2 and C-3 are control compositions comprising a TPE that does not meet the hot viscosity criterion of the invention

C-4 and C-5 are adhesive layers according to the invention.

Table 1: compositions in pce

Composition C-1 C-2 C-3 C-4 C-5

Butyl Elastomer (1) 100

Carbon black (N772) 50

Zinc oxide 1.5

Stearic acid 1,5

Sulfenamide (2) 1,2

Sulfur 1.5

TPE 1 (3) 100

TPE 2 (4) 100

TPE 3 (5) 100

TPE 4 (6) 100 (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 "DL 161" from Kraton;

(4) SIS "D 1,163" of the Kraton Company;

(5) SEBS-MA "FG1901" from Kraton;

(6) PEBA "PEBAX 3533" from Arkema.

Test results

[00147] To represent the adhesion of the adhesive layer on the inner sealing layer of the tire provided with the receiving zone, the adhesion values are measured (peel test) for the assemblies of the layers C-2 to C- 5 on the C-1 layer and the results are shown in Table 2. In the case of the C-5 / C-1 assembly, an undercoat composed of a styrene-butadiene-styrene thermoplastic elastomer and a a polyphenylene ether (66 phr) is interposed between the two layers C-5 and C-1.

Table 2

The results presented in Table 2 confirm the advantage of using as an adhesive layer a thermoplastic block composition set up as described. The adhesion values obtained for the tests according to the invention are remarkable, both room temperature only at the temperature of 60 ° C. In addition, the profiles of the adhesion layers after firing are good in the tests according to the invention, indicating a facilitated preparation.

[00149] To represent the adhesion of the member to the tire according to the invention, the adhesion values are measured (peel test) for the assemblies of the layers C-2 to C-5 on themselves and the The results are shown in Table 3.

Table 3

[00150] The results presented in Table 3 confirm the advantage of using as adhesive and fixing layers a thermoplastic block composition set up as described. The adhesion values obtained are remarkable, in particular at a temperature of 60.degree.

[00151] 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. Also, the invention allows easy preparation of the tires, without degradation of the adhesive layer of the reception area at the exit of the baking mold.

This attachment is reversible, that is to say that the two adhesive layers and fixing can be disassembled by heating above the Tg of their rigid blocks (or Tf if necessary) and then a tool passage . The adhesive layer thus disclosed can then be used again to glue the same or another member.

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

Claims

1. A tire comprising an inner and / or outer surface with a reception zone, an adhesive layer disposed on said reception zone and a protective film disposed on said adhesive layer, characterized in that the composition of said adhesive layer is based on at least one thermoplastic block elastomer ΓΡΕ) having a viscosity greater than 2000 Pa.s at the baking temperature of the tire.

2. The tire according to claim 1, wherein the TPE of the composition of the adhesive layer has a viscosity greater than 2000 Pa.s at 150 ° C., preferably greater than

2000 Pa.s at 175 ° C.

3. A tire according to any one of the preceding claims, wherein the TPE of the composition of the adhesive layer has a viscosity greater than 2200 Pa.s at the baking temperature of the tire.

A tire according to any one of the preceding claims, wherein the TPE of the composition of the adhesive layer has a viscosity of greater than 2200 Pa.s at 150 ° C, preferably greater than 2200 Pa.s at 175 ° C.

5. A tire according to any one of the preceding claims, wherein the TPE of the composition of the adhesive layer has a viscosity greater than 3000 Pa.s at the baking temperature of the tire.

6. A tire according to any one of the preceding claims, wherein the TPE of the composition of the adhesive layer has a viscosity greater than 3000 Pa.s at 150 ° C, preferably greater than 3000 Pa.s at 175 ° C.

A tire according to any one of the preceding claims, wherein the TPE elastomeric block of the composition of the adhesive layer is saturated or substantially saturated, i.e. comprising a molar ratio of unsaturated units of less than 10%. preferably less than 5%, more preferably less than 2%, relative to all the units of the elastomeric block.

8. A tire according to any one of the preceding claims, wherein the TPE of the composition of the adhesive layer has thermoplastic blocks essentially consisting of polymers selected from the group consisting of polyamides, polyesters and mixtures thereof.

9. A tire according to the preceding claim, wherein the TPE of the composition of the adhesive layer has elastomeric blocks essentially consisting of polymers selected from the group consisting of polyisobutylenes, polyethylenes, polypropylenes, polybutylenes, polyethers and their mixtures ; preferably in the group of polyethers and mixtures thereof.

A tire according to any one of claims 1 to 7, wherein the TPE of the composition of the adhesive layer is a styrenic thermoplastic elastomer (TPS), that is, whose thermoplastic block consists essentially of monomers styrenics.

A tire according to the preceding claim, wherein the TPS thermoplastic block of the composition of the adhesive layer is a polystyrene block.

Tire according to any one of claims 10 to 11, in which the TPS elastomer block of the composition of the adhesive layer is selected from the group consisting of polyisobutylenes, polyethylenes, polypropylenes, polybutylenes, and their mixtures.

A tire according to any one of claims 1 to 6 and 10 to 11, wherein the TPE of the composition of the adhesive layer is a styrenic thermoplastic elastomer (TPS), including the elastomeric block of the TPE of the composition of the layer. adhesive is unsaturated, that is to say comprising a molar ratio of unsaturated units greater than 10% relative to all the units of the elastomeric block.

Tire according to the preceding claim, wherein the elastomer block of the TPE of the composition of the adhesive layer is chosen from the group consisting of C4-C12 conjugated diene polymers and their mixtures, preferably from the group of polybutadienes, polyisoprenes, butadiene / styrene copolymers, isoprene / styrene copolymers and mixtures thereof.

A tire according to any one of the preceding claims, wherein the block thermoplastic elastomer of the adhesive layer composition is a TPE blend.

A tire according to any one of the preceding claims wherein the thermoplastic block elastomer (TPE) of the adhesive layer composition is the only elastomer of said adhesive layer composition.

17. A tire according to any one of the preceding claims, wherein the composition of the adhesive layer comprises one or more polyphenylene ethers ("EPP").

18. A tire according to the preceding claim, wherein the polyphenylene ether has a glass transition temperature greater than 150 ° C, preferably greater than 180 ° C.

19. A tire according to any one of claims 17 to 18, wherein the polyphenylene ether is selected from the group consisting of poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6- dimethyl-2,3,6-trimethyl-1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether), poly (2,6-diethyl-1) 4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), 6-dipropyl-1,4-phenylene ether), poly (2-ethyl-6-propyl-1,4-phenylene 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-phenylene ether), poly (2,6-dichloro-1,4) phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2-ethoxy-1,4-phenylene ether), poly ( 2-chloro-1,4-phenylene ether), poly (2,6-dibromo-1,4-phenylene ether), poly (3-bromo-2,6-dimethyl-1,4-phenylene ether) , their respective copolymers, and mixtures of these homopolymers or copolymers.

20. A tire according to any one of claims 17 to 18, wherein the polyphenylene ether is poly (2,6-dimethyl-1,4-phenylene ether).

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. .

22. A tire according to any one of the preceding claims, 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 0, 5 N / mm, at 20 ° C.

23. The tire of claim 22, wherein the protective film is selected from the group of polyesters and films comprising at least one fluoropolymer.

The tire of claim 23, wherein the fluoropolymer comprises a fluorinated ethylene-propylene copolymer (FEP).

A tire according to any one of the preceding claims, wherein the Tg (or Tf, if any) of the protective film is greater than the maximum firing temperature of the rubbery mixture of the receiving zone.

26. An assembly of a tire according to any one of claims 1 to 25, wherein the protective film is removed in whole or in part and a member fixed within said tire by a fixing layer.

27. Pneumatic assembly - member according to the preceding claim wherein said member comprises a fixing layer whose composition is based on at least one thermoplastic block elastomer (TPE) having a viscosity greater than 2000 Pa.s at 150 ° C .

28. Pneumatic assembly - member according to the preceding claim wherein the composition of said fixing layer is based on at least one thermoplastic block elastomer identical to said thermoplastic block elastomer of the composition of said adhesive layer of the reception zone. of said tire.

29. Pneumatic assembly - member according to any one of claims 26 to 28 wherein said member is a housing adapted to receive an electronic device.

30. Pneumatic assembly - member according to any one of claims 26 to 28 wherein said member is an electronic device.

31. A method of fastening a member provided with an attachment zone to the surface of a tire according to any one of claims 1 to 25, wherein:

- all or part of the protective film is removed;

if the attachment zone of the member is a fixing layer whose composition comprises a thermoplastic elastomer (TPE), the adhesive layer is raised to a temperature above the softening temperature of the thermoplastic blocks of the thermoplastic block elastomer (s). ;

32. The process as claimed in the preceding claim, in which the element is according to any one of claims 27 to 30, and in which the fixing layer is raised to a temperature above the softening temperature of the thermoplastic blocks of the at least one thermoplastic elastomer. blocks, before contacting the adhesive layer.