Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C1/0008—Compositions of the inner liner
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
  • B29D30/0681—Parts of pneumatic tyres; accessories, auxiliary operations
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C5/00—Inflatable pneumatic tyres or inner tubes
  • B60C5/12—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim
  • B60C5/14—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim with impervious liner or coating on the inner wall of the tyre
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
  • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
  • B29D30/0681—Parts of pneumatic tyres; accessories, auxiliary operations
  • B29D2030/0682—Inner liners
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/01—Hydrocarbons
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit

Definitions

• the present invention relates to "pneumatic" objects, i.e., by definition, objects that take their usable form when inflated with air or an equivalent inflation gas.
• the radially inner face has an airtight layer (or more generally any inflation gas) which allows the swelling and maintaining the pressure of the tire.
• airtight layer or more generally any inflation gas
• Its sealing properties enable it to guarantee a relatively low rate of pressure loss, making it possible to maintain the swollen bandage in normal operating condition for a sufficient duration, normally of several weeks or several months. It also serves to protect the carcass reinforcement from the diffusion of air from the interior space to the bandage.
• ner liner internal layer or "inner liner”
• butyl rubber isobutylene copolymer and isoprene
• compositions based on rubber or butyl elastomer are well-known disadvantages of compositions based on rubber or butyl elastomer.
• they have significant hysteretic losses, moreover over a wide temperature spectrum, a disadvantage that penalizes the rolling resistance of tires.
• the present invention relates to a pneumatic object provided with an elastomeric layer impervious to inflation gases such as air, said elastomer layer comprising at least, as majority elastomer, a styrene thermoplastic elastomer / isobutylene / styrene (abbreviated as "SIBS").
• SIBS styrene thermoplastic elastomer / isobutylene / styrene
• SIBS In comparison with butyl rubbers, SIBS also has the major advantage, because of its thermoplastic nature, of being able to be worked as is in the molten state (liquid), and therefore to offer a simplified implementation possibility. .
• the invention particularly relates to pneumatic objects of rubber such as pneumatic tires, or inner tubes, in particular tubes for pneumatic tires.
• the invention relates more particularly to pneumatic tires intended for equipping tourism-type motor vehicles, SUVs ("Sport Utility Vehicles"), two wheels (in particular motorcycles), planes, such as industrial vehicles chosen from light trucks, "heavy vehicles "- that is, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering machinery - other transport or handling vehicles.
• SUVs Sport Utility Vehicles
• two wheels in particular motorcycles
• planes such as industrial vehicles chosen from light trucks, "heavy vehicles "- that is, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering machinery - other transport or handling vehicles.
• the invention also relates to a method for sealing a pneumatic object vis-à-vis the inflation gases, wherein is incorporated in said pneumatic object during its manufacture, or is added to said pneumatic object after its manufacture, a gas-tight elastomeric layer as defined above.
• the invention also relates to the use as an inflation-tight layer, in a pneumatic object, of an elastomeric layer as defined above.
• 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 (i.e., terminals a and b excluded) while any range of values designated by the expression “from a to b” means the range from a to b (i.e., including the strict limits a and b).
• the pneumatic object according to the invention has the essential feature of being provided with at least one gastight elastomer layer or composition which comprises at least, as majority elastomer (by weight), a thermoplastic elastomer SIBS which can be associated, according to a preferred embodiment of the invention, at least one extension oil as a plasticizer.
• SIBS elastomer in the present application, by definition, any styrene / isobutylene / styrene triblock elastomer whose polyisobutylene central block may be interrupted or not by one or more unsaturated units, in particular one or more diene units such as isoprenic, possibly halogenated.
• TPE thermoplastic elastomers
• TPS styrenic thermoplastic elastomers
• the TPS elastomers are generally in the form of block copolymers based on styrene.
• thermoplastic polymers and elastomers consist of rigid polystyrene blocks connected by flexible elastomer blocks, for example polybutadiene, polyisoprene, poly (ethylene / butylene), or else polyisobutylene in the case for example of SIBS.
• rigid polystyrene blocks connected by flexible elastomer blocks, for example polybutadiene, polyisoprene, poly (ethylene / butylene), or else polyisobutylene in the case for example of SIBS.
• They are often triblock elastomers with two rigid segments connected by a flexible segment.
• the rigid and flexible segments can be arranged linearly, star or connected.
• each of these segments or blocks contains at least more than 5, usually more than 10 base units (for example styrene and isobutylene for SIBS).
• the weight content of styrene in the SIBS elastomer is between 5% and 50%. Below the minimum indicated, the thermoplastic nature of the elastomer may decrease significantly while above the maximum recommended, the elasticity of the seal layer may be affected. For these reasons, the styrene content is more preferably between 10 and 40%, in particular between 15 and 35%.
• styrene is meant in the present description any monomer containing styrene, unsubstituted as substituted; among the substituted styrenes may be mentioned for example methylstyrenes (for example ⁇ -methylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, tert-butylstyrene) and chlorostyrenes (for example monochlorostyrene, dichlorostyrene).
• methylstyrenes for example ⁇ -methylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, tert-butylstyrene
• chlorostyrenes for example monochlorostyrene, dichlorostyrene
• the glass transition temperature (Tg, measured according to ASTM D3418) of the SIBS elastomer be less than -20 ° C, more preferably less than -40 ° C.
• Tg higher than these minima can reduce the performance of the waterproof layer during use at very low temperatures; for such use, the Tg of the SIBS elastomer is more preferably still lower than -50 ° C.
• the number-average molecular weight (denoted Mn) of the SIBS elastomer is preferably between 30,000 and 500,000 g / mol, more preferably between 40,000 and 400,000 g / mol.
• Mn number-average molecular weight
• the number-average molecular weight (Mn) of the SIBS elastomer is determined in a known manner by steric exclusion chromatography (SEC).
• SEC steric exclusion chromatography
• the sample is first solubilized in tetrahydrofuran at a concentration of about 1 g / l; then the solution is filtered on a 0.45 ⁇ m porosity filter before injection.
• the equipment used is a chromatographic chain "WATERS alliance”.
• 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 ⁇ l.
• 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 SIBS elastomer may alone constitute the gas-tight elastomeric layer or may be associated in this elastomeric layer with other constituents to form an elastomer composition.
• the SIBS elastomer constitutes the majority elastomer by weight; it then preferably represents more than 50%, more preferably more than 70% by weight of all the elastomers.
• Such complementary elastomers preferably minor ones, could be, for example, diene elastomers such as natural rubber or synthetic polyisoprene, butyl rubber or thermoplastic styrene elastomers (TPS) other than SIBS, within the limits of the compatibility of their microstructures. .
• TPS elastomer other than SIBS that may be used in addition to the SIBS previously described, mention may be made in particular of a TPS elastomer chosen from the group consisting of styrene / butadiene / styrene block copolymers, styrene / isoprene / styrene block copolymers and block copolymers.
• said optional additional TPS elastomer is selected from the group consisting of styrene / ethylene / butylene / styrene block copolymers, styrene / ethylene / propylene / styrene block copolymers and mixtures of these copolymers.
• the SIBS elastomer is the only elastomer, and the only thermoplastic elastomer present in the gas-tight elastomeric composition or layer.
• SIBS elastomers can be implemented in a conventional manner for TPE, by extrusion or molding, for example from a raw material available in the form of beads or granules. They are commercially available, sold for example by KANEKA under the name "SIBSTAR" (e.g. "Sibstar 102T", “Sibstar 103T” or “Sibstar 073T”).
• the SIBS elastomer previously described is sufficient on its own for the gas-tight function to be fulfilled vis-à-vis the pneumatic objects in which it is used.
• the latter is used in a composition which also comprises, as plasticizer, an extender oil (or plasticizing oil) whose function is to facilitate the setting particularly the integration into the pneumatic object by a lowering of the module and an increase in the tackifying power of the gas-tight layer, at the cost, however, of a certain loss of tightness.
• an extender oil or plasticizing oil
• extension oil preferably of a slightly polar nature, capable of extending and 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.
• 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, naphthenic oils (low or high viscosity), aromatic oils, mineral oils, and mixtures of these oils.
• a polybutene-type oil is preferably used, in particular a polyisobutylene oil (abbreviated as "PIB"), which has demonstrated the best compromise of properties compared to the other oils tested, in particular to a conventional oil of the paraffinic type.
• PIB polyisobutylene oil
• polyisobutylene oils are sold in particular by the company UNIVAR under the name "Dynapak PoIy” (eg "Dynapak PoIy 190"), by BASF under the names “Glissopal” (eg “Glissopal 1000") or "Oppanol "(eg” Oppanol B 12 "); paraffinic oils are marketed for example by EXXON under the name “Telura 618" or by Repsol under the name "Extensol 51".
• the number-average molecular mass (Mn) of the extender oil is preferably between 200 and 25,000 g / mol, more preferably between 300 and 10,000 g / mol. For masses Mn too low, there is a risk of migration of the oil outside the composition, while too large masses can cause excessive stiffening of this composition. A mass Mn between 350 and
• 4000 g / mol in particular between 400 and 3000 g / mol, has proved to be an excellent compromise for the intended applications, in particular for use in a tire.
• the number average molecular weight (Mn) of the extender oil is determined by SEC, the sample being solubilized beforehand in tetrahydrofuran at a concentration of about 1 g / l; then the solution is filtered on a 0.45 ⁇ m porosity filter before injection.
• the equipment is the chromatographic chain "WATERS alliance”.
• the elution solvent is tetrahydrofuran, the flow rate is 1 ml / min, the temperature of the system is 35 ° C. and the analysis time is 30 minutes.
• the injected volume of the solution of the polymer sample is 100 ⁇ l.
• 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 level of extender oil is greater than 5 phr, preferably between
• the elastomeric composition may have too high rigidity for certain applications while beyond the maximum recommended, there is a risk of insufficient cohesion of the composition and loss of tightness that can be harmful depending on the application.
• the extender oil content be greater than 10 phr, in particular between 10 and 90 phr, more preferably still greater than 20 phr, especially between 20 and 80 phr.
• the airtight layer or composition described above may also include the various additives usually present in the airtight layers known to those skilled in the art.
• examples include reinforcing fillers such as carbon black or silica, non-reinforcing or inert fillers, coloring agents that can be advantageously used for coloring the composition, and lamellar fillers that further improve the sealing (eg phyllosilicates such as kaolin, talc, mica, graphite, clays or clays modified (“organo clays”), plasticizers other than the aforementioned extension oils, protective agents such as antioxidants or antiozonants, anti-UV, various agents for implementation or other stabilizers, or promoters capable of promoting adhesion to the rest of the structure of the pneumatic object.
• reinforcing fillers such as carbon black or silica
• coloring agents that can be advantageously used for coloring the composition
• lamellar fillers that further improve the sealing
• phyllosilicates such as kaolin, talc, mica,
• the gas-tight composition could also comprise, still in a minority weight fraction relative to the SIBS elastomer, polymers other than elastomers, such as for example thermoplastic polymers. compatible with SIBS elastomer.
• the gas-tight layer or composition previously described is a solid (at 23 ° C.) and elastic compound, which is particularly characterized, thanks to its specific formulation, by a very high flexibility and very high deformability.
• this gas-tight layer or composition has a secant modulus in extension, at 10% elongation (denoted MlO), which is less than 2 MPa, more preferably less than 1.5. MPa (especially less than 1 MPa). This quantity is measured at first elongation (ie without accommodation cycle) at a temperature of 23 ° C, with a pulling speed of 500 mm / min (ASTM D412), and reported in section initial test.
• the layer or composition based on SIBS previously described can be used as an airtight layer in any type of pneumatic object.
• pneumatic objects include pneumatic boats, balls or balls used for play or sport. It is particularly well suited for use as an airtight layer (or any other inflation gas, for example nitrogen) in a pneumatic object, finished or semi-finished product, of rubber, especially in a tire for a vehicle. automobile such as a two-wheeled vehicle, tourism or industrial.
• Such an airtight layer is preferentially disposed on the inner wall of the pneumatic object, but it can also be completely integrated into its internal structure.
• the thickness of the airtight layer is preferably greater than 0.05 mm, more preferably between 0.1 mm and 10 mm (especially between 0.1 and 1.0 mm).
• the preferred thickness may be between 1 and 3 mm.
• the preferred thickness may be between 2 and 10 mm.
• the airtight composition described above has the advantage of having a significantly lower hysteresis, and thus of providing reduced rolling resistance to pneumatic tires, as demonstrated in the following embodiments.
• the gas-tight elastomeric layer previously described is advantageously usable in pneumatic tires of all types of vehicles, in particular passenger vehicles or industrial vehicles such as heavy vehicles.
• the single appended figure shows very schematically (without respecting a specific scale), a radial section of a tire according to the invention.
• This tire 1 has a crown 2 reinforced by a crown reinforcement or belt 6, two sidewalls 3 and two beads 4, each of these beads 4 being reinforced with a rod 5.
• the crown 2 is surmounted by a tread represented in this schematic figure.
• 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 which is shown here mounted on its rim 9.
• 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 halfway between the two beads 4 and goes through the middle of the crown frame 6).
• radial cables for example textile or metal
• the inner wall of the tire 1 comprises an airtight layer 10, for example of a thickness equal to about 0.9 mm, on the side of the internal cavity 11 of the tire 1.
• This inner layer covers the entire inner wall of the tire, extending from one side to the other, at least to the level of the rim hook when the tire is in the mounted position. It defines the radially inner face of said tire intended to protect the carcass reinforcement from the diffusion of air coming from the space 11 inside the tire. It allows inflation and pressure maintenance of the tire; its sealing properties must enable it to guarantee a relatively low rate of pressure loss, to maintain the swollen bandage, in normal operating condition, for a sufficient duration, normally of several weeks or several months.
• the tire according to the invention uses in this example, as an airtight layer, a SIBS elastomer ("Sibstar 102T" with a styrene content). about 15%, a Tg of about -65 ° C and an Mn of about 90,000 g / mol) extended with about 55 phr of oil PIB ("Dynapak PoIy 190" - Mn of the order of 1000 g / mol).
• the tire provided with its airtight layer (10) as described above can be made before or after vulcanization (or cooking).
• the airtight layer is simply applied in a conventional manner to the desired location, for forming the layer 10.
• the vulcanization is then carried out conventionally.
• SIBS elastomers support the constraints of the vulcanization step.
• An advantageous manufacturing variant for those skilled in the tire industry, will for example consist in a first step of laying the airtight layer directly on a manufacturing drum in the form of a flat tire. a layer (“skim") of suitable thickness, before covering the latter with the rest of the structure of the tire, according to manufacturing techniques well known to those skilled in the art.
• the sealing layer is applied inside the baked tire by any appropriate means, for example by gluing, spraying or else extruding and blowing a film of appropriate thickness.
• a rigid wall permeameter was used, placed in an oven (temperature of 60 ° C in this case), provided with a pressure sensor (calibrated in the range of 0 to 6 bars) and connected to a tube equipped with an inflation valve.
• the permeameter can receive standard specimens in the form of a disc (for example 65 mm diameter in this case) and with a uniform thickness of up to 3 mm (0.5 mm in the present case).
• the pressure sensor is connected to a National Instruments data acquisition card (four-channel analog 0-10V acquisition) which is connected to a computer performing a continuous acquisition with a frequency of 0.5 Hz (1 point every two seconds).
• the coefficient of permeability (K) is measured from the linear regression line (average over 1000 points) giving the slope ⁇ of the pressure loss, through the tested test piece, as a function of time, after stabilization of the system, that is to say obtaining a steady state during which the pressure decreases linearly with time.
• the SIBS used alone that is to say without extension oil or other additive, was found to have, at equal thickness, a very low coefficient of permeability, equal to that of the usual composition based on butyl rubber; its MlO module is in turn 40% lower than that of the control composition (1.4 MPa compared to 2.3 MPa).
• the addition of an extension oil to the SIBS elastomer advantageously facilitates the integration of the elastomer composition in the pneumatic object, by a lowering of the module and an increase in tackiness of the latter.
• pneumatic tires according to the invention of the type for passenger vehicle (size 195/65 Rl 5), were manufactured; their inner wall was covered by an airtight layer (10) with a thickness of 0.9 mm (on the building drum, before manufacturing the rest of the tire), and then the vulcanized tires.
• Said airtight layer (10) was formed of SIBS extended with 55 phr of PIB oil, as described above.
• pneumatic tires according to the invention were compared to control tires (Michelin "Energy 3" brand) comprising a conventional air-tight layer of the same thickness, based on butyl rubber.
• the rolling resistance of pneumatic tires was measured on a steering wheel according to ISO 87-67 (1992).
• the invention offers tire designers the opportunity to reduce the hysteresis of the internal sealing layers very significantly, and therefore the fuel consumption of motor vehicles equipped with such tires.
• the SIBS also has the major advantage, because of its thermoplastic nature, to be able to be worked in the molten state (liquid) and thus to offer an improved implementation possibility of these internal sealing layers, compared to to the usual butyl rubber compositions.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Tires In General (AREA)
• Laminated Bodies (AREA)

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• 2007
  • 2007-05-29 FR FR0703840A patent/FR2916679B1/fr not_active Expired - Fee Related
• 2008
  • 2008-05-20 JP JP2010509711A patent/JP5485143B2/ja not_active Expired - Fee Related
  • 2008-05-20 CN CN2008800176800A patent/CN101743135B/zh not_active Expired - Fee Related
  • 2008-05-20 EP EP08758635A patent/EP2152529B1/fr not_active Not-in-force
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  • 2008-05-20 WO PCT/EP2008/004024 patent/WO2008145276A1/fr not_active Ceased
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