EP3157742A1 - Procédé de moulage d'un composite thermoplastique elastomérique pour pneumatique - Google Patents
Procédé de moulage d'un composite thermoplastique elastomérique pour pneumatiqueInfo
- Publication number
- EP3157742A1 EP3157742A1 EP15753435.5A EP15753435A EP3157742A1 EP 3157742 A1 EP3157742 A1 EP 3157742A1 EP 15753435 A EP15753435 A EP 15753435A EP 3157742 A1 EP3157742 A1 EP 3157742A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tpe
- layer
- tread
- tire
- thermoplastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- 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)
- B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
- B29D30/54—Retreading
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- 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)
- B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
- B29D30/66—Moulding treads on to tyre casings, e.g. non-skid treads with spikes
-
- 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)
- B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
- B29D30/54—Retreading
- B29D2030/544—Applying an intermediate adhesive layer, e.g. cement or cushioning element between carcass and tread
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- 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)
- B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
- B29D30/54—Retreading
- B29D2030/548—Removing the worn out tread from the carcass, e.g. by pulling a continuous wire embedded between tread and carcass
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2021/00—Use of unspecified rubbers as moulding material
- B29K2021/003—Thermoplastic elastomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
- B29K2105/0809—Fabrics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/25—Solid
- B29K2105/253—Preform
Definitions
- the present invention relates to a method for molding an elastomeric thermoplastic composite for a tire comprising a step in which a thermoplastic elastomer (TPE) layer is applied against one of the faces of the composite followed by a molding step for vulcanizing the composite and crosslinking the thermoplastic elastomer layer (TPE) with the adjacent layer of rubber material.
- TPE thermoplastic elastomer
- the patent application WO 2009/139449 A1 proposes a radial carcass tire which comprises at least one carcass layer which connects the right and left heel portions, a belt layer disposed on the outer periphery of the carcass layer. , and a tread disposed on the outer periphery of the belt layer, wherein the tread has a layered structure comprising a tread layer of the rubber-side surface, a layer-side rubber layer and a thermoplastic film layer interposed therebetween which consists of a thermoplastic resin or a thermoplastic elastomer composition obtained by mixing a thermoplastic resin with an elastomer.
- the invention also relates to a method of manufacturing a retreaded tire of the radial tire whose tread is worn, the method comprising softening the thermoplastic film layer by heating, separating and removing the rubber layer strip. rolling the surface of the side to form a tire casing, and then bonding a rubber tread layer on the fresh surface side of the tire casing.
- JP 2011042091 proposes to reduce the production cost of a tire using a thermoplastic material to a tire skeleton member.
- the pneumatic skeleton is formed using a thermoplastic material, and the rubber cushion (unvulcanized rubber) is disposed on the peripheral surface of the skeletal member.
- the vulcanized or semi-vulcanized tread rubber is disposed outside the steering tire diameter of the cushion rubber.
- the periphery of the tread is covered with a band-shaped retainer to urge the tread to the side of the pneumatic skeleton member to form a temporarily assembled article.
- the assembled article is temporarily held in a container, and vulcanization is effected by heating the interior of the container, so that the tread rubber is adhered to the pneumatic member.
- the patent application JP 201 1042229 proposes to ensure a uniform and stable joint surface on a common part of a tire skeleton member formed of a thermoplastic material with a tread.
- US 2005056361 discloses a method of retreading a tire comprising a carcass.
- the method includes a spraying step on the radially outermost surface of the rubber carcass, and comprises a thermoplastic matrix cure accelerator.
- JP2011042229 application relates to a thermoplastic tread incorporated in a tire carcass.
- a junction layer of thermoplastic material is provided at the circumferential surface of the tread. This arrangement ensures a uniform surface at the tread.
- EP2072285 discloses a retreaded tire comprising a circumferential tread layer, bonded to a circumferential rubber layer covering the carcass, without adhesive between said rubber layer and the tread layer.
- the application FR2988644 relates to a method of retreading a radial tire for a motor vehicle which has a top whose tread is provided with at least one radially outer portion for contacting the road; two inextensible beads, two flanks connect the beads to the tread, a carcass reinforcement passing in both sides and anchored in the beads; a crown reinforcement disposed circumferentially between the radially outer portion of the tread and the carcass reinforcement; a radially inner elastomeric layer, called sublayer, of different formulation formulation of the radially outer portion of the tread, this sublayer itself being disposed circumferentially between the radially outer portion of the tread and the crown frame; said underlayer comprising at least one thermoplastic elastomer, said thermoplastic elastomer being a block copolymer comprising at least one elastomer block and at least one thermoplastic block, the total content of thermoplastic elastomer being in a range ranging from 65 to 100 phr ( parts by weight
- a first object of the invention is to provide a device or a method for simplifying the retreading and decapping operations, in particular for use with tires for passenger cars or motor vehicles. personal vehicles.
- Another object of the invention is to provide a device or method for performing a decapping operation with high accuracy and good repeatability.
- Yet another object of the invention is to provide a device or method for performing retreading and decapping operations on non-industrial sites, for example service stations performing the assembly / disassembly of tires.
- Yet another object of the invention is to provide a device or method for performing retreading and retreading operations favoring retreaded tires whose adhesion characteristics between the tread and the carcass are particularly favorable, stable and sustainable.
- the invention provides a method of molding an elastomeric tire composite comprising the steps of:
- thermoplastic elastomer TPE
- thermoplastic elastomer (TPE) layer ii) applying a release film to the thermoplastic elastomer (TPE) layer; iii) molding the assembly by molding and vulcanizing a tire composite elastomer mixture comprising crosslinking agents and the adjacent thermoplastic elastomer layer free of crosslinking agents.
- TPE thermoplastic elastomer
- molding and crosslinking allow a co-crosslinking of the interface TPE / elastomeric mixture without the TPE layer is crosslinked in the mass.
- the process according to the invention makes it possible to carry out molding with vulcanization of the composite and crosslinking of the thermoplastic elastomer layer (TPE) with the adjacent layer of rubber material of the tire.
- TPE thermoplastic elastomer layer
- the crosslinking is done with the agents present in the rubber material of the tire (usual sulfur and accelerator in the rubber mixtures of the tires). These agents are absent in the TPE layer when the tire blank is produced, before baking. The low migration of these agents during cooking allows a crosslinking sulfur in the interface TPE / gum and the product TPE is not crosslinked in the mass.
- the TPE layer is in SBS or SBS / EPP.
- a step of applying a layer of tissue between the release film and the mold before performing the molding step is provided.
- the release film has a melting temperature above 180 ° C.
- the release film is advantageously selected from the family comprising FEP, PTFE, PA.
- the nonstick film layer has a thickness less than or equal to 80 ⁇ , and preferably less than 50 ⁇ .
- the invention also provides a tire tread and a tire carcass obtained by the previously described method, preferably comprising a layer of thermoplastic elastomer (TPE), and also preferably a layer of fabrics.
- TPE thermoplastic elastomer
- the tread and the carcass comprise the TPE and the release film.
- thermoplastic elastomer layer comprises a thickness of between 10 ⁇ and 1 mm, more preferably between 10 ⁇ and 200 ⁇ , and even more preferably between 10 ⁇ and 80 ⁇ .
- the tissue thickness is between 100 ⁇ and 1 mm.
- FIGS. 1A to 1E schematically illustrate the concept implemented in the context of the present invention, with a carcass and a tread forming a new tire in 1A, a tread tire used in FIG. 1B, the recess (Destroying) of the tread used in Figure 1C, the laying of a new tread (retreading) in Figure 1D, and the retreaded tire in Figure 1E;
- FIG. 2 illustrates an example of a carcass provided with a layer of thermoplastic elastomer at the zone of interface with the tread;
- FIG. 3 schematically shows a tire in two parts according to the invention
- FIG. 4 shows an architectural variant of the tire of FIG. 3;
- FIGS. 5A and 5B schematically show examples of crown zone architecture with various positions of the reinforcements
- FIG. 6 illustrates a schematic representation of a tread before application of the release film
- FIGS. 7A and 7B schematically show the molding mode of a tread such as that illustrated in FIG. 6;
- FIGS. 8A and 8B schematically show variants of treads with the circumferential reinforcements provided in the TPE layer (FIG. 8A) or in the layer of rubber material (FIG. 8B);
- FIGS. 9A and 9B show schematically an alternative embodiment in which the removable portion extends from one bead to the other, forming a ring;
- FIG. 10 is a diagram illustrating the molding of the crown illustrated in Figures 9A and 9B with a mold advantageously in several sections to facilitate demolding;
- FIG. 11 schematically illustrates an example of a molded crown seen in
- FIGS 1A to 1E schematically illustrate the basic principle of the device and the method implemented in the context of the present invention, which consist in arranging, in the tire in the new state (Figure 1A), a layer of thermoplastic elastomer material (TPE), specifically intended for the operations of decapping and retreading. With this new architecture, these latter operations can now be performed much more quickly and easily when necessary on a worn tire ( Figures 1B and 1C).
- TPE thermoplastic elastomer material
- the carcass obtained has on the surface of a layer of TPE specifically adapted to receive a new tread
- the tire comprising a TPE layer is difficult to demold with a conventional method. Indeed, the TPE layer is softened in the baking press and mold release comprising the tread pattern exerts a radial force on the tread which may cause takeoff of the tread.
- One possible solution is to cool the tire in the press before demolding. This action is very unfavorable from an energy point of view and is unrealistic on an industrial level.
- the solution of the invention overcomes this disadvantage.
- the design of the tire according to the invention is provided in two parts: a part designated by the term "carcass" and another designated by the term "tread”. i) Carcass for making a new tire or with a pre-used carcass
- the tire is manufactured in two parts: a carcass and a tread.
- a carcass is a tire that has no tread. It is useful to consider the carcasses at two points in the life of the tire, either with a new tire or with a tire whose tread is worn.
- the carcass used is either newly manufactured, or obtained by decapping the tread of a used tire whose tread is worn. This operation can be performed after wear of the tread to place a new tread on the carcass obtained by decapping.
- the carcass 1 comprises beads 7, flanks 2 and a crown area 3 for connecting the two sides 2 by their radially outer portion.
- the carcass 1 advantageously comprises one or more carcass reinforcement 5 and crown 7, a possible reinforcement at 0 °, as a standard tire.
- the radially outer region intended to come into contact with a tread is provided with a layer of thermoplastic elastomer material (TPE) as described below.
- TPE thermoplastic elastomer material
- the TPE layer may have a thickness of the order of 0.2 to 1 mm.
- this layer is of reduced thickness, between 10 and 200 ⁇ and even more advantageously between 10 and 80 ⁇ .
- Excellent endurance results were obtained during internal tests with a TPE layer between 20 and 50 ⁇ .
- the materials used successfully are SBS / PEP and the ccSBaS being ⁇ -methylstyrene.
- the carcass is advantageously manufactured by molding in a baking press / vulcanization.
- the press can be cooled to promote the formation of a TPE layer without defects.
- thermoplastic interlayer resistant to the cooking temperature.
- This material is advantageously used (without this enumeration being exhaustive) such as: ETFE (Ethyltetrafluoroethylene), PTFE (Polytetrafluoroethylene), FEP (Ethylene Propylene Fluoride), PFA (perfluoroalkoxy), PMP (Polymethylpentene) or PA (Polyamide).
- the films used advantageously have a thickness less than 100 ⁇ and more preferably between 25 and 50 ⁇ . To promote the molding, particularly avoiding the formation of gas bubbles on the surface, it is advantageous to provide a rough surface condition during molding.
- Such a surface state can be obtained for example:
- the channels are connected to each other so as to form a network
- the tread support surface obtained by means of this architecture and this method has a surface roughness which is favorable for bonding between the carcass and the tread.
- the tread 4 comprises a layer of thermoplastic elastomer (TPE) 8 at its radially lower surface. This allows an assembly with a carcass 1 also comprising a layer of thermoplastic elastomer (TPE) on its radially outer surface 6.
- TPE thermoplastic elastomer
- a release film 12 is disposed in the mold.
- Advantageously thermoplastic films resistant to the cooking temperature are used.
- the melting or softening temperature of the plastic must be greater than 180 ° C, and preferably greater than 200 ° C.
- Advantageously used (without this enumeration being exhaustive) materials such as: ETFE (Ethyltetrafluoroethylene), PTFE (Polytetrafluoroethylene), FEP (Ethylene Propylene Fluoride), PFA, (Perfluoroalkoxy), PMP (Polymethylpentene) or PA (Polyamide).
- the films used advantageously have a thickness less than 100 ⁇ and more preferably between 25 and 50 ⁇ .
- the molding of the tread 4 is performed with a radially outer mold member 10 which has the tread patterns of the tread and a radially inner mold member 1 1.
- the radially inner mold 11 is intended to mold the surface of TPE which is (totally or partially) in contact with the TPE zone of the carcass to make a thermal bonding (often referred to as "hot melt" in English).
- the mold with surface streaks can be teflon.
- the channels are connected to each other so as to form a network;
- the tread obtained has a surface roughness which is favorable to bonding between the carcass and the tread.
- Figure 7A illustrates an exemplary embodiment in which a film 12 is disposed between the mold and the TPE layer.
- Figure 7B illustrates a variant in which a fabric 13 is also provided, advantageously under the film 12.
- the fabric may be made of PA, polyester, or other, and preferably have a thickness between 0.1 and 1 mm.
- the respective TPE layers of the carcass and the tread are provided in such a way that the tread is free of reinforcements (FIG. -ci being provided at the carcass ( Figure 2).
- FIGS. 5A and 5B illustrate various variants in which the boundary between these two elements and provided according to other architectures.
- the carcass comprises the carcass reinforcements provided from one bead to the other, and the tread accommodates the other reinforcements such as the crown reinforcements.
- FIGS. 5A and 5B illustrate other architectural variants in which the crown reinforcements are distributed between the tread and the carcass (FIG. 5A), or concentrated at the level of the tread (FIG. 5B).
- the boundary is advantageously between these two layers of reinforcements.
- FIG. 9 to 11 are schematic representations of another embodiment of the invention in which the boundary between the tread 4 and the carcass 1 extends from one flank 2 to the other, or a bead 7 to the other, forming a ring 15, as shown in the example of Figure 9A.
- FIG. 10 shows an exemplary embodiment of an extended tread mold or crown 15. In order to promote demolding, this mold is advantageously made of several sections that can be disassembled with respect to one another as shown in FIG. figure 10.
- Figure 11 is a schematic representation in perspective of a crown ready for pairing with a carcass.
- the inner zone provided with TPE, allows the effective and safe bonding of the two elements, similar to what has been previously described for the previous embodiments with a tread restricted to the area of the summit.
- thermoplastic elastomers in English “phr" means within the meaning of the present patent application, part by weight per hundred parts of elastomer, thermoplastic and non-thermoplastics combined.
- thermoplastic elastomers TPE are part of the elastomers.
- 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). 1. Composition of the underlay
- the tire according to the invention has the essential feature of being provided with an elastomer layer called "underlayer" of different formulation of the outer portion, carved, of the tread, said underlayer comprising minus a thermoplastic elastomer, said thermoplastic elastomer being a block copolymer comprising at least one elastomer block and at least one thermoplastic block, and the total content of thermoplastic elastomer being in a range of from 65 to 100 phr (parts by weight per cent parts of elastomer).
- TPE Thermoplastic elastomer
- thermoplastic elastomers have an intermediate structure between thermoplastic polymers and elastomers. They are block copolymers, made up of rigid, thermoplastic blocks, connected by flexible blocks, elastomers.
- thermoplastic elastomer used for the implementation of the invention is a block copolymer whose chemical nature of thermoplastic blocks and elastomers may vary.
- 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.
- Mn number-average molecular weight
- the number-average molecular weight (Mn) of the TPE elastomer is determined in known manner, by steric exclusion chromatography (SEC).
- SEC steric exclusion chromatography
- the sample is solubilized beforehand in tetrahydrofuran at a concentration of approximately 1 g / l; then the solution is filtered on 0.45 ⁇ 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 ⁇ .
- the detector is a "WATERS 2410" differential refractometer and its associated software for the exploitation of chromatographic data is the “WATERS MILLENIUM” system.
- the calculated average molar masses relate to a calibration curve made with polystyrene standards. The conditions are adaptable by those skilled in the art.
- the TPE when reference is made to the glass transition temperature of the TPE, it is the Tg relative to the elastomeric block.
- the TPE preferably has a glass transition temperature ("Tg") which is preferably less than or equal to 25 ° C, more preferably less than or equal to 10 ° C.
- Tg glass transition temperature
- a value Tg greater than these minima can reduce the performance of the underlayment when used at very low temperatures; for such use, the Tg of the TPE is more preferably still less than or equal to -10 ° C.
- the Tg of the TPE is greater than -100 ° C.
- 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.
- Tg glass transition temperature peaks
- 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.
- the TPE must be provided with sufficiently incompatible blocks (that is to say different because of their mass, their polarity or their respective Tg) to maintain their own properties of elastomer or thermoplastic block.
- the TPEs can be copolymers with a small number of blocks (less than 5, typically 2 or 3), in which case these blocks preferably have high masses, greater than 15000 g / mol.
- These TPEs can be, for example, diblock copolymers, comprising a thermoplastic block and an elastomer block. They are 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).
- 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 masses low, for example from 500 to 5000 g / mol, these TPE will be called multiblock TPE thereafter, and are a series of elastomeric blocks - thermoplastic blocks.
- the TPE is in a linear form.
- 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 terminal thermoplastic blocks, at each of the two ends of the elastomeric block.
- the multiblock TPE can be a linear sequence of elastomeric blocks - thermoplastic blocks.
- the TPE useful for the purposes of the invention is in a star shape at least three branches.
- 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 may vary, for example from 3 to 12, and preferably from 3 to 6.
- 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.
- the elastomeric blocks of the TPE for the purposes of the invention may be all the elastomers known to those skilled in the art. They generally have a Tg less than 25 ° C, preferably less than 10 ° C, more preferably less than 0 ° C and very preferably below -10 ° C. Also preferably, the TPE block elastomer block is greater than -100 ° C.
- the elastomeric portion of the TPE does not contain ethylenic unsaturation, it will be referred to as a saturated elastomer block. If the elastomeric block of the TPE comprises ethylenic unsaturations (that is to say 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.
- ethylenic monomers mention may be made of polyalkylene blocks such as ethylene-propylene or ethylene-butylene random copolymers.
- These saturated elastomeric blocks can also be obtained by hydrogenation of unsaturated elastomeric blocks. It may also be aliphatic blocks from the family of polyethers, polyesters, or polycarbonates.
- this elastomeric block of the TPE is preferably composed mainly of ethylenic units.
- a majority is meant a weight ratio of ethylenic monomer highest relative to the total weight of the elastomeric block, and preferably a weight of more than 50%, more preferably more than 75% and even more preferably more than 85%. %.
- Conjugated C 4 -C 14 dienes may be copolymerized with the ethylenic monomers. In this case, it is a question of random copolymers.
- these conjugated dienes are chosen from isoprene, butadiene, 1-methylbutadiene, 2-methylbutadiene, 2,3-dimethyl-1,3-butadiene, 2,4-dimethyl-1,3- butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,3-dimethyl-1 , 3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 3-methyl-1,3-hexadiene, 4-methyl-1,3-hexadiene, 5-methyl- 1,3-hexadiene, 2,3- dimethyl-1,3-hexadiene, 2,4-dimethyl-1,3
- the conjugated diene is chosen from butadiene or isoprene or a mixture containing butadiene and isoprene.
- this elastomer block of the TPE is preferably composed mainly of a diene elastomer part.
- a majority is meant a weight ratio of the highest diene monomer relative to the total weight of the elastomer block, and preferably a weight content of more than 50%, more preferably of more than 75% and even more preferably of more than 85%. %.
- the unsaturation of the unsaturated elastomer block may be derived from a monomer having a double bond and a cyclic unsaturation, as is the case for example in polynorbornene.
- conjugated dienes, C 4 - Q 4 may be polymerized or copolymerized to form a diene elastomer block.
- these conjugated dienes are chosen from isoprene, butadiene, piperylene, 1-methylbutadiene, 2-methylbutadiene, 2,3-dimethyl-1,3-butadiene and 2,4-dimethyl-1.
- the conjugated diene is isoprene or butadiene or a mixture containing isoprene and / or butadiene.
- the monomers polymerized to form the elastomer part of the TPE may be randomly copolymerized with at least one other monomer so as to form an elastomer block.
- the molar fraction in polymerized monomer other than an ethylenic monomer, based on the total number of elastomeric block units, must be such that this block retains its elastomeric properties.
- the molar fraction of this other comonomer may range from 0 to 50%, more preferably from 0 to 45% and even more preferably from 0 to 40%.
- this other monomer capable of copolymerizing with the first monomer may be chosen from the ethylenic monomers as defined above (for example ethylene), the diene monomers, more particularly the conjugated diene monomers having from 4 to 14 carbon atoms as defined above (for example butadiene), the monomers of vinylaromatic type having from 8 to 20 carbon atoms as defined below or else it may be a monomer such as vinyl acetate).
- the comonomer is of vinylaromatic type, it advantageously represents a fraction in units on the total number of units of the thermoplastic block from 0 to 50%, preferably ranging from 0 to 45% and even more preferably ranging from 0 to 40%.
- vinylaromatic compounds are especially suitable the styrene monomers mentioned above, namely methylstyrenes, para-tert-butylstyrene, chlorostyrenes, bromostyrenes, fluorostyrenes or para-hydroxy-styrene.
- the vinylaromatic comonomer is styrene.
- the elastomeric 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 the use of underlayer tire.
- Mn number-average molecular weight
- the elastomer block may also be a block comprising several types of ethylenic, diene or styrenic monomers as defined above.
- the elastomeric block may also consist of several elastomeric blocks as defined above.
- 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 processing temperature is chosen to be substantially greater than the Tg of the thermoplastic block. In the specific case of a semi-crystalline polymer (or a polymer block), a melting point can be observed, then greater 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.
- 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.
- this thermoplastic block has a Tg (or Tf, if applicable) in a range of 80 ° C to 250 ° C.
- 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 the thermoplastic blocks with respect to the TPE 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 preferentially present in sufficient proportions to preserve the thermoplastic nature of the elastomer according to the invention.
- the minimum level of thermoplastic blocks having a Tg (or Tf, if any) greater than or equal to 80 ° C in the TPE may vary depending on the conditions of use of the copolymer.
- the ability of the TPE to deform during tire preparation can also contribute to determining the proportion of thermoplastic blocks having 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 formed from polymerized monomers of various kinds, in particular, they may constitute the following blocks or mixtures thereof:
- polyolefins polyethylene, polypropylene
- polyethers polyethylene oxide, polyphenylene ether
- FEP polyfluorides
- thermoplastic copolymers such as acrylonitrile-butadiene-styrene copolymer (ABS).
- 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:
- Pacenaphthylene one skilled in the art can for example refer to the article by Z. Fodor and JP 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;
- Polystyrenes are obtained from styrenic monomers.
- 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 ⁇ -methylstyrene, m-methylstyrene or p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha-4-dimethylstyrene or diphenylethylene), para-tert-butylstyrene, chlorostyrenes (for example, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene or 2,4-dichlorostyrene).
- methylstyrenes for example
- bromostyrenes for example, po-bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene or 2,4,6-tribromostyrene
- fluorostyrenes for example o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6-difluorostyrene or 2,4,6-trifluorostyrene
- para-hydroxy- styrene para-hydroxy- styrene.
- the weight content of styrene in the TPE 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 undercoat may be affected. For these reasons, the styrene content is more preferably between 10% and 40%.
- the polymerized monomer as defined above may be copolymerized with at least one other monomer so as to form a thermoplastic block having a Tg (or Tf, if appropriate) as defined. above.
- this other monomer capable of copolymerizing with the polymerized monomer may be chosen from diene monomers, more particularly conjugated diene monomers having 4 to 14 carbon atoms, and vinylaromatic-type monomers having from 8 to 20 carbon atoms, as defined in the part relating to the elastomeric block.
- 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 of tire underlayer.
- Mn number-average molecular weight
- thermoplastic block may also consist of several thermoplastic blocks as defined above.
- the TPE is a copolymer whose elastomer portion is saturated, and comprising styrenes blocks and alkylene blocks.
- the alkylene blocks are preferably ethylene, propylene or butylene. More preferably, this TPE elastomer is chosen from the following group, consisting of diblock 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 / isobuty
- the TPE is a copolymer whose elastomer part is unsaturated, and which comprises styrenic blocks and diene blocks, these diene blocks being in particular isoprene or butadiene blocks.
- this TPE 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.
- SB styrene / butadiene
- SI styrene / isoprene
- SI styrene / butadiene / isoprene / styrene
- SI styrene / buta
- the TPE is a linear copolymer or star whose elastomer part has a saturated part and an unsaturated part such as styrene / butadiene / butylene (SBB), styrene / butadiene / butylene / styrene (SBBS) ) or a mixture of these copolymers.
- SBB styrene / butadiene / butylene
- SBBS styrene / butadiene / butylene / styrene
- multiblock TPEs mention may be made of copolymers comprising random copolymer blocks of ethylene and propylene / polypropylene, polybutadiene / polyurethane (TPU), polyether / polyester (COPE), polyether / polyamide (PEBA).
- TPU polybutadiene / polyurethane
- COPE polyether / polyester
- PEBA polyether / polyamide
- TPE elastomers As examples of commercially available TPE elastomers, mention may be made of the elastomers of SEPS, SEEPS or SEBS type sold by Kraton under the name "Kraton G” (eg G1650, G1651, G1654, G1730 products).
- Kraton G eg G1650, G1651, G1654, G1730 products.
- thermoplastic elastomer (s) constitute the majority fraction by weight; they then represent at least 65%, preferably at least 70% by weight, more preferably at least 75% by weight of all the elastomers present in the elastomer composition. Also preferably, the TPE elastomer (s) represent (s) at least 95% (in particular 100%) by weight of all the elastomers present in the elastomer composition.
- the total amount of TPE elastomer is in a range from 65 to 100 phr, preferably from 70 to 100 phr and especially from 75 to 100 phr. Also preferably, the composition contains from 95 to 100 phr of TPE elastomer.
- the TPE elastomer or elastomers are preferably the one or only elastomers of the underlayer.
- thermoplastic elastomer or elastomers described above are sufficient on their own for the usable sublayer according to the invention.
- composition of the underlayer according to the invention may comprise at least one (that is to say one or more) diene rubber as non-thermoplastic elastomer, this diene rubber may be used alone, or in cutting with at least one (i.e. one or more) other non-thermoplastic rubber or elastomer.
- the optional total non-thermoplastic elastomer content is in a range from 0 to 35 phr, preferably from 0 to 30 phr, more preferably from 0 to 25 phr, and even more preferably from 0 to 5 phr. . Also preferably, the underlayer of the tire according to the invention does not contain a non-thermoplastic elastomer.
- iene elastomer or rubber it is to be understood in a known way (one or more elastomers) is to be understood, at least in part (ie a homopolymer or a copolymer) of diene monomers (monomers carrying two double bonds). carbon - carbon, conjugated or not).
- diene elastomers can be classified in two categories: "essentially unsaturated” or "essentially saturated”.
- essentially unsaturated is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (% by weight). mole).
- conjugated diene monomers having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (% by weight). mole).
- conjugated diene monomers having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (% by weight). mole).
- conjugated diene monomers having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (% by weight). mole).
- highly unsaturated diene elastomer is understood to mean in particular a diene elastomer having a degree of units of diene origin (conjugated dienes) which is greater than 50%.
- diene elastomers such as certain butyl rubbers or copolymers of dienes and alpha olefins EPDM type can be described as "essentially saturated" diene elastomers (low or very low diene origin ratio). low, always less than 15%).
- iene elastomer is used more particularly, whatever the category above, which can be used in the compositions according to the invention:
- diene elastomer Any type of diene elastomer may be used in the invention.
- essentially unsaturated elastomers in particular types (a) and (b) above, are preferably used for the manufacture of the underlayer of the tire according to the present invention.
- conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5 alkyl) -1,3-butadienes are particularly suitable.
- Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial "vinyl-toluene" mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.
- the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units.
- the elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used.
- the elastomers may for example be prepared in dispersion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.
- alkoxysilane groups such as as described for example in FR 2,765,882 or US 5,977,238), carboxylic groups (as described for example in WO 01/92402 or US 6,815,473, WO 2004/096865 or US 2006/0089445) or groups polyethers (as described for example in EP 1 127 909 or US Pat. No. 6,503,973).
- functionalized elastomers mention may also be made of elastomers (such as SBR, BR, NR or IR) of the epoxidized type.
- the underlayer described above may optionally comprise, in addition to the constituents presented above, one or more thermoplastic polymers based on polyether.
- thermoplastic polymers based on polyether When they are present in the composition, it is preferred that the total content of thermoplastic polymers based on polyether be less than 40 phr, preferably between 2 and 35 phr, more preferably between 5 and 30 phr, and very preferably between 10 and 25 pce.
- These thermoplastic polymers may in particular be polymers of poly (para-phenylene ether) (abbreviated as "EPP").
- thermoplastic polymers PPE are well known to those skilled in the art, they are solid resins at room temperature (20 ° C) compatible with styrenic polymers, which have in particular used to increase the Tg of TPE elastomers whose thermoplastic block is a styrenic block (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).
- thermoplastic elastomer described above is sufficient on its own for the usable sub-layer according to the invention, nevertheless a reinforcing filler can be used in the composition.
- a reinforcing filler When a reinforcing filler is used, it is possible to use any type of filler usually used for the manufacture of tires, for example an organic filler such as carbon black, an inorganic filler such as silica, or a plastic filler. cutting of these two types of filler, including a cut of carbon black and silica.
- an inorganic reinforcing filler it is possible, for example, to use, in a known manner, at least one bifunctional coupling agent (or bonding agent) intended to ensure a sufficient chemical and / or physical connection between the inorganic filler (surface of its particles) and the elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
- the underlayer described above may furthermore comprise the various additives usually present in the sub-layers known to those skilled in the art.
- one or more additives chosen from protective agents such as antioxidants or antiozonants, anti-UV agents, the various agents of implementation or other stabilizers, or the promoters able to promote the adhesion to the rest of the structure will be chosen.
- the underlayer does not contain all these additives at the same time and even more preferably, the underlayer contains none of these agents.
- the composition of the sublayer of the invention may contain a crosslinking system known to those skilled in the art.
- the composition does not contain a crosslinking system.
- the composition of the underlayer of the invention may contain one or more inert micrometric fillers such as lamellar fillers known to those skilled in the art.
- the composition contains no micron charge.
- the composition of the underlayer of the invention may contain a plasticizer, such as an extender oil (or plasticizing oil) or a plasticizing resin whose function is to facilitate the implementation of the underlayer, particularly its integration with the tire by a lowering of the module and an increase in the tackifying power.
- a plasticizer such as an extender oil (or plasticizing oil) or a plasticizing resin whose function is to facilitate the implementation of the underlayer, particularly its integration with the tire by a lowering of the module and an increase in the tackifying power.
- the level of plasticizer varies from 0 to 80 phr, more preferably from 0 to 50 phr, more preferably still from 0 to 30 phr, and in particular less than 10 phr, depending on the Tg and the modulus intended for the underlayer.
- the composition of the underlayer does not contain a plasticizer.
- the composition of the underlayer may also comprise, in a minority weight fraction relative to the block elastomer, thermoplastic polymers other than those based on polyether. It is preferred that the composition contains no such thermoplastic polymers other than those based on polyether, or when present in the composition, it is preferred that the total content of thermoplastic polymers other than those based on polyether be less than 30. pce, preferably less than 10 phr. Very preferably, the composition is devoid of such thermoplastic polymers other than those based on polyethers, or contains less than 5 phr.
- the TPE elastomers may be used in the usual manner for TPE, by extrusion or molding, for example from a raw material available in the form of beads or granules.
- the underlayer for the tire according to the invention is prepared in the usual manner, for example, by incorporating the various components into a twin-screw extruder, so as to carry out the fusion of the matrix and an incorporation of all the components. ingredients, then use a die to make the profile.
- This underlayer may be mounted on a tire in the usual manner, said tire comprising in addition to the underlayer required for the purposes of the invention, a tread, a crown and a crown reinforcement, and preferably, two flanks and two beads, and a carcass reinforcement anchored to the two beads and extending from one side to the other.
- a tread a crown and a crown reinforcement
- flanks and two beads a carcass reinforcement anchored to the two beads and extending from one side to the other.
- G AT represents the elastic component of the shear modulus of the undercoat at the temperature T
- GBT represents the elastic component of the shear modulus of the layer adjacent to the underlayer at the temperature T.
- the difference between the elastic modulus ratio at 200 ° C. and at 60 ° C. of the underlayer and that of the adjacent layers is such that the following equation is verified:
- the difference between the elastic modulus ratio at 200 ° C. and at 60 ° C. of the underlayer and that of the adjacent layers is such that the following equation is satisfied:
- the underlayer may be preferable for the underlayer to have elastic modulus properties such that the following equation is
- the underlayer has elastic modulus properties such that the following equation is verified:
- the underlayer has elastic modulus properties such that the following equation is satisfied:
- the underlayer has elastic modulus properties such that the following equation is satisfied: GA ('100 o C) xGA ('60 ° C)> 0.7
- the layers adjacent to the tread sub-layer are typically the tread on the one hand and on the other hand the belt (or crown reinforcement) of the tire.
- the two adjacent layers are on the one hand the upper part of the tread (radially external, subject to decapping) and secondly the lower part (radially internal to the underlayer) of the original tread.
- the two adjacent layers of the underlayer are of the same nature, or of a different nature.
- the adjacent layers may consist of compositions based on diene elastomers, which are well known to those skilled in the art, and such as those defined above as optional elastomers.
- complementary thermoplastic elastomers of the underlayer are well known to those skilled in the art, and such as those defined above as optional elastomers.
- adjacent layers are described in numerous patents well known to those skilled in the art and generally comprise, in addition to the diene elastomers described above, additives such as those described above for the composition of the sub-compound. layer and especially reinforcing fillers, such as silica and / or carbon black, plasticizers in the form of oil or plasticizing resin, a crosslinking system and other additives well known to those skilled in the art such as as antioxidants.
- additives such as those described above for the composition of the sub-compound. layer and especially reinforcing fillers, such as silica and / or carbon black, plasticizers in the form of oil or plasticizing resin, a crosslinking system and other additives well known to those skilled in the art such as as antioxidants.
- the adjacent layers may also consist of compositions based on thermoplastic elastomers or comprising thermoplastic elastomers, and in particular this may be the case of the tread.
- one of the adjacent layers may be a layer consisting of a composition based on diene elastomer (in particular the tire belt) while the other adjacent layer may consist of a composition based on thermoplastic elastomer (in particular the tread).
- the possibility of easy decapping is also represented by the difference between the elastic modulus variation between 60 ° C. and 200 ° C. of the underlayer and that of the adjacent layers, when the following equation is satisfied. with each of the adjacent layers:
- the module E '(T) is measured in compression.
- the invention can be defined by replacing the equation comprising the module ratios G 'by the equation above comprising the module ratios E'.
- the same embodiments can be envisaged and the preferences indicated above apply mutatis mutandis.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Tires In General (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1401396A FR3022488B1 (fr) | 2014-06-20 | 2014-06-20 | Procede de moulage d'un composite thermoplastique elastomerique pour pneumatique |
PCT/IB2015/000983 WO2015193721A1 (fr) | 2014-06-20 | 2015-06-16 | Procédé de moulage d'un composite thermoplastique elastomérique pour pneumatique |
Publications (1)
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EP3157742A1 true EP3157742A1 (fr) | 2017-04-26 |
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EP15753435.5A Withdrawn EP3157742A1 (fr) | 2014-06-20 | 2015-06-16 | Procédé de moulage d'un composite thermoplastique elastomérique pour pneumatique |
Country Status (5)
Country | Link |
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US (1) | US20170144398A1 (fr) |
EP (1) | EP3157742A1 (fr) |
CN (1) | CN106573430A (fr) |
FR (1) | FR3022488B1 (fr) |
WO (1) | WO2015193721A1 (fr) |
Families Citing this family (3)
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FR3022492B1 (fr) | 2014-06-20 | 2017-05-26 | Michelin & Cie | Pneumatique en deux partie adaptees au rechapage |
FR3030558B1 (fr) * | 2014-12-19 | 2016-12-23 | Michelin & Cie | Pneumatique pret a recevoir un organe a sa surface |
JP2024087581A (ja) * | 2022-12-19 | 2024-07-01 | 株式会社ブリヂストン | リトレッドタイヤ |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
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US4946899A (en) | 1988-12-16 | 1990-08-07 | The University Of Akron | Thermoplastic elastomers of isobutylene and process of preparation |
US5279784A (en) * | 1992-05-05 | 1994-01-18 | Bandag Licensing Corporation | Method of fabrication of composite tire thread |
FR2740778A1 (fr) | 1995-11-07 | 1997-05-09 | Michelin & Cie | Composition de caoutchouc a base de silice et de polymere dienique fonctionalise ayant une fonction silanol terminale |
FR2765882B1 (fr) | 1997-07-11 | 1999-09-03 | Michelin & Cie | Composition de caoutchouc a base de noir de carbone ayant de la silice fixee a sa surface et de polymere dienique fonctionnalise alcoxysilane |
JP2000079641A (ja) * | 1998-06-30 | 2000-03-21 | Bridgestone Corp | 更生タイヤ用プレキュアトレッドおよびその製造方法 |
ATE290565T1 (de) | 2000-02-24 | 2005-03-15 | Michelin Soc Tech | Vulkanisierbare kautschukmischung zur herstellung eines luftreifens und luftreifen, der eine solche zusammensetzung enthält |
JP5462428B2 (ja) | 2000-05-26 | 2014-04-02 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | タイヤトレッドとして使用可能なゴム組成物 |
US20050056361A1 (en) * | 2003-01-06 | 2005-03-17 | Michelin Recherche Et Technique S.A. | Method of recapping tires |
FR2854404B1 (fr) | 2003-04-29 | 2005-07-01 | Michelin Soc Tech | Procede d'obtention d'un elastomere greffe a groupes fonctionnels le long de la chaine et compositions de caoutchouc |
US20090159165A1 (en) * | 2007-12-20 | 2009-06-25 | Herberger Sr James Robert | Tire tread composite and retreaded rubber tire |
JP5680266B2 (ja) * | 2008-05-16 | 2015-03-04 | 横浜ゴム株式会社 | 空気入りタイヤおよび更生タイヤの製造方法 |
US20130146189A1 (en) * | 2008-12-18 | 2013-06-13 | Ramendra Nath Majumdar | Retreaded tire and method of preparation |
JP5512195B2 (ja) | 2009-08-20 | 2014-06-04 | 株式会社ブリヂストン | タイヤの製造方法及びタイヤ |
JP5404244B2 (ja) * | 2009-08-20 | 2014-01-29 | 株式会社ブリヂストン | タイヤ用トレッド、タイヤ及びタイヤの製造方法 |
FR2988644B1 (fr) * | 2012-04-02 | 2014-04-11 | Michelin & Cie | Procede de rechapage d'un pneumatique dont la zone sommet est pourvue d'une sous-couche comportant un elastomere thermoplastique |
FR2988728B1 (fr) * | 2012-04-02 | 2014-04-11 | Michelin & Cie | Pneumatique dont la zone sommet est pourvue d'une sous-couche comportant un elastomere thermoplastique |
-
2014
- 2014-06-20 FR FR1401396A patent/FR3022488B1/fr not_active Expired - Fee Related
-
2015
- 2015-06-16 WO PCT/IB2015/000983 patent/WO2015193721A1/fr active Application Filing
- 2015-06-16 EP EP15753435.5A patent/EP3157742A1/fr not_active Withdrawn
- 2015-06-16 CN CN201580039890.XA patent/CN106573430A/zh active Pending
- 2015-06-16 US US15/320,592 patent/US20170144398A1/en not_active Abandoned
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WO2015193721A1 (fr) | 2015-12-23 |
FR3022488A1 (fr) | 2015-12-25 |
FR3022488B1 (fr) | 2017-02-24 |
CN106573430A (zh) | 2017-04-19 |
US20170144398A1 (en) | 2017-05-25 |
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