WO2020095891A1 - Pneu à affaissement limité - Google Patents

Pneu à affaissement limité Download PDF

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Publication number
WO2020095891A1
WO2020095891A1 PCT/JP2019/043278 JP2019043278W WO2020095891A1 WO 2020095891 A1 WO2020095891 A1 WO 2020095891A1 JP 2019043278 W JP2019043278 W JP 2019043278W WO 2020095891 A1 WO2020095891 A1 WO 2020095891A1
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WO
WIPO (PCT)
Prior art keywords
tire
rubber
resin
carcass
inner liner
Prior art date
Application number
PCT/JP2019/043278
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English (en)
Japanese (ja)
Inventor
山本　淳
Original Assignee
株式会社ブリヂストン
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Publication date
Application filed by 株式会社ブリヂストン filed Critical 株式会社ブリヂストン
Priority to JP2020556075A priority Critical patent/JPWO2020095891A1/ja
Publication of WO2020095891A1 publication Critical patent/WO2020095891A1/fr

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    • 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
    • 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
    • B60C15/00—Tyre beads, e.g. ply turn-up or overlap
    • B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
    • 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
    • B60C17/00—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber

Definitions

  • the present disclosure relates to a run flat tire.
  • Patent Document 1 proposes a run-flat tire in which an inner liner containing a non-diene rubber and a side reinforcing rubber layer containing a diene rubber contain the same kind of vulcanization accelerator.
  • a reinforcing cord member which is a spirally wound metallic reinforcing cord, is provided on the outer periphery of the tire body.
  • a reinforcing cord member one in which a resin-coated cord having a periphery of the reinforcing cord covered with a resin is wound is also used.
  • a tire formed of at least a thermoplastic resin material and having an annular tire skeleton is wound around the outer periphery of the tire skeleton in the circumferential direction to form a reinforcing cord layer.
  • a tire having a reinforcing cord member and the reinforcing cord layer including a resin material has been proposed.
  • Patent Document 1 Patent 5629786 Patent Document 2: JP 2012-046025 A
  • Patent Document 2 describes a tire having a reinforcing cord member containing a resin material as described above.
  • the side-reinforcing rubber layer and the inner liner there is no description about the side-reinforcing rubber layer and the inner liner, and there is no description focusing on the adhesiveness between the two and the internal pressure retention by air permeation.
  • the inner liner provided for the purpose of suppressing the air permeation of the pneumatic tire to maintain the internal pressure
  • the side reinforcing rubber layer provided to reinforce the tire side portion that supports the load during run-flat traveling, A rubber material having a composition according to the purpose of is used.
  • Patent Document 1 describes a run-flat tire in which the side reinforcing rubber layer and the inner liner contain the same type of vulcanization accelerator to improve the adhesiveness between the two.
  • a rubber material having a composition according to each purpose is used for the inner liner and the side-reinforcing rubber layer.
  • the vulcanization accelerator has a high degree of freedom in selection. ..
  • the composition of the inner liner and the composition of the side reinforcing rubber layer are brought close to each other in order to enhance the adhesiveness of the interface, it becomes difficult to achieve the respective objects. Therefore, it is difficult to achieve both the tire internal pressure holding property and the run flat running property.
  • the present disclosure aims to provide a run-flat tire that has both the internal pressure holding property and the run-flat running property.
  • a pair of bead cores A carcass straddling the pair of bead cores, the end portion of which is locked to the bead core,
  • An inner liner provided on the tire inner surface side of the carcass, wherein the content of the diene rubber is 20% by mass or more based on the total amount of rubber contained in the inner liner,
  • a side reinforcing rubber layer provided in direct contact with the inner liner between the carcass of the tire side portion and the inner liner, and extending in the tire radial direction along the inner surface of the carcass
  • a belt layer provided on the outer side in the tire radial direction of the carcass, having a cord and a cord coating layer that coats the cord and contains a resin
  • a tread provided on the tire radial direction outer side of the belt layer, Run-flat tire with.
  • FIG. 3 is a half cross-sectional view showing one side of a cut surface obtained by cutting the run-flat tire according to the embodiment of the present disclosure along the tire width direction and the tire radial direction in a state of being assembled to a rim. It is a partial expanded sectional view showing a bead core in a run flat tire concerning one embodiment of this indication.
  • 1 is a perspective view showing a belt layer in a run flat tire according to an embodiment of the present disclosure.
  • FIG. 9 is a partially enlarged cross-sectional view showing a modified example in which a bead core is formed by a wire bundle in which a plurality of bead wires are coated with a coating resin in a run-flat tire according to an embodiment of the present disclosure.
  • a run-flat tire according to an embodiment of the present disclosure, a half cross-sectional view showing a modified example in which a plurality of reinforcing cords are coated with a coating resin and a belt layer is formed using a resin-coated cord having a substantially parallelogram shape in section.
  • the "resin” is a concept including a thermoplastic resin, a thermoplastic elastomer, and a thermosetting resin, and does not include a vulcanized rubber.
  • “same type” means a resin having a skeleton common to the skeleton constituting the resin main chain, such as ester-based resins and styrene-based resins.
  • a numerical range represented by “to” means a range including the numerical values before and after “to” as a lower limit value and an upper limit value.
  • the amount of each component in the composition is the sum of a plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition.
  • the “main component” means a component having the largest content by mass in the mixture, unless otherwise specified.
  • thermoplastic resin means a polymer compound in which the material softens and flows as the temperature rises and becomes relatively hard and strong when cooled, but does not have rubber-like elasticity.
  • thermoplastic elastomer as used herein means a copolymer having a hard segment and a soft segment.
  • thermoplastic elastomer for example, a polymer that constitutes a crystalline hard segment having a high melting point or a hard segment having a high cohesive force, and a polymer that constitutes an amorphous and soft segment having a low glass transition temperature, The copolymer which has is mentioned.
  • thermoplastic elastomer examples include ones in which the material softens and flows as the temperature rises, becomes relatively hard and strong when cooled, and has rubber-like elasticity.
  • the hard segment refers to a component that is relatively harder than the soft segment.
  • the hard segment is preferably a molecular constraining component that functions as a crosslinking point of the crosslinked rubber that prevents plastic deformation.
  • the hard segment for example, a segment having a structure having a rigid group such as an aromatic group or an alicyclic group in the main skeleton, or a structure capable of intermolecular packing by intermolecular hydrogen bond or ⁇ - ⁇ interaction Is mentioned.
  • the soft segment refers to a component that is relatively softer than the hard segment.
  • the soft segment is preferably a flexible component exhibiting rubber elasticity.
  • Examples of the soft segment include a segment having a long-chain group (for example, a long-chain alkylene group) in the main chain, a high degree of freedom of molecular rotation, and a stretchable structure.
  • FIG. 1 illustrates a cut surface (along a tire circumferential direction) cut along a tire width direction and a tire radial direction in an example of a run flat tire (hereinafter, referred to as “tire 10”) according to an embodiment of the present disclosure. Shows one side of the cross section as seen from the direction).
  • the arrow W in the figure indicates the width direction of the tire 10 (tire width direction), and the arrow R indicates the radial direction of the tire 10 (tire radial direction).
  • the tire width direction mentioned here refers to a direction parallel to the rotation axis of the tire 10. Further, the tire radial direction means a direction orthogonal to the rotation axis of the tire 10.
  • Reference numeral CL indicates the equatorial plane of the tire 10 (tire equatorial plane).
  • the side closer to the rotation axis of the tire 10 along the tire radial direction is “the tire radial direction inner side”, and the side farther from the rotation axis of the tire 10 along the tire radial direction is the “tire radial direction outer side”.
  • the side closer to the tire equatorial plane CL along the tire width direction is referred to as “tire width direction inner side”
  • the side farther from the tire equatorial plane CL along the tire width direction is referred to as "tire width direction outer side”.
  • FIG. 1 shows the tire 10 when assembled to a rim 30 which is a standard rim and filled with standard air pressure.
  • the "standard rim” referred to here is the rim defined by JATMA (Japan Automobile Tire Manufacturer's Association) Year Book 2018 version. Further, the standard air pressure is the air pressure corresponding to the maximum load capacity of Year Book 2018 version of JATMA (Japan Automobile Tire Manufacturers Association).
  • the tire 10 includes a pair of bead cores 26 embedded in the bead portion 12, a carcass 14 whose end portions straddle the bead core 26 are locked to the bead core 26, and a carcass 14 on the tire inner surface side.
  • the inner liner 16 provided and between the carcass 14 of the tire side portion 22 and the inner liner 16 are provided in direct contact with the inner liner 16 and extend along the inner surface of the carcass 14 in the tire radial direction (i.e., side reinforcement rubber 24).
  • a side reinforcing rubber layer) a belt layer 40 provided on the tire radial direction outer side of the tread portion 18 of the carcass 14, and a tread 20 provided on the tire radial direction outer side of the belt layer 40.
  • FIG. 1 only the bead portion 12 on one side is shown.
  • the inner liner 16 is made of a rubber material containing rubber, and the diene rubber is contained in an amount of 20% by mass or more based on the entire rubber (total amount of rubber) contained in the inner liner 16.
  • the belt layer 40 is configured to include a reinforcing cord 42C and a coating resin 42S (that is, a cord coating layer) that covers the reinforcing cord 42C and contains a resin. That is, the belt layer 40 contains resin. The details of the resin material forming the coating resin 42S will be described later.
  • the inner liner is a layer provided to enhance the internal pressure retention of the tire, and is preferably a layer having low air permeability, and therefore a rubber other than the diene rubber (that is, a non-diene rubber) is used. Often composed of a rubber material including (rubber).
  • the side-reinforcing rubber is a layer for reinforcing the tire side portion that generally bears the load acting on the tire during run-flat running, and it is desirable that the side-reinforcing rubber has a hardness high enough to enable reinforcement. Therefore, the inner liner is composed of a rubber material having a different composition.
  • the adhesive force at the interface hardly increases.
  • the adhesive strength at the interface for example, if the composition of the rubber material used for the inner liner is brought close to the composition of the rubber material used for the side reinforcing rubber, the adhesive strength at the interface increases, but the air permeability of the inner liner increases. May increase, and the internal pressure retention may decrease.
  • the inner liner 16 that is in direct contact with the side reinforcing rubber 24 contains 20 mass% or more of diene rubber with respect to the entire rubber (total amount of rubber), and the belt layer 40 contains resin. ..
  • both the internal pressure holding property and the run flat traveling property are compatible. The reason is not clear, but it is presumed as follows.
  • vulcanization is performed at a relatively high vulcanization speed in order to form a layer having a hardness that is high enough to reinforce the tire side portion 22.
  • the vulcanization speed is higher in the process of manufacturing the inner liner 16 as compared with the case where the diene rubber is not included, and the vulcanization speeds of both approaches. it is conceivable that. Therefore, if vulcanization is performed with the unvulcanized inner liner and the unvulcanized side reinforcing rubber in contact with each other, they will be vulcanized at a similar speed, which facilitates co-crosslinking and the adhesive strength of the interface.
  • the inner liner 16 when the side reinforcing rubber 24 contains a diene rubber, the inner liner 16 also contains 20% by mass or more of the diene rubber, so that further co-crosslinking occurs as compared with the case where the inner liner 16 does not contain the diene rubber. It is presumed that it will be easier and the adhesive strength at the interface will be higher. In this way, the adhesive force between the inner liner 16 and the side reinforcing rubber 24 is increased, so that peeling of the interface hardly occurs and the run-flat traveling property is improved.
  • the belt layer 40 contains the resin, the inner pressure retaining property of the entire tire 10 is easily maintained. That is, the resin is used for the belt layer provided in the tread portion, which is a region in the tire where the internal pressure retention is likely to be deteriorated due to the permeation of air. Resins generally have lower air permeability than rubbers. Therefore, even if the inner liner contains a diene rubber and the air barrier property of the inner liner itself is lowered, the air permeability in the tread portion can be kept low, and the inner pressure holding property of the tire as a whole is maintained. .. As described above, in the tire 10, it is presumed that the internal pressure holding property and the run flat running property are compatible with each other. Hereinafter, each part of the tire 10 will be described.
  • a bead core 26 including a wire bundle is embedded in each of the pair of bead portions 12.
  • the carcass 14 straddles these bead cores 26.
  • the bead core 26 can adopt various structures in a pneumatic tire, such as a circular cross section and a polygonal shape, and can adopt, for example, a hexagon as the polygon, but in the present embodiment, it is a quadrangle. There is.
  • the bead core 26 includes, for example, a bead wire 26A and a coating resin 26B that covers the bead wire 26A and contains a resin (that is, a bead coating layer).
  • the bead core 26 is formed by winding a single bead wire 26A coated with the coating resin 26B a plurality of times and laminating it. Specifically, the bead wire 26A coated with the coating resin 26B is wound in the tire width direction without gaps to form a first row, and thereafter, the rows are stacked on the tire radial direction outside with no gaps, and the cross-sectional shape is quadrangular. To form the bead core 26.
  • the coating resins 26B of the bead wires 26A that are adjacent to each other in the tire width direction and the radial direction are joined to each other.
  • the bead core 26 in which the bead wire 26A is coated with the coating resin 26B is formed.
  • the belt layer 40 but also the bead core 26 contains a resin, so that the internal pressure retention of the tire 10 is more likely to be maintained, and the internal pressure retention and the run flat traveling property are more compatible.
  • the resin material forming the coating resin 26B is the same as the resin material forming the coating resin 42S described later.
  • the bead core 26 is formed by winding one bead wire 26A coated with the coating resin 26B and laminating the bead wire 26A, but the embodiment of the present disclosure is not limited to this.
  • a wire bundle in which a plurality of bead wires 60A are coated with a coating resin 60B may be wound and laminated.
  • the interface during lamination is fused by heat welding.
  • the number of bead wires 60A included in one wire bundle is not limited to three, and may be two or four or more. Further, the number of wire bundles in each layer for stacking the wire bundles may be one as shown in FIG. 4, or may be two or more bundles adjacent to each other in the tire width direction.
  • the bead wire 26A is coated with the coating resin 26B to form the bead core 26, but the embodiment of the present disclosure is not limited to this.
  • a coating rubber containing rubber instead of the coating resin 26B, a coating rubber containing rubber may be used.
  • the tire 10 further includes a bead filler 28 embedded in the bead portion 12 and extending from the bead core 26 to the tire radial direction outer side along the outer surface of the carcass 14.
  • the bead filler 28 contains a resin and is embedded in a region of the bead portion 12 surrounded by the carcass 14 (a region outside the portion of the carcass 14 that is arranged inside the tire width direction around the bead core 26). Further, the bead filler 28 has a thickness that decreases toward the end portion 28A on the outer side in the tire radial direction.
  • the bead filler 28 contains a resin, so that the internal pressure retention of the tire 10 is more easily maintained, and the internal pressure retention and the run flat traveling property are improved. More compatible.
  • the resin material forming the bead filler 28 is the same as the resin material forming the coating resin 42S described later.
  • the bead filler 28 containing a resin is used, but the embodiment of the present disclosure is not limited to this, and includes, for example, rubber (preferably containing rubber as a main component (for example, for the whole bead filler). Bead filler may be used.
  • the carcass 14 is a tire frame member including two carcass plies 14A and 14B.
  • the carcass ply 14A is a carcass ply arranged on the tire equatorial plane CL on the outer side in the tire radial direction
  • the carcass ply 14B is a carcass ply arranged on the inner side in the tire radial direction.
  • Each of the carcass plies 14A and 14B is configured to include a plurality of cords and a coated rubber that coats the cords and contains rubber.
  • the coated rubber is not particularly limited, and examples thereof include a rubber material containing a diene rubber (for example, natural rubber).
  • the inner liner 16 contains 20% by mass or more of the diene-based rubber, whereby the inner liner 16 and the carcass 14 are The adhesiveness with is also high. Therefore, run-flat traveling performance is further improved.
  • the carcass 14 thus formed extends in a toroidal shape from one bead core 26 to the other bead core 26 to form a tire skeleton.
  • the end portion side of the carcass 14 is locked to the bead core 26.
  • the end portion side of the carcass 14 is folded back around the bead core 26 from the tire width direction inner side to the tire width direction outer side and locked.
  • the folded back end portions (end portions 14AE and 14BE) of the carcass 14 are arranged on the tire side portion 22.
  • the end portion 14AE of the carcass ply 14A is arranged inside the end portion 14BE of the carcass ply 14B in the tire radial direction.
  • the end portion of the carcass 14 is arranged on the tire side portion 22, but the present disclosure is not limited to this structure.
  • the end portion of the carcass 14 is arranged on the belt layer 40. Good.
  • the end portion side of the carcass 14 may be sandwiched between a plurality of bead cores 26 or may be wound around the bead cores 26 without being folded back.
  • "locking" the end of the carcass 14 to the bead core 26 includes various embodiments such as these.
  • the carcass 14 is a radial carcass.
  • the material of the cord included in the carcass 14 is not particularly limited, and rayon, nylon, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), aramid, glass fiber, carbon fiber, steel or the like can be used. From the viewpoint of weight reduction, the organic fiber cord is preferable. Further, the number of driving the carcass is set in the range of 20 to 60 pieces / 50 mm, but the number is not limited to this range.
  • a belt layer 40 is disposed on the outer side of the carcass 14 in the tire radial direction. As shown in FIG. 3, the belt layer 40 is a ring-shaped batter formed by spirally winding the resin-coated cord 42 around the outer peripheral surface of the carcass 14 along the tire circumferential direction.
  • the resin-coated cord 42 is formed by coating the reinforcing cord 42C with the coating resin 42S, and has a substantially square cross section as shown in FIG.
  • the coating resin 42S on the inner peripheral portion of the resin coated cord 42 in the tire radial direction is configured to be bonded to the outer peripheral surface of the carcass 14 via rubber and, if necessary, an adhesive. Further, the coating resins 42S that are adjacent to each other in the tire width direction of the resin coating cord 42 are integrally joined by heat welding or an adhesive. As a result, the belt layer 40 (resin-coated belt layer) including the reinforcing cord 42C coated with the coating resin 42S is formed.
  • the resin coated cord 42 is configured by coating one reinforcing cord 42C with the coating resin 42S, but may be configured by coating a plurality of reinforcing cords 42C with the coating resin 42S. Good.
  • bead wire 26A in the bead core 26 and the reinforcing cord 42C in the belt layer 40 of the present embodiment are steel cords.
  • This steel cord is mainly composed of steel and can contain various trace contents such as carbon, manganese, silicon, phosphorus, sulfur, copper and chromium.
  • the embodiment of the present disclosure is not limited to this, and as at least one selected from the group consisting of the bead wire 26A and the reinforcing cord 42C, a monofilament cord, a cord obtained by twisting a plurality of filaments, or the like is used instead of the steel cord. May be used. Various designs can be adopted for the twist structure, and various cross-sectional structures, twist pitches, twist directions, and distances between adjacent filaments can be used. Further, a cord obtained by twisting filaments made of different materials can be adopted, and the cross-sectional structure is not particularly limited, and various twist structures such as single twist, layer twist, and multiple twist can be adopted. A resin cord (that is, a cord containing a resin) may be used as at least one selected from the group consisting of the bead wire 26A and the reinforcing cord 42C.
  • the belt layer 40 is formed by winding the substantially square resin-coated cord 42 formed by coating one reinforcing cord 42C with the coating resin 42S around the outer peripheral surface of the carcass 14.
  • the embodiment of the present disclosure is not limited to this.
  • a resin-coated cord 72 having a substantially parallelogram-shaped cross section which is formed by coating a plurality of reinforcing cords 72C with a coating resin 72S, is wound around the outer peripheral surface of the carcass 14. You may form it.
  • a tread 20 is provided outside the belt layer 40 in the tire radial direction in the tread portion 18.
  • the tread 20 is a portion that comes into contact with the road surface during traveling, and a plurality of circumferential grooves 50 extending in the tire circumferential direction are formed on the tread surface of the tread 20.
  • the shape and the number of the circumferential grooves 50 are appropriately set according to performances such as drainage and steering stability required for the tire 10.
  • the inner liner 16 is provided as a continuous layer on the tire inner surface side of the carcass 14 (that is, the tire width direction inner side of the bead portion 12, the tire width direction inner side of the tire side portion 22, and the tread portion 18 tire radial direction inner side). ing.
  • the inner liner 16 is a layer provided to increase the internal pressure retention of the tire 10 by reducing the air permeability.
  • the inner liner 16 is provided in direct contact with at least the inner peripheral surface of the side reinforcing rubber 24 (that is, the inner surface in the tire width direction).
  • the inner liner 16 is also provided in direct contact with the inner peripheral surface (that is, the inner surface in the tire radial direction) of the tread portion 18 of the carcass 14.
  • the present invention is not limited to this, and the carcass 14 and the inner It may have another layer between it and the liner 16.
  • the inner liner 16 is provided as a continuous layer from one bead portion 12 to the other bead portion 12.
  • the inner liner 16 is not limited to this as long as it is provided in contact with at least a part of the side reinforcing rubber 24 in a region where it is desirable to block air, but from the viewpoint of the internal pressure retaining property, the tire of the tire 10 is not limited thereto. It is preferably provided on the entire inner surface.
  • the thickness of the inner liner 16 is, for example, in the range of 0.1 mm or more and 0.4 mm or less.
  • the inner liner 16 may have the same thickness from the one bead portion 12 to the other bead portion 12, and in particular, the region where it is desired to reduce the air permeability may be relatively thick.
  • the inner liner 16 contains at least a diene rubber.
  • the content ratio of the diene rubber to the entire rubber (total amount of rubber) contained in the inner liner 16 is 20% by mass or more, and from the viewpoint of adhesiveness with the side reinforcing rubber 24, 35% by mass or more is preferable, and 50% by mass. % Or more is more preferable.
  • the inner liner 16 contains the diene rubber in the above range, the adhesion between the inner liner and the side reinforcing rubber 24 becomes high.
  • the adhesion between the inner liner 16 and the carcass 14 is also high.
  • the diene rubber refers to a rubber containing a double bond in the main chain of the rubber (specifically, containing 2.5 mol% or more).
  • the diene rubber include natural rubber (NR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), and polychloroprene rubber (CR). ) And other synthetic rubbers.
  • the diene rubbers may be used alone or as a mixture of two or more.
  • natural rubber (NR) is preferable as the diene rubber from the viewpoint of adhesiveness with the side reinforcing rubber 24.
  • the inner liner 16 preferably contains a non-diene rubber in addition to the diene rubber from the viewpoint of lowering air permeability.
  • the content of the non-diene rubber with respect to the entire rubber (total amount of rubber) contained in the inner liner 16 is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass from the viewpoint of reducing air permeability. The above is more preferable. That is, the content ratio of the diene rubber to the entire rubber (total amount of rubber) contained in the inner liner 16 is preferably 80% by mass or less, more preferably 70% by mass or less, from the viewpoint of reducing air permeability. It is more preferably not more than mass%.
  • the non-diene rubber refers to a rubber that contains almost no double bonds in the main chain of the rubber (specifically, less than 2.5 mol%).
  • the non-diene rubber include butyl rubber (butyl rubber (IIR), halogenated butyl rubber, etc.), ethylene / propylene rubber (EPM, EPDM), urethane rubber (U), silicone rubber (Q), chlorosulfonated rubber. (CSM), acrylic rubber (ACM), fluororubber (FKM), chlorosulfonated polyethylene and the like.
  • butyl rubber is preferable among them from the viewpoint of reducing air permeability, and among them, butyl rubber (IIR) and bromobutyl rubber are more preferable.
  • the rubber material forming the inner liner 16 may include other components other than rubber, if necessary, in addition to rubber.
  • Other components include, for example, reinforcing materials such as carbon black, fillers (fillers, short fibers, resins, etc.), vulcanizing agents, vulcanization accelerators, fatty acids or salts thereof, metal oxides, process oils, anti-aging agents. Agents and the like.
  • the vulcanizing agent known vulcanizing agents such as sulfur, organic peroxides, resin vulcanizing agents and the like are used. Among them, it is preferable that sulfur is used as the vulcanizing agent.
  • vulcanization accelerator known vulcanization accelerators such as aldehydes, ammonias, amines, guanidines, thioureas, thiazoles, sulfenamides, thiurams, dithiocarbamates, xanthates and the like are used. Be done.
  • the fatty acid include stearic acid, palmitic acid, myristic acid, and lauric acid, and these may be blended in a salt state such as zinc stearate. Of these, stearic acid is preferred.
  • the metal oxide include zinc white (ZnO), iron oxide, magnesium oxide, and the like, and zinc white is preferable.
  • the process oil may be any of aromatic type, naphthene type and paraffin type.
  • antiaging agent amine-ketone type, imidazole type, amine type, phenol type, sulfur type, phosphorus type and the like can be mentioned.
  • the tire side portion 22 is configured to extend in the tire radial direction, connect the bead portion 12 and the tread portion 18, and can bear the load acting on the tire 10 during run flat traveling.
  • a side reinforcing rubber 24 that reinforces the tire side portion 22 is provided inside the carcass 14 in the tire width direction.
  • the side reinforcing rubber 24 is provided between the carcass 14 and the inner liner 16 and at least in direct contact with the inner liner 16.
  • the side reinforcing rubber 24 is a reinforcing rubber for traveling a predetermined distance while supporting the weight of the vehicle and an occupant when the internal pressure of the tire 10 decreases due to puncture or the like.
  • the side reinforcing rubber 24 extends in the tire radial direction from the bead portion 12 side to the tread 20 side along the inner surface of the carcass 14. Further, the side reinforcing rubber 24 has a shape in which the thickness decreases from the central portion toward the bead portion 12 side and the tread 20 side, for example, a substantially crescent shape.
  • the thickness of the side reinforcing rubber 24 referred to here means the length along the normal line of the carcass 14.
  • the lower end portion 24B of the side reinforcing rubber 24 on the bead portion 12 side overlaps the bead filler 28 with the carcass 14 in between when viewed in the tire width direction.
  • the upper end portion 24A of the side reinforcing rubber 24 on the tread 20 side overlaps with the belt layer 40 when viewed in the tire radial direction.
  • the upper end portion 24A of the side reinforcing rubber 24 overlaps the belt layer 40 with the carcass 14 interposed therebetween.
  • the upper end portion 24A of the side reinforcing rubber 24 is located inside the tire width direction end portion 40E of the belt layer 40 in the tire width direction.
  • the side reinforcing rubber 24 is formed of one type of rubber material, but the embodiment of the present disclosure is not limited to this, and may be formed of a plurality of rubber materials.
  • the side-reinforcing rubber 24 preferably contains rubber as a main component, and from the viewpoint of run-flat running property, it is preferable that the side-reinforcing rubber 24 include a diene rubber, and more preferably, a butadiene rubber (BR). It is also preferable to contain butadiene rubber (BR) and natural rubber (NR).
  • the content of the diene rubber with respect to the entire rubber (total amount of rubber) contained in the side reinforcing rubber 24 is preferably 70% by mass or more, and more preferably 90% by mass or more, from the viewpoint of run-flat traveling property.
  • the rubber material forming the side reinforcing rubber 24 may include, in addition to rubber, other components other than rubber, if necessary.
  • the other components include the same components as the other components that may be included in the rubber material forming the inner liner 16 if necessary.
  • the rubber material forming the side reinforcing rubber 24 preferably contains a thiuram accelerator as a vulcanization accelerator in order to enhance durability during run-flat running.
  • the hardness of the side reinforcing rubber 24 is preferably 70 or more and 85 or less from the viewpoint of run-flat traveling property.
  • the hardness of the side reinforcing rubber 24 refers to the hardness defined by JIS K6253 (type A durometer).
  • the loss coefficient tan ⁇ of the side reinforcing rubber 24 at a temperature of 60 ° C. and a frequency of 20 Hz is preferably 0.10 or less.
  • the loss coefficient tan ⁇ is a value measured using a viscoelastic spectrometer (a spectrometer manufactured by Toyo Seiki Seisaku-sho, Ltd.) under the conditions of a frequency of 20 Hz, an initial strain of 10%, a dynamic strain of ⁇ 2%, and a temperature of 60 ° C.
  • the resin material used for the coating resin 42S in the belt layer 40 is the same as the resin material used for the coating resin 42S in the belt layer 40.
  • the resin material contains at least a resin and may contain other components as necessary.
  • the resin material preferably contains a resin as a main component. Specifically, the resin content with respect to the total amount of the resin material is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 75% by mass or more.
  • the resin material may contain any of a thermoplastic resin, a thermoplastic elastomer, and a thermosetting resin as the resin, but preferably contains at least one selected from the group consisting of a thermoplastic resin and a thermoplastic elastomer, More preferably, it contains a thermoplastic elastomer.
  • thermoplastic resin examples include polyester-based thermoplastic resin, polyamide-based thermoplastic resin, polystyrene-based thermoplastic resin, polyurethane-based thermoplastic resin, polyolefin-based thermoplastic resin, vinyl chloride-based thermoplastic resin, and the like.
  • thermoplastic elastomer examples include polyester thermoplastic elastomer (TPC), polyamide thermoplastic elastomer (TPA), polystyrene thermoplastic elastomer (TPS), polyurethane thermoplastic elastomer (TPU), which are defined in JIS K6418.
  • TPC polyester thermoplastic elastomer
  • TPA polyamide thermoplastic elastomer
  • TPS polystyrene thermoplastic elastomer
  • TPU polyurethane thermoplastic elastomer
  • TPO polyolefin-based thermoplastic elastomer
  • TPV crosslinked thermoplastic rubber
  • TPZ thermoplastic elastomer
  • thermosetting resin examples include phenol-based thermosetting resin, urea-based thermosetting resin, melamine-based thermosetting resin, and epoxy-based thermosetting resin.
  • the resin material may contain one of these resins alone, or may contain two or more kinds of resins in combination.
  • the resin polyester-based thermoplastic elastomer, polyester-based thermoplastic resin, polyamide-based thermoplastic elastomer, polyamide-based thermoplastic resin, polystyrene-based thermoplastic elastomer, polystyrene-based thermoplastic resin, polyurethane-based thermoplastic elastomer, A polyurethane-based thermoplastic resin, a polyolefin-based thermoplastic elastomer, or a polyolefin-based thermoplastic resin is preferable.
  • the resin material preferably contains at least one selected from the group consisting of a polyester-based thermoplastic elastomer, a polyester-based thermoplastic resin, a polyamide-based thermoplastic elastomer, and a polyamide-based thermoplastic resin.
  • the polyester-based thermoplastic elastomer and the polyester It is more preferable to include at least one selected from the group consisting of thermoplastic resins.
  • polyester thermoplastic elastomer- (Polyester thermoplastic elastomer)
  • polyester-based thermoplastic elastomer for example, at least polyester forms a hard segment having a high melting point and another polymer (for example, polyester or polyether) is a soft segment having a low glass transition temperature and being amorphous.
  • the forming material is mentioned.
  • an aromatic polyester can be used as the polyester forming the hard segment.
  • the aromatic polyester can be formed from, for example, an aromatic dicarboxylic acid or its ester-forming derivative and an aliphatic diol.
  • the aromatic polyester is preferably polybutylene terephthalate derived from at least one selected from the group consisting of terephthalic acid and dimethyl terephthalate, and 1,4-butanediol.
  • the aromatic polyesters include, for example, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5
  • a dicarboxylic acid component such as sulfoisophthalic acid or an ester-forming derivative thereof, and a diol having a molecular weight of 300 or less (eg, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, etc.
  • Aliphatic diols such as 1,4-cyclohexanedimethanol and tricyclodecanedimethylol; xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2- B Sus [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4'- Aromatic diols such as dihydroxy-p-terphenyl and 4,4′-dihydroxy-p-quarterphenyl; etc.) and polyesters derived from these, or a combination of two or more of these dicarboxylic acid components and diol components It may be polymerized polyester.
  • polyester forming the hard segment examples include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate and polybutylene naphthalate, and polybutylene terephthalate is preferable.
  • Examples of the polymer that forms the soft segment include aliphatic polyester and aliphatic polyether.
  • Examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, and poly (propylene oxide).
  • An ethylene oxide addition polymer of glycol, a copolymer of ethylene oxide and tetrahydrofuran and the like can be mentioned.
  • Examples of the aliphatic polyester include poly ( ⁇ -caprolactone), polyenanthlactone, polycaprylolactone, polybutylene adipate, polyethylene adipate and the like.
  • poly (tetramethylene oxide) glycol and poly (propylene oxide) glycol are used from the viewpoint of the elastic properties of the obtained polyester block copolymer.
  • Ethylene oxide adduct, poly ( ⁇ -caprolactone), polybutylene adipate, polyethylene adipate and the like are preferable.
  • the number average molecular weight of the polymer forming the soft segment is preferably 300 to 6000 from the viewpoint of toughness and low temperature flexibility. Further, the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 99: 1 to 20:80, and more preferably 98: 2 to 30:70 from the viewpoint of moldability. ..
  • the hard segment is polybutylene terephthalate, preferably a combination in which the soft segment is an aliphatic polyether, the hard segment is polybutylene terephthalate, the soft segment More preferred is the combination where is a poly (ethylene oxide) glycol.
  • polyester thermoplastic elastomers examples include “Hytrel” series (for example, 3046, 5557, 6347, 4047N, 4767N) manufactured by Toray-Dupont Co., Ltd., "Perprene” series manufactured by Toyobo Co., Ltd. (For example, P30B, P40B, P40H, P55B, P70B, P150B, P280B, E450B, P150M, S1001, S2001, S5001, S6001, S9001, etc.) can be used.
  • Hytrel for example, 3046, 5557, 6347, 4047N, 4767N
  • Perprene manufactured by Toyobo Co., Ltd.
  • the polyester-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.
  • the polyamide-based thermoplastic elastomer is a thermoplastic resin material composed of a copolymer having a polymer that forms a crystalline and hard segment with a high melting point and an amorphous polymer that forms a soft segment with a low glass transition temperature. It means that the main chain of the polymer forming the hard segment has an amide bond (—CONH—).
  • the thermoplastic polyamide-based elastomer for example, at least polyamide is a crystalline soft segment having a high melting point, and another polymer (for example, polyester, polyether, etc.) is a soft segment having a low glass transition temperature and being amorphous.
  • the forming material is mentioned.
  • the polyamide-based thermoplastic elastomer may be formed using a chain extender such as dicarboxylic acid.
  • a chain extender such as dicarboxylic acid.
  • Specific examples of the polyamide-based thermoplastic elastomer include the amide-based thermoplastic elastomer (TPA) defined in JIS K6418: 2007, and the polyamide-based elastomer described in JP 2004-346273 A. it can.
  • examples of the polyamide that forms the hard segment include a polyamide formed by a monomer represented by the following general formula (1) or (2).
  • R 1 represents a hydrocarbon molecular chain having 2 to 20 carbon atoms (for example, an alkylene group having 2 to 20 carbon atoms).
  • R 2 represents a hydrocarbon molecular chain having 3 to 20 carbon atoms (for example, an alkylene group having 3 to 20 carbon atoms).
  • R 1 is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms, for example, an alkylene group having 3 to 18 carbon atoms, and a molecular chain of hydrocarbon having 4 to 15 carbon atoms, for example, carbon An alkylene group having 4 to 15 carbon atoms is more preferable, and a hydrocarbon molecular chain having 10 to 15 carbon atoms, for example, an alkylene group having 10 to 15 carbon atoms is particularly preferable.
  • a hydrocarbon molecular chain having 3 to 18 carbon atoms for example, an alkylene group having 3 to 18 carbon atoms is preferable, and a molecular chain of hydrocarbon having 4 to 15 carbon atoms, for example, an alkylene group having 4 to 15 carbon atoms is more preferable, and a hydrocarbon molecular chain having 10 to 15 carbon atoms, for example, an alkylene group having 10 to 15 carbon atoms is particularly preferable.
  • the monomer represented by the general formula (1) or the general formula (2) include ⁇ -aminocarboxylic acid and lactam.
  • polyamides that form the hard segment include polycondensates of these ⁇ -aminocarboxylic acids or lactams, and copolycondensates of diamines and dicarboxylic acids.
  • Examples of ⁇ -aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like having 5 to 20 carbon atoms.
  • Examples thereof include aliphatic ⁇ -aminocarboxylic acid.
  • lactams include aliphatic lactams having 5 to 20 carbon atoms such as lauryl lactam, ⁇ -caprolactam, udecane lactam, ⁇ -enanthlactam and 2-pyrrolidone.
  • diamines examples include aliphatic diamines having 2 to 20 carbon atoms and aromatic diamines having 6 to 20 carbon atoms.
  • examples of the aliphatic diamine having 2 to 20 carbon atoms and the aromatic diamine having 6 to 20 carbon atoms include, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, Examples include decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, and metaxylenediamine.
  • the dicarboxylic acid can be represented by HOOC- (R 3 ) m —COOH (R 3 : a molecular chain of a hydrocarbon having 3 to 20 carbon atoms, m: 0 or 1), and examples thereof include oxalic acid and succinic acid.
  • aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
  • a polyamide obtained by ring-opening polycondensation of lauryl lactam, ⁇ -caprolactam, or udecanlactam can be preferably used.
  • polymer that forms the soft segment examples include polyester and polyether. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and ABA type triblock polyether. These may be used alone or in combination of two or more. Further, polyether diamine or the like obtained by reacting the end of polyether with ammonia or the like can also be used.
  • ABA type triblock polyether means a polyether represented by the following general formula (3).
  • x and z represent an integer of 1 to 20.
  • y represents an integer of 4 to 50.
  • each of x and z is preferably an integer of 1 to 18, more preferably an integer of 1 to 16, even more preferably an integer of 1 to 14, and particularly preferably an integer of 1 to 12.
  • y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, further preferably an integer of 7 to 35, particularly preferably an integer of 8 to 30.
  • each combination of the hard segment and the soft segment mentioned above can be mentioned.
  • the combination of the hard segment and the soft segment the combination of lauryl lactam ring-opening polycondensate / polyethylene glycol, the combination of lauryl lactam ring-opening polycondensate / polypropylene glycol, the lauryl lactam ring-opening polycondensation Body / polytetramethylene ether glycol combination, or a combination of lauryl lactam ring-opening polycondensate / ABA type triblock polyether, and a combination of lauryl lactam ring-opening polycondensate / ABA type triblock polyether is more preferable. preferable.
  • the number average molecular weight of the polymer (polyamide) forming the hard segment is preferably 300 to 15,000 from the viewpoint of melt moldability.
  • the number average molecular weight of the polymer forming the soft segment is preferably 200 to 6000 from the viewpoint of toughness and low temperature flexibility.
  • the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 90:10, and more preferably 50:50 to 80:20 from the viewpoint of moldability. ..
  • thermoplastic polyamide-based elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.
  • polyamide-based thermoplastic elastomers include, for example, UBE Industries' UBESTA XPA series (eg, XPA9068X1, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2XPA9044, etc.), Daicel Eponic Co., Ltd. “Vestamide” series (eg, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.) can be used.
  • UBE Industries' UBESTA XPA series eg, XPA9068X1, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2XPA9044, etc.
  • Vestamide eg, E40-S3, E47-S1, E47-S3, E55-S1,
  • thermoplastic polystyrene-based elastomer for example, at least polystyrene forms a hard segment, and other polymers (for example, polybutadiene, polyisoprene, polyethylene, hydrogenated polybutadiene, hydrogenated polyisoprene) are amorphous and have a glass transition temperature. A material forming a low soft segment is included.
  • polystyrene forming the hard segment for example, those obtained by a known radical polymerization method, ionic polymerization method or the like are preferably used, and specifically, polystyrene having anion living polymerization is mentioned.
  • the polymer forming the soft segment include polybutadiene, polyisoprene, poly (2,3-dimethyl-butadiene) and the like.
  • the combination of the hard segment and the soft segment each combination of the hard segment and the soft segment mentioned above can be mentioned.
  • the combination of the hard segment and the soft segment is preferably the combination of polystyrene / polybutadiene or the combination of polystyrene / polyisoprene.
  • the soft segment is preferably hydrogenated in order to suppress an unintended crosslinking reaction of the thermoplastic elastomer.
  • the number average molecular weight of the polymer (polystyrene) forming the hard segment is preferably 5,000 to 500,000, more preferably 10,000 to 200,000.
  • the number average molecular weight of the polymer forming the soft segment is preferably 5,000 to 1,000,000, more preferably 10,000 to 800,000, and further preferably 30,000 to 500,000.
  • the volume ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 5:95 to 80:20 and more preferably 10:90 to 70:30 from the viewpoint of moldability. ..
  • thermoplastic polystyrene-based elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.
  • examples of the polystyrene-based thermoplastic elastomer include styrene-butadiene-based copolymers [SBS (polystyrene-poly (butylene) block-polystyrene), SEBS (polystyrene-poly (ethylene / butylene) block-polystyrene)], styrene-isoprene.
  • Copolymer polystyrene-polyisoprene block-polystyrene
  • styrene-propylene copolymer [SEP (polystyrene- (ethylene / propylene) block), SEPS (polystyrene-poly (ethylene / propylene) block-polystyrene), SEEPS ( Polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene), SEB (polystyrene (ethylene / butylene) block)] and the like.
  • SEP polystyrene- (ethylene / propylene) block
  • SEPS polystyrene-poly (ethylene / propylene) block-polystyrene
  • SEEPS Polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene
  • SEB polystyrene (ethylene / butylene) block
  • thermoplastic elastomers examples include, for example, "Tuftec” series manufactured by Asahi Kasei (for example, H1031, H1041, H1043, H1051, H1052, H1053, H1062, H1082, H1141, H1221, H1272, etc.), "SEBS” series (8007, 8076, etc.) and “SEPS” series (2002, 2063, etc.) manufactured by Kuraray Co., Ltd. can be used.
  • thermoplastic polyurethane-based elastomer for example, at least polyurethane forms a hard segment in which pseudo-crosslinking is formed by physical agglomeration, and another polymer forms an amorphous soft segment having a low glass transition temperature. Ingredients are listed. Specific examples of the polyurethane-based thermoplastic elastomer include a polyurethane-based thermoplastic elastomer (TPU) defined in JIS K6418: 2007. The polyurethane-based thermoplastic elastomer can be represented as a copolymer including a soft segment including a unit structure represented by the following formula A and a hard segment including a unit structure represented by the following formula B.
  • TPU polyurethane-based thermoplastic elastomer
  • P represents a long-chain aliphatic polyether or a long-chain aliphatic polyester.
  • R represents an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon.
  • P' represents a short chain aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon.
  • P is derived from a diol compound containing a long-chain aliphatic polyether represented by P and a long-chain aliphatic polyester.
  • Examples of such a diol compound include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly (butylene adipate) diol, poly- ⁇ -caprolactone diol, poly (hexamethylene carbonate) having a molecular weight within the above range.
  • diols and ABA type triblock polyethers These may be used alone or in combination of two or more.
  • R is a partial structure introduced using a diisocyanate compound containing an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon represented by R.
  • the aliphatic diisocyanate compound containing an aliphatic hydrocarbon represented by R include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate and 1,6-hexamethylene diisocyanate.
  • Examples of the diisocyanate compound containing an alicyclic hydrocarbon represented by R include 1,4-cyclohexane diisocyanate and 4,4-cyclohexane diisocyanate.
  • the aromatic diisocyanate compound containing an aromatic hydrocarbon represented by R include 4,4′-diphenylmethane diisocyanate and tolylene diisocyanate. These may be used alone or in combination of two or more.
  • alicyclic hydrocarbon or aromatic hydrocarbon represented by P ′ in the formula B for example, those having a molecular weight of less than 500 can be used.
  • P' is derived from a diol compound containing a short chain aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon represented by P '.
  • Examples of the aliphatic diol compound containing a short chain aliphatic hydrocarbon represented by P ′ include glycol and polyalkylene glycol, and specifically, ethylene glycol, propylene glycol, trimethylene glycol, 1,4 -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Decanediol and the like can be mentioned.
  • Examples of the alicyclic diol compound containing an alicyclic hydrocarbon represented by P ′ include cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, Examples thereof include cyclohexane-1,4-diol and cyclohexane-1,4-dimethanol.
  • examples of the aromatic diol compound containing an aromatic hydrocarbon represented by P ′ include hydroquinone, resorcin, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4′- Dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, bisphenol A, 1, Examples thereof include 1-di (4-hydroxyphenyl) cyclohexane, 1,2-bis (4-hydroxyphenoxy) ethane, 1,4-dihydroxynaphthalene and 2,6-dihydroxynaphthalene. These may be used alone or in combination of two or more.
  • the number average molecular weight of the polymer (polyurethane) forming the hard segment is preferably 300 to 1500 from the viewpoint of melt moldability.
  • the number average molecular weight of the polymer forming the soft segment is preferably 500 to 20,000, more preferably 500 to 5,000, and particularly preferably 500 to 3,000, from the viewpoint of the flexibility and thermal stability of the polyurethane-based thermoplastic elastomer. ..
  • the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 15:85 to 90:10, more preferably 30:70 to 90:10 from the viewpoint of moldability. ..
  • the polyurethane-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.
  • the polyurethane-based thermoplastic elastomer for example, the thermoplastic polyurethane described in JP-A-5-331256 can be used.
  • thermoplastic elastomer specifically, a combination of a hard segment made of an aromatic diol and an aromatic diisocyanate and a soft segment made of a polycarbonate is preferable, and more specifically, a tolylene diisocyanate ( TDI) / polyester type polyol copolymer, TDI / polyether type polyol copolymer, TDI / caprolactone type polyol copolymer, TDI / polycarbonate type polyol copolymer, 4,4′-diphenylmethane diisocyanate (MDI) / polyester -Based polyol copolymer, MDI / polyether-based polyol copolymer, MDI / caprolactone-based polyol copolymer, MDI / polycarbonate-based polyol copolymer, and MDI + hydroquinone / polyhexamethyi At least one selected from the group consisting of carbonate cop
  • thermoplastic elastomers examples include "Elastollan” series manufactured by BASF (for example, ET680, ET880, ET690, ET890, etc.) and “Kuramilon U” series manufactured by Kuraray Co., Ltd. (for example, , 2000-series, 3000-series, 8000-series, 9000-series, etc.), "Miractran” series manufactured by Nippon Miractolan Co., Ltd. (eg, XN-2001, XN-2004, P390RSUP, P480RSUI, P26MRNAT, E490, E590, P890 etc.) Etc. can be used.
  • thermoplastic polyolefin-based elastomer for example, at least polyolefin forms crystalline hard segments having a high melting point, and other polymers (eg, polyolefin, other polyolefins, polyvinyl compounds, etc.) are amorphous and have a glass transition temperature of The material forming the low soft segment may be mentioned.
  • polyolefin forming the hard segment include polyethylene, polypropylene, isotactic polypropylene, polybutene and the like.
  • thermoplastic polyolefin-based elastomer examples include olefin- ⁇ -olefin random copolymers and olefin block copolymers.
  • specific examples include propylene block copolymers, ethylene-propylene copolymers and propylene- 1-hexene copolymer, propylene-4-methyl-1 pentene copolymer, propylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-pentene copolymer, ethylene- 1-butene copolymer, 1-butene-1-hexene copolymer, 1-butene-4-methyl-pentene, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate Copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer Polymer, ethylene-eth
  • thermoplastic polyolefin-based elastomers include propylene block copolymers, ethylene-propylene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1pentene copolymers, propylene-1- Butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-pentene copolymer, ethylene-1-butene copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer , Ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer , Propylene-methyl methacrylate copolymer, Ropylene
  • thermoplastic polyolefin-based elastomer is preferably 50% by mass or more and 100% by mass or less.
  • the number average molecular weight of the thermoplastic polyolefin-based elastomer is preferably 5,000 to 10,000,000.
  • the number average molecular weight of the thermoplastic polyolefin-based elastomer is 5,000 to 10,000,000
  • the thermoplastic resin material has sufficient mechanical properties and excellent processability.
  • the number average molecular weight of the polyolefin-based thermoplastic elastomer is more preferably 7,000 to 1,000,000, and particularly preferably 10,000 to 1,000,000. Thereby, the mechanical properties and processability of the thermoplastic resin material can be further improved.
  • the number average molecular weight of the polymer forming the soft segment is preferably 200 to 6000 from the viewpoint of toughness and low temperature flexibility.
  • the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 95:15, more preferably 50:50 to 90:10 from the viewpoint of moldability. ..
  • the thermoplastic polyolefin-based elastomer can be synthesized by copolymerization by a known method.
  • polyolefin-based thermoplastic elastomer one obtained by acid-modifying a polyolefin-based thermoplastic elastomer may be used.
  • the "acid-modified polyolefin-based thermoplastic elastomer” refers to a polyolefin-based thermoplastic elastomer to which an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group or a phosphoric acid group is bonded.
  • an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group, and a phosphoric acid group
  • the polyolefin-based thermoplastic elastomer for example, a polyolefin-based thermoplastic elastomer
  • an unsaturated compound having an acidic group examples thereof include bonding (for example, graft polymerization) of unsaturated bond sites of unsaturated carboxylic acid (generally maleic anhydride).
  • an unsaturated compound having a carboxylic acid group which is a weak acid group, is preferable from the viewpoint of suppressing deterioration of the thermoplastic polyolefin-based elastomer.
  • the unsaturated compound having a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like.
  • thermoplastic elastomers examples include "Toughmer” series manufactured by Mitsui Chemicals, Inc. (for example, A0550S, A1050S, A4050S, A1070S, A4070S, A35070S, A1085S, A4085S, A7090, A70090, MH7007, MH7010).
  • polyester-based thermoplastic resin examples include polyesters that form the hard segment of the above-mentioned polyester-based thermoplastic elastomer.
  • Specific examples of the polyester-based thermoplastic resin include polylactic acid, polyhydroxy-3-butylbutyric acid, polyhydroxy-3-hexylbutyric acid, poly ( ⁇ -caprolactone), polyenanthlactone, polycaprylolactone, and polybutylene.
  • examples thereof include aliphatic polyesters such as adipate and polyethylene adipate, and aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polybutylene naphthalate.
  • polybutylene terephthalate is preferable as the polyester thermoplastic resin from the viewpoint of heat resistance and processability.
  • polyester-based thermoplastic resins include, for example, “Duranex” series manufactured by Polyplastics Co., Ltd. (for example, 2000, 2002, etc.) and “Novaduran” series manufactured by Mitsubishi Engineering Plastics Co., Ltd. (for example, 5010R5). , 5010R3-2, etc.), “Toraycon” series manufactured by Toray Industries, Inc. (eg, 1401X06, 1401X31, etc.) and the like can be used.
  • polyamide thermoplastic resin examples include polyamides that form the hard segment of the above-mentioned polyamide-based thermoplastic elastomer.
  • Specific examples of the polyamide-based thermoplastic resin include polyamide obtained by ring-opening polycondensation of ⁇ -caprolactam (amide 6), polyamide obtained by ring-opening polycondensation of undecane lactam (amide 11), ring-opening polycondensation of lauryl lactam.
  • examples thereof include polyamide (amide 12), polyamide (amide 66) obtained by polycondensing diamine and dibasic acid, and polyamide (amide MX) having metaxylene diamine as a constituent unit.
  • the amide 6 can be represented by, for example, ⁇ CO— (CH 2 ) 5 —NH ⁇ n .
  • the amide 11 can be represented by, for example, ⁇ CO— (CH 2 ) 10 —NH ⁇ n .
  • the amide 12 can be represented by, for example, ⁇ CO— (CH 2 ) 11 —NH ⁇ n .
  • the amide 66 can be represented by, for example, ⁇ CO (CH 2 ) 4 CONH (CH 2 ) 6 NH ⁇ n .
  • the amide MX can be represented by, for example, the following structural formula (A-1). Here, n represents the number of repeating units.
  • amide 6 for example, "UBE nylon” series (for example, 1022B, 1011FB, etc.) manufactured by Ube Industries, Ltd. can be used.
  • amide 11 for example, “Rilsan B” series manufactured by Arkema Ltd. can be used.
  • amide 12 for example, "UBE nylon” series (for example, 3024U, 3020U, 3014U, etc.) manufactured by Ube Industries, Ltd. can be used.
  • As a commercially available product of the amide 66 for example, "Leona” series (for example, 1300S, 1700S, etc.) manufactured by Asahi Kasei Co., Ltd. can be used.
  • amide MX for example, "MX Nylon” series (for example, S6001, S6021, S6011, etc.) manufactured by Mitsubishi Gas Chemical Co., Inc. can be used.
  • thermoplastic polyamide-based resin may be a homopolymer formed of only the above structural unit or a copolymer of the above structural unit and another monomer.
  • the content of the above structural units in each polyamide-based thermoplastic resin is preferably 40% by mass or more.
  • polyolefin thermoplastic resin examples include the polyolefins that form the hard segments of the above-mentioned polyolefin-based thermoplastic elastomer.
  • Specific examples of the polyolefin-based thermoplastic resin include polyethylene-based thermoplastic resin, polypropylene-based thermoplastic resin, polybutadiene-based thermoplastic resin, and the like.
  • polypropylene-based thermoplastic resin is preferable as the polyolefin-based thermoplastic resin from the viewpoint of heat resistance and processability.
  • polypropylene-based thermoplastic resin examples include propylene homopolymer, propylene- ⁇ -olefin random copolymer, propylene- ⁇ -olefin block copolymer and the like.
  • ⁇ -olefin examples include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene,
  • ⁇ -olefins having about 3 to 20 carbon atoms such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.
  • the resin material may contain other components such as additives within a range that does not impair the effect.
  • other components include rubber, various fillers (eg, silica, calcium carbonate, clay, etc.), antioxidants, oils, plasticizers, coloring agents, weathering agents, and the like.
  • an unvulcanized inner liner 16 an unvulcanized side reinforcing rubber 24, a carcass 14 including an unvulcanized rubber material, a bead core 26, and a bead filler 28 are provided on the outer periphery of a known tire forming drum (not shown). Forming an unvulcanized tire case.
  • the belt layer 40 is formed as follows. Specifically, the resin coating cord 42 is sent toward the outer peripheral surface of the belt forming drum (not shown). The resin coating cord 42 is pressed against the outer peripheral surface of the belt forming drum in a state where the coating resin 42S is heated by hot air and melted, and then cooled. In this manner, the resin-coated cord 42 is spirally wound around the outer peripheral surface of the belt forming drum and pressed against the outer peripheral surface, whereby a layer of the resin coated cord 42 is formed on the outer peripheral surface of the belt forming drum.
  • the belt layer 40 in which the resin coating cord 42 is cooled and the coating resin 42S is solidified is removed from the belt forming drum. Then, after the adhesive is applied to the inner peripheral surface of the removed belt layer 40 as required, the belt layer 40 is arranged on the tire molding drum in the radial direction outside of the unvulcanized tire case. Then, the unvulcanized tire case is expanded, and the outer peripheral surface of the tire case, in other words, the outer peripheral surface of the carcass 14 is pressure-bonded to the inner peripheral surface of the belt layer 40. Finally, an adhesive is applied to the outer peripheral surface of the belt layer 40 as needed, and then the unvulcanized tread 20 is attached to complete the green tire. The green tire manufactured in this way is vulcanized and molded by the vulcanization mold to complete the tire 10.
  • a pair of bead cores A carcass straddling the pair of bead cores, the end portion of which is locked to the bead core,
  • An inner liner provided on the tire inner surface side of the carcass, wherein the content of the diene rubber is 20% by mass or more based on the total amount of rubber contained in the inner liner,
  • a side reinforcing rubber layer provided in direct contact with the inner liner between the carcass of the tire side portion and the inner liner, and extending in the tire radial direction along the inner surface of the carcass
  • a belt layer provided on the outer side in the tire radial direction of the carcass, having a cord and a cord coating layer that coats the cord and contains a resin
  • a tread provided on the tire radial direction outer side of the belt layer, Run-flat tire with.
  • ⁇ 2> The run-flat tire according to ⁇ 1>, wherein the diene rubber contained in the inner liner contains natural rubber.
  • ⁇ 3> The run-flat tire according to ⁇ 1> or ⁇ 2>, wherein the inner liner further contains butyl rubber.
  • ⁇ 4> The run-flat tire according to any one of ⁇ 1> to ⁇ 3>, in which the side reinforcing rubber layer contains a diene rubber.
  • ⁇ 5> The run flat according to any one of ⁇ 1> to ⁇ 4>, which is arranged so as to extend from the bead core to a tire radial direction outer side along an outer surface of the carcass and further includes a bead filler containing a resin. tire.
  • ⁇ 6> The run flat tire according to any one of ⁇ 1> to ⁇ 5>, wherein the bead core has a bead wire and a bead coating layer that covers the bead wire and contains a resin.
  • Example 1 ⁇ Preparation of coated resin cord> An adhesive (made by Mitsubishi Chemical Co., Ltd.) that was heated and melted into a multifilament having an average diameter of ⁇ 1.15 mm (a monofilament having a diameter of 0.35 mm (steel, strength: 280 N, elongation: 3%) twisted wire of 7 pieces) , Maleic anhydride-modified polyester-based thermoplastic elastomer, product name: Primalloy-AP GQ730).
  • a coating resin (a polyester thermoplastic elastomer manufactured by Toray-Dupont Co., Ltd., product name: Hytrel 5557) extruded by an extruder is attached to the outer periphery of the resin to coat and cool it.
  • the extrusion conditions are that the temperature of the metal member is 200 ° C., the temperature of the coating resin is 240 ° C., and the extrusion speed is 30 m / min.
  • the coated resin cord is produced as described above.
  • ⁇ Preparation of unvulcanized side reinforcing rubber> The following components are kneaded and molded with a Banbury mixer (Mixtron BB MIXER, manufactured by Kobe Steel, Ltd.) to prepare an unvulcanized side reinforcing rubber.
  • ⁇ Preparation of unvulcanized tread> The following components are kneaded with a Banbury mixer (Mixtron BB MIXER, manufactured by Kobe Steel, Ltd.) and molded into a sheet shape to prepare an unvulcanized tread.
  • -Natural rubber RSS # 3 ... 50 parts by mass-Styrene / butadiene copolymer rubber (SBR): # 1500 (emulsion polymerization SBR), manufactured by JSR ...
  • a belt layer is installed on the outer peripheral surface of an unvulcanized tire case, and an unvulcanized tread is wound around the outer periphery of the belt layer to obtain a raw tire. Then, the obtained raw tire is vulcanized by heating at 160 ° C. for 20 minutes to obtain a tire.
  • Example 2 In the production of the unvulcanized inner liner, the tire is produced and evaluated in the same manner as in Example 1 except that the addition amount of natural rubber is 50 parts by mass and the addition amount of bromobutyl rubber is 50 parts by mass.
  • Example 3 In the production of the unvulcanized inner liner, the tire is produced and evaluated in the same manner as in Example 1 except that the addition amount of natural rubber is 80 parts by mass and the addition amount of bromobutyl rubber is 20 parts by mass.
  • Example 1 In the production of the coated resin cord, the coated rubber (natural rubber) is used instead of the coated resin, and in the production of the unvulcanized inner liner, the addition amount of the natural rubber is 0 part by mass and the addition amount of the bromobutyl rubber is 100 parts by mass A tire is manufactured and evaluated in the same manner as in Example 1 except that a coated rubber (natural rubber) is used instead of the coating resin in the bead core and a bead filler made of rubber (natural rubber) is used as the bead filler.
  • Example 2 In the production of the coated resin cord, a tire was prepared in the same manner as in Example 1 except that a coated rubber was used instead of the coated resin, a coated rubber was used instead of the coated resin in the bead core, and a bead filler made of rubber was used as a bead filler. The production and evaluation of
  • Example 3 In the production of the coated resin cord, a tire was prepared in the same manner as in Example 2 except that a coated rubber was used instead of the coated resin, a coated rubber was used instead of the coated resin in the bead core, and a bead filler made of rubber was used as a bead filler. The production and evaluation of

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  • Organic Chemistry (AREA)
  • Tires In General (AREA)

Abstract

L'invention concerne un pneu à affaissement limité pourvu : d'une paire de tringles ; d'une carcasse qui est disposée à travers la paire de tringles et qui a des extrémités verrouillées avec les tringles ; d'un revêtement interne disposé sur le côté surface interne du pneu de la carcasse et qui a une teneur en caoutchouc diénique qui n'est pas inférieure à 20 % en masse par rapport à la quantité totale de caoutchouc incluse dans le revêtement interne ; d'une couche de caoutchouc de renforcement latéral qui est disposée entre le revêtement interne et la carcasse au niveau des parties latérales du pneu de façon à être en contact direct avec le revêtement interne, et qui s'étend dans la direction radiale du pneu le long de la surface interne de la carcasse ; et d'une couche de ceinture qui est disposée vers l'extérieur dans la direction radiale du pneu de la carcasse et qui a un cordon et une couche de revêtement de cordon contenant une résine et recouvrant le cordon ; et d'une bande de roulement disposée vers l'extérieur dans la direction radiale du pneu de la couche de ceinture.
PCT/JP2019/043278 2018-11-08 2019-11-05 Pneu à affaissement limité WO2020095891A1 (fr)

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09300924A (ja) * 1996-05-13 1997-11-25 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JPH11198617A (ja) * 1998-01-09 1999-07-27 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JPH11245636A (ja) * 1998-03-06 1999-09-14 Bridgestone Corp 空気入り安全タイヤ
JP2002103925A (ja) * 2000-09-27 2002-04-09 Bridgestone Corp 空気入りランフラットラジアルタイヤ
JP2003191711A (ja) * 2001-12-26 2003-07-09 Bridgestone Corp タイヤ及びその製造方法
JP2007069775A (ja) * 2005-09-07 2007-03-22 Sumitomo Rubber Ind Ltd ランフラットタイヤ
JP2007069745A (ja) * 2005-09-07 2007-03-22 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JP2010162826A (ja) * 2009-01-19 2010-07-29 Yokohama Rubber Co Ltd:The 空気入りタイヤの製造方法及び空気入りタイヤ
JP2011235835A (ja) * 2010-05-13 2011-11-24 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JP2012051970A (ja) * 2010-08-31 2012-03-15 Toyo Tire & Rubber Co Ltd 変性ジエン系ゴムポリマーの製造方法
JP2015123905A (ja) * 2013-12-26 2015-07-06 横浜ゴム株式会社 空気入りタイヤ
JP2017114163A (ja) * 2015-12-21 2017-06-29 株式会社ブリヂストン 空気入りタイヤ及びタイヤ・リム組立体
JP2017159864A (ja) * 2016-03-11 2017-09-14 株式会社ブリヂストン 空気入りタイヤ及び空気入りタイヤの製造方法

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09300924A (ja) * 1996-05-13 1997-11-25 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JPH11198617A (ja) * 1998-01-09 1999-07-27 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JPH11245636A (ja) * 1998-03-06 1999-09-14 Bridgestone Corp 空気入り安全タイヤ
JP2002103925A (ja) * 2000-09-27 2002-04-09 Bridgestone Corp 空気入りランフラットラジアルタイヤ
JP2003191711A (ja) * 2001-12-26 2003-07-09 Bridgestone Corp タイヤ及びその製造方法
JP2007069775A (ja) * 2005-09-07 2007-03-22 Sumitomo Rubber Ind Ltd ランフラットタイヤ
JP2007069745A (ja) * 2005-09-07 2007-03-22 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JP2010162826A (ja) * 2009-01-19 2010-07-29 Yokohama Rubber Co Ltd:The 空気入りタイヤの製造方法及び空気入りタイヤ
JP2011235835A (ja) * 2010-05-13 2011-11-24 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JP2012051970A (ja) * 2010-08-31 2012-03-15 Toyo Tire & Rubber Co Ltd 変性ジエン系ゴムポリマーの製造方法
JP2015123905A (ja) * 2013-12-26 2015-07-06 横浜ゴム株式会社 空気入りタイヤ
JP2017114163A (ja) * 2015-12-21 2017-06-29 株式会社ブリヂストン 空気入りタイヤ及びタイヤ・リム組立体
JP2017159864A (ja) * 2016-03-11 2017-09-14 株式会社ブリヂストン 空気入りタイヤ及び空気入りタイヤの製造方法

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