WO2019225622A1 - Élément de talon pour pneus, et pneu - Google Patents

Élément de talon pour pneus, et pneu Download PDF

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Publication number
WO2019225622A1
WO2019225622A1 PCT/JP2019/020177 JP2019020177W WO2019225622A1 WO 2019225622 A1 WO2019225622 A1 WO 2019225622A1 JP 2019020177 W JP2019020177 W JP 2019020177W WO 2019225622 A1 WO2019225622 A1 WO 2019225622A1
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WO
WIPO (PCT)
Prior art keywords
tire
bead
resin
bead filler
thermoplastic elastomer
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PCT/JP2019/020177
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English (en)
Japanese (ja)
Inventor
壮一 京
啓之 筆本
Original Assignee
株式会社ブリヂストン
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Priority to JP2020521263A priority Critical patent/JPWO2019225622A1/ja
Publication of WO2019225622A1 publication Critical patent/WO2019225622A1/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
    • B60C15/00—Tyre beads, e.g. ply turn-up or overlap
    • B60C15/04—Bead cores
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • B60C2001/005—Compositions of the bead portions, e.g. clinch or chafer rubber or cushion rubber

Definitions

  • the present disclosure relates to a tire bead member and a tire.
  • a pneumatic tire having a pair of bead portions, a pair of tire side portions extending outward from the bead portion in the tire radial direction, and a tread portion extending from one tire side portion to the other tire side portion is used.
  • the bead portion of the pneumatic tire employs a structure in which a bead core having a bead wire is embedded and a bead filler formed of an elastic material around the bead core is employed from the viewpoint of improving the fixing performance to the rim. Has been.
  • Patent Document 1 proposes a bead wire for a tire skin including a wire rod assembly that is covered with a covering portion that is manufactured with a material having an elongation of 10% and an elongation cutting coefficient measured at room temperature equal to at least 70 MPa. .
  • Patent Document 1 Japanese Patent Laid-Open No. 63-25110
  • Patent Document 1 discloses a technique in which a bead wire covered with a resin covering portion is used for a bead portion of a tire.
  • Patent Document 1 does not suggest a material around the covering portion, and makes no mention of strength or the like regarding members around the covering portion.
  • the bead filler arranged around the bead core is also required to improve durability against impact (that is, impact resistance) while maintaining excellent rim assembly. ing.
  • an object of the present disclosure is to provide a tire bead member that achieves both excellent rim assemblability and high impact resistance, and a tire including the tire bead member.
  • the bead filler has a continuous phase containing a thermoplastic elastomer, and a discontinuous phase containing an amorphous resin and interspersed in the continuous phase,
  • a tire bead member having a tensile elastic modulus Ei of the discontinuous phase higher than a tensile elastic modulus Es of the continuous phase.
  • FIG. 1 is a tire half-sectional view illustrating one side of a cut surface obtained by cutting a tire according to a first embodiment of the present disclosure along the tire width direction.
  • FIG. 2 is a cross-sectional view in the tire width direction, showing an enlargement of the periphery of the bead portion of the tire of FIG. 1.
  • FIG. 3A is a schematic diagram of a vertical cut surface with respect to the length direction of the bead wire, illustrating an example of a bead core according to an embodiment of the present disclosure.
  • FIG. 3B is a schematic diagram of a vertical cut surface with respect to the length direction of the bead wire, illustrating an example of a bead core according to an embodiment of the present disclosure.
  • FIG. 1 is a tire half-sectional view illustrating one side of a cut surface obtained by cutting a tire according to a first embodiment of the present disclosure along the tire width direction.
  • FIG. 2 is a cross-sectional view in the tire width direction, showing an en
  • FIG. 3C is a schematic diagram of a vertical cut surface with respect to the length direction of the bead wire, illustrating an example of a bead core according to an embodiment of the present disclosure.
  • FIG. 4 is a tire half-sectional view showing one side of a cut surface obtained by cutting a tire according to a second embodiment of the present disclosure along the tire width direction.
  • FIG. 5 is a tire half-sectional view showing one side of a cut surface obtained by cutting a tire according to a third embodiment of the present disclosure along the tire width direction.
  • FIG. 6 is a cross-sectional view in the tire width direction showing the bead portion and the periphery of the tire of FIG. 5 in an enlarged manner.
  • FIG. 4 is a tire half-sectional view showing one side of a cut surface obtained by cutting a tire according to a second embodiment of the present disclosure along the tire width direction.
  • FIG. 5 is a tire half-sectional view showing one side of a cut surface obtained by cutting a tire according to
  • FIG. 7 is a cross-sectional view in the tire width direction that shows an enlarged view of the periphery of a bead portion of a tire according to a fourth embodiment of the present disclosure.
  • FIG. 8 is a cross-sectional view in the tire width direction that shows an enlarged view of the periphery of a bead portion of a tire according to a fifth embodiment of the present disclosure.
  • FIG. 9 is a cross-sectional view in the tire width direction that shows an enlarged view around the bead portion of the tire according to the sixth embodiment of the present disclosure.
  • FIG. 10 is a cross-sectional image obtained by observing a sample having a continuous phase containing a thermoplastic elastomer and a discontinuous phase containing an amorphous resin and scattered in the continuous phase with an atomic force microscope.
  • resin is a concept including a thermoplastic resin, a thermoplastic elastomer, and a thermosetting resin, and does not include vulcanized rubber.
  • resin “same species” means those having a skeleton that is common to the skeleton constituting the main chain of the resin, such as esters and styrenes.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • process includes not only an independent process but also a process that can be clearly distinguished from other processes as long as the purpose is achieved. include.
  • thermoplastic resin means a polymer compound that softens and flows as the temperature rises and becomes relatively hard and strong when cooled, but does not have rubbery elasticity.
  • thermoplastic elastomer means a copolymer having a hard segment and a soft segment. Thermoplastic elastomers include those that soften and flow as the temperature rises, become relatively hard and strong when cooled, and have rubbery elasticity. Specific examples of the thermoplastic elastomer include, for example, a polymer that forms a crystalline hard segment with a high melting point or a cohesive hard segment, and a polymer that forms an amorphous soft segment with a low glass transition temperature.
  • the copolymer which has is mentioned.
  • 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 serves as a crosslinking point of the crosslinked rubber that prevents plastic deformation.
  • the hard segment includes a segment having a rigid group such as an aromatic group or an alicyclic group in the main skeleton, or a structure enabling intermolecular packing by intermolecular hydrogen bonding or ⁇ - ⁇ interaction.
  • 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.
  • the soft segment includes a segment having a long-chain group (for example, a long-chain alkylene group) in the main chain, a high degree of molecular rotation freedom, and a stretchable structure.
  • a bead member for a tire according to an embodiment of the present disclosure (hereinafter, also simply referred to as “bead member”) includes at least a bead core having a bead wire, and is in direct contact with the bead core or through another layer. And a bead filler disposed.
  • the bead filler has a continuous phase containing a thermoplastic elastomer and a discontinuous phase containing an amorphous resin and interspersed in the continuous phase, and the discontinuous phase has a tensile modulus Ei of the continuous phase. It is higher than the tensile modulus Es.
  • the bead member according to the present embodiment is a member used for a pair of bead portions in a tire, and is a member constituting all or part of the bead portions.
  • the bead member concerning this embodiment constitutes at least a bead wire and all or a part of a bead filler in a tire.
  • the aspect of the bead member which concerns on this embodiment is demonstrated easily based on drawing.
  • size of the member in each figure is notional, The relative relationship of the magnitude
  • symbol is attached
  • the tire 10 shown in FIG. 1 has a pair of bead portions 12 on the left and right (only the bead portion 12 on one side is shown in FIG. 1).
  • a bead core 18 is embedded in the bead portion 12, and a carcass 22 straddles the pair of left and right bead cores 18.
  • a bead filler 20 extending from the bead core 18 to the outer side in the tire radial direction along the outer surface 220 of the carcass 22 is embedded in the bead portion 12.
  • the bead filler 20 is disposed, for example, in a region surrounded by the carcass main body 22A and the folded portion 22B. As shown in FIG.
  • the bead core 18 includes a plurality of bead wires 1 arranged side by side and a coating resin layer 3 that covers the bead wires 1.
  • the coating resin layer 3 may not be provided according to the specifications of the bead member of the present embodiment.
  • the tire 10 shown in FIG. 1 is a run-flat tire, and a side reinforcing rubber 26 as an example of a side reinforcing layer that reinforces the tire side portion 14 is disposed on the inner side in the tire width direction of the carcass 22 of the tire side portion 14. ing.
  • the tire 210 shown in FIG. 5 has a pair of bead portions 212 on the left and right (in FIG. 5, only one bead portion 212 is shown). And it has a pair of tire side part 214 each extended from a pair of bead part 212 to the tire radial direction outer side, and a tread part 216 extended from one tire side part 214 to the other tire side part 214.
  • a bead core 218 is embedded in the bead portion 212, and a carcass 222 straddles a pair of left and right bead cores 218.
  • a bead filler 200 including a first bead filler 201 and a second bead filler 202 extending from the bead core 218 to the outer side in the tire radial direction along the outer surface 222O of the carcass 222 is embedded.
  • the bead filler 200 is disposed in a region surrounded by the carcass main body portion 222A and the folded portion 222B.
  • the bead core 218 includes a plurality of bead wires 1 arranged side by side and a coating resin layer 3 that covers the bead wires 1. Note that the coating resin layer 3 may not be provided according to the specifications of the bead member of the present embodiment.
  • the tire 210 shown in FIG. 5 is a run-flat tire, and a side reinforcing rubber 226 as an example of a side reinforcing layer that reinforces the tire side portion 214 is disposed inside the carcass 222 of the tire side portion 214 in the tire width direction. ing.
  • the bead filler is composed of two or more members as in the tire 210 shown in FIG. 5, “the continuous phase containing the thermoplastic elastomer and the amorphous resin are scattered in the continuous phase. It is preferable that the member be closer to the bead core to satisfy the requirement that it has a discontinuous phase and the tensile elastic modulus Ei of the discontinuous phase is higher than the tensile elastic modulus Es of the continuous phase. Moreover, it is more preferable that all of two or more members constituting the bead filler satisfy the above requirements. Therefore, in the case of the tire 210 shown in FIG.
  • the first bead filler 201 closer to the bead core satisfies at least the above requirements, and both the first bead filler 201 and the second bead filler 202 satisfy the above requirements. It is more preferable to satisfy.
  • the bead member according to the present embodiment constitutes all or part of the pair of bead portions.
  • the bead member concerning this embodiment comprises at least a bead wire and all or some of bead fillers.
  • a bead core having at least a bead wire, and a bead filler disposed in direct contact with the bead core or through another layer The bead member which has is used.
  • a material containing rubber has been generally used for the members constituting the bead filler, but in recent years, a material containing a resin in the bead filler has been used from the viewpoint of ease of molding and the like. ing.
  • the bead filler is also required to improve durability against impact (that is, impact resistance). For this reason, the bead filler has excellent rim assemblability that can be deformed flexibly during rim assembly and can be easily assembled, and durability against impact (impact resistance) by increasing rigidity. It is demanded to satisfy both conflicting properties of enhancing.
  • the present inventors have a continuous phase containing a thermoplastic elastomer and a discontinuous phase containing an amorphous resin and interspersed in the continuous phase, and the tensile elastic modulus Ei of the discontinuous phase is continuous. It has been found that by using a bead filler higher than the tensile elastic modulus Es of the phase, it is possible to achieve both excellent rim assembly and high impact resistance. The reason is guessed as follows.
  • the amorphous resin When an amorphous resin is added to the bead filler in addition to the thermoplastic elastomer, the amorphous resin is not contained in the continuous phase of the thermoplastic elastomer (that is, the sea region in the sea-island structure) because of the compatibility between the two. It constitutes a continuous phase (island region in sea-island structure). Since the continuous phase (sea region) containing the thermoplastic elastomer is present throughout the bead filler, elasticity due to the thermoplastic elastomer is maintained, and excellent rim assemblability is exhibited.
  • discontinuous phases (island regions) containing amorphous resin are scattered in the continuous phase, and the tensile elastic modulus Ei of the discontinuous phase is higher than the tensile elastic modulus Es of the continuous phase.
  • the thermoplastic elastomer While retaining the elasticity of the thermoplastic elastomer inside, high rigidity is imparted to the bead filler. Thereby, the high durability with respect to an impact is acquired.
  • the bead member includes a bead core having a bead wire, and a bead filler disposed in direct contact with the bead core or through another layer.
  • the shape of the bead member according to the present embodiment is not particularly limited.
  • the bead core may have a coating resin layer disposed in direct contact with the bead wire or in contact with another layer.
  • the bead core may further have an adhesive layer between the bead wire and the coating resin layer.
  • the structure in which the bead filler is placed in direct contact with the bead core or in contact with another layer for example, the entire surface of the bead core is in direct contact with the bead filler and is covered.
  • the structure in which the covering resin layer is disposed in direct contact with the bead wire or in contact with another layer includes, for example, the entire surface of the bead wire in the covering resin layer. Directly contacted and coated state, part of the surface of the bead wire is covered with the covering resin layer via the adhesive layer, and the whole surface of the bead wire is covered with the adhesive layer And a state covered with a layer.
  • the bead filler includes at least a thermoplastic elastomer and an amorphous resin.
  • the bead filler has a continuous phase containing a thermoplastic elastomer and a discontinuous phase containing an amorphous resin and scattered in the continuous phase.
  • the bead filler has a discontinuous phase interspersed in the continuous phase (that is, has a sea-island structure), for example, the cross section of the bead filler is observed with an atomic force microscope (AFM), It can be confirmed by whether or not the domain is observed.
  • AFM atomic force microscope
  • the tensile elastic modulus Ei of the discontinuous phase in the bead filler is higher than the tensile elastic modulus Es of the continuous phase.
  • the tensile elastic modulus Ei of the discontinuous phase is preferably 500 MPa or more and 3000 MPa or less, more preferably 1000 MPa or more and 3000 MPa or less, from the viewpoint of imparting high rigidity to the bead filler and further improving impact resistance. More preferably, it is 1500 MPa or more and 3000 MPa or less.
  • the tensile elastic modulus Es of the continuous phase is preferably 100 MPa or more and 400 MPa or less, more preferably 100 MPa or more and 300 MPa or less, and further preferably, from the viewpoint that the flexibility of the bead filler is ensured and the rim assembly property is excellent. Is 100 MPa or more and 200 MPa or less.
  • the ratio (Ei / Es) of the tensile elastic modulus Ei of the discontinuous phase and the tensile elastic modulus Es of the continuous phase is 500/400 to 3000 from the viewpoint of achieving both excellent rim assembly properties and high impact resistance.
  • / 100 preferably 1000/300 to 3000/100, more preferably 1500/200 to 3000/100.
  • the shape of the discontinuous phase and the continuous phase in the bead filler can be measured by observing the cross section of the bead filler with an atomic force microscope (AFM). Specifically, the response of the sample surface is detected by separating the amplitude and phase delay of the cantilever by the tapping mode, and the shapes of the continuous phase and the discontinuous phase are measured. Moreover, the tensile elastic modulus Ei of the discontinuous phase and the tensile elastic modulus Es of the continuous phase in the bead filler are performed in accordance with JIS K7113: 1995.
  • AFM atomic force microscope
  • the tensile modulus is set to 100 mm / min and the tensile elastic modulus is measured.
  • a measurement sample of the same material as the discontinuous phase or the same material as the continuous phase may be separately prepared and the elastic modulus may be measured.
  • the tensile elastic modulus Ei of the discontinuous phase and the tensile elastic modulus Es of the continuous phase are controlled by selecting materials constituting the discontinuous phase and the continuous phase, adjusting their contents, and the like.
  • the tensile elastic modulus Ei of the discontinuous phase can be adjusted by the type of amorphous resin contained in the discontinuous phase, the content in the discontinuous phase, and the like.
  • the tensile elastic modulus Es of the continuous phase can be adjusted by the kind of the thermoplastic elastomer contained in the continuous phase, the content ratio in the continuous phase, and the like.
  • ⁇ Content of each component in bead filler (1) Content of component in discontinuous phase
  • the content of amorphous resin in the discontinuous phase gives the bead filler high rigidity and impact resistance.
  • the amorphous resin is preferably contained in an amount of 40% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, with respect to 100 parts by mass of the components constituting the discontinuous phase. More preferably, it is 70 mass% or more and 100 mass% or less.
  • the content of the thermoplastic elastomer in the continuous phase is the component 100 constituting the continuous phase from the viewpoint that the flexibility of the bead filler is ensured and the rim assembly property is excellent.
  • the thermoplastic elastomer is preferably contained in an amount of 60% by mass or more and 100% by mass or less, more preferably 75% by mass or more and 100% by mass or less, and still more preferably 90% by mass or more and 100% by mass or less. .
  • the content of the amorphous resin with respect to 100 parts by mass is preferably 5 parts by mass or more and 45 parts by mass or less, more preferably 10 parts by mass or more and 40 parts by mass or less, and further preferably 20 parts by mass or more and 30 parts by mass or less. Or less.
  • each component for example, amorphous resin, thermoplastic elastomer, etc.
  • the content rate of each component can be examined by a nuclear magnetic resonance (NMR) method.
  • the bead filler includes an amorphous resin in the discontinuous phase.
  • the “amorphous resin” means a thermoplastic resin that has a very low crystallinity or cannot be crystallized.
  • the amorphous resin contained in the discontinuous phase may be one type or two or more types.
  • the amorphous resin is preferably an amorphous resin having an ester bond (hereinafter also simply referred to as “specific amorphous resin”).
  • specific amorphous resin amorphous resin having an ester bond
  • the continuous phase of the bead filler includes a polyester-based thermoplastic elastomer as the thermoplastic elastomer
  • the specific amorphous resin has an ester bond.
  • excellent compatibility the discontinuous phase containing the specific amorphous resin has excellent dispersibility in the continuous phase, and the aggregation of the specific amorphous resin is suppressed and exists in fine domains. It is considered to be done.
  • amorphous resins include amorphous polyester-based thermoplastic resins, amorphous polycarbonate-based thermoplastic resins, and amorphous polyurethane-based thermoplastic resins.
  • amorphous polyester thermoplastic resins and amorphous polycarbonate thermoplastic resins are preferable.
  • the glass transition temperature (Tg) of the amorphous resin is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and 80 ° C. or higher. Further preferred.
  • the Tg of the specific amorphous resin is a value measured by DSC in accordance with JIS K 6240: 2011. Specifically, Tg is the temperature at the intersection of the original baseline at the DSC measurement and the tangent at the inflection point. The measurement can be performed, for example, using “DSC Q100” manufactured by TA Instruments Co., Ltd. at a sweep rate of 10 ° C./min.
  • amorphous resins examples include Toyobo's amorphous polyester resin "Byron” series, Mitsubishi Engineering Plastics' amorphous polycarbonate resin “Novalex” series, Mitsubishi Gas Chemical ( Non-crystalline polyester resin “ALTERSTER” series, etc.
  • the discontinuous phase may contain components other than the amorphous resin.
  • other components include resins, rubbers, various fillers (for example, silica, calcium carbonate, clay, etc.), antioxidants, oils, plasticizers, color formers, weathering agents, and the like.
  • thermoplastic elastomer in the continuous phase.
  • thermoplastic elastomer for example, polyester thermoplastic elastomer (TPC), polyamide thermoplastic elastomer (TPA), polystyrene thermoplastic elastomer (TPS), polyurethane thermoplastic elastomer (TPU) specified in JIS K6418, Examples thereof include an olefinic thermoplastic elastomer (TPO), a crosslinked thermoplastic rubber (TPV), and other thermoplastic elastomers (TPZ).
  • TPC polyester thermoplastic elastomer
  • TPA polyamide thermoplastic elastomer
  • TPS polystyrene thermoplastic elastomer
  • TPU polyurethane thermoplastic elastomer
  • TPO olefinic thermoplastic elastomer
  • TPV crosslinked thermoplastic rubber
  • TPZ thermoplastic elastomers
  • the continuous phase may contain these thermoplastic elastomers alone or in combination of two or more.
  • thermoplastic elastomer contained in the continuous phase a polyester-based thermoplastic elastomer is preferable.
  • the member constituting the surface of the bead core for example, a coating resin layer
  • the same kind of resin is contained in both of the contacts.
  • polyester thermoplastic elastomers for example, at least polyester forms a hard segment with a crystalline and high melting point, and other polymers (for example, polyester or polyether) are amorphous and have a glass transition. The material which forms the soft segment with low temperature is mentioned.
  • An aromatic polyester can be used as the polyester forming the hard segment.
  • the aromatic polyester can be formed, for example, from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol.
  • the aromatic polyester is preferably polybutylene terephthalate derived from at least one of terephthalic acid and dimethyl terephthalate and 1,4-butanediol.
  • the aromatic polyester includes, 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 (for example, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, etc.
  • Aliphatic diols such as: 1,4-cyclohexanedimethanol, tricyclodecane dimethylol and other alicyclic diols; xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2- Bi [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; and the like, and polyesters derived from these, or a combination of two or more of these dicarboxylic acid components and diol components Polymerized polyester may also be used.
  • polyester forming the hard segment examples include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, and polybutylene terephthalate is preferable.
  • Aliphatic polyethers include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, poly (propylene oxide) And ethylene oxide addition polymer of glycol, and a copolymer of ethylene oxide and tetrahydrofuran.
  • the aliphatic polyester include poly ( ⁇ -caprolactone), polyenantlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate.
  • poly (tetramethylene oxide) glycol poly (propylene oxide) glycol are polymers that form soft segments from the viewpoint of the elastic properties of the resulting polyester block copolymer.
  • Preferred are ethylene oxide adducts, poly ( ⁇ -caprolactone), polybutylene adipate, polyethylene adipate, and the like.
  • 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. Furthermore, the mass ratio (x: y) between the hard segment (x) and the soft segment (y) is preferably 99: 1 to 20:80, more preferably 98: 2 to 30:70, from the viewpoint of moldability. .
  • the combination of the hard segment and the soft segment described above examples include, for example, combinations of the hard segment and the soft segment mentioned above.
  • the combination of the hard segment and the soft segment described above is preferably a combination in which the hard segment is polybutylene terephthalate, the soft segment is an aliphatic polyether, and the hard segment is polybutylene terephthalate. More preferred is a combination wherein is poly (ethylene oxide) glycol.
  • polyester-based thermoplastic elastomers examples include “Hytrel” series (for example, 3046, 5557, 6347, 4047, 4767, etc.) manufactured by Toray DuPont Co., Ltd., and “Perprene” series manufactured by Toyobo Co., Ltd. (For example, P30B, P40B, P40H, P55B, P70B, P150B, P280B, P450B, P150M, S1001, S2001, S5001, S6001, S9001, etc.) can be used.
  • Hytrel for example, 3046, 5557, 6347, 4047, 4767, etc.
  • Perprene manufactured by Toyobo Co., Ltd.
  • the polyester-based thermoplastic elastomer can be synthesized by copolymerizing a polymer that forms a hard segment and a polymer that forms a soft segment by a known method.
  • Polyamide thermoplastic elastomer consists of a copolymer having a crystalline polymer that forms a hard segment with a high melting point and an amorphous polymer that forms a soft segment with a low glass transition temperature. It means a thermoplastic resin material having an amide bond (—CONH—) in the main chain of a polymer forming a hard segment.
  • a polyamide is a crystalline hard crystalline segment with a high melting point
  • other polymers for example, polyester, polyether, etc.
  • the polyamide-based thermoplastic elastomer may be formed using a chain extender such as a dicarboxylic acid in addition to the hard segment and the soft segment.
  • a chain extender such as a dicarboxylic acid
  • Specific examples of the polyamide-based thermoplastic elastomer include an amide-based thermoplastic elastomer (TPA) defined in JIS K6418: 2007, and a polyamide-based elastomer described in JP-A-2004-346273. it can.
  • examples of the polyamide forming the hard segment include polyamides produced by monomers represented by the following general formula (1) or general formula (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 molecular chain of a hydrocarbon 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, such as an alkylene group having 3 to 18 carbon atoms, and a hydrocarbon molecular chain having 4 to 15 carbon atoms, such as carbon.
  • An alkylene group having 4 to 15 carbon atoms is more preferable, and a molecular chain of a hydrocarbon having 10 to 15 carbon atoms, for example, an alkylene group having 10 to 15 carbon atoms is particularly preferable.
  • R 2 is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms, such as an alkylene group having 3 to 18 carbon atoms, and a hydrocarbon molecular chain having 4 to 15 carbon atoms,
  • an alkylene group having 4 to 15 carbon atoms is more preferable, and a molecular chain of a hydrocarbon 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 or lactam.
  • the polyamide forming the hard segment include polycondensates of these ⁇ -aminocarboxylic acids or lactams, and co-condensation polymers of diamines and dicarboxylic acids.
  • Examples of ⁇ -aminocarboxylic acids 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 acids.
  • the lactam include aliphatic lactams having 5 to 20 carbon atoms such as lauryl lactam, ⁇ -caprolactam, udecan lactam, ⁇ -enantolactam, and 2-pyrrolidone.
  • Examples of the diamine 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 ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, Examples include decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, 3-methylpentamethylene diamine, metaxylene diamine, and the like. it can.
  • the dicarboxylic acid can be represented by HOOC- (R 3 ) m —COOH (R 3 : a hydrocarbon molecular chain having 3 to 20 carbon atoms, m: 0 or 1).
  • R 3 a hydrocarbon molecular chain having 3 to 20 carbon atoms, m: 0 or 1.
  • oxalic acid, succinic acid And aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as glutaric 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 decane lactam can be preferably used.
  • polyester, polyether, etc. are mentioned, for example, Polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, ABA type
  • mold triblock polyether etc. are mentioned specifically ,. These can be used alone or in combination of two or more.
  • polyether diamine etc. which are obtained by making ammonia etc. react with the terminal of polyether can also be used.
  • the “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, still 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, still more preferably an integer of 7 to 35, and particularly preferably an integer of 8 to 30.
  • combinations of hard segment and soft segment include lauryl lactam ring-opening polycondensate / polyethylene glycol combination, lauryl lactam ring-opening polycondensate / polypropylene glycol combination, and lauryl lactam ring-opening polycondensation.
  • the number average molecular weight of the polymer (polyamide) forming the hard segment is preferably 300 to 15000 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) to 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. .
  • the polyamide-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.
  • polyamide-based thermoplastic elastomers examples include UBE Kosan's “UBESTA XPA” series (for example, XPA9068X1, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2XPA9044), Daicel Eponic Co., Ltd. “Vestamide” series (for example, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.) can be used.
  • Polyamide thermoplastic elastomer is suitable as a resin material because it satisfies the performance required as a bead part from the viewpoint of elastic modulus (flexibility) and strength.
  • polyamide-based thermoplastic elastomers often have good adhesiveness with thermoplastic resins and adhesiveness with thermoplastic elastomers.
  • polystyrene thermoplastic elastomer for example, at least polystyrene forms a hard segment, and other polymers (for example, polybutadiene, polyisoprene, polyethylene, hydrogenated polybutadiene, hydrogenated polyisoprene, etc.) are not. Examples thereof include materials that form a soft segment having a crystallinity and a low glass transition temperature.
  • the 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 can be mentioned.
  • the polymer that forms the soft segment include polybutadiene, polyisoprene, poly (2,3-dimethyl-butadiene), and the like.
  • the 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 a combination of polystyrene / polybutadiene or a combination of polystyrene / polyisoprene.
  • the soft segment is preferably hydrogenated.
  • the number average molecular weight of the polymer (polystyrene) forming the hard segment is preferably 5,000 to 500,000, and more preferably 10,000 to 200,000. Further, the number average molecular weight of the polymer forming the soft segment is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 800,000, still more preferably from 30,000 to 500,000. Furthermore, the volume ratio (x: y) to the hard segment (x) and the soft segment (y) is preferably 5:95 to 80:20, more preferably 10:90 to 70:30 from the viewpoint of moldability. .
  • the polystyrene-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.
  • examples of the polystyrene-based thermoplastic elastomer include styrene-butadiene 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 elastomer As a commercially available product of polystyrene-based thermoplastic elastomer, for example, “Tough Tech” series (for example, H1031, H1041, H1043, H1051, H1052, H1053, H1062, H1082, H1141, H1221, H1272, etc.) manufactured by Asahi Kasei Corporation, “SEBS” series (8007, 8076, etc.) and “SEPS” series (2002, 2063, etc.) manufactured by Kuraray Co., Ltd. can be used.
  • “Tough Tech” series for example, H1031, H1041, H1043, H1051, H1052, H1053, H1062, H1082, H1141, H1221, H1272, etc.
  • SEBS 8007, 8076, etc.
  • SEPS 2002, 2063, etc.
  • polyurethane-based thermoplastic elastomers for example, at least polyurethane forms a hard segment in which pseudo-crosslinking is formed by physical aggregation, and other polymers are amorphous and have a low glass transition temperature.
  • the material which forms the soft segment is mentioned.
  • Specific examples of the polyurethane-based thermoplastic elastomer include a polyurethane-based thermoplastic elastomer (TPU) defined in JIS K6418: 2007.
  • TPU polyurethane-based thermoplastic elastomer
  • 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.
  • 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.
  • Diol, ABA type triblock polyether, etc. are mentioned. These can 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, 1,6-hexamethylene diisocyanate, and the like.
  • Examples of the diisocyanate compound containing an alicyclic hydrocarbon represented by R include 1,4-cyclohexane diisocyanate and 4,4-cyclohexane diisocyanate.
  • examples of the aromatic diisocyanate compound containing an aromatic hydrocarbon represented by R include 4,4′-diphenylmethane diisocyanate and tolylene diisocyanate. These can be used alone or in combination of two or more.
  • 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.
  • 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- A decanediol etc. are 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 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′-dihydroxydiphenylsulfone, 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, 2,6-dihydroxynaphthalene and the like. These can 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 20000, more preferably 500 to 5000, and particularly preferably 500 to 3000, from the viewpoints of flexibility and thermal stability of the polyurethane-based thermoplastic elastomer.
  • the mass ratio (x: y) to 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.
  • thermoplastic polyurethane described in JP-A-5-331256 can be used.
  • thermoplastic elastomer specifically, a combination of a hard segment composed of an aromatic diol and an aromatic diisocyanate and a soft segment composed of a polycarbonate is preferable. More specifically, tolylene diisocyanate ( TDI) / polyester polyol copolymer, TDI / polyether polyol copolymer, TDI / caprolactone polyol copolymer, TDI / polycarbonate 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 / polyhexamethy At least one selected from carbonate copolymers is preferable.
  • TDI tolylene diisocyanate
  • TDI / polyester polyol copolymer TDI / polyether polyol copolymer, MDI / polyester polyol copolymer, MDI / polyether polyol copolymer And at least one selected from MDI + hydroquinone / polyhexamethylene carbonate copolymer is more preferable.
  • thermoplastic elastomers examples include, for example, “Elastollan” series (for example, ET680, ET880, ET690, ET890, etc.) manufactured by BASF, and “Clamiron U” series (for example, Kuraray Co., Ltd.) 2000 series, 3000 series, 8000 series, 9000 series, etc.) “Milactolan” series (for example, XN-2001, XN-2004, P390RSUP, P480RSUI, P26MRNAT, E490, E590, P890, etc.) manufactured by Japan Miraclan Etc. can be used.
  • “Elastollan” series for example, ET680, ET880, ET690, ET890, etc.
  • Clamiron U for example, Kuraray Co., Ltd. 2000 series, 3000 series, 8000 series, 9000 series, etc.
  • Milactolan for example, XN-2001, XN-2004, P390RSUP, P480RS
  • olefin-based thermoplastic elastomers for example, at least polyolefin forms a hard segment with a crystalline and high melting point, and other polymers (for example, polyolefins, other polyolefins, polyvinyl compounds, etc.) are amorphous. And a material forming a soft segment having a low glass transition temperature.
  • the polyolefin forming the hard segment include polyethylene, polypropylene, isotactic polypropylene, polybutene, and the like.
  • olefinic thermoplastic elastomers include olefin- ⁇ -olefin random copolymers, olefin block copolymers, and the like.
  • propylene block copolymers ethylene-propylene copolymers, 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 , Ethylene-
  • olefin-based thermoplastic elastomers include propylene block copolymers, ethylene-propylene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1-pentene 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, pro Lene
  • olefin resins such as ethylene and propylene may be used in combination.
  • 50 mass% or more and 100 mass% or less of the olefin resin content rate in an olefin type thermoplastic elastomer are preferable.
  • the number average molecular weight of the olefinic thermoplastic elastomer is preferably 5000 to 10000000.
  • the number average molecular weight of the olefinic thermoplastic elastomer is from 5,000 to 10,000,000, the mechanical properties of the thermoplastic resin material are sufficient and the processability is also excellent.
  • the number average molecular weight of the olefinic 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 workability 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) to 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 olefinic thermoplastic elastomer can be synthesized by copolymerization by a known method.
  • thermoplastic elastomer one obtained by acid-modifying a thermoplastic elastomer may be used.
  • a product obtained by acid-modifying an olefinic thermoplastic elastomer means that an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group, or a phosphoric acid group is bonded to the olefinic thermoplastic elastomer.
  • Examples of bonding an unsaturated compound having an acidic group such as a carboxylic acid group, sulfuric acid group or phosphoric acid group to an olefinic thermoplastic elastomer include, for example, an unsaturated compound having an acidic group to an olefinic thermoplastic elastomer, Examples include bonding (for example, graft polymerization) an unsaturated bond site of an unsaturated carboxylic acid (generally maleic anhydride).
  • an unsaturated compound having an acidic group an unsaturated compound having a carboxylic acid group which is a weak acid group is preferable from the viewpoint of suppressing deterioration of the olefin-based thermoplastic elastomer.
  • Examples of 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 “Tuffmer” series (for example, A0550S, A1050S, A4050S, A1070S, A4070S, A35070S, A1085S, A4085S, A7090, A70090, MH7007, MH7010, manufactured by Mitsui Chemicals, Inc.
  • Prime TPO made by prime polymers (for example, , E-2900H, F-3900H, E-2900, F-3900, J-5900, E-2910, F-3910, J-5910, E-2710, F 3710, J-5910, E-2740, F-3740, R110MP, R110E, can be used T310E, also M142E, etc.) and the like.
  • the continuous phase may contain components other than the thermoplastic elastomer.
  • other components include thermoplastic resins, rubbers, various fillers (for example, silica, calcium carbonate, clay, etc.), anti-aging agents, oils, plasticizers, color formers, weathering agents, and the like.
  • the tensile elastic modulus of the bead filler (JIS K7113: 1995) is preferably 400 MPa or more and 1500 MPa or less, preferably 500 MPa or more, from the viewpoint of achieving both excellent rim assembly properties and high impact resistance. More preferably, it is 1200 MPa or less, and further preferably 600 MPa or more and 1000 MPa or less.
  • the measurement of the tensile elastic modulus is performed according to JIS K7113: 1995. Specifically, using a Shimadzu Autograph AGS-J (5KN) manufactured by Shimadzu Corporation, the tensile modulus is set to 100 mm / min and the tensile elastic modulus is measured.
  • a measurement sample made of the same material as the bead filler may be separately prepared and the elastic modulus may be measured.
  • the adjustment of the tensile elastic modulus of the bead filler can be adjusted, for example, by selecting a material constituting the bead filler (for example, an amorphous resin, a thermoplastic elastomer, or the like).
  • a material constituting the bead filler for example, an amorphous resin, a thermoplastic elastomer, or the like.
  • Charpy impact strength (properties) Charpy impact strength bead filler (23 ° C. environment), from the viewpoint of obtaining high impact resistance, is preferably 30 kJ / m 2 or more, 50 kJ / m 2 or more preferably It is more preferable not to destroy (NB).
  • the Charpy impact strength of the bead filler is determined according to the method specified in JIS K7111-1: 2012, using a Charpy impact tester (manufactured by Yasuda Seiki Co., Ltd., product name: 141 type), and the temperature of the test piece (notched) Measure at 23 ° C.
  • the amount of energy consumed (energy) from the difference between the angle before and after the collision is measured by measuring the angle returned after colliding with the sample under the condition that the nominal pendulum energy (capacity) is 2 J and the hammer lifting angle is 150 °. Absorption amount) is calculated.
  • the adjustment of the Charpy impact strength of the bead filler can be adjusted, for example, by selecting a material constituting the bead filler (for example, an amorphous resin, a thermoplastic elastomer, or the like).
  • a material constituting the bead filler for example, an amorphous resin, a thermoplastic elastomer, or the like.
  • the bead wire is not particularly limited, and for example, a metal cord, an organic resin cord, or the like used for a conventional rubber tire can be appropriately used.
  • a metal cord such as metal fiber or organic fiber, or multifilament (twisted wire) obtained by twisting these fibers.
  • a metal cord more preferably an iron cord (steel cord) is preferable.
  • the bead wire in the present embodiment is preferably a monofilament (single wire) from the viewpoint of further improving the durability of the tire.
  • the cross-sectional shape, size (diameter), etc. of the bead wire are not particularly limited, and those suitable for the desired tire can be appropriately selected and used.
  • the bead wire is a stranded wire of a plurality of cords, the number of the plurality of cords is, for example, 2 to 10, preferably 5 to 9.
  • the thickness of the bead wire is preferably 0.3 mm to 3 mm, and more preferably 0.5 mm to 2 mm.
  • the thickness of the bead wire is the number average value of the thicknesses measured at five arbitrarily selected cross sections (vertical cross sections with respect to the length direction of the bead wire).
  • the strength of the bead wire itself is usually 1000N to 3000N, preferably 1200N to 2800N, and more preferably 1300N to 2700N.
  • the strength of the bead wire is calculated from the breaking point by drawing a stress-strain curve using a ZWICK chuck with a tensile tester.
  • the breaking elongation (tensile breaking elongation) of the bead wire itself is usually 0.1% to 15%, preferably 1% to 15%, more preferably 1% to 10%.
  • the tensile elongation at break of the bead wire can be obtained from the strain by drawing a stress-strain curve using a ZWICK chuck with a tensile tester.
  • the bead core preferably has a coating resin layer that covers the bead wire from the viewpoint of improving adhesiveness with the bead filler and reducing the rigidity step between the bead filler and the bead wire.
  • the covering resin layer is disposed in direct contact with the bead wire or in contact with another layer.
  • the coating resin layer contains a resin.
  • the resin contained in the coating resin layer include thermoplastic resins, thermoplastic elastomers, and thermosetting resins.
  • the covering resin layer preferably contains a thermoplastic resin or a thermoplastic elastomer as the resin, and more preferably contains a thermoplastic elastomer.
  • the thermoplastic elastomers it is preferable to include at least one of a polyamide-based thermoplastic elastomer and a polyester-based thermoplastic elastomer.
  • the coating resin layer only needs to contain at least a resin, and may contain other components such as additives within a range that does not impair the effects of the present disclosure.
  • the content of the resin in the coating resin layer is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 75% by mass or more based on the total amount of the coating resin layer.
  • thermoplastic resin examples include polyamide-based thermoplastic resins, polyester-based thermoplastic resins, olefin-based thermoplastic resins, polyurethane-based thermoplastic resins, vinyl chloride-based thermoplastic resins, and polystyrene-based thermoplastic resins. In the coating resin layer, these may be used alone or in combination of two or more.
  • the thermoplastic resin is preferably at least one selected from polyamide-based thermoplastic resins, polyester-based thermoplastic resins, and olefin-based thermoplastic resins, and is selected from polyamide-based thermoplastic resins and polyester-based thermoplastic resins. More preferred is at least one selected from
  • thermoplastic elastomer examples include polyamide-based thermoplastic elastomer (TPA), polyester-based thermoplastic elastomer (TPC), polystyrene-based thermoplastic elastomer (TPS), polyurethane-based thermoplastic elastomer (TPU) specified in JIS K6418, Examples thereof include an olefinic thermoplastic elastomer (TPO), a crosslinked thermoplastic rubber (TPV), and other thermoplastic elastomers (TPZ). In the coating resin layer, these may be used alone or in combination of two or more.
  • TPA polyamide-based thermoplastic elastomer
  • TPC polyester-based thermoplastic elastomer
  • TPS polystyrene-based thermoplastic elastomer
  • TPU polyurethane-based thermoplastic elastomer
  • TPO olefinic thermoplastic elastomer
  • TPV crosslinked thermoplastic rubber
  • TPZ thermoplastic elastomers
  • the bead member according to the present embodiment when the bead filler is in direct contact with the bead core, the thermoplastic resin contained in the continuous phase of the resin and the bead filler that constitute the surface of the bead core (for example, the coating resin layer). It is preferable that the elastomer has a common skeleton in the structural units constituting the main chain of the resin.
  • “having a common skeleton in the structural units constituting the main chain of the resin” means, for example, that the continuous phase of the bead filler contains “polyester thermoplastic elastomer (TPC)” and the bead core
  • TPC polyester thermoplastic elastomer
  • the surface member contains “at least one of a polyester-based thermoplastic elastomer (TPC) and a polyester-based thermoplastic resin”
  • a skeleton that is, an ester-bonded skeleton
  • thermoplastic resin or a thermoplastic elastomer containing a structural unit having the same chemical structure for example, a thermoplastic resin or a thermoplastic using a monomer having the same structure as a monomer used as a raw material of the resin
  • an elastomer for example, a thermoplastic resin or a thermoplastic elastomer containing only a structural unit having the same chemical structure (for example, a thermoplastic resin using only a monomer having the same structure as a monomer as a raw material of the resin or More preferably, a thermoplastic elastomer) is used.
  • the resin contained in the member constituting the surface of the bead core (for example, the coating resin layer) and the thermoplastic elastomer contained in the continuous phase of the bead filler have a common skeleton in the constituent units constituting the resin main chain.
  • the affinity between the surface member of the bead core and the bead filler is enhanced, and excellent adhesiveness is exhibited.
  • the coating resin layer may contain other components besides the resin.
  • other components include rubber, various fillers (for example, silica, calcium carbonate, clay, etc.), anti-aging agents, oils, plasticizers, color formers, weathering agents, and the like.
  • the thickness of the coating resin layer is not particularly limited. From the viewpoint of excellent durability and weldability, it is preferably 20 ⁇ m or more and 1000 ⁇ m or less, and more preferably 30 ⁇ m or more and 700 ⁇ m or less.
  • the thickness of the coating resin layer is from the surface on the bead wire side in the coating resin layer (for example, the interface with the bead wire or the adhesive layer) to the outer surface in the coating resin layer (the surface opposite to the bead wire side). This refers to the length of the shortest part of the length.
  • the thickness of the coating resin layer is obtained by acquiring magnified images with a microscope such as a video microscope having a cross section perpendicular to the length direction of the bead wire from arbitrary five locations, and measuring the coating resins measured from the five magnified images obtained. The thickness of the minimum thickness portion of the layer is measured and the number average value is obtained.
  • the bead member concerning this embodiment may have an adhesive bond layer between a bead wire and a covering resin layer.
  • the material in particular of an adhesive bond layer is not restrict
  • the adhesive layer is preferably a resin-containing layer (adhesive resin layer), and the resin is preferably a thermoplastic resin or a thermoplastic elastomer.
  • thermoplastic elastomer examples include polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polystyrene-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and olefin-based thermoplastic elastomers.
  • the adhesive layer preferably contains an acid-modified thermoplastic elastomer as an adhesive.
  • the acid-modified thermoplastic elastomer is a thermoplastic elastomer in which an acid group (for example, a carboxy group) is introduced into a part of the molecule of the thermoplastic elastomer.
  • thermoplastic elastomers may be used alone or in combination of two or more.
  • the resin content is preferably 50% by mass or more of the entire adhesive layer, more preferably 60% by mass or more, and further preferably 75% by mass or more. .
  • the average thickness of the adhesive layer is not particularly limited, but is preferably 5 ⁇ m to 500 ⁇ m, more preferably 20 ⁇ m to 150 ⁇ m, and more preferably 20 ⁇ m to 100 ⁇ m from the viewpoint of riding comfort during running and tire durability. More preferably it is.
  • the average thickness of the adhesive layer is the thickness of the adhesive layer measured from the magnified image obtained by acquiring magnified images with a microscope such as a video microscope having a cross section perpendicular to the length direction of the bead wire.
  • the thickness of the adhesive layer in each enlarged image is the smallest thickness part (the part where the distance between the interface between the bead wire and the adhesive layer and the interface between the adhesive layer and the coating resin layer is minimized) ).
  • the average thickness of the adhesive layer is T 1, when the average thickness of the resin coating layer was T 2, as the value of T 1 / T 2, for example, an 0.1 to 0.5, 0 .1 or more and 0.4 or less are preferable, and 0.1 or more and 0.35 or less are more preferable.
  • T 1 / T 2 is within the above range, the riding comfort during running is superior compared to the case where the value is smaller than the above range, and the durability of the tire is superior compared to the case where the value is larger than the above range.
  • FIG. 1 shows one side of a cut surface cut along the tire width direction of the tire 10 of the first embodiment.
  • the arrow TW indicates the width direction of the tire 10 (tire width direction)
  • the arrow TR indicates the radial direction of the tire 10 (tire radial direction).
  • the tire width direction here refers to a direction parallel to the rotation axis of the tire 10 and is also referred to as a tire axial direction.
  • the tire radial direction refers to a direction orthogonal to the rotation axis of the tire 10.
  • Reference sign CL indicates the equator of the tire 10 (tire equator).
  • the rotation axis side of the tire 10 along the tire radial direction is “inner side in the tire radial direction”, and the opposite side of the rotation axis of the tire 10 along the tire radial direction is “outer side in the tire radial direction”. It describes.
  • the tire equator CL side along the tire width direction is referred to as “inner side in the tire width direction”, and the side opposite to the tire equator CL along the tire width direction is referred to as “outer side in the tire width direction”.
  • FIG. 1 shows the tire 10 when mounted on a standard rim 30 (indicated by a two-dot chain line in FIG. 1) and filled with standard air pressure.
  • the standard rim refers to a standard rim at an applicable size, which is described in JATMA (Japan Automobile Tire Association) Year Book 2017 edition.
  • the standard air pressure is the air pressure corresponding to the maximum load capacity of JATMA Year Book FY2017.
  • the load is the maximum load (maximum load capacity) of a single wheel at the applicable size described in the following standard
  • the internal pressure is the maximum load of a single wheel described in the following standard.
  • the rim is a standard rim (or “Applied Rim” or “Recommended Rim”) in an applicable size described in the following standard.
  • the standards are determined by industry standards that are valid in the region where the tire is produced or used. For example, in the United States, “The Tire and Rim Association Inc. Year Book” in Europe, in Europe “The European Tire and Rim Technical Standards Manual” in Japan, and in Japan, “Japan Tire” in Japan. Has been.
  • the tire 10 of the first embodiment shown in FIG. 1 is a tire having a flatness ratio of 55 or more, and the tire cross-section height (tire section height) SH is set to 115 mm or more.
  • the section height (tire sectional height) SH referred to here is a length that is 1 ⁇ 2 of the difference between the tire outer diameter and the rim diameter when the tire 10 is assembled to the standard rim 30 and the inner pressure is the standard air pressure. Point to.
  • the flatness of the tire 10 is set to 55 or more and the tire cross-section height SH is set to 115 mm or more, but the present disclosure is not limited to this configuration.
  • the tire 10 includes a pair of left and right bead portions 12 (only one bead portion 12 is shown in FIG. 1), and a pair of tire sides that extend outward from the pair of bead portions 12 in the tire radial direction. Part 14 and a tread part 16 extending from one tire side part 14 to the other tire side part 14.
  • the tire side portion 14 bears a load acting on the tire 10 during traveling (including during run-flat traveling).
  • a bead core 18 is embedded in each of the pair of bead portions 12.
  • a carcass 22 straddles the pair of bead cores 18.
  • the end side of the carcass 22 is locked to the bead core 18.
  • the end portion side is folded and locked around the bead core 18 from the tire inner side to the outer side, and the end portion 22C of the folded portion 22B is in contact with the carcass main body portion 22A.
  • the end portion 22C of the carcass 22 is disposed in a range (region) corresponding to the tire side portion 14, but the present disclosure is not limited to this configuration.
  • the end 22C of the carcass 22 may be disposed in a range corresponding to the tread portion 16, particularly in a range corresponding to the belt layer 24A.
  • the carcass 22 extends in a toroidal shape from one bead core 18 to the other bead core 18 to constitute a skeleton of the tire 10.
  • a plurality (two layers in the first embodiment) of belt layers 24A are provided on the outer side in the tire radial direction of the carcass main body portion 22A.
  • a cap layer 24B is provided on the outer side in the tire radial direction of the belt layer 24A. The cap layer 24B covers the entire belt layer 24A.
  • a pair of layer layers 24C are provided outside the cap layer 24B in the tire radial direction so as to cover both ends of the cap layer 24B.
  • the present disclosure is not limited to the above-described configuration, and only one end of the cap layer 24B may be covered with the layer layer 24C, and one end of the cap layer 24B is continuous with one layer layer 24C in the tire width direction. It is good also as a structure covered with. Further, the cap layer 24B and the layer layer 24C may be omitted depending on the specification of the tire 10.
  • each member used in conventionally known tires can be used for the carcass 22, the belt layer 24A, the cap layer 24B, and the layer layer 24C.
  • the tread portion 16 is provided on the outer side in the tire radial direction of the belt layer 24A, the cap layer 24B, and the layer layer 24C.
  • the tread portion 16 is a part that contacts the road surface during traveling, and a plurality of circumferential grooves 16A extending in the tire circumferential direction are formed on the tread surface of the tread portion 16. Further, the tread portion 16 is formed with a not-shown width direction groove extending in the tire width direction. Note that the shape and number of the circumferential grooves 16A and the width direction grooves are appropriately set according to the performance such as drainage and steering stability required for the tire 10.
  • a bead filler 20 extending from the bead core 18 to the outer side in the tire radial direction along the outer surface 220 of the carcass 22 is embedded.
  • the bead filler 20 is disposed in a region surrounded by the carcass main body 22A and the folded portion 22B.
  • the outer surface 220 of the carcass 22 is a surface on the tire outer side in the carcass main body portion 22A, and is a surface on the inner side of the tire in the folded portion 22B.
  • the end 20 ⁇ / b> A of the bead filler 20 on the outer side in the tire radial direction enters the tire side portion 14.
  • the bead filler 20 has a thickness that decreases toward the outer side in the tire radial direction.
  • the height BH of the bead filler 20 shown in FIG. 1 is preferably set within a range of 30 to 50% of the tire cross-section height SH.
  • the height BH of the bead filler 20 here is the tip of the bead portion 12 from the end portion 20A on the outer side in the tire radial direction of the bead filler 20 when the tire 10 is assembled to the standard rim 30 and the internal pressure is set to the standard air pressure. (Height along the tire radial direction).
  • the height BH of the bead filler 20 is 30% or more of the tire cross-section height SH, for example, durability during run-flat traveling can be sufficiently ensured.
  • the height BH of the bead filler 20 is 50% or less of the tire cross-section height SH, the ride comfort is excellent.
  • the end 20A of the bead filler 20 is arranged on the inner side in the tire radial direction than the maximum width position of the tire 10.
  • the maximum width position of the tire 10 here refers to a position where the width is the widest along the tire width direction of the tire 10.
  • the bead core 18 has the some bead wire 1 arrange
  • “arranged side by side” means that a plurality of bead wires 1 are not crossed in a bead member cut to a necessary length when applied to a tire.
  • FIG. 3A is a diagram schematically showing a cross section when a part of the bead core 18 is cut perpendicular to the length direction of the bead wire 1.
  • the coating resin layer 3 is provided so as to be in direct contact with the three bead wires 1.
  • the single bead wire 1 may be stepped horizontally and vertically while being thermally welded.
  • the bead core 18 may have the adhesive layer 2 disposed between the bead wire 1 and the coating resin layer 3.
  • the adhesive layer 2 is preferably the above-described adhesive resin layer.
  • a part of the bead core 18 shown in FIG. 3B is provided with the adhesive layer 2 on the surface of the three bead wires 1, and the covering resin layer 3 is further provided on the surface.
  • the adhesive layer 2 disposed between the bead wire 1 and the coating resin layer 3 may be connected to include a plurality of bead wires 1.
  • a part of the bead core 18 shown in FIG. 3C is an aspect in which the adhesive layer 2 connected so as to include the three bead wires 1 is provided. Is provided.
  • FIGS. 3A to 3C show an embodiment in which three bead wires 1 are arranged in parallel, the number thereof may be two or less, or four or more.
  • the bead core 18 shown in FIG. 2 has three bead wires 1 and a coating resin layer 3 shown in any of FIGS. 3A to 3C (in addition, the adhesive layer 2 in FIGS. It is in the form of layer lamination.
  • the bead core 18 may be used as a single layer or may be used as a laminate of two or more layers. In that case, it is preferable to weld between coating resins.
  • the forms that the bead core 18 can take have been described with reference to FIGS. 3A to 3C, the present disclosure is not limited to this configuration.
  • the method for producing the bead core 18 is not particularly limited.
  • the bead core 18 is produced by an extrusion molding method using the bead wire 1, the material for forming the adhesive layer 2, and the material for forming the coating resin layer 3. be able to.
  • the cross-sectional shape of the adhesive layer 2 can be adjusted by a method such as changing the shape of the die used for extrusion.
  • Side reinforcement rubber 26 as an example of a side reinforcement layer that reinforces the tire side portion 14 is disposed on the tire side portion 14 on the inner side in the tire width direction of the carcass 22.
  • the side reinforcing rubber 26 is a reinforcing rubber for running a predetermined distance while supporting the weight of the vehicle and the occupant when the internal pressure of the tire 10 decreases due to puncture or the like.
  • the side reinforcing rubber 26 extends in the tire radial direction from the bead core 18 side to the tread portion 16 side along the inner surface 22I of the carcass 22. Further, the side reinforcing rubber 26 has a shape whose thickness decreases as it goes to the bead core 18 side and the tread portion 16 side, for example, a substantially crescent shape.
  • the thickness of the side reinforcing rubber 26 refers to the length along the normal line of the carcass 22 in a state where the tire 10 is assembled to the standard rim 30 and the internal pressure is set to the standard air pressure.
  • the side reinforcing rubber 26 has an end portion 26A on the tread portion 16 side that overlaps the tread portion 16 with the carcass 22 (carcass body portion 22A) interposed therebetween. Specifically, the end portion 26A of the side reinforcing rubber 26 overlaps the belt layer 24A. On the other hand, in the side reinforcing rubber 26, the end portion 26B on the bead core 18 side overlaps the bead filler 20 with the carcass 22 (carcass main body portion 22A) interposed therebetween.
  • the side reinforcing rubber 26 is preferably set to have a breaking elongation in the range of 130 to 190%.
  • the “elongation at break” here refers to the elongation at break (%) measured based on JIS K6251: 2010 (using dumbbell-shaped No. 3 test piece).
  • the side reinforcing rubber 26 is configured by one type of rubber material.
  • the present disclosure is not limited to this configuration, and the side reinforcing rubber 26 may be configured by a plurality of types of rubber materials. .
  • the side reinforcing rubber 26 mainly composed of rubber is used as an example of the side reinforcing layer.
  • the present disclosure is not limited to this configuration, and the side reinforcing layer is formed of other materials. May be.
  • the side reinforcing rubber 26 may include other materials such as fillers, short fibers, and resins.
  • the thickness GB of the side reinforcing rubber 26 at the midpoint Q is preferably set within a range of 40 to 80% of the maximum thickness GA of the side reinforcing rubber 26.
  • the thickness of the side reinforcing rubber 26 at the maximum width position P of the carcass 22 is the maximum thickness GA, but the present disclosure is not limited to this configuration.
  • the maximum width position of the carcass 22 here refers to a position where the width of the carcass 22 is the widest along the tire width direction.
  • the height LH from the end portion 26B of the side reinforcing rubber 26 to the tip end of the bead portion 12 in a state where the tire 10 is assembled to the standard rim 30 and the internal pressure is set to the standard air pressure is 50 to 80% of the height BH of the bead filler 20 It is preferable to set the height within the range.
  • the height LH is 80% or less of the height BH, durability during run-flat traveling is easily ensured.
  • the height LH is 50% or more of the height BH, the ride comfort is excellent.
  • the rim guard (rim protection) is not provided, but the present disclosure is not limited to this configuration, and the rim guard is provided. Also good.
  • An inner liner (not shown) is provided on the inner surface of the tire 10 from one bead portion 12 to the other bead portion 12.
  • the main component of the inner liner is butyl rubber as an example, but the present disclosure is not limited to this configuration, and the main component of the inner liner may be another rubber material or resin. .
  • the side reinforcing rubber 26 is composed of one type of rubber (or resin), but the present disclosure is not limited to this configuration, and the side reinforcing rubber 26 May be composed of a plurality of types of rubber (or resin).
  • the side reinforcing rubber 26 may be configured by stacking a plurality of different types of rubber (or resin) in the tire radial direction, and the side reinforcing rubber 26 may be configured by stacking a plurality of different types of rubber (or resin) in the tire width direction. It is good.
  • the tire 10 shown in FIG. 1 is mainly composed of an elastic material. That is, a region around the carcass 22 in the bead portion 12, a region outside the tire width direction of the carcass 22 in the tire side portion 14, a side reinforcing layer (side reinforcing rubber 26), a belt layer 24 ⁇ / b> A in the tread portion 16, a cap layer 24 ⁇ / b> B, An area other than the layer layer 24C, etc. is made of an elastic material.
  • the elastic material examples include a rubber material (so-called rubber tire) and a resin material (so-called resin tire).
  • the tire 10 shown in FIG. 1 is preferably a rubber tire in which each of the above parts is made of a rubber material.
  • the rubber material only needs to contain at least rubber (rubber component), and may contain other components such as additives as long as the effects of the present disclosure are not impaired.
  • the content of rubber (rubber component) in the rubber material is preferably 50% by mass or more, and more preferably 90% by mass or more based on the total amount of the rubber material.
  • the rubber component used in the tire according to the first embodiment is not particularly limited, and natural rubber and various synthetic rubbers used in conventionally known rubber blends can be used alone or in combination of two or more. .
  • a rubber as shown below or a blend of two or more of these can be used.
  • the natural rubber may be a sheet rubber or a block rubber, and all of RSS # 1 to # 5 can be used.
  • the synthetic rubber various diene synthetic rubbers, diene copolymer rubbers, special rubbers, modified rubbers, and the like can be used.
  • a butadiene polymer such as polybutadiene (BR), a copolymer of butadiene and an aromatic vinyl compound (eg, SBR, NBR, etc.), a copolymer of butadiene and another diene compound, and the like;
  • Isoprene polymers such as polyisoprene (IR), copolymers of isoprene and aromatic vinyl compounds, copolymers of isoprene and other diene compounds; chloroprene rubber (CR), butyl rubber (IIR), halogenated Examples thereof include butyl rubber (X-IIR); ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), and any blend thereof.
  • the rubber material used for the tire according to the first embodiment may add other components such as additives to the rubber depending on the purpose.
  • additives include reinforcing materials such as carbon black, fillers, vulcanizing agents, vulcanization accelerators, fatty acids or salts thereof, metal oxides, process oils, anti-aging agents, and the like. can do.
  • a tire formed of a rubber material is obtained by molding an unvulcanized rubber material in which the rubber contained is unvulcanized into a tire shape and vulcanizing the rubber by heating.
  • an inner liner made of a rubber material, a bead core 18, a bead filler 20, and a cord are made of an elastic material (not shown) on the outer periphery of a known tire molding drum.
  • An unvulcanized tire case is formed.
  • the belt layer 24A As a method of forming the belt layer 24A on the tread portion 16 of the tire case, for example, a member such as a wire wound around a reel is unwound while rotating the tire case, and the wire is wound around the tread portion 16 a predetermined number of times.
  • the belt layer 24A may be formed.
  • the wire When the wire is coated with a resin, the coated resin may be welded to the tread portion 16 by heating and pressing.
  • an unvulcanized tread is attached to the outer peripheral surface of the belt layer 24A to obtain a raw tire.
  • the green tire thus manufactured is vulcanized with a vulcanization molding mold, and the tire 10 is completed.
  • FIG. 4 shows one side of a cut surface cut along the tire width direction of the tire 110 of the second embodiment.
  • the arrow TW indicates the width direction of the tire 110 (that is, the tire width direction)
  • the arrow TR indicates the radial direction of the tire 110 (that is, the tire radial direction).
  • the tire 110 includes a pair of left and right bead portions 112 (only one bead portion 112 is shown in FIG. 4), and a pair of tire sides extending outward from the pair of bead portions 112 in the tire radial direction. Part 114 and a tread part 116 extending from one tire side part 114 to the other tire side part 114.
  • the tire 110 shown in FIG. 4 includes a tire case 140 corresponding to a tire skeleton.
  • the tire case 140 is formed using an elastic material (preferably a resin material) and has an annular shape.
  • the tire case 140 includes a bead portion 112, a tire side portion 114, and a tread portion 116.
  • a protective layer 122 is provided on the tire side portion 114 and the bead portion 112 in the tire width direction outer side, the bead portion 112 in the tire radial direction inner side, and the bead portion 112 on the tire width direction inner side.
  • the bead portion 112, the tire side portion 114, and the tread portion 116 may be integrally formed in the same process, or may be a combination of members formed in different processes. However, it is preferably formed integrally from the viewpoint of production efficiency.
  • a bead filler 120 extending along the protective layer 122 from the bead core 118 to the outer side in the tire radial direction is embedded in the bead portion 112.
  • the bead filler 120 decreases in thickness toward the outer side in the tire radial direction.
  • the bead portion 112 is a part that contacts a rim (not shown), and an annular bead core 118 extending along the tire circumferential direction is embedded.
  • the form that the bead core 118 can take is the same as the form described in the first embodiment.
  • the protective layer 122 is provided for the purpose of increasing the airtightness between the tire case 140 and the rim, and is made of a material such as a rubber material that is softer and higher in weather resistance than the tire case 140. However, it may be omitted.
  • the tread portion 116 is a portion corresponding to the ground contact surface of the tire 110, and is provided with a belt layer 124A (for example, a reinforcing member or a belt member). Further, a tread 130 is provided on the belt layer 124A via a cushion rubber 124B.
  • the material of the belt layer 124A, the cushion rubber 124B, and the tread 130 is not particularly limited, and is selected from materials generally used for manufacturing tires (for example, wires such as metal wires and organic resin wires, resins, rubber materials, etc.). it can.
  • the tire case 140 (an example of a tire frame) is formed of an elastic material. That is, as a tire skeleton body, an aspect formed with a rubber material as an elastic material (a so-called tire skeleton body for a rubber tire), an aspect formed with a resin material as an elastic material (a so-called tire skeleton body for a resin tire), etc. Is mentioned.
  • the tire 110 shown in FIG. 4 is preferably a resin tire in which each of the above parts is made of a resin material.
  • the resin material should just contain resin (namely, resin component) at least, and may contain other components, such as an additive, in the range which does not impair the effect of this indication.
  • the content of the resin (that is, the resin component) in the resin material is preferably 50% by mass or more, and more preferably 90% by mass or more based on the total amount of the resin material.
  • the tire skeleton can be formed using, for example, a resin material.
  • Examples of the resin contained in the tire skeleton include thermoplastic resins, thermoplastic elastomers, and thermosetting resins.
  • thermosetting resin examples include a phenol thermosetting resin, a urea thermosetting resin, a melamine thermosetting resin, and an epoxy thermosetting resin.
  • thermoplastic resin examples include polyamide-based thermoplastic resins, polyester-based thermoplastic resins, olefin-based thermoplastic resins, polyurethane-based thermoplastic resins, vinyl chloride-based thermoplastic resins, and polystyrene-based thermoplastic resins. You may use these individually or in combination of 2 or more types.
  • thermoplastic resin is preferably at least one selected from polyamide-based thermoplastic resins, polyester-based thermoplastic resins, and olefin-based thermoplastic resins, and is selected from polyamide-based thermoplastic resins and olefin-based thermoplastic resins. More preferably, at least one selected from the group consisting of
  • thermoplastic elastomer examples include a polyamide-based thermoplastic elastomer (TPA), a polystyrene-based thermoplastic elastomer (TPS), a polyurethane-based thermoplastic elastomer (TPU), an olefin-based thermoplastic elastomer (TPO) specified in JIS K6418, Examples thereof include polyester-based thermoplastic elastomer (TPEE), crosslinked thermoplastic rubber (TPV), and other thermoplastic elastomers (TPZ).
  • TPA polyamide-based thermoplastic elastomer
  • TPS polystyrene-based thermoplastic elastomer
  • TPU polyurethane-based thermoplastic elastomer
  • TPO olefin-based thermoplastic elastomer
  • TPEE polyester-based thermoplastic elastomer
  • TPV crosslinked thermoplastic rubber
  • TPZ thermoplastic elastomers
  • thermoplastic elastomer From the viewpoint of ride comfort, it is more preferable to include a thermoplastic elastomer. Among these, it is more preferable that at least one of a polyamide-based thermoplastic elastomer and a polyester-based thermoplastic elastomer is included.
  • the elastic material may contain other components other than rubber or resin as desired.
  • other components include resins, rubbers, various fillers (for example, silica, calcium carbonate, clay), anti-aging agents, oils, plasticizers, colorants, weathering agents, reinforcing materials, and the like.
  • the melting point of the resin contained in the resin material is, for example, about 100 ° C. to 350 ° C. From the viewpoint, about 100 ° C. to 250 ° C. is preferable, and 120 ° C. to 250 ° C. is more preferable.
  • the tensile elastic modulus defined by JIS K7113: 1995 of the elastic material (or the tire skeleton including the elastic material) itself is preferably 50 MPa to 1000 MPa, more preferably 50 MPa to 800 MPa, and particularly preferably 50 MPa to 700 MPa.
  • the elastic modulus of the elastic material is 50 MPa to 1000 MPa, the rim can be assembled efficiently while maintaining the shape of the tire frame.
  • the tensile strength specified in JIS K7113 (1995) of the elastic material (or tire skeleton including the elastic material) itself is usually about 15 MPa to 70 MPa, preferably 17 MPa to 60 MPa, and more preferably 20 MPa to 55 MPa.
  • the tensile yield strength defined in JIS K7113 (1995) of the elastic material (or the tire skeleton including the elastic material) itself is preferably 5 MPa or more, more preferably 5 MPa to 20 MPa, and particularly preferably 5 MPa to 17 MPa.
  • the tensile yield strength of the elastic material is 5 MPa or more, the elastic material can withstand deformation against a load applied to the tire during traveling.
  • the tensile yield elongation defined by JIS K7113 (1995) of the elastic material (or tire skeleton including the elastic material) itself is preferably 10% or more, more preferably 10% to 70%, and particularly preferably 15% to 60%. preferable.
  • the tensile yield elongation of the elastic material is 10% or more, the elastic region is large and the rim assembly property can be improved.
  • the elastic material itself has a tensile elongation at break as defined in JIS K7113 (1995) of preferably 50% or more, more preferably 100% or more, particularly preferably 150% or more, 200% The above is most preferable.
  • a tensile elongation at break as defined in JIS K7113 (1995) of preferably 50% or more, more preferably 100% or more, particularly preferably 150% or more, 200% The above is most preferable.
  • the tensile breaking elongation of the elastic material is 50% or more, the rim assembly property is good, and it is possible to make it difficult to break against a collision.
  • the deflection temperature under load (specifically at a load of 0.45 MPa) as defined in ISO 75-2 or ASTM D648 of the elastic material (or tire skeleton including the elastic material) itself is preferably 50 ° C. or more, 150 ° C. is more preferable, and 50 ° C. to 130 ° C. is particularly preferable. If the deflection temperature under load of the elastic material is 50 ° C. or higher, deformation of the tire frame can be suppressed even when vulcanization is performed in the manufacture of the tire.
  • the manufacturing method of the tire case 140 is not particularly limited.
  • tire case halves in a state where the tire case 140 is divided by the equator plane are respectively produced by an injection molding method or the like, and the tire case halves are joined together at the equator plane. You may produce by.
  • a method of forming the belt layer 124A on the tread portion 116 of the tire case 140 for example, a member such as a wire wound around a reel is unwound while rotating the tire case 140, and the wire is wound around the tread portion 116 a predetermined number of times.
  • the belt layer 124A may be formed.
  • the coated resin may be welded to the tread portion 116 by heating and pressing.
  • a preformed bead filler 120 and an annular member for the bead core 118 are embedded in the bead portion 112 by a known method. May be formed.
  • FIG. 5 shows one side of a cut surface cut along the tire width direction of the tire 210 of the third embodiment.
  • the arrow TW indicates the width direction of the tire 210 (that is, the tire width direction)
  • the arrow TR indicates the radial direction of the tire 210 (that is, the tire radial direction).
  • the tire width direction here refers to a direction parallel to the rotation axis of the tire 210 and is also referred to as a tire axial direction.
  • the tire radial direction refers to a direction orthogonal to the rotation axis of the tire 210.
  • Reference sign CL indicates the equator of the tire 210 (that is, the tire equator).
  • the rotation axis side of the tire 210 along the tire radial direction is “inner side in the tire radial direction”, and the opposite side of the rotation axis of the tire 210 along the tire radial direction is “outer side in the tire radial direction”. It describes.
  • the tire equator CL side along the tire width direction is referred to as “inner side in the tire width direction”, and the side opposite to the tire equator CL along the tire width direction is referred to as “outer side in the tire width direction”.
  • the standard rim refers to a standard rim at an applicable size, which is described in JATMA (Japan Automobile Tire Association) Year Book 2017 edition.
  • the standard air pressure is the air pressure corresponding to the maximum load capacity of JATMA Year Book FY2017.
  • the load is the maximum load (maximum load capacity) of a single wheel at the applicable size described in the following standard
  • the internal pressure is the maximum load of a single wheel described in the following standard.
  • the rim is a standard rim (or “Applied Rim” or “Recommended Rim”) in an applicable size described in the following standard.
  • the standards are determined by industry standards that are valid in the region where the tire is produced or used. For example, in the United States, “The Tire and Rim Association Inc. Year Book” in Europe, in Europe “The European Tire and Rim Technical Standards Manual” in Japan, and in Japan, “Japan Tire” in Japan. Has been.
  • the tire 210 of the third embodiment shown in FIG. 5 is a tire having a flatness ratio of 55 or more, and a tire cross-section height (tire section height) SH is set to 115 mm or more.
  • the section height (tire cross-section height) SH referred to here is a length that is 1 ⁇ 2 of the difference between the tire outer diameter and the rim diameter when the tire 210 is assembled to the standard rim 230 and the internal pressure is the standard air pressure. Point to.
  • the flatness of the tire 210 is set to 55 or more and the tire cross-section height SH is set to 115 mm or more, but the present disclosure is not limited to this configuration.
  • the tire 210 includes a pair of left and right bead portions 212 (only one bead portion 212 is shown in FIG. 5), and a pair of tire sides extending outward from the pair of bead portions 212 in the tire radial direction. Part 214 and a tread part 216 extending from one tire side part 214 to the other tire side part 214.
  • the tire side portion 214 bears a load acting on the tire 210 during traveling (including during run-flat traveling).
  • a bead core 218 is embedded in each of the pair of bead portions 212.
  • a carcass 222 straddles the pair of bead cores 218.
  • the end side of the carcass 222 is locked to the bead core 218.
  • the end portion of the carcass 222 of the third embodiment is folded and locked around the bead core 218 from the inside to the outside of the tire, and the end portion 222C of the folded portion 222B is in contact with the carcass main body portion 222A.
  • the end portion 222C of the carcass 222 is disposed in a range (region) corresponding to the tire side portion 214, but the present disclosure is not limited to this configuration.
  • the end portion 222C of the carcass 222 may be disposed in a range corresponding to the tread portion 216, particularly in a range corresponding to the belt layer 224A.
  • the carcass 222 extends in a toroidal shape from one bead core 218 to the other bead core 218 to constitute a skeleton of the tire 210.
  • a plurality (two layers in the third embodiment) of belt layers 224A are provided on the outer side in the tire radial direction of the carcass main body 222A.
  • a cap layer 224B is provided outside the belt layer 224A in the tire radial direction. The cap layer 224B covers the entire belt layer 224A.
  • a pair of layer layers 224C are provided outside the cap layer 224B in the tire radial direction so as to cover both ends of the cap layer 224B.
  • the present disclosure is not limited to the above-described configuration, and only one end of the cap layer 224B may be covered with the layer layer 224C, and one layer layer 224C continuous at both ends of the cap layer 224B in the tire width direction. It is good also as a structure covered with. Further, the cap layer 224B and the layer layer 224C may be omitted depending on the specification of the tire 210.
  • each member used in conventionally known tires can be used for the carcass 222, the belt layer 224A, the cap layer 224B, and the layer layer 224C.
  • a tread portion 216 is provided on the outer side in the tire radial direction of the belt layer 224A, the cap layer 224B, and the layer layer 224C.
  • the tread portion 216 is a portion that contacts the road surface during traveling, and a plurality of circumferential grooves 216A extending in the tire circumferential direction are formed on the tread surface of the tread portion 216.
  • the tread portion 216 is formed with a width direction groove (not shown) extending in the tire width direction. Note that the shape and number of the circumferential grooves 216 ⁇ / b> A and the width direction grooves are appropriately set according to the performance such as drainage and steering stability required for the tire 210.
  • a bead filler 200 extending from the bead core 218 to the outer side in the tire radial direction along the outer surface 222O of the carcass 222 is embedded.
  • the bead filler 200 is embedded in a region surrounded by the carcass main body 222A and the folded portion 222B.
  • the first bead filler 201 is disposed in a region including the outer side in the tire radial direction than the bead core 218.
  • the first bead filler 201 has a shape extending from the region where the bead core 218 is disposed toward the outer side in the tire radial direction.
  • the first bead filler 201 is formed so as to cover the entire surface of the bead core 218, that is, is disposed up to the region inside the tire radial direction of the bead core 218.
  • the second bead filler 202 is disposed in a region including the outside of the first bead filler 201.
  • the second bead filler 202 is disposed so that there is a region overlapping the region in which the first bead filler 201 is disposed and the region in which the second bead filler 202 is disposed in the tire radial direction, and the second The bead filler 202 is in contact with a part of the outer surface in the tire width direction of the first bead filler 201.
  • the second bead filler 202 has a shape extending from the contact surface of the first bead filler 201 toward the outer side in the tire radial direction.
  • the volume occupied by the first bead filler 201 is larger than the volume occupied by the second bead filler 202 as it is closer to the inner side in the tire radial direction (that is, the bead wire side).
  • the volume occupied by the second bead filler 202 is larger than the volume occupied by the first bead filler 201 as it is closer to the outer side in the tire radial direction (that is, the side opposite to the bead wire).
  • the outer surface 222O of the carcass 222 is a surface outside the tire in the carcass main body portion 222A, and is a surface inside the tire in the folded portion 222B.
  • the end portion 200 ⁇ / b> E on the outer side in the tire radial direction of the second bead filler 202 enters the tire side portion 214.
  • the height BH of the bead filler 200 shown in FIG. 5 is preferably set within a range of 30 to 50% of the tire cross-section height SH.
  • the height BH of the bead filler 200 is the tip of the bead portion 212 from the end portion 200E on the outer side in the tire radial direction of the bead filler 200 when the tire 210 is assembled to the standard rim 230 and the internal pressure is set to the standard air pressure. (Height along the tire radial direction).
  • the height BH of the bead filler 200 is 30% or more of the tire cross-section height SH, for example, durability during run-flat traveling can be sufficiently ensured.
  • the height BH of the bead filler 200 is 50% or less of the tire cross-section height SH, the ride comfort is excellent.
  • the end portion 200E of the bead filler 200 is disposed on the inner side in the tire radial direction from the maximum width position of the tire 210.
  • the maximum width position of the tire 210 here refers to a position where the width is the widest along the tire width direction of the tire 210.
  • an adhesive is applied to at least one of the bead core and the second bead filler, and the covering resin layer, the first bead filler, and the second bead filler are You may improve the adhesiveness of a 1st bead filler.
  • the bead core 218 includes a plurality of bead wires 1 arranged side by side, and a covering resin layer 3 that covers the bead wires 1 and includes the resin D.
  • “arranged side by side” means that a plurality of bead wires 1 are not crossed in a bead member cut to a necessary length when applied to a tire.
  • the possible form of the bead core 218 shown in FIG. 6 is the same as that of the bead core 18 in the first embodiment described above, and the description thereof is omitted here.
  • an inner liner (not shown) made of a rubber material, a bead core 218, a bead filler 200 (a first bead filler 201) is formed on the outer periphery of a known tire molding drum.
  • the second bead filler 202) the carcass 222 in which the cord is covered with an elastic material (eg, rubber material, resin material, etc.), and the carcass 222 in the tire side portion 214 formed of an elastic material (eg, rubber material, resin material, etc.).
  • An unvulcanized tire case made of a region outside in the tire width direction and the side reinforcing rubber 226 is formed.
  • the belt layer 224A As a method of forming the belt layer 224A on the tread portion 216 of the tire case, for example, a member such as a wire wound around a reel is unwound while rotating the tire case, and the wire is wound around the tread portion 216 a predetermined number of times.
  • the belt layer 224A may be formed.
  • the covered resin when the wire is covered with a resin, the covered resin may be welded to the tread portion 216 by heating and pressing.
  • an unvulcanized tread is attached to the outer peripheral surface of the belt layer 224A to obtain a raw tire.
  • the green tire thus manufactured is vulcanized and molded with a vulcanization molding mold, and the tire 210 is completed.
  • tires according to the fourth to sixth embodiments will be described.
  • the same components as those of the tire 210 of the third embodiment are denoted by the same reference numerals, and redundant description is omitted.
  • FIG. 7 is an enlarged sectional view in the tire width direction showing the periphery of the bead portion of the tire according to the fourth embodiment.
  • the tire of the fourth embodiment has the same configuration as that of the tire 210 of the first embodiment except that the arrangement positions of the first bead filler and the second bead filler are changed.
  • the bead filler 200A is embedded in a region surrounded by the carcass body 222A and the folded portion 222B.
  • the first bead filler 201 ⁇ / b> A is disposed in a region including the outer side in the tire radial direction than the bead core 218.
  • the first bead filler 201A has a shape extending from the region where the bead core 218 is disposed toward the outer side in the tire radial direction.
  • the first bead filler 201A is formed so as to cover the entire surface of the bead core 218, that is, the first bead filler 218 is disposed up to the inner region in the tire radial direction of the bead core 218.
  • the second bead filler 202A is disposed in a region including the outside of the first bead filler 201A.
  • the second bead filler 202A is disposed so that there is a region overlapping the region in which the first bead filler 201A is disposed and the region in which the second bead filler 202A is disposed in the tire radial direction, and the second The bead filler 202A is in contact with a part of the inner surface in the tire width direction of the first bead filler 201A.
  • the second bead filler 202A has a shape extending from the contact surface of the first bead filler 201A toward the outer side in the tire radial direction.
  • the volume occupied by the first bead filler 201A is larger than the volume occupied by the second bead filler 202A as it is closer to the inner side in the tire radial direction (that is, the bead wire side).
  • the closer to the outer side in the tire radial direction (that is, the side opposite to the bead wire) the larger the volume occupied by the second bead filler 202A than the volume occupied by the first bead filler 201A.
  • FIG. 8 is an enlarged sectional view in the tire width direction showing the periphery of the bead portion of the tire of the fifth embodiment.
  • the tire according to the fifth embodiment has the same configuration as that of the tire 210 according to the first embodiment except that the arrangement positions of the first bead filler and the second bead filler are changed.
  • the bead filler 200B is embedded in a region surrounded by the carcass body 222A and the folded portion 222B.
  • the 1st bead filler 201B is arrange
  • the first bead filler 201 ⁇ / b> B is disposed in a region including the outer side in the tire radial direction than the bead core 218.
  • the first bead filler 201B has a shape extending from the region where the bead core 218 is disposed toward the outer side in the tire radial direction.
  • the first bead filler 201B is formed so as to cover the entire surface of the bead core 218, that is, the first bead filler 201B is disposed up to the inner region in the tire radial direction of the bead core 218.
  • the second bead filler 202B is disposed in a region including the outside of the first bead filler 201B. It should be noted that there is no region overlapping the region where the first bead filler 201B is disposed and the region where the second bead filler 202B is disposed in the tire radial direction, and the second bead filler 202B is the first bead filler 201B. It is in contact with the outermost position (surface) in the tire radial direction.
  • the second bead filler 202B has a shape extending from the contact surface of the first bead filler 201B toward the outer side in the tire radial direction.
  • FIG. 9 is a cross-sectional view in the tire width direction showing the periphery of the bead portion of the tire of the sixth embodiment in an enlarged manner.
  • the tire according to the sixth embodiment is the same as the tire 210 according to the third embodiment except that the first bead filler is not disposed in a region radially inward of the bead core and the shape of the bead core is different. It is a configuration.
  • the bead portion 212 includes an annular bead core 218C in which nine bead wires 1 are covered with a coating resin layer 3C via an adhesive layer (not shown), and a bead filler 200C (first bead).
  • the first bead filler 201C is formed so as to contact only a part of the surface of the bead core 218C (the outer surface in the tire radial direction), and the first bead filler 201C is formed. Is a form that is not disposed in the inner region in the tire radial direction of the bead core 218C.
  • One embodiment of the present disclosure includes the following aspects. ⁇ 1> a bead core having at least a bead wire, and a bead filler disposed in direct contact with the bead core or through another layer,
  • the bead filler has a continuous phase containing a thermoplastic elastomer, and a discontinuous phase containing an amorphous resin and interspersed in the continuous phase,
  • a tire bead member having a tensile elastic modulus Ei of the discontinuous phase higher than a tensile elastic modulus Es of the continuous phase.
  • ⁇ 3> The bead member for tire according to ⁇ 1> or ⁇ 2>, wherein the tensile elastic modulus Es of the continuous phase is 100 MPa or more and 400 MPa or less.
  • ⁇ 4> Any one of ⁇ 1> to ⁇ 3>, wherein a ratio (Ei / Es) between the tensile elastic modulus Ei of the discontinuous phase and the tensile elastic modulus Es of the continuous phase is 500/400 to 3000/100
  • ⁇ 5> The tire bead member according to any one of ⁇ 1> to ⁇ 4>, wherein the bead filler has a tensile elastic modulus of 400 MPa to 1500 MPa.
  • ⁇ 6> The tire bead member according to any one of ⁇ 1> to ⁇ 5>, wherein the amorphous resin is an amorphous resin having an ester bond.
  • ⁇ 7> The tire resin according to ⁇ 6>, wherein the amorphous resin having an ester bond is at least one resin selected from an amorphous polyester-based thermoplastic resin and an amorphous polycarbonate-based thermoplastic resin.
  • ⁇ 8> The tire bead member according to any one of ⁇ 1> to ⁇ 7>, wherein the thermoplastic elastomer is a polyester-based thermoplastic elastomer.
  • the content of the amorphous resin in the bead filler is 5 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the total amount of the thermoplastic elastomer and the amorphous resin.
  • ⁇ 10> The tire according to any one of ⁇ 1> to ⁇ 9>, wherein the bead core has a coating resin layer disposed in direct contact with the bead wire or in contact with another layer.
  • Bead member. ⁇ 11> A tire having the tire bead member according to any one of ⁇ 1> to ⁇ 10> in a pair of bead portions.
  • Examples 1-8, Comparative Examples 1-2 ⁇ Production of bead core>
  • the bead core having the mode shown in FIG. 3B shown in the first embodiment is manufactured.
  • a monofilament (monofilament with an average diameter of 1.25 mm, made of steel, strength: 2700 N, elongation: 7%) is used as a bead wire, and the adhesive resin shown in Table 1 that is heated and melted is adhered to the bead wire for adhesion.
  • a layer to be a resin layer is formed.
  • the coating shown in Table 1 was placed in a mold so that three bead wires on which a layer to be an adhesive resin layer was formed are arranged side by side, and extruded on the outer periphery of the layer to be an adhesive resin layer with an extruder.
  • the resin is deposited and coated and cooled.
  • the extrusion conditions are a bead wire temperature of 200 ° C., a coating resin temperature of 240 ° C., and an extrusion speed of 30 m / min.
  • the member shown in FIG. 3B in which three bead wires are arranged is wound while being welded with hot air, so that the outer periphery of the nine bead wires is covered with a coating resin layer via an adhesive resin layer.
  • the thickness (average thickness of the minimum part) of the adhesive resin layer in the bead core is 50 ⁇ m
  • the thickness (average thickness of the minimum part) of the coating resin layer is 200 ⁇ m.
  • the average distance between adjacent bead wires is 200 ⁇ m.
  • a bead member (a member made of a bead core and a bead filler) having the form shown in FIGS. 1 and 2 shown in the first embodiment is manufactured.
  • a resin material for bead filler containing thermoplastic elastomer [A] and amorphous resin [B] of the type shown in Table 1 at a ratio [A] / [B] (mass%) shown in Table 1 is prepared.
  • a structure in which the bead core is set in a mold whose bead filler shape has been processed in advance and the bead filler is directly in contact with the outer periphery of the bead core by injecting the resin material for the bead filler with an injection molding machine.
  • a bead member is prepared.
  • the mold temperature is 80 to 110 ° C.
  • the molding temperature is 200 to 270 ° C.
  • the discontinuous phase (island area) of the thermoplastic elastomer [A] is scattered in the continuous phase (sea area) of the amorphous resin [B].
  • the structure is expected to be observed.
  • the tensile elastic modulus Ei of the amorphous resin [B] and the tensile elastic modulus Es of the thermoplastic elastomer [A] were measured according to JIS K7113: 1995. Specifically, the tensile modulus was measured using a Tensilon universal testing machine (RTF-1210) manufactured by A & D Co., Ltd., with the tensile speed set to 100 mm / min. The results are shown in Table 1. Specifically, the sample was molded into a JIS No. 3 shape with an injection molding machine (NEX-50, manufactured by Nissei Plastic Industry Co., Ltd.) at a cylinder temperature of 200 ° C. to 270 ° C.
  • thermoplastic elastomer [A] The tensile modulus of the entire bead filler including both the thermoplastic elastomer [A] and the amorphous resin [B] was calculated as follows. The results are shown in Table 1. First, mixed resin A containing 25% by mass of thermoplastic elastomer [A] and 75% by mass of thermoplastic elastomer 4767N (made by Toray DuPont, polyester-based thermoplastic elastomer, product name: Hytrel 4767N) is prepared. .
  • the tensile elastic modulus is measured by the same method as that described above (that is, the measuring method of the tensile elastic modulus Ei and the tensile elastic modulus Es). To do.
  • the value of the tensile modulus obtained by the measurement is plotted against the content (% by mass) of the amorphous resin [B], and the intercept of the linear function obtained by the least square method and the thermoplastic elastomer [ A]
  • the value on the straight line obtained by translating the linear function in the y-axis direction by the difference ⁇ E is defined as the tensile modulus of the entire bead filler at each mixing ratio.
  • thermoplastic elastomer [A] is a thermoplastic elastomer 5557 (manufactured by Toray DuPont, polyester-based thermoplastic elastomer, product name: Hytrel 5557) is 60% by mass as an amorphous resin [B].
  • a cross-sectional image observed with a microscope (AFM) is shown in FIG. In FIG.
  • the tire (run flat tire) of the aspect shown in FIG.1 and FIG.2 shown in the above-mentioned 1st Embodiment is produced using the said bead member for a pair of bead part.
  • a carcass made of a bead member and a polyethylene terephthalate ply cord is prepared, and a tire side portion using a mixed rubber material of natural rubber (NR) and styrene butadiene rubber (SBR) (outside of the carcass in the width direction of the tire) Region), a side reinforcing rubber, a tread portion, and a stranded wire belt layer, a green tire is produced.
  • the green tire is heated (rubber vulcanization) at 160 ° C. for 21 minutes.
  • the resulting tire has a tire size of 225 / 40R18 and a tread thickness of 10 mm.
  • Example 9 the bead filler was changed to the bead filler shown in the third embodiment shown in FIGS. 5 and 6 (that is, the bead filler consisting of the first and second bead fillers). Tires. Specifically, the production of the bead member is changed as follows.
  • a bead member (a member made up of a bead core, a first bead filler, and a second bead filler) having the mode shown in FIGS. 5 and 6 shown in the third embodiment is manufactured.
  • a resin material for a second bead filler containing thermoplastic elastomer [A] and amorphous resin [B] of the type shown in Table 2 at a ratio [A] / [B] (mass%) shown in Table 2 is prepared.
  • a second bead filler is produced by injection molding using the second bead filler resin material.
  • the first bead filler and the second bead filler are integrated by placing the bead core and the second bead filler in a mold in which the bead filler shape has been processed in advance, and injection molding the resin material for the first bead filler.
  • the resulting bead member is produced.
  • the mold temperature is 80 to 110 ° C.
  • the molding temperature is 200 to 270 ° C.
  • the tensile elastic modulus of the entire bead filler including both the thermoplastic elastomer [A] and the amorphous resin [B] (that is, the tensile elastic modulus of the entire first bead filler and the tensile elasticity of the entire second bead filler).
  • the rate was also calculated according to the calculation method in Example 1. The results are shown in Table 2.
  • an example in which the tensile modulus of the entire bead filler is equal to or lower than the tensile modulus of the entire bead filler in Comparative Example 1 or equal to or higher than the tensile modulus of the entire bead filler in Comparative Example 2 is determined as B.
  • both the tensile modulus of the whole first bead filler and the tensile modulus of the whole second bead filler are higher than the tensile modulus of the whole bead filler in Comparative Example 1, and
  • An example that is lower than the tensile elastic modulus of the entire bead filler in Comparative Example 2 is determined as A.
  • At least one of the tensile elastic modulus of the entire first bead filler and the tensile elastic modulus of the entire second bead filler is equal to or less than the tensile elastic modulus of the entire bead filler in Comparative Example 1 or the tensile elastic modulus of the entire bead filler in Comparative Example 2.
  • the above example is set as B determination.
  • Example 1 is a composition in which the tensile modulus of the whole bead filler is slightly low and impact resistance is easily obtained (specifically, the bead filler is contained by appropriately containing an amorphous resin [B]. Since the overall tensile elastic modulus is an appropriate value), it is expected to be excellent in rim assemblability, and therefore it is determined as A.
  • Example 2 the content of the amorphous resin [B] is large compared to Example 1 and the tensile modulus of the whole bead filler is somewhat high, so it is considered that the impact resistance is lower than Example 1. Although it is expected that the rim assemblability is inferior to that of the first embodiment but within the allowable range, the determination is B.
  • Comparative Example 2 since the content of the amorphous resin [B] is large and the tensile modulus of the whole bead filler is high, it is expected that the impact resistance is low and cracking is likely to occur when the rim is assembled. Judgment. About Example 4, since the content of the amorphous resin [B] is the same as that of Example 1, the type of thermoplastic elastomer [A] is different, so that the tensile elastic modulus of the whole bead filler is higher than that of Example 1. Even if it is slightly high, impact resistance is obtained and it is expected that the rim assembly property is excellent.
  • Example 5 content of amorphous resin [B] is the same as Example 1 and Example 4, and the tensile elasticity modulus of the whole bead filler is a value between Example 1 and Example 4. Therefore, even if the kind of the amorphous resin [B] is different from those in Example 1 and Example 4, it is expected that the impact resistance is obtained and the rim assemblability is excellent.
  • Example 6 since the content of the amorphous resin [B] is the same as that of Example 2, the tensile modulus of the whole bead filler is different from that of Example 2 because the kind of the amorphous resin [B] is different. Even if it is slightly higher, impact resistance equivalent to that in Example 2 is obtained, and the rim assembly property is expected to be within an allowable range.
  • Example 7 the composition of the bead filler is the same as that of Example 4, but the tensile elasticity of the coating resin is higher than that of Example 4, so that the rim assembly property becomes slightly harder as the whole tire becomes slightly harder than Example 4. Although it is inferior to the above, since it is expected to be within the allowable range, the determination is B.
  • Example 8 since the composition of the bead filler is the same as that in Example 2, it is expected that the rim assemblability is acceptable as a whole tire even if the coating resin contains an amorphous resin. Therefore, B determination is made.
  • the resin used as the coating resin in Example 8 was 80% by mass of thermoplastic elastomer 5557 (manufactured by Toray DuPont, polyester-based thermoplastic elastomer, product name: Hytrel 5557), and amorphous resin 270 (manufactured by Toyobo Co., Ltd.). , Amorphous polyester resin, product name: Byron 270) and 20% by mass.
  • Example 9 since it is a bead filler which consists of the bead filler of Example 1 and the bead filler of Example 2, it is estimated that rim assemblability is further improved as compared with Example 1 and Example 2. Therefore, A determination is made.
  • Example 10 since it is a bead filler which consists of the bead filler of Example 2 and the bead filler of Example 5, it is estimated that rim assemblability is further improved as compared with Example 2 and Example 5. Therefore, A determination is made.
  • Example 11 the 1st bead filler is the same as the 1st bead filler in Example 9 and Example 10
  • the 2nd bead filler is the whole rather than the 2nd bead filler in Example 9 and Example 10. Since it is expected that the rim assemblability equivalent to that of Example 9 and Example 10 or a further excellent rim assemblage can be obtained, it is determined as “A”.
  • (Adhesive resin layer) GQ730 manufactured by Mitsubishi Chemical Corporation, maleic anhydride-modified polyester thermoplastic elastomer, “Primalloy-AP GQ730”, melting point 200 ° C.
  • the bead filler has a continuous phase containing a thermoplastic elastomer and a discontinuous phase containing an amorphous resin and scattered in the continuous phase.
  • the tensile elastic modulus Ei is higher than the tensile elastic modulus Es of the continuous phase
  • both excellent rim assembly property and high impact resistance are achieved as compared with a comparative example that does not satisfy this requirement.

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

Abstract

Un élément de talon pour pneus, qui comprend : un noyau de talon ayant au moins une tringle ; et un bourrage sur tringle qui est agencé de façon à être en contact avec le noyau de talon directement ou avec une autre couche interposée entre ceux-ci. Le bourrage sur tringle a : une phase continue qui contient un élastomère thermoplastique ; et des phases discontinues qui contiennent une résine amorphe, tout en étant dispersées dans la phase continue. Le module d'élasticité de traction Ei des phases discontinues est supérieur au module d'élasticité de traction Es de la phase continue.
PCT/JP2019/020177 2018-05-21 2019-05-21 Élément de talon pour pneus, et pneu WO2019225622A1 (fr)

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Citations (6)

* 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
JP2002178720A (ja) * 2000-10-23 2002-06-26 Goodyear Tire & Rubber Co:The より高い荷重保持能力を有する空気入りタイヤ用の三角形ビード構成
JP2002307907A (ja) * 2001-04-13 2002-10-23 Sumitomo Rubber Ind Ltd 空気入りタイヤ
WO2005047028A1 (fr) * 2003-11-17 2005-05-26 Akihiro Yamamoto Pneu et procede de fabrication de celui-ci
JP2015123905A (ja) * 2013-12-26 2015-07-06 横浜ゴム株式会社 空気入りタイヤ
JP2017159487A (ja) * 2016-03-08 2017-09-14 住友ゴム工業株式会社 空気入りタイヤの製造方法、ゴム材料および空気入りタイヤ

Patent Citations (6)

* 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
JP2002178720A (ja) * 2000-10-23 2002-06-26 Goodyear Tire & Rubber Co:The より高い荷重保持能力を有する空気入りタイヤ用の三角形ビード構成
JP2002307907A (ja) * 2001-04-13 2002-10-23 Sumitomo Rubber Ind Ltd 空気入りタイヤ
WO2005047028A1 (fr) * 2003-11-17 2005-05-26 Akihiro Yamamoto Pneu et procede de fabrication de celui-ci
JP2015123905A (ja) * 2013-12-26 2015-07-06 横浜ゴム株式会社 空気入りタイヤ
JP2017159487A (ja) * 2016-03-08 2017-09-14 住友ゴム工業株式会社 空気入りタイヤの製造方法、ゴム材料および空気入りタイヤ

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