JPWO2019225622A1 - Bead members for tires and tires - Google Patents

Abstract

It has a bead core having at least a bead wire and a bead filler arranged in direct contact with the bead core or in contact with another layer, and the bead filler is a continuous phase containing a thermoplastic elastomer and is not. A bead member for a tire having a discontinuous phase containing a crystalline resin and scattered in a continuous phase, and having a tensile elastic modulus Ei of the discontinuous phase higher than the tensile elastic modulus Es of the continuous phase.

Description

The present disclosure relates to bead members for tires and tires.

Conventionally, a pneumatic tire having a pair of bead portions, a pair of tire side portions extending outward in the tire radial direction from the bead portion, and a tread portion extending from one tire side portion to the other tire side portion has been used. ing. In addition, in the bead part of the pneumatic tire, from the viewpoint of improving the fixing performance to the rim, a structure is adopted in which a bead core having a bead wire is embedded and a bead filler formed of an elastic material is provided around the bead core. Has been done.

For example, Patent Document 1 proposes a bead wire for a tire outer skin including a wire rod assembly coated with a covering portion 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 Unexamined Patent Publication No. 63-25110

As described above, Patent Document 1 discloses a technique of using a bead wire coated with a resin-coated portion for a bead portion of a tire. However, Patent Document 1 does not suggest the material around the covering portion, and does not mention the strength of the members around the covering portion at all.
However, from the viewpoint of improving the durability of the tire, the bead filler placed around the bead core is also required to improve the durability against impact (that is, impact resistance) while maintaining excellent rim assembly performance. ing.

In view of the above circumstances, it is an object of the present disclosure to provide a bead member for a tire having both excellent rim assembly property and high impact resistance, and a tire provided with the bead member for the tire.

Specific means for solving the above problems include the following embodiments.
<1> A bead core having at least a bead wire and a bead filler arranged in direct contact with the bead core or in contact with each other via another layer.
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.
A bead member for a tire in which the tensile elastic modulus Ei of the discontinuous phase is higher than the tensile elastic modulus Es of the continuous phase.

According to the present disclosure, it is possible to provide a bead member for a tire having both excellent rim assembly property and high impact resistance, and a tire provided with the bead member for the tire.

FIG. 1 is a half cross-sectional view of a tire showing one side of a cut surface obtained by cutting a tire according to the first embodiment of the present disclosure along the tire width direction. FIG. 2 is an enlarged cross-sectional view in the tire width direction showing the periphery of the bead portion of the tire of FIG. FIG. 3A is a schematic view of a cut surface perpendicular to the length direction of the bead wire, showing an example of the bead core according to the embodiment of the present disclosure. FIG. 3B is a schematic view of a cut surface perpendicular to the length direction of the bead wire, showing an example of the bead core according to the embodiment of the present disclosure. FIG. 3C is a schematic view of a cut surface perpendicular to the length direction of the bead wire, showing an example of the bead core according to the embodiment of the present disclosure. FIG. 4 is a half cross-sectional view of a tire showing one side of a cut surface obtained by cutting the tire according to the second embodiment of the present disclosure along the tire width direction. FIG. 5 is a half cross-sectional view of a tire 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 an enlarged cross-sectional view in the tire width direction showing the periphery of the bead portion of the tire of FIG. FIG. 7 is an enlarged cross-sectional view in the tire width direction showing the periphery of the bead portion of the tire according to the fourth embodiment of the present disclosure. FIG. 8 is an enlarged cross-sectional view in the tire width direction showing the periphery of the bead portion of the tire according to the fifth embodiment of the present disclosure. FIG. 9 is an enlarged cross-sectional view in the tire width direction showing the periphery of the bead portion of the tire according to the sixth embodiment of the present disclosure. FIG. 10 is a cross-sectional image of a sample having a continuous phase containing a thermoplastic elastomer and a discontinuous phase containing an amorphous resin and scattered in the continuous phase observed with an atomic force microscope.

Hereinafter, specific embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments, and is carried out with appropriate modifications within the scope of the purpose of the present disclosure. be able to.

As used herein, the term "resin" is a concept that includes a thermoplastic resin, a thermoplastic elastomer, and a thermosetting resin, and does not include vulcanized rubber. Further, in the following description of the resin, the “same type” means a resin having a skeleton common to the skeleton constituting the main chain of the resin, such as ester-based resins and styrene-based resins.
The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the present specification, the term "process" is used not only for an independent process but also for a process as long as the purpose is achieved even if the process cannot be clearly distinguished from other processes. include.

Further, in the present specification, the “thermoplastic resin” means a polymer compound which softens and flows as the temperature rises and becomes relatively hard and strong when cooled, but does not have rubber-like elasticity.
As used herein, the term "thermoplastic elastomer" means a copolymer having a hard segment and a soft segment. Examples of the thermoplastic elastomer include those in which the material softens and flows as the temperature rises, becomes relatively hard and strong when cooled, and has rubber-like elasticity. Specifically, as the thermoplastic elastomer, for example, a polymer constituting a crystalline hard segment having a high melting point or a hard segment having a high cohesive force, and a polymer constituting an amorphous soft segment having a low glass transition temperature may be used. Examples thereof include copolymers having.
The hard segment refers to a component that is relatively harder than the soft segment. The hard segment is preferably a molecular restraint component that serves as a cross-linking point of the cross-linked rubber that prevents plastic deformation. For example, as a hard segment, a segment having a rigid group such as an aromatic group or an alicyclic group in the main skeleton, or a structure that enables intermolecular packing by intermolecular hydrogen bonds or π-π interactions can be used. Can be mentioned.
Further, 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. For example, examples of the soft segment include a segment having a long-chain group (for example, a long-chain alkylene group) in the main chain, a high degree of freedom in molecular rotation, and a stretchable structure.

<Bead member for tires>
The tire bead member (hereinafter, also simply referred to as “bead member”) according to the embodiment of the present disclosure is in direct contact with or in contact with the bead core having at least the bead wire. It has an arranged bead filler and.
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, and the tensile elastic modulus Ei of the discontinuous phase is a 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 a part of the bead portions. Specifically, the bead member according to the present embodiment constitutes at least a bead wire and all or a part of the bead filler in the tire.

Here, the mode of the bead member according to the present embodiment will be briefly described with reference to the drawings.
The size of the members in each figure is conceptual, and the relative relationship between the sizes of the members is not limited to this. In addition, members having substantially the same function may be designated by the same reference numerals throughout the drawings, and duplicate description may be omitted.
The tire 10 shown in FIG. 1 has a pair of bead portions 12 on the left and right sides (in FIG. 1, only the bead portion 12 on one side is shown). It also has a pair of tire side portions 14 extending outward from the pair of bead portions 12 in the tire radial direction, and a tread portion 16 extending from one tire side portion 14 to the other tire side portion 14.
A bead core 18 is embedded in the bead portion 12, and a carcass 22 straddles a pair of left and right bead cores 18.
Further, a bead filler 20 extending from the bead core 18 to the outside in the tire radial direction along the outer surface 22O of the carcass 22 is embedded in the bead portion 12. The bead filler 20 is arranged in a region surrounded by, for example, the carcass main body 22A and the folded-back portion 22B.
As shown in FIG. 2, the bead core 18 has a plurality of bead wires 1 arranged side by side and a coating resin layer 3 for coating 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 for reinforcing the tire side portion 14 is arranged inside the carcass 22 of the tire side portion 14 in the tire width direction. ing.

Further, another aspect of the bead member according to the present embodiment will be briefly described with reference to the drawings.
The tire 210 shown in FIG. 5 has a pair of bead portions 212 on the left and right sides (in FIG. 5, only the bead portion 212 on one side is shown). It also has a pair of tire side portions 214 extending outward from the pair of bead portions 212 in the tire radial direction, and a tread portion 216 extending from one tire side portion 214 to the other tire side portion 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.
Further, a bead filler 200 made of a first bead filler 201 and a second bead filler 202 extending from the bead core 218 outward in the tire radial direction along the outer surface 222O of the carcass 222 is embedded in the bead portion 212. The bead filler 200 is arranged in a region surrounded by, for example, the carcass main body 222A and the folded portion 222B.
As shown in FIG. 6, the bead core 218 has a plurality of bead wires 1 arranged side by side and a coating resin layer 3 for coating 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 210 shown in FIG. 5 is a run-flat tire, and a side reinforcing rubber 226 as an example of a side reinforcing layer for reinforcing the tire side portion 214 is arranged inside the carcass 222 of the tire side portion 214 in the tire width direction. ing.

When the bead filler is composed of two or more members as in the tire 210 shown in FIG. 5, "a continuous phase containing a thermoplastic elastomer and a continuous phase containing an amorphous resin are scattered in the continuous phase. It is preferable that the member 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 "is a member closer to the bead core. Further, it is more preferable that all of the two or more members constituting the bead filler satisfy the above requirements.
Therefore, in the case of the tire 210 shown in FIG. 5, it is preferable that 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.

As described above, in the tire 10 shown in FIGS. 1 and 2 and the tire 210 shown in FIGS. 5 and 6, the bead member according to the present embodiment constitutes all or a part of the pair of bead portions. The bead member according to the present embodiment constitutes at least a bead wire and all or a part of the bead filler.

Conventionally, as a bead portion that plays a role of fixing a tire to a rim, a bead core having at least a bead wire and a bead filler arranged in direct contact with the bead core or in contact with another layer are used. The bead member to have is used. In addition, while a material containing rubber has been generally used as a member constituting a bead filler, 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.
However, from the viewpoint of improving the durability of the tire, the bead filler is also required to have improved durability against impact (that is, impact resistance). Therefore, the bead filler has excellent rim assembly properties that can be flexibly deformed during rim assembly to facilitate rim assembly, and by increasing rigidity, durability (impact resistance) is provided against impact. It is required to achieve both the contradictory properties of enhancing.

On the other hand, the present inventors have a continuous phase containing a thermoplastic elastomer and a discontinuous phase containing an amorphous resin and scattered 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 having a tensile elastic modulus Es higher than that of the phase, it is possible to achieve both excellent rim assembly property and high impact resistance.
The reason can be inferred as follows.

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) due to the compatibility between the two. It constitutes a continuous phase (island region in the sea-island structure).
The presence of a continuous phase (sea region) containing the thermoplastic elastomer throughout the bead filler retains the elasticity of the thermoplastic elastomer and exhibits excellent rim assembly properties.
On the other hand, discontinuous phases (island regions) containing amorphous resin are scattered in the continuous phase, and the tensile elastic modulus Ei of this discontinuous phase is higher than the tensile elastic modulus Es of the continuous phase, so that the continuous phase High rigidity is imparted to the bead filler while maintaining the elastic modulus of the thermoplastic elastomer inside. As a result, high durability against impact can be obtained.
From the above, it is presumed that according to the present embodiment, both excellent rim assembly property and high impact resistance are compatible.

Hereinafter, each component of the bead member will be described in detail.

The bead member has a bead core having a bead wire and a bead filler arranged in direct contact with the bead core or in contact with another layer. The shape of the bead member according to this embodiment is not particularly limited.
In addition, for example, the bead core may have a coating resin layer which is arranged in direct contact with the bead wire or in contact with another layer. Further, the bead core may further have an adhesive layer between the bead wire and the coating resin layer.

In the bead member, "a structure in which the bead filler is arranged in direct contact with the bead core or in contact with another layer" is, for example, covered with the entire surface of the bead core in direct contact with the bead filler. A state in which a part of the surface of the bead core is coated with the bead filler via an adhesive layer or the like, and a state in which the entire surface of the bead core is coated with the bead filler via an adhesive layer or the like. Can be mentioned.
Further, in the bead member, in the "structure in which the coating resin layer is arranged in direct contact with the bead wire or in contact with each other via another layer", for example, the entire surface of the bead wire is covered with the coating resin layer. A state in which the bead wire is directly contacted and coated, a state in which a part of the surface of the bead wire is coated on the coating resin layer via an adhesive layer, and a state in which the entire surface of the bead wire is coated on the coating resin via the adhesive layer. The state of being covered with a layer and the like can be mentioned.

[Bead filler]
The bead filler contains 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.

Whether or not the bead filler has discontinuous phases scattered in the continuous phase (that is, has a sea-island structure) is determined by, for example, observing the cross section of the bead filler with an atomic force microscope (AFM). It can be confirmed by whether or not the domain is observed.

-Elastic modulus of continuous phase and discontinuous phase 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 the 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, still more preferably, from the viewpoint of ensuring the flexibility of the bead filler and improving the rim assembly property. Is 100 MPa or more and 200 MPa or less.

The ratio (Ei / Es) of the tensile elastic modulus Ei of the discontinuous phase to the tensile elastic modulus Es of the continuous phase is 500/400 to 3000 from the viewpoint of achieving both excellent rim assembly property and high impact resistance. It is preferably / 100, more preferably 1000/300 to 3000/100, and even more preferably 1500/200 to 3000/100.

The shapes 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 separately by the amplitude of the cantilever and the phase delay by the tapping mode, and the shapes of the continuous phase and the discontinuous phase are measured.
Further, 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. Specifically, Shimadzu Autograph AGS-J (5KN) manufactured by Shimadzu Corporation is used, the tensile speed is set to 100 mm / min, and the tensile elastic modulus is measured. When measuring the tensile elastic modulus of a discontinuous phase or a continuous phase, for example, 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 the materials constituting the discontinuous phase and the continuous phase, adjusting their contents, and the like. For example, the tensile elastic modulus Ei of the discontinuous phase can be adjusted by the type of the amorphous resin contained in the discontinuous phase, the content in the discontinuous phase, and the like. Further, the tensile elastic modulus Es of the continuous phase can be adjusted by the type of the thermoplastic elastomer contained in the continuous phase, the content in the continuous phase, and the like.

・ Content of each component in bead filler
(1) Content of components in the discontinuous phase The content of the amorphous resin in the discontinuous phase determines the discontinuous phase from the viewpoint of imparting high rigidity to the bead filler and further improving the 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, still more preferably 70% by mass or more and 100% by mass or less, based on 100 parts by mass of the constituent components. It is mass% or less.

(2) Content of components in the continuous phase The content of the thermoplastic elastomer in the continuous phase is the component 100 that constitutes the continuous phase from the viewpoint of ensuring the flexibility of the bead filler and improving the rim assembly property. 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 further preferably 90% by mass or more and 100% by mass or less with respect to parts by mass. ..

(3) Difference in content between amorphous resin and thermoplastic elastomer In bead filler, the total amount of thermoplastic elastomer and amorphous resin from the viewpoint of achieving both excellent rim assembly and high impact resistance. 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. It is less than a part.

The content of each component (for example, amorphous resin, thermoplastic elastomer, etc.) contained in the bead filler can be examined by a nuclear magnetic resonance (NMR) method.

-(Discontinuous phase) Amorphous resin-
The bead filler contains an amorphous resin in the discontinuous phase.
As used herein, the term "amorphous resin" means a thermoplastic resin having an extremely low degree of crystallinity or which cannot be in a crystallized state. The amorphous resin contained in the discontinuous phase may be only one type or two or more types.

As the amorphous resin, an amorphous resin having an ester bond (hereinafter, also simply referred to as “specific amorphous resin”) is preferable.
In particular, when the continuous phase of the bead filler contains a polyester-based thermoplastic elastomer as the thermoplastic elastomer, the specific amorphous resin (amorphous resin having an ester bond) has an ester bond, so that it is different from the polyester-based thermoplastic elastomer. 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 a fine domain, so that the effect of improving the rigidity is exhibited better. It is thought that it will be done.

Examples of the specific amorphous resin include an amorphous polyester-based thermoplastic resin, an amorphous polycarbonate-based thermoplastic resin, and an amorphous polyurethane-based thermoplastic resin. Among these, an amorphous polyester-based thermoplastic resin and an amorphous polycarbonate-based thermoplastic resin are preferable from the viewpoint of further increasing the rigidity.

Further, from the viewpoint of improving the rigidity of the bead filler, the glass transition temperature (Tg) of the amorphous resin is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and more preferably 80 ° C. or higher. More preferred.
The Tg of the specific amorphous resin shall be a value measured by DSC in accordance with JIS K 6240: 2011. Specifically, the temperature at the intersection of the original baseline and the tangent point at the inflection point at the time of DSC measurement is defined as Tg. The measurement can be performed using, for example, "DSC Q100" of TA Instruments Co., Ltd. at a sweep rate of 10 ° C./min.

Commercially available amorphous resins include, for example, Toyo Boseki Co., Ltd.'s amorphous polyester resin "Byron" series, Mitsubishi Engineering Plastics Co., Ltd.'s amorphous polycarbonate resin "Novalex" series, and Mitsubishi Gas Chemicals Co., Ltd. Amorphous polyester resin "ALTESTER" series of Co., Ltd. can be mentioned.

-(Discontinuous phase) Other components-
The discontinuous phase may contain components other than the amorphous resin. Examples of other components include resins, rubbers, various fillers (for example, silica, calcium carbonate, clay, etc.), antiaging agents, oils, plasticizers, color formers, weather resistant agents, and the like.

-(Continuous phase) thermoplastic elastomer-
The bead filler contains a thermoplastic elastomer in the continuous phase.
Examples of the thermoplastic elastomer include polyester-based thermoplastic elastomer (TPC), polyamide-based thermoplastic elastomer (TPA), polystyrene-based thermoplastic elastomer (TPS), and polyurethane-based thermoplastic elastomer (TPU) defined in JIS K6418. Examples thereof include olefin-based thermoplastic elastomers (TPO), thermoplastic rubber cross-linked products (TPV), and other thermoplastic elastomers (TPZ). The continuous phase may contain these thermoplastic elastomers alone or in combination of two or more.

As the thermoplastic elastomer contained in the continuous phase, a polyester-based thermoplastic elastomer is preferable. In particular, when the bead filler is in direct contact with the bead core and the member constituting the surface of the bead core (for example, a coating resin layer or the like) contains at least one selected from the group consisting of the polyester-based thermoplastic elastomer and the polyester-based resin. , The same type of resin is contained in both of them that come into contact with each other. With this configuration, a material for forming can be applied to the surface of the bead core in a familiar manner when forming the bead filler, and high adhesiveness can be obtained between the two.

-Polyester-based thermoplastic elastomer As a polyester-based thermoplastic elastomer, for example, at least polyester forms a hard segment that is crystalline and has a high melting point, and other polymers (for example, polyester or polyether) are amorphous and have a glass transition. Examples include materials forming soft segments with low temperatures.

As the polyester forming the hard segment, aromatic polyester can be used. The aromatic polyester can be formed from, for example, 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 polyesters include, for example, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyetanedicarboxylic acid, 5 -Dicarboxylic acid components such as sulfoisophthalic acid or ester-forming derivatives thereof and diols having a molecular weight of 300 or less (for example, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, etc.) Aromatic diols; 1,4-cyclohexanedimethanol, alicyclic diols such as tricyclodecanedimethylol; xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2- Bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4'- Aromatic diols such as dihydroxy-p-terphenyl and 4,4'-dihydroxy-p-quarterphenyl; etc.) and polyesters derived from them, or a combination of two or more of these dicarboxylic acid components and diol components. It may be a polymerized polyester. It is also possible to copolymerize a trifunctional or higher functional polyfunctional carboxylic acid component, a polyfunctional oxyic acid component, a polyfunctional hydroxy component and the like in a range of 5 mol% or less.
Examples of the polyester forming the hard segment include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and the like, and polybutylene terephthalate is preferable.

Examples of the polymer forming the soft segment include aliphatic polyesters and aliphatic polyethers.
Examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, and poly (propylene oxide). ) Ethylene oxide addition polymer of glycol, copolymer of ethylene oxide and tetrahydrofuran, etc. can be mentioned.
Examples of the aliphatic polyester include poly (ε-caprolactone), polyenant lactone, polycaprilolactone, polybutylene adipate, polyethylene adipate and the like.
Among these aliphatic polyethers and aliphatic polyesters, poly (tetramethylene oxide) glycol and poly (propylene oxide) glycol are examples of polymers that form soft segments from the viewpoint of the elastic properties of the obtained polyester block copolymer. Ethylene oxide adduct, poly (ε-caprolactone), polybutylene adipate, polyethylene adipate and the like are preferable.

The number average molecular weight of the polymer forming the soft segment is preferably 300 to 6000 from the viewpoint of toughness and low temperature flexibility. Further, the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 99: 1 to 20:80, more preferably 98: 2 to 30:70 from the viewpoint of moldability. ..

Examples of the combination of the above-mentioned hard segment and the soft segment include the respective combinations of the above-mentioned hard segment and the soft segment. Among these, as the combination of the above-mentioned hard segment and soft segment, a combination in which the hard segment is polybutylene terephthalate and the soft segment is an aliphatic polyether is preferable, and the hard segment is polybutylene terephthalate and the soft segment. More preferably, the combination is poly (ethylene oxide) glycol.

Commercially available polyester-based thermoplastic elastomers include, for example, the "Hytrel" series manufactured by Toray DuPont Co., Ltd. (for example, 3046, 5557, 6347, 4047, 4767, etc.) and the "Perprene" series manufactured by Toyobo Co., Ltd. (For example, P30B, P40B, P40H, P55B, P70B, P150B, P280B, P450B, P150M, S1001, S2001, S5001, S6001, S9001 and the like) can be used.

The polyester-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.

-Polyamide-based thermoplastic elastomer The polyamide-based thermoplastic elastomer consists of a polymer having a polymer that forms a hard segment that is crystalline and has a high melting point and a polymer that forms a soft segment that is amorphous and has a low glass transition temperature. It means a thermoplastic resin material having an amide bond (-CONH-) in the main chain of the polymer forming the hard segment.
As the polyamide-based thermoplastic elastomer, for example, at least polyamide forms a hard segment having a high crystallinity and a high melting point, and other polymers (for example, polyester, polyether, etc.) are amorphous and have a low glass transition temperature. Examples include the forming material. Further, the polyamide-based thermoplastic elastomer may be formed by using a chain length extender such as a dicarboxylic acid in addition to the hard segment and the soft segment.
Specific examples of the polyamide-based thermoplastic elastomer include the amide-based thermoplastic elastomer (TPA) defined in JIS K6418: 2007, and the polyamide-based elastomer described in JP-A-2004-346273. it can.

In the polyamide-based thermoplastic elastomer, examples of the polyamide forming the hard segment include a polyamide produced by a monomer represented by the following general formula (1) or general formula (2).

In the general formula (1), R ¹ represents a molecular chain of a hydrocarbon having 2 to 20 carbon atoms (for example, an alkylene group having 2 to 20 carbon atoms).

In the general formula (2), 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).

In the general formula (1), as R ¹ , a molecular chain of a hydrocarbon having 3 to 18 carbon atoms, for example, an alkylene group having 3 to 18 carbon atoms is preferable, and a molecular chain of a hydrocarbon having 4 to 15 carbon atoms, for example, carbon. An alkylene group having a number of 4 to 15 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.
Further, in the general formula (2), the ^{R 2,} the molecular chains of hydrocarbon having 3 to 18 carbon atoms, for example, preferably an alkylene group having 3 to 18 carbon atoms, the molecular chain of a hydrocarbon of 4 to 15 carbon atoms, For example, 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.
Examples of the monomer represented by the general formula (1) or the general formula (2) include ω-aminocarboxylic acid and lactam. Examples of the polyamide forming the hard segment include a polycondensate of these ω-aminocarboxylic acids or lactams, a co-condensation polymer of a diamine and a dicarboxylic acid, and the like.

Examples of the ω-aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like having 5 to 20 carbon atoms. An aliphatic ω-aminocarboxylic acid and the like can be mentioned. Examples of the lactam include aliphatic lactams having 5 to 20 carbon atoms such as lauryl lactam, ε-caprolactam, udecan lactam, ω-enantractum, and 2-pyrrolidone.
Examples of the diamine include an aliphatic diamine having 2 to 20 carbon atoms and an aromatic diamine having 6 to 20 carbon atoms. Examples of the aliphatic diamine having 2 to 20 carbons and the aromatic diamine having 6 to 20 carbons include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and nonamethylenediamine. Decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, metaxamethylenediamine and the like can be mentioned. it can.
Further, the dicarboxylic acid can be represented by HOOC- (R ³ ) _m- COOH (R ³ : molecular chain of hydrocarbon having 3 to 20 carbon atoms, m: 0 or 1), for example, oxalic acid, succinic acid. , Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and other aliphatic dicarboxylic acids having 2 to 20 carbon atoms can be mentioned.
As the polyamide forming the hard segment, a polyamide obtained by ring-opening polycondensation of lauryl lactam, ε-caprolactam, or udecan lactam can be preferably used.

Examples of the polymer forming the soft segment include polyester, polyether and the like, and specific examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, ABA type triblock polyether and the like. These can be used alone or in combination of two or more. Further, a polyether diamine or the like obtained by reacting the terminal of the polyether with ammonia or the like can also be used.
Here, the "ABA-type triblock polyether" means a polyether represented by the following general formula (3).

In the general formula (3), x and z represent integers of 1 to 20. y represents an integer from 4 to 50.

In the general formula (3), x and z are preferably integers of 1 to 18, more preferably integers of 1 to 16, even more preferably integers of 1 to 14, and particularly preferably integers of 1 to 12. Further, in the general formula (3), y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, further preferably an integer of 7 to 35, and particularly preferably an integer of 8 to 30.

Examples of the combination of the hard segment and the soft segment include the respective combinations of the hard segment and the soft segment mentioned above. Among these, the combination of the hard segment and the soft segment includes a ring-opening polycondensate of lauryl lactam / polyethylene glycol, a ring-opening polycondensate of lauryl lactam / polypropylene glycol, and a ring-opening polycondensation of lauryl lactam. A combination of body / polytetramethylene ether glycol or a ring-opening polycondensate of lauryl lactam / ABA-type triblock polyether is preferable, and a combination of lauryl lactam ring-opening polycondensate / ABA-type triblock polyether is more preferable. preferable.

The number average molecular weight of the polymer (polyamide) forming the hard segment is preferably 300 to 15,000 from the viewpoint of melt moldability. The number average molecular weight of the polymer forming the soft segment is preferably 200 to 6000 from the viewpoint of toughness and low temperature flexibility. Further, the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 90:10, 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.

Examples of commercially available polyamide-based thermoplastic elastomers include Ube Industries, Ltd.'s "UBESTA XPA" series (for example, XPA9068X1, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2XPA9044, etc.), Daicel Eponic. The "bestamide" series (for example, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.) can be used.

Polyamide-based thermoplastic elastomers are suitable as resin materials because they satisfy the performance required for bead portions from the viewpoints of elastic modulus (flexibility), strength, and the like. In addition, the polyamide-based thermoplastic elastomer often has good adhesiveness to the thermoplastic resin and adhesiveness to the thermoplastic elastomer.

-Polystyrene-based thermoplastic elastomer As the polystyrene-based 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 included. Examples thereof include materials forming soft segments that are crystalline and have a low glass transition temperature. As the polystyrene forming the hard segment, for example, polystyrene obtained by a known radical polymerization method, ionic polymerization method or the like is preferably used, and specific examples thereof include polystyrene having anionic living polymerization. Examples of the polymer forming the soft segment include polybutadiene, polyisoprene, and poly (2,3-dimethyl-butadiene).

Examples of the combination of the hard segment and the soft segment include the respective combinations of the hard segment and the soft segment mentioned above. Among these, as the combination of the hard segment and the soft segment, a polystyrene / polybutadiene combination or a polystyrene / polyisoprene combination is preferable. Further, in order to suppress an unintended cross-linking reaction of the thermoplastic elastomer, it is preferable that the soft segment is hydrogenated.

The number average molecular weight of the polymer (polystyrene) forming the hard segment is preferably 5000 to 500000, more preferably 1000 to 20000.
The number average molecular weight of the polymer forming the soft segment is preferably 5000 to 1,000,000, more preferably 1000 to 8,000,000, and even more preferably 30,000 to 500000. Further, the volume ratio (x: y) of 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. ..

Polystyrene-based thermoplastic elastomers can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.
Examples of polystyrene-based thermoplastic elastomers include styrene-butadiene-based copolymers [SBS (polystyrene-poly (butylene) block-polystyrene), SEBS (polystyrene-poly (ethylene / butylene) block-polystyrene)], and styrene-isoprene. Copolymers (polystyrene-polyisoprene block-polystyrene), styrene-propylene-based copolymers [SEP (polystyrene- (ethylene / propylene) block), SEPS (polystyrene-poly (ethylene / propylene) block-polystyrene), SEEPS ( Polystyrene-poly (polystyrene-ethylene / propylene) block-polystyrene), SEB (polystyrene (ethylene / butylene) block)] and the like can be mentioned.

Commercially available polystyrene-based thermoplastic elastomers include, for example, the "Tough Tech" series manufactured by Asahi Kasei Corporation (for example, H1031, H1041, H1043, H1051, H1052, H1053, H1062, H1082, H1141, H1221, H1272, etc.). The "SEBS" series (8007, 8076, etc.) and "SEPS" series (2002, 2063, etc.) manufactured by Kuraray Co., Ltd. can be used.

-Polyurethane-based thermoplastic elastomer As a polyurethane-based thermoplastic elastomer, for example, at least polyurethane forms a hard segment in which pseudo-crosslinks are formed by physical aggregation, and other polymers are amorphous and have a low glass transition temperature. Examples include materials forming soft segments.
Specific examples of the polyurethane-based thermoplastic elastomer include the polyurethane-based thermoplastic elastomer (TPU) specified in JIS K6418: 2007. The polyurethane-based thermoplastic elastomer can be represented as a copolymer containing a soft segment containing a unit structure represented by the following formula A and a hard segment containing a unit structure represented by the following formula B.

In the formula, 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.

As the long-chain aliphatic polyether or the long-chain aliphatic polyester represented by P in the formula A, for example, those having a molecular weight of 500 to 5000 can be used. 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 diol compounds include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly (butylene adipate) diol, poly-ε-caprolactone diol, and poly (hexamethylene carbonate) having a molecular weight within the above range. Examples thereof include diols and ABA-type triblock polyethers.
These can be used alone or in combination of two or more.

In formulas A and B, R is a partial structure introduced using a diisocyanate compound containing an aliphatic hydrocarbon represented by R, an alicyclic hydrocarbon, or an aromatic hydrocarbon. Examples of the aliphatic diisocyanate compound containing an aliphatic hydrocarbon represented by R include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, and 1,6-hexamethylene diisocyanate. Can be mentioned.
Examples of the diisocyanate compound containing an alicyclic hydrocarbon represented by R include 1,4-cyclohexanediisocyanate and 4,4-cyclohexanediisocyanate. Further, 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.

In the formula B, as the short-chain aliphatic hydrocarbon represented by P', the alicyclic hydrocarbon, or the aromatic hydrocarbon, for example, those having a molecular weight of less than 500 can be used. Further, P'is derived from a diol compound containing a short-chain aliphatic hydrocarbon represented by P', an alicyclic hydrocarbon, or an aromatic hydrocarbon. Examples of the aliphatic diol compound containing a short-chain aliphatic hydrocarbon represented by P'include glycols and polyalkylene glycols, and specifically, ethylene glycol, propylene glycol, trimethylene glycol, 1,4. -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Examples thereof include decanediol.
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, and the like. Cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol and the like can be mentioned.
Further, 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'-dihydroxydiphenylsulfide, 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-dihydroxynaphthalin, and 2,6-dihydroxynaphthalin.
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 viewpoint of flexibility and thermal stability of the polyurethane-based thermoplastic elastomer. .. The mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 15:85 to 90:10, more preferably 30:70 to 90:10, from the viewpoint of moldability. ..

The polyurethane-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method. As the polyurethane-based thermoplastic elastomer, for example, the thermoplastic polyurethane described in JP-A-5-331256 can be used.

As the polyurethane-based 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 copolymer ester is preferable, and more specifically, tolylene diisocyanate (more specifically, tolylene diisocyanate ( TDI) / polyester-based polyol copolymer, TDI / polyether-based polyol copolymer, TDI / caprolactone-based polyol copolymer, TDI / polycarbonate-based polyol copolymer, 4,4'-diphenylmethane diisocyanate (MDI) / polyester At least one selected from based polyol copolymers, MDI / polyether polyol copolymers, MDI / caprolactone-based polyol copolymers, MDI / polycarbonate-based polyol copolymers, and MDI + hydroquinone / polyhexamethylene carbonate copolymers. Species are preferred, including TDI / polyester polyol copolymers, TDI / polyether polyol copolymers, MDI / polyester polyol copolymers, MDI / polyether polyol copolymers, and MDI + hydroquinone / polyhexamethylene carbonates. At least one selected from the copolymer is more preferable.

Commercially available products of polyurethane-based thermoplastic elastomers include, for example, the "Elastran" series manufactured by BASF (eg, ET680, ET880, ET690, ET890, etc.) and the "Chramiron U" series manufactured by Kuraray Co., Ltd. (for example). , 2000 series, 3000 series, 8000 series, 9000 series, etc.), "Milactran" series manufactured by Nippon Miractran Co., Ltd. (for example, XN-2001, XN-2004, P390RSUP, P480RSUI, P26MRNAT, E490, E590, P890, etc.) Etc. can be used.

-Olefin-based thermoplastic elastomer As the olefin-based thermoplastic elastomer, for example, at least polyolefin forms a hard segment having a high crystallinity and a high melting point, and other polymers (for example, polyolefin, other polyolefin, polyvinyl compound, etc.) are amorphous. Examples thereof include materials forming soft segments having a low glass transition temperature. Examples of the polyolefin forming the hard segment include polyethylene, polypropylene, isotactic polypropylene, polybutene and the like.

Examples of the olefin-based thermoplastic elastomer include an olefin-α-olefin random copolymer, an olefin block copolymer, and the like, and specific examples thereof include a propylene block copolymer, an ethylene-propylene copolymer, and a propylene-. 1-hexene copolymer, propylene-4-methyl-1pentene 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-methacrylate 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-methacrylate copolymer, propylene-methyl methacrylate copolymer Copolymer, propylene-ethyl methacrylate copolymer, propylene-butyl methacrylate copolymer, propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer, ethylene-vinyl acetate Examples thereof include a copolymer and a propylene-vinyl acetate copolymer.

Among these, as the olefin-based thermoplastic elastomer, a propylene block copolymer, an ethylene-propylene copolymer, a propylene-1-hexene copolymer, a propylene-4-methyl-1pentene copolymer, and a 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-methacrylate copolymer , Propropylene-methyl methacrylate copolymer, propylene-ethyl methacrylate copolymer, propylene-butyl methacrylate copolymer, propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer At least one selected from coalescence, ethylene-vinyl acetate copolymer, and propylene-vinyl acetate copolymer is preferable, and ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-1-butene copolymer are weighted. At least one selected from coalescing, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer is more preferable.
Further, two or more kinds of olefin resins such as ethylene and propylene may be used in combination. The olefin resin content in the olefin-based thermoplastic elastomer is preferably 50% by mass or more and 100% by mass or less.

The number average molecular weight of the olefin-based thermoplastic elastomer is preferably 5000 to 10000000. When the number average molecular weight of the olefin-based thermoplastic elastomer is 5000 to 1000000, the mechanical properties of the thermoplastic resin material are sufficient, and the processability is also excellent. From the same viewpoint, the number average molecular weight of the olefin-based thermoplastic elastomer is more preferably 7,000 to 1,000,000, and particularly preferably 1,000 to 1,000,000. Thereby, the mechanical physical characteristics 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. Further, the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 95:15, more preferably 50:50 to 90:10, from the viewpoint of moldability. ..
The olefin-based thermoplastic elastomer can be synthesized by copolymerizing by a known method.

Further, as the olefin-based thermoplastic elastomer, one obtained by acid-modifying the thermoplastic elastomer may be used.
The "acid-modified olefin-based thermoplastic elastomer" means that an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfate group, or a phosphoric acid group is bonded to the olefin-based thermoplastic elastomer.
To bond an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group, or a phosphoric acid group to an olefin-based thermoplastic elastomer, for example, as an unsaturated compound having an acidic group to an olefin-based thermoplastic elastomer. It is possible to bond (for example, graft polymerization) an unsaturated bond site of an unsaturated carboxylic acid (generally maleic anhydride).
As the 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 unsaturated compounds having a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like.

Examples of commercially available olefin-based thermoplastic elastomers include the "Toughmer" series manufactured by Mitsui Chemicals, Inc. (for example, A0550S, A1050S, A4050S, A1070S, A4070S, A35070S, A1085S, A4085S, A7090, A70090, MH7007, MH7010. , XM-7070, XM-7080, BL4000, BL2481, BL3110, BL3450, P-0275, P-0375, P-0775, P-0180, P-0280, P-0480, P-0680, etc.), Mitsui DuPont "Nucrel" series manufactured by Polychemical Co., Ltd. (for example, AN4214C, AN4225C, AN42115C, N0903HC, N0908C, AN42012C, N410, N1050H, N1108C, N1110H, N1207C, N1214, AN4221C, N1525, N1560, N0200H, AN42 N035C), etc., "Elvalois AC" series (for example, 1125AC, 1209AC, 1218AC, 1609AC, 1820AC, 1913AC, 2112AC, 2116AC, 2615AC, 2715AC, 3117AC, 3427AC, 3717AC, etc.), Sumitomo Chemical Co., Ltd. "Aklift" series , "Evertate" series, etc., "Ultrasen" series manufactured by Toso Co., Ltd., "Prime TPO" series made of prime polymer (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, T310E, M142E, etc.) can also be used.

-(Continuous phase) Other components-
The continuous phase may contain components other than the thermoplastic elastomer. Examples of other components include thermoplastic resins, rubbers, various fillers (for example, silica, calcium carbonate, clay, etc.), antioxidants, oils, plasticizers, color formers, weather resistant agents, and the like.

(Physical properties) Tension elastic modulus The tensile elastic modulus (JIS K7113: 1995) of the bead filler 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 property and high impact resistance. It is more preferably 1200 MPa or less, and further preferably 600 MPa or more and 1000 MPa or less.

The tensile elastic modulus is measured in accordance with JIS K7113: 1995. Specifically, Shimadzu Autograph AGS-J (5KN) manufactured by Shimadzu Corporation is used, the tensile speed is set to 100 mm / min, and the tensile elastic modulus is measured. When measuring the tensile elastic modulus of the bead filler, for example, a measurement sample of the same material as the bead filler may be separately prepared and the elastic modulus may be measured.

The tensile elastic modulus of the bead filler can be adjusted, for example, by selecting a material (for example, amorphous resin, thermoplastic elastomer, etc.) constituting the bead filler.

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 the temperature of the test piece (with notch processing) using a Charpy impact tester (manufactured by Yasuda Seiki Co., Ltd., product name: 141 type) according to the method specified in JIS K7111-1: 2012. Measure under the condition of 23 ° C.
For example, by measuring the angle returned after colliding with a sample under the conditions of a nominal pendulum energy (capacity) of 2J and a hammer lifting angle of 150 °, the amount of energy consumed (energy) from the difference in angle before and after the collision. Absorption amount) is calculated.

The adjustment of the Charpy impact strength of the bead filler can be adjusted, for example, by selecting the material constituting the bead filler (for example, amorphous resin, thermoplastic elastomer, etc.).

[Bead core: bead wire]
The bead wire is not particularly limited, and for example, a metal cord used for a conventional rubber tire, an organic resin cord, or the like can be appropriately used. For example, it is composed of a monofilament (single wire) such as a metal fiber or an organic fiber, or a multifilament (twisted wire) obtained by twisting these fibers. Of these, a metal cord (more preferably an iron cord (steel cord)) is preferable.

As the bead wire in the present embodiment, a monofilament (single wire) is preferable from the viewpoint of further improving the durability of the tire. The cross-sectional shape, size (diameter), and the like of the bead wire are not particularly limited, and those suitable for a desired tire can be appropriately selected and used.
When the bead wire is a stranded wire of a plurality of cords, the number of the plurality of cords includes, for example, 2 to 10, preferably 5 to 9.

From the viewpoint of achieving both internal pressure resistance and weight reduction of the tire, the thickness of the bead wire is preferably 0.3 mm to 3 mm, more preferably 0.5 mm to 2 mm. The thickness of the bead wire is a number average value of the thickness measured at five arbitrarily selected cross sections (cross sections perpendicular 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 type 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 type chuck with a tensile tester.

[Bead core: coating resin layer]
The bead core preferably has a coating resin layer that covers the bead wire from the viewpoint of improving the adhesiveness with the bead filler and reducing the rigidity step between the bead filler and the bead wire. The coating resin layer is arranged in direct contact with the bead wire or in contact with another layer.

The coating resin layer contains a resin. Examples of the resin contained in the coating resin layer include a thermoplastic resin, a thermoplastic elastomer, and a thermosetting resin.
From the viewpoint of moldability, the coating resin layer preferably contains a thermoplastic resin or a thermoplastic elastomer as the resin, and more preferably contains a thermoplastic elastomer. Among the thermoplastic elastomers, it is particularly preferable to contain at least one of a polyamide-based thermoplastic elastomer and a polyester-based thermoplastic elastomer.

The coating resin layer may contain at least a resin, and may contain other components such as additives as long as the effects of the present disclosure are not impaired. However, the content of the resin in the coated resin layer is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 75% by mass or more, based on the total amount of the coating resin layer.

Examples of the thermoplastic resin 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. Among these, as the thermoplastic resin, at least one selected from polyamide-based thermoplastic resin, polyester-based thermoplastic resin, and olefin-based thermoplastic resin is preferable, and it is selected from polyamide-based thermoplastic resin and polyester-based thermoplastic resin. At least one of these is more preferred.

Examples of the thermoplastic elastomer include polyamide-based thermoplastic elastomer (TPA), polyester-based thermoplastic elastomer (TPC), polystyrene-based thermoplastic elastomer (TPS), and polyurethane-based thermoplastic elastomer (TPU) specified in JIS K6418. Examples thereof include olefin-based thermoplastic elastomers (TPO), thermoplastic rubber cross-linked products (TPV), and other thermoplastic elastomers (TPZ). In the coating resin layer, these may be used alone or in combination of two or more.

In the bead member according to the present embodiment, when the bead filler is in direct contact with the bead core, the resin contained in the member (for example, the coating resin layer) constituting the surface of the bead core and the thermoplastic contained in the continuous phase of the bead filler. It is preferable that the elastomers have a common skeleton in the structural units that form the main chain of the resin.
Here, "having a common skeleton in the constituent units constituting the main chain of the resin" means that, for example, the continuous phase of the bead filler contains "polyester-based thermoplastic elastomer (TPC)" and the bead core. When the surface member contains "at least one of polyester-based thermoplastic elastomer (TPC) and polyester-based thermoplastic resin", a skeleton (that is, an ester-bonded skeleton) common to each other in the constituent units constituting the main chain of the resin. ).
Similarly, there is a case where the continuous phase of the bead filler and the surface member of the bead core contain the following resin.
-When both contain "polyamide-based thermoplastic elastomer (TPA)" and "at least one of polyamide-based thermoplastic elastomer (TPA) and thermoplastic polyamide" -both are "polystyrene-based thermoplastic elastomer (TPA)" When "polyplastic-based thermoplastic elastomer (TPA) and at least one kind of thermoplastic polystyrene" are contained.-Both are "polyurethane-based thermoplastic elastomer (TPA)" and "polyurethane-based thermoplastic elastomer (TPA) and thermoplastic polyurethane. When "at least one kind" is contained-When both contain "olefin-based thermoplastic elastomer (TPA)" and "at least one kind of olefin-based thermoplastic elastomer (TPA) and thermoplastic olefin"

As the structural unit constituting the molecular structure of the resin, a 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 raw material of the resin). It is more preferable to use an elastomer).
Further, as a structural unit constituting the molecular structure of the resin, a thermoplastic resin or a thermoplastic elastomer containing only a structural unit having the same chemical structure (for example, a thermoplastic resin or a thermoplastic resin using only a monomer having the same structure as a raw material of the resin). It is more preferable to use a thermoplastic elastomer).

The resin contained in the member (for example, the coating resin layer) constituting the surface of the bead core and the thermoplastic elastomer contained in the continuous phase of the bead filler have a common skeleton in the constituent units constituting the main chain of the resin. As a result, 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 in addition to the resin. Examples of other components include rubber, various fillers (for example, silica, calcium carbonate, clay, etc.), anti-aging agents, oils, plasticizers, color formers, weather resistant 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 μm or more and 1000 μm or less, and more preferably 30 μm or more and 700 μm or less.

The thickness of the coated resin layer is from the surface of the coated resin layer on the bead wire side (for example, the interface with the bead wire or the adhesive layer) to the outer surface of the coated resin layer (the surface opposite to the bead wire side). Refers to the length of the shortest part of the length of.
The thickness of the coating resin layer is measured from five magnified images obtained by acquiring magnified images of a cross section perpendicular to the length direction of the bead wire with a microscope such as a video microscope. The thickness of the minimum thickness portion of the layer is measured and used as the average value.

[Bead core: Adhesive layer]
The bead member according to the present embodiment may have an adhesive layer between the bead wire and the coating resin layer. The material of the adhesive layer is not particularly limited, and the adhesive used in the bead portion of the tire can be used.

The adhesive layer is preferably a layer containing a resin (adhesive resin layer), and the resin is preferably a thermoplastic resin or a thermoplastic elastomer.

Examples of the thermoplastic elastomer 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 the 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.
The adhesive layer may use the thermoplastic elastomer alone or in combination of two or more.

When the adhesive layer contains a resin, the content of the resin is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 75% by mass or more of the entire adhesive layer. ..

The average thickness of the adhesive layer is not particularly limited, but is preferably 5 μm to 500 μm, more preferably 20 μm to 150 μm, and 20 μm to 100 μm from the viewpoint of riding comfort during running and tire durability. It is more preferable to have.

The average thickness of the adhesive layer is the thickness of the adhesive layer measured from an enlarged image obtained by acquiring a magnified image of a cross section perpendicular to the length direction of the bead wire with a microscope such as a video microscope from any five points. Let it be the average value of the numbers. The thickness of the adhesive layer in each enlarged image is the part with the smallest thickness (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 the minimum). ) Is the value measured.

Further, 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 is preferable, and 0.1 or more and 0.35 or less is more preferable. When _{the value of T 1} / T ₂ is in the above range, the riding comfort during running is excellent as compared with the case where the value is smaller than the above range, and the durability of the tire is superior as compared with the case where the value is larger than the above range.

<Tire>
Next, a tire according to an embodiment of the present disclosure, which has a bead member for a tire according to the embodiment in a pair of bead portions, will be described.

[First Embodiment]
Hereinafter, as an example of the tire according to the present embodiment, a run-flat tire will be taken as an example and will be described with reference to the drawings.
FIG. 1 shows one side of a cut surface cut along the tire width direction of the tire 10 of the first embodiment. In the figure, the arrow TW indicates the width direction of the tire 10 (tire width direction), and the arrow TR indicates the radial direction of the tire 10 (tire radial direction). The tire width direction referred to here refers to a direction parallel to the rotation axis of the tire 10, and is also referred to as a tire axis direction. Further, the tire radial direction means a direction orthogonal to the rotation axis of the tire 10. Further, the reference numeral CL indicates the equator of the tire 10 (tire equator).

Further, in the first embodiment, the rotation axis side of the tire 10 is "inside in the tire radial direction" along the tire radial direction, and the side opposite to the rotation axis of the tire 10 is "outside in the tire radial direction" along the tire radial direction. It is described as. On the other hand, the tire equatorial CL side along the tire width direction is described as "inside in the tire width direction", and the side opposite to the tire equatorial CL along the tire width direction is described as "outside in the tire width direction".

FIG. 1 shows a 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 here refers to the standard rim in the applicable size described in the Year Book 2017 edition of JATMA (Japan Automobile Tire Association). The standard air pressure is the air pressure corresponding to the maximum load capacity of JATTA's Tire Book 2017 version.

In the following description, the load is the maximum load (maximum load capacity) of a single wheel in the applicable size described in the following standard, and the internal pressure is the maximum load of a single wheel described in the following standard. It is the air pressure corresponding to (maximum load capacity), and the rim is the standard rim (or "Approved Rim", "Recommended Rim") in the applicable size described in the following standard. The standards are set by industrial standards that are valid in the area where the tire is produced or used. For example, in the United States, "The Tire and Rim Association Inc.'s Year Book", in Europe, "The European Tire and Rim Technical Organization's Standard Tire", in Japan, Japan, Japan Has been done.

The tire 10 of the first embodiment shown in FIG. 1 is a tire having a flatness of 55 or more, and the tire cross-sectional height (tire section height) SH is set to 115 mm or more. The section height (tire cross-sectional height) SH referred to here is a length of 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 internal pressure is the standard air pressure. Point to. Further, in the first embodiment, the flatness of the tire 10 is set to 55 or more and the tire cross-sectional height SH is set to 115 mm or more, but the present disclosure is not limited to this configuration.

As shown in FIG. 1, the tire 10 has 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 extending outward in the tire radial direction from the pair of bead portions 12. It has a portion 14 and a tread portion 16 extending from one tire side portion 14 to the other tire side portion 14. The tire side portion 14 bears the load acting on the tire 10 during running (including during run-flat running).

As shown in FIG. 1, 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 carcass 22 of the first embodiment is locked by folding the end side around the bead core 18 from the inside to the outside of the tire, and the end 22C of the folded portion 22B is in contact with the carcass main body 22A. In the first embodiment, the end portion 22C of the carcass 22 is arranged in a range (region) corresponding to the tire side portion 14, but the present disclosure is not limited to this configuration. For example, the end portion 22C of the carcass 22 may be arranged in a range corresponding to the tread portion 16, particularly in a range corresponding to the belt layer 24A.

The carcass 22 extends from one bead core 18 to the other bead core 18 in a toroidal manner to form the skeleton of the tire 10.

A plurality of (two layers in the first embodiment) belt layers 24A are provided on the outer side of the carcass main body 22A in the tire radial direction. A cap layer 24B is provided on the outer side of the belt layer 24A in the tire radial direction. The cap layer 24B covers the entire belt layer 24A.

A pair of layer layers 24C are provided on the outer side of 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 configuration, and only one end of the cap layer 24B may be covered with the layer layer 24C, and both ends of the cap layer 24B may be continuous in the tire width direction. It may be covered with. Further, the cap layer 24B and the layer layer 24C may be omitted according to the specifications of the tire 10.

Further, for the carcass 22, the belt layer 24A, the cap layer 24B and the layer layer 24C, the structures of the respective members used in conventionally known tires (including run-flat tires) can be used.

A tread portion 16 is provided on the outer side of the belt layer 24A, the cap layer 24B, and the layer layer 24C in the tire radial direction. The tread portion 16 is a portion that comes into contact with 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 groove in the width direction (not shown) extending in the tire width direction. The shape and number of the circumferential groove 16A and the width direction groove are appropriately set according to the performance such as drainage property and steering stability required for the tire 10.

A bead filler 20 is embedded in the bead filler portion 12 so as to extend from the bead core 18 outward in the tire radial direction along the outer surface 22O of the carcass 22. In the first embodiment, the bead filler 20 is arranged in a region surrounded by the carcass main body portion 22A and the folded-back portion 22B. The outer surface 22O of the carcass 22 is the outer surface of the tire in the carcass main body 22A and the inner surface of the tire in the folded-back portion 22B. Further, in the first embodiment, the end portion 20A of the bead filler 20 on the outer side in the tire radial direction is inserted into the tire side portion 14. Further, the thickness of the bead filler 20 decreases toward the outside in the tire radial direction.

The height BH of the bead filler 20 shown in FIG. 1 is preferably set within the range of 30 to 50% of the tire cross-sectional height SH. The height BH of the bead filler 20 referred to 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 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. Refers to the height up to (the length along the tire radial direction). Here, when the height BH of the bead filler 20 is 30% or more of the tire cross-sectional height SH, for example, sufficient durability during run-flat running can be ensured. Further, since the height BH of the bead filler 20 is 50% or less of the tire cross-sectional height SH, the riding comfort is excellent.

Further, in the first embodiment, the end portion 20A of the bead filler 20 is arranged inside the maximum width position of the tire 10 in the tire radial direction. The maximum width position of the tire 10 here refers to the position having the widest width along the tire width direction of the tire 10.

-Bead core As shown in FIG. 2, the bead core 18 has a plurality of bead wires 1 arranged side by side and a coating resin layer 3 for coating the bead wires 1.
In the above configuration, "arranged side by side" means that a plurality of bead wires 1 do not intersect with each other in the bead member cut to a length required for application to a tire.

Here, the possible forms of the bead core 18 shown in FIG. 2 will be described with reference to a plurality of examples.
FIG. 3A is a diagram schematically showing a cross section when a part of the bead core 18 is cut perpendicularly to the length direction of the bead wire 1. In FIG. 3A, the coating resin layer 3 is provided so as to be in direct contact with the three bead wires 1. Further, one bead wire 1 may be heat-welded and stepped horizontally and vertically to produce the bead wire 1.

Further, the bead core 18 may have an adhesive layer 2 arranged between the bead wire 1 and the coating resin layer 3. The adhesive layer 2 is preferably the above-mentioned adhesive resin layer.
A part of the bead core 18 shown in FIG. 3B is provided with an adhesive layer 2 on the surface of each of the three bead wires 1, and further provided with a coating resin layer 3 on the surface thereof.

Further, the adhesive layer 2 arranged between the bead wire 1 and the coating resin layer 3 may be connected so as to include a plurality of bead wires 1.
A part of the bead core 18 shown in FIG. 3C is provided with an adhesive layer 2 connected so as to include three bead wires 1, and a coating resin layer 3 is further provided on the surface of the connected adhesive layer 2. It is provided.

Although 3A to 3C show a mode in which three bead wires 1 are arranged in parallel, the number of the bead wires 1 may be 2 or less or 4 or more.
Further, the bead core 18 shown in FIG. 2 has three bead wires 1 shown in any one of FIGS. 3A to 3C, a coating resin layer 3 (and an adhesive layer 2 in FIGS. 3B and 3C). It is in a layered form. However, the bead core 18 may be used as one layer or may be used by laminating two or more layers. In that case, it is preferable to weld between the coating resins.
Further, although the possible forms of the bead core 18 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. For example, in the case of producing the bead core 18 shown in FIG. 3B, it 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. In this case, the shape of the cross section of the adhesive layer 2 can be adjusted by a method such as changing the shape of the base used for extrusion molding.

-Side Reinforcing Layer The tire side portion 14 is provided with a side reinforcing rubber 26 as an example of a side reinforcing layer that reinforces the tire side portion 14 inside the carcass 22 in the tire width direction. The side reinforcing rubber 26 is a reinforcing rubber for traveling a predetermined distance while supporting the weights of the vehicle and the occupant when the internal pressure of the tire 10 is reduced due to a flat tire or the like.

The side reinforcing rubber 26 extends from the bead core 18 side to the tread portion 16 side in the tire radial direction along the inner surface 22I of the carcass 22. Further, the side reinforcing rubber 26 has a shape in which the thickness decreases toward 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 referred to here 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 the standard air pressure.

Further, in the side reinforcing rubber 26, the end portion 26A on the tread portion 16 side overlaps the tread portion 16 with the carcass 22 (carcass main body portion 22A) interposed therebetween. Specifically, the end portion 26A of the side reinforcing rubber 26 overlaps with 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 term "breaking elongation" as used herein refers to the breaking elongation (%) measured based on JIS K6251: 2010 (using a dumbbell-shaped No. 3 test piece). In the first embodiment, the side reinforcing rubber 26 is composed of one type of rubber material, 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 materials. ..
Further, in the first embodiment, the side reinforcing rubber 26 containing rubber as a main component is used as an example of the side reinforcing layer, but the present disclosure is not limited to this configuration, and the side reinforcing layer is formed of another material. You may. For example, a side reinforcing layer containing a thermoplastic resin or the like as a main component may be formed. The side reinforcing rubber 26 may also contain materials such as fillers, short fibers, and resins.

Further, the midpoint of the overlapping portion 28 that overlaps with the side reinforcing rubber 26 across the carcass 22 of the bead filler 20 (that is, the end portion 20A of the bead filler 20 and the end portion 26B of the side reinforcing rubber 26 along the extending direction of the carcass 22). The thickness GB of the side reinforcing rubber 26 at the midpoint) Q is preferably set within the range of 40 to 80% of the maximum thickness GA of the side reinforcing rubber 26. By setting the thickness GB of the side reinforcing rubber 26 to 40 to 80% or less of the maximum thickness GA in this way, even if a buckling phenomenon occurs in the tire side portion 14, the side reinforcing rubber It is possible to prevent the 26 from being damaged (as an example, cracking). In the first embodiment, 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. Further, the maximum width position of the carcass 22 referred to here refers to the position having the widest width along the tire width direction of the carcass 22.

The height LH from the end 26B of the side reinforcing rubber 26 to the tip of the bead portion 12 when the tire 10 is assembled to the standard rim 30 and the internal pressure is the standard air pressure is 50 to 80% of the height BH of the bead filler 20. It is preferable that the height is set within the range of. Here, when the height LH is 80% or less of the height BH, durability during run-flat running can be easily ensured. Further, since the height LH is 50% or more of the height BH, the riding comfort is excellent.

Since the tire 10 of the first embodiment is intended for the tire 10 having a high tire cross-sectional height SH, a rim guard (rim protection) is not provided. However, the present disclosure is not limited to this configuration, and a rim guard is provided. May be 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. In the tire 10 of the first embodiment, 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. ..

Further, in the above-described embodiment, as shown in FIG. 1, 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 is not limited to this configuration. May be composed of a plurality of types of rubber (or resin). For example, the side reinforcing rubber 26 may be configured by stacking a plurality of types of rubber (or resin) different in the tire radial direction, or the side reinforcing rubber 26 may be configured by stacking a plurality of types of rubber (or resin) different in the tire width direction. May be.

-Material The tire 10 shown in FIG. 1 is mainly composed of an elastic material. That is, the region around the carcass 22 in the bead portion 12, the region outside the carcass 22 in the tire width direction in the tire side portion 14, the side reinforcing layer (side reinforcing rubber 26), the belt layer 24A in the tread portion 16, the cap layer 24B, and the tread portion 16. The region other than the layer layer 24C, etc. is made of an elastic material.

Examples of the elastic material include a rubber material (so-called rubber tire), a resin material (so-called resin tire), and the like.
In particular, in the tire 10 shown in FIG. 1, it is preferable that each of the above parts is a rubber tire made of a rubber material.

(Elastic material: rubber material)
The rubber material may 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. However, the content of rubber (rubber component) in the rubber material is preferably 50% by mass or more, more preferably 90% by mass or more, based on the total amount of the rubber material.

The rubber component used for 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. .. For example, the rubbers shown below, or a blend of two or more of these rubbers 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.
As the synthetic rubber, various diene-based synthetic rubbers, diene-based copolymer rubbers, special rubbers, modified rubbers, and the like can be used. Specifically, for example, a butadiene polymer such as polybutadiene (BR), a copolymer of butadiene and an aromatic vinyl compound (for example, SBR, NBR, etc.), a copolymer of butadiene and another diene compound; Isoprene-based polymers such as polyisoprene (IR), copolymers of isoprene and aromatic vinyl compounds, copolymers of isoprene and other diene-based compounds; chloroprene rubber (CR), butyl rubber (IIR), halogenated Butyl rubber (X-IIR); ethylene-propylene-based copolymer rubber (EPM), ethylene-propylene-diene-based copolymer rubber (EPDM), and any blends thereof and the like can be mentioned.

Further, in the rubber material used for the tire according to the first embodiment, other components such as additives may be added to the rubber depending on the purpose.
Examples of the additive include a reinforcing material such as carbon black, a filler, a vulcanizing agent, a vulcanization accelerator, a fatty acid or a salt thereof, a metal oxide, a process oil, an antiaging agent, and the like, and these are appropriately blended. can do.

A tire formed of a rubber material is obtained by molding an unvulcanized rubber material in which the contained rubber is in an unvulcanized state into a tire shape and vulcanizing the rubber by heating.

-Manufacture of a tire As a method of manufacturing a tire 10 of the first embodiment, an inner liner (not shown) made of a rubber material, a bead core 18, a bead filler 20, and a cord are attached to an elastic material (not shown) on the outer circumference of a known tire forming drum. From the carcass 22 coated with (for example, rubber material, resin material, etc.), the region outside the tire width direction of the carcass 22 in the tire side portion 14 formed of the elastic material (for example, rubber material, resin material, etc.), and the side reinforcing rubber 26. Form an unrubbered tire case.

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 on 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. When the wire is coated with a resin, the coated resin may be welded to the tread portion 16 by heating and pressurizing.
Finally, an unvulcanized tread is attached to the outer peripheral surface of the belt layer 24A to obtain a raw tire. The raw tire produced in this manner is vulcanized and molded by a vulcanization molding mold to complete the tire 10.

[Second Embodiment]
Next, another embodiment of the tire according to the present embodiment will be described with reference to the drawings.
FIG. 4 shows one side of a cut surface cut along the tire width direction of the tire 110 of the second embodiment. In the figure, the arrow TW indicates the width direction of the tire 110 (that is, the tire width direction), and the arrow TR indicates the radial direction of the tire 110 (that is, the tire radial direction).

As shown in FIG. 4, the tire 110 has 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 in the tire radial direction from the pair of bead portions 112. It has a portion 114 and a tread portion 116 extending from one tire side portion 114 to the other tire side portion 114.

The tire 110 shown in FIG. 4 includes a tire case 140 corresponding to a tire skeleton body. The tire case 140 is formed by 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.

Further, a protective layer 122 is provided on a part of the tire side portion 114 and the bead portion 112 on the outside in the tire width direction, the bead portion 112 on the inside in the tire radial direction, and the bead portion 112 on the inside in the tire width direction. The tire case 140 may have a bead portion 112, a tire side portion 114, and a tread portion 116 integrally formed in the same process, or may be a combination of members formed in different processes. However, from the viewpoint of production efficiency, it is preferable that the tires are integrally formed.

Further, a bead filler 120 extending from the bead core 118 outward in the tire radial direction along the protective layer 122 is embedded in the bead portion 112. The bead filler 120 has a thickness decreasing toward the outside in the tire radial direction.

The bead portion 112 is a portion that comes into contact with a rim (not shown), and an annular bead core 118 extending along the tire circumferential direction is embedded in the bead portion 112. The form that the bead core 118 can take is the same as the form described in the first embodiment described above.

The protective layer 122 is provided for the purpose of improving 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 has higher 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 and a belt member). Further, a tread 130 is provided on the belt layer 124A via the cushion rubber 124B. The materials of the belt layer 124A, the cushion rubber 124B, and the tread 130 are not particularly limited, and can be selected from materials generally used in tire manufacturing (for example, wire such as metal wire and organic resin wire, resin, rubber material, etc.). it can.

-Material The tire case 140 (an example of a tire skeleton) is made of an elastic material. That is, the tire skeleton is formed of a rubber material as an elastic material (so-called tire skeleton for rubber tires), a mode formed of a resin material as an elastic material (so-called tire skeleton for resin tires), and the like. Can be mentioned.
In particular, in the tire 110 shown in FIG. 4, it is preferable that each of the above parts is a resin tire made of a resin material.

(Elastic material: Resin material)
The resin material may contain at least a resin (that is, a resin component), and may contain other components such as additives as long as the effects of the present disclosure are not impaired. However, the content of the resin (that is, the resin component) in the resin material is preferably 50% by mass or more, more preferably 90% by mass or more, based on the total amount of the resin material. The tire skeleton body can be formed by using, for example, a resin material.

Examples of the resin contained in the tire skeleton include a thermoplastic resin, a thermoplastic elastomer, and a thermosetting resin.

Examples of the thermosetting resin include phenol-based thermosetting resins, urea-based thermosetting resins, melamine-based thermosetting resins, epoxy-based thermosetting resins, and the like.
Examples of the thermoplastic resin 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. These may be used alone or in combination of two or more. Among these, as the thermoplastic resin, at least one selected from polyamide-based thermoplastic resin, polyester-based thermoplastic resin, and olefin-based thermoplastic resin is preferable, and selected from polyamide-based thermoplastic resin and olefin-based thermoplastic resin. At least one of these is more preferred.

Examples of the thermoplastic elastomer include a polyamide-based thermoplastic elastomer (TPA), a polystyrene-based thermoplastic elastomer (TPS), a polyurethane-based thermoplastic elastomer (TPU), and an olefin-based thermoplastic elastomer (TPO) specified in JIS K6418. Examples thereof include polyester-based thermoplastic elastomers (TPEE), thermoplastic rubber cross-linked products (TPV), and other thermoplastic elastomers (TPZ).
Considering the elasticity required during running, the moldability at the time of manufacturing, etc., it is preferable to use at least one of a thermoplastic resin and a thermoplastic elastomer as the resin material for forming the tire skeleton, and it is preferable to use at least one of the thermoplastic resin and the thermoplastic elastomer during running. From the viewpoint of riding comfort, it is more preferable to contain a thermoplastic elastomer. Above all, it is more preferable to contain at least one of a polyamide-based thermoplastic elastomer and a polyester-based thermoplastic elastomer.

-Other ingredients-
The elastic material (for example, rubber material or resin material) may contain other components other than rubber or resin, if desired. Examples of other components include resins, rubbers, various fillers (for example, silica, calcium carbonate, clay), antioxidants, oils, plasticizers, colorants, weathering agents, reinforcing materials and the like.

-Physical characteristics of elastic materials-
When a resin material is used as the elastic material (that is, in the case of a tire skeleton for a resin tire), 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 of the elastic material (or the tire skeleton body containing the elastic material) itself specified in JIS K7113: 1995 is preferably 50 MPa to 1000 MPa, more preferably 50 MPa to 800 MPa, and particularly preferably 50 MPa to 700 MPa. When the tensile elastic modulus of the elastic material is 50 MPa to 1000 MPa, the rim assembly can be efficiently performed while maintaining the shape of the tire skeleton.

The tensile strength of the elastic material (or the tire skeleton body containing the elastic material) itself specified in JIS K7113 (1995) is usually about 15 MPa to 70 MPa, preferably 17 MPa to 60 MPa, and even more preferably 20 MPa to 55 MPa.

The tensile yield strength specified in JIS K7113 (1995) of the elastic material (or the tire skeleton body containing 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. When the tensile yield strength of the elastic material is 5 MPa or more, it can withstand deformation due to a load applied to the tire during running or the like.

The tensile yield elongation specified in JIS K7113 (1995) of the elastic material (or the tire skeleton body containing the elastic material) itself is preferably 10% or more, more preferably 10% to 70%, and particularly preferably 15% to 60%. preferable. When 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 tensile elongation at break specified in JIS K7113 (1995) of the elastic material (or the tire skeleton body containing the elastic material) itself is preferably 50% or more, more preferably 100% or more, particularly preferably 150% or more, and 200%. The above is the most preferable. When the tensile elongation at break of the elastic material is 50% or more, the rim assembly property is good and it is possible to make it difficult to break due to a collision.

The deflection temperature under load (specifically, under a 0.45 MPa load) specified in ISO 75-2 or ASTM D648 of the elastic material (or the tire skeleton body containing the elastic material) is preferably 50 ° C. or higher, and is preferably 50 ° C. to 150 ° C. is more preferable, and 50 ° C. to 130 ° C. is particularly preferable. When the deflection temperature under load of the elastic material is 50 ° C. or higher, deformation of the tire skeleton can be suppressed even when vulcanization is performed in the production of the tire.

-Manufacturing of tires The method of manufacturing the tire case 140 is not particularly limited. For example, the tire case halves in a state where the tire case 140 is divided by the equator surface (the surface indicated by CL in FIG. 4) are manufactured by an injection molding method or the like, and the tire case halves are joined to each other on the equator surface. It may be produced by.
As 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 on 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. When the wire is coated with a resin, the coated resin may be welded to the tread portion 116 by heating and pressurizing.
As a method of forming the bead filler 120 and the bead core 118 in the bead portion 112 of the tire case 140, for example, 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 with.

The tires of the present disclosure have been described above with reference to the first and second embodiments, but these embodiments are examples, and the present disclosure is carried out with various modifications without departing from the gist thereof. can do. It goes without saying that the scope of rights of the present disclosure is not limited to these embodiments.

[Third Embodiment]
Next, another embodiment of the tire according to the present embodiment will be described with reference to the drawings.
FIG. 5 shows one side of a cut surface cut along the tire width direction of the tire 210 of the third embodiment. In the figure, the arrow TW indicates the width direction of the tire 210 (that is, the tire width direction), and the arrow TR indicates the radial direction of the tire 210 (that is, the tire radial direction). The tire width direction referred to here refers to a direction parallel to the rotation axis of the tire 210, and is also referred to as a tire axis direction. Further, the tire radial direction means a direction orthogonal to the rotation axis of the tire 210. Further, the reference numeral CL indicates the equator of the tire 210 (that is, the equator of the tire).

Further, in the third embodiment, the rotation axis side of the tire 210 is "inside in the tire radial direction" along the tire radial direction, and the side opposite to the rotation axis of the tire 210 is "outside in the tire radial direction" along the tire radial direction. It is described as. On the other hand, the tire equatorial CL side along the tire width direction is described as "inside in the tire width direction", and the side opposite to the tire equatorial CL along the tire width direction is described as "outside in the tire width direction".

FIG. 5 shows a tire 210 when mounted on a standard rim 230 (indicated by a chain double-dashed line in FIG. 5) and filled with standard air pressure. The standard rim here refers to the standard rim in the applicable size described in the Year Book 2017 edition of JATMA (Japan Automobile Tire Association). The standard air pressure is the air pressure corresponding to the maximum load capacity of JATTA's Tire Book 2017 version.

In the following description, the load is the maximum load (maximum load capacity) of a single wheel in the applicable size described in the following standard, and the internal pressure is the maximum load of a single wheel described in the following standard. It is the air pressure corresponding to (maximum load capacity), and the rim is the standard rim (or "Approved Rim", "Recommended Rim") in the applicable size described in the following standard. The standards are set by industrial standards that are valid in the area where the tire is produced or used. For example, in the United States, "The Tire and Rim Association Inc.'s Year Book", in Europe, "The European Tire and Rim Technical Organization's Standard Tire", in Japan, Japan, Japan Has been done.

The tire 210 of the third embodiment shown in FIG. 5 is a tire having a flatness of 55 or more, and the tire cross-sectional height (tire section height) SH is set to 115 mm or more. The section height (tire cross-sectional height) SH referred to here is the length of 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. Further, in the third embodiment, the flatness of the tire 210 is set to 55 or more and the tire cross-sectional height SH is set to 115 mm or more, but the present disclosure is not limited to this configuration.

As shown in FIG. 5, the tire 210 has 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 in the tire radial direction from the pair of bead portions 212. It has a portion 214 and a tread portion 216 extending from one tire side portion 214 to the other tire side portion 214. The tire side portion 214 bears the load acting on the tire 210 during traveling (including during run-flat traveling).

As shown in FIG. 5, bead cores 218 are embedded in the pair of bead portions 212, respectively. 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 carcass 222 of the third embodiment is locked by folding the end side around the bead core 218 from the inside to the outside of the tire, and the end 222C of the folded portion 222B is in contact with the carcass main body 222A. In the third embodiment, the end portion 222C of the carcass 222 is arranged in a range (region) corresponding to the tire side portion 214, but the present disclosure is not limited to this configuration. For example, the end 222C of the carcass 222 may be arranged in a range corresponding to the tread portion 216, particularly in a range corresponding to the belt layer 224A.

The carcass 222 extends from one bead core 218 to the other bead core 218 in a toroidal manner to form the skeleton of the tire 210.

A plurality of belt layers 224A (two layers in the third embodiment) are provided on the outer side of the carcass main body 222A in the tire radial direction. A cap layer 224B is provided on the outer side of 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 on the outer side of 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 configuration, and only one end of the cap layer 224B may be covered with the layer layer 224C, and both ends of the cap layer 224B may be continuous in the tire width direction. It may be covered with. Further, the cap layer 224B and the layer layer 224C may be omitted according to the specifications of the tire 210.

Further, for the carcass 222, the belt layer 224A, the cap layer 224B, and the layer layer 224C, the structures of the respective members used in conventionally known tires (including run-flat tires) can be used.

A tread portion 216 is provided on the outer side of the belt layer 224A, the cap layer 224B, and the layer layer 224C in the tire radial direction. The tread portion 216 is a portion that comes into contact with 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. Further, the tread portion 216 is formed with a groove in the width direction (not shown) extending in the tire width direction. The shape and number of the circumferential groove 216A and the width direction groove are appropriately set according to the performance such as drainage property and steering stability required for the tire 210.

A bead filler 200 extending from the bead core 218 to the outside in the tire radial direction along the outer surface 222O of the carcass 222 is embedded in the bead filler bead portion 212. Specifically, the bead filler 200 is embedded in a region surrounded by the carcass main body 222A and the folded portion 222B.
Specifically, the first bead filler 201 is arranged in a region including the tire radial outer side with respect to the bead core 218. The first bead filler 201 has a shape extending outward in the tire radial direction from the region where the bead core 218 is arranged. In the third embodiment, the first bead filler 201 is formed so as to cover the entire surface of the bead core 218, that is, it is arranged up to the region inside the bead core 218 in the tire radial direction.
The second bead filler 202 is arranged in a region including the outside of the first bead filler 201. The second bead filler 202 is arranged and the second bead filler 202 is arranged so that there is an area where the first bead filler 201 is arranged and the area where the second bead filler 202 is arranged in the tire radial direction. The bead filler 202 is in contact with a part of the outer surface of the first bead filler 201 in the tire width direction. The second bead filler 202 has a shape extending outward in the tire radial direction from the contact surface of the first bead filler 201.
In the bead filler 200 of the third embodiment, the closer to the inner side in the tire radial direction (that is, the bead wire side), the larger the volume occupied by the first bead filler 201 than the volume occupied by the second bead filler 202. On the other hand, 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 202 than the volume occupied by the first bead filler 201.
The outer surface 222O of the carcass 222 is the outer surface of the tire in the carcass main body 222A and the inner surface of the tire in the folded portion 222B. Further, in the third embodiment, the tire radial outer end portion 200E of the second bead filler 202 is inserted into the tire side portion 214.

The height BH of the bead filler 200 shown in FIG. 5 is preferably set within the range of 30 to 50% of the tire cross-sectional height SH. The height BH of the bead filler 200 referred to here 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 in a state where the tire 210 is assembled to the standard rim 230 and the internal pressure is set to the standard air pressure. Refers to the height up to (the length along the tire radial direction). Here, when the height BH of the bead filler 200 is 30% or more of the tire cross-sectional height SH, for example, sufficient durability during run-flat running can be ensured. Further, since the height BH of the bead filler 200 is 50% or less of the tire cross-sectional height SH, the riding comfort is excellent.

Further, in the third embodiment, the end portion 200E of the bead filler 200 is arranged inside the maximum width position of the tire 210 in the tire radial direction. The maximum width position of the tire 210 referred to here refers to the position having the widest width along the tire width direction of the tire 210.

Before forming the first bead filler (for example, by injection molding), an adhesive is applied to at least one of the bead core and the second bead filler to form the coating resin layer, the first bead filler, and the second bead filler. The adhesiveness of the first bead filler may be improved.

-Bead core As shown in FIG. 6, the bead core 218 has a plurality of bead wires 1 arranged side by side, and a coating resin layer 3 that covers the bead wires 1 and contains a resin D.
In the above configuration, "arranged side by side" means that a plurality of bead wires 1 do not intersect with each other in the bead member cut to a length required for application to a tire.

Here, the possible forms of the bead core 218 shown in FIG. 6 are the same as those of the bead core 18 in the first embodiment described above, and the description thereof will be omitted here.

-Side Reinforcing Layer The possible form of the side reinforcing rubber 226 as an example of the side reinforcing layer is the same as that of the side reinforcing rubber 26 in the first embodiment described above, and the description thereof will be omitted here.

-Manufacture of a tire As a method of manufacturing a tire 210 according to a third embodiment, an inner liner (not shown) made of a rubber material, a bead core 218, and a bead filler 200 (first bead filler 201) are formed on the outer periphery of a known tire forming drum. And the second bead filler 202), the carcass 222 whose cord is coated with an elastic material (for example, rubber material, resin material, etc.), and the carcass 222 in the tire side portion 214 formed of the elastic material (for example, rubber material, resin material, etc.). An unvulcanized tire case composed of a region outside in the tire width direction and side reinforcing rubber 226 is formed.

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 on 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. When the wire is coated with a resin, the coated resin may be welded to the tread portion 216 by heating and pressurizing.
Finally, an unvulcanized tread is attached to the outer peripheral surface of the belt layer 224A to obtain a raw tire. The raw tire produced in this manner is vulcanized and molded by a vulcanization molding mold to complete the tire 210.

Hereinafter, the tires of the fourth to sixth embodiments will be described.
In the following description, the same tires as the tire 210 of the third embodiment are designated by the same reference numerals, and duplicate description will be omitted.

[Fourth Embodiment]
FIG. 7 is an enlarged cross-sectional view in the tire width direction showing the periphery of the bead portion of the tire of the fourth embodiment.
The tire of the fourth embodiment has the same configuration as the tire 210 of the first embodiment except that the arrangement positions of the first bead filler and the second bead filler are changed.
As shown in FIG. 7, the bead filler 200A is embedded in a region surrounded by the carcass main body 222A and the folded portion 222B. In the fourth embodiment, the first bead filler 201A is arranged in a region including the outer side in the tire radial direction with respect to the bead core 218. The first bead filler 201A has a shape extending outward in the tire radial direction from the region where the bead core 218 is arranged. In the fourth embodiment, the first bead filler 201A is formed so as to cover the entire surface of the bead core 218, that is, it is arranged up to the region inside the bead core 218 in the tire radial direction.
The second bead filler 202A is arranged in a region including the outside of the first bead filler 201A. The second bead filler 202A is arranged and the second bead filler 202A is arranged so that there is an overlapping region between the region where the first bead filler 201A is arranged and the region where the second bead filler 202A is arranged in the tire radial direction. The bead filler 202A is in contact with a part of the inner surface of the first bead filler 201A in the tire width direction. The second bead filler 202A has a shape extending outward in the tire radial direction from the contact surface of the first bead filler 201A.
In the bead filler 200A of the fourth embodiment, the closer to the inner side in the tire radial direction (that is, the bead wire side), the larger the volume occupied by the first bead filler 201A than the volume occupied by the second bead filler 202A. On the other hand, 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.

[Fifth Embodiment]
FIG. 8 is an enlarged cross-sectional view in the tire width direction showing the periphery of the bead portion of the tire according to the fifth embodiment.
The tire of the fifth embodiment has the same configuration as the tire 210 of the first embodiment except that the arrangement positions of the first bead filler and the second bead filler are changed.
As shown in FIG. 8, the bead filler 200B is embedded in a region surrounded by the carcass main body 222A and the folded portion 222B. In the fifth embodiment, the first bead filler 201B is arranged in a region inside the tire radial direction from a height of about half the height BH of the bead filler 200B, and the second bead filler 202B is a tire from the above height. It is located in the radial outer region.
The first bead filler 201B is arranged in a region including the outer side in the tire radial direction with respect to the bead core 218. The first bead filler 201B has a shape extending outward in the tire radial direction from the region where the bead core 218 is arranged. In the fifth embodiment, the first bead filler 201B is formed so as to cover the entire surface of the bead core 218, that is, it is arranged up to the region inside the bead core 218 in the tire radial direction.
The second bead filler 202B is arranged in a region including the outside of the first bead filler 201B. In the tire radial direction, there is no region that overlaps the region where the first bead filler 201B is arranged and the region where the second bead filler 202B is arranged, and the second bead filler 202B is the region of 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 outward in the tire radial direction from the contact surface of the first bead filler 201B.

[Sixth Embodiment]
FIG. 9 is an enlarged cross-sectional view in the tire width direction showing the periphery of the bead portion of the tire of the sixth embodiment.
The tire of the sixth embodiment is the same as the tire 210 of the third embodiment except that the first bead filler is not arranged in the area inside the bead core in the tire radial direction and the shape of the bead core is different. It is a composition.
As shown in FIG. 9, the bead portion 212 includes an annular bead core 218C in which nine bead wires 1 are coated with a coating resin layer 3C via an adhesive layer (not shown), and a bead filler 200C (first bead). It has a filler 201C and a second bead filler 202C). In the bead portion 212 of the sixth embodiment, 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 not arranged in the area inside the bead core 218C in the tire radial direction.

The present disclosure has been described above with reference to the first to sixth embodiments, but these embodiments are examples, and the present disclosure shall be carried out with various modifications within a range not deviating from the gist thereof. Can be done. It goes without saying that the scope of rights of the present disclosure is not limited to these embodiments.

In addition, one embodiment of the present disclosure includes the following aspects.
<1> A bead core having at least a bead wire and a bead filler arranged in direct contact with the bead core or in contact with each other via another layer.
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.
A bead member for a tire in which the tensile elastic modulus Ei of the discontinuous phase is higher than the tensile elastic modulus Es of the continuous phase.
<2> The bead member for a tire according to <1>, wherein the tensile elastic modulus Ei of the discontinuous phase is 500 MPa or more and 3000 MPa or less.
<3> The bead member for a 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 of <1> to <3> in which the ratio (Ei / Es) of the tensile elastic modulus Ei of the discontinuous phase to the tensile elastic modulus Es of the continuous phase is 500/400 to 3000/100. The bead member for a tire according to item 1.
<5> The bead member for a tire according to any one of <1> to <4>, wherein the bead filler has a tensile elastic modulus of 400 MPa or more and 1500 MPa or less.
<6> The bead member for a tire according to any one of <1> to <5>, wherein the amorphous resin is an amorphous resin having an ester bond.
<7> The tire use 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. Bead member.
<8> The bead member for a tire according to any one of <1> to <7>, wherein the thermoplastic elastomer is a polyester-based thermoplastic elastomer.
<9> The bead filler contains 5 parts by mass or more and 45 parts by mass or less of the amorphous resin with respect to 100 parts by mass of the total amount of the thermoplastic elastomer and the amorphous resin. The bead member for a tire according to any one of 8>.
<10> The tire according to any one of <1> to <9>, wherein the bead core has a coating resin layer arranged in direct contact with the bead wire or in contact with another layer. Bead member for.
<11> A tire having a pair of bead members for a tire according to any one of <1> to <10>.

Hereinafter, the present disclosure will be specifically described with reference to Examples, but the present disclosure is not limited to these descriptions. Unless otherwise specified, "part" represents a mass standard.

[Examples 1 to 8 and Comparative Examples 1 to 2]
<Making bead core>
A bead core according to the embodiment shown in FIG. 3B shown in the first embodiment described above is produced.
First, a monofilament (monofilament with an average diameter of φ1.25 mm, made of steel, strength: 2700 N, elongation: 7%) is used as the bead wire, and the adhesive resin shown in Table 1 that has been heated and melted is adhered to the bead wire and adhered. A layer to be a resin layer is formed.

Next, the bead wires on which the layer to be the adhesive resin layer was formed were installed in the mold so as to be arranged side by side, and the outer periphery of the layer to be the adhesive resin layer was extruded by an extruder to cover the coating shown in Table 1. Adhere resin to cover and cool. 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. By winding the member shown in FIG. 3B in which three bead wires are arranged while welding with hot air, the outer periphery of the nine bead wires is covered with a coating resin layer via an adhesive resin layer. Make a bead core.
The thickness of the adhesive resin layer (average thickness of the minimum portion) in the bead core is 50 μm, and the thickness of the coating resin layer (average thickness of the minimum portion) is 200 μm. The average distance between adjacent bead wires is 200 μm.

<Making bead members>
A bead member (a member composed of a bead core and a bead filler) according to the embodiments shown in FIGS. 1 and 2 shown in the first embodiment described above is produced.
First, a resin material for a bead filler containing the types of thermoplastic elastomer [A] and amorphous resin [B] shown in Table 1 in a ratio [A] / [B] (mass%) shown in Table 1 is prepared.
By setting the bead core in a mold in which the bead filler shape is processed in advance and injecting the resin material for the bead filler with an injection molding machine, the bead filler is arranged in direct contact with the outer periphery of the bead core. A bead member to have is manufactured. The mold temperature is 80 to 110 ° C., and the molding temperature is 200 to 270 ° C.

・ Continuous phase and discontinuous phase in cross section of bead filler (sea island structure)
By observing the cross section of the bead filler with an atomic force microscope (AFM), in Examples 1 to 8, the amorphous resin [B] was discontinuous in the continuous phase (sea region) of the thermoplastic elastomer [A]. It is expected that structures with interspersed phases (island regions) will be observed.
Further, in Comparative Example 1, it is predicted that the structure of the continuous phase and the discontinuous phase (sea island structure) is not observed.
Further, in Comparative Example 2, contrary to the Example, the discontinuous phase (island region) of the thermoplastic elastomer [A] is scattered in the continuous phase (sea region) of the amorphous resin [B]. The structure is expected to be observed.

-Tension elastic modulus The tensile elastic modulus Ei of the amorphous resin [B] and the tensile elastic modulus Es of the thermoplastic elastomer [A] were measured in accordance with JIS K7113: 1995. Specifically, a Tencilon universal tester (RTF-1210) manufactured by A & D Co., Ltd. was used, the tensile speed was set to 100 mm / min, and the tensile elastic modulus was measured. The results are shown in Table 1.
Specifically, it was molded into the shape of JIS No. 3 at a cylinder temperature of 200 ° C. to 270 ° C. and a mold temperature of 50 ° C. to 110 ° C. using an injection molding machine (NEX-50, manufactured by Nissei Jushi Kogyo Co., Ltd.) to prepare a measurement sample. Alternatively, a flat plate having a thickness of 110 mm × 110 mm and a thickness of t = 2 mm was formed and punched into a JIS No. 3 shape with a super dumbbell (registered trademark) manufactured by Dumbbell Co., Ltd. to prepare a measurement sample.

The tensile elastic modulus of the entire bead filler containing both the thermoplastic elastomer [A] and the amorphous resin [B] was calculated as follows. The results are shown in Table 1.
First, a mixed resin A containing 25% by mass of the thermoplastic elastomer [A] and 75% by mass of the thermoplastic elastomer 4767N (manufactured by Toray DuPont, polyester-based thermoplastic elastomer, product name: Hytrel 4767N) is prepared. ..
Next, the mixed resin A alone, the mixture B of 80% by mass of the mixed resin A and 20% by mass of the amorphous resin [B], the mixture C of 60% by mass of the mixed resin A and 40% by mass of the amorphous resin [B], and the mixture. For the mixture D of the resin A 40% by mass and the amorphous resin [B] 60% by mass, the tensile elasticity is measured by the same method as the above method (that is, the method for measuring the tensile elasticity Ei and the tensile elasticity Es), respectively. To do.
The tensile modulus value obtained in the above measurement is plotted against the content (mass%) of the amorphous resin [B], and the intercept value of the linear function obtained by the least squares method and the thermoplastic elastomer [ A] The difference ΔE (that is, ΔE = tensile elastic modulus Es − intercept) from the measured value of the tensile elastic modulus of a single substance is obtained.
Then, the value on the straight line obtained by translating the linear function in the y-axis direction by the difference ΔE (that is, the value on the straight line after correction) is used as the tensile elastic modulus of the entire bead filler at each mixing ratio.

The mixed resin A in which the thermoplastic elastomer [A] is the thermoplastic elastomer 5557 (polyester-based thermoplastic elastomer manufactured by Toray DuPont, product name: Hytrel 5557) is 60% by mass, and is used as an amorphous resin [B]. The cross section of the measurement sample prepared when the tensile elasticity was applied to the mixture C containing 40% by mass of amorphous resin 270 (amorphous polyester resin manufactured by Toyo Boseki Co., Ltd., product name: Byron 270) was shown as an interatomic force. A cross-sectional image observed with a microscope (AFM) is shown in FIG. In FIG. 10, a structure in which discontinuous phases (island regions) of the amorphous resin [B], which is an amorphous resin, are scattered in the continuous phase (sea region) of the mixed resin A containing the thermoplastic elastomer. Observed.

<Manufacturing tires with bead members as bead parts>
The tires (run-flat tires) of the aspects shown in FIGS. 1 and 2 shown in the first embodiment described above are manufactured by using the bead members for a pair of bead portions.
A carcass made of the bead member and a ply cord made of polyethylene terephthalate is prepared, and a tire side portion (outside of the carcass in the tire width direction) using a mixed rubber material of natural rubber (NR) and styrene-butadiene rubber (SBR). Area), side reinforcing rubber, and tread, and a stranded belt layer are used to make a raw tire.
The raw tire is heated (vulcanization of rubber) at 160 ° C. for 21 minutes.
The obtained tire has a tire size of 225 / 40R18 and a thickness of the tread portion of 10 mm.

[Examples 9 to 11]
In the first embodiment, the bead filler is changed to the bead filler shown in the third embodiment shown in FIGS. 5 and 6 (that is, the bead filler composed of two members of the first and second bead fillers). To make a tire.
Specifically, the production of the bead member is changed as follows.

<Making bead members>
A bead member (a member composed of a bead core, a first bead filler, and a second bead filler) according to the aspects shown in FIGS. 5 and 6 shown in the third embodiment described above is produced.
First, a resin material for a first bead filler containing the types of thermoplastic elastomer [A] and amorphous resin [B] shown in Table 2 in a ratio [A] / [B] (mass%) shown in Table 2. A resin material for a second bead filler containing the types of thermoplastic elastomer [A] and amorphous resin [B] shown in Table 2 in a ratio [A] / [B] (% by mass) shown in Table 2 is prepared. To do.
Next, the second bead filler is produced by injection molding using the resin material for the second bead filler. Next, the bead core and the second bead filler are installed in a mold in which the bead filler shape is processed in advance, and the resin material for the first bead filler is injection-molded to integrate the first bead filler and the second bead filler. The bead member that has become is produced. The mold temperature is 80 to 110 ° C., and the molding temperature is 200 to 270 ° C.

・ Continuous phase and discontinuous phase in cross section of bead filler (sea island structure)
By observing the cross section of the bead filler with an atomic force microscope (AFM), in Examples 9 and 10, in both the first and second bead fillers, in the continuous phase (sea region) of the thermoplastic elastomer [A]. It is expected that a structure in which discontinuous phases (island regions) of the amorphous resin [B] are scattered is observed.
Further, in Example 11, in the first bead filler, a structure in which the discontinuous phase (island region) of the amorphous resin [B] is scattered in the continuous phase (sea region) of the thermoplastic elastomer [A] is observed. Therefore, it is expected that the structure of continuous phase and discontinuous phase (sea island structure) is not observed in the second bead filler.
-Tension elastic modulus The tensile elastic modulus Ei of the amorphous resin [B] and the tensile elastic modulus Es of the thermoplastic elastomer [A] were measured in accordance with JIS K7113: 1995. Specifically, the measurement was performed according to the measurement method in Example 1. The results are shown in Table 2.
Further, the tensile modulus of the entire bead filler containing both the thermoplastic elastomer [A] and the amorphous resin [B] (that is, the tensile modulus of the entire first bead filler and the tensile modulus 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.

[Impact resistance (23 ° C)]
The impact resistance of each bead filler at a temperature of 23 ° C. was determined based on the value of the tensile elastic modulus of the entire bead filler. The results are shown in Tables 1 and 2.
Specifically, a bead filler in which the tensile elastic modulus of the entire bead filler is lower than the tensile elastic modulus of the entire bead filler in Comparative Example 2 is determined as A. On the other hand, a bead filler in which the tensile elastic modulus of the entire bead filler is equal to or higher than the tensile elastic modulus of the entire bead filler in Comparative Example 2 is determined as B.

[Run-flat runnability]
The run-flat runnability of the tires in each Example and Comparative Example was determined based on the value of the tensile elastic modulus of the entire bead filler. The results are shown in Tables 1 and 2.
Specifically, in Examples 1 to 8 and Comparative Examples 1 and 2, the tensile elastic modulus of the entire bead filler is higher than the tensile elastic modulus of the entire bead filler in Comparative Example 1, and the bead in Comparative Example 2 An example in which the tensile elastic modulus of the entire filler is lower than that of the entire filler is judged as A. On the other hand, an example in which the tensile elastic modulus of the entire bead filler is equal to or less than the tensile elastic modulus of the entire bead filler in Comparative Example 1 or equal to or greater than the tensile elastic modulus of the entire bead filler in Comparative Example 2 is determined as B.
Further, in Examples 9 to 11, both the tensile elastic modulus of the entire first bead filler and the tensile elastic modulus of the entire second bead filler are higher than the tensile elastic modulus of the entire bead filler in Comparative Example 1 and An example in which the tensile elastic modulus of the entire bead filler in Comparative Example 2 is lower is determined as A. On the other hand, 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 referred to as B determination.

[Rim assembly]
The rim assembly properties of the tires in each of the Examples and Comparative Examples were determined as follows. The results are shown in Tables 1 and 2.
In Comparative Example 1, since it is expected that the tire shape retention will be low because the tensile elastic modulus of the entire bead filler is too low, it is judged as C.
In Example 1, the tensile elastic modulus of the entire bead filler is slightly low, and the composition is such that impact resistance can be easily obtained (specifically, the bead filler is appropriately contained with the amorphous resin [B]. Since the overall tensile elastic modulus is an appropriate value), it is expected that the rim assembly property will be excellent, so it is judged as A.
In Example 2, since the content of the amorphous resin [B] is higher than that in Example 1 and the tensile elastic modulus of the entire bead filler is slightly higher, it is considered that the impact resistance is lower than that in Example 1. Although the rim assembly property is inferior to that of the first embodiment, it is expected to be within the permissible range.

In Comparative Example 2, since the content of the amorphous resin [B] is high and the tensile elastic modulus of the entire bead filler is high, the impact resistance is low and it is expected that cracks are likely to occur during rim assembly. Judgment.
In Example 4, since the content of the amorphous resin [B] is the same as that in Example 1, the tensile elastic modulus of the entire bead filler is higher than that in Example 1 due to the difference in the type of the thermoplastic elastomer [A]. Even if it is a little high, impact resistance is obtained and it is expected that the rim assembly property is excellent, so it is judged as A.
In Example 5, the content of the amorphous resin [B] is the same as in Example 1 and Example 4, and the tensile elastic modulus of the entire bead filler is a value between Example 1 and Example 4. Therefore, even if the type of the amorphous resin [B] is different from that of Examples 1 and 4, it is expected that impact resistance will be obtained and rim assembly property will be excellent, so the determination is made A.

In Example 6, since the content of the amorphous resin [B] is the same as that in Example 2, the tensile elastic modulus of the entire bead filler is higher than that in Example 2 due to the difference in the type of the amorphous resin [B]. Even if it is slightly high, the same impact resistance as in Example 2 can be obtained, and it is expected that the rim assembly property is within the permissible range. Therefore, the judgment is made as B.
In Example 7, the composition of the bead filler is the same as that in Example 4, but since the tensile elastic modulus of the coating resin is higher than that in Example 4, the tire as a whole becomes slightly harder, so that the rim assembly property is improved in Example 4. Although it is inferior to, it is expected to be within the permissible range, so it is judged as B.
In Example 8, since the composition of the bead filler is the same as that in Example 2, it is expected that the rim assembly property of the tire as a whole is within the permissible range even if the coating resin contains an amorphous resin. Therefore, it is judged as B. The resin used as the coating resin of 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 Toyo Boseki Co., Ltd.). , Amorphous polyester resin, trade name: Byron 270) in an amount of 20% by mass.

Since Example 9 is a bead filler composed of two members, the bead filler of Example 1 and the bead filler of Example 2, it is expected that the rim assembly property is further excellent as compared with Examples 1 and 2. Therefore, it is judged as A.
Since Example 10 is a bead filler composed of two members, the bead filler of Example 2 and the bead filler of Example 5, it is expected that the rim assembly property is further excellent as compared with Examples 2 and 5. Therefore, it is judged as A.
For Example 11, the first bead filler is the same as the first bead filler in Examples 9 and 10, and the second bead filler is more overall than the second bead filler in Examples 9 and 10. Since the tensile elastic modulus of the above is low, it is expected that the same rim assembly property as that of Examples 9 and 10 or even better rim assembly property can be obtained. Therefore, the determination is made as A.

The components in the table are as follows.
(Adhesive resin layer)
-GQ730: Maleic anhydride-modified polyester-based thermoplastic elastomer manufactured by Mitsubishi Chemical Corporation, "Primaloy-AP GQ730", melting point 200 ° C.

(Coating resin layer and bead filler)
5557: Polyester-based thermoplastic elastomer manufactured by Toray DuPont, "Hytrel 5557", melting point 208 ° C.
6347: Polyester-based thermoplastic elastomer manufactured by Toray DuPont, "Hytrel 6347", melting point 215 ° C.
270: Amorphous polyester resin manufactured by Toyobo Co., Ltd., "Byron 270", glass transition point 67 ° C.
-S4500: Amorphous polyester resin manufactured by Mitsubishi Gas Chemical Company, "Altester S4500", glass transition point 110 ° C.

As can be seen from the evaluation results shown in the table, 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. In the embodiment in which the tensile modulus Ei is higher than the tensile modulus Es in the continuous phase, excellent rim assembly property and high impact resistance are compatible with each other as compared with the comparative example in which this requirement is not satisfied.

1 Bead wire 2 Adhesive layer 3, 3C Coating resin layer 10, 110, 210 Tire 12, 112, 212 Bead portion 14, 114, 214 Tire side portion 16, 116, 216 Tread portion 18, 118, 218, 218C Bead core 20 , 120, 200, 200A, 200B, 200C Bead filler 20A, 200E End 22A, 222 Carcass 22A, 222A Main body 22B, 222B Folded part 22C, 222C End 22I Inner surface 22O, 222O Outer surface 24A, 224A Belt layer 24B, 224B Cap layer 24C, 224C Layer layer 26, 226 Side reinforcing rubber 26A End (end on the tread side)
26B end (end on the bead core side)
30, 230 Standard rim 122 Protective layer 124A Belt layer 124B Cushion rubber 130 Tread 140 Tire case (tire skeleton)
201, 201A, 201B, 201C 1st bead filler 202, 202A, 202B, 202C 2nd bead filler CL Tire equatorial surface Q Midpoint

Claims (11)

It has at least a bead core having a bead wire and a bead filler arranged in direct contact with the bead core or in contact with another layer.
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.
A bead member for a tire in which the tensile elastic modulus Ei of the discontinuous phase is higher than the tensile elastic modulus Es of the continuous phase. The bead member for a tire according to claim 1, wherein the tensile elastic modulus Ei of the discontinuous phase is 500 MPa or more and 3000 MPa or less. The bead member for a tire according to claim 1 or 2, wherein the tensile elastic modulus Es of the continuous phase is 100 MPa or more and 400 MPa or less. The method according to any one of claims 1 to 3, wherein the ratio (Ei / Es) of the tensile elastic modulus Ei of the discontinuous phase to the tensile elastic modulus Es of the continuous phase is 500/400 to 3000/100. The bead member for the described tire. The bead member for a tire according to any one of claims 1 to 4, wherein the bead filler has a tensile elastic modulus of 400 MPa or more and 1500 MPa or less. The bead member for a tire according to any one of claims 1 to 5, wherein the amorphous resin is an amorphous resin having an ester bond. The bead member for a tire according to claim 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. The bead member for a tire according to any one of claims 1 to 7, wherein the thermoplastic elastomer is a polyester-based thermoplastic elastomer. The bead filler has a content of 5 parts by mass or more and 45 parts by mass or less of the amorphous resin with respect to 100 parts by mass of the total amount of the thermoplastic elastomer and the amorphous resin. The bead member for a tire according to any one of the items. The bead member for a tire according to any one of claims 1 to 9, wherein the bead core has a coating resin layer arranged in direct contact with the bead wire or in contact with another layer. .. A tire having a bead member for a tire according to any one of claims 1 to 10 in a pair of bead portions.

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