JP2019069672A - Bead member for tire and tire - Google Patents

Abstract

To provide a bead member for a tire in which a change in elasticity modulus is inhibited from occurring in a covering resin layer and a bead filler.SOLUTION: A bead member for a tire has a bead core 18 having a bead wire 1 and a covering resin layer 3 covering the bead wire 1 and containing resin A, and a bead filler 20, arranged to be brought into contact with at least a part of the covering resin layer 3, which contains resin B. The resin A and the resin B are thermoplastic resin or thermoplastic elastomer independent from each other, and the resin A and the resin B are individually resin having common frameworks in a constitutional unit constituting main chains of the resin. Melting points of the resin A and the resin B are 175°C or more and 223°C or less, and water absorption rates of the covering resin layer 3 and the bead filler 20 are 3.5 mass% or less.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a bead member for a tire, and a tire.

Conventionally, a pneumatic tire having a pair of bead portions, a pair of tire side portions extending outward from the bead portions in the tire radial direction, and a tread portion extending from one tire side portion to the other tire side portion is used. ing. In addition, in the bead portion of the pneumatic tire, in view of enhancing 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. It is done.
In addition, it is tried to use the wire coat | covered with the coating | coated part by resin as a bead wire used for such a bead part.

  For example, a bead wire for a tire skin has been proposed that includes a wire assembly coated with a covering made of a material having an elongation cutting coefficient measured at room temperature of 10% and at room temperature equal to at least 70 MPa (e.g. reference).

Japanese Patent Application Laid-Open No. 63-25110

  As described above, there is known a technology in which a bead wire coated with a resin-coated portion is used for a bead portion of a tire. However, in a bead member for a tire having a bead wire, a covering resin layer for covering the bead wire, and a bead filler in contact with the covering resin layer, when a thermoplastic resin or a thermoplastic elastomer is used for the covering resin layer and the bead filler Water absorption occurs at the time of use of a tire, etc., and the elastic modulus change of the coating resin layer and the bead filler resulting from this water absorption may occur. When elastic modulus changes occur in the coating resin layer and the bead filler, air leakage (deterioration in air sealability), rim deviation, rim out, etc. may occur.

  In view of the above circumstances, the present invention relates to a bead member for a tire, which comprises at least one of a thermoplastic resin and a thermoplastic elastomer in any of a coating resin layer coating a bead wire and a bead filler in contact with the coating resin layer. It is an object of the present invention to provide a tire bead member in which the occurrence of elastic modulus change in the layer and bead filler is suppressed.

The problems are solved by the present invention described below.
<1> A tire having a bead wire, and a bead core covering the bead wire and having a covering resin layer containing the resin A, and a bead filler disposed so as to contact at least a part of the covering resin layer and containing the resin B It is a bead member, and the resin A and the resin B are each independently a thermoplastic resin or a thermoplastic elastomer, and the resin A and the resin B are mutually contained in structural units constituting the main chain of the resin. The resin A and the resin B each have a melting point of 175 ° C. or more and 223 ° C. or less, and the covering resin layer and the bead filler each have a water absorption coefficient of 3.5 mass. % Or less of the tire bead member.
<2> The bead member for a tire according to <1>, wherein the coated resin layer and the bead filler each have a Charpy impact strength of 5 kJ / m ² or more.
<3> The bead member for a tire according to <1> or <2>, wherein each of the covering resin layer and the bead filler has a tensile elastic modulus of 274 MPa or more and 2000 MPa or less.
<4> The bead member for a tire according to any one of <1> to <3>, wherein at least one of the resin A and the resin B is a thermoplastic elastomer.
<5> The tire bead member according to <4>, wherein at least one of the resin A and the resin B is a polyamide-based thermoplastic elastomer or a polyester-based thermoplastic elastomer.
<6> The bead member for a tire according to any one of <1> to <5>, wherein the bead core is disposed between the bead wire and the covering resin layer and has an adhesive resin layer containing a resin C.
<7> The bead member for a tire according to <6>, wherein the resin C is a thermoplastic resin having a polar functional group or a thermoplastic elastomer having a polar functional group.
The bead member for tires as described in said <6> or <7> whose melting | fusing point of <8> said resin C is 139 degreeC or more and 220 degrees C or less.
The tire which has a bead member for tires in any one of said <1>-<8> in a <9> pair of bead part.

  According to the present invention, a bead member for a tire, which comprises at least one of a thermoplastic resin and a thermoplastic elastomer in any of a coating resin layer coating a bead wire and a bead filler in contact with the coating resin layer The bead member for tires in which generation | occurrence | production of the elastic modulus change in a filler was suppressed can be provided.

It is a tire half sectional view showing one side of the cut surface which cut the tire concerning one embodiment of the present invention along the width-of-tire direction. It is tire width direction sectional drawing which expands and shows the bead part periphery of the tire of FIG. It is a schematic diagram of the perpendicular cutting plane to the length direction of bead wire showing one embodiment of the bead core in the present invention It is a schematic diagram of the perpendicular cutting plane to the length direction of bead wire showing one embodiment of the bead core in the present invention It is a schematic diagram of the perpendicular cutting plane to the length direction of bead wire showing one embodiment of the bead core in the present invention It is a tire half sectional view showing one side of the cut surface which cut the tire concerning another embodiment of the present invention along the width-of-tire direction.

  Hereinafter, although specific embodiments of the present invention will be described in detail, the present invention is not limited to the following embodiments at all, and can be implemented with appropriate modifications within the scope of the object of the present invention. be able to.

In the present specification, “resin” is a concept including a thermoplastic resin, a thermoplastic elastomer, and a thermosetting resin, and does not include a vulcanized rubber. Moreover, in the following description of the resin, “same type” means one having a skeleton common to the skeleton constituting the main chain of the resin, such as esters, styrenes, etc.
The numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
In the present specification, the term “process” is not limited to an independent process, and even if it can not be clearly distinguished from other processes, the term “process” is also used if the purpose is achieved. include.

Further, in the present specification, the term "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 rubbery elasticity.
The term "thermoplastic elastomer" as used herein means a copolymer having a hard segment and a soft segment. Specifically as the thermoplastic elastomer, for example, a polymer constituting a crystalline, high melting point hard segment or a high cohesive hard segment, and an amorphous, low glass transition temperature polymer constituting a soft segment The copolymer which it has is mentioned. Further, as the thermoplastic elastomer, for example, a material softens and flows as temperature rises, and when it is cooled, it becomes a relatively hard and strong state, and one having rubbery elasticity is mentioned.
The above hard segment has, for example, a structure having a rigid group such as an aromatic group or an alicyclic group in the main skeleton, or a structure which enables intermolecular packing by intermolecular hydrogen bond or π-π interaction, etc. Segment of In addition, the soft segment has, for example, a long chain group (for example, a long chain alkylene group etc.) in the main chain, a segment having a high degree of freedom in molecular rotation, and a stretchable structure.

<Bead member for tire>
The bead member for a tire according to the present invention (hereinafter simply referred to as "bead member") comprises a bead wire and a bead core having a coating resin layer covering the bead wire, and a bead arranged to contact at least a part of the coating resin layer. And a filler.
The covering resin layer contains a resin A, the bead filler contains a resin B, and the resin A and the resin B are each independently a thermoplastic resin or a thermoplastic elastomer. Moreover, resin A and resin B are resin which has frame | skeleton which is common in the structural unit which comprises the principal chain of resin mutually.
And as for resin A and resin B, all melting | fusing point is 175 degreeC or more and 223 degrees C or less.
Moreover, as for a covering resin layer and a bead filler, water absorption is 3.5 mass% or less in all.

  The bead member of the present invention is a member used for a pair of bead portions in a tire, and is a member constituting all or part of the bead portion. Specifically, the bead member of the present invention comprises at least a bead wire, a coating resin layer, and all or part of a bead filler in a tire.

Here, an embodiment of the bead member of the present invention will be briefly described based on the drawings.
In the tire 10 shown in FIG. 1 (in FIG. 1, a run flat tire will be described as an example in one embodiment), a pair of bead portions 12 (only one bead portion 12 is shown in FIG. 1) Have. A pair of tire side portions 14 respectively extending outward in the tire radial direction from the pair of bead portions 12 and a tread portion 16 extending from one tire side portion 14 to the other tire side portion 14 are provided.
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, in the bead portion 12, a bead filler 20 extending along the outer surface 22O of the carcass 22 from the bead core 18 outward in the tire radial direction is embedded. The bead filler 20 is disposed, for example, in a region surrounded by the carcass main portion 22A and the folded portion 22B.
As shown in FIG. 2, the bead core 18 has a plurality of bead wires 1 arranged side by side, and a coated resin layer 3 that covers the bead wire 1 and includes a resin A.
In the tire 10 shown in FIG. 1 which is a run flat tire, a side reinforcing rubber 26 as an example of a side reinforcing layer for reinforcing the tire side portion 14 is disposed inside the carcass 22 of the tire side portion 14 in the tire width direction. It is set up.

Furthermore, another embodiment of the bead member of the present invention will be briefly described with reference to the drawings.
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). A pair of tire side portions 114 respectively extending outward from the pair of bead portions 112 in the tire radial direction and a tread portion 116 extending from one tire side portion 114 to the other tire side portion 114 are provided.
The tire 110 includes an annular tire case 140 corresponding to a tire frame body, and 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 the tire side portion 114 and the bead portion 112.
An annular bead core 118 extending in the tire circumferential direction is embedded in the bead portion 112. The bead core 118 has a plurality of bead wires arranged side by side and a coating resin layer that covers the bead wire and includes the resin A.
Further, in the bead portion 112, a bead filler 120 extending along the protective layer 122 from the bead core 118 outward in the tire radial direction is embedded.

  As described above, in the tire 10 shown in FIGS. 1 and 2 and the tire 110 shown in FIG. 4, it is the bead member of the present invention that constitutes all or part of the pair of bead portions. The bead member of the present invention comprises at least the resin layer and all or part of the bead filler.

As described above, in the bead portion responsible for fixing to the rim of the tire, the bead wire and the bead core having the covering resin layer covering the bead wire, and the bead arranged to be in contact with at least a part of the covering resin layer A bead member having a filler is used. And the rubber material is conventionally generally used for the member which coat | covers a bead wire and comprises a bead core, and a bead filler. On the other hand, from the viewpoint of moldability, it is required to use a thermoplastic resin or a thermoplastic elastomer for a member for covering a bead wire in a bead core and a bead filler.
However, when a thermoplastic resin or a thermoplastic elastomer is used for the covering resin layer and the bead filler in the bead member, water absorption occurs in the covering resin layer and the bead filler at the time of use of the tire such as raining, etc. Elastic modulus change may occur. When a change in elastic modulus occurs in the coating resin layer and the bead filler, the pressing force on the rim at the bead portion changes, which may cause air leakage (that is, the air sealability may be reduced). In addition, when a heavy load is applied to the bead member in a state in which a change in elastic modulus occurs in the coating resin layer and the bead filler, the rim shift or rim removal may occur.

On the other hand, in the bead member of the present invention, the covering resin layer and the bead filler contain the resin A or the resin B which is a thermoplastic resin or a thermoplastic elastomer, and the covering resin layer and the bead filler both have a water absorption of 3 .5 mass% or less.
When the coefficient of water absorption in the covering resin layer and the bead filler is in the above range, the water absorption itself in the covering resin layer and the bead filler can be suppressed even when using a tire such as raining, and the elastic modulus due to water supply Changes are also suppressed. As a result, the occurrence of air leakage (a decrease in air sealability) due to a change in elastic modulus, the occurrence of a rim shift, a rim removal or the like is suppressed.

Moreover, as for the bead member of this invention, as for resin A and resin B contained in a coating resin layer and a bead filler, all melting | fusing point is 175 degreeC or more and 223 degrees C or less.
The melting point is in the above-mentioned range, and even when the bead member has heat during traveling for a long time, etc., the coating resin layer and the bead filler are not too soft and not too hard, and an appropriate hardness is maintained. Be That is, the flexibility and strength required of the bead portion are secured. As a result, the decrease in the pressing force against the rim at the bead portion is suppressed, air leakage (decrease in air sealability) is suppressed, and the followability to the load is obtained even when a strong load is applied by traveling. Rim slippage and rim slippage are suppressed.

Furthermore, the bead member of the present invention is a resin in which the resin A and the resin B contained in the coating resin layer and the bead filler have a skeleton common to structural units constituting the main chain of the resin.
Here, “the resin having a skeleton common to the constituent units constituting the main chain of the resin” means, for example, that both of the resin A and the resin B are “at least at least polyester thermoplastic elastomer (TPC) and thermoplastic polyester In the case of containing “one kind”, it can be said that they have a skeleton (that is, an ester bond skeleton) common to the constituent units constituting the main chain of the resin. Similarly, there is a case where both of the resin A and the resin B contain the following thermoplastic resin or thermoplastic elastomer.
-When both the resin A and the resin B contain "at least one kind of a polyamide-based thermoplastic elastomer (TPA) and a thermoplastic polyamide", an amide bond skeleton is used as a skeleton common to the structural units constituting the main chain of the resin. Have.
-When both the resin A and the resin B contain "at least one of polystyrene-based thermoplastic elastomer (TPS) and thermoplastic polystyrene", a polystyrene skeleton is used as a skeleton common to structural units constituting the main chain of the resin. Have.
· When both resin A and resin B contain "at least one of polyurethane-based thermoplastic elastomer (TPU) and thermoplastic polyurethane", a urethane bond skeleton is used as a skeleton common to the structural units constituting the main chain of the resin. Have.
-When both the resin A and the resin B contain "at least one of polyolefin-based thermoplastic elastomer (TPO) and thermoplastic polyolefin", the polyolefin skeleton is used as a skeleton common to the structural units constituting the main chain of the resin. Have.

In addition, as resin A and resin B, as a structural unit which comprises the molecular structure of resin, a thermoplastic resin or thermoplastic elastomer containing the structural unit of the same chemical structure (For example, the monomer of the same structure as a monomer used as the raw material of resin) It is more preferable to use the thermoplastic resin or thermoplastic elastomer used.
In addition, thermoplastic resins or thermoplastic elastomers containing only structural units having the same chemical structure as structural units constituting the molecular structure of the resin (for example, thermoplastic resins using only monomers having the same structure as monomers serving as raw materials for resins or It is further preferable to use a thermoplastic elastomer).

  Since the resin A contained in the covering resin layer and the resin B contained in the bead filler are resins having a skeleton common to the constituent units constituting the main chain of the resin, the covering resin layer and the bead filler Affinity is enhanced, and excellent adhesion is exhibited. As a result, the occurrence of displacement at the interface between the coating resin layer and the bead filler is suppressed, and the phenomenon (displacement of the bead position) causing displacement from the state where the bead portion is rim-assembled at an appropriate position is suppressed. As a result, air leakage (deterioration in air sealability) caused by the displacement of the bead position is suppressed, and even when a strong load is applied during traveling, rim displacement or rim removal caused by the displacement of the bead position is suppressed.

  Thus, according to the present invention, the change in elastic modulus due to water absorption is suppressed, and the flexibility and strength required of the bead portion are secured even when the bead member has heat, and the covering resin layer and the bead are also provided. Excellent adhesion to the filler is obtained. As a result, the occurrence of air leakage, rim deviation, and rim deviation are suppressed, and in the present invention, excellent running durability is exhibited when provided in a tire.

・ Water absorption rate (coated resin layer, bead filler)
In the present invention, the water absorption rates of the covering resin layer and the bead filler are each 3.5% by mass or less. The water absorption rates of the coating resin layer and the bead filler are more preferably 3.0% by mass or less, further preferably 2.5% by mass or less, and more preferably closer to 0% by mass.
When the water absorption rate of both is in the above range, the change in elastic modulus of the covering resin layer and the bead filler caused by water supply is suppressed, and air leakage (decrease in air sealability) accompanied by change in elastic modulus, rim shift, rim removal, etc. Occurrence is suppressed.

  The water absorption of the coating resin layer and the bead filler represents the water absorption measured according to ISO 62 (1999).

  The adjustment of the water absorption rate of the coating resin layer and the bead filler is adjusted, for example, by the selection of the material constituting the coating resin layer and the bead filler, particularly the selection of the material of the resin A and the resin B contained in the coating resin layer and the bead filler. It can.

Melting point (Resin A, Resin B)
In the present invention, the melting points of the resin A and the resin B contained in the covering resin layer and the bead filler are all 175 ° C. or more and 223 ° C. or less. The melting points of the resin A and the resin B are more preferably 178 ° C. or more and 220 ° C. or less, and still more preferably 180 ° C. or more and 217 ° C. or less.
When the melting points of the two are in the above range, the flexibility and strength required of the bead portion can be secured even when the bead member has heat, and air leakage (decrease in air sealability), rim deviation, rim removal, etc. Occurrence is suppressed.

  The melting points of the resin A and the resin B refer to a temperature at which an endothermic peak is obtained in a curve (DSC curve) obtained by differential scanning calorimetry (DSC). The measurement of the melting point is performed according to JIS K 7121: 2012 using a differential scanning calorimeter DSC. The measurement can be performed, for example, using “DSC Q100” manufactured by TA Instruments Co., Ltd. at a sweep rate of 10 ° C./min.

  The adjustment of the melting points of the resin A and the resin B contained in the coating resin layer and the bead filler can be performed, for example, by selecting the materials of the resin A and the resin B.

・ Charpy impact strength (coated resin layer, bead filler)
Bead member of the present invention, Charpy impact strength of the coating resin layer and a bead filler of preferably both at 5 kJ / ^{m 2} or more, more preferably 6 kJ / ^{m 2} or more, still more preferably 7 kJ / ^{m 2} or more . The upper limit of both the Charpy impact strength is not particularly limited, it does not destroy (NB), more preferably 20 kJ / ^{m 2} or less, more preferably 15 kJ / ^{m 2} or less.
When the lower limit value of the Charpy impact strength is in the above-mentioned range, a crack that occurs when a load is applied to the coating resin layer or the bead filler momentarily during rim assembly or traveling (especially during run flat traveling) Occurrence is suppressed.
On the other hand, when the upper limit value of the Charpy impact strength is in the above range, the rim assembly and traveling can be performed without cracking, and the effect as a bead using a resin can be obtained.

The Charpy impact strength of the coated resin layer and the bead filler is measured according to JIS K7111-1: 2012, using a Charpy impact tester (made by Yasuda Seiki Co., Ltd., product name: 141 type), a test piece (notch Measured at a temperature of 23 ° C. with processing.
For example, the amount of energy consumed from the difference between the angles before and after the collision by measuring the angle returned after the collision with the sample under the conditions of a nominal pendulum energy (weight) of 4 J and a hammer lifting angle of 150 °. Calculate the amount of absorption).

  The adjustment of the Charpy impact strength of the coating resin layer and the bead filler may be carried out, for example, by selecting the material constituting the coating resin layer and the bead filler, in particular, selecting the material of the resin A and the resin B contained in the coating resin layer and the bead filler. It can be adjusted by

· Tensile modulus (coated resin layer, bead filler)
In the bead member of the present invention, the tensile modulus of elasticity of the coating resin layer and the bead filler is preferably 274 MPa or more and 2000 MPa or less, more preferably 274 MPa or more and 1500 MPa or less, and still more preferably 274 MPa or more and 1000 MPa or less.
When the lower limit value of the tensile modulus of elasticity is in the above range, an appropriate hardness can be imparted to the bead portion, and a load is applied to the coating resin layer and the bead filler during traveling (particularly during run flat traveling) In this case, durability against the load is obtained, and as a result, excellent running durability is exhibited. On the other hand, when the upper limit value of the tensile modulus of elasticity is in the above-mentioned range, appropriate softness, that is, flexibility can be imparted to the bead portion, and excellent rim assembling property can be obtained.

  The measurement of the tensile modulus of elasticity is carried out in accordance with JIS K7113: 1995. In detail, Shimadzu Corporation make, Shimadzu autograph AGS-J (5KN), a tensile speed is set to 100 mm / min, and a measurement of a tensile elastic modulus is performed. In addition, when measuring the tensile elasticity modulus of the coating resin layer or bead filler in a bead member, you may prepare separately the measurement sample of the same material as a coating resin layer or bead filler, for example, and may measure an elasticity modulus.

  Adjustment of the tensile elastic modulus of the coating resin layer and the bead filler can be carried out, for example, by selecting the material constituting the coating resin layer and the bead filler, particularly by selecting the material of the resin A and the resin B contained in the coating resin layer and the bead filler. It can be adjusted.

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

<Configuration of bead member>
A bead member has a bead wire and a bead core which has a covering resin layer which covers bead wire, and a bead filler arranged to touch at least one copy of a covering resin layer, and the shape in particular is not restricted. The bead core may have an adhesive layer between the bead wire and the coating resin layer.
The covering resin layer contains resin A, and the bead filler contains resin B. The adhesive layer is preferably an adhesive resin layer containing a resin C.

In the bead member, the structure having the bead wire and the coating resin layer covering the bead wire includes, for example, a state in which the entire surface of the bead wire is directly coated in contact with the coating resin layer; A state in which a portion of the surface of the bead wire is covered with the covering resin layer through the adhesive layer, and a state in which the entire surface of the bead wire is covered with the covering resin layer through the adhesive layer.
In a structure having a covering resin layer and a bead filler arranged to be in contact with at least a part of the covering resin layer, for example, a state in which the entire surface of the covering resin layer is arranged to be in direct contact with the bead filler And a state in which the bead filler is disposed in contact with part of the surface of the covering resin layer.

[Bead wire]
The bead wire is not particularly limited, and, for example, a metal or organic resin cord or the like used for a conventional rubber tire can be appropriately used. For example, it is comprised by the monofilament (single wire), such as a metal fiber and an organic fiber, or the multifilament (strand wire) which twisted these fibers. Among them, metal cords (more preferably iron cords (steel cords)) are preferable.

As a bead wire in the present invention, 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 is, for example, 2 to 10, and preferably 5 to 9.

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

  The strength of the bead wire itself is usually 1000N to 3000N, preferably 1200N to 2800N, and more preferably 1300N to 2700N. The strength of the bead wire is calculated from the breaking point by drawing a stress-strain curve using a ZWICK chuck with a tensile tester.

  The breaking elongation (tensile breaking elongation) of the bead wire itself is usually 0.1% to 15%, preferably 1% to 15%, and more preferably 1% to 10%. The tensile elongation at break of the bead wire can be determined from strain by drawing a stress-strain curve using a ZWICK type chuck in a tensile tester.

[Covered resin layer]
The covering resin layer contains at least a resin A which is a thermoplastic resin or a thermoplastic elastomer. Moreover, as resin A contained in a coating resin layer, resin which has frame | skeleton common in resin B contained in a bead filler and the structural unit which comprises the principal chain of resin mutually is selected.
In addition, as resin A, it is preferable to use a resin having a melting point of 175 ° C. or more and 223 ° C. or less, and to select a resin having a water absorption coefficient of 3.5% by mass or less of the covering resin layer.

  The coating resin layer preferably contains a thermoplastic elastomer as the resin A from the viewpoint of ease of molding and adhesiveness. Among thermoplastic elastomers, it is desirable to include at least one of polyamide thermoplastic elastomer and polyester thermoplastic elastomer.

  The covering resin layer only needs to contain at least the resin A, and may contain other resins (such as thermoplastic resin and thermoplastic elastomer) as long as the effects of the present invention are not impaired, that is, the resin A and other resins And mixtures thereof. In addition, other components such as additives may be included. However, 50 mass% or more is preferable with respect to the total amount of a coating resin layer, as for content of resin A in a coating resin layer, 60 mass% or more is more preferable, and 75 mass% or more is more preferable.

  Examples of thermoplastic resins 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 resins, polyester-based thermoplastic resins, and olefin-based thermoplastic resins is preferable, and it is selected from polyamide-based thermoplastic resins and polyester-based thermoplastic resins Further preferred is at least one of

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

(Thermoplastic elastomer)
-Polyamide-based thermoplastic elastomer-
A polyamide thermoplastic elastomer is a thermoplastic resin material comprising a copolymer having a crystalline, high melting point hard segment-forming polymer and a non-crystalline, low glass transition temperature soft segment forming polymer. It means that which has an amide bond (-CONH-) in the principal chain of the polymer which forms a hard segment.
As the polyamide-based thermoplastic elastomer, for example, at least a polyamide is crystalline and a hard segment having a high melting point is formed, and another polymer (for example, a polyester, a polyether etc.) is amorphous and a soft segment having a low glass transition temperature. The material which is forming is mentioned. In addition to the hard segment and the soft segment, the polyamide thermoplastic elastomer may be formed using a chain extender such as dicarboxylic acid.
Specific examples of polyamide-based thermoplastic elastomers include amide-based thermoplastic elastomers (TPA) and the like defined in JIS K 6418: 2007, and polyamide-based elastomers and the like described in JP-A-2004-346273. it can.

  As a polyamide which forms a hard segment in a polyamide-type thermoplastic elastomer, the polyamide produced | generated by the monomer represented by following General formula (1) or General formula (2) can be mentioned, for example.

General formula (1)

[In the general formula (1), ^{R 1} represents a molecular chain of a hydrocarbon having 2 to 20 carbon atoms (e.g., an alkylene group having 2 to 20 carbon atoms). ]

General formula (2)

[In the general formula (2), ^{R 2} represents a molecular chain of a hydrocarbon of 3 to 20 carbon atoms (e.g., an alkylene group having 3 to 20 carbon atoms). ]

In the general formula (1), R ¹ is preferably a hydrocarbon chain of 3 to 18 carbon atoms, such as an alkylene group of 3 to 18 carbon atoms, and a hydrocarbon chain of 4 to 15 carbon atoms, such as carbon An alkylene group of 4 to 15 is more preferable, and a molecular chain of a hydrocarbon having 10 to 15 carbon atoms, such as an alkylene group having 10 to 15 carbon atoms is particularly preferable.
In the general formula (2), R ² is preferably a hydrocarbon chain of 3 to 18 carbon atoms, for example, an alkylene group of 3 to 18 carbon atoms, and a hydrocarbon chain 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.
As a monomer represented by General formula (1) or General formula (2), (omega) -amino carboxylic acid or a lactam is mentioned. Moreover, as a polyamide which forms a hard segment, the polycondensate of these (omega)-amino carboxylic acids or lactams, the co-condensation polymer of diamine and dicarboxylic acid, etc. are mentioned.

As the ω-aminocarboxylic acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. Aliphatic ω-aminocarboxylic acid and the like can be mentioned. Examples of lactams include aliphatic lactams having 5 to 20 carbon atoms such as lauryl lactam, ε-caprolactam, udecane lactam, ω-enant lactam, 2-pyrrolidone and the like.
Examples of diamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, -Diamine compounds, such as C2-C20 aliphatic diamines, such as trimethyl hexa methylene diamine, 2,4, 4- trimethyl hexa methylene diamine, 3-methyl penta methylene diamine, metaxylene diamine, etc. can be mentioned.
Further, the dicarboxylic acid can be represented by HOOC- (R ³ ) _m -COOH (R ³ : a molecular chain of hydrocarbon having 3 to 20 carbon atoms, m: 0 or 1), for example, oxalic acid, succinic acid And aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and the like.
As a polyamide which forms a hard segment, the polyamide which carried out the ring-opening polycondensation of lauryl lactam, (epsilon) -caprolactam, or udecane lactam can be used preferably.

Moreover, as a polymer which forms a soft segment, polyester, a polyether, etc. are mentioned, for example, Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, ABA type triblock polyether etc. are mentioned. These can be used alone or in combination of two or more. Moreover, polyether diamine etc. which are obtained by making ammonia etc. react with the terminal of polyether can also be used.
Here, “ABA triblock polyether” means a polyether represented by the following general formula (3).

General formula (3)
[In general formula (3), x and z represent the integer of 1-20. y represents an integer of 4 to 50. ]

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

  Examples of combinations of hard segments and soft segments can include the combinations of hard segments and soft segments listed above. Among these, as combinations of hard segments and soft segments, combinations of ring-opening polycondensates of lauryl lactam / polyethylene glycol, combinations of ring-opening polycondensates of lauryl lactam / polypropylene glycol, ring-opening polycondensation of lauryl lactam Preferred is a combination of a body / polytetramethylene ether glycol, or a combination of ring opening polycondensate of lauryl lactam / ABA type triblock polyether, and a combination of a ring opening polycondensate of lauryl lactam / 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. Moreover, as a number average molecular weight of the polymer which forms a soft segment, 200-6000 are preferable from a viewpoint of toughness and low temperature flexibility. Furthermore, the mass ratio (x: y) between the hard segment (x) and the soft segment (y) is preferably 50:50 to 90:10, more preferably 50:50 to 80:20, from the viewpoint of formability. .

  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.

  Commercially available polyamide thermoplastic elastomers include, for example, "UBESTA XPA" series of Ube Industries, Ltd. (for example, XPA 9068 X1, XPA 9063 X1, XPA 90 55 X 1, XPA 9048 X 2, XPA 9048 X 1, XPA 9040 X 1, XPA 9040 X 2 X PA 9044, etc.) The "Vestamide" series (for example, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2 etc.) and the like can be used.

  A polyamide-based thermoplastic elastomer is suitable as a resin material because it meets the performance required as a bead portion from the viewpoint of elastic modulus (flexibility), strength and the like. In addition, polyamide-based thermoplastic elastomers often have good adhesion to thermoplastic resins and thermoplastic elastomers.

-Polyester-based thermoplastic elastomer-
As a polyester-based thermoplastic elastomer, for example, at least a polyester is crystalline and a hard segment having a high melting point is formed, and another polymer (for example, a polyester or a polyether etc.) is amorphous and a soft segment having a low glass transition temperature. The material which is forming is mentioned.

As polyester which forms a hard segment, aromatic polyester can be used. The aromatic polyester can be formed, for example, from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol. The aromatic polyester is preferably a polybutylene terephthalate derived from at least one of terephthalic acid and dimethyl terephthalate and 1,4-butanediol. Also, aromatic polyesters are, for example, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5 -Disulfoisophthalic acid, or dicarboxylic acid components such as ester forming derivatives thereof, and diols having a molecular weight of 300 or less (eg, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, etc.) Aliphatic diols; alicyclic diols such as 1,4-cyclohexanedimethanol and tricyclodecanedimethylol; xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane and 2,2- B Bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4'- Polyesters derived from dihydroxy-p-terphenyl, aromatic diols such as 4,4'-dihydroxy-p-quarterphenyl, etc .; and co-using two or more of these dicarboxylic acid components and diol components in combination It may be a polymerized polyester. Moreover, it is also possible to copolymerize a trifunctional or higher polyfunctional carboxylic acid component, a polyfunctional oxy acid component, a polyfunctional hydroxy component, etc. 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.

Moreover, as a polymer which forms a soft segment, aliphatic polyester, aliphatic polyether, etc. are mentioned, for example.
Aliphatic polyethers include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, poly (propylene oxide) And ethylene oxide addition polymers of glycols, copolymers of ethylene oxide and tetrahydrofuran, and the like.
Examples of aliphatic polyesters include poly (ε-caprolactone), polyenantlactone, polycaprylolactone, polybutylene adipate, polyethylene adipate and the like.
Among these aliphatic polyethers and aliphatic polyesters, poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol as a polymer forming a soft segment from the viewpoint of the elastic properties of the obtained polyester block copolymer Ethylene oxide adducts, poly (ε-caprolactone), polybutylene adipate, polyethylene adipate and the like are preferred.

  Moreover, as for the number average molecular weight of the polymer which forms a soft segment, 300-6000 are preferable from a viewpoint of toughness and low temperature flexibility. Further, the mass ratio (x: y) of the hard segment (x) to the soft segment (y) is preferably 99: 1 to 20:80, more preferably 98: 2 to 30:70, from the viewpoint of formability. .

  Examples of the combination of the hard segment and the soft segment described above can include, for example, the respective combinations of the hard segment and the soft segment listed above. Among these, as the combination of the hard segment and the soft segment described above, 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 is a soft segment More preferred is a combination wherein is poly (ethylene oxide) glycol.

  Examples of commercially available polyester-based thermoplastic elastomers include “Hytrel” series (for example, 3046, 5557, 6347, 4047, 4767, etc.) manufactured by Toray DuPont Co., Ltd., “Pelprene” 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.

-Polystyrene-based thermoplastic elastomer As the polystyrene-based thermoplastic elastomer, for example, at least polystyrene forms a hard segment, and other polymers (eg, polybutadiene, polyisoprene, polyethylene, hydrogenated polybutadiene, hydrogenated polyisoprene, etc.) are not Materials having a crystalline and low glass transition temperature soft segment can be mentioned. As a polystyrene which forms a hard segment, what is obtained by the well-known radical polymerization method, an ionic polymerization method etc. is used preferably, for example, Specifically, the polystyrene which has anion living polymerization is mentioned. Moreover, as a polymer which forms a soft segment, a polybutadiene, polyisoprene, poly (2, 3- dimethyl- butadiene) etc. are mentioned, for example.

  Examples of combinations of hard segments and soft segments can include the combinations of hard segments and soft segments listed above. Among these, as a combination of hard segment and soft segment, a combination of polystyrene / polybutadiene or a combination of polystyrene / polyisoprene is preferable. Also, in order to suppress the unintended crosslinking reaction of the thermoplastic elastomer, the soft segment is preferably hydrogenated.

5000-500000 are preferable and, as for the number average molecular weight of the polymer (polystyrene) which forms a hard segment, 10000-200000 are more preferable.
The number average molecular weight of the polymer forming the soft segment is preferably 5,000 to 1,000,000, more preferably 10,000 to 800,000, and still more preferably 30,000 to 500,000. Further, the volume ratio (x: y) to the hard segment (x) and the soft segment (y) is preferably 5:95 to 80:20, more preferably 10:90 to 70:30, from the viewpoint of formability. .

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

  As a commercial item of polystyrene type thermoplastic elastomer, for example, Asahi Kasei Co., Ltd. "Tough Tech" series (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.) etc. made by Kuraray Co., Ltd. can be used.

-Polyurethane-based thermoplastic elastomer-
As a polyurethane-based thermoplastic elastomer, for example, at least a polyurethane forms a hard segment forming a pseudo-crosslink by physical aggregation, and another polymer forms a non-crystalline soft segment having a low glass transition temperature. Materials are included.
Specifically as a polyurethane-type thermoplastic elastomer, the polyurethane-type thermoplastic elastomer (TPU) prescribed | regulated to JISK6418: 2007 is mentioned. The polyurethane thermoplastic elastomer can be represented as a copolymer including 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.

[Wherein, 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 long chain aliphatic polyester represented by P in Formula A, for example, those having a molecular weight of 500 to 5,000 can be used. P is derived from a diol compound comprising a long chain aliphatic polyether represented by P and a long chain aliphatic polyester. As such a diol compound, for example, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly (butylene adipate) diol, poly-ε-caprolactone diol, poly (hexamethylene carbonate) having a molecular weight within the above range 2.) Diols, ABA-type triblock polyethers, etc.
These can be used alone or in combination of two or more.

In Formula A and Formula 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 aliphatic diisocyanate compounds containing aliphatic hydrocarbons represented by R include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, 1,6-hexamethylene diisocyanate and the like. It can be mentioned.
Moreover, as a diisocyanate compound containing the alicyclic hydrocarbon represented by R, a 1, 4- cyclohexane diisocyanate, 4, 4- cyclohexane diisocyanate etc. are mentioned, for example. Furthermore, as an aromatic diisocyanate compound containing the aromatic hydrocarbon represented by R, 4, 4'- diphenylmethane diisocyanate, tolylene diisocyanate etc. are mentioned, for example.
These can be used alone or in combination of two or more.

As the short chain aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon represented by P ′ in the formula B, for example, one having a molecular weight of less than 500 can be used. P ′ is derived from a diol compound containing a short chain aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon represented by P ′. Examples of aliphatic diol compounds containing a short-chain aliphatic hydrocarbon represented by P ′ include glycol and polyalkylene glycol, and specifically, ethylene glycol, propylene glycol, trimethylene glycol, 1,4 -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- The decane diol etc. are mentioned.
Further, as an alicyclic diol compound containing an alicyclic hydrocarbon represented by P ′, for example, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, Examples include cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol and the like.
Further, as an aromatic diol compound containing an aromatic hydrocarbon represented by P ′, for example, hydroquinone, resorcine, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4′- Dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, bisphenol A, 1, Examples include 1-di (4-hydroxyphenyl) cyclohexane, 1,2-bis (4-hydroxyphenoxy) ethane, 1,4-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like.
These can be used alone or in combination of two or more.

  The number average molecular weight of the polymer (polyurethane) forming the hard segment is preferably 300 to 1,500 from the viewpoint of melt moldability. Further, the number average molecular weight of the polymer forming the soft segment is preferably 500 to 20,000, more preferably 500 to 5,000, and particularly preferably 500 to 3,000, from the viewpoint of the flexibility and thermal stability of the polyurethane thermoplastic elastomer. . From the viewpoint of formability, the mass ratio (x: y) between the hard segment (x) and the soft segment (y) is preferably 15:85 to 90:10, and more preferably 30:70 to 90:10. .

  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 a polyurethane type thermoplastic elastomer, the thermoplastic polyurethane of Unexamined-Japanese-Patent No. 5-331256 can be used, for example.

  Specifically, as the polyurethane-based thermoplastic elastomer, a combination of a hard segment composed of an aromatic diol and an aromatic diisocyanate and a soft segment composed of a polycarbonate ester is preferable, and more specifically, tolylene diisocyanate (more specifically, 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 -Based polyol copolymer, MDI / polyether-based polyol copolymer, MDI / caprolactone-based polyol copolymer, MDI / polycarbonate-based polyol copolymer, and MDI + hydroquinone / polyhexamethylene At least one selected from carbonate copolymers is preferable, and TDI / polyester-based polyol copolymer, TDI / polyether-based polyol copolymer, MDI / polyester-polyol copolymer, MDI / polyether-based polyol copolymer, And at least one selected from MDI + hydroquinone / polyhexamethylene carbonate copolymer.

  Moreover, as a commercial item of a polyurethane-type thermoplastic elastomer, for example, "Elastolan" series (For example, ET680, ET880, ET690, ET890 etc.) by BASF Corporation, "Kramillon U" series (for example, Kuraray Co., Ltd.) (For example, Series 2000, Series 3000, Series 8000, Series 9000, etc., “Milactolan” series manufactured by Nippon Miractoran Co., Ltd. (eg, XN-2001, XN-2004, P390 RSUP, P480 RSUI, P26 MRNAT, E490, E590, P890 etc.) Etc. can be used.

-Olefin-based thermoplastic elastomer-
As the olefin-based thermoplastic elastomer, for example, at least a polyolefin is crystalline and a hard segment having a high melting point is formed, and other polymers (eg, polyolefin, other polyolefins, polyvinyl compounds, etc.) are amorphous and have a glass transition temperature Materials that form low soft segments may be mentioned. As a polyolefin which forms a hard segment, polyethylene, a polypropylene, an isotactic polypropylene, a polybutene etc. are mentioned, for example.

  Examples of the olefin-based thermoplastic elastomer include an olefin-α-olefin random copolymer, an olefin block copolymer, etc. Specifically, a propylene block copolymer, an ethylene-propylene copolymer, propylene- 1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-pentene copolymer, ethylene- 1-butene copolymer, 1-butene-1-hexene copolymer, 1-butene-4-methyl-pentene, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate Copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer Ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer, propylene-methyl methacrylate copolymer, propylene-ethyl methacrylate copolymer, propylene-butyl methacrylate copolymer And propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, propylene-vinyl acetate copolymer and the like.

Among these, as an olefin-based thermoplastic elastomer, a propylene block copolymer, an ethylene-propylene copolymer, a propylene-1-hexene copolymer, a propylene-4-methyl-1-pentene copolymer, a propylene-1-one Butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-pentene copolymer, ethylene-1-butene copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer , Ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer Propylene-methyl methacrylate copolymer, pro Ren-ethyl methacrylate copolymer, propylene-butyl methacrylate copolymer, propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, And at least one selected from propylene-vinyl acetate copolymers; ethylene-propylene copolymers, propylene-1-butene copolymers, ethylene-1-butene copolymers, ethylene-methyl methacrylate copolymers Furthermore, at least one selected from ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer is more preferable.
Moreover, you may use combining an olefin resin of 2 or more types like ethylene and propylene. Moreover, 50 mass% or more and 100 mass% or less of the olefin resin content rate in an olefin type thermoplastic elastomer are preferable.

The number average molecular weight of the olefin-based thermoplastic elastomer is preferably 5,000 to 10,000,000. The mechanical physical property of a thermoplastic resin material is enough in the number average molecular weight of an olefin type thermoplastic elastomer being 5000-10000000, and it is excellent also in processability. From the same viewpoint, the number average molecular weight of the olefin-based thermoplastic elastomer is more preferably 7,000 to 100,000, and particularly preferably 10,000 to 100,000. Thereby, the mechanical physical properties and processability of the thermoplastic resin material can be further improved. Moreover, as a number average molecular weight of the polymer which forms a soft segment, 200-6000 are preferable from a viewpoint of toughness and low temperature flexibility. Further, the mass ratio (x: y) of the hard segment (x) to the soft segment (y) is preferably 50:50 to 95:15, and more preferably 50:50 to 90:10 from the viewpoint of formability. .
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 a thermoplastic elastomer may be used.
The term "acid-modified olefin thermoplastic elastomer" refers to bonding of an olefin thermoplastic elastomer to an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group or a phosphoric acid group.
As bonding 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 in an olefin-based thermoplastic elastomer, Bonding (for example, graft polymerization) of unsaturated bonding sites of unsaturated carboxylic acids (generally, maleic anhydride) can be mentioned.
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, and for example, acrylic acid, methacrylic acid, itaconic acid, croton Acids, isocrotonic acid, maleic acid and the like can be mentioned.

  Commercially available olefin thermoplastic elastomers include, for example, “Tafmer” series manufactured by Mitsui Chemicals, Inc. (eg, 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 "Nuclel" series (for example, AN4214C, AN4225C, AN42115C, N0903HC, N0908C, AN42012C, N410, N1050H, N1108C) manufactured by Polychemical Co., Ltd. N1110H, N1207C, N1214, AN4221C, N1525, N1560, N0200H, AN4228C, AN4213C, N035C, etc., "Elvalloy AC" series (eg, 1125 AC, 1209 AC, 1218 AC, 1609 AC, 1820 AC, 1913 AC, 2112 AC, 2116 AC 2715 AC, 3117 AC, 3427 AC, 3717 AC etc.), Sumitomo Chemical Co., Ltd.'s “Aklift” series, “Ebatete” series, etc., Tosoh Corporation's “Ultrasen” series, etc. “Prime TPO” series made by Prime Polymer (eg, E-2900H, F-3900H, E-2900, F-3900, J-5900, E-2910, F-3910, J-5910, E-2710, F- 710, J-5910, E-2740, F-3740, R110MP, R110E, can be used T310E, also M142E, etc.) and the like.

(Thermoplastic resin)
-Polyamide-based thermoplastic resin-
As a polyamide-type thermoplastic resin, the polyamide which forms the hard segment of the above-mentioned polyamide-type thermoplastic elastomer can be mentioned. Specifically, as the polyamide-based thermoplastic resin, a polyamide (amide 6) obtained by ring-opening polycondensation of ε-caprolactam, a polyamide (amide 11) obtained by ring-opening polycondensation of undecanelactam, and a ringyl polycondensation of lauryl lactam Examples thereof include polyamide (amide 12), polyamide obtained by polycondensing diamine and dibasic acid (amide 66), and polyamide (amide MX) having meta-xylene diamine as a structural unit.

Amide 6, for _example, can be expressed by _{{CO- (CH 2) 5 -NH} } n. Amide 11 can, for _example, can be expressed by _{{CO- (CH 2) 10 -NH} } n. Amide 12 can, for _example, can be expressed by _{{CO- (CH 2) 11 -NH} } n. The amide 66 can be represented, for example, by {CO (CH ₂ ) ₄ CONH (CH ₂ ) ₆ NH} _n . The amide MX can be represented, for example, by the following structural formula (A-1). Here, n represents the number of repeating units.
As a commercial item of amide 6, for example, Ube Industries, Ltd. “UBE nylon” series (for example, 1022 B, 1011 FB, etc.) can be used. As a commercial item of amide 11, for example, "Rilsan B" series manufactured by Arkema Co., Ltd. can be used. As a commercial item of amide 12, for example, Ube Industries, Ltd. "UBE nylon" series (for example, 3024U, 3020U, 3014U etc.) can be used. As a commercial item of the amide 66, for example, "UBE nylon" series (for example, 2020B, 2015B, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercial item of amide MX, "MX nylon" series (for example, S6001, S6021, S6011, etc.) of Mitsubishi Gas Chemical Co., Ltd. can be used, for example.

  The polyamide-based thermoplastic resin may be a homopolymer formed of only the above-described structural unit, or may be a copolymer of the above-described structural unit and another monomer. In the case of a copolymer, the content of the constituent unit in each polyamide-based thermoplastic resin is preferably 40% by mass or more.

-Polyester-based thermoplastic resin-
As polyester-based thermoplastic resin, polyester which forms the hard segment of the above-mentioned polyester-based thermoplastic elastomer can be mentioned.
Specific examples of polyester-based thermoplastic resins include polylactic acid, polyhydroxy-3-butylbutyric acid, polyhydroxy-3-hexylbutyric acid, poly (ε-caprolactone), polyenantlactone, polycaprylolactone and polybutylene Aliphatic polyesters such as adipate and polyethylene adipate, and aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polybutylene naphthalate can be exemplified. Among these, polybutylene terephthalate is preferable as the polyester thermoplastic resin from the viewpoint of heat resistance and processability.

  As a commercial item of polyester-based thermoplastic resin, for example, "Duranex" series (for example, 2000, 2002 etc.) made by Polyplastics Co., Ltd., "Novaduran" series made by Mitsubishi Engineering s Plastics Co., Ltd. (for example, 5010R5, 5010R3-2 and the like), Toray Co., Ltd. “Trecon” series (for example, 1401 × 06, 1401 × 31 and the like) and the like can be used.

-Olefin-based thermoplastic resin-
As an olefin thermoplastic resin, the polyolefin which forms the hard segment of the above-mentioned olefin thermoplastic elastomer can be mentioned.
Specific examples of the olefin-based thermoplastic resin include polyethylene-based thermoplastic resins, polypropylene-based thermoplastic resins, and polybutadiene-based thermoplastic resins. Among these, a polypropylene-based thermoplastic resin is preferable as the olefin-based thermoplastic resin in terms of heat resistance and processability.
Specific examples of the polypropylene-based thermoplastic resin include propylene homopolymers, propylene-α-olefin random copolymers, and propylene-α-olefin block copolymers. Examples of α-olefins include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, Examples thereof include α-olefins having about 3 to 20 carbon atoms such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.

-Other ingredients-
The coating resin layer may contain other components in addition to the resin (the resin A or a mixture of the resin A and the other resin). Other components include rubber, various fillers (for example, silica, calcium carbonate, clay and the like), antiaging agents, oils, plasticizers, color formers, weathering agents and the like.

-Thickness of coated resin layer-
The thickness of the coating resin layer is not particularly limited. From the viewpoint of excellent durability and weldability, the thickness 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 covering resin layer is from the surface on the bead wire side (for example, the interface with the bead wire or the adhesive layer) in the covering resin layer to the outer surface (the surface opposite to the bead wire side) in the covering resin layer Of the length of, the length of the shortest part is referred.
The thickness of the covering resin layer is a covering resin obtained by obtaining magnified images by a microscope such as a video microscope of a cross section perpendicular to the longitudinal direction of the bead wire from any five places and obtaining five magnified images. The thickness of the minimum thickness portion of the layer is measured and taken as the number average value.

[Bead filler]
The bead filler contains at least a resin B which is a thermoplastic resin or a thermoplastic elastomer. Moreover, as resin B contained in a bead filler, resin which has frame | skeleton which is common in the structural unit which comprises resin A contained in a coating resin layer mutually, and the principal chain of resin is selected.
In addition, as resin B, it is preferable to use a resin having a melting point of 175 ° C. or more and 223 ° C. or less, and to select a resin having a water absorption of 3.5 mass% or less of the bead filler.

  The bead filler preferably contains a thermoplastic elastomer as the resin B from the viewpoint of moldability and adhesion. Among thermoplastic elastomers, it is desirable to include at least one of polyamide thermoplastic elastomer and polyester thermoplastic elastomer.

  The bead filler only needs to contain at least the resin B, and may contain other resins (such as thermoplastic resin and thermoplastic elastomer) as long as the effects of the present invention are not impaired, that is, the resin B and the other resin It may be a mixture of In addition, other components such as additives may be included. However, 50 mass% or more is preferable with respect to the total amount of a bead filler, as for content of resin B in a bead filler, 60 mass% or more is more preferable, and 75 mass% or more is more preferable.

  Examples of thermoplastic resins 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 a bead filler, these may be used individually or in combination of 2 or more types. Among these, as the thermoplastic resin, at least one selected from polyamide-based thermoplastic resins, polyester-based thermoplastic resins, and olefin-based thermoplastic resins is preferable, and it is selected from polyamide-based thermoplastic resins and polyester-based thermoplastic resins Further preferred is at least one of

  As the thermoplastic elastomer, for example, polyamide-based thermoplastic elastomer (TPA), polyester-based thermoplastic elastomer (TPEE), polystyrene-based thermoplastic elastomer (TPS), polyurethane-based thermoplastic elastomer (TPU) defined in JIS K6418, Examples thereof include olefin-based thermoplastic elastomer (TPO), crosslinked thermoplastic rubber (TPV), and other thermoplastic elastomers (TPZ).

In addition, about the specific example of a thermoplastic resin and a thermoplastic elastomer etc., the various thermoplastic resin and thermoplastic elastomer which were enumerated in the description column of the above-mentioned coating resin layer can be mentioned, The preferable aspect is also as above-mentioned. is there.
Moreover, the other components listed in the description column of the above-mentioned coating resin layer can be mentioned also about other components which can be contained in a feed filler.

[Adhesive layer]
The material of the adhesive layer is not particularly limited, and an adhesive used in the bead portion of the tire can be used.

The adhesive layer is preferably a layer containing a resin C (adhesive resin layer), and as the resin C, a thermoplastic resin or a thermoplastic elastomer is preferable.
When the adhesive layer contains the resin C, the content is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 75% by mass or more of the entire adhesive layer. .

As specific examples of the thermoplastic resin and the thermoplastic elastomer, various thermoplastic resins and thermoplastic elastomers listed in the description column of the above-mentioned covering resin layer can be mentioned.
However, the resin C contained in the adhesive layer is more preferably a thermoplastic resin having a polar functional group or a thermoplastic elastomer having a polar functional group (hereinafter, also referred to simply as a “polar functional group-containing resin”) .

The “polar functional group” refers to a group that exhibits chemical reactivity (functionality) and causes a charge bias (polarity) in the molecule.
In the present invention, by including the polar functional group-containing resin in the adhesive layer, the charge bias due to the polar functional group makes it possible, in the case where the bead wire is a metal wire, to the hydrated hydroxyl group present on the surface. It is considered that an interaction occurs to create attractive force between the two or form a complex to obtain high adhesion between the bead wire (metal wire) and the adhesive layer.
And, by providing the covering resin layer through the adhesive layer, the difference in rigidity between the bead wire (metal wire) and the bead filler can be alleviated, so the bead member provided with the bead wire is excellent. It is surmised that the adhesion durability can be realized.

-Polar functional group containing resin-
As a thermoplastic resin which has a polar functional group, the polyester-type thermoplastic resin which has a polar functional group, an olefin type thermoplastic resin, a polystyrene-type thermoplastic resin etc. can be illustrated, for example.
As a thermoplastic elastomer which has a polar functional group, the polyester-type thermoplastic elastomer which has a polar functional group, an olefin type thermoplastic elastomer, a polystyrene type thermoplastic elastomer etc. are mentioned, for example.
You may use these individually or in combination of 2 or more types.

The polar functional group contained in the polar functional group-containing resin is an epoxy group (a group shown in the following (1), and further, R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an organic group (for example, an alkyl group)) Carboxy group (-COOH) and its anhydride group, amino group (-NH ₂ ), isocyanate group (-NCO), hydroxy group (-OH), imino group (= NH), silanol group (-SiOH), etc. It can be mentioned.
The above "anhydride group" refers to an anhydride group obtained by removing H ₂ O from two carboxy groups (an anhydride group shown in the following (2-1), and R ²¹ represents a single bond or a substituted group. R ²² and R ²³ each independently represent a hydrogen atom or an organic group (eg, an alkyl group). The anhydride group shown in the following (2-1) becomes a state shown in the following (2-2), that is, a state having two carboxy groups, when H ₂ O is given.
Among these, an epoxy group, a carboxy group and its anhydride group, a hydroxy group, and an amino group are preferable from the viewpoint of adhesion to a bead wire.
The polar functional group is preferably a carboxy group and its anhydride group, a hydroxy group, and an amino group from the viewpoint of the reactivity with the epoxy group.

  The polar functional group-containing resin is obtained by modifying a thermoplastic resin or a thermoplastic elastomer with a compound (derivative) having a group to be a polar functional group. For example, a compound having a group to be a polar functional group in a thermoplastic resin or a thermoplastic elastomer and having a reactive group (for example, an unsaturated group (such as an ethylenic carbon-carbon double bond)) separately therefrom is chemically (Addition reaction, grafting reaction, etc.).

  As a thermoplastic resin or a derivative that modifies a thermoplastic elastomer (a compound having a group to become a polar functional group), for example, an epoxy compound having a reactive group, unsaturated carboxylic acid (methacrylic acid, maleic acid, fumaric acid, itaconic) Acids, etc.), unsaturated carboxylic acid anhydrides (maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, glutaconic acid acid etc.), carboxylic acids having other reactive groups and their anhydrides, amine compounds having reactive groups, Examples thereof include isocyanate compounds having a reactive group, alcohols having a reactive group, silane compounds having a reactive group, and derivatives thereof.

  Examples of polyester-based thermoplastic resins include aliphatic polyester-based thermoplastic resins and aromatic polyester-based thermoplastic resins. The polyester-based thermoplastic resin before being modified with a compound (derivative) having a group to be a polar functional group is the same as the polyester-based thermoplastic resin used for the above-mentioned coating resin layer.

  Examples of the olefin-based thermoplastic resin include polyethylene-based thermoplastic resins, polypropylene-based thermoplastic resins, and polybutadiene-based thermoplastic resins. The olefin-based thermoplastic resin before being modified with a compound (derivative) having a group to be a polar functional group is the same as the olefin-based thermoplastic resin used for the above-mentioned coating resin layer.

  As polyester-based thermoplastic elastomers, olefin-based thermoplastic elastomers, and polystyrene-based thermoplastic elastomers before being modified with a compound (derivative) having a group to be a polar functional group, polyester-based thermal elastomers used in the above-mentioned coating resin layer The same as the plasticizable elastomer, the olefin-based thermoplastic elastomer, and the polystyrene-based thermoplastic elastomer.

(Composition method)
Here, the method of synthesizing the polar functional group-containing resin will be specifically described.
For example, a styrene-based elastomer having a polar functional group can be obtained by introducing a polar functional group into an unmodified styrene-based elastomer. Specifically, in the case of a styrenic elastomer having an epoxy group as a polar functional group, it can be obtained by reacting an unmodified styrenic elastomer with an epoxidizing agent, if necessary, in the presence of a solvent and a catalyst. . Examples of the epoxidizing agent include hydroperoxides such as hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, and the like; peracids such as formic acid, peracetic acid, perbenzoic acid and trifluoroperacetic acid; Etc.

  Also, as an example of the synthesis method, a method of modifying a polyester-based thermoplastic elastomer (TPC) with an unsaturated carboxylic acid or an anhydride thereof will be described in detail below.

  Polyester-based thermoplastic elastomers having polar functional groups (hereinafter, also simply referred to as “polar group-containing TPCs”) are, for example, melts of saturated polyester-based thermoplastic elastomers containing polyalkylene ether glycol segments, unsaturated carboxylic acids or Obtained by denaturation treatment with the derivative

  The term "modification" refers to graft modification with saturated carboxylic acid or a derivative thereof of a saturated polyester thermoplastic elastomer containing a polyalkylene ether glycol segment, modification with terminal modification and transesterification reaction, modification with decomposition reaction, and the like. Specifically, a terminal functional group or an alkyl chain moiety is considered as a site to which an unsaturated carboxylic acid or derivative thereof is bonded, and in particular to the ether bond of terminal carboxylic acid, terminal hydroxyl group and polyalkylene ether glycol segment Examples include carbon at the alpha position and beta position. In particular, it is presumed that many bonds are made at the alpha position to the ether bond of the polyalkylene ether glycol segment.

(1) Compounding Material (A) Saturated Polyester-Based Thermoplastic Elastomer A saturated polyester-based thermoplastic elastomer is usually a block copolymer consisting of a soft segment containing a polyalkylene ether glycol segment and a hard segment containing a polyester. is there.

  Further, the content of the polyalkylene ether glycol segment in the saturated polyester-based thermoplastic elastomer is preferably 58 to 73% by mass, more preferably 60 to 70% by mass in the polyester-based elastomer.

  Examples of polyalkylene ether glycols constituting this soft segment include polyethylene glycol, poly (1,2 and 1,3-propylene ether) glycol, poly (tetramethylene ether) glycol, poly (hexamethylene ether) glycol and the like. It can be mentioned. Particularly preferred is poly (tetramethylene ether) glycol. In the present invention, as the polyalkylene ether glycol, one having a number average molecular weight of 400 to 6,000 is preferable, one having 600 to 4,000 is more preferable, and one having 1,000 to 3,000 is particularly preferable. . In addition, "number average molecular weight" here is measured by gel permeation chromatography (GPC). For calibration of GPC, POLYTETRAHYDROFURAN calibration kit from POLYMER LABORATORIES, UK may be used.

  The saturated polyester-based thermoplastic elastomers include, for example, i) aliphatic and / or alicyclic diols having 2 to 12 carbon atoms, ii) aromatic dicarboxylic acids and / or alicyclic dicarboxylic acids or their alkyl esters, And iii) can be obtained by polycondensing an oligomer obtained by an esterification reaction or a transesterification reaction using a polyalkylene ether glycol having a number average molecular weight of 400 to 6,000 as a raw material.

  As the aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, a raw material of polyester, in particular, one which is usually used as a raw material of polyester-based thermoplastic elastomer can be used. For example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned, among which 1,4-butanediol and ethylene glycol are preferable. Particularly preferred is 1,4-butanediol. These diols can be used alone or in combination of two or more.

  As the aromatic dicarboxylic acid and / or alicyclic dicarboxylic acid, materials generally used as raw materials of polyester, particularly polyester-based thermoplastic elastomer can be used, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, 2, 6- naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, etc. are mentioned. Among these, terephthalic acid and 2,6-naphthalene dicarboxylic acid are preferable, and terephthalic acid is particularly preferable. Moreover, these dicarboxylic acids may use 2 or more types together. When an alkyl ester of an aromatic dicarboxylic acid and / or an alicyclic dicarboxylic acid is used, dimethyl ester or diethyl ester of the above dicarboxylic acid is used. Preferred are dimethyl terephthalate and 2,6-dimethyl naphthalate.

In addition to the above components, trifunctional triols, tricarboxylic acids or esters thereof may be copolymerized in small amounts, and aliphatic dicarboxylic acids such as adipic acid or dialkyl esters thereof can also be used as copolymerization components.
Examples of commercial products of such polyester-based thermoplastic elastomers include “Primalloy” manufactured by Mitsubishi Chemical Co., Ltd., “Pelprene” manufactured by Toyobo Co., Ltd., “Hytrel” manufactured by Toray DuPont Co., and the like.

(B) Unsaturated Carboxylic Acids or Derivatives Thereof As unsaturated carboxylic acids or derivatives thereof, for example, unsaturated such as acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, etc. Carboxylic acid; for example, 2-octene-1-yl succinic acid, 2-dodecen-1-yl succinic acid, 2-octadecen-1-yl succinic acid, maleic anhydride, 2,3- Dimethylmaleic anhydride, bromomaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, 1-butene-3,4-dicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic acid Acid anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, exo-3 , 6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, endo-bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid anhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid anhydride, etc. Unsaturated carboxylic acid anhydrides; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl methacrylate, dimethyl maleate, maleic acid Hexyl Le), and unsaturated carboxylic acid esters such as 2-hydroxyethyl methacrylate. Of these, unsaturated carboxylic acid anhydrides are preferred. The compound having these unsaturated bonds may be appropriately selected depending on the copolymer containing the polyalkylene ether glycol segment to be modified or the modifying conditions, and two or more kinds may be used in combination. The compound having this unsaturated bond can also be added by dissolving in an organic solvent or the like.

(C) Radical Generator The radical generator used to carry out the radical reaction in the modification treatment is, for example, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydro Peroxide, 2,5-dimethyl-2,5-bis (tertiary butyloxy) hexane, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxybenzoate, benzoyl peroxide, dicumyl peroxide Organic and inorganic peroxides such as 1,3-bis (t-butylperoxyisopropyl) benzene, dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide etc., 2,2′-azobisisobutyro Nitrile, 2,2'-azobis (isobutylamido) diha Id, 2,2'-azobis [2-methyl-N-(2-hydroxyethyl) propionamide], azo compounds such as azodi -t- butane, and carbon radical generators such as dicumyl can be exemplified. These radical generating agents may be appropriately selected according to the type of saturated polyester thermoplastic elastomer containing a polyalkylene ether glycol segment used for modification treatment, the type of unsaturated carboxylic acid or its derivative, and modification conditions. And two or more may be used in combination. The radical generator can also be added as dissolved in an organic solvent or the like. Moreover, in order to further improve the adhesion, not only a radical generator but also a compound having an unsaturated bond (the following (D)) can be used in combination as a modification assistant.

(D) Compound Having Unsaturated Bond A compound having an unsaturated bond refers to a compound having a carbon-carbon multiple bond other than the above-mentioned (B) radical generator, and specifically, styrene, methylstyrene, Vinyl aromatic monomers such as ethylstyrene, isopropylstyrene, phenylstyrene, o-methylstyrene, 2,4-dimethylstyrene, o-chlorostyrene, o-chloromethylstyrene and the like can be mentioned. By these combinations, improvement in modification efficiency can be expected.

(2) Additional blended materials (optional components)
The adhesive for forming the adhesive layer may contain any component other than the polar group-containing TPC. Specifically, resin components, rubber components, fillers such as talc, calcium carbonate, mica, glass fibers, etc., plasticizers such as paraffin oil, antioxidants, heat stabilizers, light stabilizers, light stabilizers, ultraviolet light absorbers, neutralizers Add various additives such as lubricant, anti-fogging agent, anti-blocking agent, slip agent, crosslinking agent, crosslinking aid, coloring agent, flame retardant, dispersant, antistatic agent, antifungal agent, fluorescent brightener be able to. Among them, it is preferable to add at least one of various antioxidants such as phenol type, phosphite type, thioether type and aromatic amine type.

(3) Compounding Ratio The compounding ratio of each component constituting the polar group-containing TPC is preferably (B) unsaturated carboxylic acid or a derivative thereof with respect to 100 parts by mass of (A) the saturated polyester-based thermoplastic elastomer. The compounding ratio of .01 to 30 parts by mass, more preferably 0.05 to 5 parts by mass, still more preferably 0.1 to 2 parts by mass, and particularly preferably 0.1 to 1 parts by mass, C) The radical generating agent is preferably 0.001 to 3 parts by mass, more preferably 0.005 to 0.5 parts by mass, still more preferably 0.01 to 0.2 parts by mass, particularly preferably 0.01 to 0.01 The compounding ratio is 0.1 parts by mass.

The modification amount of the polar group-containing TPC by infrared absorption spectroscopy is preferably 0.01 to 15 in the value of the following formula A ₁₇₈₆ / (Ast × r), and preferably 0.03 to 2.5. More preferably, it is 0.1 to 2.0, and particularly preferably 0.2 to 1.8.
[However, A ₁₇₈₆ is a peak intensity of 1786 cm ⁻¹ measured for a film with a thickness of 20 μm of polar group-containing TPC, and Ast is a standard sample (the content of the polyalkylene ether glycol segment is 65% by mass The peak intensity of the base wavenumber measured for a 20 μm thick film of a saturated polyester-based elastomer), r is the molar fraction of the polyester segment in the polar group-containing TPC, It is the value divided by the mole fraction. ]

The method of calculating | requiring the value of modification | denaturation amount by the infrared absorption spectrum method of polar group containing TPC is as follows. That is, a film-like sample with a thickness of 20 μm is dried under reduced pressure at 100 ° C. for 15 hours to remove unreacted material, and an infrared absorption spectrum is measured. From the obtained spectrum, the tangent line connecting the both sides of the foot of the mountain of the absorption band the baseline in the range of the absorption peak (1750~1820cm ^-1 by stretching vibration of the carbonyl group derived from an acid anhydride appears at 1786 cm ^-1 The peak height of) is calculated as "peak intensity A ₁₇₈₆ ". On the other hand, the infrared absorption spectrum is similarly measured for a film of 20 μm in thickness of a standard sample (saturated polyester elastomer having a content of polyalkylene ether glycol segment of 65% by mass). From the obtained spectrum, the peak of the reference wave number, for example in the case of an aromatic polyester elastomer having a benzene ring, the absorption peak due to out-of-plane deformation of the C-H in benzene ring appearing at 872cm ^-1 (850~900cm ^-1 The peak height of the tangent line which connects the mountain foot on both sides of the absorption band in the range of (a) is used as a “peak intensity Ast”. The reference wave number peak may be selected from a hard segment-derived peak which is not affected by denaturation and has no absorption peak overlapping in the vicinity thereof. From these two peak intensities, the amount of modification by infrared absorption spectroscopy is calculated according to the above equation. At this time, as r, a value obtained by dividing the mole fraction of the polyester segment in the polar group-containing TPC for which the amount of modification is to be obtained by the mole fraction of the polyester segment in the standard sample is used. Further, the molar fraction mr of the polyester segment of each sample is the mass fraction (w ₁ and w ₂ ) of the polyester segment and the polyalkylene ether glycol segment and the molecular weight (e ₁ and e) of the monomer units constituting both segments. ₂ ) and the following equation.
mr = (w ₁ / e ₁ ) / [(w ₁ / e ₁ ) + (w ₂ / e ₂ )]

(4) Compounding method Synthesis of polar group-containing TPC is carried out, for example, by modifying (A) a saturated polyester thermoplastic elastomer with (B) an unsaturated carboxylic acid or a derivative thereof in the presence of (C) a radical generator. It takes place in At this time, when the component (A) is a melt, it is preferable because the reaction with the component (B) can be performed more efficiently and sufficient denaturation can be realized. For example, after mixing the component (B) with the component (A) in the non-molten state preliminarily, a method of melting the component (A) and reacting it with the component (B) can also be preferably used.
Further, in order to mix the component (B) with the component (A), it is preferable to select a so-called melt-kneading method using a kneader capable of giving sufficient shear stress. As kneaders used for the melt-kneading method, conventional kneaders such as mixing rolls, sigma type rotary bladed kneaders, Banbury mixers, high-speed twin-screw continuous mixers, single-screw, twin-screw, multi-screw extruder type kneaders You can choose any one. Among them, a twin screw extruder is preferable because of high reaction efficiency and low production cost. Melt-kneading is carried out in the form of powdery or granular component (A), component (B) and component (C), and, if necessary, component (D), other materials mentioned as the additional compounding material (optional component) The compounding agents of the present invention can also be mixed after being uniformly mixed using a Henschel mixer, a ribbon blender, a V-type blender or the like at a predetermined mixing ratio. The temperature for kneading each component is preferably in the range of 100 ° C. to 300 ° C., more preferably in the range of 120 ° C. to 280 ° C., in consideration of thermal degradation decomposition of the component (A) and the half life temperature of the component (C). Particularly preferably, it is in the range of 150 ° C to 250 ° C. For practical use, the optimum kneading temperature is a temperature range from a temperature 20 ° C. higher than the melting point of component (A) to the melting point. Furthermore, the kneading order and method of each component are not particularly limited, and component (A), component (B) and component (C), and additional compounding materials such as component (D) are collectively A method of kneading, or a method of kneading a part of the components (A) to (D) and then kneading the remaining components including the additional compounding material may be used. However, when the component (C) is blended, it is preferable to simultaneously add the component (B) and the component (D) from the viewpoint of improving adhesion.

  The adhesive layer may contain other components other than the adhesive such as resin C. Other components include carbon black, radical scavengers, rubbers, elastomers, various fillers (eg, silica, calcium carbonate, clay, etc.), antioxidants, oils, plasticizers, color formers, weathering agents, etc.

(Physical properties)
-Tensile elastic modulus of adhesive layer It is preferable that an adhesive layer is a layer whose tensile elastic modulus is higher than a coating resin layer. The tensile elastic modulus of the adhesive layer can be controlled, for example, by the type of adhesive used for forming the adhesive layer, the forming conditions of the adhesive layer, the heat history (for example, heating temperature, heating time, etc.), and the like.
For example, the lower limit value of the tensile elastic modulus of the adhesive layer is preferably 1 MPa or more, more preferably 20 MPa or more, and still more preferably 50 MPa or more. It is excellent in the adhesion | attachment performance with a bead wire, and tire durability because a tensile elasticity modulus is more than the said lower limit.
The upper limit value of the tensile modulus of elasticity of the adhesive layer is preferably 1500 MPa or less, more preferably 600 MPa or less, and still more preferably 400 MPa or less from the viewpoint of ride comfort.
In addition, the measurement of the tensile elasticity modulus of an adhesive bond layer can be performed by the method similar to the tensile elasticity modulus of the said coating resin layer.
Further, the tensile elastic modulus of the adhesive layer and E _1, when the tensile modulus of the coating resin layer was E _2, as the value of E 1 _/ E _2, for example, an 0.5 to 10, 0 7 or more and 7 or less are preferable, and 0.7 or more and 5 or less are more preferable. When the value of E ₁ / E ₂ is in the above range, the handling property is excellent as compared with the case where the value is smaller than the above range, and the running durability is excellent as compared with the case where the value is larger than the above range.

· Melting point of adhesive layer The melting point of the resin C contained in the adhesive layer is preferably 139 ° C or more and 225 ° C or less, more preferably 139 ° C or more and 220 ° C or less.
When the lower limit value of the melting point is in the above range, the heat resistance to heating (for example, vulcanization) at the time of manufacturing a tire is excellent. In addition, when the melting point is in the above range, it is easy to set the melting point close to that of the resin A contained in the covering resin layer, and by setting the melting point close, a more excellent adhesion can be obtained.
The measurement of the melting point of the resin C can be performed by the same method as the melting point of the resin A in the covering resin layer.

· Thickness of Adhesive Layer Although the average thickness of the adhesive layer is not particularly limited, it is preferably 5 μm to 500 μm, more preferably 20 μm to 150 μm from the viewpoint of ride comfort during running and durability of the tire. Preferably, it is more preferably 20 μm to 100 μm.

  The average thickness of the adhesive layer is the thickness of the adhesive layer measured from an enlarged image obtained by obtaining an enlarged image by a microscope such as a video microscope or the like of a cross section perpendicular to the longitudinal direction of the bead wire The average number of The thickness of the adhesive layer in each magnified image is the portion with the smallest thickness (the portion where the distance between the interface between the bead wire and the adhesive layer and the interface between the adhesive layer and the covering resin layer is the smallest) It is the value measured by).

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 are preferable, and 0.1 or more and 0.35 or less are more preferable. When the value of T ₁ / T ₂ is in the above range, the ride comfort at the time of traveling is excellent as compared with the case where it is smaller than the above range, and the tire durability is excellent as compared with the case where it is larger than the above range.

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

First Embodiment
Hereinafter, as an embodiment of a tire according to the present invention, a run flat tire will be described as an example based on the drawings.
One side of the cut surface cut along the tire width direction of the tire 10 of the first embodiment is shown in FIG. 1. In the drawings, arrow TW indicates the width direction (tire width direction) of the tire 10, and arrow TR indicates the radial direction of the tire 10 (tire radial direction). The tire width direction referred to herein indicates a direction parallel to the rotation axis of the tire 10, and is also referred to as a tire axial direction. Further, the tire radial direction means a direction orthogonal to the rotation axis of the tire 10. Moreover, code | symbol CL has shown the equator (tire equator) of the tire 10. As shown in FIG.

  In the first embodiment, the rotary shaft side of the tire 10 is "inward in the tire radial direction" along the tire radial direction, and the opposite side of the rotary shaft of the tire 10 is "outward in the tire radial direction" along the tire radial direction. And write. On the other hand, the tire equator CL side is referred to as "the tire width direction inner side" along the tire width direction, and the side opposite to the tire equator CL along the tire width direction is referred to as the "tire width direction outer side".

  FIG. 1 shows the tire 10 mounted on a standard rim 30 (indicated by a two-dot chain line in FIG. 1) and filled with a standard air pressure. The standard rim mentioned here refers to the standard rim in the application size described in the Year Book 2017 edition of JATMA (Japan Automobile Tires Association). The standard air pressure is the air pressure corresponding to the maximum load capacity of JATMA's Year Book 2017 edition.

  In the following description, the load is the maximum load (maximum load capacity) of a single wheel in the application size described in the following standard, and the internal pressure is the maximum load of a single wheel described in the following standard The air pressure corresponding to the (maximum load capacity), the rim is the standard rim (or "Approved Rim", "Recommended Rim") in the application size described in the following standard. The standards are determined by the industry standards that are valid for the area where the tire is produced or used. For example, in the United States, "The Tire and Rim Association Inc.'s Year Book", and in Europe, "The European Tire and Rim Technical Organization Standards Manual", and in Japan, the Japan Automobile Tire Association "JATMA Year Book". It is 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 mentioned here is half the length of the difference between the outer diameter of the tire 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 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 invention 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 from the pair of bead portions 12 in the tire radial direction. 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 a load acting on the tire 10 during traveling (including run-flat traveling).

  As shown in FIG. 1, bead cores 18 are embedded in the pair of bead portions 12 respectively. A carcass 22 straddles a pair of bead cores 18. The end side of the carcass 22 is locked to the bead core 18. In the carcass 22 of the first embodiment, the end side is folded back and locked 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 portion 22A. In the first embodiment, the end 22C of the carcass 22 is disposed in the range (region) corresponding to the tire side portion 14, but the present invention is not limited to this configuration. For example, the end 22C of the carcass 22 may be disposed in the range corresponding to the tread portion 16, in particular, the range corresponding to the belt layer 24A.

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

  Plural (2 layers in the first embodiment) belt layers 24A are provided on the radially outer side of the carcass main portion 22A. A cap layer 24B is provided on the outer side in the tire radial direction of the belt layer 24A. The cap layer 24B covers the entire belt layer 24A.

  A pair of layer layers 24C is provided on the outer side in the tire radial direction of the cap layer 24B so as to cover both ends of the cap layer 24B. The present invention is not limited to the above configuration, and only one end of the cap layer 24B may be covered with the layer layer 24C. One layer layer 24C in which both ends of the cap layer 24B are continuous in the tire width direction It is good also as composition covered with. Further, depending on the specification of the tire 10, the cap layer 24B and the layer layer 24C may be omitted.

  Further, for the carcass 22, the belt layer 24A, the cap layer 24B and the layer layer 24C, the structure of each member used in a conventionally known tire (including a run flat tire) can be used.

  A tread portion 16 is provided on the outer side in the tire radial direction of the belt layer 24A, the cap layer 24B, and the layer layer 24C. The tread portion 16 is a portion that contacts the road surface during traveling, and a plurality of circumferential grooves 16A extending in the tire circumferential direction are formed on the tread surface of the tread portion 16. Further, in the tread portion 16, a not-shown width direction groove extending in the tire width direction is formed. The shapes and the number of the circumferential grooves 16A and the width direction grooves are appropriately set according to the performance required for the tire 10 such as drainage performance and steering stability.

-Bead filler In the bead portion 12, a bead filler 20 extending along the outer surface 22O of the carcass 22 from the bead core 18 outward in the tire radial direction is embedded. In the first embodiment, the bead filler 20 is disposed in a region surrounded by the carcass main portion 22A and the folded back portion 22B. The outer surface 22O of the carcass 22 is a surface on the tire outer side in the carcass main portion 22A, and is a surface on the tire inner side in the folded-back portion 22B. Further, in the first embodiment, the end 20 </ b> A on the tire radial direction outer side of the bead filler 20 is intruding into the tire side portion 14. In addition, the bead filler 20 has a thickness decreasing outward in the tire radial direction.

  The height BH of the bead filler 20 shown in FIG. 1 is preferably set in the range of 30 to 50% of the tire cross-sectional height SH. The height BH of the bead filler 20 referred to here means the end 20A of the bead filler 20 on the outer side in the tire radial direction of the bead filler 20 in a state in which the tire 10 is assembled to the standard rim 30 and the internal pressure is the standard air pressure. This refers to the height (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, the durability during run flat traveling can be sufficiently ensured. Moreover, the ride comfort is excellent when the height BH of the bead filler 20 is 50% or less of the tire cross-sectional height SH.

  Further, in the first embodiment, the end portion 20A of the bead filler 20 is disposed on the inner side in the tire radial direction than the maximum width position of the tire 10. Here, the maximum width position of the tire 10 refers to a position where the width is the largest 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 that covers the bead wire 1 and includes a resin A.
In the above configuration, “arranged arrangement” means that a plurality of bead wires 1 do not cross each other in a bead member cut into a length necessary for application to a tire.

Here, several examples are given and demonstrated about the form which the bead core 18 shown by FIG. 2 may take.
FIG. 3A is a view schematically showing a cross section when a portion of the bead core 18 is cut perpendicularly to the longitudinal direction of the bead wire 1. In FIG. 3A, the covering resin layer 3 is provided to be in direct contact with the three bead wires 1. In addition, while one bead wire 1 is heat-welded, it may be stepped horizontally or vertically.

Also, the bead core 18 may have the adhesive layer 2 disposed between the bead wire 1 and the covering resin layer 3. The adhesive layer 2 is preferably an adhesive resin layer containing the resin C described above.
In part of the bead core 18 shown in FIG. 3B, the adhesive layer 2 is provided on the surface of each of the three bead wires 1, and the covering resin layer 3 is provided on the surface thereof.

Furthermore, the adhesive layer 2 disposed between the bead wire 1 and the coating resin layer 3 may be connected in such a manner as to include a plurality of bead wires 1.
Part of the bead core 18 shown in FIG. 3C is an embodiment in which the adhesive layer 2 connected so as to include three bead wires 1 is provided, and the coating resin is further applied to the surface of the adhesive layer 2 connected further. Layer 3 is provided.

3A to 3C show an embodiment in which three bead wires 1 are arranged in parallel, but the number may be two or less or four or more.
Further, in the bead core 18 shown in FIG. 2, the three bead wires 1 shown in any one of FIGS. 3A to 3C, the coating resin layer 3 and the like (FIGS. 3B and 3C) are further added. The adhesive layer 2 and 3) are laminated in three layers. However, the bead core 18 may be used in a single layer or may be used by laminating two or more layers. In that case, it is preferable to weld between coating resins.
Furthermore, although the form which the bead core 18 can take is demonstrated using FIG. 3 (A)-(C), this invention is not limited to this structure.

  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. 3 (B), the bead wire 1, the material forming the adhesive layer 2 (preferably the material containing the resin C), and the covering resin layer 3 are formed. A material containing a resin B can be used to produce by an extrusion molding method. In this case, the cross-sectional shape of the adhesive layer 2 can be adjusted by a method such as changing the shape of a die used for extrusion molding.

-Side reinforcement layer The side reinforcement rubber 26 as an example of the side reinforcement layer which reinforces the tire side part 14 in the tire width direction inner side of the carcass 22 is arrange | positioned by the tire side part 14. As shown in FIG. The side reinforcing rubber 26 is a reinforcing rubber for traveling a predetermined distance while supporting the weight of the vehicle and the occupant when the internal pressure of the tire 10 decreases due to a puncture or the like.

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

  The side reinforcing rubber 26 overlaps the tread portion 16 with the end portion 26A on the tread portion 16 side sandwiching the carcass 22 (carcass main body portion 22A). Specifically, the end 26A of the side reinforcing rubber 26 overlaps the belt layer 24A. On the other hand, in the side reinforcing rubber 26, the end 26B on the bead core 18 side overlaps the bead filler 20 with the carcass 22 (carcass main body 22A) interposed therebetween.

The side reinforcing rubber 26 preferably has a breaking elongation in the range of 130 to 190%. In addition, "the elongation at break" here refers to the elongation at break (%) measured based on JISK6251: 2010 (dumbbell shape 3 type | mold test piece use). In the first embodiment, the side reinforcing rubber 26 is made of one kind of rubber material, but the present invention is not limited to this configuration, and the side reinforcing rubber 26 may be made of plural kinds of rubber materials.
In the first embodiment, the side reinforcing rubber 26 mainly composed of rubber is used as an example of the side reinforcing layer, but the present invention is not limited to this configuration, and the side reinforcing layer is formed of another material. You may For example, you may form the side reinforcement layer which has a thermoplastic resin etc. as a main component. The side reinforcing rubber 26 may also contain materials such as fillers, short fibers, and resins.

  Further, the middle point of the overlapping portion 28 overlapping the side reinforcing rubber 26 with the carcass 22 of the bead filler 20 interposed therebetween (that is, the end 20A of the bead filler 20 and the end 26B of the side reinforcing rubber 26 along the extending direction of the carcass 22) Preferably, the thickness GB of the side reinforcing rubber 26 at the middle point Q) is set in the range of 40 to 80% of the maximum thickness GA of the side reinforcing rubber 26. As described above, by setting the thickness GB of the side reinforcing rubber 26 to 40 to 80% or less of the maximum thickness GA, even if a buckling phenomenon occurs in the tire side portion 14, the side reinforcing rubber It is possible to suppress the occurrence of breakage (as an example, cracking) at 26. In the first embodiment, the thickness of the side reinforcing rubber 26 at the maximum width position of the carcass 22 is the maximum thickness GA, but the present invention is not limited to this configuration. Further, the maximum width position of the carcass 22 mentioned here indicates a position having the largest 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 in a state where the tire 10 is assembled to the standard rim 30 and the internal pressure is a standard air pressure is 50 to 80% of the height BH of the bead filler 20 It is preferable to set the height within the range of Here, when the height LH is 80% or less of the height BH, the durability at the time of run flat traveling is easily ensured. In addition, when the height LH is 50% or more of the height BH, the ride comfort is excellent.

  In the tire 10 according to the first embodiment, the rim guard (rim protection) is not provided because the tire 10 having a high tire cross-sectional height SH is targeted, but the present invention is not limited to this configuration, and a rim guard is provided. It is also good.

  An inner liner (not shown) is provided on the inner surface of the tire 10 from one bead portion 12 to the other bead portion 12. In the tire 10 of the first embodiment, the main component of the inner liner is, for example, butyl rubber, but the present invention is not limited to this configuration, and the main component of the inner liner may be another rubber material or resin .

  In the above embodiment, as shown in FIG. 1, the side reinforcing rubber 26 is made of one type of rubber (or resin), but the present invention is not limited to this configuration. May be composed of multiple types of rubber (or resin). For example, the side reinforcing rubber 26 may have a structure in which a plurality of different rubbers (or resins) different in the tire radial direction may be stacked, or the side reinforcing rubber 26 may have a plurality of different rubbers (or resins) in the tire width direction. It may be

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

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

(Elastic material: rubber material)
The rubber material only needs to contain at least a rubber (rubber component), and may contain other components such as additives as long as the effects of the present invention are not impaired. However, the content of the rubber (rubber component) in the rubber material is preferably 50% by mass or more, and more preferably 90% by mass or more based on the total amount of the rubber material.

The rubber component used in the tire according to the first embodiment is not particularly limited, and natural rubber and various synthetic rubbers used in conventionally known rubber compounds can be used singly or in combination of two or more. . For example, rubbers as shown below, or a blend of two or more of them can be used.
As the above-mentioned natural rubber, sheet rubber or block rubber may be used, 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, butadiene based polymers such as polybutadiene (BR), a copolymer of butadiene and an aromatic vinyl compound (eg, SBR, NBR, etc.), a copolymer of butadiene and another diene compound, etc .; Isoprene polymers such as polyisoprene (IR), copolymer of isoprene and aromatic vinyl compound, copolymer of isoprene and other diene compound; chloroprene rubber (CR), butyl rubber (IIR), halogenation Examples thereof include butyl rubber (X-IIR); ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), and optional blends thereof.

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 additives include reinforcing materials such as carbon black, fillers, vulcanizing agents, vulcanization accelerators, fatty acids or salts thereof, metal oxides, process oils, antiaging agents, etc. can do.

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

-Manufacturing of Tire As a method of manufacturing the 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 made of an elastic material A rubber material, a resin material, etc.), a carcass 22 formed of an elastic material (rubber material, resin material, etc.), and a region on the tire width direction outer side of the carcass 22 in the tire side portion 14 Form a vulcanized tire case.

As a method of forming the belt layer 24A in the tread portion 16 of the tire case, for example, a member such as a wire wound on a reel is wound 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 pressing.
Finally, an unvulcanized tread is attached to the outer peripheral surface of the belt layer 24A to obtain a green tire. The green tire manufactured in this manner is vulcanized and formed by a vulcanized mold, and the tire 10 is completed.

Second Embodiment
Next, another embodiment of the tire according to the present invention will be described based on the drawings.
FIG. 4 shows one side of a cut surface of the tire 110 of the second embodiment cut in the tire width direction. In the drawings, arrow TW indicates the width direction (tire width direction) of the tire 110, and arrow TR indicates the radial direction of the tire 110 (tire radial direction).

  As shown in FIG. 4, the tire 110 includes a pair of left and right bead portions 112 (only one bead portion 112 is shown in FIG. 4) and a pair of tire sides extending outward 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 is provided with a tire case 140 corresponding to a tire frame. The tire case 140 is formed using an elastic material (preferably a resin material), and has an annular shape. The tire case 140 includes a bead portion 112, a tire side portion 114, and a tread portion 116.

  In addition, a protective layer 122 is provided on the tire width direction outer side of the tire side portion 114 and the bead portion 112, the tire radial direction inner side of the bead portion 112, and a part on the tire width direction inner side of the bead portion 112. The tire case 140 may be one in which the bead portion 112, the tire side portion 114, and the tread portion 116 are 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 they are integrally formed.

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

  The bead portion 112 is a portion in contact with a rim (not shown), and an annular bead core 118 extending along the tire circumferential direction is embedded. The form which 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 enhancing 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. But may be omitted.

  The tread portion 116 is a portion corresponding to the contact surface of the tire 110, and is provided with a belt layer 124A (reinforcement member, belt member). Further, a tread 130 is provided on the belt layer 124A via a cushion rubber 124B. The material of the belt layer 124A, the cushion rubber 124B, and the tread 130 is not particularly limited, and can be selected from materials (a wire such as a metal wire and an organic resin wire, a resin, a rubber material, etc.) generally used for manufacturing a tire.

-Material The tire case 140 (tire frame body) is formed of an elastic material. That is, as the tire frame body, an aspect formed of a rubber material as an elastic material (a so-called tire skeleton body for a rubber tire), an aspect formed of a resin material as an elastic material Can be mentioned.
In particular, in the tire 110 shown in FIG. 4, it is preferable that the above-described portions be a resin tire made of a resin material.

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

  As a resin contained in a tire frame body, thermoplastic resin, thermoplastic elastomer, and thermosetting resin are mentioned.

As a thermosetting resin, a phenol-type thermosetting resin, a urea-type thermosetting resin, a melamine-type thermosetting resin, an epoxy-type thermosetting resin etc. are mentioned, for example.
Examples of thermoplastic resins include polyamide-based thermoplastic resins, polyester-based thermoplastic resins, olefin-based thermoplastic resins, polyurethane-based thermoplastic resins, vinyl chloride-based thermoplastic resins, and polystyrene-based thermoplastic resins. You may use these individually or in combination of 2 or more types. Among these, as the thermoplastic resin, at least one selected from polyamide-based thermoplastic resins, polyester-based thermoplastic resins, and olefin-based thermoplastic resins is preferable, and it is selected from polyamide-based thermoplastic resins and olefin-based thermoplastic resins Further preferred is at least one of

As the thermoplastic elastomer, for example, polyamide-based thermoplastic elastomer (TPA), polystyrene-based thermoplastic elastomer (TPS), polyurethane-based thermoplastic elastomer (TPU), olefin-based thermoplastic elastomer (TPO), which are defined in JIS K6418, Examples include polyester-based thermoplastic elastomer (TPEE), crosslinked thermoplastic rubber (TPV), and other thermoplastic elastomers (TPZ).
In addition, in consideration of the elasticity required at the time of traveling, the moldability at the time of manufacture, etc., it is preferable to use at least one of a thermoplastic resin and a thermoplastic elastomer as a resin material forming the tire frame. From the viewpoint of ride comfort, it is more preferable to include a thermoplastic elastomer. Among them, it is more preferable to include at least one of a polyamide-based thermoplastic elastomer and a polyester-based thermoplastic elastomer.

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

-Physical properties 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 a viewpoint, about 100 degreeC-250 degreeC is preferable, and 120 degreeC-250 degreeC is still more preferable.

  The tensile elastic modulus defined in JIS K7113: 1995 of the elastic material (tire frame) itself 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 frame.

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

  5 MPa or more is preferable, 5 MPa-20 MPa are still more preferable, and, as for the tensile yield strength prescribed | regulated to JISK7113 (1995) of elastic material (tire frame body) itself, 5 MPa-17 MPa are especially preferable. When the tensile yield strength of the elastic material is 5 MPa or more, it is possible to withstand the deformation due to the load applied to the tire during traveling or the like.

  10% or more is preferable, 10%-70% of an elastic material (tire frame body) itself prescribed | regulated to JISK7113 (1995) is preferable, 10%-70% is still more preferable, and 15%-60% is especially preferable. When the tensile yield elongation of the elastic material is 10% or more, the elastic region is large, and the rim setability can be improved.

  The tensile elongation at break defined in JIS K7113 (1995) of the elastic material (tire frame) itself is preferably 50% or more, more preferably 100% or more, particularly preferably 150% or more, and most preferably 200% or more. When the tensile elongation at break of the elastic material is 50% or more, the rim assembling property is good and it is possible to make it difficult to be broken against a collision.

  The deflection temperature under load (at 0.45 MPa load) specified in ISO 75-2 or ASTM D 648 of the elastic material (tire frame body) itself is preferably 50 ° C. or higher, more preferably 50 ° C. to 150 ° C., and 50 ° C. to 130 ° C. is particularly preferred. When the deflection temperature under load of the elastic material is 50 ° C. or higher, deformation of the tire frame can be suppressed even when vulcanization is performed in the manufacture of a tire.

-Manufacture of tire The manufacturing method in particular of tire case 140 is not restricted. For example, a tire case half in a state in which the tire case 140 is divided at the equatorial plane (a plane indicated by CL in FIG. 4) is manufactured by injection molding or the like, and the tire case halves are joined at the equatorial plane. 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 pressing.
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, embedding a previously formed bead filler 120 and an annular member for the bead core 118 in the bead portion 112 by a known method It may be formed of

  The present invention has been described above with reference to the first and second embodiments, but these embodiments are merely examples, and the present invention can be implemented with various modifications without departing from the scope of the present invention. Can. Further, it goes without saying that the scope of rights of the present invention is not limited to these embodiments.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these descriptions. In addition, unless otherwise indicated, "part" represents a mass reference | standard.

Example, Comparative Example
<Preparation of bead core>
The bead core of the aspect shown to FIG. 3 (B) shown in the above-mentioned 1st Embodiment was produced.
First, using monofilaments (monofilaments of average diameter φ1.25 mm, steel, strength: 2700 N, elongation: 7%) as bead wires, the adhesive resins (resins shown in Tables 1 and 2) are heated and melted in the bead wires. C) was attached to form a layer to be an adhesive resin layer.

Next, the bead wire was placed in a mold so that three bead wires on which a layer to be an adhesive resin layer was formed were arranged side by side, and extruded by an extruder around the outer layer to be an adhesive resin layer. The coating resin (resin A) shown in was applied, coated, and cooled. The extrusion conditions were such that the temperature of the bead wire was 200 ° C., the temperature of the coating resin (resin A) was 240 ° C., and the extrusion speed was 30 m / min. The outer periphery of nine bead wires was coated with a covering resin layer through an adhesive resin layer by winding and winding the member shown in FIG. 3 (B) in which three bead wires are arranged with hot air. A bead core having a structure was produced.
The thickness (average thickness of the minimum portion) of the adhesive resin layer in the bead core was 50 μm, and the thickness of the coating resin layer (average thickness of the minimum portion) was 200 μm. Moreover, the average distance between adjacent bead wires was 200 μm.

<Preparation of bead member>
The bead member (member consisting of a bead core and a bead filler) of the aspect shown in FIG.1 and FIG.2 shown in above-mentioned 1st Embodiment was produced.
The bead core obtained from the above is set in a mold in which the bead filler shape is processed in advance, and the resin (resin B) for bead filler is injected by an injection molding machine, whereby the bead filler is arranged to contact the outer periphery of the bead core. A bead member having the following structure was produced. The mold temperature was 80 to 110 ° C., and the molding temperature was 200 to 270 ° C.

<Preparation of a tire provided with a bead member as a bead portion>
The tire (run flat tire) of the aspect shown in FIG.1 and FIG.2 shown in the above-mentioned 1st Embodiment was produced using the bead member obtained from the above for a pair of bead part.
A tire side portion (carcass tire width using a mixed rubber material of natural rubber (NR) and styrene butadiene rubber (SBR) is prepared by preparing a bead member obtained from the above and a polyethylene phthalate ply cord. A green tire was produced using the direction outer area), the side reinforcing rubber, the tread portion, and the belt layer of the stranded wire.
About the produced green tire, Comparative Examples 1-3, Examples 1-9 heat at 150 ° C, 25 minutes, Comparative Examples 4-5, Examples 10, 11 at 170 ° C, 20 minutes conditions (vulcanization of rubber ) Was done.
The obtained tire had a tire size of 225 / 40R18 and a tread portion thickness of 10 mm.

[Method of measuring various physical properties]
The melting points of the coated resin layer (resin A), the bead filler (resin B), and the adhesive resin layer (resin C) are endothermic peaks in a curve (DSC curve) obtained by differential scanning calorimetry (DSC). Refers to the temperature at which The measurement of melting | fusing point was performed based on JISK7121: 2012 using differential scanning calorimeter DSC. The measurement was performed at a sweep rate of 10 ° C./min using “DSC Q100” manufactured by TA Instruments Co., Ltd.

  The water absorption of the coating resin layer and the bead filler was measured according to ISO 62 (1999).

The measurement of the tensile elasticity modulus of a coating resin layer and a bead filler was performed based on JISK7113: 1995. Specifically, using a Shimadzu Autograph AGS-J (5 KN) manufactured by Shimadzu Corporation, the tensile modulus was set at 100 mm / min to measure the tensile modulus.
In addition, the measurement sample was separately prepared using the same material as a coating resin layer or a bead filler. Specifically, the shape of JIS No. 3 was molded at a cylinder temperature of 180 ° C. to 260 ° C. and a mold temperature of 50 ° C. to 110 ° C. using an injection molding machine (NEX-50, manufactured by Nissei Resin Industry Co., Ltd.) to obtain a measurement sample. Alternatively, a flat plate of 110 mm × 110 mm and thickness t = 2 mm was formed, and punched into a shape of JIS No. 3 with Super Dumbbell (registered trademark) manufactured by Dumbbell Co., Ltd. to prepare a measurement sample.

The Charpy impact strength of the coated resin layer and the bead filler is measured according to JIS K7111-1: 2012, using a Charpy impact tester (made by Yasuda Seiki Co., Ltd., product name: 141 type), a test piece (notch. It measured on the conditions of the temperature of 23 degreeC of processing presence.
Specifically, the amount of energy consumed from the difference between the angles before and after the collision by measuring the angle returned after collision with the sample under the conditions of a nominal pendulum energy (weight) of 4 J and a hammer lifting angle of 150 °. (Energy absorption amount) was calculated.
In addition, the measurement sample was shape | molded in the shape of A1 of JISK7139: 2009 on said shaping | molding conditions.

[Rim setability]
As a pneumatic tire, prepare 225 / 40R18 tire size, standard rim 7.5J × 18 corresponding to the tire size, and let one worker carry out rim assembly work three times, at the time of rim assembly work It was determined whether or not "cracks (cracks in bead members)" occurred.

[Run flat runnability]
In the indoor drum test based on the ISO standard, run flat travel was performed at an internal pressure of 0 kPa and at a speed of 80 km / h. The distance was measured until driving was not possible due to tire failure or support failure. If no failure occurs even after traveling 300 km, the test was ended at that time.
A (○): travelable for over 100 km B (△): travelable for over 80 km and less than 100 km C (×): travelable under 80 km

[Modulus change during moisture absorption]
The material of the bead portion (a measurement sample prepared using the same material as the bead filler in the measurement of the tensile modulus) was made to absorb moisture by the following method, and the change in the tensile modulus was measured before and after the moisture absorption .
As a method of absorbing moisture, the measurement samples were kept out of contact with each other in distilled water, and immersion was performed for 75 days at room temperature (23 ° C.).
The measurement of the tensile modulus after water supply for 75 days was also performed in accordance with JIS K7113: 1995, as described above. Specifically, using a Shimadzu Autograph AGS-J (5 KN) manufactured by Shimadzu Corporation, the tensile modulus was set at 100 mm / min to measure the tensile modulus. However, the conditioning at a temperature of 23 + 2 ° C and a relative humidity of (50 ± 5)% for at least 48 hours before the test specified in JIS K7113: 1995 "3. The test was carried out promptly after immersion for 75 days in distilled water.

The components in the table are as follows.
(Adhesive resin layer)
PA 66: Toray Industries, Inc., nylon 66, product name "Amilan CM1017", melting point 265 ° C.
・ QE060: Mitsui Chemicals, Inc., maleic anhydride-modified propylene, "Admer QE060", melting point 139 ° C
・ QF500: Mitsui Chemicals, Inc., maleic anhydride modified polypropylene, "Admar QF500", melting point 165 ° C
· GQ 730: manufactured by Mitsubishi Chemical Co., Ltd., a maleic anhydride-modified polyester thermoplastic elastomer, "Primalloy-AP GQ 730", melting point 200 ° C

(Coating resin layer and bead filler)
-PA6: Ube Industries, Ltd., nylon 6, product name "UBE nylon 1013 B", melting point 225 ° C.
PA11: manufactured by Arkema Co., Ltd., nylon 11, product name "BMNO TLD", melting point 188 ° C.
・ PA12: Ube Industries, Ltd., nylon 12, product name “UBESTA 3024U”, melting point 178 ° C.
-PA 610: manufactured by Arkema Co., nylon 610, product name "Hiprolon 70NN", melting point 222 ° C.
-PA 612: manufactured by Arkema, nylon 612, product name "Hiprolon 90NN", melting point 215 ° C
-PA1010: manufactured by Arkema Co., Ltd., nylon 1010, product name "Hiprolon 200NN", melting point 202 ° C.
-PA1012: manufactured by Arkema, nylon 1012, product name "Hiprolon 400NN", melting point 190 ° C
· XPA 9055: Ube Industries, Ltd., product name "UBESTA XPA 9055", melting point 164 ° C
· XPA 9068: manufactured by Ube Industries, Ltd., product name "UBESTA XPA 9068", melting point 175 ° C
Hytrel 5557: Toray Dupont Co., Ltd., polyester thermoplastic elastomer, "Hytrel 5557", melting point 208 ° C.
Hytrel 6347: manufactured by Toray Dupont, polyester thermoplastic elastomer, "Hytrel 6347", melting point 215 ° C
Hytrel 7247: manufactured by Toray Dupont, polyester thermoplastic elastomer, "Hytrel 7247", melting point 216 ° C
PBT: Toray Industries, Inc., polybutylene terephthalate resin (PBT), "Trecon 1401 X 06", melting point 224 ° C

  As can be seen from the evaluation results shown in Table 1 or Table 2, the resin A contained in the covering resin layer and the resin B contained in the bead filler are each independently a thermoplastic resin or a thermoplastic elastomer, and the resin A and the resin B is a resin having a skeleton common to the constituent units constituting the main chain of the resin, and both of the resin A and the resin B have a melting point of 175 ° C. or more and 223 ° C. or less, and both of the coating resin layer and the bead filler are In the present example using a bead member having a water absorption rate of 3.5% by mass or less, the occurrence of change in elastic modulus due to moisture absorption is suppressed and run flat running performance (running durability) is excellent, as compared with the comparative example. It was found that the fracture at the time of assembling the rim was also suppressed.

1 bead wire 2 adhesive layer 3 coated resin layer 10 tire (run flat tire)
12 bead portion 14 tire side portion 16 tread portion 18 bead core 20, 120 bead filler 20A end portion 22 carcass 22A main portion 22B folded back portion 22C end portion 22I inner surface 22O outer surface 26 side reinforcing rubber 26A end portion (end portion on tread side)
26B end (end on bead core side)
Reference Signs List 30 standard rim 110 tire 112 bead portion 114 tire side portion 116 tread portion 118 bead core 122 protective layer 124A belt layer 124B cushion rubber 130 tread 140 tire case (tire frame)
CL tire equatorial plane Q middle point

Claims (9)

A bead member for a tire, comprising: a bead wire; and a bead core covering the bead wire and having a covering resin layer containing a resin A; and a bead filler disposed so as to contact at least a part of the covering resin layer and containing a resin B There,
The resin A and the resin B are each independently a thermoplastic resin or a thermoplastic elastomer,
The resin A and the resin B are resins having a skeleton common to structural units constituting the main chain of the resin,
The resin A and the resin B each have a melting point of 175 ° C. or more and 223 ° C. or less,
The bead member for a tire, wherein the covering resin layer and the bead filler each have a water absorption of 3.5% by mass or less. The bead member for a tire according to claim 1, wherein the coating resin layer and the bead filler each have a Charpy impact strength of 5 kJ / m ² or more.   The bead member for a tire according to claim 1 or 2, wherein each of the covering resin layer and the bead filler has a tensile modulus of elasticity of 274 MPa or more and 2000 MPa or less.   The tire bead member according to any one of claims 1 to 3, wherein at least one of the resin A and the resin B is a thermoplastic elastomer.   The tire bead member according to claim 4, wherein at least one of the resin A and the resin B is a polyamide-based thermoplastic elastomer or a polyester-based thermoplastic elastomer.   The bead member for a tire according to any one of claims 1 to 5, wherein the bead core has an adhesive resin layer disposed between the bead wire and the covering resin layer and containing a resin C.   7. The bead member for a tire according to claim 6, wherein the resin C is a thermoplastic resin having a polar functional group or a thermoplastic elastomer having a polar functional group.   The bead member for a tire according to claim 6 or 7, wherein the melting point of the resin C is 139 ° C or more and 220 ° C or less.   The tire which has the bead member for tires of any one of Claims 1-8 in a pair of bead part.