JP2019001358A - tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tire having excellent plunger property and cornering power. SOLUTION: A tire skeleton formed of a resin material containing a thermoplastic resin A, a reinforcing cord member wound around the outer peripheral portion of the tire skeleton in the circumferential direction, and the reinforcing cord member are coated and thermoplastic. A reinforcing cord layer having a coating resin layer containing a resin B and a filler is provided, and the thermoplastic resin A and the thermoplastic resin B have a common skeleton in a structural unit constituting the main chain of the resin. A tire that is a thermoplastic resin and in which the content of the filler in the coating resin layer is in the range of 0% by mass or more and 20% by mass or less. [Selection diagram] None

Description

  The present invention relates to a tire.

  Conventionally, in pneumatic tires used for passenger cars and other vehicles, tires using resin materials, particularly thermoplastic resins and thermoplastic elastomers, as materials, have been studied from the viewpoint of weight reduction, ease of molding, and ease of recycling. Has been. These thermoplastic polymer materials (thermoplastic resins) have many advantages from the viewpoint of improving productivity, such as being capable of injection molding.

  For example, a tire that is formed of a thermoplastic resin material and has an annular tire skeleton, and has a reinforcing cord member that is wound in the circumferential direction around the outer periphery of the tire skeleton to form a reinforcing cord layer, There has been proposed a tire in which a plastic resin material contains at least a polyester-based thermoplastic elastomer (see Patent Document 1).

JP 2012-046025 A

Pressure from the road surface is applied to the tire during traveling, that is, force is applied from the tire radial direction side. In particular, when unevenness is present on the road surface, a locally strong force is applied from the tire radial direction side. On the other hand, a force from the cornering direction is applied to the tire when the vehicle body is curved, that is, a force from the tire axial direction side is also applied.
Here, when a tire including a reinforcing cord layer coated with a coating resin layer on the outer peripheral portion of the tire frame member is used, reinforcement is performed for both the force from the tire radial direction side and the force from the tire axial direction side. It has been difficult to improve both the rigidity and durability of the cord layer in the coating resin layer and the durability at the interface between the tire frame body and the reinforcing cord layer. Therefore, it has been desired to achieve rigidity and durability against the force from the tire radial direction side and the force from the tire axial direction side, specifically, excellent plunger properties and cornering power.

  In view of the above circumstances, an object of the present invention is to provide a tire having a tire skeleton including a thermoplastic resin and having excellent plunger properties and cornering power.

  The above problems are solved by the present invention described below.

<1> a tire skeleton formed of a resin material containing the thermoplastic resin A;
A reinforcing cord layer wound around an outer periphery of the tire frame body in a circumferential direction, and a reinforcing cord layer having a covering resin layer covering the reinforcing cord member and containing a thermoplastic resin B and a filler;
With
The thermoplastic resin A and the thermoplastic resin B are thermoplastic resins having a common skeleton in structural units constituting the main chain of the resin,
The tire in which the content of the filler in the coating resin layer is in the range of more than 0% by mass and 20% by mass or less.
<2> The tire according to <1>, wherein the filler is an inorganic filler.
<3> The tire according to <1> or <2>, wherein the filler is a filler having a particle shape or a plate shape.
<4> The tire according to <3>, wherein the particle-shaped filler has an average particle diameter of 0.1 μm to 50 μm, and the plate-shaped filler has an average particle diameter of 0.1 μm to 50 μm.
<5> The tire according to <3> or <4>, wherein the particle-shaped or plate-shaped filler is glass or talc.
<6> The tire according to <1> or <2>, wherein the filler is a fibrous filler.
<7> The tire according to <6>, wherein the fiber-shaped filler has a length in a major axis direction of 50 μm to 1000 μm.
<8> The tire according to <6> or <7>, wherein the fiber-shaped filler is glass fiber.
<9> Any one of the above <1> to <8>, wherein the thermoplastic resin A and the thermoplastic resin B are both polyester-based thermoplastic elastomers or all are polyamide-based thermoplastic elastomers. The tire according to item.
<10> Any of the above <1> to <9>, wherein the tire skeleton and the coating resin layer each include only a polyester-based thermoplastic elastomer as a thermoplastic resin or only a polyamide-based thermoplastic elastomer. The tire according to claim 1.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the tire which has a tire frame | skeleton body containing a thermoplastic resin, and is excellent in plunger property and cornering power.

1 is a perspective view showing a partial cross section of a tire according to an embodiment of the present invention. It is sectional drawing of the bead part with which the rim | limb was mounted | worn. It is sectional drawing along the tire rotating shaft which shows the state by which the reinforcement cord was embed | buried under the crown part of the tire case of the tire of this embodiment. It is explanatory drawing for demonstrating the operation | movement which embeds a reinforcement cord in the crown part of a tire case using a cord heating apparatus and rollers.

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

In this specification, the “resin” is a concept including a thermoplastic resin (including a thermoplastic elastomer) and a thermosetting resin, and does not include a vulcanized rubber.
In the present specification, the term “thermoplastic elastomer” means a crystalline polymer having a high melting point hard segment or a high cohesion hard segment, and an amorphous polymer having a low glass transition temperature soft segment. It means a polymer compound having a rubber-like elasticity, which becomes a relatively hard and strong state when cooled, and which softens and flows as the temperature rises.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the term “process” includes not only an independent process but also a process that can be clearly distinguished from other processes as long as the purpose is achieved. include.

<Tire>
The tire of the present invention includes a tire frame body and a reinforcing cord layer provided on an outer peripheral portion of the tire frame body.
The tire frame is formed of a resin material containing the thermoplastic resin A.
The reinforcing cord layer includes a reinforcing cord member that is wound around the outer periphery of the tire frame body in the circumferential direction, and a covering resin layer that covers the reinforcing cord member. The coating resin layer contains the thermoplastic resin B and a filler.
Note that the thermoplastic resin A contained in the tire skeleton and the thermoplastic resin B contained in the coating resin layer are thermoplastic resins having a skeleton that is common in the structural units constituting the main chain of the resin.
And the content rate of the filler in a coating resin layer is the range of more than 0 mass% and 20 mass% or less.

According to the study by the present inventors, the thermoplastic resin A contained in the tire skeleton and the thermoplastic resin B contained in the coating resin layer have a common skeleton in the constituent units constituting the main chain of the resin. A tire which is a thermoplastic resin and contains a filler with a content of 0% by mass or more and 20% by mass or less in the coating resin layer in which the reinforcing cord layer covers the reinforcing cord member is thermoplastic resin A and thermoplastic resin B. It is clear that the plunger property and cornering power are superior to those of a tire that does not have a common skeleton in the structural units constituting the resin main chain, or a tire that does not contain a filler in the coating resin layer. .
The reason is presumed as follows.

The thermoplastic resin A contained in the tire skeleton and the thermoplastic resin B contained in the coating resin layer are thermoplastic resins having a common skeleton in the constituent units constituting the main chain of the resin, The affinity between the tire frame and the reinforcing cord layer is enhanced, and excellent adhesion is exhibited.
On the other hand, when the reinforcing cord layer contains a filler in the covering resin layer, the rigidity of the covering resin layer can be increased and the strength of the reinforcing cord layer can be improved.
That is, according to the present invention, the strength applied to the tire from the radial direction side is improved by improving the strength of the reinforcing cord layer itself and improving the adhesion at the interface between the reinforcing cord layer and the tire frame body. Both the rigidity and durability against the force and the rigidity and durability against the force applied from the axial direction side are enhanced. As a result, both excellent plunger performance and high cornering power can be achieved.

Here, “a thermoplastic resin having a common skeleton in structural units constituting the main chain of the resin” means that, for example, both the thermoplastic resins A and B are “polyester thermoplastic elastomer (TPC) and thermoplastic resin”. In the case of containing “at least one kind of polyester”, it can be said that the structural units constituting the main chain of the resin have a common skeleton (that is, an ester bond skeleton). Similarly, a case where both of the thermoplastic resins A and B include the following thermoplastic resins is exemplified.
-When both the thermoplastic resins A and B contain "at least one of polyamide-based thermoplastic elastomer (TPA) and thermoplastic polyamide": they have an amide bond skeleton in common with each other-Both the thermoplastic resins A and B are " When containing at least one of a polystyrene-based thermoplastic elastomer (TPS) and a thermoplastic polystyrene ": having a polystyrene skeleton in common with each other-Both the thermoplastic resins A and B are" polyurethane-based thermoplastic elastomer (TPU) and thermoplastic When containing "at least one kind of polyurethane": having a urethane bond skeleton in common with each other-When both the thermoplastic resins A and B contain "at least one kind of polyolefin-based thermoplastic elastomer (TPO) and thermoplastic polyolefin": Polyolefin in common with each other With a down skeleton

As the thermoplastic resins A and B, a thermoplastic resin containing a structural unit having the same chemical structure as a structural unit constituting the molecular structure of the resin (for example, heat using a monomer having the same structure as a monomer used as a raw material of the resin). It is more preferable to use a plastic resin.
In addition, as a constituent unit constituting the molecular structure of the resin, a thermoplastic resin containing only a constituent unit having the same chemical structure (for example, a thermoplastic resin using only a monomer having the same structure as a monomer as a raw material of the resin) is used. Further preferred.

[Tire frame]
The resin material forming the tire frame body contains a thermoplastic resin (thermoplastic resin A) and may further contain an additive. The thermoplastic resin does not include vulcanized rubber. The tire frame member contains 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more of a thermoplastic resin with respect to the total mass. Thermoplastic resins also include thermoplastic elastomers.

・ Thermoplastic resin A
A thermoplastic resin (including a thermoplastic elastomer) refers to a high molecular compound that softens and flows as the temperature rises and becomes relatively hard and strong when cooled. In the present specification, among these, the polymer softens and flows with increasing temperature and becomes a relatively hard and strong state when cooled, and a polymer compound having rubber-like elasticity is referred to as a thermoplastic elastomer.

  As the thermoplastic resin (including the thermoplastic elastomer), a thermoplastic resin having elasticity equivalent to that of rubber used for a general tire, a thermoplastic elastomer (TPE), and the like can be used. In consideration of elasticity during running and moldability during production, it is desirable to use a thermoplastic elastomer.

Examples of the thermoplastic elastomer include a polyester-based thermoplastic elastomer (TPC), a polyamide-based thermoplastic elastomer (TPA), a polystyrene-based thermoplastic elastomer (TPS), a polyurethane-based thermoplastic elastomer (TPU), and a polyolefin-based thermoplastic elastomer ( TPO), crosslinked thermoplastic rubber (TPV), and other thermoplastic elastomers (TPZ). For the definition and classification of the thermoplastic elastomer, JIS K6418 can be referred to.
Examples of the thermoplastic resin other than the thermoplastic elastomer include thermoplastic polyesters, thermoplastic polyamides, thermoplastic polystyrenes, thermoplastic polyurethanes, thermoplastic polyolefins, and other thermoplastic resins.

  Among these, as the thermoplastic elastomer, a polyester-based thermoplastic elastomer is preferable because of its advantage that heat resistance and bending fatigue resistance are higher than those of other thermoplastic elastomers. A tire constituted by including a polyester-based thermoplastic elastomer exhibits high durability by suppressing the occurrence and growth of fatigue cracks against repeated bending due to its high bending fatigue resistance.

  The thermoplastic elastomer is preferably a polyamide thermoplastic elastomer from the viewpoint of mechanical durability. Furthermore, from the viewpoint of heat resistance and moist heat resistance, the polymer that forms the hard segment is polyamide (polyamide 12 or the like), and the polyamide-based thermoplastic elastomer in which the polymer that forms the soft segment is polyether is more preferable, and the hard segment is formed. More preferably, the polymer to be formed is polyamide 12, the polymer forming the soft segment is a polyether, the hard segment and the soft segment are bonded by an amide bond, and the polyamide-based thermoplastic elastomer having no ester bond is used.

-Polyester thermoplastic elastomer-
The polyester-based thermoplastic elastomer is a polymer compound having elasticity, and includes a polymer containing a polyester that forms a hard segment with a high melting point and a polymer that forms an amorphous soft segment with a low glass transition temperature. Means a thermoplastic resin material comprising a copolymer having a partial structure comprising polyester in its structure. Examples of the polyester-based thermoplastic elastomer include ester-based thermoplastic elastomer (TPC) defined in JIS K6418: 2007.
As the 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 (eg, polyester or polyether) is amorphous and has a low glass transition temperature. The material which forms is mentioned.

  An aromatic polyester can be used as the polyester forming the hard segment. The aromatic polyester can be formed, for example, from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol.

Examples of the aromatic polyester include polybutylene terephthalate derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol. Further, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or these A dicarboxylic acid component such as an ester-forming derivative, and a diol having a molecular weight of 300 or less (for example, an aliphatic diol such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, Cycloaliphatic diols such as 4-cyclohexanedimethanol and tricyclodecane dimethylol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2- Hydroxyethoxy) Phenyl] propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4′-dihydroxy-p-terphenyl, 4,4 Polyesters derived from aromatic diols such as' -dihydroxy-p-quarterphenyl) or the like, or copolymer polyesters in which two or more of these dicarboxylic acid components and diol components are used in combination. It is also possible to copolymerize a trifunctional or higher polyfunctional carboxylic acid component, polyfunctional oxyacid component, polyfunctional hydroxy component and the like in a range of 5 mol% or less.
Examples of the polyester forming the hard segment include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, and polybutylene terephthalate is preferable.

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 polymer of glycol, and a copolymer of ethylene oxide and tetrahydrofuran.
Examples of the aliphatic polyester include poly (ε-caprolactone), polyenantlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate.

  Among these aliphatic polyethers and aliphatic polyesters, poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol are polymers that form soft segments from the viewpoint of the elastic properties of the resulting polyester block copolymer. Preferred are ethylene oxide adducts, poly (ε-caprolactone), polybutylene adipate, polyethylene adipate, and the like.

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

  As a combination of the above-mentioned hard segment and a soft segment, each combination of the above-mentioned hard segment and a soft segment can be mentioned, for example. Among these, the combination of the hard segment and the soft segment described above is preferably a combination in which the hard segment is polybutylene terephthalate, the soft segment is an aliphatic polyether, and the hard segment is polybutylene terephthalate. More preferred is a combination wherein is poly (ethylene oxide) glycol.

  Examples of commercially available polyester-based thermoplastic elastomers include “Hytrel” series (for example, 3046, 5557, 6347, 4047N, 4767N, etc.) manufactured by Toray DuPont Co., Ltd., and “Perprene” series manufactured by Toyobo Co., Ltd. (For example, P30B, P40B, P40H, P55B, P70B, P150B, P280B, E450B, P150M, S1001, S2001, S5001, S6001, S9001, etc.) can be used.

  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.

  In the present invention, when a polyester thermoplastic elastomer is included in the resin material, the content of the polyester thermoplastic elastomer in the total thermoplastic resin contained is not particularly limited, but the total amount of all resins. On the other hand, 50 mass% or more is preferable, 80 mass% or more is more preferable, and 90 mass% or more is more preferable. When the content of the polyester-based thermoplastic elastomer is 50% by mass or more with respect to the total amount of the thermoplastic resin material, the polyester-based thermoplastic elastomer can fully exhibit the characteristics, and the durability of the tire is further improved. It becomes easy to let.

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

  In the polyamide-based thermoplastic elastomer, examples of the polyamide that forms the hard segment include polyamides produced from monomers represented by the following general formula (1) or general formula (2).

General formula (1)

[In General Formula (1), R ¹ represents a molecular chain of a hydrocarbon having 2 to 20 carbon atoms (for example, an alkylene group having 2 to 20 carbon atoms). ]

General formula (2)

[In General Formula (2), R ² represents a molecular chain of a hydrocarbon having 3 to 20 carbon atoms (for example, an alkylene group having 3 to 20 carbon atoms). ]

In general formula (1), R ¹ is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms, such as an alkylene group having 3 to 18 carbon atoms, and a hydrocarbon molecular chain having 4 to 15 carbon atoms, such as carbon. An alkylene group having 4 to 15 carbon atoms is more preferable, and a molecular chain of a hydrocarbon having 10 to 15 carbon atoms, for example, an alkylene group having 10 to 15 carbon atoms is particularly preferable.
In general formula (2), R ² is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms, such as an alkylene group having 3 to 18 carbon atoms, and a hydrocarbon molecular chain having 4 to 15 carbon atoms, For example, an alkylene group having 4 to 15 carbon atoms is more preferable, and a molecular chain of a hydrocarbon having 10 to 15 carbon atoms, for example, an alkylene group having 10 to 15 carbon atoms is particularly preferable.
Examples of the monomer represented by the general formula (1) or the general formula (2) include ω-aminocarboxylic acid or lactam. Examples of the polyamide forming the hard segment include polycondensates of these ω-aminocarboxylic acids or lactams, and co-condensation polymers of diamines and dicarboxylic acids.

The ω-aminocarboxylic acid has 6 to 20 carbon atoms such as 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Aliphatic omega-aminocarboxylic acid etc. can be mentioned. Moreover, as a lactam, C5-C20 aliphatic lactams, such as lauryl lactam, (epsilon) -caprolactam, udecan lactam, (omega) -enantolactam, 2-pyrrolidone, etc. can be mentioned.
Examples of the diamine include ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2, 2, 4 Examples include diamine compounds such as aliphatic diamines having 2 to 20 carbon atoms such as trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, and metaxylenediamine.
Further, dicarboxylic _{^{acids, HOOC- (R 3) m -COOH}} (R 3: the molecular chain of a hydrocarbon of 3 to 20 carbon atoms, m: 0 or 1) can be represented by, 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 and dodecanedioic acid.
As the polyamide that forms the hard segment, polyamide obtained by ring-opening polycondensation of lauryl lactam, ε-caprolactam, or udecan lactam can be preferably used.

Moreover, as a polymer which forms a soft segment, polyester, polyether, etc. are mentioned, for example, Polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, ABA type | mold triblock polyether etc. are mentioned specifically ,. These can be used alone or in combination of two or more. Moreover, polyether diamine etc. which are obtained by making ammonia etc. react with the terminal of polyether can also be used.
Here, the “ABA type 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 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.

  As a combination of a hard segment and a soft segment, each combination of the hard segment and the soft segment mentioned above can be mentioned. Among these, combinations of hard segment and soft segment include lauryl lactam ring-opening polycondensate / polyethylene glycol combination, lauryl lactam ring-opening polycondensate / polypropylene glycol combination, and lauryl lactam ring-opening polycondensation. Preferred is a combination of isomers / polytetramethylene ether glycol, or a ring-opening polycondensate of lauryl lactam / ABA type triblock polyether, and a combination of 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 15000 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) to the hard segment (x) and the soft segment (y) is preferably 50:50 to 90:10, more preferably 50:50 to 80:20, from the viewpoint of moldability. .

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

  Examples of commercially available products of polyamide-based thermoplastic elastomer include UBE Kosan's “UBESTA XPA” series (for example, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2XPA9044, etc.) and “Vestamide” of Daicel Eponic Corporation. ”Series (for example, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.) and the like can be used.

  In the present invention, when the resin material contains a polyamide-based thermoplastic elastomer, the content of the polyamide-based thermoplastic elastomer in the total thermoplastic resin contained is not particularly limited, but the total amount of all resins. On the other hand, 50 mass% or more is preferable, 80 mass% or more is more preferable, and 90 mass% or more is more preferable. When the content of the polyamide-based thermoplastic elastomer is 50% by mass or more based on the total amount of the thermoplastic resin material, the properties of the polyamide-based thermoplastic elastomer can be sufficiently exerted, and the mechanical durability of the tire can be improved. It becomes easier to improve.

-Polystyrene thermoplastic elastomer As the polystyrene thermoplastic elastomer, for example, at least polystyrene forms a hard segment, and other polymers (for example, polybutadiene, polyisoprene, polyethylene, hydrogenated polybutadiene, hydrogenated polyisoprene, etc.) are not. Examples thereof include materials that form a soft segment having a crystallinity and a low glass transition temperature. As the polystyrene forming the hard segment, for example, those obtained by a known radical polymerization method, ionic polymerization method and the like are preferably used, and specifically, polystyrene having anion living polymerization can be mentioned. Examples of the polymer that forms the soft segment include polybutadiene, polyisoprene, and poly (2,3-dimethyl-butadiene).

  As a combination of a hard segment and a soft segment, each combination of the hard segment and the soft segment mentioned above can be mentioned. Among these, the combination of the hard segment and the soft segment is preferably a combination of polystyrene / polybutadiene or a combination of polystyrene / polyisoprene. Moreover, in order to suppress the unintended cross-linking reaction of the thermoplastic elastomer, the soft segment is preferably hydrogenated.

The number average molecular weight of the polymer (polystyrene) forming the hard segment is preferably 5,000 to 500,000, and more preferably 10,000 to 200,000.
Moreover, as a number average molecular weight of the polymer which forms a soft segment, 5000-1 million are preferable, 10000-800000 are more preferable, and 30000-500000 are still more preferable. Furthermore, the volume ratio (x: y) to the hard segment (x) and the soft segment (y) is preferably 5:95 to 80:20 and more preferably 10:90 to 70:30 from the viewpoint of moldability. .

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

  As a commercially available product of polystyrene-based thermoplastic elastomer, for example, “Tough Tech” series (for example, H1031, H1041, H1043, H1051, H1052, H1053, H1062, H1082, H1141, H1221, H1272, etc.) manufactured by Asahi Kasei Corporation, “SEBS” series (8007, 8076, etc.) and “SEPS” series (2002, 2063, etc.) manufactured by Kuraray Co., Ltd. can be used.

-Polyurethane thermoplastic elastomer-
As polyurethane-based thermoplastic elastomers, for example, at least polyurethane forms a hard segment in which pseudo-crosslinking is formed by physical aggregation, and other polymers form a soft segment with a low glass transition temperature that is amorphous. Material.
Specific examples of the polyurethane-based thermoplastic elastomer include a polyurethane-based thermoplastic elastomer (TPU) defined in JIS K6418: 2007. The polyurethane-based thermoplastic elastomer can be represented as a copolymer including a soft segment including a unit structure represented by the following formula A and a hard segment including a unit structure represented by the following formula B.

[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. ]

In the formula A, as the long-chain aliphatic polyether or long-chain aliphatic polyester represented by P, for example, those having a molecular weight of 500 to 5000 can be used. P is derived from a diol compound containing a long-chain aliphatic polyether represented by P and a long-chain aliphatic polyester. Examples of such a diol compound include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly (butylene abido) diol, poly-ε-caprolactone diol, poly (hexamethylene carbonate) having a molecular weight within the above range. ) Diol, ABA type triblock polyether and the like.
These can be used alone or in combination of two or more.

In Formula A and Formula B, R is derived from a diisocyanate compound containing an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon represented by R. Examples of the aliphatic diisocyanate compound containing an aliphatic hydrocarbon represented by R include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, 1,6-hexamethylene diisocyanate, and the like. Can be mentioned.
Examples of the diisocyanate compound containing an alicyclic hydrocarbon represented by R include 1,4-cyclohexane diisocyanate and 4,4-cyclohexane diisocyanate. Furthermore, examples of the aromatic diisocyanate compound containing an aromatic hydrocarbon represented by R include 4,4′-diphenylmethane diisocyanate and tolylene diisocyanate.
These can be used alone or in combination of two or more.

In the formula B, as the short chain aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon represented by P ′, for example, those having a molecular weight of less than 500 can be used. P ′ is derived from a diol compound containing a short-chain aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon represented by P ′. Examples of the aliphatic diol compound containing a short-chain aliphatic hydrocarbon represented by P ′ include glycol and polyalkylene glycol. 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- A decanediol etc. are mentioned.
Examples of the alicyclic diol compound containing an alicyclic hydrocarbon represented by P ′ include cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, Examples include cyclohexane-1,4-diol and cyclohexane-1,4-dimethanol.
Furthermore, examples of the aromatic diol compound containing an aromatic hydrocarbon represented by P ′ include hydroquinone, resorcin, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4′- Dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxydiphenylmethane, bisphenol A, 1, Examples include 1-di (4-hydroxyphenyl) cyclohexane, 1,2-bis (4-hydroxyphenoxy) ethane, 1,4-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like.
These can be used alone or in combination of two or more.

  The number average molecular weight of the polymer (polyurethane) forming the hard segment is preferably 300 to 1500 from the viewpoint of melt moldability. Further, the number average molecular weight of the polymer forming the soft segment is preferably 500 to 20000, more preferably 500 to 5000, and particularly preferably 500 to 3000 from the viewpoints of flexibility and thermal stability of the polyurethane-based thermoplastic elastomer. . Further, the mass ratio (x: y) to the hard segment (x) and the soft segment (y) is preferably 15:85 to 90:10, more preferably 30:70 to 90:10, from the viewpoint of moldability. .

The polyurethane-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method. As the polyurethane-based thermoplastic elastomer, for example, thermoplastic polyurethane described in JP-A-5-331256 can be used.
As the polyurethane-based thermoplastic elastomer, specifically, a combination of a hard segment composed of an aromatic diol and an aromatic diisocyanate and a soft segment composed of a polycarbonate is preferable. More specifically, tolylene diisocyanate ( TDI) / polyester-based polyol copolymer, TDI / polyether-based polyol copolymer, TDI / caprolactone-based polyol copolymer, TDI / polycarbonate-based polyol copolymer, 4,4′-diphenylmethane diisocyanate (MDI) / polyester -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, TDI / polyester polyol copolymer, TDI / polyether polyol copolymer, MDI / polyester polyol copolymer, MDI / polyether polyol copolymer, And at least one selected from MDI + hydroquinone / polyhexamethylene carbonate copolymer is more preferable.

  Examples of commercially available polyurethane-based thermoplastic elastomers include, for example, “Elastollan” series (for example, ET680, ET880, ET690, ET890, etc.) manufactured by BASF, and “Clamiron U” series (for example, Kuraray Co., Ltd.) 2000 series, 3000 series, 8000 series, 9000 series, etc.) "Milactolan" series (for example, XN-2001, XN-2004, P390RSUP, P480RSUI, P26MRNAT, E490, E590, P890, etc.) manufactured by Japan Miraclan Co., Ltd. Etc. can be used.

-Olefin thermoplastic elastomer-
As the olefin-based thermoplastic elastomer, for example, at least a polyolefin forms a hard segment with a crystalline and high melting point, and other polymers (for example, polyolefin, other polyolefins, polyvinyl compounds, etc.) are amorphous and have a glass transition temperature. Examples include materials that form low soft segments. Examples of the polyolefin forming the hard segment include polyethylene, polypropylene, isotactic polypropylene, polybutene, and the like.
Examples of the olefinic thermoplastic elastomer include olefin-α-olefin random copolymers, olefin block copolymers, and the like. Specifically, propylene block copolymers, ethylene-propylene copolymers, propylene- 1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-pentene copolymer, ethylene- 1-butene copolymer, 1-butene-1-hexene copolymer, 1-butene-4-methyl-pentene, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate Copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer Ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer, propylene-methyl methacrylate copolymer, propylene-ethyl methacrylate copolymer, propylene-butyl methacrylate copolymer , 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 the olefinic thermoplastic elastomer, propylene block copolymer, 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, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer , Ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer , Propylene-methyl methacrylate copolymer, pro Lene-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 copolymer, ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-methyl methacrylate copolymer More preferred is at least one selected from ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer.
Further, two or more olefin resins such as ethylene and propylene may be used in combination. 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 olefinic thermoplastic elastomer is preferably 5,000 to 10,000,000. When the number average molecular weight of the olefinic thermoplastic elastomer is 5,000 to 10,000,000, the mechanical properties of the thermoplastic resin material are sufficient and the processability is also excellent. From the same viewpoint, the number average molecular weight of the olefinic thermoplastic elastomer is more preferably 7,000 to 1,000,000, and particularly preferably 10,000 to 1,000,000. Thereby, the mechanical properties and 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. Furthermore, the mass ratio (x: y) to the hard segment (x) and the soft segment (y) is preferably 50:50 to 95:15, and more preferably 50:50 to 90:10, from the viewpoint of moldability. .
The olefinic thermoplastic elastomer can be synthesized by copolymerization by a known method.

Further, as the olefin thermoplastic elastomer, one obtained by acid-modifying a thermoplastic elastomer may be used.
“A product obtained by acid-modifying an olefin thermoplastic elastomer” means that an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group, or a phosphoric acid group is bonded to the olefin thermoplastic elastomer.
Examples of bonding an unsaturated compound having an acidic group such as a carboxylic acid group, sulfuric acid group, and phosphoric acid group to an olefin thermoplastic elastomer include, for example, an unsaturated compound having an acidic group as an unsaturated compound having an acidic group. Examples include bonding (for example, graft polymerization) an unsaturated bond site of a saturated carboxylic acid (generally maleic anhydride).
The unsaturated compound having an acidic group is preferably an unsaturated compound having a carboxylic acid group which is a weak acid group from the viewpoint of suppressing deterioration of the olefin thermoplastic elastomer, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid. , Isocrotonic acid, maleic acid and the like.

  Examples of commercially available olefin-based thermoplastic elastomers include “Tuffmer” series (for example, A0550S, A1050S, A4050S, A1070S, A4070S, A35070S, A1085S, A4085S, A7090, A70090, MH7007, MH7010, manufactured by Mitsui Chemicals, Inc. 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 “Nucleel” 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 (for example, 1125AC, 1209AC, 1218AC, 1609AC, 1820AC, 1913AC, 2112AC, 2116AC, 2615AC, 2715AC, etc. 3117AC, 3427AC, 3717AC, etc.), Sumitomo Chemical Co., Ltd.'s "Acryt" series, "Evaate" series, etc., Tosoh Corporation's "Ultrasen" series, etc., "Prime TPO" series made by prime polymers (for example, E-2900H, F-3900H, E-2900, F-3900, J-5900, E-2910, F-3910, J-5910, E-2710, F- 710, J-5910, E-2740, F-3740, R110MP, R110E, can be used T310E, also M142E, etc.) and the like.

-Additives-
The resin material may contain components other than the thermoplastic resin as desired. Examples of components other than the thermoplastic resin include rubbers, fillers (silica, calcium carbonate, clay, etc.), antioxidants, oils, plasticizers, color formers, weathering agents, and the like.

  It has been found that the addition of a plasticizer to the resin material provides the effects of improving tire rolling performance and improving injection moldability. On the other hand, if the blending amount of the plasticizer is too large, the adhesion to other materials may be affected due to the occurrence of bloom / bleed phenomenon. Therefore, by selecting and using a plasticizer that is highly compatible with the thermoplastic elastomer to be used, it is considered that the bloom and bleed phenomenon can be prevented, the rolling performance of the tire can be improved, and the moldability and safety can be secured. .

  When the resin material contains a component other than the thermoplastic resin, the content of the thermoplastic resin in the resin material is preferably 50% by mass or more from the viewpoint of sufficiently achieving the effects of the present invention, and 80% by mass. More preferably, it is more preferably 90% by mass or more.

-Physical properties of resin materials-
The melting point of the resin material is usually about 100 ° C. to 350 ° C., but is preferably about 100 ° C. to 250 ° C., more preferably 120 ° C. to 250 ° C. from the viewpoint of tire durability and productivity.

  The tensile modulus of elasticity defined in JIS K7113: 1995 of the resin 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 resin material is 50 MPa to 1000 MPa, the rim can be assembled efficiently while maintaining the shape of the tire frame.

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

  The tensile yield strength defined in JIS K7113 (1995) of the resin material (tire frame) itself is preferably 5 MPa or more, more preferably 5 MPa to 20 MPa, and particularly preferably 5 MPa to 17 MPa. When the tensile yield strength of the resin material is 5 MPa or more, the resin material can withstand deformation against a load applied to the tire during traveling.

  The tensile yield elongation defined by JIS K7113 (1995) of the resin material (tire frame) itself is preferably 10% or more, more preferably 10% to 70%, and particularly preferably 15% to 60%. When the tensile yield elongation of the resin material is 10% or more, the elastic region is large and the rim assembly property can be improved.

  The tensile elongation at break specified in JIS K7113 (1995) of the resin 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 resin material is 50% or more, the rim assemblability is good, and it is difficult to break against a collision.

  The load deflection temperature (at 0.45 MPa load) specified in ISO 75-2 or ASTM D648 of the resin material (tire frame) itself is preferably 50 ° C. or more, more preferably 50 ° C. to 150 ° C., and more preferably 50 ° C. to 50 ° C. 130 ° C. is particularly preferred. When the deflection temperature under load of the resin material is 50 ° C. or higher, deformation of the tire skeleton can be suppressed even when vulcanization is performed in the manufacture of the tire.

  The Vicat softening temperature (Method A) defined in JIS K7206 (2016) of the resin material (tire frame) itself is preferably 130 ° C. or higher, preferably 130 to 250 ° C., and more preferably 130 to 220 ° C. When the softening temperature (Method A) of the thermoplastic resin material is 130 ° C. or higher, softening and deformation of the tire in the use environment can be suppressed. In addition, even when vulcanization is performed during joining in manufacturing a tire, deformation of the tire frame body can be suppressed.

[Reinforcement cord layer]
The tire of the present invention has a reinforcing cord member that is wound around the outer periphery of the tire frame body in the circumferential direction, and a reinforcing cord layer that covers the reinforcing cord member and has a covering resin layer containing a thermoplastic resin B and a filler. . The filler content in the coating resin layer is in the range of more than 0% by mass and 20% by mass or less.

As described above, when the reinforcing cord layer is covered with the covering resin layer, the difference in hardness between the tire and the reinforcing cord layer can be reduced as compared with the case where the reinforcing cord member is fixed with the cushion rubber. The reinforcing cord member can be adhered and fixed to the tire frame.
Furthermore, when the reinforcing cord member is a steel cord, when trying to separate the reinforcing cord member from the cushion rubber at the time of disposal of the tire, it is difficult to separate the vulcanized rubber from the reinforcing cord member by heating alone. The plastic resin can be easily separated from the reinforcing cord member only by heating. This is advantageous in terms of tire recyclability. In addition, a thermoplastic resin usually has a lower loss factor (Tanδ) than vulcanized rubber. For this reason, the rolling property of a tire can be improved. Furthermore, a thermoplastic resin having a relatively high modulus of elasticity compared to vulcanized rubber has the advantage that the in-plane shear rigidity is large and the stability and wear resistance during running of the tire are excellent.

-Thermoplastic resin B-
As the thermoplastic resin B included in the coating resin layer, a thermoplastic resin having a skeleton common in the structural units constituting the main chain of the resin is used with respect to the thermoplastic resin A included in the tire skeleton.
For example, both the thermoplastic resins A and B contain “at least one of a polyester-based thermoplastic elastomer (TPC) and a thermoplastic polyester”, and both “a polyamide-based thermoplastic elastomer (TPA) and at least one of a thermoplastic polyamide”. An embodiment containing both, an embodiment containing "at least one of polystyrene-based thermoplastic elastomer (TPS) and thermoplastic polystyrene", and an embodiment containing both "at least one of polyurethane-based thermoplastic elastomer (TPU) and thermoplastic polyurethane" And an embodiment containing both “polyolefin-based thermoplastic elastomer (TPO) and thermoplastic polyolefin”.
Furthermore, as the thermoplastic resins A and B, a thermoplastic resin containing a structural unit having the same chemical structure as a structural unit constituting the molecular structure of the resin (for example, heat using a monomer having the same structure as a monomer used as a raw material of the resin) It is more preferable to use a plastic resin.
In addition, as a constituent unit constituting the molecular structure of the resin, a thermoplastic resin containing only a constituent unit having the same chemical structure (for example, a thermoplastic resin using only a monomer having the same structure as a monomer as a raw material of the resin) is used. Further preferred.
Specific examples of the thermoplastic resin used as the thermoplastic resin B include the examples of the thermoplastic resin A used in the above-described tire frame.
In view of elasticity during running and moldability during production, it is desirable to use a thermoplastic elastomer. Among these, from the viewpoint of durability of the coating resin layer, at least one of a polyester-based thermoplastic elastomer and a polyamide-based thermoplastic elastomer is preferable.
The content of the thermoplastic resin B in the coating resin layer is preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more.

  The tensile elastic modulus (JIS K7113: 1995) of the covering resin layer of the reinforcing cord layer is preferably set within the range of 0.1 to 10 times the tensile elastic modulus of the resin material (tire frame). When the tensile elastic modulus of the coating resin layer is 10 times or less than the tensile elastic modulus of the tire frame body, the crown portion is not too hard and rim assembly is facilitated. In addition, when the tensile elastic modulus of the coating resin layer is 0.1 times or more of the tensile elastic modulus of the tire frame body, the resin constituting the reinforcing cord layer is not too soft and has excellent in-plane shear rigidity and cornering force. improves.

-Filler-
The reinforcing cord layer contains a filler at a content of more than 0% by mass and 20% by mass or less in the coating resin layer that covers the reinforcing cord member.
When the filler content is 20% by mass or less based on the total amount of the coating resin layer, excellent adhesion between the tire frame body and the reinforcing cord member can be obtained.
The filler content relative to the total amount of the coating resin layer is preferably 3% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less.

As the filler, for example, an inorganic filler is preferably used.
Examples of the shape of the filler include a particle shape, a plate shape (flat shape), and a fiber shape filler.
Note that the particle shape is three-dimensionally measured from three of x, y, and z when the X direction length (x), the Y direction length (y), and the Z direction length (z) are measured three-dimensionally. Both refer to shapes that fall within a length range of ½ or more and 2 or less.
The plate shape is one of x, y, and z when three-dimensionally measuring the length in the X direction (x), the length in the Y direction (y), and the length in the Z direction (z). One has a length less than ½ than the remaining two, and the remaining two indicate shapes that fall within a range of ½ to 2 in length.
Furthermore, when the fiber shape is measured three-dimensionally in the X direction length (x), the Y direction length (y), and the Z direction length (z), two of x, y and z are The length is less than ½ than the remaining one, and the remaining two indicate shapes that fall within the range of ½ to 2 in length.

  When the fiber-shaped filler is included, the elastic modulus can be easily increased as compared with the case where only the filler having another shape is included, so that the durability can be increased by adding a smaller amount, and the plunger property and the cornering force can be increased. On the other hand, when including at least one filler of particle shape and plate shape, the difference in rigidity and durability (anisotropy) due to the direction in which external force is applied is suppressed compared to the case of including only other shape fillers, Plunger and cornering power can be improved.

  In addition, while using a fiber-shaped filler and at least one filler in a particle shape and a plate shape, while suppressing a difference in rigidity and durability (anisotropy) depending on the direction in which an external force is applied, and Durability is increased by adding a smaller amount, and plunger properties and cornering power can be improved.

Examples of the particulate filler include glass (eg, glass beads), calcium carbonate, silica, magnesium carbonate, magnesium oxide, alumina, barium sulfate, carbon black, graphite, ferrite, aluminum hydroxide, magnesium hydroxide, antimony oxide, and titanium oxide. And zinc oxide.
Examples of the plate-like filler include talc, kaolin, mica, and montmorillonite.
Examples of the fiber-shaped filler include glass (for example, glass fiber), carbon fiber, metal fiber, wollastonite, calcium titanate, zonotrite, basic magnesium sulfate, and the like.

In the case of a particulate filler, the average particle size is preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 30 μm, and even more preferably 1 μm to 20 μm.
In the case of a plate-like filler, the average particle size is preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 20 μm, and even more preferably 1 μm to 20 μm.
In the case of a fibrous filler, the length in the major axis direction is preferably 50 μm to 1000 μm, more preferably 100 μm to 800 μm, and further preferably 200 μm to 700 μm.

The average particle diameter of the particle-shaped or plate-shaped filler and the length in the major axis direction of the fiber-shaped filler are measured by the following methods.
The average particle diameter is measured by introducing each particle into a particle size distribution measuring machine (Mastersizer 2000, manufactured by Malvern Instruments Ltd.) and measuring the particle size distribution. With the attached software, the average particle size is defined as a particle size in which 50% of the particles are larger than this and 50% are smaller than this on a volume basis.
The length in the long axis direction is determined by burning the resin component of the coating resin layer filled with the fiber-shaped filler using an electric furnace, observing the remaining filler under a microscope, and analyzing the image for 20 fillers in the long axis direction. The average value is obtained by measuring the length, and this average value is defined as the “length in the major axis direction”.

-Tensile modulus of coated resin layer-
The tensile elastic modulus defined in JIS K7113: 1995 of the coating resin layer is preferably 250 MPa to 1300 MPa, more preferably 300 MPa to 1200 MPa, and further preferably 400 MPa to 1100 MPa.
When the tensile elastic modulus is in the above range, rigidity and durability are improved, and plunger properties and cornering power are excellent.

-Reinforcement cord member-
As the reinforcing cord member, a monofilament (single wire) such as a metal fiber or an organic fiber, or a multifilament (twisted wire) obtained by twisting these fibers such as a steel cord twisted with a steel fiber or an organic fiber can be used. .
The diameter and the number of driving-in of the reinforcing cord member can be appropriately set depending on the structure of the reinforcing layer, the type of reinforcing cord member to be used, and the type of tire.
A known method can be appropriately used for covering the reinforcing cord member with the coating resin layer. Details will be described later.

-Adhesive layer-
The reinforcing cord member and the covering resin layer may be fixed via an adhesive layer. The material of the adhesive layer is not particularly limited as long as the reinforcing cord member and the covering resin layer can be bonded. For example, the adhesive layer can be formed using an adhesive, and an aqueous dispersion adhesive, a solventless adhesive, a solution adhesive, a solid adhesive (for example, a hot melt adhesive), or the like is used. be able to.

[Tire composition]
Hereinafter, embodiments of the tire of the present invention will be described with reference to the drawings.
FIG. 1A is a perspective view showing a cross section of a part of the tire 10 of the present embodiment. FIG. 1B is a cross-sectional view of a bead portion when the tire 10 of the present embodiment is mounted on a rim. As shown in FIG. 1A, the tire 10 has substantially the same cross-sectional shape as a conventional rubber pneumatic tire. As shown in FIG. 1A, the tire 10 includes a pair of bead portions 12 that contact the bead seat 21 and the rim flange 22 of the rim 20 shown in FIG. 1B, and side portions 14 that extend outward from the bead portion 12 in the tire radial direction. A tire case 17 is provided that includes a crown portion 16 (outer peripheral portion) that connects an outer end in the tire radial direction of one side portion 14 and an outer end in the tire radial direction of the other side portion 14.

  The tire case 17 corresponds to the tire skeleton described above, and is formed from the resin material described above. In the present embodiment, the tire case 17 is entirely formed of the resin material described above. However, the present invention is not limited to this configuration, and the tire case 17 is similar to a conventional rubber pneumatic tire. Different resin materials may be used for each portion (side portion 14, crown portion 16, bead portion 12, etc.). Further, in order to reinforce each part of the tire case 17, a reinforcing material (polymer material, metal fiber, cord, nonwoven fabric, woven fabric, or the like) may be embedded and disposed.

  The tire case 17 of the present embodiment produces two tire case halves (tire frame pieces) having a shape in which the tread width is equally divided along the circumferential direction of the tire case 17, and these are prepared as the equator plane of the tire. It is formed by joining parts. The tire case 17 is not limited to the one formed by joining two members, and may be formed by joining three or more members.

  The tire case half can be produced by a method such as vacuum forming, pressure forming, injection molding, melt casting, or the like. For this reason, it is not necessary to perform vulcanization compared to the case where the tire case is molded with rubber as in the prior art, the manufacturing process can be greatly simplified, and the molding time can be omitted.

  In the present embodiment, an annular bead core 18 is embedded in the bead portion 12 shown in FIG. 1B in the same manner as a conventional general pneumatic tire. In this embodiment, a steel cord is used as the bead core 18, but an organic fiber cord, a resin-coated organic fiber cord, a hard resin cord, or the like may be used. Note that the bead core 18 can be omitted if the rigidity of the bead portion 12 is ensured and there is no problem in fitting with the rim 20.

  In the present embodiment, the portion of the bead portion 12 that comes into contact with the rim 20 and at least the portion that comes into contact with the rim flange 22 of the rim 20 are made of a circle made of a material having a better sealing property than the resin material constituting the tire case 17. An annular seal layer 24 is formed. The seal layer 24 may also be formed in a portion where the tire case 17 (bead portion 12) and the bead sheet 21 are in contact with each other. Note that the seal layer 24 may be omitted as long as the sealing property between the rim 20 and the resin material constituting the tire case 17 can be secured. Examples of the material having better sealing performance than the resin material constituting the tire case 17 include softer materials than the resin material constituting the tire case 17, such as rubber, thermoplastic resin and thermoplastic elastomer softer than the resin material. Can be mentioned.

  As shown in FIG. 1A, a reinforcing cord 26 having higher rigidity than the resin material constituting the tire case 17 is wound around the crown portion 16 in the circumferential direction of the tire case 17. The reinforcing cord 26 is wound spirally in a state in which at least a part thereof is embedded in the crown portion 16 in a cross-sectional view along the axial direction of the tire case 17, thereby forming a reinforcing cord layer 28. On the outer circumferential side of the reinforcing cord layer 28 in the tire radial direction, a tread 30 made of a material having higher wear resistance than the resin material constituting the tire case 17, for example, rubber, is disposed.

In the present embodiment, as shown in FIG. 2, the reinforcing cord 26 is a state in which a metal member 26A (an example of a reinforcing cord member) such as a steel cord is covered with a coating resin material 27 (an example of a covering resin layer). Member).
In this embodiment, the filler is contained in the coating resin material 27 in the range of more than 0% by mass and 20% by mass or less. Further, as the thermoplastic resin B contained in the coating resin material 27, the same thermoplastic resin as the thermoplastic resin A contained in the resin material forming the tire case 17 (that is, as a structural unit constituting the molecular structure of the resin, A thermoplastic resin containing only structural units of the same chemical structure). However, if the thermoplastic resin A contained in the resin material forming the tire case 17 is a thermoplastic resin having a common skeleton in the structural unit constituting the main chain of the resin, another thermoplastic resin is used. May be.
The reinforcing cord 26 is joined at a contact portion with the crown portion 16 by a method such as welding or bonding with an adhesive.

  In the present embodiment, as shown in FIG. 2, the reinforcing cord 26 has a substantially trapezoidal cross section. In the following, the upper surface (surface on the outer side in the tire radial direction) of the reinforcing cord 26 is denoted by reference numeral 26U, and the lower surface (surface on the inner side in the tire radial direction) is denoted by reference numeral 26D. In the present embodiment, the cross-sectional shape of the reinforcing cord 26 is a substantially trapezoidal shape. However, the present invention is not limited to this configuration, and the cross-sectional shape changes from the lower surface 26D side (the tire radial direction inner side) to the upper surface 26U side. Any shape may be used as long as it is a shape excluding a shape that becomes wider toward the outer side in the tire radial direction.

  As shown in FIG. 2, since the reinforcing cords 26 are arranged at intervals in the circumferential direction, a gap 28 </ b> A is formed between adjacent reinforcing cords 26. For this reason, the outer peripheral surface of the reinforcing cord layer 28 has a shape with irregularities, and the outer peripheral surface 17S of the tire case 17 in which the reinforcing cord layer 28 constitutes the outer peripheral portion also has an irregular shape.

  A fine roughened unevenness 96 is formed on the outer peripheral surface 17S (including the unevenness) of the tire case 17, and a cushion rubber 29 is bonded thereon via a bonding agent. The cushion rubber 29 flows into the contact surface with the reinforcing cord 26 so as to fill the rough unevenness 96.

  The above-described tread 30 is joined to the cushion rubber 29 (on the tire outer peripheral surface side). The tread 30 is formed with a tread pattern (not shown) including a plurality of grooves on the ground contact surface with the road surface in the same manner as a conventional rubber pneumatic tire.

[Tire manufacturing method]
Next, the manufacturing method of the tire of this embodiment is demonstrated.
(Tire case molding process)
First, the tire case half is molded by injection molding or the like (molding process).
Next, the annular tire case halves obtained in the molding process are faced to each other and joined at the tire equatorial plane part to form a tire case (joining process). In addition, the tire case is not limited to the one formed by joining two members, and may be formed by joining three or more members.
The joining will be described. The tire case halves supported by a thin metal support ring face each other. Next, a joining mold is installed so as to contact the outer peripheral surface of the abutting portion of the tire case half. The joining mold is configured to press the periphery of the joining portion (butting portion) of the tire case half with a predetermined pressure. Next, the periphery of the joint part of the tire case half is pressed at a temperature equal to or higher than the melting point of the resin material constituting the tire case, so that the joint part is melted and the tire case halves are fused together to form a tire. Case 17 is formed.
In this embodiment, the joining portion of the tire case half is heated using the joining mold, but the present invention is not limited to this, for example, the joining portion is heated by a separately provided high-frequency heater or the like. The tire case halves may be joined by being softened or melted by irradiation with hot air, infrared rays, or the like, and pressurized by a joining mold.

(Reinforcement cord member winding process)
Next, the winding process of winding the reinforcing cord 26 around the tire case 17 will be described with reference to FIG. FIG. 3 is an explanatory diagram for explaining the operation of embedding the reinforcing cord 26 in the crown portion of the tire case 17 using a cord heating device and rollers.
In FIG. 3, the cord supply device 56 is disposed on the reel 58 around which the reinforcing cord 26 is wound, the cord heating device 59 disposed on the downstream side of the reel 58 in the cord transport direction, and the downstream side of the reinforcing cord 26 in the transport direction. The first roller 60, the first cylinder device 62 that moves the first roller 60 in the direction of contacting and separating from the outer peripheral surface of the tire, and the downstream side in the conveying direction of the reinforcing cord 26 of the first roller 60 A second roller 64, and a second cylinder device 66 that moves the second roller 64 in a direction in which the second roller 64 comes into contact with and separates from the tire outer peripheral surface. The second roller 64 can be used as a metal cooling roller.
In the present embodiment, the surface of the first roller 60 or the second roller 64 is subjected to a treatment (for example, fluororesin coating) for suppressing adhesion of the molten or softened coating resin material 27. The roller itself may be formed of a material to which the coating resin material 27 is difficult to adhere. In the present embodiment, the cord supply device 56 includes the two rollers of the first roller 60 or the second roller 64, but may include only one of the rollers.

  The cord heating device 59 includes a heater 70 and a fan 72 that generate hot air. Further, the cord heating device 59 includes a heating box 74 through which the reinforcing cord 26 passes through an internal space in which hot air is supplied, and a discharge port 76 for discharging the heated reinforcing cord 26.

  In this step, first, the temperature of the heater 70 of the cord heating device 59 is raised, and the ambient air heated by the heater 70 is sent to the heating box 74 by the wind generated by the rotation of the fan 72. Next, the reinforcing cord 26 unwound from the reel 58 is sent and heated into a heating box 74 in which the internal space is heated with hot air. The heating temperature is set to a temperature at which the covering resin material 27 of the reinforcing cord 26 is melted or softened.

  The heated reinforcing cord 26 passes through the discharge port 76 and is wound spirally around the outer peripheral surface of the crown portion 16 of the tire case 17 rotating in the direction of arrow R in FIG. At this time, the lower surface 26 </ b> D of the reinforcing cord 26 contacts the outer peripheral surface of the crown portion 16. The coating resin material 27 melted or softened by heating spreads on the outer peripheral surface of the crown portion 16, and the reinforcing cord 26 is welded to the outer peripheral surface of the crown portion 16. Thereby, the joint strength between the crown portion 16 and the reinforcing cord 26 is improved.

  In the present embodiment, the reinforcing cord 26 is joined to the outer peripheral surface of the crown portion 16 as described above, but joining may be performed by other methods. For example, joining may be performed so that a part or the whole of the reinforcing cord 26 is embedded in the crown portion 16.

(Roughening process)
Next, a blasting device (not shown) emits a projection material at a high speed toward the outer peripheral surface 17S while rotating the tire case 17 side toward the outer peripheral surface 17S of the tire case 17. The ejected projection material collides with the outer peripheral surface 17S, and fine roughening unevenness 96 having an arithmetic average roughness Ra of 0.05 mm or more is formed on the outer peripheral surface 17S. By forming the fine roughened irregularities 96 on the outer peripheral surface 17S of the tire case 17, the outer peripheral surface 17S becomes hydrophilic, and the wettability of the bonding agent described later is improved.

(Lamination process)
Next, a bonding agent for bonding the cushion rubber 29 is applied to the outer peripheral surface 17S of the tire case 17 subjected to the roughening treatment. The bonding agent is not particularly limited, and a triazine thiol adhesive, a chlorinated rubber adhesive, a phenolic resin adhesive, an isocyanate adhesive, a halogenated rubber adhesive, a rubber adhesive, and the like can be used. It is preferable that the cushion rubber 29 reacts at a temperature (90 ° C. to 140 ° C.) at which vulcanization is possible.

  Next, the unvulcanized cushion rubber 29 is wound around the outer peripheral surface 17 </ b> S to which the bonding agent has been applied for one round, and a bonding agent such as a rubber cement composition is applied onto the cushion rubber 29. Next, the vulcanized or semi-cured tread rubber 30A is wound on the cushion rubber 29 to which the bonding agent has been applied for one round to form a raw tire case.

(Vulcanization process)
Next, the raw tire case is accommodated in a vulcanizing can or mold and vulcanized. At this time, the unvulcanized cushion rubber 29 flows into the roughened irregularities 96 formed on the outer peripheral surface 17S of the tire case 17 by the roughening treatment. When the vulcanization is completed, the anchor rubber is exerted by the cushion rubber 29 flowing into the roughened unevenness 96, and the bonding strength between the tire case 17 and the cushion rubber 29 is improved. That is, the bonding strength between the tire case 17 and the tread 30 is improved via the cushion rubber 29.

  And if the sealing layer 24 mentioned above is adhere | attached on the bead part 12 of the tire case 17 using an adhesive agent etc., the tire 10 will be completed.

  The embodiments of the present invention have been described above with reference to the embodiments. However, these embodiments are merely examples, and various modifications can be made without departing from the scope of the invention. It goes without saying that the scope of rights of the present invention is not limited to these embodiments. For details of the embodiments applicable to the present invention, for example, the description in JP 2012-46025 A can be referred to.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to this.

[Production of tires]
As tires in the examples and comparative examples, tires having the configurations shown in the above-described embodiments were produced by a known method. In addition, in producing the tire case and the tire in each Example and Comparative Example using the thermoplastic resin described in Table 1 or Table 2 below as the thermoplastic resin A, the temperature of the cylinder at the time of injection molding was 260 ° C. The mold temperature was 80 ° C., the heating temperature during vulcanization was 160 ° C., and the heating time was 20 minutes.

  The reinforcing cord layer is bonded to multifilaments with an average diameter of 1.15 mm (twisted strands of 5 monofilaments with an average diameter of 0.35 mm (made of steel, strength: 280 N, elongation: 3%)) Primalloy AP GQ730 (manufactured by Mitsubishi Chemical Corporation) or Admer QE060 (manufactured by Mitsui Chemicals) as the layer, and then the thermoplastic resin B described in Table 1 or 2 below on the adhesive layer are extruded and coated And cooled.

<Jointability with tire case>
When the end of the reinforcing cord layer (resin coating layer portion) is peeled from the tire case by holding it with a pliers and pulling it with a hand after joining, the one peeled off from the interface between the coating resin layer of the reinforcing cord layer and the tire case is “ B (x) ”, which does not peel off at the interface with the tire case, but peels off at the interface between the reinforcing cord member and the coating resin layer in the reinforcing cord layer, or a case where cohesive failure of the adhesive layer occurs is“ A ( ○) ”.

<Plunger energy>
The obtained tire was assembled to a rim, filled with a normal internal pressure, and a plunger energy test was performed in accordance with JIS D4230 (1998). The results are shown as an index with the plunger energy of the tire of Comparative Example 1 as 100. The higher the number, the better the result.

<Cornering power>
As for cornering power, the tire wheel to which air pressure: 230 kPa (relative pressure) is applied is placed on the flat belt tester, and the tire wheel is rotated at a running speed equivalent to 80 km / h. The force was evaluated by measuring. Specifically, the difference between the lateral force when the slip angle was 0 ° and the lateral force when the slip angle was 1 ° was used as the cornering power, and the tire of Comparative Example 1 was displayed as an index. The higher the number, the better the result.

“Tire could not be manufactured” means that the tire could not be manufactured because the adhesiveness of the resin coating layer to the tire case was low.
The unit of the composition shown in the table is “part” unless otherwise specified.
Details of the thermoplastic elastomer described in Table 1 or 2 are shown below.
・ 5557: Toray Deyupon polyester thermoplastic elastomer "Hytrel 5557"
・ 4767: Toray Deyupon polyester thermoplastic elastomer "Hytrel 4767N"
9055: Ube Industries' polyamide-based thermoplastic elastomer “UBESTA XPA9055X01”
・ 5557G05H: Polyester-based thermoplastic elastomer “Hytrel 5557G05H” manufactured by Toray Deyupon (5% by mass of glass fiber added to Hytrel 5557)
・ 5557G10H: Toray Deyupon polyester-based thermoplastic elastomer “Hytrel 5557G10H” (10% by mass of glass fiber added to Hytrel 5557)
GF: Nittobo glass fiber CS3PE-941 Fiber diameter (length in the long axis direction): 13 μm
GB: Potters Barotini glass beads EGB731 Average particle size: 20 μm
・ Talc: Nippon Talc P-4 average particle size D50: 4.5 μm

  As shown in Table 1 or Table 2, the thermoplastic resin A contained in the tire skeleton and the thermoplastic resin B contained in the coating resin layer are common to the constituent units constituting the main chain of the resin. In each example which is a thermoplastic resin having a skeleton and a tire in which a reinforcing cord layer contains a filler at a content of 0% by mass to 20% by mass in a covering resin layer covering the reinforcing cord member, Compared to each comparative example in which the thermoplastic resin A and the thermoplastic resin B are tires that do not have a common skeleton in the constituent units constituting the main chain of the resin, or tires that do not contain a filler in the coating resin layer, It turns out that it is excellent in plunger property and cornering power.

  10 tires; 12 bead parts; 16 crown parts; 18 bead cores; 20 rims; 21 bead seats; 22 rim flanges; 17 tire cases; 24 seal layers; 26 reinforcing cords; 26A metal members; 29 cushion rubber; 30 treads; 96 roughening irregularities

Claims (10)

A tire skeleton formed of a resin material containing the thermoplastic resin A;
A reinforcing cord layer wound around an outer periphery of the tire frame body in a circumferential direction, and a reinforcing cord layer having a covering resin layer covering the reinforcing cord member and containing a thermoplastic resin B and a filler;
With
The thermoplastic resin A and the thermoplastic resin B are thermoplastic resins having a common skeleton in structural units constituting the main chain of the resin,
The tire in which the content of the filler in the coating resin layer is in the range of more than 0% by mass and 20% by mass or less.   The tire according to claim 1, wherein the filler is an inorganic filler.   The tire according to claim 1, wherein the filler is a filler having a particle shape or a plate shape.   4. The tire according to claim 3, wherein the particle-shaped filler has an average particle diameter of 0.1 μm to 50 μm, and the plate-shaped filler has an average particle diameter of 0.5 μm to 50 μm.   The tire according to claim 3 or 4, wherein the particulate or plate-like filler is glass or talc.   The tire according to claim 1, wherein the filler is a fiber-shaped filler.   The tire according to claim 6, wherein a length of the fibrous filler in a major axis direction is 50 μm to 1000 μm.   The tire according to claim 6 or 7, wherein the fiber-shaped filler is glass fiber.   The thermoplastic resin A and the thermoplastic resin B are both polyester-based thermoplastic elastomers, or both are polyamide-based thermoplastic elastomers, according to any one of claims 1 to 8. tire.   The tire frame body and the coating resin layer both include only a polyester-based thermoplastic elastomer as a thermoplastic resin, or include only a polyamide-based thermoplastic elastomer. The described tire.