WO2013154205A1

WO2013154205A1 - Tire

Info

Publication number: WO2013154205A1
Application number: PCT/JP2013/061228
Authority: WO
Inventors: 福島　敦; 啓之筆本; 原田　高志
Original assignee: 株式会社ブリヂストン
Priority date: 2012-04-13
Filing date: 2013-04-15
Publication date: 2013-10-17
Also published as: JP2013220692A

Abstract

Provided is a tire which is formed from a resin material, and has an annular skeletal body and low temperature dependence. A polyester-based thermoplastic elastomer or polyamide-based thermoplastic elastomer, which has such low temperature dependence that the tensile modulus of elasticity at 85°C is 0.25 times or more the tensile modulus of elasticity at 23°C as measured at 200 mm/min, is used as the resin material for the tire.

Description

tire

The present invention relates to a tire mounted on a rim, and particularly relates to a tire in which at least a part of a tire case is formed of a resin material.

Conventionally, pneumatic tires made of rubber, organic fiber materials, steel members, and the like are used for vehicles such as passenger cars.

In recent years, from the viewpoint of weight reduction, ease of molding, and ease of recycling, the use of resin materials, particularly thermoplastic resins and thermoplastic elastomers, as tire materials has been studied.
For example, Patent Document 1 (Japanese Patent Laid-Open No. 2003-104008) and Patent Document 2 (Japanese Patent Laid-Open No. 03-143701) disclose a pneumatic tire molded using a thermoplastic polymer material. .

In addition, it is composed of a plurality of polymer materials such as rubber and thermoplastic resin, and the rigidity is gradually decreased from the center position of the crown portion to the shoulder portion and further to the maximum width position of the sidewall portion, and the maximum of the sidewall portion. There has been proposed a pneumatic tire in which the rigidity is gradually increased from the large position to the bead portion (Patent Document 3: Japanese Patent No. 4501326).
[Prior art documents]
[Patent Document 1] JP 2003-104008 [Patent Document 2] JP 03-143701 [Patent Document 3] Japanese Patent No. 4501326

A tire using a thermoplastic polymer material is easier to manufacture and lower in cost than a conventional rubber tire. However, when the tire frame is formed of a uniform thermoplastic polymer material that does not have a reinforcing member such as a carcass ply, it is improved in terms of stress resistance and internal pressure resistance compared to conventional rubber tires. There is room.
In particular, a conventional rubber tire is used to maintain its shape when an internal pressure is applied to the tire by using a carcass or ply. On the other hand, in a tire using a polymer material (resin) as described above, a reinforcing member such as a carcass or a ply is not an indispensable constituent element. ) Has been proposed. As described above, in a tire using a polymer material, it is assumed that a reinforcing member is not used in the side portion. Therefore, it is required that the tire shape can be maintained by the polymer material itself. In particular, since tires are used under various temperature conditions, there is a demand for development of tires in which tire performance such as maintenance of tire shape and riding comfort does not vary significantly depending on operating temperatures.

On the other hand, Patent Document 3 discloses a tire having a prescribed rigidity by combining a plurality of polymer materials. However, in this document, it is described that the ground contact shape in the standard air pressure filling state is improved by forming a stiffness distribution in the tire part, but the temperature dependence of the tire performance is described in detail. Not.

Furthermore, the physical properties required for conventional rubber tires differ from those required for tires using polymer materials. In particular, when a reinforcing member is not used for the side portion, physical properties that are completely different from those of conventional rubber tires are required. However, it is not easy to develop a tire case having physical properties suitable for a tire using a polymer material as described above, and early development is required.

In view of the above circumstances, an object of the present invention is to provide a tire that is formed using a resin material and has a small temperature dependency with respect to shape maintenance and riding comfort.

(1) It is formed of a resin material and has an annular tire skeleton, and the resin material is a tire in which X in (1) is 25 or more.

Condition (1): X = (E ₈₅ / E ₂₃ ) × 100
[In the condition (1), _E85 represents the tensile elastic modulus of the resin material at 85 ° C. E ₂₃ represents a tensile modulus of the resin material at 23 ° C.. ]

According to the present invention, it is possible to provide a tire that is formed using a resin material and has a small temperature dependency with respect to shape maintenance and riding comfort.

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 1st 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. BRIEF DESCRIPTION OF THE DRAWINGS These are sectional drawings along the tire width direction of the tire which concerns on one Embodiment of this invention. It is an enlarged view of the section along the tire width direction of the bead part in the state where the rim was fitted to the tire. It is sectional drawing along the tire width direction which shows the circumference | surroundings of the reinforcement layer of the tire of 2nd Embodiment.

The tire of the present invention is formed of a resin material and has an annular tire skeleton, and X in the following (1) is 25 or more.

The “tensile modulus” of the resin material means that an injection-molded sample is punched out to produce a dumbbell-shaped specimen (No. 5 specimen) as defined in JIS K6251: 1993, and JIS K7113: Means the tensile modulus measured according to 1995. Here, the _{E 23} in the condition (1) under conditions of temperature 23 ° C. · humidity 50 RH%, it means a tensile modulus of the resin material was measured at a test rate of 200 mm / min. The E ₂₃ is preferably 50 MPa or more, more preferably 50 to 1000 MPa, and particularly preferably 50 to 800 MPa, from the viewpoint of improving shape maintenance at 23 ° C. and riding comfort.
_{Also, E 85} under conditions of temperature 85 ° C. · humidity 50 RH%, means a tensile modulus of the resin material was measured at a test rate of 200 mm / min. For the measurement, a tensile tester such as an autograph such as Shimadzu Autograph AGS-J (5KN) manufactured by Shimadzu Corporation can be used. The E ₈₅ is preferably 30 MPa or more, more preferably 30 to 500 MPa, and particularly preferably 30 to 400 MPa, from the viewpoint of improving shape maintenance at 85 ° C. and riding comfort.

X in the said condition (1) of the resin material in this invention is 25 or more. As described above, when the resin material having X of 25 or more is used as the resin material included in the tire frame body, the temperature dependency of the tire shape maintaining property and the riding comfort can be reduced. On the other hand, if the X is less than 25, the shape maintaining property and riding comfort at high temperatures cannot be maintained. For this reason, the temperature dependence of tire performance will become high. X of the resin material is preferably 30 or more, and more preferably 40 or more. Furthermore, since the tire is formed of a resin material, the vulcanization process, which is an essential process in the conventional rubber tire, is not essential, and the tire frame body can be molded by, for example, injection molding. Furthermore, when the resin material is used for the tire frame, the structure of the tire can be simplified as compared with the conventional rubber tire, and as a result, the weight of the tire can be reduced.
In particular, when a rubber material such as a tread is attached to a tire skeleton formed of a resin material, the degree of change in elastic modulus due to temperature dependence between the rubber material and the resin material is in a close range. Is preferred. That is, when the temperature of the tire rises, it is preferable that the resin material of the tire frame body becomes soft as much as the rubber material softens. For this reason, the upper limit value of X of the resin material is not particularly limited. From the viewpoint of making the degree of change in the elastic modulus depending on the temperature between the case material and the rubber (for example, the tread portion) surrounding the case material constant, 100 Or less, more preferably 95 or less, and particularly preferably 90 or less.

Here, the temperature dependence of the “shape maintenance” of the tire means, for example, the degree of deformation of the tire shape at 85 ° C. with respect to the shape of the tire at 23 ° C., and the temperature dependence of the shape maintenance is smaller as the degree of deformation is smaller. This means that the property is small (excellent in tire performance). In this case, for example, the tire width at 23 ° C./internal pressure of 300 kPa and the tire width at 85 ° C./internal pressure of 300 kPa are measured, and the tire width at 85 ° C. when the tire width at 23 ° C. is taken as 100. Can be based on the index value.

In addition, the temperature dependence of the “riding comfort” of a tire is when there is no difference in riding comfort by performing a sensory evaluation of the difference between the riding comfort at 23 ° C. and the riding comfort when the tire is heated to 85 ° C. Therefore, the temperature dependence of ride comfort is small (excellent).

Hereinafter, the resin material contained in the tire skeleton in the present invention will be described, and then specific embodiments of the tire of the present invention will be described with reference to the drawings.

[Resin material]
The resin material in the present invention contains a resin, but the resin is selected so that X in the condition (1) of the resin material is 25 or more.
In the present invention, the “resin material” includes at least a resin (resin component) and may include other components such as an additive. When the resin material does not contain any component other than the resin component, the resin material is composed only of resin. However, the resin material is a material containing 50% or more of a resin other than natural rubber or synthetic rubber.

Further, in this specification, “resin” is a concept including a thermoplastic resin and a thermosetting resin, but does not include natural rubber. Further, the thermoplastic resin includes a thermoplastic elastomer.
Here, the “elastomer” is a copolymer having a crystalline polymer having a high melting point or a hard cohesive polymer and an amorphous polymer having a low glass transition temperature. The resin consisting of

〔resin〕
Examples of the resin include thermoplastic resins (including thermoplastic elastomers) and thermosetting resins. The resin material may be, for example, a thermoplastic elastomer described later alone, or a combination of a plurality of these, or a combination of a thermoplastic elastomer and a thermoplastic resin that is not an elastomer. Also good. When the resin material contains only a single resin, the tensile elastic modulus of the resin becomes the tensile elastic modulus of the resin material.

The resin material contained in the tire skeleton is preferably a thermoplastic resin, and more preferably a thermoplastic elastomer. Hereinafter, the resin used for the resin material forming the tire frame will be described with a focus on the thermoplastic resin.

-Thermoplastic resins (including thermoplastic elastomers)-
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 thermoplastic resins, the material softens and flows as the temperature rises, becomes a relatively hard and strong state when cooled, and the polymer compound having rubber-like elasticity is heated. A plastic elastomer is used. On the other hand, among the thermoplastic resins, as the temperature rises, the material softens and flows, and when cooled, it becomes a relatively hard and strong state, but a polymer compound that does not have rubbery elasticity is used as a non-elastomer thermoplastic resin. To distinguish.

Thermoplastic resins (including thermoplastic elastomers) include polyolefin-based thermoplastic elastomers (TPO), polystyrene-based thermoplastic elastomers (TPS), polyamide-based thermoplastic elastomers (TPA), polyurethane-based thermoplastic elastomers (TPU), and polyesters. Thermoplastic elastomer (TPC) and dynamically cross-linked thermoplastic elastomer (TPV), and non-elastomer polyolefin thermoplastic resin, non-elastomer polystyrene thermoplastic resin, non-elastomer polyamide thermoplastic resin, and elastomer Non-polyester thermoplastic resin etc. are mentioned. The thermoplastic resin contained in the resin material is preferably at least one selected from polyester-based thermoplastic elastomers and polyamide-based thermoplastic elastomers.

(Polyester thermoplastic elastomer)
Polyester-based thermoplastic elastomers consist of hard segments with at least a crystalline polyester and a high melting point, and soft segments with other polymers (such as polyester or polyether) that are amorphous and have a low glass transition temperature. Material.
The polyester-based thermoplastic elastomer may be referred to as “TPC” (Thermo Plastic Polymer Elastomer).

An aromatic polyester can be used as the polyester forming the hard segment. The aromatic polyester can be formed, for example, from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol. The aromatic polyester is preferably terephthalic acid and / or polybutylene terephthalate derived from dimethyl terephthalate and 1,4-butanediol. Further, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, Dicarboxylic acid components such as naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or ester-forming derivatives thereof, and diols having a molecular weight of 300 or less For example, aliphatic diols such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, 1,4-cyclohexanedimethanol, tricyclodecane dimethylo Alicyclic diols such as alcohol, 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′-dihydroxy-p- It may be a polyester derived from an aromatic diol such as quarterphenyl, or a copolyester 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 that forms the hard segment include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, and polybutylene terephthalate is preferable.

Examples of the polymer that forms the soft segment include aliphatic polyesters and aliphatic polyethers.
Examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, and poly (propylene oxide). 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.
Of these aliphatic polyethers and aliphatic polyesters, poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol ethylene oxide adduct, poly (ε -Caprolactone), polybutylene adipate, polyethylene adipate and the like are preferred.

The number average molecular weight of the polymer constituting the soft segment is preferably 300 to 6000 from the viewpoint of toughness and low temperature flexibility. Further, the mass ratio (x: y) to 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. preferable.

The combination of the hard segment and the soft segment described above can include the combination of the hard segment and the soft segment mentioned above. Among these, a combination of polybutylene terephthalate and soft segment aliphatic polyether is preferable for the hard segment, polybutylene terephthalate for the hard segment, and poly (ethylene oxide) glycol for the soft segment is more preferable.

Examples of the polyester-based thermoplastic elastomer include, for example, a commercially available “Hytrel” series (for example, 3046, 5557, 6347, 4047, 4767, 7247, etc.) manufactured by Toray DuPont, and “Velprene” series (P30B, manufactured by Toyobo). P40B, P40H, P55B, P70B, P150B, P280B, P450B, P150M, S1001, S2001, S5001, S6001, S9001, etc.) can be used.

(Polyamide thermoplastic elastomer)
In the present invention, the “polyamide thermoplastic elastomer” is a copolymer having a crystalline polymer having a high melting point and a non-crystalline polymer having a low glass transition temperature. It means a thermoplastic resin material having an amide bond (—CONH—) in the main chain of the polymer constituting the hard segment.
The polyamide-based thermoplastic elastomer may be simply referred to as “TPA” (Thermoplastic Amid elastomer).

The polyamide-based thermoplastic elastomer comprises at least a hard segment having a crystalline and high melting point, and other polymers (for example, polyester or polyether) are non-crystalline and have a soft segment having a low glass transition temperature. Materials. The polyamide thermoplastic elastomer may use a chain extender such as dicarboxylic acid in addition to the hard segment and the soft segment. Examples of the polyamide forming the hard segment include polyamides produced by monomers represented by the following general formula (1) or general formula (2).

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

In the general formula (2), R ² represents a hydrocarbon molecular chain having 3 to 20 carbon atoms or 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 or an alkylene group having 3 to 18 carbon atoms, and a hydrocarbon molecular chain having 4 to 15 carbon atoms or 4 carbon atoms. An alkylene group having 15 to 15 carbon atoms is more preferable, and a molecular chain of a hydrocarbon having 10 to 15 carbon atoms or an alkylene group having 10 to 15 carbon atoms is particularly preferable. In general formula (2), R ² is preferably a hydrocarbon molecular chain of 3 to 18 carbon atoms or an alkylene group of 3 to 18 carbon atoms, and a hydrocarbon molecular chain of 4 to 15 carbon atoms or carbon An alkylene group having 4 to 15 carbon atoms is more preferable, and a hydrocarbon molecular chain having 10 to 15 carbon atoms or an alkylene group having 10 to 15 carbon atoms is particularly preferable.
Examples of the monomer represented by the general formula (1) or the general formula (2) include ω-aminocarboxylic acid and lactam. Examples of the polyamide forming the hard segment include polycondensates of these ω-aminocarboxylic acids and lactams, and co-condensation polymers of diamines and dicarboxylic acids.

Examples of the ω-aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. And aliphatic ω-aminocarboxylic acid. Examples of the lactam include aliphatic lactams having 5 to 20 carbon atoms such as lauryl lactam, ε-caprolactam, udecan lactam, ω-enantolactam, and 2-pyrrolidone.
Examples of the diamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2, Examples thereof include diamine compounds such as aliphatic diamines having 2 to 20 carbon atoms such as 4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, and metaxylenediamine. The dicarboxylic acid can be represented by HOOC- (R ³ ) m-COOH (R ³ : a hydrocarbon molecular chain 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 and dodecanedioic acid.
As the polyamide that forms the hard segment, a polyamide obtained by ring-opening polycondensation of lauryl lactam, ε-caprolactam, or udecan lactam can be preferably used.

Examples of the polymer that forms the soft segment include polyesters and polyethers, such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and ABA type triblock polyether. Or two or more can be used. Moreover, polyether diamine etc. which are obtained by making animonia etc. react with the terminal of polyether can be used.
Here, the “ABA type triblock polyether” means a polyether represented by the following general formula (3).

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

As the combination of the hard segment and the soft segment, the combination of the hard segment and the soft segment mentioned above can be given. Among these, lauryl lactam ring-opening polycondensate / polyethylene glycol combination, lauryl lactam ring-opening polycondensate / polypropylene glycol combination, lauryl lactam ring-opening polycondensate / polytetramethylene ether glycol combination, lauryl lactam The ring-opening polycondensate / ABA triblock polyether combination is preferred, and the lauryl lactam ring-opening polycondensate / ABA triblock polyether combination is particularly preferred.

The number average molecular weight of the polymer (polyamide) constituting the hard segment is preferably 300 to 15000 from the viewpoint of melt moldability. The number average molecular weight of the polymer constituting the soft segment is preferably 200 to 6000 from the viewpoint of toughness and low temperature flexibility. Further, 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. preferable.

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

Examples of the polyamide-based thermoplastic elastomer include, for example, “UBESTA XPA” series (for example, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9044, etc.) from Ube Industries, Ltd., “Vestamide” from Daicel Eponic Corporation. Series (for example, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, E55-S4, E55-K1W2, EX9200, E50-R2) and the like can be used.

(Polyolefin thermoplastic elastomer)
“Polyolefin thermoplastic elastomer” means a hard segment having at least a polyolefin having a crystalline and high melting point, and other polymers (for example, the above-mentioned polyolefin or other polyolefin) being amorphous and having a low glass transition temperature. The material which comprises is mentioned. Examples of the polyolefin forming the hard segment include polyethylene, polypropylene, isotactic polypropylene, polybutene, and the like.
The polyolefin-based thermoplastic elastomer may be simply referred to as “TPO” (Thermo Plastic Olefin elastomer).

The polyolefin-based thermoplastic elastomer is not particularly limited. However, a crystalline polyolefin constitutes a hard segment having a high melting point, and an amorphous polymer constitutes a soft segment having a low glass transition temperature. A polymer is mentioned.

Examples of the polyolefin-based thermoplastic elastomer include olefin-α-olefin random copolymers, olefin block copolymers, and the like. For example, propylene block copolymers, ethylene-propylene copolymers, propylene-1-hexene copolymers. Polymer, propylene-4-methyl-1-pentene copolymer, propylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-pentene copolymer, ethylene-1-butene copolymer Polymer, 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, Tylene-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.

Examples of the polyolefin-based thermoplastic elastomer include propylene block copolymer, ethylene-propylene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1-butene copolymer. Polymer, 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, propylene Ethyl tacrylate copolymer, propylene-butyl methacrylate copolymer, propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, propylene- Vinyl acetate copolymers are preferred, ethylene-propylene copolymers, propylene-1-butene copolymers, ethylene-1-butene copolymers, ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, More preferred are ethylene-ethyl acrylate copolymers and ethylene-butyl acrylate copolymers.
Moreover, you may use combining 2 or more types of polyolefin resin like ethylene and propylene. The polyolefin content in the polyolefin-based thermoplastic elastomer is preferably 50% by mass or more and 100% by mass or less.

The number average molecular weight of the polyolefin-based thermoplastic elastomer is preferably 5,000 to 10,000,000. When the number average molecular weight of the polyolefin-based thermoplastic elastomer is 5,000 to 10,000,000, the mechanical properties of the resin material are sufficient, and the processability is also excellent. From the same viewpoint, it 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 resin material can be further improved. The number average molecular weight of the polymer constituting the soft segment is preferably 200 to 6000 from the viewpoint of toughness and low temperature flexibility. Further, the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 95: 5, and more preferably 50:50 to 90:10, from the viewpoint of moldability. .

The polyolefin-based thermoplastic elastomer can be synthesized by copolymerizing the polymer that forms the hard segment and the polymer that forms the soft segment by a known method.

Moreover, as the polyolefin thermoplastic elastomer, one obtained by acid-modifying a thermoplastic elastomer may be used.
The above “obtained by acid-modifying a polyolefin 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 polyolefin thermoplastic elastomer. For example, when an unsaturated carboxylic acid (generally maleic anhydride) is used as the unsaturated compound having an acidic group, an unsaturated bond site of the unsaturated carboxylic acid is bonded to the olefin-based thermoplastic elastomer (for example, Graft polymerization).

The compound having an acidic group is preferably a compound having a carboxylic acid group which is a weak acid group from the viewpoint of suppressing deterioration of the polyolefin thermoplastic elastomer, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid. An acid etc. are mentioned.

Examples of the polyolefin-based thermoplastic elastomer as described above include commercially available “Tuffmer” series manufactured by Mitsui Chemicals (for example, A0550S, A1050S, A4050S, A1070S, A4070S, A35070S, A1085S, A4085S, A7090, A70090, MH7007). MH7010, XM-7070, XM-7080, BL4000, BL2481, BL3110, BL3450, P-0275, P-0375, P-0775, P-0180, P-0280, P-0480, P-0680), Mitsui DuPont Polychemical Co., Ltd. “Nuclele” series (for example, AN4214C, AN4225C, AN42115C, N0903HC, N0908C, AN42012C, N410, N1050H, N11 8C, N1110H, N1207C, N1214, AN4221C, N1525, N1560, N0200H, AN4228C, AN4213C, N035C, “Elvalloy AC” series (for example, 1125AC, 1209AC, 1218AC, 1609AC, 1820AC, 1913AC, 2112AC, 2116AC, 2615AC, 2715 3117AC, 3427AC, 3717AC), Sumitomo Chemical Co., Ltd. “Aclift” series, “Evertate” series, Tosoh Corporation “Ultrasen” series, and the like.
Further, as the polyolefin-based thermoplastic elastomer, for example, “Prime TPO” series made of a commercially available prime polymer (for example, E-2900H, F-3900H, E-2900, F-3900, J-5900, E- 2910, F-3910, J-5710, E-2710, F-3710, J-5910, E-2740, F-3740, R110MP, R110E, T310E, M142E, etc.) can also be used.

(Polyurethane thermoplastic elastomer)
Polyurethane-based thermoplastic elastomers consist of hard segments in which at least polyurethane forms pseudo-crosslinks due to physical aggregation, and other polymers are amorphous and have soft segments with low glass transition temperatures. Can be mentioned.
The polyurethane-based thermoplastic elastomer may be simply referred to as “TPU” (ThermoPlastic Urethan elastomer).

Specific examples of the polyurethane-based thermoplastic elastomer include a soft segment including a unit structure represented by the following structural unit (U-1) and a unit structure represented by the following structural unit (U-2). It can represent as a copolymer containing the hard segment to contain.

In the structural unit (U-1) and the structural unit (U-2), 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 structural unit (U-1), as the long-chain aliphatic polyether and long-chain aliphatic polyester represented by P, for example, those having a molecular weight of 500 to 5000 can be used. The P is derived from a diol compound containing a long-chain aliphatic polyether represented by the 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, the ABA triblock polyether [polyether represented by the general formula (3)], and the like.
These may be used alone or in combination of two or more.

In the structural unit (U-1) and the structural unit (U-2), the R is derived from a diisocyanate compound containing an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon represented by the 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, and 1,6-hexamethylene diisocyanate. Etc.
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 may be used alone or in combination of two or more.

In the structural unit (U-2), 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 may be used. it can. The P ′ is derived from a diol compound containing a short chain aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon represented by the P ′. Examples of the aliphatic diol compound containing a short-chain aliphatic hydrocarbon represented by P ′ include glycol and polyalkylene glycol, such as 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 and 1,10-decanediol It is done.
Examples of the alicyclic diol compound containing the alicyclic hydrocarbon represented by P ′ include cyclopentane-1,2-diol, cyclohexane-1,2-diol, and cyclohexane-1,3-diol. , Cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol and the like.
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'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, bisphenol A, 1 , 1-di (4-hydroxyphenyl) cyclohexane, 1,2-bis (4-hydroxyphenoxy) ethane, 1,4-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, etc. .
These may be used alone or in combination of two or more.

The number average molecular weight of the polymer (polyurethane) constituting the hard segment is preferably 300 to 1500 from the viewpoint of melt moldability. In addition, the number average molecular weight of the polymer constituting the soft segment is preferably 500 to 20000, more preferably 500 to 5000, and particularly preferably 500 to 5000, from the viewpoint of flexibility and thermal stability of the polyurethane-based thermoplastic elastomer. 3000. 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. preferable.
The polyurethane-based thermoplastic elastomer can be synthesized by copolymerizing the polymer that forms the hard segment and the polymer that forms the 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. Tolylene diisocyanate (TDI) / polyester-based polyol Polymer, TDI / polyether polyol copolymer, TDI / caprolactone polyol copolymer, TDI / polycarbonate polyol copolymer, 4,4′-diphenylmethane diisocyanate (MDI) / polyester polyol copolymer, MDI / Polyether-based polyol copolymer, MDI / caprolactone-based polyol copolymer, MDI / polycarbonate-based polyol copolymer, MDI + hydroquinone / polyhexamethylene carbonate copolymer TDI / polyester polyol copolymer, TDI / polyether polyol copolymer, MDI / polyester polyol copolymer, MDI / polyether polyol copolymer, MDI + hydroquinone / polyhexamethylene carbonate copolymer Is more preferable.

Examples of the polyurethane-based thermoplastic elastomer include “Elastollan” series (for example, ET680, ET880, ET858D, ET690, ET890, etc.) manufactured by BASF, and “Kuramylon U” manufactured by Kuraray Co., Ltd. Series (for example, 2000 series, 3000 series, 8000 series, 9000 series), “Milactolan” series (for example, XN-2001, XN-2004, P390RSUP, P480RSUI, P26MRNAT, E490, E590, P890) manufactured by Japan Miraclan Co., Ltd. ) Etc. can be used.

(Polystyrene thermoplastic elastomer)
In the polystyrene-based thermoplastic elastomer, at least polystyrene constitutes a hard segment, and other polymers (eg, polybutadiene, polyisoprene, polyethylene, hydrogenated polybutadiene, hydrogenated polyisoprene, etc.) constitute a soft segment having a low glass transition temperature. Materials.
The polystyrene-based thermoplastic elastomer may also be referred to as “TPS” (Thermoplastic Stylene elastomer).

As the polystyrene-based thermoplastic elastomer, either an acid-modified polystyrene-based thermoplastic elastomer modified with an acid group or an unmodified polystyrene-based thermoplastic elastomer can be used.

As the polystyrene forming the hard segment, for example, those obtained by a known radical polymerization method or ionic polymerization method can be suitably used, and examples thereof include polystyrene having anion living polymerization. Examples of the polymer that forms the soft segment include polybutadiene, polyisoprene, poly (2,3-dimethyl-butadiene), and the like. The acid-modified polystyrene-based thermoplastic elastomer can be obtained by acid-modifying an unmodified polystyrene-based thermoplastic elastomer as described later.

The combination of the hard segment and the soft segment described above can include the combination of the hard segment and the soft segment mentioned above. Among these, a combination of polystyrene / polybutadiene and a combination of polystyrene / polyisoprene are preferable. 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) constituting the hard segment is preferably 5,000 to 500,000, and preferably 10,000 to 200,000.
The number average molecular weight of the polymer constituting the soft segment is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 800,000, particularly preferably from 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 moldability. preferable.

The polystyrene-based thermoplastic elastomer can be synthesized by copolymerizing the polymer that forms the hard segment and the polymer that forms the soft segment by a known method.
Examples of the polystyrene-based thermoplastic elastomer include styrene-butadiene copolymers [SBS (polystyrene-poly (butylene) block-polystyrene), SEBS (polystyrene-poly (ethylene / butylene) block-polystyrene)], styrene-isoprene copolymer. Polymer [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, and SEBS is particularly preferred.

Examples of the unmodified polystyrene-based thermoplastic elastomer include “Tough Tech” series manufactured by Asahi Kasei Corporation (for example, H1031, H1041, H1043, H1051, H1052, H1053, H1062, H1082, H1141, H1221, H1272), SEBS ("Hibler" 5127, 5125, etc.) manufactured by Kuraray Co., Ltd., SEPS ("Septon" 2002, 2063, S2004, S2006, etc.) and the like can be used.

-Acid-modified polystyrene-based thermoplastic elastomer-
“Acid-modified polystyrene-based thermoplastic elastomer” is an unmodified polystyrene-based thermoplastic elastomer that is acid-modified by bonding an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group, or a phosphoric acid group. It means a plastic elastomer. The acid-modified polystyrene-based thermoplastic elastomer can be obtained, for example, by bonding (for example, graft polymerization) an unsaturated bond site of unsaturated carboxylic acid or unsaturated carboxylic acid anhydride to the polystyrene-based thermoplastic elastomer.

As the (unsaturated) compound having an acidic group, a compound having a carboxylic acid group which is a weak acid group is preferable from the viewpoint of suppressing deterioration of the polyamide-based thermoplastic elastomer. For example, acrylic acid, methacrylic acid, itaconic acid, croton Examples include acids, isocrotonic acid, maleic acid and the like.

Examples of the acid-modified polystyrene-based thermoplastic elastomer include Asahi Kasei Corporation, Tuftec, for example, M1943, M1911, M1913, Kraton, FG19181G, and the like.

The acid value of the acid-modified polystyrene thermoplastic _{elastomers, 0mg (CH 3 ONa) /} g , greater 20mg _(CH 3 ONa) / g is preferably less _{that, 0mg (CH 3 ONa) /} g and beyond 17 mg (CH ₃ ONa) / g or less, more preferably 0 mg (CH ₃ ONa) / g and particularly preferably 15 mg (CH ₃ ONa) / g or less.

The above-mentioned thermoplastic elastomer can be synthesized by copolymerizing the polymer forming the hard segment and the polymer forming the soft segment by a known method.

Next, various thermoplastic resins that are not elastomers will be described.

(Polyolefin thermoplastic resin that is not an elastomer)
The polyolefin-based resin that is not an elastomer is a polyolefin-based resin having a higher elastic modulus than the polyolefin-based thermoplastic elastomer described above.
Examples of polyolefin-based thermoplastic resins that are not elastomers include homopolymers, random copolymers, block copolymers, and the like of α-olefins such as propylene and ethylene, and cyclic olefins such as cycloolefin. Specific examples include polyethylene-based thermoplastic resins, polypropylene-based thermoplastic resins, polybutadiene-based thermoplastic resins, and polypropylene-based thermoplastic resins are particularly preferable from the viewpoint of heat resistance and processability.
Specific examples of the polypropylene-based thermoplastic resin that is not an elastomer include a propylene homopolymer, a propylene-α-olefin random copolymer, a propylene-α-olefin block copolymer, and the like. Examples of the α-olefin 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 and 1-eicocene.

The polyolefin-based thermoplastic resin may be a chlorinated polyolefin-based resin in which some or all of the hydrogen atoms in the molecule are replaced with chlorine atoms. Examples of the chlorinated polyolefin resin include chlorinated polyethylene resins.

(Polystyrene thermoplastic resin that is not an elastomer)
The polystyrene-based thermoplastic resin that is not an elastomer is a polystyrene-based thermoplastic resin having a higher elastic modulus than the polystyrene-based thermoplastic elastomer described above.
As the polystyrene-based thermoplastic resin, for example, those obtained by a known radical polymerization method or ionic polymerization method can be suitably used, and examples thereof include polystyrene having anion living polymerization. Examples of the polystyrene-based thermoplastic resin include a polymer containing a styrene molecular skeleton and a copolymer of styrene and acrylonitrile.
Among these, an acrylonitrile / butadiene / styrene copolymer and a hydrogenated product thereof; a blend of acrylonitrile / styrene copolymer and polybutadiene or a hydrogenated product thereof are preferable. Specific examples of the polystyrene-based thermoplastic resin include polystyrene (so-called PS resin), acrylonitrile / styrene resin (so-called AS resin), acrylic-styrene-acrylonitrile resin (so-called ASA resin), and acrylonitrile / butadiene / styrene resin (so-called “so-called AS resin”). Examples thereof include ABS resins (including blends and copolymers), hydrogenated products of ABS resins (so-called AES resins), acrylonitrile-chlorinated polyethylene-styrene copolymers (so-called ACS resins), and the like.

As described above, the AS resin is an acrylonitrile / styrene resin, which is a copolymer having styrene and acrylonitrile as main components, but is an aromatic vinyl compound such as α-methylstyrene, vinyltoluene, divinylbenzene, or cimethacrylonitrile. (Meth) acrylic acid alkyl esters such as methyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, stearyl acrylate, maleimide, N- Maleimide monomers such as methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, vinyl alcohols Or the like may be further copolymerized ether.

Further, as the AS resin, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or those obtained by graft polymerization or copolymerization of epoxy group-containing vinyl monomers are preferable, and unsaturated acid anhydrides or More preferred is a graft polymerized or copolymerized epoxy group-containing vinyl monomer.

Such epoxy group-containing vinyl monomers are compounds that share both radically polymerizable vinyl groups and epoxy groups in one molecule. Specific examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and itacon. Examples thereof include glycidyl esters of unsaturated organic acids such as glycidyl acid, glycidyl ethers such as allyl glycidyl ether, and the aforementioned derivatives such as 2-methylglycidyl methacrylate, among which glycidyl acrylate and glycidyl methacrylate are preferably used. . Moreover, these can be used individually or in combination of 2 or more types.

Unsaturated acid anhydrides are compounds that share both radically polymerizable vinyl groups and acid anhydrides in one molecule, and preferred examples include maleic anhydride.

ASA resin is composed of an acrylate monomer, a styrene monomer, and an acrylonitrile monomer, and has rubbery properties and thermoplasticity.

Examples of the ABS resin include a resin obtained by graft-polymerizing acrylonitrile-styrene resin with olefin rubber (for example, polybutadiene rubber) to about 40% by mass or less. Examples of the AES resin include a resin obtained by graft polymerization of acrylonitrile-styrene resin with ethylene-propylene copolymer rubber (for example, EP rubber) to about 40% by mass or less.

(Non-elastomer thermoplastic resin)
The polyamide-based resin that is not an elastomer is a polyamide-based resin having a higher elastic modulus than the polyamide-based thermoplastic elastomer described above.
Examples of the polyamide-based thermoplastic resin include polyamides that constitute the hard segment of the above-described polyamide-based thermoplastic elastomer. Examples of the polyamide-based thermoplastic resin include polyamide (amide 6) obtained by ring-opening polycondensation of ε-caprolactam, polyamide (amide 11) obtained by ring-opening polycondensation of undecane lactam, and polyamide (amide 11) obtained by ring-opening polycondensation of lauryl lactam ( Examples include amide 12), polycondensation polyamide (amide 66) of diamine and dibasic acid, or polyamide (amide MX) having metaxylenediamine as a structural unit.

The amide 6 can be represented by, for example, {CO— (CH ₂ ) ₅ —NH} _n (n represents the number of repeating units).
The amide 11 can be represented by, for example, {CO— (CH ₂ ) ₁₀ —NH} _n (n represents the number of repeating units).
The amide 12 can be represented by, for example, {CO— (CH ₂ ) ₁₁ —NH} _n (n represents the number of repeating units).
The amide 66 can be represented by, for example, {CO (CH ₂ ) ₄ CONH (CH ₂ ) ₆ NH} _n (n represents the number of repeating units).

The amide MX having meta-xylenediamine as a structural unit can be represented by, for example, the following structural unit (A-1) [in (A-1), n represents the number of repeating units].

The polyamide-based thermoplastic resin may be a homopolymer composed only of the structural unit, or may be a copolymer of the structural unit (A-1) and another monomer. In the case of a copolymer, the content of the structural unit (A-1) in each polyamide-based thermoplastic resin is preferably 60% by mass or more.

The number average molecular weight of the polyamide-based thermoplastic resin is preferably 300 to 30000. The number average molecular weight of the polymer constituting the soft segment is preferably 200 to 20000 from the viewpoint of toughness and low temperature flexibility.

A commercially available product may be used as the polyamide-based resin that is not an elastomer.
As the amide 6, for example, “UBE nylon” 1022B, 1011FB manufactured by Ube Industries, Ltd. and the like can be used.
As the amide 12, “UBE nylon” manufactured by Ube Industries, for example, 3024U can be used. As the amide 66, “UBE nylon 2020B” or the like can be used. In addition, as the amide MX, for example, commercially available MX nylon (S6001, S6021, S6011) manufactured by Mitsubishi Gas Chemical Co., Inc. can be used.

(Non-elastomer thermoplastic resin)
A polyester-based resin that is not an elastomer is a resin having a higher elastic modulus than the polyester-based thermoplastic elastomer described above and having an ester bond in the main chain.
Although it does not specifically limit as a polyester-type thermoplastic resin, It is preferable that it is the same kind of resin as the polyester-type thermoplastic resin which the hard segment in the above-mentioned polyester-type thermoplastic elastomer contains. The polyester resin that is not an elastomer may be crystalline or amorphous, and examples thereof include aliphatic polyesters and aromatic polyesters. The aliphatic polyester may be a saturated aliphatic polyester or an unsaturated aliphatic polyester.

The aromatic polyester is usually crystalline, and can be formed from, for example, an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol.
Examples of the aromatic polyester include polyethylene terephthalate, polybutylene terephthalate, polystyrene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, and polybutylene terephthalate is preferable.

One of the aromatic polyesters includes terephthalic acid and / or polybutylene terephthalate derived from dimethyl terephthalate and 1,4-butanediol, and further, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid A dicarboxylic acid component such as naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or an ester-forming derivative thereof, and a molecular weight of 300 or less Diols [eg, aliphatic diols such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, 1,4-cyclohexanedimethanol, tricyclodecane dimethyloyl Alicyclic diols such as ruthenium, 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'-dihydroxy-p-quarter It may be a polyester derived from an aromatic diol such as phenyl] or a copolyester 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.

As the polyester-based thermoplastic resin that is not an elastomer as described above, a commercially available product may be used. For example, “Duranex” series (for example, 2000, 2002, etc.) manufactured by Polyplastics Co., Ltd., Mitsubishi Engineering Plastics Co., Ltd. ) NOVADURAN series (for example, 5010R5, 5010R3-2, etc.) manufactured by Toray Industries, Inc. and “Trecon” series (for example, 1401X06, 1401X31, etc.) manufactured by Toray Industries, Inc.

As the aliphatic polyester, any of a dicarboxylic acid / diol condensation system and a hydroxycarboxylic acid condensation system can be used. Examples thereof include polylactic acid, polyhydroxy-3-butylbutyric acid, polyhydroxy-3-hexylbutyric acid, poly (ε-caprolactone), polyenanthlactone, polycaprylolactone, polybutylene adipate, polyethylene adipate, and the like. Polylactic acid is a typical resin as a biodegradable plastic, and a preferred embodiment of polylactic acid will be described later.

(Dynamic cross-linked thermoplastic elastomer)
Moreover, you may use a dynamic bridge | crosslinking type thermoplastic elastomer as a resin material.
The dynamic crosslinkable thermoplastic elastomer is a thermoplastic elastomer produced by mixing a rubber into a molten thermoplastic resin, adding a crosslinker and kneading the rubber component under kneading conditions.
Hereinafter, the dynamically crosslinked thermoplastic elastomer is sometimes simply referred to as “TPV” (Thermo Plastic Vulcanizate elastomer).

Examples of the thermoplastic resin that can be used for the production of TPV include the thermoplastic resins described above (including thermoplastic elastomers).
Examples of rubber components that can be used in the production of TPV include diene rubbers and hydrogenated products thereof (for example, NR, IR, epoxidized natural rubber, SBR, BR (high cis BR and low cis BR), NBR, hydrogenated NBR, Hydrogenated SBR), olefin rubber (for example, ethylene propylene rubber (EPDM, EPM), maleic acid modified ethylene propylene rubber (M-EPM), IIR, isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber ( ACM), ionomer), halogen-containing rubber (for example, Br-IIR, Cl-IIR, brominated product of isobutylene paramethylstyrene copolymer (Br-IPMS), chloroprene rubber (CR), hydrin rubber (CHR), chlorosulfonated Polyethylene (CSM), chlorinated polyethylene (CM), maleic acid modified Plain polyethylene (M-CM), silicone rubber (eg, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber), sulfur-containing rubber (eg, polysulfide rubber), fluoro rubber (eg, vinylidene fluoride rubber) Fluorine-containing vinyl ether rubbers, tetrafluoroethylene-propylene rubbers, fluorine-containing silicone rubbers, fluorine-containing phosphazene rubbers), etc., and in particular, isobutylene-isoprene copolymer having a halogen group introduced therein as a modified polyisobutylene rubber. Polymeric rubber and / or halogen-containing copolymer rubber of isomonoolefin and p-alkylstyrene such as isobutylene-paramethylstyrene copolymer rubber having a halogen group introduced therein can be used effectively. Exxpro "is preferably used.

Various additives such as rubber, various fillers (for example, silica, calcium carbonate, clay), anti-aging agents, oils, plasticizers, colorants, weathering agents, and reinforcing materials are added to the resin material as desired. You may make it contain. The content of the additive in the resin material (tire frame) is not particularly limited, and can be appropriately used as long as the effects of the present invention are not impaired. When a component other than a resin such as an additive is added to the resin material, the content of the resin component in the resin material is preferably 50% by mass or more, and more preferably 90% by mass or more based on the total amount of the resin material. The content of the resin component in the resin material is the balance obtained by subtracting the total content of various additives from the total amount of the resin component.

(Physical properties of resin materials)
Next, the preferable physical property of the resin material which comprises a tire frame body is demonstrated.

The tire skeleton in the present invention uses a resin material in which X in the condition (1) is 25 or more. For this reason, it is preferable that the resin material which comprises the crown part and side part of the tire frame of a tire frame is also the above-mentioned range, respectively. The X of the resin material in each part of the tire skeleton may be the same in the crown portion and the side portion, or may be different as desired.

At this time, the thickness of the crown portion of the tire skeleton can be selected as appropriate in order to adjust the X, but considering the tire weight and the like, it is preferably 0.5 mm to 10 mm, more preferably 1 mm to 5 mm. 1 mm to 4 mm is particularly preferable. Similarly, the thickness of the side portion of the tire frame is more preferably 0.5 mm to 10 mm, and particularly preferably 1 mm to 5 mm. About the thickness of the crown part and side part of these tire frame bodies, it can be based on the average thickness of the test piece at the time of calculating the above-mentioned X. In addition, you may measure the thickness of a tire frame body suitably using a well-known method and apparatus. For example, when a rubber tire skeleton is used, even if X is 25 or more, if the thickness of the tire skeleton is in the range of 0.5 mm to 10 mm, the elastic modulus is not sufficient and a reinforcing material such as carcass is used. If not used, it will be difficult to establish a tire.
In addition, the crown part and side part of a tire frame will be described later.

The melting point (or softening point) of the resin material (tire frame) itself is usually 100 ° C. to 350 ° C., preferably about 100 ° C. to 250 ° C., but from the viewpoint of tire productivity, 120 ° C. to 250 ° C. C. is preferably about 120.degree. C., more preferably 120.degree.
In this way, by using a resin material having a melting point of 120 ° C. to 250 ° C., for example, when a tire skeleton is formed by fusing the divided bodies (frame pieces), the periphery of 120 ° C. to 250 ° C. Even if the frame body is fused in the temperature range, the bonding strength between the tire frame pieces is sufficient. For this reason, the tire of this invention is excellent in durability at the time of driving | running | working, such as puncture resistance and abrasion resistance. The heating temperature is preferably 10 ° C to 150 ° C higher than the melting point (or softening point) of the resin material forming the tire frame piece, and more preferably 10 ° C to 100 ° C higher.

The resin material can be obtained by adding various additives as necessary and mixing them appropriately by a known method (for example, melt mixing).
The resin material obtained by melt mixing can be used in the form of pellets if necessary.

The tensile yield strength defined in JIS K7113: 1995 of the resin material (tire frame) itself is preferably 5 MPa or more, preferably 5 MPa to 20 MPa, and more 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, preferably 10% to 70%, and more 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, preferably 100% or more, more preferably 150% or more, and particularly preferably 200% or more. When the tensile elongation at break of the resin material is 50% or more, the rim assembly property is good and it is possible to make it difficult to break against a collision.

The deflection temperature under load (when loaded with 0.45 MPa) as defined in ISO 75-2 or ASTM D648 of the resin material (tire frame) itself is preferably 50 ° C. or more, preferably 50 ° C. to 150 ° C., and preferably 50 ° C. to 50 ° C. 130 ° C. is more preferable. 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.

[First Embodiment]
A tire according to a first embodiment of the tire of the present invention will be described below with reference to the drawings.
The tire 10 of this embodiment will be described. FIG. 1A is a perspective view showing a partial cross section of a tire according to an embodiment of the present invention. FIG. 1B is a cross-sectional view of a bead portion attached to a rim. As shown in FIG. 1, the tire 10 of the present embodiment has a cross-sectional shape substantially similar to that of a conventional general 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.

Here, the tire case 17 of the present embodiment is configured using a resin material containing a single polyamide-based thermoplastic elastomer (for example, “UBESTA XPA9048X1” manufactured by Ube Industries, Ltd.) as a resin material. At this time, X in the condition (1) of the resin material is 45.

In the present embodiment, the tire case 17 is formed of a single resin material (polyamide thermoplastic resin), but the present invention is not limited to this configuration, and is similar to a conventional general rubber pneumatic tire. Moreover, you may use the thermoplastic resin material which has a different characteristic for every site | part (the side part 14, the crown part 16, the bead part 12, etc.) of the tire case 17. FIG. Further, a reinforcing material (polymer material, metal fiber, cord, non-woven fabric, woven fabric, etc.) is embedded in the tire case 17 (for example, the bead portion 12, the side portion 14, the crown portion 16, etc.), and the reinforcing material is provided. The tire case 17 may be reinforced.

The tire case 17 of the present embodiment is obtained by joining a pair of tire case halves (tire frame pieces) 17A formed of a resin material. The tire case half 17A is formed by injection molding or the like so that one bead portion 12, one side portion 14, and a half-width crown portion 16 are integrated with each other so as to face each other. It is formed by joining at the tire equator part. 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 17A formed of the resin material can be formed by, for example, 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 a tire case is molded with rubber as in the prior art, the manufacturing process can be greatly simplified, and molding time can be omitted.
In the present embodiment, the tire case half body 17A has a bilaterally symmetric shape, that is, one tire case half body 17A and the other tire case half body 17A have the same shape. There is also an advantage that only one type of mold is required.

In this embodiment, as shown in FIG. 1B, an annular bead core 18 made of a steel cord is embedded in the bead portion 12, similar to a conventional general pneumatic tire. However, the present invention is not limited to this configuration, and 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 addition to the steel cord, an organic fiber cord, a resin-coated organic fiber cord, or a hard resin may be used.

In the present embodiment, a material having a better sealing property than a resin material constituting the tire case 17 at a portion that contacts the rim 20 of the bead portion 12 or at least a portion that contacts the rim flange 22 of the rim 20, for example, rubber An annular seal layer 24 made of is formed. The seal layer 24 may also be formed at a portion where the tire case 17 (bead portion 12) and the bead sheet 21 are in contact with each other. As a material having better sealing properties than the resin material constituting the tire case 17, a softer material than the resin material constituting the tire case 17 can be used. As the rubber that can be used for the seal layer 24, it is preferable to use the same type of rubber as that used on the outer surface of the bead portion of a conventional general rubber pneumatic tire. Further, if the sealing property between the rim 20 can be ensured only by the resin material forming the tire case 17, the rubber seal layer 24 may be omitted, and other thermoplastic resins having a sealing property superior to the resin material. (Thermoplastic elastomer) may be used. Examples of such other thermoplastic resins include polyurethane resins, polyolefin resins, polystyrene thermoplastic resins, polyester resins, and the like, and blends of these resins with rubbers or elastomers. Thermoplastic elastomers can also be used. For example, polyester-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polystyrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, combinations of these elastomers, and blends with rubber Thing etc. are mentioned.

As shown in FIG. 1A, a reinforcement 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 peripheral side of the reinforcing cord layer 28 in the tire radial direction, a crown 30 made of a material having higher wear resistance than the resin material constituting the tire case 17, such as rubber, is disposed.

The reinforcing cord layer 28 formed by the reinforcing cord 26 will be described with reference to FIG. FIG. 2 is a cross-sectional view along the tire rotation axis showing a state where a reinforcing cord is embedded in the crown portion of the tire case of the tire of the first embodiment. As shown in FIG. 2, the reinforcing cord 26 is spirally wound in a state in which at least a part is embedded in the crown portion 16 in a sectional view along the axial direction of the tire case 17. A reinforcing cord layer 28 indicated by a broken line portion in FIG. 2 is formed together with a part of the outer peripheral portion 17. The portion embedded in the crown portion 16 of the reinforcing cord 26 is in close contact with the resin material constituting the crown portion 16 (tire case 17). As the reinforcing cord 26, 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 can be used. In the present embodiment, a steel cord is used as the reinforcing cord 26.

Further, in FIG. 2, the burying amount L indicates the burying amount of the reinforcing cord 26 in the tire rotation axis direction with respect to the tire case 17 (crown portion 16). The embedding amount L of the reinforcing cord 26 in the crown portion 16 is preferably 1/5 or more of the diameter D of the reinforcing cord 26, and more preferably more than 1/2. Most preferably, the entire reinforcing cord 26 is embedded in the crown portion 16. When the embedment amount L of the reinforcing cord 26 exceeds 1/2 of the diameter D of the reinforcing cord 26, it is difficult to jump out of the embedded portion due to the size of the reinforcing cord 26. Further, when the entire reinforcing cord 26 is embedded in the crown portion 16, the surface (outer peripheral surface) becomes flat, and even if a member is placed on the crown portion 16 where the reinforcing cord 26 is embedded, Air can be prevented from entering. The reinforcing cord layer 28 corresponds to a belt disposed on the outer peripheral surface of the carcass of a conventional rubber pneumatic tire.

As described above, the crown 30 is disposed on the outer peripheral side of the reinforcing cord layer 28 in the tire radial direction. The rubber used for the crown 30 is preferably the same type of rubber used in conventional rubber pneumatic tires. Instead of the crown 30, a crown formed of another type of resin material that is more excellent in wear resistance than the resin material constituting the tire case 17 may be used. Moreover, the crown 30 is formed with a crown pattern including a plurality of grooves on the ground contact surface with the road surface in the same manner as a conventional rubber pneumatic tire.
Hereinafter, the manufacturing method of the tire of this embodiment is explained.

(Tire case molding process)
First, tire case halves supported by a thin metal support ring face each other. Next, a joining mold (not shown) is installed so as to contact the outer peripheral surface of the abutting portion of the tire case half. Here, the said joining metal mold | die is comprised so that the periphery of the junction part (butting part) of the tire case half body A may be pressed with a predetermined pressure. Next, the periphery of the joint portion of the tire case half 17 is pressed at a temperature equal to or higher than the melting point (or softening point) of the resin material constituting the tire case. When the joining portion of the tire case half is heated and pressurized by the joining mold, the joining portion is melted and the tire case halves are fused together, and the tire case 17 is formed by integrating these members. In the present embodiment, the joining portion of the tire case half is heated using a 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. Or softened or melted beforehand by hot air, infrared irradiation, etc., and pressed by a joining mold. The tire case halves may be joined.

(Reinforcement cord member winding process)
Next, the reinforcing cord winding process will be described with reference to FIG. FIG. 3 is an explanatory diagram for explaining an operation of embedding a reinforcing cord in a crown portion of a tire case 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 in contact with and separates from the tire outer peripheral surface. The second roller 64 can be used as a metal cooling roller. Further, in the present embodiment, the surface of the first roller 60 or the second roller 64 is made of fluororesin (in this embodiment, Teflon (registered trademark)) in order to suppress adhesion of a molten or softened resin material. It is coated. In the present embodiment, the cord supply device 56 includes two rollers, the first roller 60 and the second roller 64, but the present invention is not limited to this configuration, and any one of the rollers. It is also possible to have only one (that is, one roller).

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 fed into a heating box 74 in which the internal space is heated with hot air (for example, the temperature of the reinforcing cord 26 is heated to about 100 to 200 ° C.). 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. Here, when the heated reinforcing cord 26 comes into contact with the outer peripheral surface of the crown portion 16, the resin material at the contact portion melts or softens, and at least a part of the heated reinforcing cord 26 is embedded in the outer peripheral surface of the crown portion 16. Is done. At this time, since the heated reinforcing cord 26 is embedded in the molten or softened resin material, there is no gap between the resin material and the reinforcing cord 26, that is, a tight contact state. Thereby, the air entering to the portion where the reinforcing cord 26 is embedded is suppressed. In addition, by heating the reinforcing cord 26 to a temperature higher than the melting point (or softening point) of the resin material of the tire case 17, melting or softening of the resin material in a portion in contact with the reinforcing cord 26 is promoted. By doing in this way, it becomes easy to embed the reinforcement cord 26 in the outer peripheral surface of the crown part 16, and air entry can be effectively suppressed.

Further, the burying amount L of the reinforcing cord 26 can be adjusted by the heating temperature of the reinforcing cord 26, the tension applied to the reinforcing cord 26, the pressing force by the first roller 60, and the like. In the present embodiment, the embedding amount L of the reinforcing cord 26 is set to be 1/5 or more of the diameter D of the reinforcing cord 26. The burying amount L of the reinforcing cord 26 is more preferably more than 1/2 of the diameter D, and most preferably the entire reinforcing cord 26 is embedded.

Thus, the reinforcing cord layer 28 is formed on the outer peripheral side of the crown portion 16 of the tire case 17 by winding the heated reinforcing cord 26 while being embedded in the outer peripheral surface of the crown portion 16.

Next, the vulcanized belt-like crown 30 is wound around the outer peripheral surface of the tire case 17 by one turn, and the crown 30 is bonded to the outer peripheral surface of the tire case 17 using an adhesive or the like. The crown 30 may be, for example, a precure crown that is used in conventionally known retreaded tires. This step is the same step as the step of bonding the precure crown to the outer peripheral surface of the base tire of the retreaded tire.

Then, if the seal layer 24 made of vulcanized rubber is bonded to the bead portion 12 of the tire case 17 using an adhesive or the like, the tire 10 is completed.

(Function)
In the tire 10 of the present embodiment, since the tire case 17 is formed of a resin material containing a polyamide-based thermoplastic resin in which X in (1) is in the range of 25 or more, the shape dependency and the temperature dependence of ride comfort Can be reduced. The tire 10 is light in weight because it has a simple structure as compared with a conventional rubber tire. For this reason, the tire 10 of this embodiment has high friction resistance and durability.

Further, in the tire 10 of the present embodiment, a reinforcing cord 26 having a rigidity higher than that of the resin material is spirally wound in the circumferential direction on the outer peripheral surface of the crown portion 16 of the tire case 17 formed of a resin material. Therefore, puncture resistance, cut resistance, and circumferential rigidity of the tire 10 are improved. In addition, creep of the tire case 17 formed of a resin material is prevented by improving the circumferential rigidity of the tire 10.

Further, at least a part of the reinforcing cord 26 is embedded in the outer peripheral surface of the crown portion 16 of the tire case 17 formed of a resin material in a cross-sectional view along the axial direction of the tire case 17 (the cross section shown in FIG. 1A). In addition, since it is in close contact with the resin material, entry of air at the time of manufacture is suppressed, and movement of the reinforcing cord 26 due to input during travel is suppressed. Thereby, it is suppressed that peeling etc. arise in the reinforcement cord 26, the tire case 17, and the crown 30, and the durability of the tire 10 is improved.

When the reinforcing cord layer 28 is configured to include a resin material as described above, the difference in hardness between the tire case 17 and the reinforcing cord layer 28 is reduced as compared with the case where the reinforcing cord 26 is fixed with cushion rubber. Therefore, the reinforcing cord 26 can be further adhered and fixed to the tire case 17. Thereby, the above-mentioned air entering can be prevented effectively, and it can control effectively that a reinforcement cord member moves at the time of driving.
Furthermore, when the reinforcing cord 26 is a steel cord, the reinforcing cord 26 can be easily separated and collected from the resin material by heating at the time of disposal of the tire, which is advantageous in terms of recyclability of the tire 10. Also, since the resin material has a lower loss coefficient (tan δ) than vulcanized rubber, if the reinforcing cord layer 28 contains a large amount of the resin material, the rolling property of the tire can be improved. Furthermore, the resin material has an advantage that the in-plane shear rigidity is larger than that of the vulcanized rubber, and the handling property and wear resistance during running of the tire are excellent.

And since the embedding amount L of the reinforcement cord 26 is 1/5 or more of the diameter D as shown in FIG. 2, the air entry at the time of manufacture is suppressed effectively, the input at the time of driving, etc. This further suppresses the movement of the reinforcing cord 26.

Further, since the crown 30 in contact with the road surface is made of a rubber material that is more resistant to wear than the resin material constituting the tire case 17, the wear resistance of the tire 10 is improved.
Further, since an annular bead core 18 made of a metal material is embedded in the bead portion 12, the tire case 17, that is, the tire 10 is strong against the rim 20 like the conventional rubber pneumatic tire. Retained.

Furthermore, since a seal layer 24 made of a rubber material having a sealing property than the resin material constituting the tire case 17 is provided at a portion of the bead portion 12 that contacts the rim 20, the tire 10 and the rim 20 The sealing performance between the two is improved. For this reason, compared with the case where it seals only with the rim | limb 20 and the resin material which comprises the tire case 17, the air leak in a tire is suppressed further. Further, the rim fit property is improved by providing the seal layer 24.

In the above-described embodiment, the reinforcing cord 26 is heated and the surface of the tire case 17 where the heated reinforcing cord 26 contacts is melted or softened. However, the present invention is not limited to this configuration, and the reinforcing cord is used. It is also possible to use a hot air generating device without heating 26 and heat the outer peripheral surface of the crown portion 16 in which the reinforcing cord 26 is embedded, and then embed the reinforcing cord 26 in the crown portion 16.

In the first embodiment, the heat source of the cord heating device 59 is a heater and a fan. However, the present invention is not limited to this configuration, and the reinforcement cord 26 may be directly heated by radiant heat (for example, infrared rays). Good.

Furthermore, in the first embodiment, the portion in which the resin material in which the reinforcing cord 26 is embedded is melted or softened is forcibly cooled by the metal second roller 64, but the present invention is limited to this configuration. Alternatively, a configuration may be adopted in which cold air is directly blown onto a portion where the resin material is melted or softened to forcibly cool and solidify the melted or softened portion of the resin material.

In the first embodiment, the reinforcing cord 26 is heated. However, for example, the outer periphery of the reinforcing cord 26 may be covered with the same resin material as the tire case 17. In this case, the covering reinforcing cord is used. When the wire is wound around the crown portion 16 of the tire case 17, the resin material covered with the reinforcing cord 26 is also heated, so that the air can be effectively suppressed when being embedded in the crown portion 16.

In addition, it is easy to manufacture the reinforcing cord 26 in a spiral manner, but a method of making the reinforcing cord 26 discontinuous in the width direction is also conceivable.

The tire 10 of the first embodiment is a so-called tubeless tire in which an air chamber is formed between the tire 10 and the rim 20 by attaching the bead portion 12 to the rim 20, but the present invention is limited to this configuration. It may be a complete tube shape.

[Second Embodiment]
Next, a tire manufacturing method and a second embodiment of the tire according to the present invention will be described with reference to the drawings. Similar to the first embodiment, the tire according to the present embodiment has a cross-sectional shape substantially similar to that of a conventional general rubber pneumatic tire. For this reason, in the following figures, the same number is attached | subjected about the structure similar to the said 1st Embodiment. FIG. 4A is a cross-sectional view along the tire width direction of the tire of the second embodiment, and FIG. 4B is a cross section along the tire width direction of the bead portion in a state where a rim is fitted to the tire of the second embodiment. FIG. FIG. 5 is a cross-sectional view along the tire width direction showing the periphery of the reinforcing layer of the tire of the second embodiment.

In the tire according to the second embodiment, the tire case 17 is configured using a resin material containing a polyester-based thermoplastic resin (for example, “Hytrel 5557” manufactured by Toray DuPont), as in the first embodiment. ing. At this time, X of the resin material is 54.

In the present embodiment, as shown in FIGS. 4A and 5, the tire 200 includes a reinforcing cord layer 28 (indicated by a broken line in FIG. 5) formed by winding a covering cord member 26 B around the crown portion 16 in the circumferential direction. Are stacked. The reinforcing cord layer 28 constitutes the outer peripheral portion of the tire case 17 and reinforces the circumferential rigidity of the crown portion 16. The outer peripheral surface of the reinforcing cord layer 28 is included in the outer peripheral surface 17S of the tire case 17.

The covering cord member 26B is formed by coating a covering resin material 27 separate from the resin material forming the tire case 17 on the cord member 26A having higher rigidity than the resin material forming the tire case 17. . Further, the covering cord member 26B is joined (for example, welded or adhered with an adhesive) at the contact portion with the crown portion 16 where the covering cord member 26B and the crown portion 16 are joined.

Further, it is preferable that the tensile elastic modulus of the coating resin material 27 is set within a range of 0.1 to 10 times the tensile elastic modulus of the resin material forming the tire case 17. When the tensile elastic modulus of the resin material 27 for covering is 10 times or less than the tensile elastic modulus of the resin material forming the tire case 17, the crown portion does not become too hard and rim assembly is facilitated. When the tensile elastic modulus of the resin material 27 for covering is 0.1 times or more of the tensile elastic modulus of the resin material forming the tire case 17, the resin constituting the reinforcing cord layer 28 is not too soft and the belt surface Excellent internal shear rigidity and improved cornering force. In the present embodiment, a material similar to the resin material forming the tire frame is used as the coating resin material 27.

Further, as shown in FIG. 5, the covering cord member 26B has a substantially trapezoidal cross section. In the following description, the upper surface (the surface on the outer side in the tire radial direction) of the covering cord member 26B is denoted by reference numeral 26U, and the lower surface (the 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 covering cord member 26B is a substantially trapezoidal shape. However, the present invention is not limited to this configuration, and the cross-sectional shape is from the lower surface 26D side (the tire radial direction inner side) to the upper surface 26U. Any shape may be used as long as the shape excluding the shape that becomes wider toward the side (the tire radial direction outer side).

As shown in FIG. 5, since the covering cord members 26B are arranged at intervals in the circumferential direction, a gap 28A is formed between the adjacent covering cord members 26B. For this reason, the outer peripheral surface of the reinforcing cord layer 28 is uneven, and the outer peripheral surface 17S of the tire case 17 in which the reinforcing cord layer 28 forms the outer peripheral portion is also uneven.

On the outer peripheral surface 17S (including the unevenness) of the tire case 17, fine roughened unevenness is uniformly formed, and a cushion rubber 29 is bonded thereon via a bonding agent. In the cushion rubber 29, the radially inner rubber portion flows into the roughened irregularities.

Further, on the cushion rubber 29 (outer peripheral surface), a material superior in wear resistance to the resin material forming the tire case 17, for example, a crown 30 made of rubber is joined.

The rubber used for the crown 30 (crown rubber 30A) is preferably the same type of rubber as that used in conventional rubber pneumatic tires. Further, instead of the crown 30, a crown formed of another type of resin material that is more excellent in wear resistance than the resin material forming the tire case 17 may be used. The crown 30 is formed with a crown 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.
Next, the manufacturing method of the tire of this embodiment is demonstrated.

(Tire case molding process)
First, in the same manner as in the first embodiment described above, the tire case half 17A is formed, and this is heated and pressed by a joining mold to form the tire case 17.

(Reinforcement cord member winding process)
The tire manufacturing apparatus according to the present embodiment is the same as that of the first embodiment described above. In the cord supply apparatus 56 shown in FIG. 3 of the first embodiment described above, the cord member 26A is attached to the reel 58 with the coating resin material 27. In this embodiment, the one in which the covering cord member 26B having a substantially trapezoidal cross-sectional shape covered with (the same resin material as the tire case) is used is used.

First, the temperature of the heater 70 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. The coated cord member 26B unwound from the reel 58 is fed into a heating box 74 in which the internal space is heated with hot air (for example, the temperature of the outer peripheral surface of the coated cord member 26B is set to the melting point of the coating resin material 27 (or Softening point) or more). Here, when the covering cord member 26B is heated, the covering resin material 27 is melted or softened.

The covering cord member 26B is spirally wound around the outer peripheral surface of the crown portion 16 of the tire case 17 that rotates in the front direction of the paper through the discharge port 76 with a certain tension. At this time, the lower surface 26 D of the covering cord member 26 B contacts the outer peripheral surface of the crown portion 16. Then, the molten or softened covering resin material 27 in the contacted portion spreads on the outer peripheral surface of the crown portion 16, and the covering cord member 26 B is welded to the outer peripheral surface of the crown portion 16. Thereby, the joint strength between the crown portion 16 and the covering cord member 26B is improved.

(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.
Thus, by forming the fine roughening unevenness 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 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, such as triazine thiol adhesive, chlorinated rubber adhesive, phenolic resin adhesive, isocyanate adhesive, halogenated rubber adhesive, rubber adhesive, etc. It is preferable to react at a temperature (90 ° C. to 140 ° C.) at which the rubber 29 can be vulcanized.

Next, the cushion rubber 29 in an unvulcanized state is wound around the outer peripheral surface 17S to which the bonding agent is applied for one round, and a bonding agent such as a rubber cement composition is applied on the cushion rubber 29, The vulcanized or semi-cured crown rubber 30A is wound for one turn to obtain a raw tire case state.

(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 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 crown 30 is improved via the cushion rubber 29.

Then, if the seal layer 24 made of a soft material softer than the resin material is bonded to the bead portion 12 of the tire case 17 using an adhesive or the like, the tire 200 is completed.

(Function)
In the tire 200 of the present embodiment, since the tire case 17 is formed of a resin material containing a polyester-based thermoplastic resin in which X in (1) is in the range of 25 or more, the shape dependency and the temperature dependence of ride comfort Can be reduced. The tire 200 is light in weight because it has a simple structure as compared with a conventional rubber tire.

In the tire manufacturing method of the present embodiment, since the outer peripheral surface 17S of the tire case 17 is roughened when the tire case 17, the cushion rubber 29, and the crown rubber 30A are integrated, the bondability is achieved by the anchor effect. (Adhesiveness) is improved. Further, since the resin material forming the tire case 17 is dug up by the collision of the projection material, the wettability of the bonding agent is improved. Thereby, the bonding agent is held in a uniform applied state on the outer peripheral surface 17S of the tire case 17, and the bonding strength between the tire case 17 and the cushion rubber 29 can be ensured.

In particular, even when the outer peripheral surface 17S of the tire case 17 is uneven, the projection case is collided with the projection (gap 28A) to roughen the periphery of the recess (concave wall, bottom), so that the tire case 17 The bonding strength between the cushion rubber 29 and the cushion rubber 29 can be ensured.

On the other hand, since the cushion rubber 29 is laminated in the roughened region of the outer peripheral surface 17S of the tire case 17, the bonding strength between the tire case 17 and the cushion rubber can be effectively ensured.

In the vulcanization step, when the cushion rubber 29 is vulcanized, the cushion rubber 29 flows into the roughened irregularities formed on the outer peripheral surface 17S of the tire case 17 by the roughening process. When the vulcanization is completed, the anchor rubber is exerted by the cushion rubber 29 flowing into the roughened unevenness, and the bonding strength between the tire case 17 and the cushion rubber 29 is improved.

The tire 200 manufactured by such a tire manufacturing method ensures the bonding strength between the tire case 17 and the cushion rubber 29, that is, the bonding between the tire case 17 and the crown 30 via the cushion rubber 29. Strength is secured. Thereby, the peeling between the outer peripheral surface 17S of the tire case 17 of the tire 200 and the cushion rubber 29 is suppressed during traveling or the like.

Further, since the outer peripheral portion of the tire case 17 is configured by the reinforcing cord layer 28, the puncture resistance and the cut resistance are improved as compared with the outer peripheral portion configured by other than the reinforcing cord layer 28. To do.

Also, since the reinforcing cord layer 28 is formed by winding the covering cord member 26B, the circumferential rigidity of the tire 200 is improved. By improving the circumferential rigidity, creep of the tire case 17 (a phenomenon in which plastic deformation of the tire case 17 increases with time under a constant stress) is suppressed, and pressure resistance against air pressure from the inner side in the tire radial direction is suppressed. improves.

Further, when the reinforcing cord layer 28 includes the covering cord member 26B, the hardness of the tire case 17 and the reinforcing cord layer 28 is higher than that when the reinforcing cord 26A is simply fixed by the cushion rubber 29. Since the difference can be reduced, the covering cord member 26B can be further adhered and fixed to the tire case 17. Thereby, the above-mentioned air entering can be prevented effectively, and it can control effectively that a reinforcement cord member moves at the time of driving.
Further, when the reinforcing cord 26A is a steel cord, the cord member 26A can be easily separated and recovered from the coated cord member 26B by heating at the time of disposal of the tire, which is advantageous in terms of the recyclability of the tire 200. Also, since the resin material has a lower loss coefficient (tan δ) than vulcanized rubber, if the reinforcing cord layer 28 contains a large amount of the resin material, the rolling property of the tire can be improved. Furthermore, the resin material has an advantage that the in-plane shear rigidity is larger than that of the vulcanized rubber, and the handling property and wear resistance during running of the tire are excellent.

In this embodiment, although the unevenness | corrugation was comprised in the outer peripheral surface 17S of the tire case 17, this invention is not restricted to this, It is good also as a structure which forms the outer peripheral surface 17S flatly.
Further, the tire case 17 may be formed with a reinforcing cord layer so as to cover the coated cord member wound and joined to the crown portion of the tire case with a thermoplastic material for coating. In this case, the coating thermoplastic material can be ejected onto the reinforcing cord layer 28 in the molten or softened state to form the coating layer. Further, without using an extruder, the welding sheet may be heated to be in a molten or softened state and attached to the surface (outer peripheral surface) of the reinforcing cord layer 28 to form a coating layer.

In the second embodiment described above, the case case 17 (the tire case half 17A) is joined to form the tire case 17. However, the present invention is not limited to this configuration, and the tire case is formed using a mold or the like. 17 may be integrally formed.

The tire 200 of the second embodiment is a so-called tubeless tire in which an air chamber is formed between the tire 200 and the rim 20 by attaching the bead portion 12 to the rim 20, but the present invention is limited to this configuration. Instead, the tire 200 may have a complete tube shape, for example.

In the second embodiment, the cushion rubber 29 is disposed between the tire case 17 and the crown 30. However, the present invention is not limited thereto, and the cushion rubber 29 may not be disposed.

In the second embodiment, the covering cord member 26B is spirally wound around the crown portion 16. However, the present invention is not limited thereto, and the covering cord member 26B is discontinuous in the width direction. It is good also as a structure wound up.

In the second embodiment, the covering resin material 27 for forming the covering cord member 26B is made of a thermoplastic material, and the covering resin material 27 is heated to be melted or softened to be coated on the outer peripheral surface of the crown portion 16. Although the member 26B is welded, the present invention is not limited to this structure, and the covering cord member 26B is bonded to the outer peripheral surface of the crown portion 16 using an adhesive or the like without heating the covering resin material 27. It is good also as a structure.
The covering resin material 27 for forming the covering cord member 26B may be a thermosetting resin, and the covering cord member 26B may be bonded to the outer peripheral surface of the crown portion 16 using an adhesive or the like without being heated.
Further, the covering resin material 27 for forming the covering cord member 26B may be a thermosetting resin, and the tire case 17 may be formed of a resin material. In this case, the covering cord member 26B may be bonded to the outer peripheral surface of the crown portion 16 using an adhesive or the like, and the portion of the tire case 17 where the covering cord member 26B is disposed is heated to be melted or softened. The coated cord member 26B may be welded to the outer peripheral surface of the crown portion 16 in a state.
Further, the covering resin material 27 for forming the covering cord member 26B may be a thermoplastic material, and the tire case 17 may be formed of a resin material. In this case, the covering cord member 26B may be bonded to the outer peripheral surface of the crown portion 16 using an adhesive or the like, and the portion of the tire case 17 where the covering cord member 26B is disposed is heated to be melted or softened. While being in the state, the covering resin material 27 may be heated to be melted or softened, and the covering cord member 26 B may be welded to the outer peripheral surface of the crown portion 16. In addition, when both the tire case 17 and the covering cord member 26B are heated and melted or softened, the two are mixed well, so that the bonding strength is improved. When the resin material forming the tire case 17 and the coating resin material 27 forming the covering cord member 26B are both resin materials, the same kind of thermoplastic material, particularly the same thermoplastic material may be used. preferable.
Further, the outer peripheral surface 17S of the tire case 17 subjected to further roughening treatment may be applied with corona treatment, plasma treatment or the like to activate the surface of the outer peripheral surface 17S and increase the hydrophilicity, and then apply the adhesive.

Furthermore, the order for manufacturing the tire 200 is not limited to the order of the second embodiment, and may be changed as appropriate.

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.

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

[Measurement of tensile modulus]
Using an injection molding machine (SE30D manufactured by Sumitomo Heavy Industries, Ltd.), injection molding is performed to obtain a sample having a molding temperature of 180 ° C. to 260 ° C. and a mold temperature of 50 ° C. to 70 ° C., 130 mm × 30 mm, 2.0 mm in thickness. It was.
Each sample was punched out to produce a dumbbell-shaped specimen (No. 5 specimen) defined in JIS-K6251: 1993. In Comparative Example 1, the test piece was prepared using rubber in the same manner as in the other examples.

Next, using a Shimadzu Autograph AGS-J (5KN) manufactured by Shimadzu Corporation, the tensile speed was set to 200 mm / min, and the tensile elastic modulus at 23 ° C. and 85 ° C. of each of the dumbbell-shaped sample pieces was measured. did. The results are shown in the table below.

[Shape maintenance (tire width)]
A tire having the same configuration as that of the first embodiment described above was formed using the resin material and rubber described in the following table. At this time, the thickness of the side portion was 3 mm, and the thickness of the crown portion was 3 mm. The tire was mounted on a rim and filled with air so that the internal pressure was 300 kPa, and the maximum value of the tire width at 23 ° C. and the maximum value of the tire width at 85 ° C. were obtained. Subsequently, the maximum value of the tire width at 85 ° C. when the maximum value of the tire width at 23 ° C. was set to 100 was calculated. The results are shown in the table below.
At this time, what the tire ruptured when an internal pressure of 300 kPa was applied at each temperature was defined as “rupture”.

[Changes in ride comfort]
Tires were formed using the resin materials described in the following table in the same manner as in the first embodiment described above. The tire with the rim mounted was mounted on the vehicle, and the tire was heated with a tire warmer until the temperature reached 23 ° C. Next, a veteran test driver ran on a vehicle with tires on a test course. Similarly, the tire was heated with a tire warmer until the temperature reached 85 ° C. Next, a veteran test driver ran on a vehicle with tires on a test course.
Using the above-mentioned veteran test driver, sensory evaluation of the change in ride comfort at 23 ° C. and ride comfort at 85 ° C. was performed according to the following criteria.

A: There was no change in ride comfort (especially a change in vibration from the road surface experienced).
B: A slight change in the ride comfort (particularly vibration from the road surface experienced) was felt.
C: It did not hold as a tire, or felt a great change in riding comfort (especially vibration from the road surface experienced).

The ingredients in the table are as follows.

・ TPA1: Polyamide-based thermoplastic elastomer ("UBESTA XPA9048X1" manufactured by Ube Industries)
・ TPA2: Polyamide thermoplastic elastomer ("UBESTA XPA9055X1" manufactured by Ube Industries)
・ TPA3: Polyamide thermoplastic elastomer ("UBESTA XPA9063X1" manufactured by Ube Industries)
・ TPA4: Polyamide thermoplastic elastomer ("UBESTA XPA90E55-S4" manufactured by Ube Industries)
・ TPA5: Polyamide thermoplastic elastomer ("Vestamide E55-K1W1" manufactured by Daicel-Eponic)

TPC1: Polyester thermoplastic elastomer ("Hytrel 5557" manufactured by Toray DuPont)
-TPC2: Polyester thermoplastic elastomer ("Hytrel 6347" manufactured by Toray DuPont)

-TPU: polyurethane-based thermoplastic elastomer ("Elastolan ET155D" manufactured by BASF

PO1: Polyolefin thermoplastic resin (ethylene / methacrylic acid copolymer resin)
(EMAA: “Nucleel N1035” manufactured by Mitsui DuPont Polychemicals)
PO2: Polyolefin thermoplastic resin ("Prime TPO E2900" manufactured by Prime Polymer)

TPS: Polystyrene thermoplastic elastomer (trade name “Soft Shine A1535” manufactured by Toyobo Co., Ltd.)

Rubber: The composition shown in Table 2 below was kneaded with a Banbury mixer.

Each material in the said Table 2 shows the following.
・ Butadiene rubber: “BR01” manufactured by JSR
Anti-aging agent: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine: “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Co., Ltd.
・ Vulcanization accelerator DG: N, N'-diphenylguanidine ("Sunseller DG" manufactured by Sanshin Chemical Industry Co., Ltd.)
・ Vulcanization accelerator NS-P: Nt-butyl-2-benzothiazolylsulfenamide ("Noxeller NS-P" manufactured by Ouchi Shinsei Chemical Co., Ltd.)

As can be seen from Table 1, when X in the condition (1) is 25 or more, the shape maintenance property and the temperature dependence of the riding comfort are small. It can also be seen that when the tensile elastic modulus at 80 ° C. is 30 MPa or more, the shape maintainability is excellent and the ride comfort with respect to temperature is small.

Note that the disclosure of Japanese Patent Application 2012-092464 is incorporated herein by reference.

Claims

Formed of a resin material and having an annular tire frame,
The resin material is a tire in which X in (1) is 25 or more.
Condition (1): X = (E 85 / E 23 ) × 100
[In the condition (1), E85 represents the tensile elastic modulus of the resin material at 85 ° C. E 23 represents a tensile modulus of the resin material at 23 ° C.. ]
The tire according to claim 1, wherein the resin material has a tensile elastic modulus at 85 ° C of 30 MPa or more.
The tire according to claim 1 or 2, wherein the resin material includes a thermoplastic resin.
The tire according to any one of claims 1 to 3, wherein the resin material includes a thermoplastic elastomer.
The tire according to any one of claims 1 to 4, wherein the resin material includes at least one selected from a polyester-based thermoplastic elastomer and a polyamide-based thermoplastic elastomer.