JP6590679B2 - tire - Google Patents

Description

  The present invention relates to a tire.

  In recent years, tires using a resin material as a component have been developed for reasons such as weight reduction, ease of molding, and ease of recycling. As one of the attempts to increase the durability (stress resistance, internal pressure resistance and rigidity) of tires containing resin materials, a method of spirally winding a reinforcing cord around a resin tire body (hereinafter also referred to as a tire frame body) is proposed. Has been.

  In order to improve the durability of the tire having the above structure, it is important to improve the adhesion durability between the tire frame body and the reinforcing cord. Therefore, for example, by covering a metal cord such as a steel cord with a resin material, the difference in rigidity between the metal cord and the tire frame body is alleviated, and the adhesion durability between the tire frame body and the reinforcement cord is improved. There is a proposed method.

  As a method of coating a metal cord with a resin material, a method of adhering a metal cord and a resin layer covering the metal cord via an adhesive layer containing a thermoplastic resin has been proposed (see, for example, Patent Document 1). ).

International Publication No. 2014/175453

  In the method described in Patent Document 1, since the metal cord and the resin layer are bonded by the adhesive layer, the metal cord and the resin layer can be firmly bonded. However, there is room for further improvement in the durability of the adhesive layer. Further, it is required to maintain good adhesion durability of the adhesive layer to the metal cord.

  This invention makes it a subject to provide the tire which is excellent in durability and the adhesive durability between members in view of the said situation.

Specific means for solving the above problems include the following embodiments.
<1> An annular tire skeleton and a metal resin composite, wherein the metal resin composite has a structure in which a metal member, an adhesive layer containing a thermoplastic resin, and a resin layer are arranged in this order. The tire has an average thickness of 20 μm to 1500 μm and includes 0.1% by mass to 5% by mass of a radical scavenger in the total mass of the resin layer.
<2> The radical scavenger includes at least one selected from the group consisting of a semi-hindered phenol radical scavenger, a hindered phenol radical scavenger, and a hindered phenol radical scavenger. The described tire.
<3> The tire according to <1> or <2>, wherein the thermoplastic resin includes a polyolefin-based resin.
<4> The tire skeleton includes a resin material, and the resin material includes 0.1% by mass to 5% by mass of a radical scavenger in the total mass of the resin material. The tire according to any one of claims.
<5> The tire according to any one of <1> to <4>, wherein the content of the radical scavenger in the adhesive layer is 0% by mass to 1% by mass in the total mass of the adhesive layer. .

  According to the present invention, a tire excellent in durability and adhesion durability between members is provided.

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 metal resin composite was embed | buried under the crown part of the tire frame body of the tire of 1st embodiment. It is explanatory drawing for demonstrating the operation | movement which installs a metal resin composite in the crown part of a tire frame body using a metal resin composite heating apparatus and rollers.

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

In this specification, “resin” is a concept including a thermoplastic resin, a thermoplastic elastomer, and a thermosetting resin, and does not include vulcanized rubber. In the following description of the resin, “same species” means those having a skeleton that is common to the skeleton constituting the main chain of the resin, such as esters and styrenes.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the purpose of the process can be achieved even when it cannot be clearly distinguished from other processes. It is.

  The tire of the present invention includes a tire frame and a metal resin composite, and the metal resin composite has a structure in which a metal member, an adhesive layer containing a thermoplastic resin, and a resin layer are arranged in this order. And the said resin layer is 20 micrometers-1500 micrometers in average thickness, and contains 0.1 mass%-5 mass% radical scavenger in the total mass of the said resin layer.

  Since the tire of the present invention has the above configuration, the durability of the adhesive layer disposed between the metal member and the resin layer in the metal resin composite and the adhesion durability of the adhesive layer to the metal member are excellent.

  When the metal resin composite is placed at a high temperature and in the presence of oxygen, the adhesive layer containing the thermoplastic resin tends to become brittle. When the present inventors examined sincerely, it was found that the brittleness of the adhesive layer was suppressed by adding a radical scavenger to the adhesive layer. On the other hand, it has been found that if the amount of the radical scavenger added to the adhesive layer is too large, the durability of the tire decreases. The reason is not clear, but it is presumed that an excessive amount of radical scavenger becomes a fracture nucleus, resulting in a decrease in material strength and a decrease in adhesion to metal.

  As a result of further investigations based on the above findings, the present inventors have determined that the average thickness of the resin layer is within a specific range, and that the resin layer contains a radical scavenger at a specific content rate, whereby the metal member of the adhesive layer It was found that embrittlement of the adhesive layer can be suppressed while maintaining good adhesion durability with respect to the adhesive layer.

  Hereinafter, after sequentially describing a metal member, an adhesive layer and a resin layer, and a tire skeleton constituting the metal resin composite included in the tire of the present invention, a specific embodiment of the tire of the present invention is referred to the drawings. While explaining.

[Metal resin composite]
The metal resin composite has a structure in which a metal member, an adhesive layer, and a resin layer are arranged in this order, and the shape and the position in the tire are not particularly limited. Examples of the shape of the metal resin composite include a cord shape and a sheet shape. Examples of the position of the metal resin composite in the tire include an outer peripheral portion (crown) and an end portion (bead) of the tire skeleton.

  The metal resin composite includes, for example, a belt layer formed by arranging one or a plurality of cord-like metal members on the outer periphery of the tire frame body along the circumferential direction of the tire, and a plurality of cord-like metals. The member can be used as an intersecting belt layer disposed so as to intersect with each other at an angle with respect to the circumferential direction of the tire, an annular bead core used in a bead portion of a tire skeleton body described later, and the like.

  In the metal-resin composite, “the structure in which the metal member, the adhesive layer, and the resin layer are arranged in this order” includes, for example, a state in which the entire surface of the metal member is covered with the resin layer via the adhesive layer. And a state in which a part of the surface of the metal member is covered with a resin layer via an adhesive layer. When the metal resin composite is used by being wound in the circumferential direction of the skeleton, a structure in which the metal member, the adhesive layer, and the resin layer are arranged in this order at least in a region where the metal resin composite and the skeleton are in contact with each other. It is preferable that

[Metal members]
The metal member is not particularly limited, and for example, a metal cord used for a conventional rubber tire can be used as appropriate. Examples of the metal cord include a monofilament (single wire) of a metal fiber, a multifilament (twisted wire) such as a steel cord twisted with a steel fiber, and the like. The metal member in the present invention is preferably a multifilament from the viewpoint of further improving the durability of the tire. The cross-sectional shape, size (diameter), etc. of the metal member are not particularly limited, and those suitable for the desired tire can be appropriately selected and used.

  The tensile elastic modulus of the metal member itself (hereinafter, unless otherwise specified, “elastic modulus” means a tensile elastic modulus in the present specification) is usually about 100000 MPa to 300000 MPa, and 120,000 MPa to 270000 MPa. Preferably, it is 150,000 MPa-250,000 MPa. The tensile modulus of the metal member is calculated from the slope of a stress-strain curve drawn on a tensile tester using a ZWICK type chuck.

  The breaking elongation (tensile breaking elongation) of the metal member itself is usually about 0.1% to 15%, preferably 1% to 15%, and more preferably 1% to 10%. The tensile elongation at break of the metal member can be obtained from the strain by drawing a stress-strain curve using a ZWICK chuck with a tensile tester.

[Resin layer]
The material of the resin layer is not particularly limited, and for example, at least one thermoplastic material selected from the group consisting of a thermoplastic resin and a thermoplastic elastomer can be used.

In the present specification, the term “thermoplastic resin” means a polymer compound that softens and flows as the temperature rises and becomes relatively hard and strong when cooled, but does not have rubbery elasticity.
In the present specification, the term “thermoplastic elastomer” means a crystalline polymer having a high melting point hard segment or a high cohesion hard segment, and an amorphous polymer having a low glass transition temperature soft segment. It means a polymer compound having a rubber-like elasticity, which becomes a relatively hard and strong state when cooled, and the material softens and flows as the temperature rises.

(Thermoplastic resin)
Examples of the thermoplastic resin include the same types of thermoplastic resins used in tire skeleton bodies described later, specifically, polyamide-based thermoplastic resins, polyester-based thermoplastic resins, olefin-based thermoplastic resins, Examples thereof include polyurethane-based thermoplastic resins, vinyl chloride-based thermoplastic resins, and polystyrene-based thermoplastic resins. You may use these individually or in combination of 2 or more types. Among these, the thermoplastic resin is preferably at least one selected from polyamide-based thermoplastic resins, polyester-based thermoplastic resins, and olefin-based thermoplastic resins, and is selected from polyamide-based thermoplastic resins and olefin-based thermoplastic resins. More preferably, at least one selected from the group consisting of
When the resin layer contains at least one of a polyamide-based thermoplastic resin and an olefin-based thermoplastic resin, the adhesiveness with the adhesive layer tends to increase. Therefore, the metal member and the resin layer are more firmly fixed, and the resistance of the metal member to the resin layer can be further enhanced.

  When the resin layer includes a thermoplastic resin, the thermoplastic resin is preferably selected in consideration of adhesiveness with a resin material used for the tire frame. In particular, when the resin material forming the tire frame body and the thermoplastic resin contained in the resin layer are the same type of resin, the adhesion between the tire frame body and the resin layer can be further enhanced. For example, when a polyamide-based thermoplastic resin is used as the thermoplastic resin contained in the resin layer, it is preferable to use a polyamide-based thermoplastic elastomer as a resin material for forming the tire skeleton.

-Polyamide thermoplastic resin-
Examples of the polyamide-based thermoplastic resin include a polyamide that forms a hard segment of a polyamide-based thermoplastic elastomer used in a tire skeleton, which will be described later. Specifically, as the polyamide-based thermoplastic resin, polyamide (amide 6) obtained by ring-opening polycondensation of ε-caprolactam, polyamide (amide 11) obtained by ring-opening polycondensation of undecane lactam, and ring-opening polycondensation of lauryl lactam. Examples thereof include polyamide (amide 12), polyamide (amide 66) obtained by polycondensation of diamine and dibasic acid, and polyamide (amide MX) having metaxylenediamine as a structural unit.

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

  The polyamide-based thermoplastic resin may be a homopolymer formed only from the above structural unit, or may be a copolymer of the above structural unit and another monomer. In the case of a copolymer, it is preferable that the content rate of the said structural unit in each polyamide-type thermoplastic resin is 40 mass% or more.

-Polyester thermoplastic resin-
Examples of the polyester-based thermoplastic resin include a polyester that forms a hard segment of a polyester-based thermoplastic elastomer used for a tire skeleton, which will be described later.
Specific examples of the polyester-based thermoplastic resin include polylactic acid, polyhydroxy-3-butylbutyric acid, polyhydroxy-3-hexylbutyric acid, poly (ε-caprolactone), polyenantlactone, polycaprylolactone, and polybutylene. Examples include aliphatic polyesters such as adipate and polyethylene adipate, and aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. Among these, from the viewpoint of heat resistance and processability, polybutylene terephthalate is preferable as the polyester-based thermoplastic resin.

  Examples of commercially available polyester-based thermoplastic resins include “Duranex” series (for example, 2000, 2002, etc.) manufactured by Polyplastics Co., Ltd., and “Novaduran” series (for example, 5010R5) manufactured by Mitsubishi Engineering Plastics Co., Ltd. 5010R3-2 etc.), “Toraycon” series (for example, 1401X06, 1401X31 etc.) manufactured by Toray Industries, Inc. can be used.

-Olefin-based thermoplastic resin-
Examples of the olefinic thermoplastic resin include polyolefin that forms a hard segment of an olefinic thermoplastic elastomer used in a tire skeleton described later.
Specific examples of the olefin-based thermoplastic resin include a polyethylene-based thermoplastic resin, a polypropylene-based thermoplastic resin, a polybutadiene-based thermoplastic resin, and the like. Among these, from the viewpoints of heat resistance and processability, the olefin thermoplastic resin is preferably a polypropylene thermoplastic resin.
Specific examples of the polypropylene-based thermoplastic resin 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 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.

(Thermoplastic elastomer)
As a thermoplastic elastomer, the same kind as a thermoplastic elastomer used for a tire skeleton mentioned below can be mentioned.
Specific examples of the thermoplastic elastomer include polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and the like. You may use these individually or in combination of 2 or more types. Among these, the thermoplastic elastomer is preferably at least one selected from polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and olefin-based thermoplastic elastomers, and is selected from polyamide-based thermoplastic elastomers and olefin-based thermoplastic elastomers. More preferably, at least one selected from the group consisting of When at least one of a polyamide-based thermoplastic elastomer and an olefin-based thermoplastic elastomer is used as the thermoplastic material contained in the resin layer, the adhesiveness between the adhesive layer and the resin layer tends to increase. Therefore, the metal member and the resin layer are more firmly fixed, and the resistance of the metal member to the resin layer can be further enhanced.

  When the resin layer includes a thermoplastic elastomer, the thermoplastic elastomer is preferably selected in consideration of adhesiveness with a resin material used for the tire frame. In particular, when the resin material forming the tire frame body and the thermoplastic elastomer contained in the resin layer are the same type of resin, the adhesion between the tire frame body and the resin layer can be further enhanced. For example, when a polyamide-based thermoplastic elastomer is used as the thermoplastic elastomer contained in the resin layer, it is preferable to use a polyamide-based thermoplastic elastomer as the resin material forming the tire skeleton.

-Polyamide thermoplastic elastomer-
The polyamide-based thermoplastic elastomer is the same as the polyamide-based thermoplastic elastomer used for the tire skeleton described later, and the preferred embodiment is also the same. Therefore, detailed description is omitted here.

-Polyester thermoplastic elastomer-
The polyester-based thermoplastic elastomer is the same as the polyester-based thermoplastic elastomer used in the tire skeleton described later, and the preferred embodiment is also the same. Therefore, detailed description is omitted here.

-Olefin thermoplastic elastomer-
The olefin-based thermoplastic elastomer is the same as the olefin-based thermoplastic elastomer used for the tire skeleton described later, and the preferred embodiment is also the same. Therefore, detailed description is omitted here.

  Even if the resin layer includes both a thermoplastic resin and a thermoplastic elastomer and has a sea phase that is a matrix phase including the thermoplastic resin and an island phase that is a dispersed phase including the thermoplastic elastomer. Good. Since the resin layer has a sea-island structure in which a thermoplastic elastomer is dispersed in a thermoplastic resin matrix, it is possible to further improve the pull-out resistance of the metal member to the resin layer.

  When the resin layer has a sea-island structure, the mass ratio (p / e) of the thermoplastic resin (p) and the thermoplastic elastomer (e) in the resin layer includes the sea phase containing the thermoplastic resin and the thermoplastic elastomer. From the viewpoint of easily forming a sea-island structure composed of island phases, it is preferably 95/5 to 55/45, more preferably 90/10 to 60/40, and 85/15 to 70 / More preferably, it is 30.

  Whether or not the island phase containing the thermoplastic elastomer in the resin layer is dispersed in the sea phase containing the thermoplastic resin can be confirmed by photographic observation using an SEM (scanning electron microscope). it can.

  Further, the size of the island phase containing the thermoplastic elastomer (island major axis) is preferably about 0.4 μm to 10.0 μm, more preferably about 0.5 μm to 7 μm, and more preferably 0.5 μm to More preferably, it is about 5 μm. The size of each phase can be measured using an observation photograph using SEM.

(Radical scavenger)
A resin layer contains 0.1 mass%-5 mass% of radical scavengers in the total mass of a resin layer. When the resin layer contains 0.1% by mass or more of the radical scavenger, radicals generated in the resin layer are suppressed from moving to the adhesive layer, and the embrittlement of the adhesive layer is effectively suppressed. Moreover, the content rate of the radical scavenger in a resin layer shall be 5 mass% or less, and the fall of the adhesiveness with respect to the resin layer and the member which touches a resin layer by the bleeding out of a radical scavenger, etc. is suppressed.
In the present specification, the “radical scavenger” means a compound having an action of capturing the generated radical and stopping the radical chain reaction.

  The kind of radical scavenger is not particularly limited, and examples thereof include a phenol radical scavenger, a hindered amine radical scavenger, a phosphorus radical scavenger, a sulfur radical scavenger, and a hydroxylamine radical scavenger. The radical scavenger may be used alone or in combination of two or more.

  Examples of the phenol-based radical scavenger include 2,6-di-tert-butyl-phenol, 2,6-di-tert-butyl-4-methylphenol, BHT, pentaerythritol tetrakis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], n-octadecyl-3- (3,5-di-) tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, , 3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, calcium diethylbis [[ [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -p-cresol, hexamethylenebis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol and other hinders Phenol-based radical scavenger and ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], 2,4-dimethyl-6- (1-methylpentadecyl) Phenol, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetra Semi-hindered phenol radical scavengers such as oxaspiro [5,5] undecane, 2,2′-methylenebis- (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis- (3-methyl) -6-tert-butylphenol), 1- (3-methyl-6-tert-butylphenyl) -2-methyl-4,4'-bis- (3- Resin hindered phenol radical scavengers such as methyl-6-tert-butylphenyl) butane and 4,4'-thiobis- (2-tert-butyl-5-methylphenol).

  As the hindered amine radical scavenger, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N -(2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine -2,4-diyl} {2,2,6,6-tetramethyl-4-piperidyl} imino] hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}), succinic acid Polycondensate of dimethyl and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, olefin (C20-C24), maleic anhydride, 4-amino-2,2,6,6-tetramethyl Piperidine copolymer, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidylsebacate, bis (2,2,6,6- Tetramethyl-4-piperidyl) sebacate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N′-diformylhexamethylenediamine, methyl-1-octadecane ether- 2,2,6,6-pentamethyl-4-piperidyl sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxyl , Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,3-3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4- Piperidyl / tridecyl) -1,2,3,4-butanetetracarbochelate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarbochelate Chelate, methacrylic acid-1,2,2,6,6-pentamethyl-4-piperidyl ester, methacrylic acid-2,2,6,6-tetramethyl-4-piperidyl ester, {2,2,6,6- Tetramethyl-4-piperidyl 1 / β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2, , 3, 4 Butanetetracarbochelate, {1,2,2,6,6-pentamethyl-4-piperidyl 1 / β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetra And oxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarbochelate.

  Phosphorus radical scavengers include trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl). ) Pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tetrakis (2,4-Di-tert-butylphenyl) -4,4'-biphenylene-diphosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorus An acid etc. are mentioned.

  Examples of the sulfur radical scavenger include didodecyl-3,3′-thiodipropionate, dioctadecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, dioctadecyl-3, 3'-thiodipropionate, distearyl-3,3'-thiodipropionate, dioctadecyl-3,3'-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate) and the like. .

  Examples of the hydroxylamine radical scavenger include dioctadecane hydroxylamine.

  Of the durability, from the viewpoint of durability due to thermal deterioration, the radical scavenger is preferably a phenol radical scavenger, a semi-hindered radical scavenger, a hindered phenol radical scavenger, and a hindered phenol radical. More preferably, it is at least one selected from the group consisting of scavengers.

  The content of the radical scavenger in the resin layer is preferably 3% by mass or less, more preferably 2% by mass or less, and more preferably 1% by mass from the viewpoint of suppression of bleed-out and material cost. More preferably, it is as follows. From the viewpoint of durability due to thermal deterioration, it is preferably 0.15% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more.

  In this specification, the content of the radical scavenger in the resin layer is a value measured by a liquid chromatograph mass spectrometer (LC / MS) after separating the radical scavenger from the resin layer by Soxhlet extraction. . The content of the radical scavenger in the members other than the resin layer is also a value measured in the same manner as described above.

(Average thickness of resin layer)
In the present invention, the average thickness of the resin layer is 20 μm to 1500 μm, and preferably 50 μm to 700 μm.
When the average thickness of the resin layer is 20 μm or more, welding of the metal resin composite to the tire skeleton is sufficiently achieved, and the initial adhesiveness is good. In addition, by supplying a sufficient amount of radical scavenger from the resin layer, the adhesive force between the resin layer / adhesive layer / metal member is sufficiently maintained even in a high temperature environment for a long period of time, and tire durability is improved. It is good.
When the average thickness of the resin layer is 1500 μm or less, when the metal resin composite is wound around the outer periphery of the tire frame body, the interval does not become too wide and a sufficient reinforcing effect is obtained.

  The average thickness of the resin layer is obtained by obtaining SEM images of cross sections obtained by cutting the metal resin composite along the lamination direction of the metal member, the adhesive layer, and the resin layer from arbitrary five locations, and measuring from the obtained SEM images. It is set as the number average value of the thickness of the resin layer. The thickness of the resin layer in each SEM image is a value measured at the thinnest part (the part where the distance between the interface between the adhesive layer and the resin layer and the outer periphery of the metal-resin composite is minimum). .

[Adhesive layer]
The adhesive layer includes a thermoplastic resin and is disposed between the metal member and the resin layer.
The thermoplastic resin contained in the adhesive layer is not particularly limited. Examples of the thermoplastic resin include modified olefin resins (modified polyethylene resins, modified polypropylene resins, etc.), polyamide resins, polyurethane resins, polyester resins, ethylene-ethyl acrylate copolymers, ethylene-vinyl acetate. One type or two or more types of thermoplastic resins such as a copolymer may be used. Among these, from the viewpoint of adhesion to the metal member and the resin layer, at least selected from the group consisting of a modified olefin resin, a polyester resin, an ethylene-ethyl acrylate copolymer, and an ethylene-vinyl acetate copolymer. 1 type is preferable and the modified olefin resin (acid modified olefin resin) acid-modified with unsaturated carboxylic acid is more preferable.
Here, “modified olefin resin acid-modified with an unsaturated carboxylic acid” means a modified olefin resin obtained by graft copolymerization of an unsaturated carboxylic acid with a polyolefin.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and the like.
Examples of the olefin resin include a polyethylene resin, a polypropylene resin, and a polybutadiene resin.
From the viewpoint of resistance to environmental changes in temperature and humidity, high adhesion to the metal member and the resin layer, and excellent resistance to pulling of the metal member against the resin layer, the thermoplastic resin may be an acid-modified olefin resin, particularly maleic acid. At least one selected from the group consisting of a modified polyethylene resin and a maleic acid modified polypropylene resin is preferably used.
In the present invention, the adhesive layer may contain one or more types of thermoplastic resins. Since the tire may become high temperature during use, it is preferable that the tire includes a thermoplastic resin having a softening point exceeding 100 ° C.

  The adhesive layer is preferably formed using a hot melt adhesive. In the present specification, the “hot melt adhesive” is mainly composed of a thermoplastic resin, and the solid content is 95% by mass or more, preferably 99% by mass or more, more preferably 99.5% by mass or more, Preferably, it means a 100% adhesive that is solid or semi-solid at normal temperature (room temperature) but melts by heating.

  The hot melt adhesive is applied to the adherend while being heated and melted, and solidifies by cooling and adheres to the adherend. Therefore, even if the surface of the adherend has irregularities, the hot melt adhesive is used. It is possible to adhere closely. For this reason, it is thought that the metal member which is a to-be-adhered body and a resin layer can be fixed firmly, and the extraction tolerance of the metal member with respect to a resin layer improves. Moreover, since the hot-melt adhesive does not contain an organic solvent or has a small content of the organic solvent, a drying step for removing the solvent is unnecessary, which is excellent from the viewpoints of environment and production.

  In the present invention, the average thickness of the adhesive layer is not particularly limited. From the viewpoint of easy formation of the adhesive layer, adhesive performance, etc., the thickness is preferably 5 μm to 200 μm, more preferably 20 μm to 150 μm, and still more preferably 20 μm to 100 μm.

  The average thickness of the adhesive layer is obtained from SEM images of cross sections obtained by cutting the metal-resin composite along the lamination direction of the metal member, the adhesive layer, and the resin layer from any five locations, and from the obtained SEM images It is set as the number average value of the thickness of the adhesive layer to be measured. The thickness of the adhesive layer in each SEM image is measured at the thinnest part (the part where the distance between the interface between the metal member and the adhesive layer and the interface between the adhesive layer and the resin layer is minimum). Value.

The adhesive layer may contain components other than the thermoplastic resin. For example, rubbers, elastomers, thermoplastic resins, various fillers (for example, silica, calcium carbonate, clay, etc.), anti-aging agents, oils, plasticizers, color formers, weathering agents, carbon black and the like may be included.
The adhesive layer may contain a radical scavenger or may not contain a radical scavenger. In the case where the adhesive layer contains a radical scavenger, the content thereof is preferably set in a range that does not hinder the adhesion to the metal member and the durability of the tire. For example, it is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.3% by mass or less in the total mass of the adhesive layer. When the adhesive layer contains a radical scavenger, by setting the content to 1% by mass or less, the adhesion to the metal member and the tire durability are reduced due to bleeding out of the radical scavenger in the adhesive layer. It is suppressed. When the adhesive layer contains a radical scavenger, for example, one or more selected from the compounds exemplified as the radical scavenger contained in the resin layer can be used as the radical scavenger.

[Tire frame]
The tire frame includes a resin material. The resin material may contain a radical scavenger or may not contain a radical scavenger.
When the resin material contains a radical scavenger, the content is preferably 0.1% by mass to 5% by mass in the total mass of the resin material. When the resin material contains a radical scavenger and the content thereof is 0.1% by mass or more, the durability of the tire is further improved. When the resin material contains a radical scavenger and the content thereof is 5% by mass or less, a decrease in adhesion to a member in contact with the tire frame body due to bleeding out of the radical scavenger in the resin material is suppressed. The When the resin material contains a radical scavenger, for example, one or more selected from the compounds exemplified as the radical scavenger contained in the resin layer can be used as the radical scavenger.

  When the resin material contains a radical scavenger, the content of the radical scavenger in the resin material is more preferably 0.15% by mass to 3% by mass, and 0.2% by mass to 1% by mass. Is more preferable.

Examples of the resin material included in the tire skeleton include thermosetting resins, thermoplastic resins, and thermoplastic elastomers. A resin material may be used individually by 1 type, or may be used in combination of 2 or more type.
Examples of the thermosetting resin include phenol-based thermosetting resins, urea-based thermosetting resins, melamine-based thermosetting resins, and epoxy-based thermosetting resins.
Examples of the thermoplastic resin include polyamide-based thermoplastic resins, polyester-based thermoplastic resins, olefin-based thermoplastic resins, polyurethane-based thermoplastic resins, vinyl chloride-based thermoplastic resins, polystyrene-based thermoplastic resins, and the like. Among these, the thermoplastic resin is preferably at least one selected from polyamide-based thermoplastic resins, polyester-based thermoplastic resins, and olefin-based thermoplastic resins, and is selected from polyamide-based thermoplastic resins and olefin-based thermoplastic resins. More preferably, at least one selected from the group consisting of

  Examples of the thermoplastic elastomer include a polyamide-based thermoplastic elastomer (TPA), a polystyrene-based thermoplastic elastomer (TPS), a polyurethane-based thermoplastic elastomer (TPU), an olefin-based thermoplastic elastomer (TPO) defined in JIS K6418, Examples thereof include polyester-based thermoplastic elastomer (TPEE), crosslinked thermoplastic rubber (TPV), and other thermoplastic elastomers (TPZ). In consideration of elasticity required during traveling, moldability during production, and the like, it is preferable to use a thermoplastic resin as the resin material forming the tire frame, and it is more preferable to use a thermoplastic elastomer. Furthermore, when using a polyamide-type thermoplastic resin as a resin layer contained in a metal resin composite, it is preferable to use a polyamide-type thermoplastic elastomer.

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

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

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

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

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

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

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

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

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

  As a combination of a hard segment and a soft segment, each combination of the hard segment and the soft segment mentioned above can be mentioned. Among these, combinations of hard segment and soft segment include lauryl lactam ring-opening polycondensate / polyethylene glycol combination, lauryl lactam ring-opening polycondensate / polypropylene glycol combination, and lauryl lactam ring-opening polycondensation. Preferred is a combination of isomers / polytetramethylene ether glycol, or a ring-opening polycondensate of lauryl lactam / ABA type triblock polyether, and more preferably a combination of ring-opening polycondensate of lauryl lactam / ABA type triblock polyether. preferable.

  The number average molecular weight of the polymer (polyamide) forming the hard segment is preferably 300 to 15000 from the viewpoint of melt moldability. Moreover, as a number average molecular weight of the polymer which forms a soft segment, 200-6000 are preferable from a viewpoint of toughness and low temperature flexibility. Furthermore, the mass ratio (x: y) to the hard segment (x) and the soft segment (y) is preferably 50:50 to 90:10, more preferably 50:50 to 80:20, from the viewpoint of moldability. .

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

  Examples of commercially available polyamide-based thermoplastic elastomers include “UBESTA XPA” series (for example, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2XPA9044, etc.) manufactured by Ube Industries, Ltd., and “Vestamide” manufactured by Daicel Eponic Corporation. ”Series (for example, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.) and the like can be used.

  The polyamide-based thermoplastic elastomer is suitable as a resin material because it satisfies the performance required as a tire frame from the viewpoint of elastic modulus (flexibility), strength, and the like. In addition, polyamide-based thermoplastic elastomers often have good adhesion to thermoplastic resins and thermoplastic elastomers. Therefore, when a polyamide-based thermoplastic elastomer is used as a resin material for forming a tire skeleton, the material of the coating composition can be freely selected from the viewpoint of adhesiveness between the tire skeleton and the resin layer included in the metal resin composite. Tend to be higher.

-Polystyrene thermoplastic elastomer-
As the polystyrene-based thermoplastic elastomer, for example, at least polystyrene forms a hard segment, and other polymers (for example, polybutadiene, polyisoprene, polyethylene, hydrogenated polybutadiene, hydrogenated polyisoprene, etc.) are amorphous and have a glass transition temperature. The material which forms the soft segment of low is mentioned. As the polystyrene forming the hard segment, for example, those obtained by a known radical polymerization method, ionic polymerization method and the like are preferably used, and specifically, polystyrene having anion living polymerization can be mentioned. Examples of the polymer that forms the soft segment include polybutadiene, polyisoprene, and poly (2,3-dimethyl-butadiene).

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

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

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

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

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

[Wherein P represents a long-chain aliphatic polyether or a long-chain aliphatic polyester. R represents an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon. P ′ represents a short-chain aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon. ]

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

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

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

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

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

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

-Olefin thermoplastic elastomer-
As the olefin-based thermoplastic elastomer, for example, at least a polyolefin forms a hard segment with a crystalline and high melting point, and other polymers (for example, polyolefin, other polyolefins, polyvinyl compounds, etc.) are amorphous and have a glass transition temperature. Examples include materials that form low soft segments. Examples of the polyolefin forming the hard segment include polyethylene, polypropylene, isotactic polypropylene, polybutene, and the like.
Examples of the olefinic thermoplastic elastomer include olefin-α-olefin random copolymers, olefin block copolymers, and the like. Specifically, propylene block copolymers, ethylene-propylene copolymers, propylene- 1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-pentene copolymer, ethylene- 1-butene copolymer, 1-butene-1-hexene copolymer, 1-butene-4-methyl-pentene, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate Copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer Ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer, propylene-methyl methacrylate copolymer, propylene-ethyl methacrylate copolymer, propylene-butyl methacrylate copolymer , Propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, propylene-vinyl acetate copolymer, and the like.

Among these, as the olefinic thermoplastic elastomer, propylene block copolymer, ethylene-propylene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1- Butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-pentene copolymer, ethylene-1-butene copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer , Ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer , Propylene-methyl methacrylate copolymer, pro Lene-ethyl methacrylate copolymer, propylene-butyl methacrylate copolymer, propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, And at least one selected from propylene-vinyl acetate copolymer, ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-methyl methacrylate copolymer More preferred is at least one selected from ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer.
Further, two or more olefin resins such as ethylene and propylene may be used in combination. Moreover, 50 mass% or more and 100 mass% or less of the olefin resin content rate in an olefin type thermoplastic elastomer are preferable.

The number average molecular weight of the olefinic thermoplastic elastomer is preferably 5,000 to 10,000,000. When the number average molecular weight of the olefinic thermoplastic elastomer is 5,000 to 10,000,000, the mechanical properties of the thermoplastic resin material are sufficient and the processability is also excellent. From the same viewpoint, the number average molecular weight of the olefinic thermoplastic elastomer is more preferably 7,000 to 1,000,000, and particularly preferably 10,000 to 1,000,000. Thereby, the mechanical properties and processability of the thermoplastic resin material can be further improved. Moreover, as a number average molecular weight of the polymer which forms a soft segment, 200-6000 are preferable from a viewpoint of toughness and low temperature flexibility. Furthermore, the mass ratio (x: y) to the hard segment (x) and the soft segment (y) is preferably 50:50 to 95:15, and more preferably 50:50 to 90:10, from the viewpoint of moldability. .
The olefinic thermoplastic elastomer can be synthesized by copolymerization by a known method.

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

  Examples of commercially available olefin-based thermoplastic elastomers include “Tuffmer” series (for example, A0550S, A1050S, A4050S, A1070S, A4070S, A35070S, A1085S, A4085S, A7090, A70090, MH7007, MH7010, manufactured by Mitsui Chemicals, Inc. XM-7070, XM-7080, BL4000, BL2481, BL3110, BL3450, P-0275, P-0375, P-0775, P-0180, P-0280, P-0480, P-0680, etc.), Mitsui DuPont “Nucleel” series (for example, AN4214C, AN4225C, AN42115C, N0903HC, N0908C, AN42012C, N410, N1050H, N1108C manufactured by Polychemical Co., Ltd. N1110H, N1207C, N1214, AN4221C, N1525, N1560, N0200H, AN4228C, AN4213C, N035C, etc. "Elvalloy AC" series (for example, 1125AC, 1209AC, 1218AC, 1609AC, 1820AC, 1913AC, 2112AC, 2116AC, 2615AC, 2715AC, etc. 3117AC, 3427AC, 3717AC, etc.), Sumitomo Chemical Co., Ltd.'s "Acryt" series, "Evaate" series, etc., Tosoh Corporation's "Ultrasen" series, etc., "Prime TPO" series (for example, E-2900H, F-3900H, E-2900, F-3900, J-5900, E-2910, F-3910, J-5910, E-2710, F- 710, J-5910, E-2740, F-3740, R110MP, R110E, can be used T310E, also M142E, etc.) and the like.

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

An aromatic polyester can be used as the polyester forming the hard segment. The aromatic polyester can be formed, for example, from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol. The aromatic polyester is preferably polybutylene terephthalate derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol, and 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 a molecular weight of 300 or less Diols such as aliphatic diols such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, 1,4-cyclohexanedimethanol, tricyclodecane dimethylol, etc. Alicyclic diol, 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-quarterphenyl, etc. Polyesters derived from aromatic diols or the like, or copolymerized polyesters in which two or more of these dicarboxylic acid components and diol components are used in combination. It is also possible to copolymerize a trifunctional or higher polyfunctional carboxylic acid component, polyfunctional oxyacid component, polyfunctional hydroxy component and the like in a range of 5 mol% or less.
Examples of the polyester forming the hard segment include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, and polybutylene terephthalate is preferable.

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

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

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

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

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

The melting point of the resin material is usually about 100 ° C. to 350 ° C., but is preferably about 100 ° C. to 250 ° C., more preferably 120 ° C. to 250 ° C. from the viewpoint of tire durability and productivity.
In addition, the resin material may be rubber, elastomer, thermoplastic resin, various fillers (for example, silica, calcium carbonate, clay, etc.), anti-aging agent, oil, plasticizer, color former, weathering agent, etc., as desired. These various additives may be contained (blended).

  The tensile modulus of elasticity defined in JIS K7113: 1995 of the resin material (tire frame) itself is preferably 50 MPa to 1000 MPa, more preferably 50 MPa to 800 MPa, and particularly preferably 50 MPa to 700 MPa. When the tensile elastic modulus of the resin material is 50 MPa to 1000 MPa, the rim can be assembled efficiently while maintaining the shape of the tire frame.

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

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

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

  The tensile elongation at break specified in JIS K7113 (1995) of the resin material (tire frame) itself is preferably 50% or more, more preferably 100% or more, particularly preferably 150% or more, and most preferably 200% or more. When the tensile elongation at break of the resin material is 50% or more, the rim assemblability is good, and it is difficult to break against a collision.

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

  In the tire of the present invention, it is preferable that the Martens hardness (d1) of the tire frame body, the Martens hardness (d2) of the resin layer, and the Martens hardness (d3) of the adhesive layer satisfy the relationship of d1 ≦ d2 <d3. By setting the Martens hardness of the resin layer to be smaller than the Martens hardness of the adhesive layer and greater than or equal to the Martens hardness of the tire frame body, a rigidity step between the resin material constituting the tire frame body and the metal member Is effectively mitigated. As a result, the durability of the tire can be further improved.

  Hereinafter, tires according to embodiments of the present invention will be described with reference to the drawings. In addition, each figure (FIG. 1A, FIG. 1B, FIG. 2, FIG. 3, and FIG. 4) shown below is the figure shown typically, and the size and shape of each part are for ease of understanding. And exaggerated as appropriate. In the following embodiments, the metal resin composite is applied to the belt portion, but the metal resin composite may be applied to other portions such as a bead portion.

[First embodiment]
First, a tire 10 according to a first embodiment of the present invention will be described with reference to FIGS. 1A and 1B.
FIG. 1A is a perspective view showing a cross section of a part of the tire according to the first embodiment. FIG. 1B is a cross-sectional view of a bead portion attached to a rim. As shown in FIG. 1A, a tire 10 according to the first embodiment has a cross-sectional shape substantially similar to that of a conventional general rubber pneumatic tire.

  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, a side portion 14 that extends outward in the tire radial direction from the bead portion 12, and a tire radial direction of one side portion 14. A tire frame body 17 including a crown portion (outer peripheral portion) 16 that connects an outer end and an outer end in the tire radial direction of the other side portion 14 is provided. The tire skeleton 17 is formed using a resin material.

  The tire frame body 17 includes an annular tire frame half body (tire frame piece) 17A having the same shape, which is injection-molded by integrating one bead portion 12, one side portion 14, and a half-width crown portion 16 together. It is formed by facing each other and joining at the tire equatorial plane.

  An annular bead core 18 made of a steel cord is embedded in the bead portion 12 in the same manner as a conventional general pneumatic tire. Further, the portion of the bead portion 12 that comes into contact with the rim 20 and at least the portion that comes into contact with the rim flange 22 of the rim 20 are made of rubber, which is a material having better sealing properties than the resin material constituting the tire frame body 17. An annular seal layer 24 is formed.

  In the crown portion 16, the metal resin composite 26, which is a reinforcement cord, is embedded in the crown portion 16 in a cross-sectional view along the axial direction of the tire frame body 17. It is spirally wound in the circumferential direction. Further, a tread 30 made of rubber, which is a material superior in wear resistance to the resin material constituting the tire skeleton 17, is disposed on the outer side of the metal resin composite 26 in the tire radial direction. The details of the metal resin composite 26 will be described later.

  According to the tire 10 according to the first embodiment of the present invention, since the tire skeleton 17 is formed of a resin material, unlike the conventional rubber tire skeleton, it is not necessary to perform vulcanization and manufacture. The process can be greatly simplified, and the molding time can be shortened. Further, the tire frame half body 17A has a bilaterally symmetric shape, that is, since one tire frame half body 17A and the other tire frame half body 17A have the same shape, the metal for forming the tire frame half body 17A There is an advantage that only one type is required.

  In the tire 10 according to the first embodiment of the present invention, the tire skeleton 17 is formed of a single resin material, but is not limited to such an embodiment, and is made of a conventional general rubber. Similarly to the pneumatic tire, a resin material having different characteristics for each portion (for example, the side portion 14, the crown portion 16, the bead portion 12, etc.) of the tire skeleton 17 may be used. Further, reinforcing materials (polymer materials, metal fibers, cords, non-woven fabrics, woven fabrics, etc.) are embedded in each part of the tire skeleton body 17 (for example, the side portion 14, the crown portion 16, the bead portion 12, etc.). The tire frame body 17 may be reinforced with the reinforcing material.

  In the tire 10 according to the first embodiment of the present invention, the tire frame half body 17A is molded by injection molding, but is not limited thereto, and is molded by, for example, vacuum molding, pressure molding, melt casting, or the like. It may be. Further, in the tire 10 according to the first embodiment, the tire skeleton 17 is formed by joining two members (tire skeleton half 17A), but is not limited thereto, and a low melting point metal is used. The tire skeleton body may be formed as one member by the melting core method, the split core method, or the blow molding used, or may be formed by joining three or more members.

An annular bead core 18 made of a steel cord is embedded in the bead portion 12 of the tire 10. The bead core 18 may be formed of an organic fiber cord, a resin-coated organic fiber cord, or a hard resin in addition to the steel cord. The bead core 18 may be omitted if the rigidity of the bead portion 12 is ensured and there is no problem in fitting with the rim 20.
An annular seal layer 24 made of rubber is formed on a portion of the bead portion 12 that contacts the rim 20 and at least a portion of the rim 20 that contacts the rim flange 22. The seal layer 24 may also be formed in a portion where the tire skeleton 17 (bead portion 12) and the bead sheet 21 are in contact with each other. When rubber is used as the material for forming 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. The rubber seal layer 24 may be omitted if only the resin material forming the tire skeleton 17 can secure the sealing performance with the rim 20.

  The seal layer 24 may be formed using another thermoplastic resin or a thermoplastic elastomer that is more excellent in sealability than the resin material forming the tire frame body 17. Examples of such other thermoplastic resins include resins such as polyurethane resins, olefin resins, polystyrene resins, and polyester resins, and blends of these resins with rubbers or elastomers. Thermoplastic elastomers can also be used, and examples thereof include polyester-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, olefin-based thermoplastic elastomers, combinations of these elastomers, and blends with rubber.

Next, the metal resin composite 26 will be described with reference to FIG. FIG. 2 is a cross-sectional view along the tire rotation axis of the tire 10 according to the first embodiment, and shows a state in which the metal resin composite 26 is embedded in the crown portion of the tire skeleton 17.
As shown in FIG. 2, the metal resin composite 26 is spirally wound 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 frame body 17. . And the part embed | buried under the crown part 16 of the metal resin composite 26 is in the state closely_contact | adhered with the resin material which comprises the crown part 16 (tire frame 17). L in FIG. 2 indicates the embedment depth in the tire rotation axis direction of the metal resin composite 26 with respect to the crown portion 16 (tire frame 17). In one embodiment, the embedding depth L of the metal resin composite 26 with respect to the crown portion 16 is ½ of the diameter D of the metal resin composite 26.

The metal-resin composite 26 has a metal member 27 (for example, a steel cord twisted with steel fibers) as a core, and the outer periphery of the metal member 27 has a resin layer 28 (for example, polyamide-based thermoplastic via an adhesive layer 25). And a structure coated with an elastomer-containing coating composition). The resin layer 28 contains a specific amount of radical scavenger.
A rubber tread 30 is disposed on the outer peripheral side of the metal resin composite 26 in the tire radial direction. Further, the tread 30 is formed with a tread 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.

  In an embodiment, in the tire 10, the metal resin composite 26 covered with the resin layer 28 containing a polyamide-based thermoplastic elastomer is formed on the tire skeleton 17 formed of a resin material containing the same type of polyamide-based thermoplastic elastomer. It is buried in close contact. Therefore, the contact area between the resin layer 28 covering the metal member 27 and the tire frame body 17 is increased, and the durability of adhesion between the metal resin composite 26 and the tire frame body 17 is improved. As a result, the durability of the tire is increased. Will be excellent. In addition, since the resin layer 28 contains a specific amount of radical scavenger, the adhesive layer 25 is excellent in thermal durability and adhesion durability of the coating resin to the metal member is good.

  The embedding depth L of the metal resin composite 26 with respect to the crown portion 16 is preferably 1/5 or more of the diameter D of the metal resin composite 26, and more preferably more than 1/2. It is further preferable that the entire metal resin composite 26 is embedded in the crown portion 16. When the embedding depth L of the metal resin composite 26 exceeds 1/2 of the diameter D of the metal resin composite 26, it is difficult to jump out of the embedded portion due to the size of the metal resin composite 26. When the entire metal resin composite 26 is embedded in the crown portion 16, the surface (outer peripheral surface) becomes flat, and the member is placed on the crown portion 16 in which the metal resin composite 26 is embedded. Even so, it is possible to prevent air from entering the peripheral portion of the metal resin composite 26.

  The layer thickness of the resin layer 28 covering the metal member 27 is not particularly limited, and the average layer thickness is preferably 0.2 mm to 4.0 mm, and preferably 0.5 mm to 3.0 mm. More preferably, it is 0.5 mm-2.5 mm especially preferable.

  In the tire 10 according to the first embodiment of the present invention, the tread 30 is formed of rubber. However, instead of rubber, other types of tires having higher wear resistance than the resin material constituting the tire skeleton 17 are used. A tread formed of a thermoplastic resin material may be used.

Hereinafter, the manufacturing method of the tire concerning a first embodiment of the present invention is explained.
[Tire skeleton molding process]
First, the tire skeleton halves supported by a thin metal support ring face each other. Next, a joining mold is installed so as to contact the outer peripheral surface of the abutting portion of the tire skeleton half. Here, the said joining metal mold | die is comprised so that the periphery of the junction part (butting part) of a tire frame half body may be pressed with a predetermined pressure (not shown). Next, the periphery of the joint portion of the tire frame half body is pressed at a temperature equal to or higher than the melting point (or softening point) of the thermoplastic resin material (in this embodiment, a polyamide-based thermoplastic elastomer) that forms the tire frame body. When the joint portion of the tire frame half body is heated and pressurized by the bonding mold, the joint portion is melted, the tire frame half halves are fused together, and these members are integrated into the tire frame body 17. Is formed.

[Metal resin composite molding process]
Next, the metal resin composite molding process will be described. The metal member 27 is unwound from the reel and the surface thereof is cleaned. Next, the outer periphery of the metal member 27 is covered with a thermoplastic resin extruded from an extruder. The outer periphery of the metal member 27 on which the adhesive layer is formed is covered with a resin layer extruded from an extruder, so that the outer periphery of the metal member 27 is covered with the resin layer 28 via the adhesive layer. A body 26 is formed. Then, the formed metal resin composite 26 is wound around a reel 58.

[Metal resin composite winding process]
Next, the metal resin composite winding step will be described with reference to FIG. FIG. 3 is an explanatory diagram for explaining an operation of installing the metal resin composite on the crown portion of the tire frame body using the metal resin composite heating device and rollers. In FIG. 3, the metal resin composite supply device 56 includes a reel 58 around which the metal resin composite 26 is wound, a metal resin composite heating device 59 disposed downstream of the reel 58 in the code conveying direction, and a metal resin composite. A first roller 60 disposed on the downstream side of the body 26 in the conveying direction, a first cylinder device 62 that moves the first roller 60 in a direction in which the first roller 60 contacts and separates from the tire outer peripheral surface, and a first roller 60. A second roller 64 disposed on the downstream side of the metal resin composite 26 in the conveying direction, and a second cylinder device 66 that moves the second roller 64 in a direction of contacting and separating from the tire outer peripheral surface, It has. The second roller 64 can be used as a metal cooling roller. Further, the surface of the first roller 60 or the second roller 64 is coated with a fluororesin (in this embodiment, Teflon (registered trademark)) in order to suppress adhesion of a molten or softened resin material. . As described above, the heated metal resin composite is firmly integrated with the case resin of the tire frame.

  The metal resin composite heating device 59 includes a heater 70 and a fan 72 that generate hot air. The metal resin composite heating device 59 includes a heating box 74 through which the hot air is supplied and the metal resin composite 26 passes through the internal space, and a discharge port 76 that discharges the heated metal resin composite 26. It has.

  In this step, first, the temperature of the heater 70 of the metal resin composite 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 metal resin composite 26 unwound from the reel 58 is sent into a heating box 74 whose internal space is heated with hot air, and heated (for example, the temperature of the metal resin composite 26 is set to about 100 ° C. to 250 ° C. Heat). The heated metal resin composite 26 passes through the discharge port 76 and is spirally wound around the outer peripheral surface of the crown portion 16 of the tire skeleton 17 rotating in the direction of arrow R in FIG. Here, when the resin layer of the heated metal resin composite 26 comes into contact with the outer peripheral surface of the crown portion 16, the resin material in the contact portion melts or softens, and melts and joins with the resin of the tire frame body to form the crown portion 16. It is integrated with the outer peripheral surface. At this time, since the metal resin composite is melt-bonded to the adjacent metal resin composite, the metal resin composite is wound without a gap. Thereby, the air entering to the portion where the metal resin composite 26 is embedded is suppressed.

  The embedding depth L of the metal resin composite 26 can be adjusted by the heating temperature of the metal resin composite 26, the tension applied to the metal resin composite 26, the pressing force by the first roller 60, and the like. In an embodiment, the embedding depth L of the metal resin composite 26 is set to be 1/5 or more of the diameter D of the metal resin composite 26.

Next, a belt-like tread 30 is wound around the outer peripheral surface of the tire frame body 17 in which the metal resin composite 26 is embedded, and this is accommodated in a vulcanizing can or a mold and heated (vulcanized). The tread 30 may be unvulcanized rubber or vulcanized rubber.
And if the sealing layer 24 which consists of vulcanized rubber is adhere | attached on the bead part 12 of the tire frame | skeleton body 17 using an adhesive agent etc., the tire 10 will be completed.

  In the method for manufacturing a tire according to the first embodiment of the present invention, the bonding portion of the tire frame half body 17A is heated using a bonding mold, but the present invention is not limited to this, and for example, provided separately. The tire frame half body 17A may be joined by heating the joining portion with a high-frequency heater or the like, softening or melting in advance by hot air or infrared irradiation, and pressurizing with a joining mold.

  In the method for manufacturing a tire according to the first embodiment of the present invention, the metal resin composite supply device 56 has two rollers, that is, a first roller 60 and a second roller 64. It is not limited to this, You may have only any one roller (namely, one roller).

In the method for manufacturing a tire according to the first embodiment of the present invention, the metal resin composite 26 is heated, and the surface of the tire skeleton body 17 at the part where the heated metal resin composite 26 contacts is melted or softened. However, the present invention is not limited to this embodiment, and after heating the outer peripheral surface of the crown portion 16 in which the metal resin composite 26 is embedded using a hot air generator without heating the metal resin composite 26, the metal The resin composite 26 may be embedded in the crown portion 16.
In the tire manufacturing method according to the first embodiment of the present invention, the heat source of the metal resin composite heating device 59 is a heater and a fan. However, the present invention is not limited to this mode, and the metal resin is used. The composite 26 may be directly heated with radiant heat (for example, infrared rays).

Furthermore, in the method for manufacturing a tire according to the first embodiment of the present invention, a portion where the thermoplastic resin material in which the metal resin composite 26 is embedded is melted or softened is forced by the metal second roller 64. However, the present invention is not limited to this mode, and cold air is directly blown onto a portion where the thermoplastic resin material is melted or softened, thereby forcing the melted or softened portion of the thermoplastic resin material. Alternatively, it may be cooled and solidified.
Although it is easy to manufacture the metal resin composite 26 spirally, a method of disposing the metal resin composite 26 discontinuously in the width direction is also conceivable.

  The tire 10 according to the first embodiment of the present invention 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. It is not limited to this aspect, A perfect tube shape may be sufficient.

  The present invention has been described with reference to the embodiments. However, these embodiments are merely examples, and the present invention can be implemented with various modifications without departing from the scope of the present 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 specifically described according to the present invention, but the present invention is not limited to these descriptions.

[Example 1]
In accordance with the metal resin composite molding process described above, a multifilament (φ0.35 mm monofilament (steel, strength: 280 N, elongation: 3%) twisted as a metal member) , Hot melt adhesive ("Admer QE-060" manufactured by Mitsui Chemicals, Inc. (maleic acid-modified olefin resin (polypropylene resin), melting point: 143 ° C)) having an average thickness of 100 µm It was made to adhere so that the adhesion layer was formed.
Thereafter, the adhesive layer is covered with a coating composition for forming a resin layer extruded by an extruder, and a metal having a structure in which a metal member, an adhesive layer, and a resin layer are arranged in this order. A resin composite was prepared. The average thickness of the resin layer was 400 μm.
The composition for forming the resin layer was prepared by adding a semi-hindered phenol radical scavenger (trade name “Irganox245” manufactured by BASF Corporation) to the polyamide elastomer A prepared by the following method. It added and prepared so that it might become 0.7 mass% of total mass.

<Preparation of polyamide elastomer A>
(1) Into a reaction vessel having a volume of 2 liters equipped with a stirrer, a nitrogen gas inlet and a condensed water outlet, 470 g of caprolactam manufactured by Aldrich, 173 g of dodecanedioic acid, and 37 g of aminohexanoic acid are placed, and the inside of the container is sufficiently purged with nitrogen After that, the temperature was raised to 250 ° C., and the reaction was carried out under a pressure of 0.6 MPa for 4 hours. After releasing the pressure, the reaction was further continued for 1 hour under a nitrogen stream. After that, a white solid which was a PA6 (nylon (registered trademark) 6) polymer (number average molecular weight: about 1200) was obtained through a water washing step.
(2) 200 g of the above PA6 polymer as a polymer for forming a hard segment, and 164 g of PPG / PTMG / PPG (polymer for forming a soft segment, manufactured by HUNTSMAN, trade name: JEFFAMINE RT-1000) as a polymer for forming a soft segment And mixed. This mixture was stirred at 230 ° C. for 57 hours under a nitrogen stream to obtain a white polyamide elastomer A.

  A tire was produced using the produced metal resin composite by the same method as in the first embodiment described above. The same resin as that used for the resin layer was used as the material for forming the tire frame. The tire size was 245/35 R18.

[Example 2 ]
A metal resin composite and a tire were produced in the same manner as in Example 1 except that the content of the radical scavenger contained in the resin layer was changed as shown in Table 1 .

[Example 3 ]
The metal-resin composite and the tire were the same as in Example 1 except that the same radical scavenger as that contained in the resin layer was added to the tire skeleton forming material so that the content was 0.3% by mass. Was made.

[Comparative Example 1 ]
A metal resin composite and a tire were produced in the same manner as in Example 1 except that the content of the radical scavenger contained in the resin layer was changed as shown in Table 1.

<Evaluation>
The following evaluation was performed using the metal resin composites and tires produced in Examples 1 to 3 and Comparative Example 1 . The results are shown in Table 1, respectively.

1. Initial adhesion between resin layer / adhesion layer / metal member (adhesion immediately after production of metal resin composite)
As an index of initial adhesiveness between the resin layer / adhesive layer / metal member, the peel force when the adhesive layer and the resin layer were peeled from the metal member immediately after the production of the metal resin composite was measured. Specifically, the peel force (unit: N) was measured according to JIS K6854-2: 1999, using a tensile tester (trade name “TENSIRON RTF-1210”) manufactured by A & D Co., Ltd. Evaluation was performed according to the following evaluation criteria.
[Evaluation criteria]
Peeling force is 10N or more ... Good adhesion (A)
Peeling force is less than 10N ... adhesiveness is insufficient (B)

2 . Adhesion after heat treatment between resin layer / adhesion layer / metal member (adhesion after heat treatment of metal resin composite at 120 ° C. for 2 weeks)
The metal resin composites produced in the examples and comparative examples were heat-treated for 2 weeks in an oven heated to 120 ° C. Thereafter, the peeling force (unit: N) was measured in the same manner as in “1. Initial adhesion between resin layer / adhesive layer / metal member” and evaluated according to the following evaluation criteria.
[Evaluation criteria]
The peel strength after the heat treatment is 50% or more of the peel strength immediately after the production. Good adhesion (A)
The peel strength after the heat treatment is less than 50% of the peel strength immediately after the production ... adhesiveness is insufficient (B)

As shown in Table 1, the tires produced in Examples 1 to 3 were excellent in the initial adhesion between the resin layer / adhesive layer / metal member, and maintained good adhesion even after heat treatment. Also, the initial adhesiveness between the resin layer / tread rubber was good. As a result, the evaluation of tire durability was also good.
In Comparative Example 1 containing no radical scavenger in the resin layer, the evaluation of the adhesion between the resin layer / adhesive layer / metal member after heat treatment was low, and the evaluation of tire durability was also low .

  As described above, the tire of the present invention is excellent in durability of the adhesive layer disposed between the metal member and the resin layer in the metal-resin composite and adhesion durability of the adhesive layer to the metal member. It was found to be excellent in performance.

  10 tires, 12 bead parts, 16 crown parts (peripheral parts), 18 bead cores, 20 rims, 21 bead sheets, 22 rim flanges, 17 tire frame bodies, 24 seal layers, 25 adhesive layers, 26 metal resin composites, 27 metals Member, 28 resin layer, 30 tread, D metal member diameter, L metal member embedment depth

Claims (4)

Including an annular tire frame and a metal resin composite,
The metal resin composite has a structure in which a metal member, an adhesive layer containing a thermoplastic resin, and a resin layer are arranged in this order,
The resin layer has an average thickness is 20Myuemu～1500myuemu, viewed contains a radical scavenger 0.1% to 5% by weight in the total mass of the resin layer, the adhesive layer does not comprise a radical scavenger, tire.   2. The tire according to claim 1, wherein the radical scavenger includes at least one selected from the group consisting of a semi-hindered phenol radical scavenger, a hindered phenol radical scavenger, and a hindered phenol radical scavenger. .   The tire according to claim 1 or 2, wherein the thermoplastic resin includes a polyolefin-based resin.   The tire structure includes a resin material, and the resin material includes 0.1% by mass to 5% by mass of a radical scavenger in the total mass of the resin material. The tire according to item.