JP2024006378A - Resin-rubber composite and tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin-rubber composite which is formed by bonding a member containing a resin and a member containing rubber without using an adhesive, and a tire having the resin-rubber composite.

SOLUTION: A resin-rubber composite includes a member containing a resin and a member containing rubber bonded to the member containing the resin, wherein the resin contains an amino group, and the member containing the rubber contains an organic peroxide and a maleimide compound.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present disclosure relates to a resin rubber composite and a tire.

BACKGROUND ART In recent years, from the viewpoints of weight reduction, ease of molding, recycling, etc., the use of resin-containing members as part of tire members has been considered, for example, in the field of tires. For example, Patent Document 1 proposes a tire using a member containing a polyamide thermoplastic elastomer.

Japanese Patent Application Publication No. 2012-46030

When resin is used as a tire member, there may be a portion where the resin and rubber come into contact. One way to bond resin and rubber is to use adhesives, but from the viewpoint of improving productivity and reducing the burden on the environment or living organisms, it is desirable to bond them together without using adhesives. It is rare.
In view of the above circumstances, one aspect of the present disclosure provides a resin-rubber composite formed by adhering a resin-containing member and a rubber-containing member without using an adhesive, and a tire having the resin-rubber composite. The purpose is to

Specific means for solving the above problems include the following aspects.
<1> A member containing a resin and a member containing a rubber adhered to the member containing the resin, the resin containing an amino group, and the member containing the rubber containing an organic peroxide and a maleimide compound. A resin-rubber composite containing.
<2> The resin-rubber composite according to <1>, wherein the resin includes at least one selected from the group consisting of polyamide-based thermoplastic elastomer and polyamide.
<3> The resin-rubber composite according to <1> or <2>, wherein the resin has an amino group at the end of the molecule, and the content of the amino group is 0.01 mmol/g or more.
<4> The resin-rubber composite according to any one of <1> to <3>, wherein the sulfur content of the rubber-containing member is 0% to 2% by mass of the entire rubber-containing member. body.
<5> The resin-rubber composite according to any one of <1> to <4>, further comprising a member containing another rubber adhered to the member containing rubber.
<6> A tire comprising the resin rubber composite according to any one of <1> to <5>.

According to one aspect of the present disclosure, there are provided a resin-rubber composite formed by adhering a resin-containing member and a rubber-containing member without using an adhesive, and a tire having the resin-rubber composite.

FIG. 1 is a perspective view showing a cross section of a part of the tire according to the first embodiment. FIG. 1 is a cross-sectional view along the tire width direction showing the configuration of a tire according to a first embodiment. FIG. 2 is a cross-sectional view along the tire width direction showing the configuration of a tire according to a second embodiment. FIG. 3 is a cross-sectional view along the tire width direction showing the configuration of a tire according to a third embodiment. FIG. 7 is an enlarged cross-sectional view of a bead portion of a tire according to a fourth embodiment.

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

In this specification, the term "resin" is a concept that includes thermoplastic resins, thermoplastic elastomers, and thermosetting resins, but does not include rubber (thermosetting elastomers).
In this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
As used herein, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the purpose is achieved. include.
In the present specification, if there are multiple substances corresponding to each component in the composition, the amount of each component in the composition is the total amount of the multiple substances present in the composition, unless otherwise specified. means quantity.
In the present specification, the term "main component" means the component having the highest content on a mass basis in the mixture, unless otherwise specified.

As used herein, the term "thermoplastic resin" refers to a polymer compound whose material softens and flows as the temperature rises and becomes relatively hard and strong when cooled, but does not have rubber-like elasticity.
In this specification, the term "thermoplastic elastomer" refers to a material that softens and flows as the temperature rises, becomes relatively hard and strong when cooled, and has rubber-like elasticity.
Specific examples of thermoplastic elastomers include copolymers having a hard segment that is crystalline and has a high melting point or cohesive force, and a soft segment that is amorphous and has a low glass transition temperature.
Hard segments include, for example, structures having rigid groups such as aromatic groups or alicyclic groups in the main skeleton, or segments that enable intermolecular packing through intermolecular hydrogen bonds or π-π interactions. can be mentioned. Examples of soft segments include segments with a structure that has a long-chain group (such as an alkylene group) in the main chain, has a high degree of freedom in molecular rotation, and has elasticity.

[Resin rubber composite]
A resin-rubber composite according to the present disclosure includes a member containing a resin, and a member containing rubber adhered to the member containing the resin,
The resin contains an amino group,
The member containing rubber contains an organic peroxide and a maleimide compound.
Hereinafter, a member containing resin may be referred to as a "resin member", and a member containing rubber may be referred to as a "rubber member".

In the resin-rubber composite according to the present disclosure, the resin member and the rubber member are adhesive to each other without using an adhesive. The reason is presumed to be as follows, for example.
In the resin-rubber composite according to the present disclosure, the resin contained in the resin member contains an amino group. Therefore, it is assumed that at the interface between the resin member and the rubber member, a reaction occurs between the amino groups contained in the resin and the maleimide compound contained in the rubber member, contributing to the adhesion between the resin member and the rubber member. Ru.
Furthermore, the rubber member contains an organic peroxide, ie, a sulfur-free compound, as a crosslinking agent for the rubber. Therefore, the deactivation of the maleimide compound due to the reaction between the maleimide compound and sulfur in the rubber member is suppressed. As a result, the reaction between the amino groups contained in the resin member and the maleimide compound occurs sufficiently, and good adhesion is achieved.

<Resin member>
The type of resin contained in the resin member is not particularly limited as long as it contains an amino group, and may be any one of a thermoplastic resin, a thermoplastic elastomer, and a thermosetting resin.
The resin member may contain only one type of resin or two or more types of resin.

In the present disclosure, "resin containing an amino group" means a resin in which either or both of a primary amino group (-NH ₂ ) and a secondary amino group (-NHR) are present in the molecule.

Specific examples of the resin containing amino groups include various polyamide thermoplastic elastomers and polyamides. These resins each have a primary amino group and a carboxy group at the end of the molecule.

(Polyamide thermoplastic elastomer)
The polyamide thermoplastic elastomer means a thermoplastic elastomer having an amide bond (-CONH-) in the main chain of the polymer forming the hard segment.
As a polyamide-based thermoplastic elastomer, for example, at least polyamide forms a hard segment that is crystalline and has a high melting point, and other polymers (e.g., polyester, polyether, etc.) form a soft segment that is amorphous and has a low glass transition temperature. Examples include the material from which it is formed. Further, the thermoplastic polyamide elastomer may be formed using a chain extender such as a dicarboxylic acid in addition to the hard segment and the soft segment.
Specific examples of the polyamide thermoplastic elastomer include thermoplastic amide elastomer (TPA) defined in JIS K6418:2007, polyamide elastomer described in JP-A No. 2004-346273, and the like.

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

General formula (1)

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

General formula (2)

[In the general formula (2), R ² represents a hydrocarbon molecular chain 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 preferably a hydrocarbon molecular chain having 4 to 15 carbon atoms, such as a carbon An alkylene group having 4 to 15 carbon atoms is more preferred, and a hydrocarbon molecular chain having 10 to 15 carbon atoms, such as an alkylene group having 10 to 15 carbon atoms, is particularly preferred.
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; For example, an alkylene group having 4 to 15 carbon atoms is more preferred, and a hydrocarbon molecular chain having 10 to 15 carbon atoms, such as an alkylene group having 10 to 15 carbon atoms, is particularly preferred.
Examples of the monomer represented by general formula (1) or 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, cocondensates of diamines and dicarboxylic acids, and the like.

Examples of ω-aminocarboxylic acids include those having 5 to 20 carbon atoms, such as 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Examples include aliphatic ω-aminocarboxylic acids. Examples of the lactam include aliphatic lactams having 5 to 20 carbon atoms such as lauryllactam, ε-caprolactam, udecanelactam, ω-enantholactam, and 2-pyrrolidone.
Examples of the diamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4 Examples include diamine compounds such as aliphatic diamines having 2 to 20 carbon atoms such as -trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, 3-methylpentamethylene diamine, and metaxylene diamine.
Dicarboxylic acid can be represented by HOOC-(R ³ )m-COOH (R ³ : molecular chain of hydrocarbon having 3 to 20 carbon atoms, m: 0 or 1), and includes, for example, oxalic acid, succinic acid, glutaric acid. Examples include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
As the polyamide forming the hard segment, polyamide obtained by ring-opening polycondensation of lauryllactam, ε-caprolactam, or udecane lactam can be preferably used.

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

General formula (3)

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

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

Examples of the combination of hard segments and soft segments include the above-mentioned combinations of hard segments and soft segments. Among these, combinations of hard segments and soft segments include ring-opening polycondensates of lauryllactam/polyethylene glycol, ring-opening polycondensates of lauryllactam/polypropylene glycol, and ring-opening polycondensates of lauryllactam. A combination of polytetramethylene ether glycol/polytetramethylene ether glycol or a ring-opening polycondensate of lauryllactam/ABA-type triblock polyether is preferred, and a combination of a ring-opening polycondensate of lauryllactam/ABA-type triblock polyether is more preferred. preferable.

The number average molecular weight of the polymer (polyamide) forming the hard segment is preferably 300 to 15,000 from the viewpoint of melt moldability. Further, the number average molecular weight of the polymer forming the soft segment is preferably 200 to 6,000 from the viewpoint of toughness and low temperature flexibility. Furthermore, the mass ratio (x:y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 90:10, more preferably 50:50 to 80:20, from the viewpoint of moldability. .

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

As a commercially available product of Polyamide -based thermoplastic elastomers, for example, Ube Kosan's "Ubesta XPA" series (for example, XPA90633X1, XPA90555X1, XPA9048X2, XPA9048X1, XPA9048X1, XPA9040X1, XPA9040X2, XPA9040X2, XPA9040X2. PA9044), Daisel Eponic Co., Ltd. Examples include the "Vestamide" series (eg, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.).

(polyamide)
Examples of the polyamide include homopolymers and copolymers made of monomers that form the hard segments of the polyamide thermoplastic elastomer described above.
Specifically, the polyamides include polyamide (nylon 6) obtained by ring-opening polycondensation of ε-caprolactam, polyamide (nylon 11) obtained by ring-opening polycondensation of undecane lactam, polyamide (nylon 12) obtained by ring-opening polycondensation of lauryllactam, Examples include polyamide (nylon 66) obtained by polycondensing hexamethylene diamine and adipic acid, polyamide having meta-xylene diamine as a constituent unit (nylon MXD6), and the like.

The structural unit of nylon 6 can be represented by, for example, {CO-(CH ₂ ) ₅ -NH} _n . The structural unit of nylon 11 can be represented by, for example, {CO—(CH ₂ ) ₁₀ —NH} _n . The structural unit of nylon 12 can be represented by, for example, {CO-(CH ₂ ) ₁₁ -NH} _n . The structural unit of nylon 66 can be represented by, for example, {CO(CH ₂ ) ₄ CONH(CH ₂ ) ₆ NH} _n . The structural unit of nylon MXD6 can be represented by, for example, the following structural formula (A-1). Here, n represents the number of structural units.

As a commercially available nylon 6, for example, the "UBE Nylon" series (for example, 1022B, 1011FB, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercially available nylon 11, for example, the "Rilsan B" series manufactured by Arkema Co., Ltd. can be used. As a commercially available nylon 12, for example, the "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, the "Leona" series (for example, 1300S, 1700S, etc.) manufactured by Asahi Kasei Corporation can be used. As a commercially available nylon MXD6, for example, the "MX Nylon" series (for example, S6001, S6021, S6011, etc.) manufactured by Mitsubishi Gas Chemical Co., Ltd. can be used.

From the viewpoint of adhesiveness of the resin member to the rubber member, the content of terminal amino groups in the resin is preferably 0.01 mmol/g or more, more preferably 0.02 mmol/g or more, and 0.03 mmol It is more preferable that it is at least /g.
There is no particular upper limit to the content of terminal amino groups in the resin. For example, it may be 1 mmol/g or less.

In the present disclosure, the content of terminal amino groups in the resin is measured by a neutralization titration method. Specifically, the measurement is performed at room temperature (25° C.) using a mixed solvent of phenol and methanol (mixed volume ratio 9:1) as a solvent and 0.01 mol/M hydrochloric acid as a titrant.

The resin member may contain only resin or may contain components other than resin. Specific examples of components other than resin include various fillers (silica, calcium carbonate, clay, carbon black, etc.), anti-aging agents, oils, plasticizers, colorants, weathering agents, and the like.

When the resin member contains components other than resin, the amount thereof is not particularly limited. For example, the total amount of components other than resin may be in the range of 1 part by mass to 70 parts by mass, may be in the range of 5 parts by mass to 50 parts by mass, or 10 parts by mass, based on 100 parts by mass of resin. and 30 parts by weight.

<Rubber member>
The type of rubber contained in the rubber member is not particularly limited.
Specifically, the rubbers include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), chloroprene rubber (CR), acrylonitrile-butadiene copolymer rubber ( Examples include diene rubbers such as NBR), and non-diene rubbers such as butyl rubber (IIR), ethylene propylene rubber (EPM), urethane rubber, silicone rubber, and acrylic rubber.
From the viewpoint of adhesiveness with the resin member, it is preferable that the rubber member contains diene rubber.
The rubber member may contain only one type of rubber or two or more types of rubber.

The content of rubber contained in the rubber member is not particularly limited, and can be selected from the range of 30% by mass to 100% by mass.
The content of rubber contained in the rubber member may be, for example, 50% by mass or more, 60% by mass or more, or 65% by mass or more.
The content of rubber contained in the rubber member may be, for example, 95% by mass or less, 85% by mass or less, or 75% by mass or less.

The type of organic peroxide contained in the rubber member is not particularly limited. Specifically, dicumyl peroxide, 1,3-di(t-butylperoxyisopropyl)benzene, 1,4-di(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5- Di(t-butylperoxy)hexane, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, n-butyl-4,4-di(t -butylperoxy) parerate, 1,1-di(t-butylperoxy)cyclohexane, di(2,4-dichlorobenzoyl) peroxide, and the like.
The rubber member may contain only one kind of organic peroxide or two or more kinds of organic peroxides.

The amount of organic peroxide contained in the rubber member is not particularly limited. For example, the amount of organic peroxide contained in the rubber member is preferably 0.1 parts by mass to 10 parts by mass, and preferably 0.5 parts by mass to 5 parts by mass, based on 100 parts by mass of rubber. More preferably, the amount is 1 part by mass to 3 parts by mass.

The type of maleimide compound contained in the rubber member is not particularly limited. Specifically, N,N'-m-phenylenebismaleimide, 4,4'-bis(maleimido)diphenylmethane, 1-maleimido-3-maleimidomethyl-3,5,5-trimethylcyclohexane, N,N'- p-phenylenebismaleimide, 1,1'-(cyclohexane-1,3-diylbis(methylene))bis(1H-pyrrole-2,5-dione), 1,1'-(4,4'-methylenebis(cyclohexane) -4,1-diyl))bis(1H-pyrrole-2,5-dione), 1,1'-(3,3'-(piperazine-1,4-diyl)bis(propane-3,1-diyl) )) Bis(1H-pyrrole-2,5-dione), 2,2'-(ethylenedioxy)bis(ethylmaleimide), 1,2-bis(maleimido)ethane, N-succinimidyl-3-maleimidopropio and succinimidyl-4-(N-maleimidomethyl)cyclohexane-1-carboxylate.
The rubber member may contain only one type of maleimide compound or two or more types of maleimide compounds.

The amount of maleimide compound contained in the rubber member is not particularly limited. For example, the amount of maleimide compound contained in the rubber member is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, based on 100 parts by mass of rubber. , more preferably from 1 part by mass to 3 parts by mass.

If necessary, the rubber member may contain components other than rubber, organic peroxide, and maleimide compound.
Components other than rubber, organic peroxides and maleimide compounds include carbon black, crosslinking accelerators, fatty acids, metal oxides, process oils, anti-aging agents, tackifiers, anti-scorch agents and the like.

From the viewpoint of improving the strength of the rubber member, it is preferable that the rubber member contains carbon black.
The type of carbon black is not particularly limited. Specific examples include furnace black obtained by a furnace method, channel black obtained by a channel method, acetylene black obtained by an acetylene method, thermal black obtained by a thermal method, and the like.
The rubber member may contain only one type of carbon black or two or more types of carbon black.

The amount of carbon black contained in the rubber member is not particularly limited. For example, it is preferably 25 parts by mass to 65 parts by mass, more preferably 30 parts by mass to 60 parts by mass, and 35 parts by mass to 55 parts by mass, based on 100 parts by mass of rubber contained in the rubber member. It is even more preferable.

Specific examples of the crosslinking accelerator include aldehydes and the like.
Specific examples of fatty acids include stearic acid, palmitic acid, myristic acid, lauric acid, and metal salts thereof. Among these, stearic acid is preferred.
Specific examples of the metal oxide include zinc white (ZnO), iron oxide, magnesium oxide, and the like.
Examples of process oil include aromatic process oil, naphthenic process oil, paraffin process oil, etc.>
Examples of anti-aging agents include amine-ketone anti-aging agents, imidazole anti-aging agents, amine anti-aging agents, phenolic anti-aging agents, phosphorus anti-aging agents and the like.
Examples of the tackifier include phenolic resins, rosin resins, and terpene resins.

From the viewpoint of adhesiveness with the resin member, it is preferable that the rubber member does not contain sulfur or has a sulfur content of 2 mass or less of the entire rubber member; is more preferably 0.5% by mass or less of the entire rubber member, and even more preferably does not contain sulfur (that is, the sulfur content is 0% by mass).

In addition to the resin member and the rubber member, the resin-rubber composite according to the present disclosure may further include another rubber member adhered to the rubber member.
Hereinafter, the rubber member adhered to the resin member may be referred to as a first rubber member, and the rubber member adhered to the first rubber member may be referred to as a second rubber member.

The method of bonding the first rubber member and the second rubber member is not particularly limited, and any known method can be used.
For example, by heating an uncrosslinked first rubber member and an uncrosslinked second rubber member in contact with each other to crosslink the rubber contained therein, the first rubber member and the second rubber member are bonded together. Examples include a method of bonding a first rubber member and a second rubber member using an adhesive, and the like.

The compositions of the first rubber member and the second rubber member may be the same or different.
Examples of the second rubber member having a different composition from the first rubber member include a rubber member containing sulfur as a crosslinking agent.

(Method for manufacturing resin rubber composite)
A method for producing a resin-rubber composite includes, for example, a step of bringing a resin member into contact with an uncrosslinked rubber member;
The method includes a step of crosslinking the uncrosslinked rubber member.

An uncrosslinked rubber member can be obtained, for example, by kneading materials constituting the rubber member and molding the mixture into a desired shape. The kneading temperature of the material is, for example, in the range of 80° C. to 180° C. from the viewpoint of maintaining an uncrosslinked state. Examples of the kneading machine include common kneading machines such as a mixing roll, a Sigma-type rotary blade kneader, a Banbury mixer, a high-speed twin-screw continuous mixer, and a single-screw, twin-screw, and multi-screw extruder-type kneader. Examples of the molding method include extrusion molding, rolling molding, and the like.

The resin member can be obtained, for example, by kneading materials constituting the resin member and molding it into a desired shape. The kneading temperature of the materials is not particularly limited and can be set depending on the materials used.
The kneader used for kneading is the same as the kneader used to obtain an uncrosslinked rubber member. Examples of the molding method include injection molding, vacuum molding, pressure molding, and melt casting.

The heating temperature in the step of crosslinking an uncrosslinked rubber member can be set depending on the material of the rubber member. For example, the temperature range is 110°C to 220°C. The heating time may be, for example, 1 minute to 30 hours.

(Applications of resin rubber composites)
Resin-rubber composites can be applied to various uses. Applications of resin-rubber composites include tires, anti-vibration rubber, rubber hoses, rubber-resin composite hoses, belts, rubber crawlers, golf balls, bellows, seismic isolation rubber, sealants, caulking materials, bicycle parts, etc. .

When a resin-rubber composite is used for a tire, examples of the combinations of resin members and rubber members in the resin-rubber composite include the following combinations.
- A combination of a belt member as a resin member and at least one member selected from the group consisting of a tread as a rubber member, a tire frame member, and a rubber sheet adhered to the surface of the belt member.
- A combination of a bead member as a resin member, a tire frame member as an epoxy rubber member, and at least one member selected from the group consisting of a rubber sheet adhered to the surface of the bead member.
- A tire frame member as a resin member, and at least one member selected from the group consisting of a tread, a belt member, a bead member as an epoxy rubber member, and a rubber sheet adhered to the surface of the tire frame member. combination.
- At least one member selected from the group consisting of a belt cord as a resin member, a cord covering member covering the belt cord as an epoxy rubber member, and a rubber sheet adhered to the surface of the belt cord. combination (i.e. the belt member is a composite).
- At least one member selected from the group consisting of a ply cord as a resin member, a cord covering member covering the ply cord as an epoxy rubber member, and a rubber sheet adhered to the surface of the ply cord. Combination (i.e. the carcass ply is a composite).
- At least one member selected from the group consisting of a bead wire as a resin member, a wire covering member covering the bead wire as an epoxy rubber member, and a rubber sheet adhered to the surface of the bead wire. combination (i.e. the bead core is a composite).

When the resin-rubber composite includes a resin member, a first rubber member adhered to the resin member, and a second rubber member adhered to the first rubber member, examples of combinations thereof include the following combinations: can be mentioned.
- A combination of a belt member as a resin member, a rubber sheet as a first rubber member, and at least one member selected from the group consisting of a tread and a tire frame member as a second rubber member.
- A combination of a bead member as a resin member, a rubber sheet as a first rubber member, and a tire frame member as a second rubber member.
- A combination of a tire frame member as a resin member, a rubber sheet as a first rubber member, and at least one member selected from the group consisting of a tread, a belt member, and a bead member as a second rubber member.
- A combination of a belt cord as a resin member, a rubber sheet as a first rubber member, and a cord covering member as a second rubber member.
- A combination of a ply cord as a resin member, a rubber sheet as a first rubber member, and a cord covering member as a second rubber member.
- A combination of a bead wire as a resin member, a rubber sheet as a first rubber member, and a wire covering member as a second rubber member.

[tire]
The tire of the present invention has at least the above-mentioned composite body.
Hereinafter, embodiments of a tire having the aforementioned composite body will be described with reference to the drawings, but the tire of the present invention is not limited to these examples.

<First embodiment>
The tire of the first embodiment includes: an annular tire frame member containing resin; a belt member provided on the outside of the tire frame member in the tire radial direction and including a plurality of reinforcing cords and a covering resin covering the reinforcing cords; It has a rubber sheet provided on the outer surface of the member in the tire radial direction in direct contact with the coating resin of the belt member, and a tread provided on the outer surface of the rubber sheet in the tire radial direction in direct contact with the rubber sheet.
The tire of the first embodiment includes a resin covering the belt member corresponding to the resin member, a rubber sheet corresponding to the first rubber member, and a tread corresponding to the second rubber member. The tread may be a composite of multiple rubber layers.
Note that the tread may be arranged so as to be in contact with the coating resin of the belt member without using the rubber sheet. That is, the tread may correspond to the first rubber member.

The first embodiment will be described below with reference to FIGS. 1 and 2. In addition, in FIG. 2, arrow W indicates a direction parallel to the tire rotation axis (hereinafter sometimes referred to as "tire width direction"), and arrow S indicates a direction passing through the tire rotation axis and perpendicular to the tire width direction ( (hereinafter sometimes referred to as "tire radial direction"). Furthermore, a dashed line CL indicates the center line of the tire (hereinafter also referred to as "tire equatorial plane").

FIG. 1 is a perspective view showing a cross section of a part of a tire according to a first embodiment, and FIG. 2 is a cross-sectional view along the tire width direction showing the configuration of the tire according to a first embodiment.
As shown in FIGS. 1 and 2, the tire 10 according to the first embodiment includes a tire case 17, which is an annular tire frame member made of a resin material containing resin, and a tire radially outward side of the tire case 17. The provided belt member 12, the region of the tire radially outer surface of the tire case 17 where the belt member 12 is not provided, the tire radially outer surface of the belt member 12, and the tire width direction outer surface. The tire includes a rubber sheet 11 and a tread 30 provided on the outer surface of the rubber sheet 11 in the tire radial direction. The belt member 12 includes a plurality of reinforcing cords 24 covered with a coating resin 26.

-Tire frame components-
The tire case 17 is made of, for example, thermoplastic elastomer, which is an example of a resin material, and is formed in an annular shape in the tire circumferential direction.
The tire case 17 includes a pair of bead portions 14 arranged at intervals in the tire width direction, a pair of side portions 16 extending outward in the tire radial direction from the pair of bead portions 14, and a pair of side portions. 16 and a crown portion 18 connecting the two. The bead portion 14 is a portion that comes into contact with a rim (not shown). Further, the side portion 16 forms a side portion of the tire 10, and is gently curved so as to be convex outward in the tire width direction from the bead portion 14 toward the crown portion 18.

The crown portion 18 is a portion that connects the outer end in the tire radial direction of one side portion 16 and the outer end in the tire radial direction of the other side portion 16, and supports the tread 30 disposed on the outer side in the tire radial direction. .

The outer circumferential surface 18A of the crown portion 18 of the tire case 17 may be formed in a flat shape in a cross section in the tire width direction, or may be in a curved shape bulging outward in the tire radial direction. 18 A of outer peripheral surfaces of the crown part 18 of this embodiment are the outer peripheries of the tire case 17 in which the belt member 12 is provided.

The tire case 17 has a pair of annular tire halves 17H each having one bead part 14, one side part 16, and a half-width crown part 18. It is formed by joining the ends of the half-width crown portion 18 at the tire equatorial plane CL. These end portions are joined using, for example, welding resin material 17A.

An annular bead core 20 extending along the tire circumferential direction is embedded in the bead portion 14 . This bead core 20 is composed of a bead cord (not shown). This bead cord is composed of a metal cord such as a steel cord, an organic fiber cord, a resin-coated organic fiber cord, a hard resin, or the like. Note that the bead core 20 itself may be omitted if sufficient rigidity of the bead portion 14 can be ensured.

The tire case 17 may be an integrally molded product, or the tire case 17 may be manufactured by dividing into three or more resin members, and these may be joined together. For example, the tire case 17 may be manufactured separately for each part (for example, the bead part 14, the side part 16, and the crown part 18), and these parts may be joined together. At this time, each part of the tire case 17 (for example, the bead part 14, the side part 16, and the crown part 18) may be formed of a resin material having different characteristics.

If necessary, a reinforcing material (polymer material, metal fiber, cord, nonwoven fabric, woven fabric, etc.) may be embedded in the tire case 17.

A coating layer 21 may be formed on the surface of the bead portion 14 at the portion that contacts the rim (not shown) in order to improve airtightness between the bead portion 14 and the rim. Examples of the material for the coating layer 21 include materials such as rubber that are softer than the tire case 17 and have higher weather resistance. The coating layer 21 is folded back from the inner surface of the bead portion 14 on the inner side in the tire width direction to the outer side in the tire width direction, and extends through the outer surface of the side portion 16 to the vicinity of the outer end of the belt member 12 in the tire width direction. It may be provided as follows. The extending end portion of the covering layer may be covered by a tread 30, which will be described later. However, if sealability (airtightness) between the tire case 17 and the rim (not shown) can be ensured only by the bead portion 14 of the tire case 17, the coating layer 21 may not be provided.
When the covering layer 21 contains rubber, the tire case 17 may correspond to the resin member of the resin-rubber composite, and the covering layer 21 may correspond to the rubber member of the resin-rubber composite.

-Belt parts-
Next, the belt member 12 will be explained.
In the belt member 12, a resin-coated cord 28 is spirally wound around the outer periphery of the tire case 17 in the tire circumferential direction and joined to the tire case 17, and portions of the resin-coated cord 28 that are adjacent to each other in the tire width direction are connected to each other. It consists of being joined. The resin-coated cord 28 is constructed by coating the reinforcing cord 24 with a coating resin 26.

The reinforcing cord 24 is made of monofilament (single wire) such as metal fiber or organic fiber, or multifilament (stranded wire) made by twisting these fibers, and the covering resin 26 is made of a resin material.
The reinforcing cord 24 is preferably a multifilament from the viewpoint of further improving the durability of the tire. The number of the plurality of metal cords is, for example, 2 to 10, preferably 5 to 9.
From the viewpoint of achieving both internal pressure resistance and weight reduction of the tire, the thickness of the reinforcing cord 24 is preferably 0.2 mm to 2 mm, more preferably 0.8 mm to 1.6 mm.

In the belt member 12 shown in FIGS. 1 and 2, the resin-coated cord 28 has a single layer, and the reinforcing cords 24 are arranged in a line in the tire width direction, but the present invention is not limited to this. The belt member 12 may have a laminated structure in which the resin-coated cord 28 is spirally wound in the circumferential direction of the tire to form a layer, and then the resin-coated cord 28 is further wound around the outer peripheral surface of the layer. good.

The belt member 12 shown in FIGS. 1 and 2 is constructed by spirally winding and joining a resin-coated cord 28 around the outer peripheral surface of the tire case 17, but the present invention is not limited thereto. For example, a belt member may be formed by winding a plurality of reinforcing cords 24 and coating resin 26 integrated into a sheet shape around the outer peripheral surface of the tire case 17.

-Rubber sheets and treads-
Next, the rubber sheet 11 and tread 30 will be explained.
As shown in FIGS. 1 and 2, a rubber sheet 11 is disposed on the belt member 12 on the outside of the belt member 12 in the tire radial direction, and a tread 30 is disposed on the outside of the rubber sheet 11 in the tire radial direction.
The rubber sheet 11 and the tread 30 each contain rubber. The tread 30 may be a multilayer body made of multiple rubber layers.
The thickness of the rubber sheet 11 may be, for example, 0.1 mm to 100 mm.

A drainage groove 30A extending in the tire circumferential direction is formed on the outer peripheral surface of the tread 30 in the tire radial direction. In this embodiment, two grooves 30A are formed, but the present invention is not limited to this, and more grooves 30A may be formed. A known tread pattern can be used as the tread pattern.

In FIGS. 1 and 2, the tread 30 is provided on the belt member 12 via the rubber sheet 11, but the invention is not limited thereto. For example, the tread 30 may be in contact with the belt member 12 without the rubber sheet 11 interposed therebetween.

-Tire manufacturing method-
Next, a method for manufacturing the tire 10 of this embodiment will be explained. First, a pair of tire halves 17H including the bead core 20 are formed by injection molding using a thermoplastic resin material.
Next, the ends of the portions of the pair of tire halves 17H that will become the crown portions 18 are abutted against each other, and the molten welding resin material 17A is applied to the abutted portions to join the pair of tire halves 17H. In this way, an annular tire case 17 is formed.

Next, the process of wrapping the resin-coated cord 28 around the outer periphery of the tire case 17 will be explained. Specifically, while feeding the resin-coated cord 28 toward the outer circumferential surface 18A of the crown portion 18, hot air is blown onto the thermoplastic resin of the resin-coated cord 28 and the outer circumferential surface 18A of the crown portion 18 to heat and melt it. Then, the resin-coated cord 28 in which the thermoplastic resin is molten is pressed against the outer circumferential surface 18A of the molten crown portion 18 to be joined, and the cords are cooled and solidified.
In this way, a layer of resin-coated cord 28 is formed on the outer periphery of the tire case 17, specifically, on the outer periphery of the crown portion 18, thereby forming the belt member 12.

Next, the rubber sheet 11 and the tread 30 are formed on the outer peripheral surface of the belt member 12.
Specifically, first, an uncrosslinked rubber sheet is wrapped around the outer peripheral surface of the belt member 12. Next, an uncrosslinked tread is wrapped around the outer peripheral surface of the uncrosslinked rubber sheet. Then, the tire case 17 (ie, green tire) in which the belt member 12, the uncrosslinked rubber sheet, and the uncrosslinked tread are laminated is crosslinked. Specifically, by heating the tire case 17, the uncrosslinked rubber sheet is crosslinked to form the rubber sheet 11, and the uncrosslinked tread is crosslinked to form the tread 30. The heating temperature for crosslinking may be, for example, 110° C. to 220° C., and the heating time may be, for example, 1 minute to 30 hours.
In the manner described above, the tire 10 of the first embodiment is obtained.

<Second embodiment>
The tire of the second embodiment includes: an annular tire frame member containing rubber; a belt member provided on the outside of the tire frame member in the tire radial direction and including a plurality of reinforcing cords and a coating resin covering the reinforcing cords; The tire includes a tread provided on the outer surface of the member in the tire radial direction, and a rubber sheet arranged between the tire frame member and the belt member and between the belt member and the tread.
In the second embodiment, a tire frame member includes a coating resin of a belt member corresponding to a resin member of a resin-rubber composite, a rubber sheet corresponding to a first rubber member, and a rubber layer corresponding to a second rubber member. and a tread corresponding to the rubber layer. The tread may be a composite of multiple rubber layers.
Note that the rubber layer may be placed in contact with the coating resin of the belt member without interposing the rubber sheet. That is, the rubber layer may correspond to the first rubber member.

The second embodiment will be described below with reference to FIG. 3.
FIG. 3 is a cross-sectional view along the tire width direction showing the configuration of the tire according to the second embodiment. In FIG. 3, members common to other figures are given the same reference numerals and explanations are omitted.
As shown in FIG. 3, the tire 80 according to the second embodiment includes a tire case 94, which is an example of an annular tire frame member including a rubber material containing rubber, a belt member 12, and a rubber sheet. 11 and a tread 30.
The belt member 12, the rubber sheet 11, and the tread 30 are the same as those in the first embodiment, so their explanations will be omitted.

As shown in FIG. 3, the tire 80 of this embodiment is, for example, a so-called radial tire, and includes a pair of bead portions 14 in which bead cores 20 are embedded. A carcass 86 made of one carcass ply 82 straddles between them. Note that FIG. 3 shows the shape of the tire 80 in its natural state before being filled with air.

The carcass ply 82 is formed by covering a plurality of cords (not shown) extending in the radial direction of the pneumatic tire 80 with a coating rubber (not shown).

The end portion of the carcass ply 82 in the tire width direction is folded back toward the outside in the tire radial direction at the bead core 20. In the carcass ply 82, a portion spanning from one bead core 20 to the other bead core 20 is called a main body portion 82A, and a portion folded back from the bead core 20 is called a folded portion 82B.

A bead filler 88 whose thickness gradually decreases from the bead core 20 toward the outside in the tire radial direction is arranged between the main body portion 82A and the folded portion 82B of the carcass ply 82. In the tire 80, the bead portion 14 is a portion of the bead filler 88 on the inner side in the tire radial direction from the outer end 88A in the tire radial direction.

An inner liner 90 made of rubber is arranged inside the carcass 86, and a side rubber layer 92 made of a rubber material containing rubber is arranged outside the carcass 86 in the tire width direction.
In this embodiment, a tire case 94 is composed of a bead core 20, a carcass 86, a bead filler 88, an inner liner 90, and a side rubber layer 92.

In FIG. 3, the belt member 12 is provided on the outside of the carcass 86 in the tire radial direction via the rubber sheet 11, but the invention is not limited thereto. For example, a carcass made of a carcass ply formed by covering a cord with coating rubber may be in contact with the belt member 12.
In FIG. 3, the tread 30 is arranged on the outside of the belt member 12 in the tire radial direction with the rubber sheet 11 in between, but the invention is not limited thereto. For example, the tread may be in contact with the belt member 12.
A drainage groove 30A is formed in the tread 30. A conventionally known pattern is used for the grooves 30A of the tread 30.

(Tire manufacturing method)
Next, an example of a method for manufacturing the tire 80 of this embodiment will be described.
First, an inner liner 90 made of a rubber material, a bead core 20, a bead filler 88 made of a rubber material, a carcass ply 82 in which a cord is covered with a rubber material, and a side rubber layer 92 are formed on the outer periphery of a known tire forming drum (not shown). An uncrosslinked tire case 94 is formed.

On the other hand, the belt member 12 is formed as follows.
Specifically, the resin-coated cord 28 is sent out toward the outer peripheral surface of a belt forming drum (not shown). The resin-coated cord 28 is heated by hot air and pressed against the outer peripheral surface of the belt forming drum in a molten state, and then cooled. In this way, a layer of resin-coated cord 28 is formed on the outer peripheral surface of the belt forming drum.

Next, the belt member 12 in which the resin coated cord 28 has been cooled and the coated resin 26 has solidified is removed from the belt forming drum. Then, an uncrosslinked rubber sheet 11 is attached to the inner peripheral surface of the removed belt member 12, and then the belt member 12 is placed radially outside of the uncrosslinked tire case 94 on the tire forming drum. Thereafter, the tire case 94 is expanded, and the outer circumferential surface of the tire case 94, in other words, the outer circumferential surface of the carcass 86, is pressed onto the inner circumferential surface of the belt member 12.
Finally, the uncrosslinked rubber sheet 11 is attached to the outer peripheral surface of the belt member 12, and then the uncrosslinked tread 30 is attached on the uncrosslinked rubber sheet 11 to obtain a green tire. The obtained green tire is heated to crosslink the rubber to complete the tire 80.

<Third embodiment>
The tire of the third embodiment includes: an annular tire frame member containing a resin; a belt member provided on the outside of the tire frame member in the tire radial direction and including a plurality of reinforcing cords and a covering resin covering the reinforcing cords; A rubber sheet provided on the outer surface in the tire radial direction of the member in contact with the coating resin of the belt member, a tread provided on the outer surface in the tire radial direction of the rubber sheet in contact with the rubber sheet, and a tire of the tire frame member. It has a side rubber provided on the outside in the width direction.
The third embodiment includes a tire frame member corresponding to the resin member of the resin-rubber composite, and a side rubber member corresponding to the rubber member.
Note that a rubber sheet may be disposed between the side rubber and the tire frame member. That is, the rubber sheet may correspond to the first rubber member, and the side rubber may correspond to the second rubber member.

FIG. 4 is a cross-sectional view along the tire width direction showing the configuration of a tire according to a third embodiment. In FIG. 4, members common to other figures are given the same reference numerals and their explanations are omitted.
As shown in FIG. 4, the tire 110 according to the third embodiment includes a tire case 17, which is an annular tire frame member made of a resin material containing resin, and a tire case 17 provided on the outside of the tire case 17 in the tire radial direction. A rubber sheet provided on the belt member 12, the area where the belt member 12 is not provided on the tire radially outer surface of the tire case 17, and the tire radially outer surface and tire width direction outer surface of the belt member 12. 11, a tread 30 provided on the outer surface of the rubber sheet 11 in the tire radial direction, and a side rubber 13 provided on the outer surface of the tire case 17 in the tire width direction.
The tire case 17, the belt member 12, the rubber sheet 11, and the tread 30 are the same as those in the first embodiment, so their explanations will be omitted. The side rubber 13 is made of a material containing rubber.

In the third embodiment, the side rubber 13 is provided as an epoxy rubber member in direct contact with the outer side of the tire case 17 in the tire width direction, but the inner rubber member corresponding to the rubber member is provided in direct contact with the inner side of the tire case 17 in the tire width direction. Rubber may be provided, and an inner rubber corresponding to a diene rubber layer may be provided inside the tire case 17 in the tire width direction via a rubber sheet corresponding to a rubber member.

<Fourth embodiment>
The fourth embodiment is an example of a form in which a resin-rubber composite is provided in a bead portion of an annular tire frame member containing rubber. Specifically, the carcass includes a bead core in which a bead wire is coated with a coating resin, a main body portion located between the bead cores, and a folded portion folded back from inside to outside around the bead core, and a bead core and the main body portion. A tire frame member is constituted by a resin bead filler provided between the folded portion and the folded portion, a rubber sheet provided around the bead core and the bead filler, and a rubber member provided around the rubber sheet. has been done.
In the fourth embodiment, the coating resin of the bead core and the bead filler correspond to the resin member of the resin-rubber composite, the rubber sheet corresponds to the first rubber member, and the rubber member corresponds to the second rubber member.
Note that the rubber member may be in contact with the coating resin of the bead core and the bead filler without interposing the rubber sheet. That is, the rubber member may correspond to the first rubber member.

In the fourth embodiment, both the bead core and the bead filler have a resin layer, but either the bead core or the bead filler may have a resin layer. For example, when the bead filler is made of rubber, the bead filler corresponding to the second rubber member is provided around the coating resin of the bead core corresponding to the resin member via a rubber sheet corresponding to the first rubber member. Alternatively, a bead filler, which corresponds to a rubber member, may be provided in contact with the coating resin of the bead core, which corresponds to a resin member.

FIG. 5 is an enlarged sectional view of a bead portion of a tire according to a fourth embodiment. In FIG. 5, members common to other figures are given the same reference numerals and explanations are omitted.
As shown in FIG. 5, the bead portion 14 of the tire according to the fourth embodiment includes a rubber member 91, a resin bead filler 89, a bead core 20, and a rubber sheet 11 surrounding the bead filler 89 and the bead core 20. and a carcass 86.
In the bead portion 14 shown in FIG. 5, a bead core 20 and a bead filler 89 are embedded in a rubber member 91, and the bead core 20 and bead filler 89 constitute a core-filler member 50 that is integrally configured. A rubber sheet 11 is provided around the periphery. However, the bead core 20 and bead filler 89 may be separate bodies.

As shown in FIG. 5, the bead core 20 includes a bead wire bundle 62 and a covering layer 65 disposed around the bead wire bundle 62.
In the example of FIG. 5, the bead filler 89 is made of the same resin material as the covering layer 65 of the bead core 20, but is not limited thereto. For example, the resin material forming the bead filler 89 may be different from the resin material forming the coating layer 65 of the bead core 20. Further, the resin material constituting the bead filler 89 may be different for each portion of the bead filler 89.
In the example of FIG. 5, both the coating layer 65 of the bead core 20 and the bead filler 89 are made of a resin material, but either one may be made of a resin material. For example, when the covering layer 65 of the bead core 20 is made of a resin material, the bead filler 89 may be made of rubber, and when the bead filler 89 is made of resin, the covering layer 65 may be made of a rubber material. You can leave it there.

The actual number of bead wires constituting the bead core 20 may be one or more. That is, the bead wire bundle 62 may be configured by one bead wire being wound multiple times in the tire circumferential direction, or each of a plurality of bead wires being wound once or multiple times in the tire circumferential direction. It may be configured by being wound over the entire length.
The bead wire can be made of any known material, such as steel cord. The steel cord may, for example, consist of steel monofilament or stranded wire. Moreover, organic fibers, carbon fibers, etc. can also be used.

The tire of this embodiment is manufactured in the same manner as the tire of the second embodiment described above.
In this embodiment, a core filler member 50 obtained by integrally molding a bead filler 89 and a bead core 20 is used. In this embodiment, an uncrosslinked rubber sheet is pasted around the core filler member 50, and then an uncrosslinked rubber member 91 is pasted to form an uncrosslinked tire case. The member and uncrosslinked tread are placed in a tire case to obtain a green tire. The obtained green tire is heated and crosslinked to obtain a tire.

An example of a method for manufacturing the core filler member 50 will be described below.
The method for manufacturing the core filler member 50 includes, for example, an annular body forming step, an injection molding step, and a cooling step.

In the annular body forming step, a strip member formed by coating one or more bead wires with coating resin 63 is wound to form an annular body. The bead core 20 shown in FIG. 5 has a three-layer structure obtained by winding a strip member formed by covering three bead wires with a coating resin 63 three times.
In this step, a strip member is formed by coating the outer peripheral side of the bead wire with a molten coating resin 63 and solidifying the coating resin by cooling. The annular body is formed by winding the strip member.
When two or more layers of strip members are stacked, the layers may be bonded together by solidifying molten resin or may be bonded together using an adhesive or the like.

Following the annular body forming step, in the injection molding step, the annular body formed in the annular body forming step is covered with the material of the covering layer 65 to form the covering layer 65 and the bead filler 89 integrated with the covering layer 65. .

In a cooling step following the injection molding step, the coating layer 65 and bead filler 89 are solidified by cooling. The bead core 20 in the core filler member 50 has a structure in which the periphery of the annular body is covered with a solidified coating layer 65. Furthermore, a bead filler 89 is integrally formed with the coating layer 65 on the outer side of the coating layer 65 in the tire radial direction.

Although one example of the embodiments of the present invention has been described above, the present invention is not limited to these embodiments, and various other embodiments are possible.
Furthermore, the first to fourth embodiments can be combined as appropriate.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these descriptions in any way. Note that unless otherwise specified, "parts" represent mass standards.

<Example 1>
(1) Preparation of uncrosslinked rubber sheet Materials having the following composition were kneaded, and the resulting kneaded product was used to prepare an uncrosslinked rubber sheet with a thickness of 1 mm.
Natural rubber (85 parts by mass)
Butadiene rubber (15 parts by mass)
Carbon black (40 parts by mass)
Process oil (2.64 parts by mass)
Dicumyl peroxide (PO) (0.7 parts by mass)
4,4'-bis(maleimido)diphenylmethane (BMI) (0.7 parts by mass)

(2) Preparation of test piece An uncrosslinked rubber sheet was pasted on one side of a 2.5 mm thick resin sheet made of the resin shown in Table 1, and the rubber sheet was heated under the conditions shown in Table 1 while applying a pressure of 3 MPa. was crosslinked to obtain a test piece consisting of a resin sheet and a crosslinked rubber sheet.
The heating temperature and time are shown in Table 1.

(3) Evaluation of adhesive strength A test was conducted to peel off the crosslinked rubber sheet from the resin sheet of the obtained test piece at room temperature (25°C), 90°C, and 150°C, and the results were evaluated according to the following criteria. evaluated. The results are shown in Table 1.
(Evaluation criteria)
Adhesion: There was no peeling at the interface between the rubber sheet and resin sheet, and damage occurred inside the rubber sheet.
Non-adhesion...Peeling occurred at the interface between the rubber sheet and the resin sheet.

<Comparative example 1>
A test piece was prepared in the same manner as in Example 1, except that the amount of PO was changed to 2 parts by mass and the amount of BMI was changed to 0 parts by mass in the materials used for manufacturing the rubber sheet, and the adhesive strength was determined. evaluated. The results are shown in Table 1.

<Comparative example 2>
A test piece was prepared in the same manner as in Example 1, except that the amount of PO was changed to 4 parts by mass and the amount of BMI was changed to 0 parts by mass in the materials used for manufacturing the rubber sheet, and the adhesive strength was determined. evaluated. The results are shown in Table 1.

<Comparative example 3>
In the materials used to produce the rubber sheet, the amounts of PO and BM were each changed to 0 parts by mass, and stearic acid and zinc white (total of 6 parts by mass) and sulfur and crosslinking accelerator (total of 4.56 parts by mass) were added. A test piece was prepared in the same manner as in Example 1 except that the following was added, and the adhesive strength was evaluated. The results are shown in Table 1.

Details of Resins 1 to 3 shown in Table 1 are as follows.
Resin 1... Acrylonitrile-butadiene-styrene copolymer (content of terminal amino groups: 0 mmol/g)
Resin 2... Polyamide thermoplastic elastomer (content of terminal amino groups: 0.01 mmol/g or more)
Resin 3...Nylon 6 (content of terminal amino groups: 0.01 mmol/g or more)

As shown in Table 1, the test piece made of Resin 2 or Resin 3, in which the rubber sheet contains an organic peroxide and a maleimide compound, and the resin sheet contains amino groups, is different from Resin 1, in which the resin sheet does not contain amino groups. It showed superior adhesion compared to the test piece made of.
Comparative Examples 1 and 2, in which the rubber sheet contains an organic peroxide but no maleimide compound, and Comparative Example 3, in which the rubber sheet contains sulfur without an organic peroxide or a maleimide compound, constitute a resin sheet. No adhesion was exhibited regardless of whether the resin contained amino groups or not.

10 Tire 11 Rubber sheet 12 Belt member 13 Side rubber 14 Bead portion 16 Side portion 17 Tire case 17A Welding resin material 17H Tire half 18 Crown portion 18A Crown portion outer peripheral surface 20 Bead core 24 Reinforcement cord 26 Coating resin 28 Resin coating cord 30 Tread 30A Tread groove 50 Core filler member 62 Bead wire bundle 63 Covering resin 65 Covering layer 80 Tire 82 Carcass ply 86 Carcass 88 Bead filler 89 Bead filler 90 Inner liner 91 Rubber member 92 Side rubber layer 94 Tire case 110 Tire

Claims (6)

comprising a member containing resin and a member containing rubber adhered to the member containing resin,
The resin contains an amino group,
The member containing rubber is a resin-rubber composite containing an organic peroxide and a maleimide compound. The resin-rubber composite according to claim 1, wherein the resin contains at least one selected from the group consisting of polyamide-based thermoplastic elastomer and polyamide. The resin-rubber composite according to claim 1, wherein the resin has an amino group at the end of the molecule, and the content of the amino group is 0.01 mmol/g or more. The resin-rubber composite according to claim 1, wherein the sulfur content of the rubber-containing member is 0% to 2% by mass of the entire rubber-containing member. The resin-rubber composite according to claim 1, further comprising another rubber-containing member adhered to the rubber-containing member. A tire comprising the resin rubber composite according to any one of claims 1 to 5.